Synthetics, Mineral Oils, and Bio-Based Lubricants Chemistry and Technology

Synthetics, Mineral Oils, and Bio-Based Lubricants Chemistry and Technology Copyright 2006 by Taylor & Francis Group, L...

Author: Leslie R. Rudnick (Editor)

1027 downloads 6333 Views 8MB Size Report

This content was uploaded by our users and we assume good faith they have the permission to share this book. If you own the copyright to this book and it is wrongfully on our website, we offer a simple DMCA procedure to remove your content from our site. Start by pressing the button below!
Report copyright / DMCA form

DOWNLOAD PDF

Synthetics, Mineral Oils, and Bio-Based Lubricants Chemistry and Technology

Copyright 2006 by Taylor & Francis Group, LLC

CHEMICAL INDUSTRIES A Series of Reference Books and Textbooks

Consulting Editor HEINZ HEINEMANN

Berkeley, California

1. 2. 3. 4. 5. 6. 7. 8.

9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21.

22. 23. 24. 25. 26. 27.

Fluid Catalytic Cracking with Zeolite Catalysts, Paul B. Venuto and E. Thomas Habib, Jr. Ethylene: Keystone to the Petrochemical Industry, Ludwig Kniel, Olaf Winter, and Karl Stork The Chemistry and Technology of Petroleum, James G. Speight The Desulfurization of Heavy Oils and Residua, James G. Speight Catalysis of Organic Reactions, edited by William R. Moser Acetylene-Based Chemicals from Coal and Other Natural Resources, Robert J. Tedeschi Chemically Resistant Masonry, Walter Lee Sheppard, Jr. Compressors and Expanders: Selection and Application for the Process Industry, Heinz P. Bloch, Joseph A. Cameron, Frank M. Danowski, Jr., Ralph James, Jr., Judson S. Swearingen, and Marilyn E. Weightman Metering Pumps: Selection and Application, James P. Poynton Hydrocarbons from Methanol, Clarence D. Chang Form Flotation: Theory and Applications, Ann N. Clarke and David J. Wilson The Chemistry and Technology of Coal, James G. Speight Pneumatic and Hydraulic Conveying of Solids, O. A. Williams Catalyst Manufacture: Laboratory and Commercial Preparations, Alvin B. Stiles Characterization of Heterogeneous Catalysts, edited by Francis Delannay BASIC Programs for Chemical Engineering Design, James H. Weber Catalyst Poisoning, L. Louis Hegedus and Robert W. McCabe Catalysis of Organic Reactions, edited by John R. Kosak Adsorption Technology: A Step-by-Step Approach to Process Evaluation and Application, edited by Frank L. Slejko Deactivation and Poisoning of Catalysts, edited by Jacques Oudar and Henry Wise Catalysis and Surface Science: Developments in Chemicals from Methanol, Hydrotreating of Hydrocarbons, Catalyst Preparation, Monomers and Polymers, Photocatalysis and Photovoltaics, edited by Heinz Heinemann and Gabor A. Somorjai Catalysis of Organic Reactions, edited by Robert L. Augustine Modern Control Techniques for the Processing Industries, T. H. Tsai, J. W. Lane, and C. S. Lin Temperature-Programmed Reduction for Solid Materials Characterization, Alan Jones and Brian McNichol Catalytic Cracking: Catalysts, Chemistry, and Kinetics, Bohdan W. Wojciechowski and Avelino Corma Chemical Reaction and Reactor Engineering, edited by J. J. Carberry and A. Varma Filtration: Principles and Practices: Second Edition, edited by Michael J. Matteson and Clyde Orr


28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65. 66.

Corrosion Mechanisms, edited by Florian Mansfeld Catalysis and Surface Properties of Liquid Metals and Alloys, Yoshisada Ogino Catalyst Deactivation, edited by Eugene E. Petersen and Alexis T. Bell Hydrogen Effects in Catalysis: Fundamentals and Practical Applications, edited by Zoltán Paál and P. G. Menon Flow Management for Engineers and Scientists, Nicholas P. Cheremisinoff and Paul N. Cheremisinoff Catalysis of Organic Reactions, edited by Paul N. Rylander, Harold Greenfield, and Robert L. Augustine Powder and Bulk Solids Handling Processes: Instrumentation and Control, Koichi Iinoya, Hiroaki Masuda, and Kinnosuke Watanabe Reverse Osmosis Technology: Applications for High-Purity-Water Production, edited by Bipin S. Parekh Shape Selective Catalysis in Industrial Applications, N. Y. Chen, William E. Garwood, and Frank G. Dwyer Alpha Olefins Applications Handbook, edited by George R. Lappin and Joseph L. Sauer Process Modeling and Control in Chemical Industries, edited by Kaddour Najim Clathrate Hydrates of Natural Gases, E. Dendy Sloan, Jr. Catalysis of Organic Reactions, edited by Dale W. Blackburn Fuel Science and Technology Handbook, edited by James G. Speight Octane-Enhancing Zeolitic FCC Catalysts, Julius Scherzer Oxygen in Catalysis, Adam Bielanski and Jerzy Haber The Chemistry and Technology of Petroleum: Second Edition, Revised and Expanded, James G. Speight Industrial Drying Equipment: Selection and Application, C. M. van’t Land Novel Production Methods for Ethylene, Light Hydrocarbons, and Aromatics, edited by Lyle F. Albright, Billy L. Crynes, and Siegfried Nowak Catalysis of Organic Reactions, edited by William E. Pascoe Synthetic Lubricants and High-Performance Functional Fluids, edited by Ronald L. Shubkin Acetic Acid and Its Derivatives, edited by Victor H. Agreda and Joseph R. Zoeller Properties and Applications of Perovskite-Type Oxides, edited by L. G. Tejuca and J. L. G. Fierro Computer-Aided Design of Catalysts, edited by E. Robert Becker and Carmo J. Pereira Models for Thermodynamic and Phase Equilibria Calculations, edited by Stanley I. Sandler Catalysis of Organic Reactions, edited by John R. Kosak and Thomas A. Johnson Composition and Analysis of Heavy Petroleum Fractions, Klaus H. Altgelt and Mieczyslaw M. Boduszynski NMR Techniques in Catalysis, edited by Alexis T. Bell and Alexander Pines Upgrading Petroleum Residues and Heavy Oils, Murray R. Gray Methanol Production and Use, edited by Wu-Hsun Cheng and Harold H. Kung Catalytic Hydroprocessing of Petroleum and Distillates, edited by Michael C. Oballah and Stuart S. Shih The Chemistry and Technology of Coal: Second Edition, Revised and Expanded, James G. Speight Lubricant Base Oil and Wax Processing, Avilino Sequeira, Jr. Catalytic Naphtha Reforming: Science and Technology, edited by George J. Antos, Abdullah M. Aitani, and José M. Parera Catalysis of Organic Reactions, edited by Mike G. Scaros and Michael L. Prunier Catalyst Manufacture, Alvin B. Stiles and Theodore A. Koch Handbook of Grignard Reagents, edited by Gary S. Silverman and Philip E. Rakita Shape Selective Catalysis in Industrial Applications: Second Edition, Revised and Expanded, N. Y. Chen, William E. Garwood, and Francis G. Dwyer Hydrocracking Science and Technology, Julius Scherzer and A. J. Gruia


67. Hydrotreating Technology for Pollution Control: Catalysts, Catalysis, and Processes, edited by Mario L. Occelli and Russell Chianelli 68. Catalysis of Organic Reactions, edited by Russell E. Malz, Jr. 69. Synthesis of Porous Materials: Zeolites, Clays, and Nanostructures, edited by Mario L. Occelli and Henri Kessler 70. Methane and Its Derivatives, Sunggyu Lee 71. Structured Catalysts and Reactors, edited by Andrzej Cybulski and Jacob A. Moulijn 72. Industrial Gases in Petrochemical Processing, Harold Gunardson 73. Clathrate Hydrates of Natural Gases: Second Edition, Revised and Expanded, E. Dendy Sloan, Jr. 74. Fluid Cracking Catalysts, edited by Mario L. Occelli and Paul O’Connor 75. Catalysis of Organic Reactions, edited by Frank E. Herkes 76. The Chemistry and Technology of Petroleum: Third Edition, Revised and Expanded, James G. Speight 77. Synthetic Lubricants and High-Performance Functional Fluids: Second Edition, Revised and Expanded, Leslie R. Rudnick and Ronald L. Shubkin 78. The Desulfurization of Heavy Oils and Residua, Second Edition, Revised and Expanded, James G. Speight 79. Reaction Kinetics and Reactor Design: Second Edition, Revised and Expanded, John B. Butt 80. Regulatory Chemicals Handbook, Jennifer M. Spero, Bella Devito, and Louis Theodore 81. Applied Parameter Estimation for Chemical Engineers, Peter Englezos and Nicolas Kalogerakis 82. Catalysis of Organic Reactions, edited by Michael E. Ford 83. The Chemical Process Industries Infrastructure: Function and Economics, James R. Couper, O. Thomas Beasley, and W. Roy Penney 84. Transport Phenomena Fundamentals, Joel L. Plawsky 85. Petroleum Refining Processes, James G. Speight and Baki Özüm 86. Health, Safety, and Accident Management in the Chemical Process Industries, Ann Marie Flynn and Louis Theodore 87. Plantwide Dynamic Simulators in Chemical Processing and Control, William L. Luyben 88. Chemical Reactor Design, Peter Harriott 89. Catalysis of Organic Reactions, edited by Dennis G. Morrell 90. Lubricant Additives: Chemistry and Applications, edited by Leslie R. Rudnick 91. Handbook of Fluidization and Fluid-Particle Systems, edited by Wen-Ching Yang 92. Conservation Equations and Modeling of Chemical and Biochemical Processes, Said S. E. H. Elnashaie and Parag Garhyan 93. Batch Fermentation: Modeling, Monitoring, and Control, Ali Çinar, Gülnur Birol, Satish J. Parulekar, and Cenk Ündey 94. Industrial Solvents Handbook, Second Edition, Nicholas P. Cheremisinoff 95. Petroleum and Gas Field Processing, H. K. Abdel-Aal, Mohamed Aggour, and M. Fahim 96. Chemical Process Engineering: Design and Economics, Harry Silla 97. Process Engineering Economics, James R. Couper 98. Re-Engineering the Chemical Processing Plant: Process Intensification, edited by Andrzej Stankiewicz and Jacob A. Moulijn 99. Thermodynamic Cycles: Computer-Aided Design and Optimization, Chih Wu 100. Catalytic Naphtha Reforming: Second Edition, Revised and Expanded, edited by George T. Antos and Abdullah M. Aitani 101. Handbook of MTBE and Other Gasoline Oxygenates, edited by S. Halim Hamid and Mohammad Ashraf Ali 102. Industrial Chemical Cresols and Downstream Derivatives, Asim Kumar Mukhopadhyay 103. Polymer Processing Instabilities: Control and Understanding, edited by Savvas Hatzikiriakos and Kalman B . Migler 104. Catalysis of Organic Reactions, John Sowa


105. Gasification Technologies: A Primer for Engineers and Scientists, edited by John Rezaiyan and Nicholas P. Cheremisinoff 106. Batch Processes, edited by Ekaterini Korovessi and Andreas A. Linninger 107. Introduction to Process Control, Jose A. Romagnoli and Ahmet Palazoglu 108. Metal Oxides: Chemistry and Applications, edited by J. L. G. Fierro 109. Molecular Modeling in Heavy Hydrocarbon Conversions, Michael T. Klein, Ralph J. Bertolacini, Linda J. Broadbelt, Ankush Kumar and Gang Hou 110. Structured Catalysts and Reactors, Second Edition, edited by Andrzej Cybulski and Jacob A. Moulijn 111. Synthetics, Mineral Oils, and Bio-Based Lubricants: Chemistry and Technology, edited by Leslie R. Rudnick


Synthetics, Mineral Oils, and Bio-Based Lubricants Chemistry and Technology

Leslie R. Rudnick Pennsylvania State University State College, Pennsylvania

Boca Raton London New York

A CRC title, part of the Taylor & Francis imprint, a member of the Taylor & Francis Group, the academic division of T&F Informa plc.


Published in 2006 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2006 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number-10: 1-57444-723-8 (Hardcover) International Standard Book Number-13: 978-1-57444-723-1 (Hardcover) Library of Congress Card Number 2005054272 This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC) 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Synthetics, mineral oils, and bio based lubricants / edited by Leslie R. Rudnick. p. cm. -- (Chemical industries ; 111) Includes bibliographical references and index. ISBN 1-57444-723-8 (alk. paper) 1. Lubrication and lubricants. I. Rudnick, Leslie R., 1947- II. Chemical industries ; v. 111. TJ1077.S55 2005 621.8'9--dc22

2005054272

Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com Taylor & Francis Group is the Academic Division of Informa plc.


and the CRC Press Web site at http://www.crcpress.com

Preface Lubricants are necessary for the efficient use of machinery. Because of this, the variety of lubricating fluids has grown to meet the demands of new machines having more stringent requirements due to their operation under more severe conditions or in challenging environments. This book is a collection of chapters on lubricating base fluids, applications and trends and provides detailed information on the chemical and physical properties and performance characteristics of all of the major areas of lubrication. An authority in their respective area has written each chapter. This book follows the format of Synthetic Lubricants and High-Performance Functional Fluids, Second Edition but has been greatly expanded to include new chapters on: cyclohydrocarbons, gas-to-liquids (GTL), natural oils as lubricants, chemically modified vegetable oils, the biotechnological enhancement of soybean oil, automatic and continuously variable transmission fluids, environmentally friendly hydraulic fluids, fire-resistant hydraulic fluids, vegetable oil-based engine oils, magnetizable fluids, lubricants for the disk drive industry, fluids for food-grade applications, the critical cleaning of advanced lubricants from surfaces, and diesel automotive trends. A new convention, first described by Stephen Godfree, publisher of the Journal of Synthetic Lubrication (Vol.17, Number 1, 2000) has been adopted for the description of upgraded mineral oil base fluids. This editorial has been included in Appendix 1 of this book. First and foremost I would like to acknowledge the assistance of Rita Lazazzaro throughout the several publishing projects we have worked on together. I have valued her input and suggestions in making the previous titles and this current project successful. I also want to thank


Marianne Russell and Laurie Passano for their help in early stages of this current project and to Russell Dekker for his support in publishing this and the previous books on lubricants and lubricant additives. I want to thank Anita Lekhwani, Fred Coppersmith, Michael Masiello, Vanessa Hodgkinson and Susan Fox-Greenberg of Taylor and Francis Books and K. Mohan Kemar of Newgen Imaging Systems for all of their efforts in bringing this book to completion. For this book, which includes over 60 contributing authors, I am very fortunate to have worked with colleagues who helped me to take this project to completion. I sincerely thank each and every one of you. The real credit goes to you individually and collectively. I dedicate this book to the memory of my father, Robert H. Rudnick, for encouraging me to follow my instincts to become a scientist, to my father-in-law, Sydney M. Miner for teaching me the need to describe the more theoretical and difficult aspects of my work in layman’s terms so as to promote the "useful" aspects of my work, and to two very close friends, Anne Arnstein Diamond and Becky Sidore Spitz who always shared their love of the written word and many other aspects of human endeavor. Finally, thank you to Paula, Eric and Rachel for your constant support and encouragement. In doing a project like this one gains experience, colleagues, friends, a deeper knowledge about the subject and even an appreciation for the process of publishing. I am constantly pleased to see each of you grow in the fields that you have chosen and to have you tell me of your experiences. Leslie R. Rudnick

Editor Leslie R. Rudnick is a Senior Scientist at The Energy Institute, The Pennsylvania State University, University Park. The author, coauthor, editor and coeditor of over 75 journal articles, book chapters, and books, including Synthetic Lubricants and High-Performance Functional Fluids, Second Edition (Marcel Dekker, Inc.) and Lubricant Additives: Chemistry and Applications (Marcel Dekker, Inc.), he holds 29 patents and is a member of the Society of Tribologists and Lubrication Engineers,


the American Chemical Society, the American Society for Testing Materials, and the Society of Automotive Engineers. Dr. Rudnick serves on the editorial board of the Journal of Synthetic Lubrication and received a B.S. degree (1969) in chemistry from the University of Iowa, Iowa City, and M.S. (1972) and Ph.D. (1975) degrees in chemistry from Rutgers University, New Brunswick, New Jersey.

Contributors Atanu Adhvaryu The Pennsylvania State University University Park, Pennsylvania

J. David Carlson Lord Corporation Cary, North Carolina

Garrett M. Grega Anderol Inc. East Hanover, New Jersey

Ewa A. Bardasz The Lubrizol Corporation Wickliffe, Ohio

Maryann Casserino Innovene Naperville, Illinois

Wilfried J. Bartz Technische Akademie Esslingen Ostfildern, Germany

Lois J. Gschwender Air Force Research Laboratory Wright-Patterson Air Force Base Ohio

Massimo Ciali (Retired) Sasol Italy S.p.A Milan, Italy

Gregory A. Bell E. I. DuPont de Nemours and Co., Inc. Deepwater, New Jersey

Roscoe R. Cooley Sasol North America Inc. Houston, Texas

Tom Black Ferrotec (USA) Corp. Nashua, New Hampshire

Serge Decroocq Innovene Lavéra, France

Lynnette Bowen Clarity Chemicals Limited Harrow, England

Kevin L. Dickey Quaker Chemical Corporation Conshohocken, Pennsylvania

Joseph F. Braza Nye Lubricants, Incorporated Fairhaven, Massachusetts

Charles R. Dietrich USDA-ARS Plant Genetics Research Unit Donald Danforth Plant Science Center St. Louis, Missouri

William L. Brown Union Carbide Corporation Tarrytown, New York Stephen A. Burian Santovac Fluids, Inc. Findett Corporation St. Charles, Missouri Richard G. Butler Chemtool Incorporated Crystal Lake, Illinois Edgar B. Cahoon USDA-ARS Plant Genetics Research Unit Donald Danforth Plant Science Center St. Louis, Missouri


Ronald M. Epstein (Retired) Halocarbon Products Corporation River Edge, New Jersey Sevim Z. Erhan USDA, ARS, NCAUR Peoria, Illinois Louis L. Ferstandig Halocarbon Products Corporation River Edge, New Jersey Frank J. Gomba (Retired) United States Naval Academy Annapolis, Maryland

Sibtain Hamid Santovac Fluids, Inc. Findett Corporation St. Charles, Missouri H. Ernest Henderson Lithcon Petroleum USA Inc. Tulsa, Oklahoma Suzzy Ho ExxonMobil Chemical Company Edison, New Jersey Jon Howell E.I. DuPont de Nemours and Co., Inc. Deepwater, New Jersey Barbara F. Kanegsberg BFK Solutions, LLC Pacific Palisades, California Tom E. Karis Hitachi Global Storage Technologies San Jose, California John J. Kurosky Anderol Inc. Oakville, Ontario Stephen C. Lakes Cognis Corporation Cincinnati, Ohio Dennis A. Lauer Klüber Lubrication North America L.P. Londonderry, New Hampshire

Saurabh Lawate Lubrizol Corporation Wickliffe, Ohio

W. David Phillips Great Lakes Chemical Corp. Manchester, England

Simon Lawford Cognis Performance Chemicals UK Ltd Southampton, Hantz, UK

Douglas C. Placek Degussa-RohMax Oil Additives Horsham, Pennsylvania

Darren J. Lesinski Anderol Inc. East Hanover, New Jersey Kenneth C. Lilje CPI Engineering Services, Inc. Midland, Michigan Michael P. Marino Consultant Pocono Pines, Pennsylvania Michael L. McMillan General Motors Research & Development Warren, Michigan Kedar Murthy GE Silicones Waterford, New York Francesca Navarrini Sasol Italy S.p.A P. Dugnano, Italy

Clay Quinn GE Silicones Waterford, New York Michael John Raab Anderol Inc. East Hanover, New Jersey Steven James Randles Uniqema Redcar Cleveland England Blaine N. Rhodes Bellevue, Washington Leslie R. Rudnick The Energy Institute The Pennsylvania State University University Park, Pennsylvania Monica A. Schmidt USDA-ARS Plant Genetics Research Unit Donald Danforth Plant Science Center St. Louis, Missouri

Robert Perry GE Silicones Waterford, New York

Shirley E. Schwartz (Retired) General Motors Corporation

F. Alexander Pettigrew Ethyl Corporation Richmond, Virginia

Brajendra K. Sharma The Pennsylvania State University University Park, Pennsylvania


Ronald L. Shubkin Baton Rouge, Louisiana Robert Silverstein The Orelube Corporation Plainview, New York Robert E. Singler Raytheon Material Engineering Lexington, Massachussets Carl E. Synder Air Force Research Laboratory Wright-Patterson Air Force Base Ohio Z. Ahmed Tahir Anderol Inc. East Hanover, New Jersey Frank Traver GE Silicones Waterford, New York Simon Tung General Motors Research & Development Warren, Michigan Clifford G. Venier (Retired) Shell Global Solutions US, Inc. Houston, Texas Uwe Wallfahrer Akzo Nobel Chemicals GmbH Dueren, Germany R. David Whitby Pathmaster Marketing Ltd Woking, England Margaret M. Wu ExxonMobil Research & Engineering Company Annandale, New Jersey

Contents

Part I

Fluids

Chapter 1

Polyalphaolefins Leslie R. Rudnick

Chapter 2

Polyinternalolefins Francesca Navarrini, Massimo Ciali, and Roscoe Cooley

Chapter 3

Esters Steven James Randles

Chapter 4

Neutral Phosphate Esters W. David Phillips, Douglas C. Placek, and Michael P. Marino

Chapter 5

Polymer Esters Uwe Wallfahrer and Lynnette Bowen

Chapter 6

Polyalkylene Glycols Simon Lawford

Chapter 7

Alkylated Aromatics Margaret M. Wu and Suzzy Ho

Chapter 8

Perfluoroalkylpolyethers Gregory A. Bell and Jon Howell

Chapter 9

Polyphenyl Ether Lubricants Sibtain Hamid and Stephen A. Burian

Chapter 10

Cyclohydrocarbons Sibtain Hamid

Chapter 11

Polychlorotrifluoroethylene Ronald M. Epstein and Louis L. Ferstandig

Chapter 12

Silicones Robert Perry, Clay Quinn, Frank Traver, and Kedar Murthy

Chapter 13

Silahydrocarbons Carl E. Snyder and F. Alexander Pettigrew

Chapter 14

Phosphazenes Robert E. Singler and Frank J. Gomba


Chapter 15

Dialkyl Carbonates Leslie R. Rudnick

Chapter 16

Alkylcyclopentanes Clifford G. Venier

Chapter 17

Polybutenes Serge Decroocq and Maryann Casserino

Chapter 18

Chemically Modified Mineral Oils H. Ernest Henderson

Chapter 19

Gas to Liquids H. Ernest Henderson

Chapter 20

Comparison of Synthetic, Mineral Oil, and Bio-Based Lubricant Fluids Leslie R. Rudnick and Wilfried J. Bartz

Part II

Bio-Based Lubricants

Chapter 21

Natural Oils as Lubricants Leslie R. Rudnick and Sevim Z. Erhan

Chapter 22

Chemically Functionalized Vegetable Oils Sevim Z. Erhan, Atanu Adhvaryu, and Brajendra K. Sharma

Chapter 23

Biotechnological Enhancement of Soybean Oil for Lubricant Applications Monica A. Schmidt, Charles R. Dietrich, and Edgar B. Cahoon

Part III

Applications

Chapter 24

Automotive Crankcase Oils Stephen C. Lakes

Chapter 25

Fluids for Conventional Automatic and Continuously Variable Transmissionns (CVTs) Sibtain Hamid

Chapter 26

Automotive Gear Lubricants Stephen C. Lakes

Chapter 27

Industrial Gear Lubricants Dennis A. Lauer

Chapter 28

Synthetic Greases Joseph F. Braza

Chapter 29

Compressors and Pumps Kenneth C. Lilje

Chapter 30

Refrigeration Lubricants Steven James Randles


Chapter 31

Hydraulics Douglas G. Placek

Chapter 32

Environmentally Friendly Hydraulic Fluids Saurabh Lawate

Chapter 33

Fire-Resistant Hydraulic Fluids Kevin L. Dickey

Chapter 34

Vegetable Oil Based Internal Combustion Engine Oil Blaine N. Rhodes

Chapter 35

Magnetizable Fluids Tom Black and J. David Carlson

Chapter 36

Metalworking Fluids William L. Brown and Richard G. Butler

Chapter 37

Lubricants for Near Dry Machining Robert Silverstein

Chapter 38

Lubricants for the Disk Drive Industry Tom E. Karis

Chapter 39

Synthetic-Based Food-Grade Lubricants and Greases Michael J. Raab

Chapter 40

Critical Cleaning of Advanced Lubricants from Surfaces Ronald L. Shubkin and Barbara F. Kanegsberg

Part IV

Trends

Chapter 41

Automotive Trends in Europe R. David Whitby

Chapter 42

Automotive Trends in North America Simon C. Tung, Michael L. McMillan, and Shirley E. Schwartz

Chapter 43

Diesel Automotive Trends Ewa A. Bardasz

Chapter 44

Automotive Trends in Asia R. David Whitby

Chapter 45

Automotive Trends in South America R. David Whitby

Chapter 46

Industrial Lubricant Trends Garrett M. Grega, John J. Kurosky, Darren J. Lesinski, Michael J. Raab, and Z. Ahmed Tahir

Chapter 47

Trends Toward Synthetic Fluids and Lubricants in Aerospace Carl E. Snyder, Jr. and Lois J. Gschwender


Chapter 48

Part V

Commercial Developments R. David Whitby

Methods and Resources

Chapter 49

Lubricant Performance Test Methods and Some Product Specifications Leslie R. Rudnick

Chapter 50

Lubricant Industry Related Terms and Acronyms Leslie R. Rudnick

Chapter 51

Lubricant Industry Internet Resources Leslie R. Rudnick

Appendix

Publisher’s Note: The Meaning of “Synthetic”


Part I Fluids


1

Polyalphaolefins Leslie R. Rudnick CONTENTS 1.1 1.2

1.3 1.4

1.5

Introduction Historical Development 1.2.1 Technical 1.2.2 Commercial 1.2.2.1 AMSOIL, Inc. 1.2.2.2 Mobil Oil Corporation 1.2.2.3 Gulf Oil Company 1.2.2.4 Chevron Corporation 1.2.2.5 Amoco 1.2.2.6 Ethyl Corporation 1.2.2.7 Exxon Corporation 1.2.2.8 Quantum Chemical Corporation 1.2.2.9 Castrol Limited 1.2.2.10 Uniroyal Chemical Company 1.2.2.11 Neste Chemical 1.2.2.12 Texaco 1.2.2.13 Shell Chemical 1.2.2.14 Idemitsu Petrochemicals 1.2.2.15 Sasol Chemistry Properties 1.4.1 Physical Properties 1.4.1.1 Commercial PAOs 1.4.1.2 Comparison to Mineral Oils 1.4.1.3 Properties of Blends 1.4.2 Chemical Properties 1.4.2.1 Thermal Stability 1.4.2.2 Hydrolytic Stability 1.4.2.3 Oxidative Stability Applications and Performance Characteristics 1.5.1 Overview of Application Areas 1.5.2 Performance Testing for Automotive Applications 1.5.2.1 Crankcase 1.5.2.2 Transmissions 1.5.2.3 Gears 1.5.2.4 Seal Compatibility 1.5.2.5 Economy 1.5.3 Performance Testing for Industrial Applications 1.5.3.1 Refrigeration Compressors 1.5.3.2 Gear Oils 1.5.3.3 Turbines 1.5.3.4 Hydraulic Oil Performance 1.5.3.5 Metal Working Performance 1.5.3.6 Cost Savings


1.5.4

Applications Sensitive to Health and Environmental Issues 1.5.4.1 Food contact 1.5.4.2 Cosmetics and Toiletries 1.5.4.3 Off-Shore Drilling 1.5.4.4 Miscellaneous 1.5.5 Military Applications 1.5.6 Space Applications 1.6 Markets and Production Capacities 1.6.1 Demand by Segment and Region 1.6.2 Emerging Markets 1.6.3 PAO Production Capacity 1.6.4 Competitive Products 1.6.4.1 Very High Viscosity Index Oils 1.6.4.2 High Viscosity Index Oils 1.6.4.3 Polyinternalolefins 1.7 Conclusion 1.7.1 Regulatory 1.7.2 Performance and Cost-Effectiveness 1.7.3 Original Equipment Manufacturers 1.7.4 Petroleum Companies and Blenders 1.7.5 Consumer 1.7.6 New Technology 1.7.6.1 Dodecene-Based PAOs 1.7.6.2 Mid-Viscosity PAOs Acknowledgements References

1.1 INTRODUCTION Further development in versatility and quality of Polyalphaolefins (PAOs) continues to improve this class of synthetic base fluids. In addition to synthetic esters, PAOs are the most commonly used synthetic base fluids in lubricants. PAOs are true synthetics since they are prepared under carefully controlled conditions from essentially pure alphaolefins, which are themselves synthesized. PAOs have been used in lubricants since the early 1950s and new versions are being introduced to provide lubricant formulators “mid-vis” properties, between the conventional 2 to 10 cSt fluids and the high-viscosity PAOs. For example, ExxonMobil Chemical has announced a planned upgrading of their plant in Beaumont, Texas that will make additional synthetic PAO. This will include new products expected to have lower volatility, better lowtemperature properties, and higher viscosity index (VI). ExxonMobil have a SpectraSyn™ line of PAOs ranging in viscosity from 2 to 100 cSt. They also offer a SpectraSyn™ Ultra line of PAOs with viscosities >100 cSt. The term “polyalphaolefin,” or PAO, is commonly used to designate these fluids, actually saturated olefin oligomers, and this designation will be used in this chapter. This class of synthetic high-performance functional fluids has been developed to meet the increasingly stringent demands placed on today’s working fluids. The term PAO


was first used by Gulf Oil Company (later acquired by Chevron), but it has now become an accepted generic appellation for hydrocarbons manufactured by the catalytic oligomerization (polymerization to low molecular weight products) of linear-olefins having six or more (usually ten) carbon atoms [1]. Technological advances are often accompanied by a variety of problems and complications not previously anticipated. Advances in the function and efficient operation of modern machines and engines have brought new challenges relating to the satisfactory use and performance of existing functional fluids. Sum of these challenges are as follows: • Operation under increasingly severe conditions. • The need for more cost-effective and, hence, competitive

operations. • The need to reduce the dependence on the availability of

crude oil stocks. • The specialized performance requirements of emerging

end-use applications. • The necessity of accounting for the critically impor-

tant, but long-ignored, toxicological and biodegradable characteristics of the fluids being used. Today, mineral oil base stocks are being refined to give products that are certainly superior to those available a few years ago. But the limits to which mineral oils

can be economically refined are being strained. In order to satisfactorily address the challenge of solving the problems listed, industry is turning to synthetic alternatives. Polyalphaolefins are gaining rapid acceptance as highperformance lubricants and functional fluids because they exhibit certain inherent, and highly desirable, characteristics [1]. Some of these favorable properties are as follows: • • • • • • • • • • • •

A wide operational temperature range. Good viscometrics (high VI). Thermal stability. Oxidative stability. Hydrolytic stability. Biodegradability (for low viscosity grades). Shear stability. Low corrosivity. Compatibility with mineral oils. Compatibility with various materials of construction. Low toxicity. Manufacturing flexibility that allows “tailoring” products to specific end-use application requirements.

1.2 HISTORICAL DEVELOPMENT 1.2.1 Technical Synthetic oils consisting only of hydrocarbon molecules were first produced in 1877 by the prominent chemists Charles Friedel and James Mason Crafts [2]. Standard Oil Company of Indiana attempted to commercialize a synthetic hydrocarbon oil in 1929 but was unsuccessful because of a lack of demand. In 1931, Standard Oil in a paper by Sullivan et al. [3] disclosed a process for the polymerization of olefins to form liquid products. These workers used cationic polymerization catalysts such as aluminum chloride to polymerize olefin mixtures obtained from the thermal cracking of wax. At about the same time that this work was being carried out, H. Zorn of I.G. Farben Industries independently discovered the same process [4]. The first use of a linear α-olefin to synthesize an oil was disclosed by Montgomery et al. in a patent issued to Gulf Oil Company in 1951 [5]. Aluminum chloride was used in these experiments as it was in the earlier work with olefins from cracked wax. The use of free-radical initiators as α-olefin oligomerization catalysts was first patented by Garwood of SoconyMobil in 1960 [6]. Coordination complex catalysts such as the ethylaluminum sesquichloride/titanium tetrachloride system were disclosed in a patent issued to Southern et al. at Shell Research in 1961 [7]. The fluids produced by the various catalyst systems described earlier in this chapter contained oligomers with a wide range of molecular weights. The compositions and internal structures of these fluids resulted in viscosity/


temperature characteristics that gave them no particular advantage over the readily available and significantly less expensive mineral oils of the day. In 1968, Brennan at Mobil Oil patented a process for the oligomerization of α-olefins using a BF3 catalyst system [8]. Prior to this, BF3 catalysis had given irreproducible results. Brennan showed that the reaction could be controlled if two streams of olefins were mixed in the reactor. The first stream contained the olefin plus a BF3 ·ROH complex, where ROH is an alcohol. The second stream contained the olefin saturated with gaseous BF3 . Of particular interest was the fact that this catalyst system produced a product consisting of a mixture of oligomers that was markedly peaked at the trimer. Shubkin of Ethyl Corporation showed that H2 O [9], as well as other protic cocatalysts such as alcohols and carboxylic acids [10], could be used in conjunction with BF3 to produce oligomers of uniform quality. The experimental technique employed a molar excess of BF3 in relation to the cocatalyst. The excess was achieved either by sparging the reaction medium with BF3 gas throughout the course of the reaction or by conducting the reaction under a slight pressure of BF3 . These studies showed that the oligomerization products exhibited pour points that were well below those anticipated for such compounds, even when dimeric products were allowed to remain in the final mixture. The molecular structure of the dimer was believed to consist of a straight carbon chain containing a single methyl group near the middle. Such branched structures were known to exhibit relatively high pour points. More pertinent to the current subject, these were the first patents to address the potential importance of PAOs derived from such BF3 · ROH catalyst systems as synthetic lubricants. Shubkin et al. later showed that the unique low-temperature properties could be attributed to a high degree of branching in the molecular structure [11].

1.2.2 Commercial The commercial development of PAO fluids as lubricants and high-performance functional fluids began in the early 1970s, but significant growth in markets and in the variety of end-use applications did not begin until the latter part of the 1980s. During this time, several companies played significant roles with both R&D and market development efforts [12]. 1.2.2.1 AMSOIL, Inc. AMSOIL, Inc. was apparently the first company to introduce a full synthetic API certified lubricant into the market in 1972. However, this product was 100% diester based. In 1973, AMSOIL introduced the first synthetic-based two-cycle oil. It was not until late 1977 that AMSOIL introduced full-synthetic 10W-40 motor oil based on PAO/ester [13]. AMSOIL has also introduced hydraulic

and compressor oils and a semisynthetic diesel engine oil, a full-synthetic gear oil based on PAO/ester, and PAObased greases. In 1996, they introduced a PAO/ester based 0W-30 motor oil. 1.2.2.2 Mobil Oil Corporation Mobil Oil Corporation was the first company to introduce a PAO-based synthetic lubricant. In 1973, Mobil began marketing a synthetic motor oil for use in automotive engines in overseas markets. Circulating oils and gear oils were added to the Mobil line in 1974. The first U.S. test marketing of Mobil 1 Synthesized Engine Lubricant began in the autumn of 1974. The test was expanded to eight cities in September 1975, and to all Mobil marketing areas in April 1976. Mobil 1 was initially an SAE 5W-20 product, but it was later replaced by a 5W-30 fluid based on PAO and a neopentyl polyol ester. The polyol ester improved additive solubility and increased seal swell. Mobil’s product distribution was extended to Canada, Japan, and several European countries in 1977. In the same year, Mobil introduced Delvac 1, a PAO-based product aimed at the truck fleet market. Mobil also pioneered PAObased industrial lubricants with its line of Mobil SHC products. Mobil’s PAO plant in the United States has an estimated annual capacity of 52,000 mt. A new plant at Notre Dame de Gravenchon, France, reportedly has an annual capacity of 50,000 mt. Mobil purchases 1-octene, 1-decene, and 1-dodecene for its PAO production. In addition to the low-viscosity PAOs, Mobil also produces two grades of high-viscosity PAO. The annual sales for these products is believed to be around 4000 mt. Mobil was purchased by Exxon that has created the world’s most versatile supplier and marketer of synthetic base fluids. These include PAOs from 2 to 1000 cSt. 1.2.2.3 Gulf Oil Company Gulf Oil Company appears to have had an interest in synthetic hydrocarbons in the 1940s. Developmental work at the Gulf laboratories in Harmarville, Pennsylvania, continued into the 1960s and 1970s. In 1974, Gulf built a semiworks plant with a capacity of 1125 mt/yr. The first commercial sale from this plant was in December 1974. During the years 1976–1980, Gulf introduced an arctic super duty 5W-20 CD/SE crankcase lubricant and an arctic universal oil/transmission oil. In Canada, Gulf began marketing PAO-based gear lubricants, synthetic greases, and a partial synthetic 5W-30 crankcase oil. Gulf began commercial production in their PAO plant in Cedar Bayou, Texas, in December 1980. The initial production capacity was 15,400 mt/yr, and the facility was strategically located next to Gulf’s olefin plant. In 1981– 1983, Gulf added several new PAO-based products to their line of synthetic fluids. These included Gulf Super


Duty II, a full-synthetic 0W-30 crankcase oil, Gulf SL-H, a hydraulic fluid for high- and low-temperature operation, and Gulf Syngear, a 75W-90 gear oil for long life and fuel economy. In addition to their fully formulated products, Gulf marketed PAO to the merchant market under the trade name Synfluid Synthetic Fluids. Gulf Oil Corporation was acquired by Chevron Corporation in 1984. 1.2.2.4 Chevron Corporation Prior to 1984, Chevron marketed a single synlube-based product. That product was Chevron Sub Zero Fluid, a 7.5W-20 CD/SE crankcase oil for use in construction equipment and vehicles employed in the Alyeska pipeline project in Alaska. In June 1984, Chevron acquired Gulf Oil Company. In late 1985, the PAO manufacturing and marketing responsibilities were transferred to the Oronite Division of Chevron Chemical. Chevron continued to offer the PAO-based arctic oil plus Chevron Tegra PAO-based synthetic lubricants, which included the old Gulf Syngear and three grades of compressor oils. Unlike Mobil, who chose to market aggressively under their own name, Chevron decided to focus on the merchant market. The capacity of the Chevron plant has been increased to approximately 54,000 mt. Chevron, like Amoco Corporation, but unlike Mobil, is basic in the α-olefin raw material used to manufacture PAO fluids. In July 2001, Chevron Corporation merged their chemical assets (except for the Oronit Additives Division) with the chemicals part of Phillips Petroleum forming the joint venture Chevron Phillips Chemical Company LP. 1.2.2.5 Amoco Amoco, formerly Standard Oil Company (Indiana), was probably the first U.S. petroleum company to investigate synthetic hydrocarbon fluids. The pioneering work by Sullivan in the early 1930s has already been mentioned [3]. Those efforts led to a patent that described the aluminum chloride-catalyzed polymerization of olefins derived from cracked wax [14]. An attempt to commercialize a synthetic lubricating fluid in 1929 was abandoned because of lack of demand. In 1982, Amoco Oil Company began test marketing a 100% PAO-based lubricant. This venture was followed in April 1984 with the introduction of Amoco’s Ultimate line of crankcase oils for both gasoline and diesel oils. Amoco later expanded the product line to include gear oils and grease bases. All of the PAOs for the Ultimate products were purchased until 1996 when Amoco purchased both the alphaolefin and PAO technology plants from Albemarle Corporation. Amoco was purchased by BP (British Petroleum), however, BP has recently announced interest in selling its linear alphaolefins and PAOs business to adopt a new strategy for its petrochemicals business.

BP currently has the technology and resources to produce PAOs directly from its own ethylene. 1.2.2.6 Ethyl Corporation In 1970, Ethyl began conducting research on a process for the polymerization of linear α-olefins to form lowviscosity functional fluids. The concept was attractive since Ethyl was one of the world’s largest manufacturers of linear α-olefins. The target application was a hydraulic fluid specification for military jet aircraft. As it turned out, the specifications were written around an experimental fluid from Mobil, and the independent research at Ethyl led to a similar BF3 -catalyzed process and decene-based product as that developed by Mobil. Ethyl chose not to commercialize its findings because of the small potential market that existed at that time. Following the oil embargo of 1974, and the subsequent introduction of Mobil 1, Ethyl reinstituted a PAO research program. They entered the merchant market for PAO base fluids in the late 1970s through a toll manufacturing arrangement with Bray Oil in California. In 1981, Ethyl decided to build a Market Development Unit (MDU) to manufacture PAO in Baton Rouge, Louisiana. The 7000 mt MDU came on stream in mid-1982, and Ethyl intended that this plant would operate until the market had grown to a size that would justify a world-scale plant. Marketing of the PAO was handled by Ethyl’s Edwin Cooper Division, which was responsible for the manufacture and marketing of Ethyl’s lube oil additives, and the Division trade name HiTEC was used for the fluids. The division name was later changed to Ethyl Petroleum Additives Division (EPAD). Slow growth in the PAO market prompted Ethyl to shut down the MDU in 1985 and return to a toll arrangement. In 1987, Ethyl entered into an agreement with Quantum Chemical whereby Quantum would manufacture PAO from Ethyl’s decene. Ethyl’s PAO sales in Europe began to grow rapidly, and a decision was made to build a plant at Ethyl’s manufacturing site at Feluy, Belgium, where a large new α-olefin plant was also being planned. In early 1989, Ethyl transferred responsibility for the PAO project from the EPAD to the Industrial Chemicals Division. This decision reflected the philosophy that PAO is a base stock rather than a lube additive, and the action allowed Ethyl to expand the scope of the sales effort to include a broader potential market. In keeping with the philosophy of PAO being a base stock, the trade name for the bulk fluids was changed to ETHYLFLO PAO fluids, and an aggressive marketing campaign was launched in North America. In 1989, Quantum sold its Emery Division to Henkel, but retained its PAO plant at Deer Park, Texas, leaving Quantum in the difficult situation of having neither its own source of 1-decene nor its own marketing organization. In 1990, Ethyl purchased Quantum’s Deer Park plant, which


is located only a few miles from Ethyl’s large α-olefin plant at Pasadena. The Deer Park facility has two PAO production trains and an annual capacity of 77,000 mt. Ethyl’s 36,000 mt Feluy plant came on stream in January 1991. Ethyl split off Albemarle as a separate company in 1994 that owned and operated the PAO business until March 1996 when Amoco purchased the alphaolefin and PAO business from Albemarle. BP now markets these PAOs under the DURASYN™ PAO trade name. 1.2.2.7 Exxon Corporation Exxon introduced Esso Ultra Oil in Europe in mid-1986. This lubricant is a partial synthetic oil containing PAO. Exxon has produced small quantities of PAO in its alkylation facility at its chemical plant in Port Jerome, France. Plans to convert that plant to full-scale PAO operation appear to have been shelved. ExxonMobil Chemical has recently announced a planned upgrading of their plant in Beaumont, Texas, that will increase capacity and provide additional synthetic PAO. The products are expected to have lower volatility, better low-temperature properties and a higher VI. ExxonMobil have a SpectraSyn™ line of PAOs ranging in viscosity from 2 to 100 cSt. They also offer a SpectraSyn™ Ultra line of PAOs with viscosities >100 cSt. 1.2.2.8 Quantum Chemical Corporation Quantum Chemical Corporation is the name adopted in 1988 by the former National Distillers and Chemical Corporation. National Distillers entered the synthetic lubricants business in 1978 with the purchase of Emery Industries, an important producer of ester-based synlubes. In December 1980, National Distillers announced the construction of a 15,400 mt PAO plant at their manufacturing facility in Deer Park, Texas. The plant did not actually come on stream until late 1983. In 1987, they entered into a manufacturing and marketing agreement with Ethyl Corporation, as described in Section 1.2.2.6. The 1-decene feedstock was supplied by Ethyl. By 1989, Quantum had debottlenecked the PAO plant and built a second, larger plant at the same location, bringing the total capacity to 77,000 mt. In 1990, they sold their PAO business and manufacturing site to Ethyl Corporation. In 1994, Ethyl spun off Albemarle Corporation. The PAO business and manufacturing site became part of Albemarle Corporation, but, as mentioned above, was sold to Amoco in March of 1996. 1.2.2.9 Castrol Limited Castrol, originally The Burmah Oil Public Limited Company, and then Burmah-Castrol, has historically been an innovator in automotive lubricant marketing. In 1981, they purchased Bray Oil Company, a small manufacturer of synthetic lubricants based in California. Bray Oil at that

time had been toll producing PAO for Ethyl Corporation. Although Castrol maintained a strong interest in marketing synthetic lubricants, they chose to close the PAO plant and purchase their PAO requirements. Castrol was an early marketer of synthetic automotive lubricants in Europe. They have introduced a full line of synthetic and semisynthetic gear lubes and compressor oils as well as higher-performance jet turbine oils, military hydraulic fluids, and jet lube products. They introduced Syntron X — a 5W-50 PAO-based automotive synlube — into the United Kingdom in 1988, and a new line of PAObased automotive products, under the trade names Syntorq and Transmax, was introduced into the United States in 1991. They introduced a 5W-50, Syntec PCMO in 1993 followed by a 10W-30 oil. They also introduced Syntec Blend, a part synthetic, in late 1995. 1.2.2.10 Uniroyal Chemical Company Uniroyal has produced high-viscosity PAOs (KV100◦ C = 40 and 100 cSt) since 1980 in a small plant at Elmira, Ontario, Canada. Uniroyal and ExxonMobil are the only two producers of these grades of PAO in the world. Total production capacity is about 2000 mt/yr. Uniroyal merged with Witco in September 1999 to become CK-Witco. This transitioned to Crompton Corporation in mid-2001 that now has the responsibility for the production and marketing of these heavy PAO products. 1.2.2.11 Neste Chemical Neste Chemical has a PAO plant in Berigen, Belgium. The facility came on stream in 1991 and is estimated to have a capacity of 28,000 mt. Neste have since changed their company name to Fortum and now manufacture and sell these products under the trade name NEXBASE™ 2000 series. 1.2.2.12 Texaco Texaco has conducted research on PAOs and holds several patents but has no commercial production. They do, however, market PAO-based lubricants under the trade name Havoline. 1.2.2.13 Shell Chemical Shell Chemical has conducted extensive research on PAOs but has never begun commercial manufacturing. Shell, along with Chevron and Amoco (now BP), is basic in the α-olefin raw material. 1.2.2.14 Idemitsu Petrochemicals Polyalphaolefins are not currently produced in Japan, however, Idemitsu Petrochemicals raised interest in plant construction several years ago. To date, they have not made


any announcement to build a PAO plant on their own or with another company. 1.2.2.15 Sasol In South Africa, Sasol produces 1.4 million (MM) mt/yr of mixed alphaolefins from its coal to hydrocarbons process via Fischer-Tropsch (FT) chemistry. Making plans to produce PAOs and oxo alcohols in the future [15]. Sasol had previously announced plans to double its alphaolefins capacity at its coal to synthetic fluids facility in South Africa [16]. By the forth quarter of 1997, Sasol had a capacity of 110,000 mt/yr of hexane with further expansion planned in 1998–1999 that is expected to include pentene capacity. Sasol was expected to spend $50 MM to build a 50,000 mt/yr 1-octene unit at the facility that was expected to be on stream by 1999. They are considering licenses for China, with the objective of maximizing output of ultra-clean diesel fuel. Sasol has announced several gasto-liquids concepts including low-temperature FT that offers the potential to generate chemical products including C10 –C17 paraffins, waxes, and base fluids.

1.3 CHEMISTRY Polyalphaolefins are manufactured by a two-step reaction sequence from linear alpha-olefins, which are derived from ethylene. The first step is synthesis of a mixture of oligomers, that are polymers of relatively low-molecular weight. alpha-Olefin → Dimer + Trimer + Tetramer + Pentamer, etc. For the production of low-viscosity PAOs (2 to 10 cSt), the catalyst for the oligomerization reaction is usually boron trifluoride (PAOs are commonly classified according to their approximate kinematic viscosity (kV) at 100◦ C — this convention will be used throughout this chapter). The BF3 catalyst is used in conjunction with a protic cocatalyst such as water, an alcohol, or a weak carboxylic acid. It is necessary that the BF3 , a gas, be maintained in a molar excess relative to the protic cocatalyst. Although this stoichiometry may be accomplished by sparging the reaction mixture with a stream of BF3 , it is more practical, on a commercial basis, to conduct the reaction under a slight BF3 pressure (10 to 50 psig). For convenience, a general designation for the catalyst system is BF3 · ROH, where ROH represents any protic species such as those noted above, and the presence of excess BF3 is understood. The BF3 · ROH catalyst system is unique for two reasons. First, this catalyst combination produces an oligomer distribution that is markedly peaked at trimer. Figure 1.1 shows a gas chromatography (GC) trace indicating the

• • • • • • •

Trimers

Tetramers Dimers

Pentamers Hexamers

0

5

10

15

20

25

Time (min)

FIGURE 1.1 Gas chromatography of typical oligomer

oligomer distribution of a typical reaction product derived from 1-decene using a BF3 · n-C4 H9 OH catalyst combination at a reaction temperature of 30◦ C. The chromatogram indicates that only a relatively small amount of dimer is formed. The bulk of the product is the trimer, with only much smaller amounts of higher oligomers present. A second unique feature of the BF3 · ROH catalyst system is that it produces products that have exceptionally good low-temperature properties. The extremely low pour-point values were puzzling to the early workers in the field until it was shown that the resulting oligomers exhibit a greater degree of skeletal branching than would be predicted by a conventional cationic polymerization mechanism [11]. The reason that BF3 catalysis causes excess skeletal branching during the oligomerization process is unclear. The first researcher who recognized the phenomenon proposed a mechanism involving a skeletal rearrangement of the dimer [11]. A later paper proposed that the monomer undergoes rearrangement [17]. A third paper proposed that the excess branching arose from positional isomerization of the double bond in the monomer prior to oligomerization [18]. In fact, the large number of isomers that are formed cannot be explained by any single mechanism, and the role of BF3 · ROH in promoting the necessary rearrangements remains unexplained. Even though the mechanism of the BF3 · ROHcatalyzed oligomerization remains to be fully elucidated, researchers have learned how to advantageously control the composition of the final PAO product so as to tailor the oligomer distribution to fit the requirements of specialized end-use applications [19]. This customizing is done by manipulation of the reaction variables that include the following: • • • •

Chain length of olefin raw material Temperature Time Pressure


Catalyst concentration Cocatalyst type and concentration Cocatalyst feed rate Olefin feed rate Reaction quench and recovery procedures Hydrogenation catalyst and conditions Distillation

In addition to controlling the relative distribution of the oligomers by manipulation of the reaction parameters, the PAO manufacturer can also make major alterations in the product properties by varying the choice of starting olefin. Today, the commercial PAO market is dominated by decene-derived material because these products have the broadest range of properties, but a knowledgeable producer has the option of choosing other starting olefins in order to better satisfy the requirements for a particular enduse application. For example, PAO based on C12 -olefin is manufactured commercially by Chevron and Mobil. Mobil also makes PAO material containing oligomers based on 1-octene, 1-decene, and 1-dodecene mixtures. More detail on the potential use of alternate olefin streams are discussed later. The crude reaction product is quenched with water or caustic, allowed to settle, and then washed again with more water to remove all traces of the BF3 catalyst. Gaseous BF3 can be recovered by concentration of the wash water and treating the solution with concentrated sulfuric acid. A second step in the manufacturing process entails hydrogenation of the unsaturated oligomer. The hydrogenation may be carried out before or after distillation. Distillation is required to remove any unreacted monomer, to separate the dimer, which is marketed as a 2.0 cSt product, and in some cases to coproduce a lighter and a heavier grade of PAO. The hydrogenation is typically performed over a supported metal catalyst such as nickel/kieselguhr or palladium/alumina. Hydrogenation is necessary to give the final product enhanced chemical inertness and added oxidative stability. The term PAO is used even though the fluid is saturated in a subsequent chemical hydrogenation. It is normally not possible to manufacture the higher viscosity PAO (40 and 100 cSt) products using the BF3 · ROH technology. However, several other catalyst systems are known that can give the desired products. One class of catalysts employs alkylaluminum compounds in conjunction with TiCI4 [7] or alkyl halides [20]. The latter system is preferred by Uniroyal, which uses ethylaluminum sesquichloride with allyl chloride. It has also been reported in a Mobil Oil European patent application that high-viscosity PAOs may be produced by dimerizing lower oligomers with peroxides [21]. The patent describes the use of stoichiometric quantities of di-tert-butyl peroxide, which would probably not be economically feasible. On the other hand, a system that

employs hydrogen peroxide directly or the regeneration of an active intermediate might be commercially attractive. Mobil has also obtained a large number of patents describing the use of supported chromium catalysts [22]. The system actually employed by Mobil for commercial manufacture has not been disclosed, but it is believed to employ an aluminum chloride catalyst. Recently, a 25 cSt PAO derived from 1-decene has been commercially produced through a patented process by Chevron Phillips. The catalyst system has not been disclosed but is not based on BF3 or the systems described for the 40 and 100 cSt PAOs. This is described in detail in Section 1.7.6.2.

with changes in temperature compared with the viscosity changes of a low-VI fluid. A practical consequence of this property is that PAOs do not require viscosity index improvers (VIIs) in many applications. The presence of a VII is often undesirable because many tend to be unstable toward shear. Once the VII begins to break down, the fully formulated fluid goes “out of grade” (i.e., fails to retain the original viscosity grade). Several other important physical properties of commercial PAOs are shown in Table 1.1. All products have extremely low pour points and have low viscosities at low temperatures. These properties make PAOs very attractive in the cold-climate applications for which they were first used. At the other end of the spectrum, all but the 2.0 cSt product have low volatilities as demonstrated by the low percentage loss of material at 250˚C in the standard NOACK volatility test. Low volatility is important in hightemperature operations to reduce the need for “topping up” and to prevent a fluid from losing its lighter components and thus becoming too viscous at low or ambient temperatures. Low volatility is also important as it relates to flash and fire points. The typical physical properties of conventional commercial high-viscosity PAO fluids are given in Table 1.2. The two grades available on the market today are the 40 and 100 cSt fluids. As with the low-viscosity PAOs, these fluids have a very broad temperature operating range.

1.4 PROPERTIES The physical and chemical properties of PAO fluids make them attractive for a variety of applications requiring a wider temperature operating range than can normally be achieved by petroleum-based products (mineral oils). An excellent review of PAO-based fluids as highperformance lubricants has recently been published [23]. A summary of the properties of commercially available PAOs is shown in Appendix I.

1.4.1 Physical Properties 1.4.1.1 Commercial PAOs Table 1.1 lists the typical physical properties of the five grades of commercial low-viscosity PAOs available today. These products are all manufactured using 1-decene as the starting material, and the final properties are determined by control of the reaction parameters and (depending on the manufacturer) selective distillation of the light oligomers. Table 1.1 shows that all commercial grades of lowviscosity PAOs have relatively high VIs of around 135 (Note: No VI is shown for PAO 2 because VI is undefined for fluids having a KV of less than 2.0 cSt at 100◦ C). The viscosity of a high-VI fluid changes less dramatically

1.4.1.2 Comparison to mineral oils The excellent physical properties of the commercial PAO fluids are most readily apparent when they are compared directly with those of petroleum-based mineral oils. The fairest comparison is to look at fluids with nearly identical KVs at 100◦ C. The differences in both low- and high-temperature properties can then be examined. Table 1.3 compares the physical properties of a commercial 4.0 cSt PAO with those of two 100N (neutral) mineral oils, a 100NLP (low pour) mineral oil, and

TABLE 1.1 Physical Properties of Commercial Low-Viscosity PAOs Parameter

Test method

KV at 100◦ C (cSt)

ASTM D 445 ASTM D 445 ASTM D 445 ASTM D 2270 ASTM D 97 ASTM D 92 DIN 51581

KV at 40◦ C (cSt) KV at −40◦ C (cSt) Viscosity index Pour point (◦ C) Flash point (◦ C) NOACKa (% loss)

PAO 2

PAO 4

PAO 6

PAO 8

PAO 10

1.80 5.54 306 — −63 165 99.5

3.84 16.68 2,390 124 −72 213 11.8

5.98 30.89 7,830 143 −64 235 6.1

7.74 46.30 18,200 136 −57 258 3.1

9.87 64.50 34,600 137 −53 270 1.8

a Volatility at 250◦ C after 1 h. Alternative procedure is ASTM D 5800.


TABLE 1.2 Physical Properties of Commercial High-Viscosity PAOs Parameter

Test method

KV at 100◦ C (cSt)



PAO 40 40–42 399–423 39,000–41,000 147 −36 to −45 275–280 0.8–1.4

PAO 100 103–110 1,260–1,390 176,000–203,000 170 −21 to −27 280–290 0.6–1.1

a Volatility at 250◦ C after 1 h. Alternative procedure is ASTM D 5800.

TABLE 1.3 4.0 cSt Fluids Parameter

Test method

PAO

100N

100N

100NLP

VHVI

VHVI

VHVI


IV 3.84 16.7 2390 124 −72 213 11.8

I 3.81 18.6 Solid 89 −15 200 37.2

I 4.06 20.2 Solid 98 −12 212 30.0

I 4.02 20.1 Solid 94 −15 197 29.5

III 3.75 16.2 Solid 121 −27 206 22.2

III 4.2 NRb Solid 127 −18 210 13

III 3.98 16.61 Solid 141 −38c 225 13.3

Base Oil Groupa

KV at 100◦ C (cSt) KV at 40◦ C (cSt) KV at −40◦ C (cSt) Viscosity index Pour point (◦ C) Flash point (◦ C) NOACKd (% loss)

a Base Stock Classification as defined by SAE Classification J357. b NR = Not Reported. c Probably pour point depressed. d Volatility at 250◦ C after 1 h. Alternative procedure is ASTM D 5800.

a hydrotreated HVI (high viscosity index) mineral oil. The PAO shows markedly better properties at both high and low temperatures. At high temperatures, the PAO has lower volatility and a higher flash point. A relatively high flash point is, of course, often important for safety considerations. At the low end of the temperature scale the differences are equally dramatic with the highest degree of difference occurring in the low-temperature low-shear regime as is the case with KV. However, similar differences have been observed in Brookfield viscosities. The pour point of the PAO is −72◦ C, while that of three 100N mineral oils and the HVI oil are −15, −12, −15, and −27◦ C, respectively. Table 1.4 compares a commercial 6.0 cSt PAO with a 160HT (hydrotreated) mineral oil, a 240N oil, a 200SN (solvent neutral) mineral oil, and a VHVI (very high viscosity index) mineral oil that is currently considered to be the best of the mineral oils on the market. The broader temperature range of the PAO is again apparent. Table 1.5 makes similar comparisons for 8.0 cSt fluids.


The ability of PAO products to outperform petroleumbased products of similar viscosity at both ends of the temperature spectrum can be easily understood if one compares the GC traces. Figure 1.2 contains chromatograms run under identical conditions of a 4.0 cSt HVI oil and a 4.0 cSt PAO. The PAO product is essentially decene trimer with a small amount of tetramer present. The fine structure of the trimer peak is attributable to the presence of a variety of trimer isomers (same molecular weight, different structure). The HVI oil, on the other hand, has a broad spectrum of different molecular weight products. The oil contains low-molecular-weight materials that adversely affect the volatility and flash point characteristics. It also contains high molecular-weight components that increase the lowtemperature viscosity and linear paraffins that increase the pour point. Figure 1.3 compares the GC traces of a very highquality 6.0 cSt VHVI fluid with a PAO of similar viscosity. The PAO has a well-defined chemical composition consisting of decene trimer, tetramer, pentamer, and a small


Test method

PAO

160HT

240N

200SN

VHVI

VHVI


IV 5.98 30.9 7830 143 −64 235 6.1

II 5.77 33.1 Solid 116 −15 220 16.6

I 6.98 47.4 Solid 103 −12 235 10.3

I 6.31 40.8 Solid 102 −6 212 18.8

III 5.14 24.1 Solid 149 −15 230 8.8

III 5.9

Base oil groupa

KV at 100◦ C (cSt) KV at 40◦ C (cSt) KV at −40◦ C (cSt) Viscosity index Pour point (◦ C) Flash point (◦ C) NOACKc (% loss)

NRb 127 −12 225 6

a Base Stock Classification as defined by SAE Classification J357. b NR = Not Reported.

c Volatility at 250◦ C after 1 h. Alternative procedure is ASTM D 5800.

VHVI


Test method

PAO


IV 7.74 46.3 18.200 136 −57 258 3.1

Base Oil Groupa

KV at 100◦ C (cSt) KV at 40◦ C (cSt) KV at −40◦ C (cSt) Viscosity index Pour point (◦ C) Flash point (◦ C) NOACKb (% loss)

325SN

325N

I 8.30 63.7 Solid 99 −12 236 7.2

I 8.20 58.0 Solid 110 −12 250 5.1

5

10 15 20 25 30 35 40 45 PAO

a Base Stock Classification as defined by SAE Classification J357. b Volatility at 250◦ C after 1 h. Alternative procedure is ASTM D 5800.

5

10 15 20 25 30 35 40 45 Time (min)

FIGURE 1.3 Gas chromatography traces of 6.0 cSt fluids

HVI

amount of hexamer. The VHVI fluid, like the HVI fluid in the previous example, contains a wide range of components that degrade performance at both ends of the temperature scale. 5

10

15

20

25

30

35

PAO

5

10

15

20

25

30

35

Time (min)

FIGURE 1.2 Gas chromatography traces of 4.0 cSt fluids


1.4.1.3 Properties of blends The excellent combination of high- and low-temperature physical properties of PAOs, combined with their total miscibility with mineral oils, makes them attractive candidates for blending with certain base stocks in order to improve the base-stock quality and bring it into specification for a particular application. This practice has indeed become widespread (but little publicized) as refiners scramble to meet the newer and more stringent API classification requirements. Figure 1.4 shows the effect on volatility and viscosity upon blending 4.0 cSt PAO with a light (100N) mineral

6.5 6 Viscosity 5.5 5 4.5 4 3.5 80 100 Volatility

30 20 10 0 0

10

20

40

60

Viscosity at 100°C (cSt)

Volatility index (wt% loss)

40

PAO in blend, wt%

40

6.5 6 Viscosity 5.5 5 4.5 4 3.5 80 100 Volatility

30 20 10 0 0

10

20

40

60

Viscosity at 100°C (cSt)

Volatility index (wt% loss)

FIGURE 1.4 Effect of blending 4.0 cSt PAO with 100N mineral oil. (1) In-house test designed to give approximate correlation to ASTM D 972. (2) Weight percentage loss after 2.0 h at 204◦ C under flow of N2

PAO in blend, wt%

FIGURE 1.5 Effect of blending 4.0 cSt PAO with 200N mineral oil. (1) In-house test designed to give approximate correlation to ASTM D 972. (2) Weight percentage loss after 2 h at 204◦ C under flow of N2

oil [24]. The “Volatility Index” depicted in Figure 1.4 and the following Figure 1.5 is derived from an in-house test. A defined quantity of the test sample is placed in a small dish or “planchet,” that is placed in an oven for 2.0 h at 204◦ C. A constant flow of nitrogen is maintained over the sample throughout the test. The values are not the same as obtained in the standard ASTM D 972 or NOACK tests, but they have been shown to correlate well on a relative basis. Small amounts of PAO have a dramatic effect in reducing the volatility of the mineral oil, while having essentially no effect on viscosity. Figure 1.5 shows the effect of blending the same 4.0 cSt PAO with a heavy (200N) mineral oil. In this case, small amounts of the PAO have a large effect in reducing the viscosity of the mineral oil without increasing the volatility.

1.4.2 Chemical Properties In addition to the physical properties, the chemical properties of a functional fluid must be considered. The most important chemical property requirements are that the fluid must be thermally stable and chemically inert. Under normal operating conditions a working fluid must not thermally degrade nor react with the atmosphere, the materials of construction, seals, paints, varnishes, performance-enhancing additives, other fluids with which it is intentionally contacted, or inadvertent contaminants.


1.4.2.1 Thermal stability Many of the operations for which a functional fluid is required are carried out at elevated temperatures. For this reason it is important that the fluid employed not be degraded under the operating conditions. The choice of an appropriate bench test, however, is often difficult. It is important that the test differentiate between thermal and oxidative degradation while simulating real-world operating conditions. It is also important that the test differentiate between thermal degradation and volatility. Some evaluations based on oven-aging or thermogravimetric analysis (TGA) have led to erroneous conclusions because the loss in sample weight and increase in viscosity could be attributed to volatilization of the lighter components rather than chemical degradation. One test commonly employed that avoids the danger of misinterpreting volatility for thermal instability is the Panel Coker Thermal Stability Test. In this test, an aluminum panel heated to 310◦ C is alternately splashed by the test oil for 6 min and baked for 1.5 min. At the end of the test, the panels are rated for cleanliness. A completely clean panel has a rating of 10. Table 1.6 summarizes the results of one study that compared the performance characteristics of mineral oil and various synthetic base stocks for crankcase applications [25]. Under these severe conditions, the mineral oil panel was covered with deposits, indicating a lack of thermal stability. An alkylated aromatic also

1.4.2.2 Hydrolytic stability

performed poorly. By comparison, both a PAO of comparable viscosity and a dibasic ester performed well. The best performance was achieved using a mixture of PAO and a polyol ester. Dibasic and polyol esters are commonly used in conjunction with PAO in crankcase formulations. The thermal stability of PAOs was also investigated regarding use in aviation lubricants [26]. In this evaluation, thermal stability was determined by heating the fluid at 370◦ C under a nitrogen atmosphere for 6.0 h in a sealed autoclave. Thermal degradation was measured by the change in viscosity and by gas chromatographic analysis. The tests show that the thermal-stability of PAO products can be ranked as:

For a functional fluid, the importance of inertness to reaction with water is important for a variety of reasons. Hydrolytic degradation of many substances leads to acidic products which, in turn, promote corrosion. Hydrolysis may also materially change the physical and chemical properties of a base fluid, making it unsuitable for the intended use. Systems in which the working fluid may occasionally contact water or high levels of moisture are particularly at risk. Also at risk are systems that operate at low-temperature or cycle between high and low temperatures. The excellent hydrolytic stability of PAO fluids was reported as a result of tests conducted to find a replacement for 2-ethylbutyl silicate ester as an aircraft coolant/dielectric fluid used by the U.S. military in aircraft radar systems [27]. The test method required treating the fluids with 0.1% water (or 0.1% seawater) and maintaining the fluid at 170 or 250◦ F for up to 200 h. Samples were withdrawn at 20-h intervals, and the flash points were measured by the closed cup method. A decrease in flash point was interpreted as being indicative of hydrolytic breakdown to form lower molecular-weight products. The PAO showed no decrease in flash point under any of the test conditions, whereas the 2-ethylbutyl silicate ester showed marked decreases. Figure 1.6 shows the results for tests at 250◦ F.

Dimer > Trimer > Tetramer These findings are consistent with the molecular structures of the oligomers. The least thermally stable parts of the molecule are the tertiary carbon positions, that is, the points where there are branches in the carbon chains. The higher oligomers have more branches and are thus more subject to thermal degradation. Thermal stability as measured by Federal Test Method 791B (modified) shows that the thermal stability of PAOs is related to the amounts of dimer, trimer, tetramer, and pentamer present (Table 1.7).

TABLE 1.6 Panel Coker Thermal Stability Test Base fluid

1.4.2.3 Oxidative stability

Cleanliness

4.0 cSt mineral oil 4.0 cSt PAO 5.0 cSt Alkylated aromatic 5.4 cSt Dibasic ester 4.0 cSt PAO/(polyol ester)

0 8.0 2.0 8.0 9.5

Test conditions Panel temp. Sump temp. Operation Rating

310◦ C 121◦ C 6 min splash/1.5 min bake 10 = clean

A high level of oxidative stability is essential to the performance of a functional fluid. In many applications the fluid is required to perform at elevated temperatures and in contact with air. The results from attempts toward evaluation of fluids for oxidative stability, however, are often confusing. The results are dependent on the test methodology. Tests involving thin films tend to give different results than tests using bulk fluids. Not only the presence or absence of metals that catalyze oxidation is very important, but also the fact different metals interact differently with different fluids. In addition, oxidative stability may be enhanced

TABLE 1.7 Thermal Stability as a Function of Oligmer Viscosity loss at

2 cSt 4 cSt 6 cSt 8 cSt 10 cSt


Oligmer (%)

250◦ C

300◦ C

371◦ C

Dimer

Trimer

Tetramer

Pentamer

−0.2 −0.9 −2.4 −4.0 −4.4

−1.1 −5.3 −16.9 −22.4 −22.9

−49.9 −79.7 −88.4 −92.3 −94.3

90 0.6 0.1 — —

9.0 84.4 33.9 6.0 1.1

— 14.5 43.5 55.7 42.5

— 0.5 17.4 27.2 32.3

300

Flash point,°F

280 270

PAO Silicate ester

260 250 240 230

Induction time, min

180

290

Formulation: 100 SEN mineral oil 4.2 cSt PAO 13.7% DI 8.0% VII

170 160 150 140

220

0

210

10

20

30

Wt% PAO in oil 0

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 Time (h) at 250°F with 0.1% H2O

FIGURE 1.6 Hydrolytic stability

by the use of antioxidants, but different fluids respond differently to different antioxidants. One set of experiments that attempted to differentiate between PAOs and mineral oils entailed using Differential Scanning Calorimetry (DSC) [24]. In this test, the fluid is heated in a pan at a controlled rate, and the temperature at which there is an onset of oxidation is determined by the accompanying exotherm. All of the commercial PAO products (with the exception of 2.0 cSt fluid) were tested. The onset temperatures for the six viscosity grades fell in the very narrow range of 187.3 to 191.6◦ C. Two 6.0 cSt mineral oils gave values of 189.2 and 200.6◦ C, respectively. Quite a different result was reported for a laboratory oxidation test in which the fluid was heated at 163◦ C for 40 h in the presence of steel, aluminum, copper, and lead coupons [25]. In this test a 4.0 cSt mineral oil exhibited a 560% viscosity increase and a light sludge appearance, whereas a 4.0 cSt PAO showed only a 211% viscosity increase and no sludge. These results seem to indicate better performance for the PAO, but the loss of weight by the lead coupon in the PAO was 2.8 times that of the coupon in the mineral oil. The same paper reports better performance for mineral oils in a rotary bomb test that measures the time for a specific pressure drop, but better performance for PAOs in beaker oxidation tests in which the increase in viscosity is measured. It has been reported that the failure of unstabilized PAO to outperform unstabilized mineral oil in oxidative stability tests may be attributed to the presence of natural antioxidants in the latter [28]. The lack of inhibitors in the pure PAO is then given as the rationale for the greater responsiveness of the PAOs to the addition of small amounts of antioxidants. An interesting and somewhat similar rationale has been given for the unusually good responsiveness of PAOs to the addition of antiwear and other performance additives [29]. These researchers from the All-Union Scientific Institute of Oil Refining in Moscow conclude that the efficiency of small concentrations of additives in PAO oils is related to the fast adsorption of the additives on the


FIGURE 1.7 Thin-film oxygen uptake test (TFOUT)

metal surfaces, because there is little interference of the process in transportation from the bulk oil to the tribosurface. The low level of interference is a result of weak cohesive forces between the additive molecules and the PAO substrate. The arguments noted above are supported by results obtained from oxidative stability testing of fully formulated part-synthetic engine oils [30]. A thin film oxygen uptake test (TFOUT) was used for these studies. This test is a modified rotary bomb oxidation procedure in which the bomb is charged with sample, a small amount of water, a fuel catalyst, and a metal catalyst. The bomb is then pressurized with pure oxygen, placed in a bath at 160◦ C, and rotated axially at 100 rpm at a 30◦ angle from the horizontal. The time from the start of the test until a drop in pressure is noted and is defined as the oxidation induction time of the oil. The test oils each contained 13.7% of a detergent-inhibitor package (DI) and 8.0% of a VII. The base stock consisted of a 100 SN mineral oil blended with a 4.2 cSt PAO. Figure 1.7 shows that as the percentage of PAO in the sample was increased from 0 to 30%, the induction time for the onset of oxidation increased from 143 to 173 min. Two other papers of interest concerning the oxidative stability of PAOs are also referenced [31,32].

1.5 APPLICATIONS AND PERFORMANCE CHARACTERISTICS The use of PAO-based functional fluids is growing rapidly. Conventional applications, such as automotive crankcase, are being spurred on by tighter specifications and an increasing demand for higher performance. Nonconventional applications are also beginning to grow rapidly, especially where specific properties of PAO fluids give them particular advantages in performance, cost-effectiveness, or environmental acceptability. OEM confidence in PAObased synthetic formulations is demonstrated by factory fill crankcase use in expensive high-performance vehicles such as the Chevrolet Corvette, and the Dodge Viper. Porsche has also recently announced the approval of PAO-based full-synthetic SAE 5W-40 and SAE 10W-40

Mobil 1 for factory fill for all Porsche passenger cars. Audi uses PAO-based full-synthetic (0W-30) in larger automobiles. BMW factory fill full-synthetic gear oils are used for rear axle and manual transmission in passenger cars and Ford-Europe has a factory fill partial synthetic for its manual transmissions.

The Society of Automotive Engineers (SAE) [63]. In Appendix B of the SAE book, the editors summarize the “eight superior performance features of synthetic engine oils.” Their conclusions are based on a compilation of data in the various papers. The eight features which they identify are the following:

1.5.1 Overview of Application Areas

1. Improved engine cleanliness. This is based on a test using four taxicabs employing an SAE 5W-20 PAObased oil. Oil changes at 12,000 mi for 60,000 mi were followed by a 40,000 “no drain” period. 2. Improved fuel economy. The results of ten different test programs involving a total of 182 vehicles showed a weighted average fuel savings of 4.2%. 3. Improved oil economy. In ten different tests on oil consumption, the percentage of improvement in miles per quart ranged from 0% (for a military arctic lubricant) to 156%. The average improvement was 55.9%. 4. Excellent cold starting. Automobiles with 400 CID V-8 engines could be started at −39◦ F when the crankcase contained an SAE 5W-20 PAO-based synthetic oil. With a mineral oil of the same viscosity grade the lowest engine-starting temperature was −29◦ F. 5. Excellent low-temperature fluidity. For the two oils described in item 4, the PAO-based oil exhibited a pour point of −65◦ F, whereas the mineral oil had a pour point of −37◦ F. 6. Outstanding performance in extended oil drain. This conclusion was based on 100,000-mi tests using parkway police cruisers, which are normally operated at speeds ranging from 55 to 100 mi/h. The test vehicles used a PAO-based SAE 5W-20 “SE-CC” oil. Oil and filter changes were performed every 25,000 mi. The baseline consisted of a series of tests carried out in identical vehicles operated on SAE 10W-40 “SE” mineral oil with oil and filter changes every 5,000 mi. 7. High-temperature oxidation resistance. Viscosity increase was measured in a 2-l Renault after 64 h of operation with an oil-sump temperature of 302◦ F. The synthetic oil showed a 10% increase in viscosity and the mineral oil showed a 135% increase. Both samples were SAE 10W-50 oils. 8. Outstanding single- and double-length SAE-ASTMAPI “SE” performance tests. The results of all of these tests are presented in the reference. The PAO-based synthetic oils met or exceeded all of the requirements.

The following is a listing of both established and emerging application areas for PAOs. The list of applications has grown to such a degree in the last few years that a comprehensive review of the PAO performance attributes found advantageous in each and every application would require more space than is available here. Instead, where possible, a reference is cited so that the reader may refer to published information and data in the specific area of interest. Following this section, some performance data for areas of the broadest interest are presented. For detailed reviews of the most prominent areas of application, the reader is referred to the appropriate chapters in Part II of this book. Engine crankcase [33,34] Hydraulic fluids [35] Gear oils [36–39] Greases [4,40–42] Brake fluids [43] Shock absorbers [44] Automatic transmission fluids [45] Metal working fluids [46] Pumps [38] Mining and conveyor [47]

Compressor oils [38,48–50] Heat transfer media [51] Dielectric fluids [24,52] Gels for coating optical fibers [53] Off-shore drilling [54] Cosmetics and personal care products [55] Textiles [56–58] Polymers [59] Space applications [60] Turbine Oils [61,62]

1.5.2 Performance Testing for Automotive Applications Although physical properties are obviously important in choosing a fluid for a particular application, it is essential that the fluid be subjected to performance testing under conditions that simulate the limits to which the final product will be stressed. But, as indicated above, the list of applications for PAOs has grown to the point that it precludes a comprehensive discussion of performance testing for all applications. Because the requirements for the wide variety of automotive applications encompass much of the broader spectrum of applications, this section will focus on tests specifically designed and conducted by the automotive industry. An excellent summary of the automotive testing conducted in the 1970s and early 1980s may be found in a collection of 26 papers published in one volume by


More recent data show that PAO-based fluids continue to provide superior performance for the increasingly sophisticated cars being built today. Today’s automobiles tend to have smaller, more demanding engines. Increased emphasis on aerodynamics means less cooling under the hood, resulting in higher operating temperatures in both the engine and the transmission. In addition to the ability to meet this challenge with excellent thermal and oxidative

stability, PAOs offer another advantage over mineral oils under these severe operating conditions. Both the thermal conductivity and the heat capacity of PAO fluids are about 10% higher than values for the comparable mineral oils. The net result is that PAO-lubricated equipment tends to run cooler. Fully synthetic automotive lubricants for engine oils, automatic transmission fluids, gear oils, and grease applications provide improved protection of hardware [64]. The following sections examine, in somewhat greater detail, the results of testing for all the major areas of automotive applications. 1.5.2.1 Crankcase It is now widely accepted that synthesized fluids, such as PAOs and PAO/ester blends, offer inherent performance advantages over conventional petroleum — based fluids for the formulation of modern automotive and commercial engine oils. Proof-of-performance field testing is essential to validate bench test results and document oil quality reserve features [65–70]. The importance of oil quality as a major factor in its durability have been discussed in recent reports [71,72]. Quality differences in engine oil can account for differences of 2 to 3 times the levels of equipment wear. Tables 1.8–1.11 illustrate the results of tests related to the use of PAO in automotive crankcase applications [24]. Table 1.8 contains data relating to the hot oil oxidation test (HOOT), which is designed to measure the thermal and oxidative stability of the fluid inside an engine [73]. A PAO and a mineral oil were compared employing identical additive packages at identical concentrations. In this test, air is bubbled through 25 g of the test oil at a rate of 10 l/h for 5 days at 160◦ C. The oil contains 178 ppm iron(III) acetylacetonate and 17 ppm copper(II) acetylacetonate as oxidation catalysts. The significantly superior performance of the PAO has two possible implications. First, the PAO-based fluid can be used for longer drain intervals, resulting in less down-time and lower maintenance costs. Second, PAO can be used with lower levels of additives and other stabilizers, thus reducing the price differential between PAO and a comparable mineral oil. Table 1.9 contains the results of the Petter W1 Engine Test after 108 h. The test measures both the increase in viscosity of the fluid and the amount of wear, as determined by bearing weight loss. In this test, the advantages of employing a part-synthetic oil mixture are shown. When PAO is used as only 25% of the base oil, the percentage of viscosity increase is halved. The data in Table 1.10 was acquired from a Sequence IIIE Engine Test, which is commonly used in North America. Table 1.11 contains data relating to the VW Digiphant Test, which is more widely used in Europe. In both tests a 5W50 full-synthetic PAO-based oil is compared with a 15W-40 mineral oil. As indicated by the SAE


TABLE 1.8 Hot Oil Oxidation Crankcase)a Fluid

Test

(Automotive

Start (KV40◦ C , cSt)

Finish (KV40◦ C , cSt)

95 94

146.3 96.8

Mineral PAO

% Change 54.0 3.0

a Conditions: Same additive package at same concentration; temperature = 160◦ C; time = 5 days. Test described

in Shubkin, R.L. (1994). Lubrication Engineering 50, 196–201.

TABLE 1.9 Petter W1 Engine Testa Oil

Grade

KV40◦ C % increase

Mineral PAO-25% PAO-50% PAO-100%

15W-40 10W-40 10W-40 15W-40

108 54 45 20

Bearing weight loss, (mg) 14.1 9.7 11.5 14.5

a Conditions: Same additive package at same concentration;

time = 108 h.

TABLE 1.10 Sequence IIIE Engine (North America) Oil

Grade

Mineral PAO

15W-40 5W-50

Test

KV40◦ C % increase 167 62

TABLE 1.11 VW Digiphant Test (Europe)a Oil

Grade

KV40◦ C % increase

Mineral PAO

15W-40 5W-50

108 25

KV100◦ C % increase 62 9

a Time = 147 h.

classifications, the PAO-based oil is rated for operation at temperatures both lower and higher than the comparable mineral-oil-based fluid. Nevertheless, the PAO lubricant still out-performed the mineral oil by a wide margin.

The significant performance advantages of PAO-based synthetic engine oils compared with highly refined mineral oils has been reported [74]. Under the high-temperature conditions of a quadruple length (256 h) Sequence IIIE test, a PAO-based formulation resulted in excellent performance. Sequence VE sludge and wear testing is one of the most severe overall passenger car engine oil tests. This test simulates low temperature, stop and go driving conditions by measuring sludge, varnish and wear in a 2.3-L Ford engine. In double length tests, PAO-based formulations clearly outperformed oils blended with severely hydroprocessed mineral oil. In triple length CRC L-38 tests, PAO-based formulation showed exceptional wear and corrosion protection. In diesel engine testing a PAO-based formulation outperformed a commercial-oil-based on severely hydroprocessed mineral oil. Superior deposit and wear results were found for the PAO-based engine oil. Double length VW 1431 turbo diesel tests demonstrated the superior thermal/oxidative stability of the PAO-based formulation. Durability of an optimized PAO-based synthetic formulation compared with a commercial high-quality mineral oil was also measured. Chassie rolls testing was done at 55 mph and at 85 mph with 15,000 mi (24,123 km) oil drains intervals. Wear for the engine having the PAO-based formulation was essentially nil. The engine run on the commercial mineral oil formulation showed several wear parameters that exceeded factory limits. Final proof of performance was evaluated using over the road extended drain vehicle tests. In recent extended drain fleet testing studies, PAObased fully formulated full-synthetic oil outperformed mineral oil by having better viscosity control, less oil consumption, and better end-of-test vehicle engine ratings [75]. An added benefit from using synthetic oils over mineral oils (including hydrocracked oils) is the improved performance in regard to filter plugging. Goyal [76] has shown that overall filter life was improved using synthetic oils. The synthetic oils tested showed no filter plugging in extended drain up to 25,000 mi (40,000 km) over-the-road tests. Synthetic fluids, such as PAO/ester blends, offer a number of inherent performance advantages over conventional petroleum-based oils for the formulation of modern automotive engine oils. Another important feature that must be considered in automotive crankcase applications is low-temperature performance. The most widely recognized property benefit of PAO-based fluids is excellent low-temperature performance [77]. Table 1.12 and Table 1.13 compare the low-temperature characteristics of base fluid PAOs with HVI and VHVI mineral oils of comparable viscosity [24]. Highly refined mineral oil stocks are improved over conventional mineral oils, however, they suffer in


TABLE 1.12 Low-Temperature Performance (Crankcase)

Oil PAO VHVI HVI 100SN

KV100◦ C (cSt)

Pour point (◦ C)

Cold crank simulation −25◦ C (mPa sec)

3.90 3.79 4.50 3.79

−64 −27 −12 −21

490 580 1350 1280

Brookfield viscosity −25◦ C (cP) 600 1160 Solid Solid

TABLE 1.13 Low-Temperature Performance (Crankcase)

Oil PAO VHVI HVI HVI 150SN

KV100◦ C (cSt)

Pour point (◦ C)

Cold crank simulation −25◦ C (mPa sec)

5.86 5.38 5.84 5.79 5.17

−58 −9 −9 −9 −12

1300 1530 3250 2740 4600

Brookfield viscosity −25◦ C (cP) 1550 Solid Solid Solid Solid

low-temperature performance even with the addition of pour-point depressants. The Cold Crank Simulation Test is of vital interest to any car owner who has ever lived in a cold climate. The advantage of a PAO-based formulation in the crankcase is immediate and obvious on a cold winter morning – it is the difference of being able to start the car or not. The superior low-temperature operation of synthetic automotive lubricants in automotive engine oils, gear oils, and automatic transmission fluid formulations has been demonstrated [78]. Piston cleanliness is another important factor in choosing a crankcase oil. Table 1.14 presents the results of three different tests commonly used to rate piston cleanliness [24]. The PAO formulations performed well compared with the mineral oils, even when used (as in the Fiat test) at only a 15% level in a part-synthetic formulation. The results of a Caterpillar 1-G evaluation are given in Table 1.15 [24]. Both a part-synthetic and a full-synthetic PAO-based oil outperformed an equivalent 10W-40 mineral oil. The high performance of a new synthetic PAO-based SAE 5W-40 heavy duty oil has been recently demonstrated [79]. This oil exceeds API CG-4, CF-4, CF-2, CF, SH, and EC performance specifications. High performance levels were first measured in standard and extended length laboratory testing. On the road testing using greatly extended oil drain intervals validated high performance levels in Cummins engines. Field testing at extended

TABLE 1.14 Piston Cleanliness Test VW1431 Fiat TIPO MWM B

Base oil

Grade

Mineral PAO Mineral PAO (15%) Mineral PAO (50%)

15W-40 5W-50 15W-40 15W-40 15W-40 10W-40

Piston merit 63.7 72.6 6.4 7.6 73.0 82.8

KV100◦ C , cSt

TABLE 1.15 Caterpillar 1-G Tests Results for Mineral Oil and Synthetic Formulations

Oil

Grade

Total groove fill (80% maximum)

Mineral Part-synthetic Full-synthetic

10W-40 10W-40 10W-40

76 67 53

Total weighted demerits (300 maximum) 294 243 103

drain intervals demonstrated performance benefits compared with industry recognized mineral-oil-based 15W-40 diesel engine oils. The successful arctic experience of synthetic-based multi-viscosity engine oils by the U.S. Army has also been described [80]. 1.5.2.2 Transmissions The advantages of synthetic automotive transmission fluids based on PAO that have been recently reported are favorable low-temperature properties, lower volatility and better wear performance than non-PAO-based ATFs [81]. Synthetics have also been promoted as a way to improve bottomline operating performance by extending component service life and reliability [82]. Hot oil oxidation tests are used to screen oils for use in manual transmissions and rear axles. The test is conducted at a more severe temperature (200◦ C) than used in the evaluation of crankcase oils, and the KV at 100◦ C is measured at specified time intervals. A comparison of the performance of mineral- and PAO-based fully formulated oils is shown in Table 1.16 [24]. After 16 h, the viscosity of the PAO fluid increased only 19%, whereas the viscosity of the mineral oil fluid increased nearly 500%. After 24 h, the viscosity of the PAO fluid increased by only 21%, but that of the mineral oil product became too viscous to measure. The HOOT is also used as an indicator of performance for automatic transmission fluids. A less viscous oil is


TABLE 1.16 Hot Oil Oxidation Testa (Manual Transmission and Rear Axle Oils)

Time (h)

PAO

Mineral oil

0 4 8 16 24

10.00 10.45 11.54 11.92 12.10

10.50 12.60 12.90 51.24 TVTMb

a Temperature of test = 200◦ C. b TVTM = too viscous to measure.

Test described in Shubkin, R.L. (1994). Lubrication Engineering 50, 196–201.

used for automatic transmissions than for manual transmissions (7.5 vs. 10.0 cSt), but the test is still conducted at 200◦ C. The results of the test are presented graphically on Figure 1.8 [24]. The PAO-based formulation showed only an 8.6% increase in 100◦ C viscosity after 24 h. The viscosity of the mineral oil formulation increased 550% in the same time period. A 4 cSt full-synthetic ATF has been tested to demonstrate fuel economy potential and the ability to provide adequate transmission performance and protection. The PAO-based ATF demonstrated remarkable lubricant stability. Results showed adequate transmission performance over 20,000 cycles in the GM Dexron® IIE cycling test (THCT), light wear of applicable transmission parts, and trace sludge formation [83]. There was no shear down of the full-synthetic. The fluid remained in grade throughout the test. Although the tests described above indicate that PAObased transmission fluids show better durability and performance than mineral oils at a given temperature, another important phenomenon has been observed. Measurement of transmission lubricant temperatures under high-speed driving conditions shows that the synthetic-based oils run as much as 30◦ C cooler than their mineral oil counterparts [84]. The improved wear characteristics of PAO-based transmission fluid in ASTM D 4172 Shell Four ball testing over mineral-oil-based formulations has been reported [85]. Lower coefficients of friction were also reported for the PAO-based formulation. Lower temperature and lower coefficients of friction will result in less wear and fatigue failure. A lower rate of oxidation means that replacement of oil will also be reduced. These factors will result in more economical performance — less oil usage and lower maintenance.

KV 100 °C, cSt

62 48 44 40 36 32 28 24 20 16 12 8 4 0

Mineral oil PAO

0

4

8

12 Time (h)

16

20

24

FIGURE 1.8 Hot oil oxidation test (automatic transmission, 200◦ C)

TABLE 1.17 Mercedes Benz Gear Rig Performance Oil Mineral PAO

Grade 90 75W-90

Tensile strength (%)

Elongation (%)

Volume (%)

+1.80 −1.20 −50/0

−12.0 −13.0 −60/0

+1.0 +0.6 0/+5

0 0 0/+5

Acrylate 150SN PAO Limits

+5.40 −12.00 −15/+10

−7.70 −30.00 −35/+10

+3.40 −1.50 −5/+5

0 +4.0 −5/+5

Silicone 150SN PAO Limits

−66.0 −9.60 −30/+10

−60.0 −15.0 −20/+10

+14.80 +18.00 0/+30

−16.0 −13.0 −25/0

Nitrile 150SN PAO Limits

+11.0 +13.0 −20/0

−11.0 −19.0 −50/0

+2.40 −1.90 −5/+5

+1.00 +2.00 −5/+5

Time to tooth breakage (h) 85 135

1.5.2.3 Gears The Mercedes Benz Spur Gear Rig Performance Test is used to evaluate the performance of gear oils. In the test, the elapsed time to gear-tooth breakage is used as the indicator of performance. An SAE 75W-90 synthetic formulation showed a 60% improvement over an SAE 90 mineral oil [24]. The data are presented in Table 1.17. 1.5.2.4 Seal compatibility Seal compatibility is an important factor for any functional fluid. Unlike mineral oils, PAO does not have a tendency to swell elastomeric materials. Early commercial PAO products were not formulated properly to allow for this difference in behavior. Consequently, early PAOs gained an undeserved reputation for leakage. Extensive tests have since shown that the addition of small quantities of an ester to the formulation easily alleviates this problem. Recent work has indicated that the proper choice of other performance additives may eliminate the need to employ esters, but this approach is not yet in practice for crankcase applications. Table 1.18 shows the results obtained in the CCMC G5 Seal Compatibility Test for base fluids [24]. A 6.0 cSt PAO was compared with a 150SN mineral oil. The four seal materials studied were


TABLE 1.18 Seal Compatibility (CCMC G5 Specification)

Elastomer Fluoroelastomer 150SN PAO Limits

Hardness (points)

acrylate, silicone, nitrile, and fluoroelastomer. The seals were evaluated at the end of the test for changes in tensile strength, elongation, volume (seal swell) and hardness. The PAO performance fell within the specification limits for all four elastomers. The mineral oil failed with silicone. Similar tests have been carried out with fully formulated part- and full-synthetic PAO oils. In all cases the fluids met the specifications. Additional information on choosing the proper seal materials for use with PAO fluids may be found in References 86 and 87.

30

TABLE 1.19 Automotive Economy

Total savings Same oil drains ($) One drain for fullsynthetic

25.2(+5%) 595 714.00 36.00

.00 30.00

2.00 45.00

4.00 75.00

—

15.00

39.00

— —

3.00 3.00

−3.00 11.00

8.8

10

5 0

FIGURE 1.9 Volatility of fully formulated oils

1.5.2.5 Economy The performance benefits demonstrated by the various tests that have been described are meaningful to the automotive engineer or tribologist, but the average consumer is most interested in how much savings the use of a PAO-based product is going to generate. Table 1.19 describes the results of one study that considered both the increased fuel economy and the extended oil drain interval made possible with part- and fullsynthetic PAO crankcase oils. The original calculations [88] have been updated to reflect current prices for gasoline and oil in North America. The calculations are based on 15,000 mi of driving and a “do-it-yourself” oil change regimen. A pump price of $1.20/gal for gasoline has been chosen, and the oil has been priced at $1.00, $2.00, and $4.00/qt for the mineral oil, the part-synthetic, and the fullsynthetic, respectively. If the oil is changed every 5,000 mi, there is almost no cost differential for the three oils because of the improved fuel economy gained with the synthetics. For the 15,000 mi distance, the saving over the mineral oil formulation is $3.00 with the part-synthetic oil and a deficit of $3.00 is experienced with the full-synthetic. If, however, there is only one drain for the full-synthetic, the savings goes up to $11.00. In Europe, where gasoline is much more expensive and the differential in oil prices is less, the savings accrued by the use of synthetic crankcase oils will be much greater. The use of lighter grades of crankcase oil is one answer to the need for increased fuel economy. The possible downside to this strategy would be a concurrent increase in oil consumption and the loss of sufficient high-temperature viscosity for adequate engine protection. Studies show, however, that properly formulated PAO-based synthetic


10

Mineral 5W–30

24.6(+2.5%) 610 732.00 18.00

12.4

Mineral 10W–30

24 625 750.00 —

15.6 15

Mineral 10W–40

Fullsynthetic

Mineral 15W–40

Partsynthetic

Mineral 20W–50

Oil Cost ($/qt) Cost of 3 × 5 qt changes plus 3 × $5 filters ($) Additional cost ($)

Mineral oil

20

Synthetic 5W–50

Fuel Economy (miles/gal) Use (gal/15,000 mi) Cost ($1.20/gal) Savings ($/15,000 mi)

20.9 Volatility, %

Parameter

25.7 25

crankcase oils, with wide multigrade SAE performance classifications, can outperform mineral-oil-based formulations in both fuel and oil consumption, while maintaining superior engine protection [63]. Figures 1.9 to 1.12 from this study illustrate the point. Figure 1.9 shows the relative volatility of a 5W-50 full-synthetic formulation compared with five different mineral oil fluids. For European driving, a limit of 13% maximum volatility is specified for Association des Constructeurs Europiens d’Automobiles (ACEA) for top grade for passenger car and diesel engine passenger cars and commercial HDDO performance. It may be seen that a 15W-40 mineral-oil-based formulation is required to meet this specification. The 5W-30 mineral oil formulation, which is used in North America for fuel economy and cold-starting reasons, does not come close to meeting the volatility standard. Figure 1.10 compares the “high-temperature/highshear” viscosity at 150◦ C of the full-synthetic 5W-50 formulation and the mineral oil formulations. The viscosity of the synthetic oil is even higher than the 20W-50 mineral oil. The outstanding performance of the synthetic oil is attributable to the naturally high VI of the PAO in combination with a shear-stable VII. Figure 1.9 and Figure 1.10 indicate that oil consumption should be under control with a full-synthetic formulation because of the superior volatility and viscosity performance. Figure 1.11 shows the results of a 12-car field test in which the oil consumption for the 5W-50 synthetic oil was compared with a 15W-50 mineral oil. The oil consumption for the synthetic oil was 25% less than for the mineral oil. The data just presented for gasoline engines is equally valid for diesel engines. The CCMC D3 standard for super high-performance diesel (SHPD) engine oils can be met with a 5W-30 synthetic blend. Figure 1.12 shows that the full-synthetic SHPD oil gave approximately 2% increased fuel efficiency compared with the 15W-40 mineral oil SHPD across a range of typical driving modes.

4.9

5

Low load Med load High load

4.4 4.1

2.8

3 2

% fuel saving

4 3.7

4

3 2 1

1

0 1200

1500

1800

2200

Speed (rpm) Mineral 5W–30

Mineral 10W–40

Mineral 15W–40

Mineral 20W–50

0 Synthetic 5W–50

Volatility at 150 °C, cp* (*Shear Rate=106/S)

5

FIGURE 1.10 High-temperature/high-shear viscosity of fully formulated oils

FIGURE 1.12 Fuel efficiency: super-high-performance diesel formulation. Percentage fuel saving for 5W-30 full-synthetic vs. 15W-40 mineral oil • Packing seal lubricants for chemical injectors for oil and

gas field applications.

Miles per liter of oil

12,500

• Lubricant/coolant for double mechanical seals of cen10,800

10,000

trifugal pumps handling corrosive, abrasive chloride slurries. 8,600

Specific reports of performance advantages in industrial applications are discussed in the following sections.

7,000 6,000

1.5.3.1 Refrigeration compressors

2,500 0 Synthetic 5W-50

Mineral 16W-60

FIGURE 1.11 Average oil consumption for a range of modern cars

1.5.3 Performance Testing for Industrial Applications Industrial applications in which PAOs have served as the lubricant of choice have been known for over a decade [38]. Some of these include sealing fluids and lubricants for pumps handling polystyrene process liquid at 232.2◦ C (450◦ F) in nitrogen atmosphere. PAOs have also been used as a replacement for polyolester as a hightemperature bearing and gear lubricant in blowers used as steam booster compressors. Rotary and reciprocating mechanical vacuum pumps are lubricated using ISO 46 PAO formulations. The chemical inertness of PAOs has been demonstrated in chemical applications. PAOs give satisfactory performance as: • Lubricants for large conveyor chains with exposure to

sulfuric acid vapors. • Lubricants for reactor gearboxes handling nitric and

sulfuric acid mixtures.


Polyalphaolefins have also been used in ammonia and fluorocarbon refrigeration compressors because of their low pour points. Other performance advantages reported for PAO fluids include lower operating temperature and less equipment vibration. Bloch and Williams [39] discuss many benefits that high film strength synthetic lubricants offer over other lubricants. Using process plant applications as examples, these authors show that two significant advantages of using high film strength synthetic lubricants are lower operating temperatures (in excess of 20˚C) and reduced vibration. These two performance advantages increased the life of high torque worm speed reducers by 200 to 300% and extended oil replacement intervals by a factor of four in one application. In other applications, in addition to reduced operating temperature and vibration levels, the motor amperages were reduced when using the synthetic lubricant. Properly formulated high film strength synthetic lubricant based on diesters, PAOs, and combinations of these base stocks can result in reduced bearing and gear operating temperature. 1.5.3.2 Gear oils The use of PAO-based gear oils in industrial settings can lead to important savings in energy consumption, as well as decreased down-time and lower maintenance requirements. The wide range of operating temperatures allows the use of less viscous oils, which results in greater

energy efficiency. The relatively low coefficient of friction for PAOs reduces the amount of internal friction created by the normal shearing of an oil film during operation. Improved scuffing performance for gear/circulating oils has been demonstrated [89]. Jackson et al. have studied the influence of lubricant traction characteristics on the load at which scuffing occurs. The study compared low traction polyalphaolefin (PAO)-based lubricants with mineral oils in additive-free, antiwear, and extreme pressure (EP) formulations. Benefits of 25 to 220% were observed for the PAO-based synthetic lubricants over mineral oils. Among the conclusions reported, low traction PAO-based lubricants uniformly gave higher scuffing loads/unit width than the mineral-based fluids tested at both high and low specific film thickness. PAO-based gear and circulating oils outperformed mineral-oil-based gear and circulating oils, respectively. PAOs were also shown to be very responsive to additives. The advantages of PAOs as lubricants in conveyor applications has been demonstrated by Paton. Gear boxes lubricated with a fully synthetic PAO-based gear oil (75W-90) was studied. An all-season PAO-based fluid was chosen for pulley shaft bearing lubrication [47]. In wind turbine gear boxes the high VI of a synthetic fluid would insure that the change in viscosity with temperature would be less than with equiviscous mineral oils. A further advantage of a synthetic fluid for these types of applications is that synthetics have lower pour points than mineral oils [61]. Polyalpholefins provide both excellent VI and low pour point. These properties make PAOs a fluid of choice for an application where there will be a wide range of operating temperatures. Table 1.20 is a compilation of data from ten reports relating to the benefits of increased efficiency found when industrial transmissions were switched from a mineral-oilto PAO-based gear oils [90–99]. The increases ranged from 2.2 to 8.8%. It is interesting to note that the efficiency increase observed in worm gears has a close positive correlation with the reduction ratio. This correlation exists despite the fact that the data was reported by different companies and was collected on different types of equipment. 1.5.3.3 Turbines Wind turbine gear boxes are also subject to wear and pitting fatigue failure. Water contamination can also occur. Among the many lubricant related factors, film thickness under operating conditions must also be considered in the formulation of a wind turbine lubricant. Excellent low-temperature properties and high load performance is possible with a PAO-based wind turbine lubricant (Tribol 1510) [62]. Polyalphaolefins have been employed in larger General Electric (GE) and EGT industrial gas turbines. Oils used


TABLE 1.20 Industrial Gear Oil Applications Transmission type Worm gear Worm gear Worm gear Worm gear Worm gear Worm gear Spur gear/chain Spur gear Series of nine worm gears Series of five worm gears

Reduction ratio

Power (hp)

Load Efficiency (% rated) increase (%)

10:1 15:1 25:1 30:1 50:1 50:1 — 24:1 15:1

3.0 1.55–2.0 6.5–8.1 3.2–3.9 3.0–6.0 0.5–1.0 35 200 122–142

100 100–130 100 96–117 100–200 50–100 — — 100–112

2.2 3.8 4.4 5.6 7.7 8.8 2 6 6

39:1

75

—

5.8

in these applications must have enhanced oxidation resistance to withstand journal heat soak temperatures that can go as high as 250 to 300◦ C. Mineral oils volatilize and form deposits whereas lubricants formulated with PAOs give cleaner running performance and extended useful life of the lubricant (from 4 to 5 yr up to 15 yr) [62]. Mobil Industrial Lubricants has developed Mobil SHC 800 for land-based gas turbines. This fluid, based on PAO, provides low maintenance and reliability over wide temperature ranges. 1.5.3.4 Hydraulic oil performance Polyalphaolefins offer a variety of property and performance features and benefits that cannot be achieved using alternative base fluids. PAOs have excellent lowtemperature fluidity and excellent VI when compared with all but the most expensive base fluids. They have very low volatility and excellent hydrolytic, thermal, and oxidative stability relative to many other oils. 1.5.3.5 Metal working performance Antiseizure properties of lubricants, as measured by their maximum workable die temperature (MWT), have been reported [46]. The MWT of lubricating oils reported were as follows: PAO oils: 160 to 170◦ C, polybutene oils: 150◦ C, mineral oils: 100 to 120◦ C, ester oils: 90◦ C. Addition of phosphorus containing extreme pressure (EP) agents to mineral oils or PAOs enhanced the workable die temperature to about 300◦ C. 1.5.3.6 Cost savings The open literature contains a number of reports of savings that have accrued to industrial concerns after they switched from a mineral oil to a PAO-based gear or bearing oil.

Table 1.21 is a short tabulation of some of these reports [100]. The table shows a diverse type of manufacturing for the companies included, and a diverse selection of applications for which the PAO-based lubricants were applied. The annual savings for these companies ranged from $12,000 to $98,000/yr. The largest reported savings on Table 1.21 was $98,000.00/yr when a PAO-based gear oil was used on the felt roll bearings in a paper mill. The high speed of the huge rolls in a paper mill is critical to their competitive operation, and the use of PAO-based fluids is becoming an important part of the over-all strategy for cost-effective operation.

1.5.4 Applications Sensitive to Health and Environmental Issues Results to demonstrate the favorable biodegradability of PAO fluids has recently been published [101–103]. In a comparison of PAOs with equiviscous mineral oils, PAOs were found to be significantly more biodegradable (Figure 1.13).

TABLE 1.21 Savings with PAO-Based Gear Oils Company type

Application

Soybean processing Plastics Copper wire Paper mill Steel mill

X Biodegradation (CEC-L33-A93)

Pharmaceutical Aluminum cans Manufacturing

100 90 80 70 60 50 40 30 20 10 0

Aeration blower Bearing circulation system Line gears Felt roll bearings Fly ash blower shaft thrust bearings Gear reducers Gear reducers Various

Annual savings $2100/unit $12,000 $19,000 $98,000 $77,000 $70,000 $35,000 $80,000

PAOs

Time extended CEC-L-33-A-94 testing has also shown that 2, 4, and 8 cSt PAOs continue to biodegrade well past the 21-day period prescribed in the standard method (Figure 1.14). PAO fluids are also considered to be nontoxic and nonirritating to mammals (Table 1.22). PAOs are not expected to be toxic to aquatic organisms. For example, in the Microtox test with bioluminescent bacteria, there were no effects for 49,500 ppm of the water-soluble fraction (Table 1.23). Results have also been presented that demonstrate that low viscosity (2 and 4 cSt) PAOs are significantly biodegradable (in the CEC L33 T82 biodegradability test) [104]. 1.5.4.1 Food contact Polyalphaolefin base stocks are pure, saturated hydrocarbons. They contain no aromatics (except for small amounts in the 40 and 100 cSt fluids produced by Mobil) and no functional groups. As such, the toxicity is expected to be as low or lower than the most highly refined white mineral oils. The PAOs have Food and Drug Administration (FDA) approval for use in both “indirect” and “incidental” foodcontact applications. They fall within the definition of a white mineral oil according to the Code of Federal Regulations, 21 CFR 178.3620, paragraph B. The applications for which FDA approval is required, and for which PAO is qualified, are listed in Table 1.24. In essence, PAO fluids may be used as a component of any material that contacts food or as a lubricant for any machinery that processes food. Direct food contact approval (i.e., as a component to be purposely ingested) has not yet been obtained in the United States, but probably could be obtained if there was an application that warranted the effort and expense of obtaining the approval. Fortum’s (previously named Neste) food grade PAO fulfills 21 CFR

Mineral oils 2 cSt

PAO2

MVI

4 cSt

HVI

PAO4

LVI

Bass stock

FIGURE 1.13 Biodegradability of base stocks poly(α-olefins) vs. equiviscous mineral oils: MVI, medium viscosity index (naphthenic base stock, aromatic content 1.9%); HVI, high viscosity index (paraffinic base stock, aromatic content 2.6%); LVI, low viscosity index (naphthenic base stock, aromatic content 12.3%)


% Blodegradation (Time-extended CEC L33 T82)

100 90 2 cSt

80 70

4 cSt

60 50 40 8 cSt

30 20 10 0 0

7

14

21

28

35

42

49

56

63

70

77

84

91

98

105

112

119

Days

FIGURE 1.14 Biodegradability vs. time for PAO fluids

TABLE 1.22 Acute Mammalian Toxicity of PAO Fluids PAO fluid Oral LD50 a Skin Eye (cSt) (g/kg) Irritationb Irritationc Comedogenicityd 2 4 6 8 10

>5 >5 >5 >5 >5

Negative Negative Negative Negative Negative



a Rat Oral LD (statistically calculated dose needed to kill 50% of the 50

rats in the study) is determined by single dose administration of undiluted test material. Rat oral LD50 values of >50 g/kg are considered nontoxic. b Where heated material or oil mists could be generated, consult the MSDS for recommended handling procedures. c According to criteria of Federal Hazardous Substance Act (FHSA, 16CFR 1500). d Comedogenicity refers to the ability of the test material to induce the enhanced collection of increased sebaceous material and keratin likened to acne blemishes.

TABLE 1.23 Acute Aquatic Toxicity of the Water Soluble Fraction of POA Fluids by the Microtox® Method PAO Fluid (cSt)

EC50 (5 min)

2 4 6 8 10 40 100

NR* NR NR NR NR NR NR

* NR — No observable effects at concentrations up to 49,500 ppm.

1.5.4.2 Cosmetics and toiletries 172.878 and 178.3620a for direct food contact. Fortum has approval for PAO 6 (Food Grade) as a food additive in Finland. Work is proceeding to get Europe-wide approval for PAO (Food Grade) as a food additive. Fortum has been selling PAO 6 (Food Grade) for use as a glazing agent for sweets in Finland since 1992. Polyalphaolefin specifications for food additive use in Finland are very strict on purity. There can be no oxygen containing components, and hydrogenation of the poly-1-decene must be complete. One test that is used to check purity is the “hot acid test” also referred to as the “readily carbonizable substances test,” described in the pharmacopoeias.


Polyalphaolefin fluids are nontoxic when given orally to rats. The lethal dosage for 50% of the test subjects (LD50 ) is greater than 5 g/Kg of body weight. PAOs are also nonirritating to the eyes and skin of test animals, and they are not expected to induce sensitization reactions. They have low vapor pressures and therefore are not hazardous by inhalation. Subjectively, PAOs are said to have a better “feel” on human skin than white mineral oils. For all of these reasons, a small but growing market for PAO is developing in the cosmetics industry [55]. A national brand of lipstick contains PAO as a major component, and in Europe, PAOs (polydecene) can be found in a variety of cosmetic products such as make up removers, body oil, shampoos, lotions, shower and bath oils, and make up creams.

TABLE 1.24 FDA-Approved Applications for PAO Sectiona 175.105 176.200 176.210 177.2260 177.2600 177.2800 178.3570 178-3620 178.3910

Application Adhesives Defoaming agents used in coatings Defoaming agents used in the manufacture of paper and paperboard Production of resin-bonded filters Rubber articles (plasticizers) intended for repeated use Production of textiles and textile fibers Lubricants with incidental food contact Technical grade white mineral oil Surface lubricants used in the manufacture of metallic articles (e.g., metallic foil)

a Food and Drug Administration, HHS-21 CFR Ch. 1 (4-

1-88 edition).

1.5.4.3 Off-shore drilling Regulations on the marine toxicity of fluids used to lubricate the drill-head in off-shore drilling operations are becoming tighter, especially in the North Sea. PAO fluids have been used as a base stock for synthetic-based drilling fluids in off-shore applications. The purpose of these fluids is wellbore cleaning, bit cooling and lubrication, and shale stabilization. The discharge of cuttings using syntheticbased muds is considered less harmful to the marine environment. PAOs offer excellent marine toxicity. This technology was developed in the early 1990s [105,106]. This technology has been displaced by alternative technologies. Leading alternative technologies include linear alphaolefins [107] and isomerized olefins [108]. 1.5.4.4 Miscellaneous Other environmentally sensitive areas for which PAO fluids are being evaluated are: logging operations (chain saws), marine outboard engines, and hydraulic systems for large farm machinery. In addition to low toxicity, it is important that fluids used in these applications exhibit biodegradation and low levels of bioaccumulation. Preliminary evaluations indicate that PAOs do not bioaccumulate and that their rate of biodegradation is faster than that of mineral oils of comparable viscosity. On the other hand, the rate of biodegradation is slower than for some ester-based drilling muds that are also undergoing evaluations for this application. For a full discussion of this very complex issue, the reader is referred to Chapter 25 of this book.

1.5.5 Military Applications The earliest applications for PAO fluids were in the military. Mil-H-83282 is a specification for a hydraulic fluid


for jet aircraft. The specification was built around an experimental 4.0 cSt decene-based PAO produced by Mobil in the late 1960s. The requirements included extreme lowtemperature fluidity as well as high flash and fire point values. The latter requirement was to minimize the risk of loss due to fire in the event that a hydraulic line was severed by enemy gunfire. Mil-H-83282 remains an important military fluid today. An interesting, if not publicized, example of superior performance for PAO came to light as a result of the war in the Persian Gulf in January 1991. Under harsh desert conditions, the U.S. weapons that were lubricated and cleaned with PAO-based oils performed better than similar Allied weapons using conventional fluids, resulting in some rush orders to the lubricant formulators from Allied commanders. Table 1.25 contains a short summary of military specifications that either require or often use PAO fluids.

1.5.6 Space Applications Precision space craft mechanisms require critical selection of lubricants to maximize reliable performance in space where low or no maintenance situations exist. Communication, global surveillance, meteorological and navigational space craft contain a variety of moving mechanical assemblies (MMAs). These mechanical sub-systems have become life-limiting for many space craft [60]. Most problems have been lubricant related problems including loss of bearing contact and chemical degradation. Results of recent studies advocate the use of formulated PAO oils and greases for most high-cycle precision bearings [60].

1.6 MARKETS AND PRODUCTION CAPACITIES By the end of 1990, world PAO demand had grown to 188.4 MM lb [9]. This volume represents a remarkable 14-fold increase since 1975, but still represented less than 0.05% of the total world lubricant base-stock market at that time. By the end of 1993, world PAO demand had grown to 260 MM lb [109]. U.S. capacity as of June 1, 1993 has been reported to be 287 MM lb [110] and was predicted to grow to 458 MM lb/yr by the year 2000 [109]. The worldwide consumption of PAO in 1998 was 600 MM lb/yr. PAO global capacity was on the order of 700 MM lb/yr in 2002. During 1975–1980, demand for PAO grew at 33% per year. Synthetic engine oils were a novelty on the market during this period, and they were growing from a base near zero. Growth slowed during the 1980–1985 period to around 7%. Some early product entrants to the market were improperly formulated, and the resultant poor performance attached some stigma to the use of synthetics. The 1985–1990 time period saw a strong new interest in synthetic lubricants because of the enactment of stringent new specifications and governmental regulations that were

TABLE 1.25 Military Applications Specification number

Applications

Lubricant highlights

MIL-PRF-46170

Type I: Tank recoil and hydraulic systems

4 cSt PAO: ester: TCP PAO base stock specs Finished fluid specs

MIL-PRF-83282

Aircraft and missile hydraulic systems

4 cSt PAO: ester: TCP PAO base stock specs Finished fluid specs

MIL-PRF-(83282 low temperature)

Aircraft and missile hydraulic systems

Dimer/trimer ∼3 cSt PAO: ester: TCP No pour point or VII additives Finished fluid specs only

MIL-PRF-10924

Multipurpose grease for all ground vehicles, artillery, and equipment

Typically 6 cSt PAO base stock Finished grease specs only Formulation and constituents Confidential and proprietary

MIL-PRF-63460

Small large caliber weapons cleaner, lubricant, and preservative, −65◦ C to 150◦ F

Mineral oil and syntheticbased 2 and/or 3 cSt PAO Finished lube specs only

MIL-PRF-81322

Multipurpose grease for aircraft

Mixture of PAO fluids

MIL-PRF-32014

Multipurpose grease for aircraft

Mixture of PAO fluids

MIL-PRF-2104

I/C engine oil and power transmission fluids All types of military tactical/ combat ground equipment

Mineral oil, synthetic, or combination base stock

MIL-PRF-2105

Gear oil for units, heavy-duty industrial type gear units, steering gear units, and universal joints

Mineral oil, synthetic, or combination base stock Finished lube specs by grade only

MIL-PRF-87252

Dielectric coolant for electronic applications Hydrolytically stable Replacing silicate ester coolant

PAO base stock specified 2 cSt dimer ∼99.5% PAO Oxidation/corrosion inhibitor Finished fluid specs only

difficult to meet with mineral oil base stocks. The growth rate for PAO during this period was approximately 19% per year. Current growth rate is on the order of 7% per year.

1.6.1 Demand by Segment and Region Strong growth for the PAO market is predicted to continue in the foreseeable future. Table 1.26 shows the expected rate of growth for PAO into the automotive, industrial, military, and emerging market segments. The total market was expected to grow from 185 MM lb in 1990 to 450 MM lb in 1995 — an annual growth rate of about 20% per year [24,100]. Although the size of the PAO markets in 1990 were approximately the same in Europe and North America, the breakdown by segments was considerably different. The European market was driven primarily by the automotive demand whereas the North American market was more


balanced. In 1990 in Europe, 78% of the PAO demand was in the automotive sector, with the rest going into industrial applications. The PAO demand for the automotive sector in 1996 was 80%, little change from the early 1990s. In North America, the automotive and industrial markets each took about 38% of the PAO, while the military used 17%. The remainder went into “emerging” markets, which will be discussed in more detail Section 1.6.2. Table 1.27 is a breakdown of PAO market growth by both segment and region. It should be noted that the 1995 forecasts predict that the demand distributions by segment for PAO in Europe and North America will converge. North America in fact began catching up with Europe in the automotive applications area while Europe began catching up with North America in industrial applications. Both continents undertook vigorous development of the “emerging” segments. Overall market growth and trends are generally consistent with the predictions made earlier and the global

1.6.2 Emerging Markets

TABLE 1.26 PAO Market Segment 1990 (MM lb)

Predicted 1995 (MM lb)

Automotive Industrial Military Emerging

110 55 15 5

230 100 20 100

18 13 6 85

Total

185

450

20

Market segment

Predicted growth rate (% year)

1.6.3 PAO Production Capacity

TABLE 1.27 PAO Market Segment Growth by Region

Region and segment

1990 (MM lb)

1995 (MM lb)

Growth rate (% year)

1998 (MM lb)

North America Automotive Industrial Military Emerging Total

35 35 15 5 90

100 60 20 40 220

23 11 6 51 20

110

Europe Automotive Industrial Military Emerging Total

70 20 — — 90

110 40 — 60 210

10 15 — N/A 19

240 38 22 — 300

Far East Automotive Industrial Military Emerging Total

4 1 — — 5

15 5 — — 20

30 38 — — 32

230

80

PAO capacity is on the order of 350 kMT/yr. This means that there is strong PAO growth in terms of demand and production capacity. Furthermore, the fact that there are several new linear alphaolefin plants that have gone on stream during 2000–2002, means that there is adequate supply of precursor for the production of needed PAO for lubricant applications. The development of markets and applications for PAO has been generally confined to North America and Europe. In 1990, the Far East accounted for only 2.7% of the demand for PAO. Between 1990 and 1995, the consumption of PAO in the Far East grew at an annual rate of about 30% — reminiscent of the growth in the West during the 1975–1980 time frame. The non-European and U.S. consumption of PAO is on the order of 80 MM lb and is expected to grow.


A substantial portion of the growth being forecast for PAO has been described as “emerging” markets. The term “emerging” is used to designate application areas where there is a high potential for PAO to capture a part of the market now being serviced by other types of fluids. Table 1.28 lists seven areas where PAO fluids and formulations are continuing to be developed to fulfill specific requirements not being met by the fluids currently in use. The three driving forces for shifting from the current functional fluid to PAO are cost, performance, and toxicity.

At the end of 1990, the worldwide production capacity for PAO was 325 MM lb/yr. Sales for 1990 were 57% of production capacity, which represented a major reversal of the demand/supply situation of the mid-1980s. Because of the shortage of PAO available at that time, formulators were forced to seek alternative (if sometimes less satisfactory) solutions for their performance requirements. There was a strong and understandable hesitancy among equipment manufacturers, formulators, and end-users to place themselves in a precarious supply situation. As a result of the excellent supply situation that now exists, there is a new surge of activity in the development of new markets and applications for PAO fluids. Table 1.29 is a summary of the PAO producers and their capacities in 1990. Ethyl Corporation brought their 80 MM lb/yr plant in Feluy, Belgium, on-stream in January 1991. As mentioned earlier, Ethyl split off Albemarle as a separate company in 1994, which owned and operated the PAO business until March 1996 when Amoco purchased the alphaolefin and PAO business from Albemarle. BP announced in March 2004 that it was putting its linear alphaolefins and PAOs businesses up for sale. This is still pending at the time of this writing. Neste brought their 45 MM lb/yr plant in Berigen, Belgium, on-stream in 1991. Neste has now become Fortum. PAO production capacities are summarized in Table 1.29. A summary of synthetic lubricants including markets and consumption for PAOs has been published [111].

1.6.4 Competitive Products Chemically modified mineral oils (CMMOs) (highly refined mineral oils) approach PAO in some performance characteristics. These mineral oils fall into three categories. 1.6.4.1 Very high viscosity index oils The premier product derived from crude oil sources is Shell Oil’s patented extra high viscosity index (XHVI) oil. It is produced in France and Australia from a special cut of

TABLE 1.28 Emerging Markets

Product line

Current volume (MM lb)

Polymer Personal care Refrigeration Textile Dielectric fluids Brake fluid Shock absorbers Total

200 150 45 25 90 440 110 1060

Fluid type

Driving force

WMOa WMO/estersa Polyalkyl glycols Silicones/WMO Mineral/silicones/PCB Polyethylene glycol/silicones Mineral oil

Toxicity/performance Toxicity Performance Cost and performance Cost/performance/toxicity Cost and performance Performance

a White mineral oil.

TABLE 1.29 PAO Capacity (WorldWide) (Low and High Viscosity)

Manufacturer Amoco (BP)c Albemarle Ethyl Exxon-Mobila Mobil Chevron Exxon Neste Fortumb Uniroyal (Crompton) Total

1990 (MM lb/yr)

1993 (MM lb/yr) (109)

1996 (MM lb/yr) (112)

0 0 170

0 256 0

249 0 0

80 55 20 0

157 88 0 66

224

0 325

0 567

4.4 592.4

0 62

2002 (MM lb/yr) 260 0 0 275 0 90 0 0 70 5 695

a Formerly Exxon and Mobil separately. b Formerly Neste. c now innorene.

refinery slack wax by a severe hydrocracking procedure. Shell’s capacity is 150 MM lb/yr. Shell is apparently currently manufacturing XHVI base stocks from Syn Gas in Malaysia. The product exhibits very good performance characteristics, but it is deficient relative to PAO in both low-temperature properties and volatility (Table 1.4). Petro Canada has recently begun production of a 100 MM gal/yr base oil plant in Mississauga, Ontario, Canada [113]. This production includes a series of severely hydroprocessed mineral oils, one of which is a high VI line of API Group III VHVI Specialty Base Fluids under the name of Phoenix. These generally have higher pour points and higher NOACK volatility than the equiviscous PAOs, but are improved over conventional mineral oil base stocks.


BP currently manufactures LaVera Hydrocracked Residue (LHC) fluids in LaVera, France. LHC fluids are available in 3, 4, 6, and 8 cSt grades. Processing consists of hydrocracking of a middle distillate stream, followed by vacuum distillation and a dewaxing step. These stocks are wax isomerates that are highly isoparaffinic. Chevron has also recently announced that it will produce unconventional base oils (UCBOs) at its lubricant base oil facility in Richmond, California. These new base oils are reported to be in the range of 115 to 135 VI [114]. Conoco and Pennzoil have announced a joint venture, Excel Paralubes, to produce 18,000 bbl/day base oil at Conoco’s plant in Lake Charles, Louisiana. These materials are processed (Chevron’s isodewaxing process)

to produce higher quality base stocks [113]. Conoco is marketing a new line of clear lube oils under the name Hydroclear™ produced using hydrocracking technology. SK Corporation (formerly Yukong) produce a slate of VHVI base stocks at its plant in Ulsan, South Korea using a combination of hydrocracking and catalytic dewaxing processes. This was developed with Raytheon Corporation. These materials are described in greater detail in Chapter 18 of this book.

1.6.4.2 High viscosity index oils High viscosity index (HVI) base stocks are intermediate in properties between the VHVI fluids and conventional solvent-refined oils (Table 1.3). HVI oils are manufactured by a process that involves hydrotreating, redistilling, and solvent refining. HVI fluids were first produced by BP in 1976 and are now produced by BP at LaVera and Dunkerque in France. HVIs are also produced by Modrica in Yugoslavia and DEA in Germany. HVI fluids are less costly than either PAO or VHVI fluids, but 1.4 to 2.0 times more material is generally required to blend with an off-specification mineral oil to bring a formulation into 10W-30 specifications. Exxon begun producing screening samples of its new EHC™ (Raffinate Hydroconversion) base stocks at its Baytown refinery in 1999. These high viscosity index oils are in the range of 105 to 119 VI. These materials are described in greater detail in Chapter 18 of this book.

1.6.4.3 Polyinternalolefins Polyinternalolefins (PIO) fluids are similar to PAO fluids in that they are both manufactured by the oligomerization of linear olefins. The olefins used for PIO manufacture, however, are derived from the cracking of paraffinic base stocks. The internal olefins are more difficult to oligomerize than the α-olefins derived from ethylene chain growth, and the products have VIs that are 10 to 20 units lower than comparable PAOs. These materials are described in greater detail in Chapter 2 of this book.

1.7 CONCLUSION A number of forces will drive the growth of highperformance functional fluids for the next decade and beyond. These forces derive from diverse societal needs, but they have a common goal rooted in the uniquely human belief that there must be a better way to do whatever it is that has to be done. Some of these forces and the consequences they imply for the growth of PAO fluids are discussed in the following sections.


1.7.1 Regulatory U.S. regulations for Corporate Average Fuel Economy (CAFE) are having a significant effect in both the design of new automobiles and the lubricant requirements and recommendations for them. In order to meet the fuel economy standards, which will now include a cold-start cycle specification, the Original equipment manufacturers (OEMs) are being forced into recommending SAE 5W multigrade crankcase oils. In addition, increased emphasis on aerodynamics results in higher engine operating temperatures, which affects not only the crankcase lubricant but also the transmission fluid, the gear oils, and the greases. All these factors will require fluids with lower low-temperature viscosity coupled with lower volatility, higher thermal and oxidative stability, higher heat capacity, and higher heat conductivity. Consumer protection, worker safety, and environmental regulations are becoming increasingly stringent in their requirements for nontoxic, nonhazardous, environmentally friendly products. Regulatory agencies are beginning to recognize potential toxicological problems associated with white mineral oils. PAOs are being put forward as high-performance, safe substitutes.

1.7.2 Performance and Cost-Effectiveness The need for improved performance remains a critical factor in the drive toward increased usage of PAO-based lubricants and functional fluids. In many applications mineral-oil-based products either cannot meet the more stringent requirements or are only marginally satisfactory. The use of PAO for blending with marginal base stocks in order to bring them into specification is increasing. Fleet operators, who are much more sensitive to costeffectiveness than the general public, will continue to increase their usage of synthetics as they recognize the potential long-term savings. Operators of large industrial machinery are beginning to recognize the increased cost-effectiveness of lubrication with PAO-based products. Machines that operate at lower temperatures, are less subject to wear, require less maintenance and down-time, consume less oil, and operate longer between lubricant drain cycles. The value of PAObased products for the lubrication of heavy-duty, off-road mobile equipment is also being recognized, especially in situations where routine maintenance is difficult.

1.7.3 Original Equipment Manufacturers The diversity and regional availability of mineral oil base stocks make standardization based on mineral oils difficult. In those applications where performance requirements are exacting, there will be a shift by Original Equipment Manufacturers (OEMs) to require synthetic fluids in order to assure uniformity.

Industrial and automotive OEMs are under pressure from the consumer and from their competition to extend warranty periods. At the same time, OEMs are under pressure to reduce the required amount of maintenance and down-time. Both avenues may be addressed by switching from mineral oil to PAO-based fluids. General Motors used a full-synthetic, PAO-based oil as the factory fill and recommended crankcase fluid for the first time when it introduced the 1992 Chevrolet Corvette. Today, fullsynthetic PAO-based oil is still recommended for the highperformance vehicle. The latest trend to address consumer convenience as well as protection of equipment from inadvertent contamination of the working fluid is the “fill-for-life” concept. General Motors is studying a “fill-for-life” PAO-based automatic transmission fluid for its future models.

1.7.4 Petroleum Companies and Blenders Lubricant producers have historically had low profit margins. Base stock prices have been closely tied to crude oil prices, and the selling price for finished fluids has remained tied to base stock costs. Lubricant companies are beginning to recognize that high-performance, high-image products based on PAO afford the opportunity for higher selling prices and increased margins. European companies have been the leader in this regard, but North American companies are expected to catch up. While Mobil Oil has been the leader in the United States with Mobil 1 since the mid-1970s, most of the major lubricant producers have introduced, or plan to introduce, full-synthetic motor oils to the market in 1990s. Another large factor in the forecasted growth for PAO is the recognition that there are insufficient high-quality base fluids to meet new product requirements. PAOs will be used to blend mineral oil stocks into specification. Some of these products will be sold and marketed as “part-synthetic” oils at a price between the top-tier mineral oils and the “fullsynthetics.” In other cases, the blender or formulator will use PAO in an “in again–out again” basis, depending on the availability of mineral oil base stocks of sufficiently high quality. In these cases, the consumers will never know that they have purchased a “part-synthetic.”

1.7.5 Consumer The role of the consumer will be important to the growth of PAO fluids. Manufacturer’s recommendations will have little effect if the consumer does not pay attention to them. Studies show that the traditional attitude in the United States has been that all oils are “pretty much the same,” but this attitude is beginning to change. Consumers are becoming more aware of fuel economy, cleaner air, higher performance, lower maintenance, and longer vehicle life. All of these concerns, coupled with the increased availability of oils to meet the demand, will lead to a shift by a


segment of the consumer population toward the premium synthetic oils.

1.7.6 New Technology The final area that will provide an impetus to the increased use of PAO fluids will be the development of new technology. Two areas are clearly important. The first is the development of new additives and formulation packages specifically designed for use with PAO fluids. Formulation development is being actively pursued by PAO producers, additive manufacturers, formulators, lubrication specialty companies, and OEMs. Some of this work is in the form of joint efforts, and much of the information being developed is proprietary. The second important area to be impacted by new technology is the development of new PAO fluids from new starting materials and with new catalyst systems. The objective in this research is to produce products with particular characteristics needed for specialty applications. The use of alternative (other than 1-decene) olefin streams as the starting olefin for PAO manufacture offers the opportunity to “tailor-make” products for niche markets [19]. Table 1.30 gives an indication of what happens when different linear α-olefins are reacted in an identical way. As mentioned earlier, decene was chosen as the raw material of choice by all of the PAO producers because it gives products with the broadest temperature operating range. But for many applications, properties exhibited at one end of the temperature range may be more important than those at the other. For instance, a piece of industrial machinery that runs continuously at high temperature may have few, if any, low-temperature requirements but may require a very stringent volatility or flash-point specification. In such a case, a PAO based on 1-dodecene or 1-tetradecene may be more appropriate. Performance characteristics that can be enhanced by the appropriate choice of starting olefin and reaction conditions include volatility, pour point, VI, low-temperature viscosity, flash and fire points, thermal and oxidative stability, and biodegradability [115]. The development of new catalyst systems for the production of olefin oligomers having specific isomer distributions also holds the potential for the development of new PAO products with enhanced characteristics [116]. 1.7.6.1 Dodecene-based PAOs Initially dodecene-based PAOs were investigated due to a shortage in decene during the mid-1990s but have now found a home due to their unique combination of properties. PAOs based on 1-dodecene are now being manufactured by Chevron Phillips Chemical Company in the same way as 1-decene based PAOs [117]. The products are distilled to different viscosities since the oligomers are multiples of dodecene rather than decene and the KV at

TABLE 1.30 Physical Properties: Effect of Olefin Chain Length Carbon number of initial olefin Property KV at 100◦ C (cSt)


Test method

8

10

12


2.77 11.2 195 82 copper. The rate of


TABLE 3.11 The effect of Process Residuals on the Deposits Formation of a Trimellitate in the Panel Coker test (275◦ C for 22 h in air) Residual metals in ppm 0 to 5 6 to 10 11 to 15

Visual demerit rating 0.5 1.01 1.33

catalytic activity on the deposit formation in decreasing order of activity was found to be: low-carbon steel > stainless steel > aluminium > brass > copper > lead [11]. Esters made from linear acids generally have higher flashpoints than those made from branched chains or a mixture of linear and branched chains. Increasing molecular weight also increases the flashpoints. The volatility of esters depends on several parameters: • • • •

Increasing molecular weight decreases volatility Increasing the degree of branching increases volatility Increasing polarity decreases volatility Oxidative stability: Esters with low oxidative stability break down to form molecules of low molecular weight

3.3.1.2 Hydrolytic stability Ester lubricant base fluids are manufactured by the reaction of acids and alcohols, with the elimination of water. This reaction is reversible and the ester products can undergo hydrolysis, that is, reaction with water to regenerate the starting materials. The reaction between pure ester and water is very slow. Ester lubricants containing less than 500-ppm water can be stored for several years at ambient temperature and undergo essentially no reaction. For hydrolysis to occur at a significant rate the following are required: some form of heat (>60◦ C), the presence of a catalyst (metal or acid), and a source of water (>100 ppm). Ester hydrolysis reactions have been widely used as model reactions for studying factors affecting the rates of organic reactions, and a wide variety of measurement techniques have been used to study them and to elucidate the reaction kinetics. This work has shown that under ideal conditions, the rate of acid-catalyzed ester hydrolysis is proportional to the concentration of the reagents, ester and water, and to the concentration of the hydrogen-ion catalyst. However, real-life systems are more complex than the ideal systems studied in the laboratory. In the field, the rate of hydrolysis is dependent on several factors, namely the: • Temperature • Presence of contaminants (particularly water or acidic

species)

250

10

0.7

0.5

150

0.4 100

0.3 0.2

5

50

0.1 0

0 0

2

4

6

8

Time (days) Water value

Linear acid

1 0.5 Branched acid

0.2 0.1 0.05

0.01

2500

1

10

100

1000

Time (hours)

7 2000

6 5

1500

4 1000

3 2

Water value (ppm)

Acid value (mg KOH/g)

2

0.02

Acid value

8

500

1 0

Change in acid value (mg KOH/g)

200

0.6

Water value (ppm)

Acid value (mg KOH/g)

0.8

0

10

20

30

40

0

Time (days) Water value

Acid value

FIGURE 3.7 Polyol ester tested at 2000 and 200 ppm water at 150◦ C in a sealed tube containing a metal coupon • Presence of metals (which can act as catalysts) • Chemical structure of the lubricant (degree of branching) • Specification of the ester (low acid and hydroxyl value,

no residual catalysts) • Presence, dose rate, and type of additives

Hydrolysis occurs via an acid-catalyzed mechanism. A hydrogen ion adds to the carboxyl oxygen of the ester linkage, converting it transiently to a carbonium ion, which rapidly adds on water to form a positively charged tetrahedral intermediate. This tetrahedral intermediate then separates into carboxylic acid and alcohol, regenerating a proton that can then catalyze further reaction. The reaction is therefore autocatalytic. The more the acid that forms the faster the breakdown, which in turn creates more acid. Low initial acid values are therefore important and acidic contaminants should be avoided. From Figure 3.7 it can be clearly seen that as water is consumed the acid value of the polyol ester increases. When the water is completely consumed the acid value reaches a plateau. This degree of “de-esterification” or


FIGURE 3.8 Hydrolytic stability of a linear acid vs. a branched acid polyol ester tested at 2000 ppm water at 150◦ C in a sealed tube containing a metal coupon

hydrolysis is primarily related to the amount of water present. The reaction rate constants typically show temperature dependence consistent with an activation process following the Arrhenius equation (roughly the rate doubles for every 10◦ C increase in temperature). The first step in hydrolysis is cleavage at the ester linkage. As such, if the cleavage at the ester linkage can be hindered, hydrolysis will occur at a much slower rate. One obvious way of causing hindrance is to use a branched acid, especially those branched near the ester linkage (e.g., 2-ethyl hexyl or neo acids). Branching will have an effect on the rate of hydrolysis, but ultimately the degree of hydrolysis will be determined by the total amount of water present, that is, given time both linear and branched esters will equilibrate to similar levels (Figure 3.8). Also, there are penalties to be paid when using these branched feedstocks, namely very long reaction times to achieve complete esterification. This of course may translate into more expensive products. The hydrolytic stability of the polyols is generally regarded as superior to that of the diesters. Aromatic diesters, due to the higher degree of steric hindrance, are more stable than alkyl diesters. Metals, such as lead [12], can have a major impact on the rate of reaction. The acids produced by hydrolysis can react with metals to form soluble metal salts, thereby reducing the acid value and limiting the rate of reaction. On the other hand, the dissolved metal salts and to a lesser extent metal surfaces can act as hydrolysis catalysts and increase the rate of reaction. Phosphate esters, typically used as antiwear additives, are known to be less hydrolytically stable than ester lubricants. It is therefore vital that additives have the greatest

possible stability. Although the phosphates are not the best additive at reducing wear, they do process posses an excellent trade-off between stability and lubricity. Acidic additives (e.g., certain anticorrosion and antiwear additives) can have a major negative effect on the stability of the ester. High levels of acidity can autocatalyze the breakdown of the ester (organic acids can act as a catalyst). Phosphate ester antiwear agents, such as Tricresyl Phosphate (TCP), are less hydrolytically stable than most esters. These additives can break down to produce acid that can again autocatalyze the breakdown of the ester. The best way to avoid hydrolysis is to keep the level of water in the system low, avoid high temperatures, and avoid contact with certain metals that can act as catalysts. 3.3.1.3 Environmental performance 3.3.1.3.1 Esters from renewable resources Renewable raw materials can be used in ester lubricants through the hydrolysis of fats and oils to produce the constituent fatty acids as raw materials for chemical synthesis. A wide variety of natural sources, including solid fats and low-grade or waste materials such as tallow from rendering of animal carcasses or tall oil from wood pulp processing, can be converted through controlled chemical processing into pure fatty acids of consistent quality. Fatty acids of appropriate chain lengths and degree of unsaturation are used in the manufacture of synthetic ester base fluids with molecular structures designed for optimum application performance. Synthetic esters therefore represent an overlap between the synthetic and biolubricant product categories, since they can be designed to be readily biodegradable and to incorporate renewable raw materials, although they are not normally derived exclusively from renewables and indeed many of their useful properties depend on the use of raw materials that are (currently) derived from petrochemical sources. For example, replacement of the glycerol component of a triglyceride by a petrochemically derived neopentyl polyol ester such as TMP substantially increases the thermal and hydrolytic stability [13]. Saturated short-chain (C8 to C10) fatty acids are used to make high stability polyol esters that are used in high performance synthetic car engine oils, jet engine lubricants, and compressor oils. Esters of longer chain cis-unsaturated acids for example, trimethyolpropane trioleate (TMPO) are used in applications such as biodegradable hydraulic fluids and cutting fluids, where oxidative stability is less critical. (Esters of longer chain saturated acids are normally too high melting for use as lubricant basefluids tend to be waxy solids.) Unsaturated long-chain acids are oligomerized and isomerized to give dimer and isostearic acids. Esters of these acids are used in two-stroke oils, car engine oils, and chain oils. Unsaturated long-chain acids are also converted to


short-chain diacids that are used to make ester base fluids for aviation engine oils and automotive gear oils. In addition to their use in lubricant ester base fluids, fatty acids from renewable sources are also used extensively in manufacture of lubricant additives. Both saturated and unsaturated longer chain fatty acids, and their derivatives such as amides and glycerol monoesters, are used as friction modifiers. Although they have good low temperature fluidity, polyunsaturated acids are not preferred for use in lubricant applications because of their poor oxidative stability. However, with oleic acid, they can be converted by acid catalyzed oligomerisation and isomerisation, followed by hydrogenation, to give branched C18 monoacid (isostearic), C36 diacid (dimer acid), and C52C54 triacid (trimer acid), which are useful raw materials for the synthesis of high-viscosity ester fluids [13]. The double bond in the unsaturated acids offers many obvious possibilities for chemical derivatization, some of which are already commercially exploited. For example, the linear diacids azelaic acid (C9) and sebacic acid (C10) are manufactured industrially by oxidation of oleic acid and alkali fusion of ricinoleic acid, respectively. These diacids are raw materials for synthetic ester base fluids such as the respective diesters of 2-ethyl hexanol. The production of azelaic acid gives the C-odd numbered monoacid nonanoic acid as coproduct. Another C-odd monoacid, heptanoic acid, is derived from ricinoleic acid by pyrolysis, as a coproduct in the manufacture of undecenoic acid. Nonanoic and heptanoic acids are used in the same way as their C-even homologues in manufacture of neopentyl polyol esters, where the C-odd chain lengths confers some low-temperature fluidity benefits. Manufacture of these C-odd monoacids from renewable resources is economically competitive with petrochemical routes, although the supply from the renewable route is limited by the demand for the more valuable coproduct, in each case [13]. 3.3.1.3.2 Biodegradability The biochemistry of microbial attack on esters is well known in general outline and has been well reviewed [14–17]. The main steps are: • Ester hydrolysis • beta-Oxidation of long chain hydrocarbons • Oxygenase attack on aromatic nuclei

The main features that slow or reduce microbial breakdown are the: • • • •

Position and degree of branching Degree of saturation in the molecule Presence of aromatic groups High molecular weight

Table 3.12 gives biodegradabilities for a range of esters measured by two types of tests. Generally, linear polyol

Ester type Monoesters Diesters Phthalates Dimerates Trimellitates Linear polyols Branched polyol Complex polyols

% Biodegradability CEC-L-33-A-95 (21 days) 70 to 100 70 to 100 40 to 100 20 to 80 20 to 80 80 to 100 20 to 50 0 to 90

% Biodegradability OECD 301B (28 days) 30 to 95 10 to 80 5 to 70 10 to 50 0 to 40 50 to 99 5 to 40 10 to 90

esters tend to be used if high biodegradabilities are required. The biodegradability of esters is discussed in greater length in the chapter on environment, Chapter 34. 3.3.1.3.3 Toxicity and ecotoxicity Considerable environmental testing has been carried out on ester fluids. It is clear from this work that these substances are of a low order of toxicity. 3.3.1.3.4 Handling In general, esters cause minimal acute toxicity by ingestion and skin absorption. Neither mineral oils nor esters show significant skin irritancy response. However, mineral oils have been known to cause skin problems with people who are constantly exposed and who take inadequate precautions. The solvency of the mineral oils can remove some of the fat from the skin. This defatting can lead to mild dermatitis after prolonged contact. Esters are polar and therefore tend to be superior solvents to mineral oil. There is potential, therefore, to give such responses more quickly. Where contact with esters is likely to be high, gloves should be worn. Due to the hygroscopic nature of esters and their potential for hydrolysis, wherever possible, they should be stored in a dry sealed drum and contact with moist air should be minimized. 3.3.1.3.5 Recycling and reuse Energy recovery is the most common form of lubricant waste disposal. The major environmental issue when disposing of used esters by incineration is the other possible components/contaminants of the waste. Predominant among these are contamination by polychlorobiphenyls (PCBs), halogens (especially chlorine), and metals. Many countries have limits on the maximum total halocarbon, PCB, and metal allowable in the lubricant that can be used as fuel supplement. No PCBs are present in the raw materials or production process used to synthesize esters, nor do esters decompose to form such products.


Viscosity at 100°C in cSt

TABLE 3.12 Biodegradabilities of Various Ester Lubricant Groups

7 6 5 4 3 2 1 0

NPG

4

TMP

5

6

PE

7

8

9

10

11

Linear acid chain length

FIGURE 3.9 The effect of chain length on the viscosity of linear acid polyol esters

Waste ester is not a fuel in the strict technical sense because its volatility and viscosity are unlikely to conform to fuel oil standards. In conventional combustion plants, waste oil is burned in an admixture of lubricant to diesel fuel or coal in proportions that promote efficient combustion and that allow the overall level of contamination to be controlled. Trials on the combustion of used ester oils in concentrations of 5 to 20% have been carried out. In comparison with diesel oil, no differences were noted when burning such mixtures and all the emission readings were the same order of magnitude. Used ester oils are currently being recycled and reused in the same applications as their original use in several areas (e.g., hydraulic, metalworking, and transformer fluids, etc.). Recycling trials on polyol ester using a thin-film evaporator have shown great promise.

3.3.2 Physical Properties Much of the early work correlating the structure of esters with their physical properties was conducted by scientists such as: Zorn [18], Barnes and Fainman [4], McTurk [19], and Niedzielski [20,21]. 3.3.2.1 Viscosity The viscosity of ester lubricants can be increased by: • Increasing the molecular weight of the molecule by

increasing the • • • • • • • •

Chain length of the acid Chain length of the alcohol Degree of polymerization Functionality of the ester

Increasing the size and the degree of branching Including cyclic groups in the molecular backbone Maximizing dipolar interactions Decreasing the flexibility of the molecule

Figure 3.9 shows the change in viscosity at 100◦ C with acid chain length for a range of polyol esters.

TABLE 3.13 The Effect of Branching on Viscosity Polyol ester

Viscosity at 100◦ C in cSt

PE linear octanoate PE 2-ethyl hexanoate PE isooctanoate

5.58 6.36 8.35

Branching can also have a marked effect on viscosity: For very viscous molecules, branched aromatic esters, branched diPE polyols, or polymeric esters tend to be used. For low viscosity esters, short-chain diesters, NPG polyols, or monoesters are used. 3.3.2.2 Flow properties The VI of an ester can be improved by: • Increasing the acid or alcohol carbon chain length • Increasing the linearity of the molecule: Branching

restricts the rotational freedom around the ester linkage and also decreases the ratio of length to cross-section. Both effects contribute to lowering the VI. • Not using cyclic groups in the backbone, which tend to lower VI even more than aliphatic branches • Molecular configuration: Viscosity indices of polyol esters tend to be somewhat lower than their diester analogues, due to the more compact configuration of the polyol molecule. The pour point of the lubricant can be improved by: • Increasing the level of unsaturation (e.g., TMP oleate,

−51◦ C

• •

• •

an unsaturated C18 has a pour point and TMP Stearate, a saturated C18 has a pour point +45◦ C) Increasing the amount of branching (e.g., TMP isostearate has a pour point of −30◦ C) The positioning of the branch: Branching in the center of the molecule gives better pour points than branches near the end. Decreasing the acid or alcohol carbon chain length Decreasing the internal symmetry of the molecule (e.g., NPG oleate has a pour point of −24◦ C, TMP oleate −51◦ C, and PE oleate −21◦ C)

Esters made from mixtures of linear and branched chains have VIs between those of linear and branched, but have lower pour points than the esters obtained from either branched or linear chains. Pour-point depressants can also be used, but they tend to be much less effective in esters than they are in mineral oil. Clearly, there is a trade-off between VI and pour point. For instance, by increasing the linearity of the ester, the VI improves but the pour point deteriorates.


TABLE 3.14 Viscosity-Pressure Coefficients for a Variety of Lubricants Lubricant

Viscosity-pressure coefficient Gpa−1

ISO 32 alkyl benzene ISO 32 napthenic mineral oil ISO 32 PE polyol ester ISO 68 PE polyol ester ISO 68 trimellitate

30.2 26.1 15.2 19.3 16.6

22.0 19.0 12.8 14.9 13.9

3.3.2.3 Lubricity To understand how an ester lubricates, it is first important to understand its behavior in the different lubrication regimes. 3.3.2.3.1 Hydrodynamic lubrication The viscosity of a lubricant has a marked effect on wear (viscosity being related to film thickness). Viscosities of lubricating oils are often quoted at 40◦ C (ISO grade) or 100◦ C. In reality the viscosity under operating conditions is the controlling factor. For systems experiencing hydrodynamic and elastrohydrodynamic lubrication (EHL), the viscosity of the lubricant is a key requirement. The viscosity of the lubricant is dependent on the: • Viscosity at 40◦ C • Temperature (which is related to the VI) • Pressure (which is related to viscosity pressure coeffi-

cient) • Dilution of the lubricant by absorbed gases (which is

related to vapor liquid equilibrium, VLE) • Effect of shear rate on viscosity

The viscosity of an ester at 40◦ C can be modified by the factors discussed in 3.3.3.1. The VI of the lubricant is dependent primarily on the degree of linearity and the length of the acid chain. Wholly linear acid polyol esters (POE) tend to have indices in the region of 110 to 130 while wholly branched POEs have VIs in the region 55 to 65. Esters generally have poorer viscosity-pressure coefficients than mineral oil but this is somewhat offset by the esters’ superior VI and boundary lubricity. The pressure-viscosity coefficients of various lubricants have been measured at various temperatures. These are listed in Table 3.14. These compare well with literature values at 40◦ C [22– 25] for TMP ester (8.4 to 9.8 GPa−1 ), PE esters (7.5 to 12.2 GPa−1 ), phthalates (13.6 GPa−1 ), and diesters (6.6 to 7.6 GPa−1 ).

The viscosity-pressure coefficient of a lubricant is influenced by: • The length of the side chains in branched esters (the

longer the better) • The degree of branching (the more the better) • Aromaticity (the more the better)

Large, inflexible, unsymmetrical esters have large free volume and are much harder to pack together under pressure. This explains their superior viscosity-pressure coefficients. As the temperature increases, the pressure-viscosity coefficient decreases due to an increase in the free volume of the molecules. This results in less interaction between the molecules. Inter- and intra-molecular bonding will also play a role but this area has not yet been sufficiently explored to comment. Dissolved gases in the lubricant can seriously reduce the viscosity of lubricants and causes wear by removing protective lubricant films, for example, on the cylinder walls in reciprocating compressors. For certain types of gases, synthetics are much better at resisting this dilution effect. This area is discussed at greater length in the Chapter on refrigeration lubricants. 3.3.2.3.2 Elastrohydrodynamic lubrication As the lubrication regime passes from hydrodynamic into EHL, the materials of construction become more and more important. EHL films are thin and require smooth surfaces to prevent asperity contact. The hardness and surface treatment of materials used is therefore important. As the contact pressures increase, the viscosity-pressure coefficient of the lubricant will become increasingly important. The polarity of the ester can also be very important. Recent work suggests that when a small amount of a highviscosity polar ester is added to a low-viscosity nonpolar base fluid (e.g., PAO) the ester will preferentially stick to the surface. When the two metal surfaces are far apart the bulk viscosity is controlled by the PAO. When the surfaces come closer together the PAO is squeezed out of the contact zone. The polar ester sticks to the surface and stays in the contact area. As the ester has high viscosity the bulk viscosity of the oil will increase as the surfaces come closer together. Finally, a point will be reached where only the more viscous polar ester remains [26]. Such an effect can be very beneficial in EHD lubrication. Low levels of polymeric esters have been used as additives. This has allowed the reduction in dose rate of certain types of active antiwear additives (chloroparafins, zinc diaryl dithiophosphates [ZDDPs], etc.) in several industrial applications. 3.3.2.3.3 Mixed film Mixed film lubrication, as the term implies, is actually a combination of boundary, hydrodynamic, and EHL regimes. In the mixed lubrication regime the contact characteristics are determined by varying combinations of


fluid film and boundary lubrication effects. Some asperity contact may occur and interaction takes place between mono- and multi-layer boundary lubricating films while a partial fluid-film lubrication action develops in the bulk of the space between the metal surfaces. It follows that both the physical properties of the lubricant (as per EHL) and the chemical properties of the lubricant (as per boundary) are important. 3.3.2.3.4 Boundary lubrication The properties of the bulk lubricant, (e.g., viscosity), are of minor importance in boundary lubrication. The surface phenomena that determines the behavior of boundary lubricants can be described in the following terms: • Physically absorbed layers of gas, liquid, or solid

lubricants • Chemically absorbed layers • Films formed by chemical reaction

Esters have a high degree of polarity due to the lone pair of electrons on the oxygen atom of the ester linkage. Polar molecules are very effective boundary lubricants as they tend to form physical bonds with metal surfaces (i.e., they stick to the surface better than mineral oil). Most metal oxide surfaces are partially hydroxylated in the presence of water vapor. This hydroxylated surface can participate in hydrogen bonding either as a hydrogen-atom donor or as an acceptor. Thus, absorption of hydrogen-atom acceptors such as ester lubricants (or decomposition by-products such as alcohols and carboxylic acids) leads to wear protection and friction reduction [27]. Esters therefore tend to be more effective lubricants than nonpolar mineral oils. Hydrogen bonds tend to be quite weak and as loads and temperature increase they will break down. However, at higher loads esters will tend to form chemisorbed films. As viscosity is reduced, or if shear rate or load is increased, the chance of boundary lubrication occurring increases. This is especially true under conditions of compressor start-up where the lubricant film may not yet have formed. The properties of the lubricant that affect boundary lubrication are the: • • • •

Degree of branching Molecular weight Polarity Additives present in the lubricant

Figure 3.10 shows a simplistic model of a monoester on a metal surface. As the chain length of the acid increases the film thickness of the lubricant increases. Linear chains also increase the degree an ester can pack together on the metal surface. As discussed in Section 3.3.2.1, branched chains give a higher viscosity than linear ones of the same length. Therefore, for a given ISO grade linear esters will have a longer

Linear

Branched Acid chain Polar ester head Oxide layer

Bulk metal

Bulk metal

FIGURE 3.10 Schematic of a surface packing of a monoester

chain and therefore potentially a thicker film. Surface force apparatus experiments on linear and branched alkanes have shown that even a small amount a of branching (a methyl side chain) can significantly reduce the ability of molecules to form discrete layers between solid surfaces [28]. Chemisorbed films are produced by the formation of soaps. Soaps tend to act as a friction modifier. The effectiveness of these films is limited by the melting point of the soap. Many metal soaps have melting points in the range 120 to 200◦ C, when reached they desorb and the boundary lubricating properties are lost. Under extreme boundary conditions esters tend to break down to form acids. Preliminary work suggests these acids further react to form metal carboxylate soaps. Metal carboxylates have been shown to convey good extreme pressure (EP) protection. A form of boundary lubrication can be given at higher temperatures by the incorporation of EP or load carrying (antiwear) agents. Sulfur, for instance, will start to react with metals at about 100◦ C to form sulfides with melting points in excess of 1000◦ C. It is worth noting that oxygen from the atmosphere, or free oxygen in the lubricant, is a valuable EP lubricant. It forms oxide layers that generally provide a low shear strength film capable of reducing friction and wear between bearing materials. Mineral oil contains small but important quantities of more reactive substances like sulfur, nitrogen, and oxygen. These chemicals readily react with newly exposed metal surfaces to provide boundary lubrication. Because of these different interactions, the lubricity of an ester in a fully formulated fluid is not always easy to predict. As ester groups are polar, they can compete with antiwear or EP agent for the metal surface. When a very polar base fluid is used, it can cover the metal surfaces instead of the antiwear additives. This can result in higher wear characteristics because, although esters have superior lubricity properties to mineral oil, under high load conditions they are certainly less efficient than antiwear additives. It is therefore very important to choose the correct additive and to optimize its concentration to get the full lubricity benefit of using ester basestocks. Often, more polar antiwear agents or the same antiwear agent at a higher dose rate are used to offset this factor. Alternatively, the ester can be modified to decrease its polarity.


Esters can be classified in terms of their polarity, or non-polarity by using the formulae below [29]: Non polarity index (NPI) =

Total no of C atoms × RMM No of carboxylate groups × 100

where RMM is the Relative Molecular Mass. As a rule, the higher the NPI of the ester the lower its affinity for the metal surface. Esters with high NPI will therefore compete less with the antiwear package. For a particular additive package there will be a trade-off between dose rate and the NPI of the ester that is, esters with high NPI can generally be used at higher dose rates before competition at the surface becomes an issue. NPI does not allow for structural effects that is, the degree of branching, unsaturation, etc. More sophisticated spectrophometric based techniques are now being developed that allow for polarity measurements to be taken directly [30]. 3.3.2.4 Energy efficiency Under hydrodynamic lubrication conditions, the only energy lost is that required to overcome viscous drag in the lubricant film at key bearing surfaces. The energy losses in hydrodynamic lubrication have a linear dependence on the fluid kinematic viscosity at the operating conditions. Many applications (e.g., engine oils, compressor lubricants, etc.) have therefore moved to lower viscosity oils. Under boundary conditions the relative velocity is insufficient to entrain a load-supporting hydrodynamic film. There is asperity contact between the surfaces, and the load is mainly carried through these solid contacts. Under boundary lubrication a range of physical mechanisms that may contribute to frictional losses come into play. Although a partial fluid film is present that undergoes viscous shearing, this is only a minor contribution to the overall friction coefficient, and boundary friction coefficients generally show little dependence on lubricant viscosity. In the boundary regime, the major contribution to the frictional force is the energy required for deformation of contacting asperities. Lubricant base fluids or additives that form an adsorbed surface layer can modify the boundary friction coefficient. In particular, components that form a

coherent chemisorbed or physisorbed layer that deforms more readily than the underlying metal or metal oxide surface may reduce the boundary friction coefficients. Lubricants having a high polarity or affinity for metal oxide surfaces, such as esters, have a greater tendency to form such adsorbed layers than less polar fluids, such as mineral oils or synthetic hydrocarbons, and therefore have lower boundary friction coefficients. Esters containing predominantly linear alkyl substituents can form a more coherently packed adsorbed film, and consequently show lower boundary friction coefficients, than those with branched alkyl substituents. This principle can be extended to use of components with longer linear alkyl chains and polar head-groups that are widely used as friction modifying additives in a range of lubrication applications, particularly in low polarity base fluids such as hydrocarbons. Organic friction modifiers act predominantly by absorption to the metal surface with the formation of absorbed layers due to the polar nature of the molecules. Friction modifiers dissolved in oil are attracted to metal surfaces by strong adhesive forces, which can be as high as 13 kcal/mol [31]. The polar head is anchored to the metal surface and the hydrocarbon tail is left solubilized in the oil, perpendicular to the metal surface. Other frictionmodifier molecules have their polar heads attracted to each other by hydrogen bonding and Debye orientation forces resulting in dimer clusters. Forces are about 15 kcal/mol in strength [31]. Cohesive Van der Waal’s forces will cause the molecules to align themselves such that they form multimolecular clusters that are parallel to each other. The orienting field of the absorbed layer induces further clusters to position themselves with their methyl groups stacking on to the methyl groups of the tails of the absorbed monolayer. An overview of these forces can be seen in Figure 3.11. Volumetric efficiency also plays an important role in the energy efficiency of reciprocating compressors and engines. If the viscosity of the lubricant is reduced to too low a level, piston blow-by occurs. Excessive foaming can also reduce volumetric efficiency. On the down-stroke of the piston the foamy layer is compacted. This compaction absorbs energy and can thereby further reduce energy efficiency. 3.3.2.5 Solvency 3.3.2.5.1 Compatibility with additives and other lubricants Esters have excellent compatibility with most types of lubricants. This results in a number of advantages:

Van der Waals forces

Long, nonpolar chains

Polar heads O

Van der Waals forces

Dipole–dipole interactions

O

Adhesive hydrogen bonding

Oxidized and hydroxylated metal surface

FIGURE 3.11 Overview of molecular interactions affecting ester FMs

• Most additive technology is based on mineral oil and it

is therefore usually directly applicable to esters. • Esters can be blended with mineral oil or natural oils

(semisynthetics) to boost their performance. • Esters can be blended with other synthetics such as;

PAOs, PAGs and PIBs. This gives esters great flexibility and unrivalled opportunities to balance the cost of different lubricant blends against performance. Solubility problems can often result from the use of additives with PAOs due to their low polarity. This is especially true for VI Improvers (VII). In many applications esters are often combined with PAOs to overcome these solubility problems. As PAOs shrink seals and esters swell them an optimum combination of the two can therefore be used to obtain a desired seal-swell target. The low friction of the ester component also compensates the poor fictional properties of the PAO. Ester/PAO combinations are therefore used in many applications (e.g., engine oils, air compressor lubricants, gear oils, etc.). 3.3.2.5.2 Materials compatibility Elastomers that are brought into contact with liquid lubricants will undergo an interaction with the liquid via diffusion through the polymer network. There are two possible kinds of interaction: • Chemical interactions • Physical interactions

Chemical interactions of elastomers with esters are rare. During a physical interaction of an ester lubricant and an elastomer two different processes occur: • Absorption of the lubricant by the elastomer causing

• There are no contamination problems, esters can be used

in machinery that previously used mineral oil, PAO, PIBs, and in most cases PAGs.


swelling. • Extraction of soluble components out of the elastomer

causing shrinkage.

The degree of swelling of elastomeric material can depend on the: • Molecular size of the lubricant component (generally the

larger the lubricant the smaller the swelling). • Closeness of the solubility parameters of the lubricant

and the elastomer. Generally, the “like-dissolves-like” rule is obeyed. • Molecular dynamics of the lubricant: Linear molecules containing flexible linkages allowing rotation can diffuse into elastomers more easily than branched or cyclic ones. • Polarity of the lubricant: It is known that several elastomers are sensitive to polar lubricants.

It is important to note that the processing of the elastomer can have a major impact on its performance. As esters can be efficient solvents they have the potential to extract any substances used during the manufacture of the elastomer. Elastomers from different suppliers can be highly different in terms of the degree of cross-linking, fillers and process residuals in the elastomer. Therefore, any information on ester compatibility with elastomers in general should be confirmed by tests on the specific material. The data in the Table 3.15 that follows are only to be used as rough guidelines. Compatibility will be highly dependent on the specific ester used, end application, and environment.

TABLE 3.15 Compatibility Data for Esters Suitable Elastomers Nitrile rubber (buna-N, NBR) only if nitrile exceeds 36% Fluorosilicone rubber Fluorocarbon (viton, teflon)

Marginal

Unsuitable

Nitrile rubber (buna-N, NBR) with nitrile content 30 to 36% Polyurethane Ethyl propylene terpolymer (EPDM) Polyacrylate rubber Ethylenepropylene co-polymer (EPR) Silicone rubber Polysulfide (thiokol)

Nitrile rubber (Buna-N, NBR) with nitrile content below 30% Natural rubber Styrene-butadiene rubber (SBR) Butyl rubber Chlorosulfonated polyethylene (very marginal?) Polychloroprene (neoprene) (very marginal?) Ethylene/acrylic (EAE)

Paints Epoxy Baked phenolic Two-component urethane Moisture-cured urethane

Oil resistant alkyds Phenolic Single-component urethane Industrial latex

Acrylic Household latex Polyvinyl chloride (PVC) Varnish Lacquer

Plastics Nylon Fluorocarbon Polyacetal (delrin) Acrynitrile-butadiene (celcon) Acetals Polyamides

Polyurethane Polyethylene Polyproylene Polysulfone Melamine Phenylene oxide (Noryl)

Polystyrene PVC Styrene (ABS) Styrene acrylonitrile (SAN) Polysulfones Acrylic (lucite, plexiglas) (very marginal?) Polycarbonate (lexan) (very marginal?) Polyphenyloxide

Cadmium Zinc Magnesium

Lead

Polyester (hytrel)

Metals Steel and alloys Aluminium and alloys Copper and alloys Nickel and alloys Titanium Silver Chromium Tin Iconel


3.3.3 Application Areas 3.3.3.1 Engine oils The main automotive lubricant market trends are: • Reduced emissions which requires

• • • •

Lower volatility Improved wear protection Deposit control Reduced sulphated ash, phosphorus, and sulfur (SAPS) to meet OEMs’ concerns on catalyst system durability

• Extended drain which requires

• Increased oxidation stability • Lower deposit forming tendency • Improvements in fuel economy and fuel economy reten-

tion which requires • Lower viscosity oils • Improved oxidation stability Esters’ low volatility, highs VIs, clean burn, and excellent frictional properties make them excellent basestocks for automotive applications. In 1969, the first semisynthetic 10W-50 engine oil based on diester was put on the market. In 1977, this was followed by a fully synthetic crankcase oil containing a PAO blended with a diester. A typical 5W-40 engine oil formulation can be seen in Table 3.16. 3.3.3.1.1 Lubricant Low temperature viscosity is perhaps the single most important technical feature of a modern crankcase lubricant. Cold starts are a prime cause of engine wear and can be mitigated only by immediately effective lubricant circulation. Low temperature viscosity can also have the benefit

TABLE 3.16 Typical Synthetic Formulation Component

Passenger % Dose rate

Ester basestock

5 to 20

Friction modifier (FM)

0 to 3

Hydrocarbon Oil

40 to 70

VI improver Additive pack

8 to 15 10 to 20


Car

Motor

Oil

Chemistry Diesters or TMP polyol esters Amide/ester organic FM Mo based inorganic FM PAO, hydrocracked, alkyl napthalene — Antiwear, detergent inhibition pack, etc.

of reducing start-up load and stresses, reduce battery current drain and making starting easier [32]. Oils are moving to lower viscosity specifications (5W and 0W) to meet the new energy fuel efficiency requirements. As lower viscosity oils tend to be more volatile, this has created the need to move increasingly towards synthetics. Low volatility is especially important in the context of the modern trend towards smaller sump capacities and longer oil-change intervals. The superior thermal stability of ester allows the use of low-viscosity oils while at the same time offering the benefits of low deposits (extended drain, cleaner systems) and low-temperature fluidity (reduced wear on engine startup). As the requirements placed on the engine oil increase there is a growing trend to higher synthetic contents in engine oils. It is now widely accepted that synthetic fluids, such as PAO/ester blends, offer a number of inherent performance advantages over conventional petroleum-based oils for the formulation of modern automotive engine oils. Practical benefits that may derive from their use include improved cold starting, better fuel and oil economy plus improved engine cleanliness, wear protection, and viscosity retention during service. Initial formulations were based on PAOs with a small amount of a phthalate (to act as a seal swellant). These formulations were followed by PAO/adipate ester blends where the diester was used at between 5 and 20%. Here, the ester acted as a seal swellant and as an additive solubilizer and made an important contribution to the desired deposit/volatility targets. Adipates can also be used with mineral oil to produce semisynthetics. With the increased needs for superior thermal stability, TMP esters have substituted for adipate esters. For reason of cost, hydrocracked oils are increasingly being substituted for the PAO. 3.3.3.1.2 Friction modifier Friction modifiers have been around for many years. Their first use in automotive applications was during the world’s oil crisis in the 70s, to reduce crude oil consumption. Since fuel economy became an international issue, FMs have also been introduced into automotive crankcase lubricants to improve fuel efficiency via the lubricant. Currently, FMs are applied in engine oils both to reduce fuel consumption and to reduce exhaust emissions. In the US, additional pressure was imposed on OEM’s by legislation covering corporate average fuel economy (CAFE), a federal regulation putting requirements on average production model car fuel consumption as well as substantial fines if these requirements are not met. Reduction of emissions is driven by a number of factors, of which the Kyoto agreement is the most recent one. This agreement urges governments to reduce the emission of carbon dioxide into the atmosphere and the OEM’s have to face a part of this challenge. Consequently, the interest

in using FMs has further increased. Both reduction of fuel consumption and reduction of emissions can be achieved by reduction of engine friction. In practice, the friction-reducing additives applied in automotive engine oils are selected from two specific groups: 1. Organic friction modifiers: These are long and slim molecules with a hydrocarbon chain consisting of at least ten carbon atoms and a polar group at one end. The hydrocarbon chain provides oil solubility whilst the polar group is one of the crucial factors with regard to the effectiveness of the molecule as a friction modifier. Chemically, organic friction modifiers can be based on: carboxylic acids and their ester, imides, amines, and their derivatives. 2. Organo-metallic compounds: These compounds are products that contain molybdenum especially such as molybdenum dithiophosphate, -dithiocarbamate, and -dithiolate. Out of the above group, molybdenum dithiocarbamate seems to be almost exclusively recommended for use as FM. Esters (e.g., Glycerol mono oleate [GMO]) are typically used in combination with organo-metallic modifiers. Improvements have been made to ester based friction modifiers to decrease their friction while at the same time increasing their retention of friction reducing properties. 3.3.3.2 Automotive gear oils

the superior shear stability of ester based oils give major performance advantages. Like engine oils, diester and polyol ester blended with PAO at between 15 and 30% are favored. A typical ester based 75 W gear oil can be found in Table 3.17. Low polarity polymeric esters are under evaluation as a potential replacement for PAO 100. 3.3.3.3 Two-stroke oils Ester lubricants offer a number of advantages over mineral oils as the lubricant component of two-stroke engine mixtures. The clean-burn characteristics result in less engine fouling with much reduced ring stick and lower levels of dirt build-up on ring grooves, skirts, and undercrowns. Ignition performance and plug life are also enhanced. Owing to the presence of polar ester groups in the molecule, giving increased adhesiveness to metal surfaces, esters have much better lubricity than hydrocarbons. This removes the need to use bright stock and simultaneously permits the use of leaner burn ratios. In turn, this significantly reduces smoke levels. About 95% of the particulates in the exhaust fumes were found to be from the unburnt lubricant [33]. The excellent solubility of esters also allows them to be used without solvents (which are usually added to conventional two-stroke oil to help miscibility with the fuel and low temperature fluidity). A typical ester based formulation can be seen in Table 3.18. The leaner burn ratios result in reduced oil emissions, which is a benefit in environmentally sensitive applications such as marine outboard engines and chainsaw motors.

The following market trends are present: • Filled for life which requires

• Improved thermal and oxidative stability • Increased shear stability • Improved fuel efficiency which requires

• Lower oil viscosities • New transmission designs (CVT)

TABLE 3.17 Typical Synthetic Gear Oil Formulation for Example, 75 W Component

% Dose rate

Ester PAO Additive pack

15 to 30 60 to 85 7 to 13

Chemistry Diesters polyols Blends of PAO 4, 6, 40, and 100 —

• Smooth shifting which requires

• Improved lubricity • Smaller and lighter units which requires

• Improved thermal and oxidative stability • Improved lubricity The main advantages of esters in this sector are their excellent oxidative stability, VIs, and low temperature flow properties. This allows synthetic gear oils to operate over a much wider temperature range than conventional oils. Also


TABLE 3.18 Typical Ester based Two-Stroke Formulation Component

% Dose rate

Ester basestock

50 to 60

Bright stock

10 to 30

Add pack Solvent

10 to 15 15 to 20

Chemistry Dimerate NPG and TMP Polyol esters PIB (low smoke) trimellitate or polymeric ester — White spirit Low viscosity ester

The high biodegradabilities of esters and low ecotoxicity and clean burn characteristics of ester formulations make them excellent candidates for “environmental considerate” labeling such as Blue Angel in Germany. Where biodegradability is an important factor NPG and TMP based polyols have replaced dimerates. Biodegradable polyol ester formulations (>70% OECD 301B) for use in chainsaw and Jet Ski applications are in commercial use. PIBs are commonly used as a bright stock in many formulations to achieve low smoke. Trimellitates and complex esters gave have also been used as brightstocks. Low temperature performance is important in some applications, such as engines used to power snowmobile type vehicles. Therefore, esters with low pour points of down to −56◦ C are very suitable for these applications. 3.3.3.4 Aviation turbine lubricants The bulk of aviation lubricant demand is for gas turbine lubricants for both military and civilian use. Hydrocarbon oils cannot meet the requirements placed on the jet engine lubricant in terms of thermal stresses. The first generation of oils (Type I) were diesters, but these have slowly lost ground over the last 25 years to the more expensive but more thermally stable Type II and Type III polyol esters. Diesters are still used in less demanding applications such as small private aircraft or turbo-prop engines. Type II aviation gas turbine lubricants are produced to a viscosity of 5 cSt (at 100◦ C). For some military applications, where operability at low temperatures is vital, the corresponding viscosity is reduced to 3 cSt. Type III oils are available at 4 and 5 cSts at 100◦ C. With increasing jet engine capabilities the need for more thermally stable oils has increased. The additive package usually consists of an antiwear package (e.g., TCP) and an aminic antioxidant. There has been some concern over the potential reaction of TMP polyols and TCP to form TMP-P a potent neurotoxin [34,35]. 3.3.3.5 Hydraulic fluids 3.3.3.5.1 Biohydraulics Hydraulic fluids represent a major growth area for biolubricants. The specific application is in mobile hydraulic equipment used in environmentally sensitive areas. In such equipment, pumping hydraulic fluid at high pressure through flexible hoses transmits power. Any damage to the hoses results in loss of fluid to the environment. Hydraulic fluids should therefore be biodegradable and there are also increasing demands for the lubricant to have a high renewability content (i.e., to use natural based feedstocks). Table 3.19 compares the biodegradability vs. renewable content for a range of lubricants [36]. It can


TABLE 3.19 Comparison of Renewability

Vegetable oil Mineral oil PAO Alkyl benzene Diesters Aromatic ester Polyol ester Complex ester Polyalkylene glycol

Lubricant

Biodegradability

and

% OECD 301B biodegradability

% Renewability

70 to 100 20 to 40 20 to 60 5 to 20 40 to 80 5 to 70 20 to 99 20 to 90 10 to 70

100 0 0 0 0 to 80 0 0 to 85 0 to 100 0

be clearly seen that esters allow for the development of high biodegradability and renewable and high performance hydraulic fluids. There are three market segments for biohydraulics, defined by type of equipment and operating temperature. For low severity, high-loss equipment operating up to 60◦ C, mainly farming equipment, vegetable oils may be used. For medium severity, medium-loss applications up to 100◦ C, mainly in forestry operations, synthetic esters with a high content of renewable raw materials for example, TMP oleates are used. However, some applications, particularly in the construction industry, require fluids capable of extended lifetimes at operating temperatures in excess of 100◦ C. Development of biodegradable fluids with the necessary high oxidative and thermal stability has been a major challenge for the industry. It is also essential for hydraulic fluids intended for outdoor use in mobile equipment to possess satisfactory pumpability at the prevailing ambient temperatures during the initial period of operation with cold fluid. Unfortunately, starting procedures using too viscous a hydraulic fluid may easily cause excessively high pressures that pressure control valves are incapable of handling satisfactorily, and hence result in expensive repair costs. All types of hydraulic fluids increase in viscosity and eventually solidify as temperature decreases. An understanding of structure–property relationships has been used to develop two distinct approaches to higher performing biodegradable hydraulic fluids. The first route is to improve TMP Oleate type products by modifying the fatty acid raw material composition so as to increase the degree of saturation, reduce the average alkyl chain length, and to decrease molecular symmetry. Using this approach it has been possible to design products containing 85% renewable raw materials, but with oxidative stability and low temperature fluidity greatly superior to standard TMP Oleate products. Figure 3.12 compares the change in viscosity with time during storage at −30◦ C for standard TMP Oleate and new generation product [36,37].

Viscosity (cSt)

Viscosity vs. storage time at – 30°C 18,000 16,000 14,000 12,000 10,000 8000 6000 4000 2000 0

TABLE 3.21 Typical Ester based HFDU Fluid TMPO Modified

0

50

100

150

Component

% Dose rate

Ester basestock

>96

VII Additive pack

1 to 2 1 to 2

200

Chemistry NPG, TMP, PE, Polyol ester (e.g., TMP oleate) Droplet modifier Antiwear, antioxidant, anticorrosion, etc.

Time (h)

FIGURE 3.12 Low temperature storage stability of standard TMP oleate vs. modified

TABLE 3.20 Typical Ester based Biodegradable Hydraulic Fluid Component Ester basestock

Antioxidant Metal decativator Antiwear Antifoam

% Dose rate >95

1 to 2 0.2 to 0.5 0.4 to 1.0 Diesters > Modified TMP oleates > TMP oleates > High oleic sunflower oil > Rapeseed. Table 3.20 gives a typical formulation for an ester based biohydraulic fluid. The ester selected will be dependent on the trade-off between cost, renewability, oxidative stability, biodegradability, and low temperature pumpability. 3.3.3.5.2 Fire resistant hydraulic fluids Diesters blended with PAOs have been used for a number of years in military application as fire resistant hydraulic fluids (MIL-H-83288C spec). However, polyol esters now tend to be used, especially esters of oleic acid and most commonly the TMP ester of this acid. Polyol esters are classified as HFDU fluids. They compete in this market sector with phosphate ester technology.


There are increasing concerns about the toxicity aspects around phosphate esters and the fact that their thermal decomposition products are highly noxious. Polyol esters are therefore beginning to replace phosphate esters in certain areas. Polyols have several advantages over phosphate esters: • • • • •

They are more cost effective Have better flow properties Are easier to recover from water Are less aggressive to seals They are better lubricants

Phosphate esters, however, are superior in their fire resistance. To enable polyol esters to pass certain fire resistance tests, for example, the factory spray test, 95 0 to 1000 ppm 0 to 5 0 to 1000 ppm

Chemistry Polyol ester (e.g., NPG, PE, DiPE) Storage stabilizer To reduce wear To reduce noise

3.3.3.7 Refrigeration lubricants For the past 50 years, lubricants produced from naphthenic and paraffinic mineral oils have been used in refrigerator compressor systems. These oils were fully compatible with the traditional chloro fluoro carbon (CFC) refrigerants for example, R12 and fully met system requirements. Due to the chemical differences between CFCs and the new alternative refrigerants for example, R134a, traditional mineral oils are not capable of meeting these requirements. Ester lubricants based on polyol ester chemistry have been developed that achieve the key characteristics of this application, namely good [41]: • • • • • •

Lubricity Materials compatibility Energy efficiency Resistance to copper plating Chemical, thermal, and hydrolytic stability Solubility with R134a, mineral oil, and additives

A typical based polyol ester formulation can be seen in Table 3. 23. Low-viscosity oils (ISO 150) are based on diPE polyols. Viscosities in between are based on pure PE polyol themselves or blended with NPG or DiPE polyols. TMP polyols are usually avoided mainly due to the TMP-P problem mention in the aviation turbine section. 3.3.3.8 High temperature chain oils Many manufacturing products today require extreme heat, either in the manufacturing, finishing, curing, or drying

TABLE 3.24 Typical Ester based Chain Oil Formulation Component Ester

% Dose rate >75

Tackifier/thickener

2 to 20

Additive pack

2 to 8

Chemistry Dimerate Trimellitate ester Polyol ester VII (PIB, PMMA) Polymeric esters Antioxidant, antiwear, and anticorrosion

process. Application areas such as: textile factories, car plants and pottery/glass kilns use roller chains, stenter chains, and sliding chains. Lubricants for these chains see temperatures above 150◦ C, and sometimes as high as a 1000◦ C. Esters that have high oxidative stabilities, low volatilities, and excellent clean burn properties are required. A typical ester based chain oil formulation can be seen in Table 3.24. Dimerates tend to be used in cost effective formulations. For higher temperatures trimellitates and PE/diPE polyol esters tend to be favored. Trimellitates tend to a poorer stability than POEs but decompose to leave a soft (easy to remove) deposit. Polyol esters decompose at higher temperature but can leave behind a harder deposit (varnish). Often blends of trimellitates and polyols are used to obtain the correct balance. VIIs are often used as tackifiers/thickeners. For very oxidative stable formulations high viscosity polymeric esters have been used as a tackifier. 3.3.3.9 Metalworking fluids Esters have the following advantages in this application area: • Environmentally considerate (biodegradable, low eco-

toxicity, etc.). • Good boundary lubricants. • Act as FMs. • Have good surface wetting ability letting them penetrate

between the work tool and workpiece. This has led to their use in steel rolling, aluminum drawing, and cutting oils. Esters are starting to see some use as quenching fluids as well. Most esters have poor solubility with water. However, complex polyalkylene glycol esters that are ethoxylated are fully water soluble. These esters show synergism with many types of corrosion inhibitors. Natural and synthetic esters are considered an integral part of today’s high performance and neat oil and water miscible metalworking fluids. The primary reason for using an ester is to reduce the friction between tool and work


piece, with the specific aims of improving surface finish and extending tool life. The use of esters is set to increase as machining techniques develop and as greater consideration is given to the environmental and health aspects of metalworking formulations. The normal function of an ester, be it used in a neat (straight) oil or in a water-miscible formulation, is to reduce the friction between a tool and component or roller and metal strip in order to minimize tool or roller wear and to improve surface finish. A wide range of esters is used in neat oils, which can include esters such as monoesters (e.g., methyl oleate or isopropyl palmitate), diesters (e.g., propylene glycol dioleate), and polyol esters (e.g., trimethylolpropane trioleate). In water-miscible fluids, the most commonly used esters are isopropyl oleate, isobutyl stearate, neopentylglycol dioleate, and a number of trimethylolpropane derivatives. A common feature of the esters used in water-miscible formulations is their greater resistance to hydrolysis. Esters can be used either as additives (typically used at a treat-rate of 5 to 15%) or as the base oil. When used as an additive, the ester will improve the lubrication performance of a given formulation with the specific intention of improving surface finish and increasing tool life. Their use as base oils is usually the result of some additional requirement, such as higher lubricity, minimizing misting or a desire for a high level of biodegradability. Natural oils and fats, such as coconut and palm oils, and synthetic esters, for example, esters of NPG, TMP, and PE, are widely used in many rolling formulations. Following a recent development, low-viscosity complex esters are now a very interesting addition to the range of products suitable for use in rolling applications, particularly steel rolling [42]. With the restricted use of some additives, for example, chlorinated paraffins, formulators are being forced to develop new formulations of similar or higher performance but exclude the use of such additives. As discussed in Section 3.3.2.3.2, high viscosity complex esters (e.g., 1,000 to 45,000 cSt) are particularly suited for use as EP additives either alone or in combination with other performance additives, such as phosphate esters and sulfurized esters or olefins. 3.3.3.10 Greases Esters are commonly used as basestocks for greases when one or more of the following properties are required: • • • •

Low temperature flow (e.g., aircraft wheel bearings) High temperature applications Biodegradability Low toxicity (e.g., food use applications)

A range of ester types: diesters, phthalates, trimellitates, pyromellitates, and polyols are used in this application. 3.3.3.11 Drilling mud lubricants Ester based organic compounds are one type of synthetic base fluid (SBF) added to drilling muds used during offshore oil-drilling operations. Since 1990, the oil and gas extraction industry developed SBFs with synthetic and nonsynthetic oil-like materials as the base fluid to provide the drilling performance characteristics of traditional oilbased fluids (OBFs) based on diesel and mineral oil. Ester SBFs are needed to cool and lubricate the drill bit, and to help bring rock cuttings to the surface. Ester based drilling fluids have the following advantages over OBFs: • Faster and deeper drilling • Greater worker safety through lower toxicity • Elimination of polynuclear aromatic hydrocarbons

(PAHs) • Excellent biodegradability and lower bioaccumulation

potential

3.3.3.12 Transformer fluids/capacitor fluids Synthetic ester dielectric fluids, most commonly pentaerythritol polyol esters, have suitable dielectric properties and are significantly more biodegradable then mineral oil. Their use in electrical equipment is governed by IEC Standard 1099 and IEC standard 1203. Esters have been used as PCB substitutes in compact railroad traction transformers since 1984, and in klystron modulators where their low viscosity, high lubricity, and very low pour points justify their higher costs. Failure rates of traction transformers have significantly decreased since the replacement of PCBs with synthetic POEs [44]. Transformers require a highly efficient heat-transfer fluid. The fluid should also maintain a high dielectric integrity. In the case of capacitors, in addition to low cost, non-toxicity, and biodegradability the fluid should have a low viscosity, a low power factor, and exceptional resistance to discharge and in certain cases, a high permittivity. Trimellitate esters have been found to be suitable for this application [45]. To prevent a decrease in electrical strength it is vital that the moisture content of ester dielectric fluids remains low.

3.4 MANUFACTURERS, MARKETING, AND ECONOMICS

• Potentially less drilling waste volume • Reduced drilling costs

3.4.1 Manufacturers

Drilling engineers have published numerous technical papers that describe the successful application of substitute drilling fluids. In many instances, this substitution has resulted in significant cost savings. Government and industry research found that several synthetic-based fluids used in mud formulations exhibited similar biodegradation profiles to mineral oils offering no apparent benefits. As a result the UK government decided to reduce the discharge of a number of synthetic fluids. Esters were not subjected to the same reduction program because of their rapid biodegradation [43]. A typical ester based drilling formulation can be seen in Table 3.25.

A list of current ester lubricant suppliers and the type of esters they make are given in Table 3.26. Typically, these plants will produce esters not only for lubricant use but other applications as well (cosmetics, plasticizers, biodiesel, etc.). Several of these ester plants are large (>100,000 t), which means there is no shortage of ester lubricant capacity. In recent years several acquisitions have occurred: • Uniqema, ICI (formed from ICI, Unichema, and Mona.

Great Lakes ester business then acquired) • Exxon acquired Mobil • Fuchs acquired DEA

Table 3.26 does not include companies who produce esters only for internal use. TABLE 3.25 Typical Ester based Drilling Lubricant Formulation Component Ester Water Calcium chloride brine Viscosifier Emulsifiers/wetting agent Fluid loss control Lime Weighting agent


% Dose rate

Chemistry

28 14 5.6 1 2 0.4 1 48

— — Alkalinity — — — Alkalinity —

3.4.2 Markets One difficulty in deciding the size of the ester lubricant market is deciding exactly what market segments should be included. For instance should dielectric fluids, fuel additives, mould release, biodiesel, plasticizers, or hydraulic fluids be included even though they are not lubricants? It is also very difficult to differentiate between the amounts of ester produced in Europe vs. the amount consumed (Europe is a net exporter of ester). For several application (e.g., metalworking) formulators may also produce much of their ester requirements internally.

Other industrial 8%

TABLE 3.26 Ester Lubricant Manufacturers Company

Esters produced

Uniqema, ICI Cognis

1, 2, 3, 4, 5, 6, 7 1, 2, 3, 4, 5, 6, 7

Oleofina Nyco Hatco Oleon Degussa Nippon oil and fat Exxon/mobil Aqualon Union camp ADK KAO

7 1, 2, 3, 7 2, 3, 4, 5, 6, 7 7 2, 7 6, 7 2, 3, 4, 7 7 1, 2, 6, 7 5, 6, 7 2, 4, 5, 6, 7

Witco BASF Akzo Inolex

— 2 3 2, 3, 6, 7

Trademark Emkarate ProEco, Edenor, Emery, EMgaurd — Nycobase Hatcol Radialube Drivolan Unister Esterex Hercolube Uniflex Adeka Kaolube, Exceparl, Vinycizer, Trimex Witcosyne Glissofluid Ketjenlube Lexolube

Figure 3.13 shows the size of the Western European ester market and its growth rate. The Americas ester market is probably in the region of 100 Kt with Asia being considerably smaller. In several application areas, polyol esters are expected to replace diesters because of their superior thermal and chemical stability. Therefore, polyols will have a higher growth rate than diesters.

3.5 OUTLOOK Modern lubricants are complex formulations, which are continually developing to meet increasing requirements for performance and durability. Taken as a whole, over the last decade, several general trends in lubricant properties have been seen, namely: Higher thermal stability Improved environmental performance Longer lubricant life Improved cost effectiveness

Esters have performance characteristics to meet all these developing trends. Major areas for growth will be the industrial refrigeration sector (Phase out of R-22), biodegradable hydraulic fluids, engine oils (fuel efficiency), and gear oils (CVT, windmills, etc.).


Air compressor 4% Refrigeration 12%

Esters produced key: 1 = C36 Dimerates; 2 = Diesters; 3 = Complex Esters; 4 = Phthalates; 5 = Trimellitates; 6 = Monoesters; and 7 = Polyols.

• • • •

Aviation 5%

HF 32%

MWF 20%

2T 3%

4T 16%

Total market size 125 Kt (5 to 6% CAGR)

FIGURE 3.13 2002 Western Europe ester sales split by application; MWF = metal working fluids = includes roling, drawing, cutting, etc. HF = hydraulic fluids = Bio HF + fire resistant HF

As companies get larger and developing markets takeoff, new lubricants will be expected to be available globally. New environmental legislation and toxicity registration schemes are being generated at an ever-increasing pace. The cost of registering a brand new lubricant globally could potentially cost several hundred thousand dollars. Such costs can potentially curtail work on radically different chemistries. One way to minimize costs is to work on polymeric materials, which either have exemption or reduced toxicity costs under many nations’ registration programs. Polymers also allow a great deal of chemical flexibility. This has led to considerable ester research in the areas of: complex polyols, PAG esters, polycarbonates, etc. Research is also continuing in the more traditional diester, phthalate, and polyol ester areas as new raw materials or production routes are developed. The area of renewable resource materials is particularly fertile as it offers not only the advantage of improved environmental performance but also reduced costs as well. Sustained development of ester chemistry can therefore be expected to continue for at least the foreseeable future.

ACKNOWLEDGMENTS I would like to acknowledge Steven Stephen Boyde and Ron Pearce (Uniqema) whose help was very useful invaluable in putting this chapter together.

REFERENCES 1. Spaght, M.E. (July 1945). The Manufacture and Application of Lubricants in Germany. Combined Intelligence Objectives Sub-Committee. Nav Tec Miseu, CIOS TARGET NO. 30.303, Fuels and Lubricants. (http://www.fischertropsch.org/primary_documents/gvt_reports/CIOSC/ cios_30_32_68.htm). Report PB-110034. Tables of physical characteristics of a wide range of esters. I.G.Farenindustrie, Library of Congress. 2. Hoogendoorn, R. (June 1999). Field test results of self emulsifying ester based metalworking fluids demonstrate: reduced

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

13.

14.

15.

16.

17.

18.

fluid consumption, lower disposal costs and good recyclability. In Proceedings of the 6th International LFE Congress, Brussels, Belgium. Sommers, E.A. and Crowell, T.L. (1953). High temperature anti-oxidants for synthetic base oils, Part 3. The thermal decomposition of Di (2-ethyl hexyl) sebacate, W.A.D.C Technical Report, pp. 53–293. Barnes, R.S. and Fainman, M.Z. (August 1957). Synthetic ester lubricants. Lubrication Engineering. 13, pp. 454–458. Critchley, S. and Miles, P. (March 1965). Synthetic Lubricants – selection of ester types for different temperature environments. Presented at International Industrial Lubricants Exhibition, Royal Horticultural Society‘s New Hall, Westminster, London, England. Lockwood, F.E. and Klaus, E.E. (May 1980). Ester oxidation under simulated boundary lubrication conditions. In Proceedings of the 35th ASLE meeting, preprint No. 80-AM-2E-1. Lansdown, A.R. (1994). High Temperature Lubrication. Mechanical Engineering Publications Limited, London, U.K. Cottington, R.I. and Ravner, H. (February 1968), Neopentyl polyol esters for jet engine lubricants – effects of tricresyl phosphate on thermal stability and corrosivity. Naval Research Laboratory Report No. 6667. Sniegoski, P.J. (1976). Selectivity of the oxidative attack on a model ester lubricant. ASLE Transactions, 20, pp. 282–286. Krevalis, M.A, Duncan, C.B., and Davis, G.W. (May 1994). The effect of structure on the performance of polyol esters as synthetic lubricants. In Proceedings of the 49th STLE meeting, Pittsburgh, USA. Lahijani, J., Lockwood, F.E., and Klaus, E.E. (1980). The influence of metals on sludge. ASLE Transactions, 25, pp. 25–32. Murphy, C.M., Ravner, H., and Timmons, C.O. (January 1961). Factors influencing the lead corrosivity of ester oils during long term storage. Journal of Chemical and Engineering Data. 6, pp. 135–141. Boyde, S. (May 2002). High Performance Lubricants from Renewable Raw Materials. Actin Seminar, University of Warwick. Various authors. (1992). Mini review compilation on biodegradation and biotransformations of oils and fats. Journal of Chemical Technology and Biotechnology, 55, 397–414. Wright, M.A., Taylor, F., Randles, S.J., Brown, D.E., and Higgins, I.J. (1993). Biodegradation of a synthetic lubricant by micrococcus roseues. Applied and Environmental Microbiology, 59, pp. 1072–1076. Wyatt, J.M., Cain, R.B., and Higgins, I.J. (1987). Formation from synthetic two-stroke lubricants and degradation of 2-ethyl hexanol by lakewater bacteria. Applied Microbiology and Biotechnology, 25, pp. 558–567. Witton, K.E. (1988). The Degradation of a Synthetic 2-Stroke Lubricating Oil in Freshwater Systems. Ph.D. thesis. University of Kent, Canterbury, UK. Zorn, (July 1947). Esters as Lubricants, US Air Force Translation Report No. F-TS-957-RE.


19. McTurk, W.E. (October 1953). Synthetic Lubricants. Wright Air Development Centre, Air Research and Development Command, United States Air force, Wright-Patterson Air Force Base, Ohio, WADC Technical Report, pp. 53–88. Contract AF 33(038)-14593, RDO No. 613–15. 20. Niedzielski, E.L. (1976). Neopentyl polyol ester lubricants – bulk property optimisation, Ind. Eng. Chem. Prod. Res. Dev. 15, 54–58. 21. Niedzielski, E.L. (1977). Neopently Polyol ester lubricants – boundary composition limits, Presented at 173rd National Meeting of the AIChE, Div, Petroleum Chem., Chicago, Illinois, USA. 22. Chang, H.S., Spikes, H.A., and Bunemann, T.F. (1991). The shear stress properties of ester lubricants in elastrohydrodynamic contacts. Journal of synthetic lubricants, 9, pp. 91–114. 23. Anderin, M., Johnston, G.J., Spikes, H.A., and Caporiccio, G. (1992). The elastrohydrodynamic properties of some advanced non hydrocarbon-based lubricants. Lubrication Engineering, 48, pp. 633–638. 24. Gunsel, S, Spikes, H.A., and Anderin, M. (1993). Tribology transactions, 36, pp. 276–282. 25. Guangteng, G. and Spikes, H.A. (May 1995). Boundary film formation by lubricant base fluids. Presented at 50th STLE meeting, Chicago, USA. Presentation 95-NP-7D-3. 26. Smeeth, M. and Spikes, H.A. (May 1995). The formation of viscous surface films by polymer solutions: boundary or elastrodynamic lubrication? Presented at 50th STLE Meeting, Chicago, USA. Presentation 95-NP-7D-2. 27. Bovington, C.H. (1997). Friction, wear and the role of additives. Chapter? Chemistry and Technology of Lubricant, R.M. Mortier, and S.T. Orzulik, (Eds), 2nd edn, Blackie Academic and Professional, London. 28. Wang.Y., Hill, K., and Harris, J.G. (1993). Comparison of branched and linear octanes in the surface force apparatus: a molecular dynamics study. Langmuir, 9, p. 1983. 29. Van der Waal, G. (1985). The relationship between chemical structure of ester base fluids and their influence on elastomers seals and wear characteristics. Journal of Synthetic Lubricants, 1, p. 281. 30. Ter Haar, R. (January 2004). A new polarity measurements technique for lubricants and some of its applications. In Proceedings of the 14th International Colloquium Tribology, Esslingen, Germany, pp. 1869–1873. 31. Bunemann, T., Kenbeek, D., Koen, P., and Wald, W. (October 2002). Friction modifiers for automotive applications. In Proceedings of the International Symposium on Fuels and Lubricants, New Delhi, India. 32. Coffin, P.S., Lindsay, C.M., Mills, A.J., Lindencamp, H., and Fuhrmann, J. (1979). The application of synthetic fluids to automotive lubricant development trends today and tomorrow. Journal of synthetic lubricants, 7, p. 123. 33. Suigura, K. and M.Kagaya. (June 1977). A Study of Visible Smoke Reduction from a Small Two-Stroke Engine Using Various Lubricants, SAE paper 770623. 34. Wright, L. (May 1996). Formation of the neurotoxin TMPP from TMPE-phosphate formulations. In Proceedings of the 51st STLE Meeting, Cincinnati, preprint No. 96-AM-7A-1.

35. Wyman, F.J., Porvaznik, M., Serve, P., Hobson, D., and Uddin, D.E. (1987). High temperature decomposition of military specification L-23699 synthetic aircraft lubricants. Journal of Fire Sciences, 5, pp. 162-177. 36. Ridderikhoff, H. (April 2003). SHE considerations in the selection and development of base-fluids for industrial lubricants. In Proceedings of the 15th ELGI Annual General Meeting, Vienna. 37. Ridderikhoff, H. and Oosterman, J. (January 2004). Biodegradable hydraulic fluids: rhelogical behaviour at low temperatures of several oleochemical derived synthetic esters. In Proceedings of the 14th International Colloquium Tribology, Esslingen, Germany. 38. Van ormer, H.P. (February 1987). Trim compressed-air cost with synthetic lubricants. Power, 6, pp. 43–45. 39. Whiting, R. (1988). Monitoring energy savings of diester compressor oils, Technische Akademie Esslingen. In Proceedings of the 6th International Colloquium, Talk 14.4.


40. Witts, J.J. (1989). Diester lubricants in petroleum and chemical plant service. Journal of synthetic Lubricants, 5, p. 321. 41. Corr, S., Randles, S.J., and Stewart, A. (October 1993). Synthetic lubricants for freon replacement gases, The petroleum industry faces the environmental problems, Brussels, Belgium. 42. Eastwood, J. (October 2002). High Performance Components for Use in the Machining of Aluminium and Steel: An Evaluation of Ester Lubricant Properties. VII Giornata Europea del Lubrorefrigerante, Milan. 43. Spencer, S.J. (September 2000). Governments, operators eyeing effects of synthetic-based drilling fluids. Oil and Gas Journal, pp. 88–89. 44. McShane, C.P. (May/June 2000). New safety dielectric coolants for distribution and power transformers. IEEE Industry Application Magazine, pp. 24–32. 45. Waddington, F.B. (1983). High temperature esters: new dielectric fluids for power engineering applications. GEC Journal of Science and Technology, 49, pp. 18–22.

4

Neutral Phosphate Esters W. David Phillips, Douglas C. Placek, and Michael P. Marino CONTENTS 4.1

Introduction 4.1.1 Historical Development 4.2 Chemistry 4.2.1 Structure 4.2.2 Production 4.2.2.1 Triaryl Phosphates 4.2.2.2 Trialkyl Phosphates 4.2.2.3 Alkyl Aryl Phosphates 4.3 Properties and Performance Characteristics 4.3.1 Chemical Properties 4.3.1.1 Thermal Stability 4.3.1.2 Oxidative Stability 4.3.1.3 Hydrolytic Stability 4.3.2 Physical Properties 4.3.2.1 Vapor Pressure and Boiling Point 4.3.2.2 Viscosity 4.3.2.3 Other Properties 4.3.3 Performance Properties 4.3.3.1 Flammability 4.3.3.2 Lubricity 4.3.3.3 Corrosion and Rust Inhibition 4.3.3.4 Solvent Properties 4.3.3.5 Additive Response 4.3.3.6 Foaming and Air Release 4.3.3.7 Toxicology 4.3.4 Maintenance of Systems 4.4 Manufacture, Marketing, and Economics 4.4.1 Manufacturers 4.4.2 Suppliers 4.4.3 Economics 4.5 Outlook References

4.1 INTRODUCTION Since the discovery of their excellent antiwear and fire-resistance properties in the 1940s, the use of phosphate esters by the lubricants industry has steadily increased. As a result of many years of research and practical experience, M.P. Marino and D.G. Placek originally authored this chapter when working for FMC Corp, Philadelphia.


industry has learnt to manufacture and formulate these versatile chemicals to satisfy a wide variety of demanding applications. Although the basic composition of products currently in commercial use has remained unchanged for over 30 yr, new applications continue to be found and the products are, today, regarded as cost-effective lubricant additives and safe, non-hazardous, hydraulic fluids and lubricants.

Phosphate esters are the most fire resistant of the nonaqueous synthetic basestocks in common use. Their high ignition temperatures, good oxidation stability, and very low vapor pressures make them difficult to burn while their low heats of combustion result in self-extinguishing fluids. Over 60 yr of use have shown them to be excellent lubricating additives and fluids with early shortcomings, for example, hydrolytic instability and neurotoxicity overcome by optimizing manufacturing techniques, raw materials, and stabilizer systems. This chapter describes the chemistry and manufacture of neutral esters of phosphoric acid. It outlines the physical and chemical properties that make them practical and useful industrial chemicals. The formulation of phosphate esters into lubricants and hydraulic fluids, with emphasis on commercial applications, is reviewed. Finally, the practical methods of managing systems employing phosphate esters to achieve optimum working life and costeffective performance in the industrial environment are indicated.

4.1.1 Historical Development Although thousands of organophosphorus compounds have been synthesized, only those classified as neutral, metal free, phosphate esters, or fully substituted esters of orthophosphoric acid (H3 PO4 ), have been used as synthetic lubricants or fire-resistant fluids. By contrast mono-, di-, and trisubstituted esters have all found commercial use as lubricant additives, but only neutral tertiary esters are the subjects of this study. Tertiary orthophosphate esters have been known for about 150 yr, the trialkyls having been synthesized in about 1849 [1] and the triaryls in about 1854 [2]. The development, after World War I, of less flammable nitrocellulose lacquers plasticized with tricresyl phosphate (TCP) as industrial and automotive coatings [3], led to the investigation of phosphate esters as safer hydraulic fluids and lubricants. Principally during the early 1940s, a number of investigators [4–7] examined the lubricating properties of phosphate esters, especially their usefulness as antiwear agents. During World War II and the years that followed immediately following, the development of increasingly sophisticated military and commercial aircraft, which used hydraulic rather than mechanical control systems, created a need for safe, nonflammable hydraulic fluids. Patents were awarded to J.D. Morgan, at the Cities Service Oil Company, in 1944 and 1946 [8,9], on lubricant and hydraulic fluid compositions having wide operating temperature ranges (−40 to 200◦ F) based on tributyl and other trialkyl phosphates. Also in 1946, W.F. Hamilton and coworkers at the Lockheed Aircraft Corporation [10] were awarded a patent on what can be considered the forerunner of today’s commercial aircraft hydraulic fluids.


The use of both trialkyl and triaryl phosphates as synthetic basestocks was more thoroughly defined and developed in a major program jointly sponsored by the U.S. Navy and Air Force at the Shell Development Company between 1949 and 1953 [11]. As a result of this work, F.J. Watson was awarded several patents for fluid compositions based on tributyl phosphate and TCP [12–14]. At about the same time, the Douglas Aircraft Company and Monsanto Chemical Company helped pioneer the use of phosphate esters in commercial jet aircraft [15–18]. By the late 1950s, such planes as the Douglas DC-8, Boeing 707, and Convair 880 were flying on Monsanto’s Skydrol® 500A fluid, which was based on a mixed alkyl aryl phosphate. Concurrent with the use in aircraft, other commercial uses developed. TCP and other esters became widely used during the l950s as deposit modifiers in leaded gasoline. By the late 1950s, Monsanto, Celanese Corporation of America, and the E.F. Houghton Company had complete lines of phosphate ester-based industrial hydraulic fluids, which were readily adopted by the steel, aluminum, foundry, and casting industries. Each company also marketed phosphate-ester products for use as fireresistant compressor lubricants. The U.S. Navy, in 1961, adopted specification MIL-H-19457, a fire-resistant fluid then based on trixylenyl phosphate (TXP), for use in aircraft carrier elevators. Some of the early industrial fluids developed both in the United States and Europe were based on blends of alkyl aryl phosphates and chlorinated aromatic hydrocarbons (chlorinated biphenyls). However, the environmental and toxicological problems that subsequently arose with chlorinated biphenyls resulted in their complete disappearance from commercial use in the 1970s. The industrial phosphateester fluids in use today as lubricant additives or synthetic basestocks, therefore, are all based on triaryl phosphates free from halogenated components. Commercially available phosphate-ester hydraulic fluids for general industrial applications are categorized as type HFDR fluids according to ISO standard 6743, Part 4: Lubricants, industrial oils, and related products (class L) — Classification.

4.2 CHEMISTRY 4.2.1 Structure Numerous organic phosphorus compounds including phosphites, phosphonates, and phosphates have found application as additives in a variety of lubricant formulations as stabilizers, antiwear additives, antioxidants, metal passivators, and extreme pressure additives. Of these, the zinc dialkyl dithiophosphates, found in virtually all automotive engine lubricants, are the most widely used. Only one group of phosphates, the trisubstituted (tertiary), neutral esters of H3 PO4 , has found significant use as

synthetic basestocks. These compounds have the general structure: O R⬘

O

P

O

R⬙

O R⵮

where R , R , and R are the same or different and are alkyl C4 –C12 , aryl C6 or alkylaryl C7 –C14 . None of the commercially important basestocks contains nitrogen, sulfur, chlorine, or other elements substituted in the R groups. Although metallic or amide derivatives of the partial esters have found use as lubricant additives, all the significant commercial synthetic lubricant basestocks are compounds in which all three R groups are alkyl or aryl moieties containing four or more carbon atoms, hydrogen, and oxygen. Thus, the important phosphate-ester basestocks fall into three broad classes: triaryl, trialkyl, and alkyl aryl phosphates, and the rest of this chapter focuses on these compounds. The triaryl phosphates are the most commercially important products. The earliest products of significance, TCP and TXP, were often referred to as “natural” esters because the cresol and xylenol raw materials came from the distillation of coal. In this group of compounds all three organic groups are usually the same:

of different xylenol isomers, principally 2,4-; 3,4-; and 3,5-xylenol, together with ethyl phenols, etc. The trend toward products with improved hydrolytic stability has led to the use of feedstocks containing increased amounts of 3,5-xylenol [19]. Cresol, xylenol, and phenol can be blended and used to produce mixed esters; cresyl diphenyl phosphate (CDP) is the most significant of these but XDP, etc. have also been produced commercially. During the l960s, “synthetic” analogues of the natural esters were developed from the alkylation of phenol, which reduced both toxicological concerns and production costs. Isopropylphenyl and tertiarybutylphenyl phosphates are now commercially available in a variety of viscosity grades. Because these products are always made from a mixed feedstock of phenol and the respective alkyl phenol, they are also referred to as triphenyl phosphate (TPP), propylated or isopropylphenyl phenyl phosphate (IPPP), and TPP, butylated or tert-butylphenyl phenyl phosphate (TBPP). The structure of diphenyl-para-t-butylphenyl phosphate, the dominant species in a widely used ISO 46 basestock, is as follows:

Diphenyl-para-t-butylphenyl phosphate

Today, commercial production of TCP usually starts with the mixed meta/para isomer feedstock. This is because the presence of the ortho isomer can lead to the production of the highly neurotoxic triorthocresyl phosphate (TOCP). As a consequence the level of the ortho isomer in the feedstock has been significantly reduced over the years and is now normally well below 0.2%. The raw materials for the manufacture of TXP also contain a complex mixture


All commercial synthetic triaryl phosphate fluid basestocks are mixtures of varying molecular weights. The location of substituents on the phenyl ring can vary between the ortho, meta, and para positions. In the lower viscosity synthetic products, unsubstituted TPP is usually the most significant component species. Increasing the proportion of alkyl phenol in the feedstock increases average molecular weight, viscosity, and the complexity of the mixture but lowers the phosphorus content and specific gravity of the final product. Commercially available trialkyl phosphates are typically symmetrical (R = R = R ). Tri-n-butyl phosphate (TBP) and triisobutyl phosphate (TiBP) are widely used in aircraft hydraulic fluids while tributoxyethyl phosphate (TBEP) and trioctyl phosphate (TOP) are currently of interest as phenol-free antiwear additives. Dibutyl phenyl phosphate (DBPP), also used in aircraft fluids, is the most common alkyl aryl ester. Although a significant patent estate developed on alkyl aryl esters and several of them were used widely at one time as industrial fluid basestocks, there is little significant commercial use of these esters today other than the dibutyl phenyl and the isodecyl diphenyl esters because of their good low temperature properties. Most alkyl aryl esters find

use as flame-retardant plasticizers in the thermoplastics industry.

4.2.2 Production Although the tertiary phosphates are described as esters of H3 PO4 , preparation from the acid gives poor yields because the water produced readily hydrolyzes the ester in the acidic conditions of the reaction. Because of the differences in the reactivity of starting materials and the chemistry of the products, distinct commercial routes have developed to produce triaryl, trialkyl, and alkyl aryl esters.

4.2.2.1 Triaryl phosphates The simplest laboratory preparation of triaryl esters and the most important commercial route is the phosphorylation of an aromatic alcohol — that is, a phenolic compound — with phosphorus oxychloride in the presence of magnesium or aluminum chloride [20]: 3ROH + POCl3

100–200◦ C

−→

(RO)3 P=O + 3HCl

(4.1)

An excess of the phenolic compound is maintained to avoid the presence of the intermediate chloridates, (RO)(Cl)2 P=O and (RO)2 (Cl)P=O, which would reduce yields and produce acidic partial esters during subsequent processing. Prior to the early 1960s, cresylic acids were the phenolic raw materials used in this preparation. The common cresylic acids (cresol, xylenol, and mesitol) have one, two, and three methyl groups on the ring, respectively, in any of the ortho, meta, and para positions. TXP became the most commonly used industrial fluid basestock of the triaryl esters. The range of viscosities required for industrial applications could be achieved by carefully selecting the xylenol isomers used as the starting material. For example, an isomer mixture consisting of mostly 3,5-xylenol gives a higher viscosity than a mixture rich in the 2,6-isomer. Work by the Albright & Wilson Company [21] and the Ciba-Geigy Corporation [22] in the United Kingdom in the 1960s resulted in the development of a more easily controlled and less expensive route to the range of products desired. Work at both companies involved the catalytic alkylation of phenol with propylene or butylene and the subsequent reaction of this “synthetic alkylate” with phosphorus oxychloride. In the synthetic process, the viscosity of the final product can be controlled in either or both of two ways: by the degree of alkylation of the phenol (i.e., by the number of alkyl groups on the phenol ring) and by using a variable, mixed feed of phenol and alkyl phenol to the phosphorylation reaction [23]. As the degree of alkylation increases,


or the proportion of unalkylated phenol decreases, the viscosity of the product increases. Thermodynamics and steric hindrance determine the order in which the phenols react (phenol is fastest) and thus determine the molecular weight and isomer distribution in the final product. The commercial process is therefore more appropriately described as follows: xROH + (3 − x)R OH + POCl3 → (RO)3 P=O + (RO)2 (R O)P=O + (RO)(R O)2 P=O +(R O)3 P=O + 3HCl

(4.2)

For both the natural and synthetic esters, a variety of refining steps are used to produce the final product. By-product hydrogen chloride (HCl) can be removed from the reaction by heating, use of a partial vacuum, sweeping with an inert gas, or reaction with an organic base such as pyridine. The most common method combines heating and vacuum followed by washing with water to recover the HCl as a by-product in the form of a dilute acid solution. Following the HCl extraction, the crude product is refined. A series of distillation steps removes the unreacted phenols and alkyl phenols for recycling, isolates the refined product, and leaves the catalyst and high-boiling by-products in the still residue [24,25]. The crude product can, if necessary, be re-distilled to remove unreacted raw materials then, in order to remove residual acid and water, either washed with aqueous alkali and dried under vacuum [20] or treated with an adsorbent solid and dried. The foregoing discussion of the production chemistry and raw materials indicates that most commercial triaryl esters are not symmetrical products. The asymmetry in the phosphate-ester molecule is a significant determinant of its physical properties. Symmetrical products are crystalline or waxy solids. Indeed, the only truly symmetrical, pure triaryl phosphate of commercial importance is TPP, which melts at about 49◦ C and is therefore not useful as a fluid basestock. Conversely, controlling the degree of asymmetry produces liquids with varying physical properties, which can be tailored to a variety of application conditions. As implied by Equation (4.2), the asymmetry can be introduced into the molecule by using a mixed feed to the reaction. As long as the reactivity of the phenolic compounds is reasonably close, this method is acceptable, as is the case in the production of cresyldiphenyl phosphate, isopropylphenyl, and t-butylphenyl phenyl phosphates. Also with TCP or TXP, the similar reactivity of the ortho, meta, and para isomers makes the preparative reaction straightforward. Asymmetry can also be introduced into the triaryl phosphate molecule by stepwise reaction of the sodium salt of a phenol with an intermediate chloridate [13]. The following

reaction scheme is one of several possible alternatives: 2ROH + POCl3 → (RO)2 (Cl)P=O + 2HCl

(4.3)

R ONa + (RO)2 (Cl)P=O → (RO)2 (R O)P=O + NaCl (4.4) The properties of the mixtures prepared by these reactions can be quite similar to those of symmetrical triaryl phosphates with similar alkylaryl content. 4.2.2.2 Trialkyl phosphates Trialkyl phosphates can be prepared using reactions similar to those used for triaryl compounds. However, because trialkyls are generally less stable than triaryls, the reaction (Equation [4.1], phosphorylation of an alcohol) is usually carried out at more moderate temperatures. To drive the reaction to completion, greater excesses of alcohol are needed, and the by-product HCl must be removed as rapidly as possible. The higher molecular weight trialkyl phosphates can be purified by stripping the unreacted alcohol, alkaline washing, and distillation drying, in steps similar to those used for the triaryl processes. The lower molecular weight esters, below tripropyl phosphate, can be isolated only by dry techniques because they are soluble in water. Because of the inefficiencies of the aliphatic alcohol phosphorylation process, trialkyl phosphates are commercially produced by the reaction of sodium alkoxide with phosphorus oxychloride: 3RONa + POCl3 → (RO)3 P=O + 3NaCl

(4.5)

In this process, commonly referred to as the alkoxide process, the chloride is rapidly converted to sodium chloride, NaCl, which can then be removed by water washing, with further purification of the phosphate accomplished by distillation under vacuum. Mixed or unsymmetrical trialkyl phosphates can be produced by using mixed alcohol feeds or by stepwise reaction of the intermediate chloridate with an alkoxide as in Equations (4.3) and (4.4). 4.2.2.3 Alkyl aryl phosphates The alkyl aryl phosphates, either alkyl diaryl or dialkyl aryl esters, can be produced by the reaction of the appropriate purified intermediate alkyl or aryl phosphochloridate with the desired alcohol or phenol under reactions and purification techniques similar to those described above. The lower molecular weight dialkyl aryl phosphate esters (e.g., DBPP) are apparently best obtained [26] by the preparation of the dialkyl phosphoryl chloride (dialkyl phosphorochloridate) as in Equation (4.6), which is purified by distillation under reduced pressure. The chloridate


is then reacted with the sodium arylate in water: (RO)2 (Cl)P=O + R ONa → (RO)2 (R O)P=O + NaCl (4.6) The dialkyl aryl esters can then be isolated and purified by the techniques already described. In the interest of economics, actual commercial processes often vary in some degree from the preceding relatively simple reaction schemes. Such variations often produce mixtures rather than pure products. For example, commercial DBPP may be a mixture containing TPP, TBP, monobutyl, diphenyl phosphate as well as DBPP. These factors need to be kept in mind in the evaluation of a variety of performance characteristics. Much of the process development in recent years on the production of the triaryl phosphate esters has involved improvements in process efficiency [23–28], including development of continuous process steps [29], which have replaced the batchwise operations of some earlier processes. Another focus has been on reducing the level of TPP in synthetic phosphates. TPP, while very oxidatively stable, has poor hydrolytic stability and its presence accelerates the rate of degradation of the fluid in the presence of moisture. In order, therefore, to reduce the TPP content two procedures have been developed. One distills the phosphate ester to reduce the TPP down to ∼2% [30] while the other is a two-step reaction in which pure alkylated phenol is first reacted with phosphorous oxychloride followed by reaction with phenol. This avoids the presence of significant amounts (>5%) of TPP [31].

4.3 PROPERTIES AND PERFORMANCE CHARACTERISTICS 4.3.1 Chemical Properties Chemical inertness is one of the primary attributes of any lubricant or fluid basestock. The fluid should not react with the metals or other materials from which the mechanical system is constructed. Since additives are commonly used, the basestockshould not be reactive with or attacked by other classes of chemical compounds. The trisubstituted phosphate esters, being neutral, have proven chemical stability over a wide temperature range through many years of industrial service. They are generally unreactive with organic compounds and are excellent solvents for most commonly-used lubricant additives. Other aspects of chemical stability for synthetic basestocks — their thermal, oxidative, and hydrolytic stability — are more significant. The following section discusses these latter properties. As noted above, most of the commercially important phosphate-ester fluids are actually mixtures in which asymmetry plays an important role in determining their useful properties. (The alkyl phosphates are exceptions to this rule.) To provide the most practical applications data,

the most commercially important products are emphasized. To facilitate the presentation, the following abbreviations are used for commonly occurring fluid/lubricant products: Triaryl phosphate esters: CDP IPPP

Cresyl diphenyl phosphate Isopropylphenyl phenyl phosphates (TPP, propylated) TBPP t-Butylphenyl phenyl phosphates (TPP, butylated) TCP Tricresyl phosphate TPP Triphenyl phosphate TXP Trixylenyl phosphate (trixylyl phosphate) Trialkyl phosphate esters: TBP Tributyl phosphate (tri-n-butyl phosphate) TBEP Tributoxyethyl phosphate TiBP Triisobutyl phosphate TOP Trioctyl phosphate (tri-2-ethylhexyl phosphate unless otherwise noted) Alkyl aryl phosphate esters: DBPP Dibutyl phenyl phosphate EHDPP 2-Ethylhexyl diphenyl phosphate IDDPP Isodecyl diphenyl phosphate Where appropriate, to further describe the product if it is used commercially as a basestock, the ISO viscosity grade number follows the ester designation. For example, IPPP 46 defines an ISO VG 46 phosphate-ester basestock derived from isopropyl phenol; TBPP 32 defines an ISO VG 32 basestock made from t-butyl phenol. The information presented below attempts to give a concise and accurate summary of the properties and usefulness of commercial phosphate esters. For information on the early technical development of phosphates see reference [18] while the properties of TBP have been thoroughly reported in [32]. Additional physical and chemical data, directed more toward field use of fluids, are contained in several volumes edited by Booser [33,34]. A further in-depth review of the physical and chemical properties, handling, and operating procedures directed toward practical use of phosphate-ester fluids and lubricants is also available [35]. 4.3.1.1 Thermal stability Thermal stability will generally define the temperatures at which a fluid can be used. Although in practice some oxygen is always present in the system, a study of the thermal stability in the absence of oxygen gives a clearer picture of the effect of temperature alone. It is also dependent on both temperature and time, that is, the shorter the time of exposure at a given temperature, the higher the temperature that can be tolerated.


Over the years, a number of studies [18,36,37] have attempted to define and rank the relative thermal stability of phosphate esters. The general conclusions from these studies indicate that the triaryls are the most stable and the trialkyls the least, with the alkyl aryls intermediate. A more recent attempt to evaluate thermal stability [38] employed thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC). ASTM Methods D-3850 and E-537 respectively, were used, except that the samples were tested under nitrogen to eliminate oxidation effects. The DSC method estimates the “onset of decomposition” as the temperature at which an endotherm occurs when the sample is heated at a constant rate of 10◦ C/min. The TGA method measures the decomposition by determining the weight loss as the sample is heated, and the data are recorded as the temperature at which a given percent weight loss is reached. In both DSC and TGA techniques, the temperature recorded as the “onset of decomposition” could be influenced by evaporation of the most volatile component if the test fluid is a mixture. Evaporation is endothermic in DSC and will result in weight loss in TGA. This is especially true for compounds such as IPPP and TBPP, which are mixtures of monomeric compounds and can contain appreciable amounts of TPP. The DSC data in Table 4.1 show that commercially used triaryl phosphates begin to show an endotherm, whether decomposition or evaporation, over 300◦ C, well above common operating temperatures. TPP content apparently

TABLE 4.1 Relative Thermal Stability of Phosphate Esters Under a Nitrogen Atmosphere (ASTM E-537) by DSC

Phosphate ester TPP TCP TXP CDP TBPP 22–46 IPPP 22–46 EHDPP IDDPP TBP TOP TBEP

Initiation of decomposition (endotherm) temperature (◦ C) —a 333 311 306 338–347 311–314 252 264 283 281 276

a Does not decompose under these conditions. Source: From Shankwalkar, S.G. and Cruz, C., Ind. Eng. Chem. Res., 33, 740–743 (1994). With permission.

has little influence on the data, since it did not decompose below 360◦ C in a similar test conducted in a sealed tube. The three common trialkyls begin to decompose in the 275 to 285◦ C range. The TGA data in Table 4.2 also show that significant weight loss does not begin to occur until well above common system operating temperatures. The data on the commercial IPPP and TBPP fluids show the influence of evaporation of TPP, currently a significant component and the most volatile present in these basestocks. The data in Tables 4.1 and 4.2 support the prior studies regarding the relative stability as well as the practical experience developed over the years, namely, that the triaryl esters are more stable than the alkyl aryl esters and significantly more so than the trialkyl esters. Several studies [18,39–41] of the pyrolysis of phosphate esters have shown that the decomposition products are mainly unsaturated hydrocarbons and acidic phosphate esters. Results are similar with both the trialkyl

and alkyl aryl esters, indicating that the weakest link in the decomposition is the aliphatic carbon–oxygen bond. Again, the triaryl esters are the more stable. Alkylation of the ring in the triaryls tends to reduce the thermal stability but this, in turn, can be affected by the length and branching of the alkyl chain. Overall, all three classes of phosphate esters exhibit sufficient thermal stability for most commercial applications, although the triaryls have achieved the widest use. 4.3.1.2 Oxidative stability The oxidative stability of phosphate esters has proven to be quite high and has therefore encouraged their commercial use. Cho and Klaus [42] investigated the oxidative degradation of trialkyl and triaryl phosphates using the apparatus known as the Penn State Micro-Oxidation Tester. The results of this study (Table 4.3) confirmed again that the triaryl esters are more stable than the trialkyl esters

TABLE 4.2 Relative Thermal Stability of Phosphate Esters Under Nitrogen by TGA (ASTM D-3850) Temperature (◦ C) for

Weight loss (%)

TPP

IPPP 22

IPPP 32

IPPP 46

TBPP 46

TCP

TBP

TBEP

TOP

10 20 30 50 75

261 281 294 310 323

274 292 304 320 334

272 294 307 324 339

265 285 297 313 327

301 320 333 350 365

278 298 310 325 325

154 173 183 196 207

221 242 254 269 279

208 231 242 257 268

Source: From Shankwalkar, S.G. and Cruz, C., Ind. Eng. Chem. Res., 33, 740–743 (1994). With permission.

TABLE 4.3 Oxidative Stability of Phosphate Estersa Phosphate ester TBP TCP TCP TXP TCP TXP DBPP

Time (min) 5 10 30 60 30 30 15 15 360 180

Percent of original product

Temperature (◦ C)

Unoxidized

Oxidized

Evaporated

225 225 225 225 250 250 270 270 250 270

13 19 85 67 57 65 60 55 77 81

6 8 1 2 3 4 5 6 ISO VG 320). Due to the presence of EO, molecular weight restrictions do not generally apply and high percentages of allyl functionality do not occur. Random, EO containing molecules are therefore available at viscosity grades up to and surpassing 90,000 cSt (40◦ C) (∼30,000 Da). However, di- or polyfunctional initiators are used in order to reduce reactor batch times. Furthermore, FDA approved lubricants (21 CFR 178.3570 Incidental contact with food) can also be produced with these base stocks (as they can with monol [C4 ] initiated propoxylates). The increased load carrying capacity and superior EP performance of this class of fluid make them particularly useful when manufacturing fluids intended for use under high load conditions. Examples include wind turbine transmissions and large worm gears. The following tables detail some typical data for the major classes of PAG based fluid [6]. Tables 6.1 and 6.2 describe the general properties of random copolymers of EO and PO. These tables have two families of structurally related compounds. The mono-butyl ethers (Table 6.1) polymers are derived from a butyl starter and are formed from equal weights of EO and PO. These materials have very low pour points. A comparison with propoxylates (Table 6.3) shows the values to be very similar. PAGs containing higher percentages of EO (Table 6.2) however have much higher pour points (even taking into account molecular weight). Viscosity index increases with increasing EO content. The diol polymers (Table 6.2) are derived from water giving them two hydroxyl groups. The oxide incorporated in these is 75 wt% EO and 25 wt% PO.

TABLE 6.1 General Properties 50:50 wt% Mixed Oxide Random Co-Polymer — Monol Viscosity Viscosity Viscosity index Pour point, ◦ C Refractive index Specific gravity Flash point, ◦ C Vapor pressure Specific heat Surface tension, 20◦ C

cSt at 40◦ C cSt at 100◦ C ASTM D 2270 ASTM D 97 N20 D 20/20◦ C COC mm Hg 20◦ C kJ/kg K Dyn/cm

19 4.6 165 −58

52 11 212 −53

66 13.5 210 −50

133 25.5 230 −48

1.02 183

1.03 220

1.04 232

1.05 240

217 41 239 −42 1.46 1.06 240 100 100 —

a TEA, Triethanolamine; FA, fatty acid b Product is a solid at room temperature due to high ethylene oxide content.

TABLE 36.4 Lathe Test Results for Cloud Point Studya Condition 1

Condition 2

Condition 3

Condition 4

Condition 5

Sample

T

F

T

F

T

F

T

F

T

F

A B

94 92

490 500

100 100

540 540

104 104

550 570

114 116

610 640

122 126

680 710

C

100

500

102

540

108

540

108

640

D E

96 96

500 510

102 106

540 540

108 102

570 580

F

100

520

186

500

Failure

Failure

Failure

a T, cutting tool temperature in Celsius; F, vertical cutting force in pounds-force; Failure

either severe vibration or tool breakage.


PAG 40 30 20 10 0

Lubricity additive

TEA

Water

0 10 20 30 40

40 40 40 40 40

20 20 20 20 20

Cutting force (N × 10–3)

2.42

TABLE 36.5 MWF Concentrates (%) Used in the Lathe Synergy Study

2.40 2.38 2.36 2.34 2.32 2.30 0

10

20

30

40 Pag

40

30

20

10

0 Fatty acid

Percent lubricity additive in concentrate

104 102 100 98 0

10

20

30

40 Pag

40

30

20

10

0 Fatty acid


FIGURE 36.9 Demonstration of the synergy between PAGs and fatty acids in chemical MWFs: data obtained from tests on an instrumented lathe. From Brown, W. L., Lubr. Eng., 44, 168–171 (1988) Cutting force (N × 10–3)

so that the sum of the PAG and the lubricity additive was equal to 40% by weight. The percentage of polymer ranged from 40 to 0 while the percentage of lubricity additive went from 0 to 40. The concentrates, shown in Table 36.5, were then diluted 20:1 with water and evaluated on the lathe. Two different studies were run. In the first, the lubricity additive was a fatty acid. The results from this study are shown in Figure 36.9. The minimum cutting force was achieved with PAG levels of between 20 and 30%. Maximum cooling, represented by the minimum tool temperature, occurred with between 10 and 20% polymer in the concentrate. These curves show that combinations of the PAG and fatty acid perform better than either additive by itself. In the second study, a water-soluble phosphate acid ester was employed as the EP lubricity additive. The data from this study are shown in Figure 36.10. In this case, minimum cutting force was achieved with PAG levels of between 10 and 20% in the concentrate. The minimum tool temperature occurred between 0 and 30% polymer. Again, combinations of PAG and lubricity additive performed better than either additive used individually. This synergy is further evidence supporting the cloud point mechanism of chemical MWFs containing PAGs.

Tool temerature °C

106

2.55 2.53 2.51 2.49 2.47 2.45 0 40


20 20

30 10

40 Pag 0 Phosphate


36.5.3 Modified PAGs in Chemical MWFs 105 Tool Temerature °C

Polyalkylene glycols provide good lubricating properties in a large number of metalworking operations. They are also very stable in hard water, low foaming, and resistant to biological attack. When used in combination with additives such as fatty acids or phosphate esters, the lubricating and cooling properties of the MWF are enhanced. Unfortunately, both fatty acids and phosphate esters are sensitive to hard water, prone to foaming, and susceptible to biodegradation. In an attempt to achieve the benefits of these combinations without the drawbacks, two types of modified PAGs have been commercialized. These modified PAGs are either esterified or grafted with organic acids. Polyalkylene glycol esters are made from the condensation reaction between organic acids and the terminal

10 30

104 103 102 101 100 0 40

10 30

20 20

30 10

40 Pag 0 Phosphate


FIGURE 36.10 Demonstration of the synergy between PAG and phosphate esters in chemical MWFs: data obtained from tests on an instrumented lathe. From Brown, W. L., Lubr. Eng., 44, 168–171 (1988)

hydroxyl groups of the alkoxylated polymer. These products, like PAGs, exhibit inverse solubility in water and thus behave in an analogous manner. PAG esters exhibit good boundary lubricating properties [36,54], yet have better hard-water stability and are less likely to foam than blends of fatty acids and unmodified PAGs [22]. A second method of modifying PAGs that has gained commercial acceptance is the addition of organic acid functionalities through grafting technology. The result is an anionic PAG that has organic acid groups randomly attached to the polymer’s backbone with hydrolytically stable covalent bonds. These modified PAG polymers exhibit inverse solubility and excellent hydrodynamic and boundary lubricity. Because the acid groups are randomly attached to the polymer, the foaming tendencies of this type of product are significantly lower than those of blends of fatty acids and PAGs. Since the PAG itself is very water soluble at room temperature, the grafted polymer has excellent hard-water stability. Its resistance to biological attack is also very good [55].

36.5.4 Applications of PAGs in Chemical MWFs Polyalkylene glycols have been used in chemical MWFs for the past 40 yr. Because of their good lubricity and synergy with other water-soluble lubricity additives, they have helped expand the applications of chemical MWFs. Chemical MWFs containing PAGs have all of the advantages characteristic of this product class. These advantages include excellent cooling, good biological and hard-water stability, transparency, and cleanliness. The presence of the PAGs in chemical MWFs enables the formulation of products with enhanced lubricity properties, allowing them to compete directly with heavy-duty soluble oils in many applications. While PAGs or modified versions have been used in chemical MWFs for many years [19,24,37], performance data comparing these products to other types of MWFs is relatively scarce. Articles comparing different classes of MWFs to each other, like chemical solutions to soluble oils or soluble oils to straight oils are readily found in the literature. However, the specific formulation information needed to examine the effects of synthetic lubricants in these products is rarely included. The rest of this section reviews some of the documented work that demonstrates the effect of PAGs, both normal and modified, in chemical MWFs. The use of PAG based MWFs in grinding, tapping, hobbing, rolling, drawing, and forming operations is also described. 36.5.4.1 Grinding Levesque et al. [55] published a paper in 1983 describing their experience with an acid grafted PAG in three different grinding operations.


In the first case a mineral seal oil fortified with approximately 5% of a fatty acid was used to grind hardened steel balls. Odor, general housekeeping problems, and a concern about the flammability of the oil caused them to switch to a water based MWF. A chemical MWF based on a mixture of caprylic acid and a PAG was selected for the ball grinding operation. Initially the product worked very well. During use, however, the effectiveness of this fluid gradually decreased. The addition of concentrate was necessary to return the coolant to acceptable performance levels. Analytical testing of the coolant during use showed that the drop in performance was due to the selective depletion or biodegradation of caprylic acid. Rather than continually monitor their fluid for acid concentration, the authors switched to a dilute solution of an amine neutralized, acid grafted PAG. This modified PAG performed well. The second case study involved a centerless roller grinding operation. A heavily fortified soluble oil was used in a 7000 gal central sump. The problem with the soluble oil was that it covered the regulatory wheels with a layer of oil and metal fines that prevented the achievement of the desired tolerances. The authors decided to switch to a chemical MWF because of the cleanliness that was possible with this type of product. The soluble oil was replaced with a chemical MWF containing a fatty acid ester, a boric acid corrosion inhibitor, and a biocide. Initially the product worked well, but within a month the surface finishes degraded to an unacceptable level. The depletion of the fatty ester was determined to be the problem. The authors then switched this system to the amine neutralized, acid grafted PAG fortified with a carboxylic acid based corrosion inhibitor. At the time the paper was written the roller grinding operation had been using this chemical MWFs for 16 months with essentially no problems due depletion or biodegradation. In the third study conducted by the authors, the same chemical MWF based on the acid grafted PAG was used in a double-disk surface grinding operation. The life of this coolant system was more than 8 months, whereas the life of the previously used soluble oil was only 2 to 3 months. 36.5.4.2 Tapping In 1984 Nash and Colakovic [54] published a study on the affect of a PAG ester and three other lubricity additives on the performance of chemical MWFs during the tapping of high silicone content aluminum blanks. The fluids were evaluated using a tapping torque test machine [56]. The taps employed were HSS, 3-flute, 10 to 15 mm. The tap surface speed was 0.508 m/sec. The nut blanks were made from high silicone A380.1 aluminum with a 16 to 25 mm nonheat-treated surface finish.

of a single component come from the addition of the PAG ester or the alkyl acid phosphate. Furthermore, the combination of the PAG ester and phosphate was synergistic, providing lower tapping torques and thus better efficiency than the sulfurized, chlorinated reference oil. The addition of the sulfurized oleic acid resulted in a small improvement over the base formulation and also showed synergy when combined with the PAG ester. The use of the chlorinated oleic acid had no significant affect on tapping efficiency.

The chemical MWFs were diluted to 10% of their original concentration with 140 ppm hard water. The torque required to tap the nut blanks was recorded and compared to that achieved when using a straight-oil MWF. This control oil was a neat cutting fluid fortified with chlorine and sulfur containing lubricity additives. The percent tapping efficiency was then calculated using the equation: % Efficiency = (Control oil torque/Test fluid torque) × 100%

36.5.4.3 Hobbing

The higher the % tapping efficiency, the better the MWF. A series of chemical MWFs was made up to determine the effects of four water-soluble lubricity additives on tapping efficiency. The additives tested were a PAG ester, which exhibits inverse solubility, an alkyl acid phosphate, a sulfurized oleic acid, and a chlorinated oleic acid. Each fluid also contained a carboxylate salt for corrosion protection and TEA to solubilize the lubricity additives and provide reserve alkalinity. The physical characteristics of the components used to make up the test concentrates are shown in Table 36.6. The compositions of the different fluids tested and their average percent tapping efficiency are shown in Table 36.7. It can be seen from these data that the largest positive effects

Katsuki et al. [57] described work that they had done to evaluate the performance of water based MWFs in a gear hobbing operation. In this study the durability of the hob was evaluated using a fly-tool cutting test on a milling machine. This fly-tool cutting evaluation was set up to correlate closely with an actual gear hobbing operation. The MWF concentrates were diluted with water. During the cutting operation, the face of the hob was flooded with the diluted MWF. Grooves were cut into the workpiece to correspond to the manufacture of 14.7 gears. The corner and center wear of the hob were then evaluated. The smaller the wear scars, the more effective the MWF. Four water-soluble PAGs of different molecular weights were evaluated and compared to a chlorinated fatty

TABLE 36.6 Physical Characteristics of Fluid Components Kinematic viscosity (cSt) Component

At 40◦ C

At 100◦ C

Total acid number

— 300 222 2750 95 190 150

— — 14 230 18 20 22

— 170 — 15 330 185 140

Water Carboxylate salt TEA PAG ester Alkyl acid phosphate Sulfurized oleic acid Chlorinated oleic acid

Miscellaneous properties 140 ppm hardness 140 ppm base number 1% cloud point, 77 ◦ C 11% phosphorous 8.5% sulfur 30% chlorine

TABLE 36.7 Test Fluid Concentrate Compositions and Aluminum Tapping Torque Efficiency Solution concentrates Component

Base

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

Water Carboxylate salt TEA PAG ester Phosphate Sulfurized acid Chlorinated acid

84 8 8 — — — —

74 8 8 10 — — —

80 8 8 10 4 — —

70 8 8 10 4 — —

80 8 8 — — 4 —

70 8 8 10 — 4 —

76 8 8 — 4 4 —

66 8 8 10 4 4 —

80 8 8 — — — 4

70 8 8 10 — — 4

76 8 8 — 4 — 4

66 8 8 10 4 — 4

76 8 8 — — 4 4

66 8 8 10 — 4 4

72 8 8 — 4 4 4

62 8 8 10 4 4 4

% Efficiency, mean value

79

91

90

101

84

97

92

101

80

81

97

99

88

91

84

91


oil that was considered an excellent gear cutting lubricant. The PAGs were all diluted ten times with water and then compared to the oil based standard. The PAGs evaluated are characterized in Table 36.8. The results are shown in Table 36.9. It can be seen from the data in Table 36.9 that the center wear of the chlorinated fatty oil control is lower than that of any of the PAGs. The differences are more extreme at the intermediate cutting speeds of 86 and 117 m/min. At these intermediate speeds, increasing the molecular weight of the PAG tends to decrease the center wear. However, at cutting speeds of 62 and 159 m/min, there was essentially no difference seen between the performance of the different molecular weight polymers. The corner wear experienced when using the PAGs was equivalent to that of the chlorinated fatty oil at a cutting speed of 62 m/min. As cutting speed increased, however, the corner wear seen when using the oil based control rose much more quickly than with the PAGs. There was no significant affect of PAG molecular weight on corner wear. A second study was performed to determine the affect of PAG concentration on hobbing performance. Polymer PAG-4 was tested over a wide range of dilutions and compared to water and the chlorinated fatty oil control at a cutting speed of 159 m/min. The results are shown in Table 36.10. From this study it can be seen that even at very low concentrations the presence of the PAG yields very low corner wear relative to water. At concentrations equal to or greater than 0.62%, the use of the PAG-4 solution also results in

TABLE 36.8 PAGs Evaluated in Hobbing Study

Sample

MW

Viscosity at 30◦ C (cSt)

PAG-1 PAG-2 PAG-3 PAG-4

1,675 2,430 4,750 11,800

205 276 1,590 27,500

VI

Diluted viscosity at 40◦ C (cSt)

203 210 290 427

1.29 1.41 2.16 5.26

lower corner wear than the chlorinated fatty oil control and equivalent center wear. It is interesting to note that while corner wear decreased with increasing PAG concentration, center wear increased. The authors of this study found that while the use of the PAGs provided superior performance as measured by lower wear, the corrosion protection provided by these solutions was insufficient. It was found that the addition of rust preventatives could significantly improve the corrosion protection provided by the PAG. However, the addition of these corrosion inhibitors did cause hob wear to increase at higher cutting speeds. 36.5.4.4 Machining and rolling A number of chemical MWF formulations based on PAGs and mixtures of these polymers with polyvinylpyrrolidone, polyvinyl alcohol, polyacrylates, and polymethacrylates were patented by Marx [47]. Several of these formulations and their applications are shown in Table 36.11. The formulations in this table were used successfully in a number of machining and sheet rolling operations. Marx also described how the replacement of soluble oils with chemical MWFs containing the aforementioned water-soluble polymers enabled cutting speeds to be increased in a number of sawing, planing, and drilling applications. These MWFs were also successful at replacing straight oils in deep-hole drilling operations. This resulted in significant cost savings. Marx then relates how aqueous solutions containing 15 to 20% PAG or mixtures of PAGs and some of the higher molecular weight polymers mentioned previously can be used for deep drawing steel and stainless steel parts. These solutions can also be used for the drawing of wire and tubing. An advantage of these polymers in drawing operations is that their residues can be easily washed off with water. 36.5.4.5 Blanking and drawing The early use of PAG solutions in blanking and drawing operations was documented by Sweatt and Langer in 1951 [37]. The properties of the PAG used in these chemical MWFs are shown in Table 36.12.

TABLE 36.9 Results from Hobbing Evaluation Cutting speed (m/min) 62 86 117 159


Center wear (mm)

Corner wear (mm)

Control

PAG-1

PAG-2

PAG-3

PAG-4

Control

PAG-1

PAG-2

PAG-3

PAG-4

0.07 0.10 0.14 0.18

0.11 0.28 0.48 0.21

0.12 0.22 0.50 0.20

0.11 0.16 0.37 0.20

0.12 0.18 0.29 0.20

0.10 0.17 0.27 0.50

0.10 0.11 0.12 0.16

0.10 0.11 0.12 0.16

0.10 0.11 0.12 0.16

0.10 0.11 0.15 0.15

TABLE 36.10 Effect of Polyalkylene Dilution Ratio on Hobbing Performance PAG-4 concentration (%) 0.10 0.20 0.33 0.62 1.25 2.50 5.00 10.00

Center wear (mm)

Corner wear (mm)

PAG-4

Water

Control oil

PAG-4

Water

Control oil

0.11 0.11 0.12 0.16 0.17 0.18 0.16 0.20

0.11

0.18

0.60 0.48 0.60 0.22 0.21 0.20 0.11 0.11

1.02

0.50

TABLE 36.11 Formulations and Applications of Chemical MWFs Containing PAGs Concentrate formulations (%) Component

Fluid 1

Fluid 2

Fluid 3

Fluid 4

PAG Polyvinylpyrrolidone Polyvinyl alcohol Amine phosphate CIa TEA Water

20 — — — — 6 74

15 5 — — — 6 74

15 5 — — 46 — 24

20

Dilution ratio

20:1

20:1

20:1

10:1

Applications

Steel sheet rolling: brass and copper sheet formation

Rolling of thin (Cu, Sn, Au, brass)

Steel tapping: rod and channel formation

Steel planning, milling, and cutting

4 — 46 — 30

a Corrosion inhibitor package containing 16 parts of benzoic acid, 9 parts of TEA (tri-

ethanolamine), 15 parts of triethanolamine phosphate, and 6 parts of morpholine.

TABLE 36.12 PAG Characteristics Property

Value

Molecular weight Viscosity At 40◦ C At 100◦ C Specific gravity, 20/20◦ C Water solubility at 25◦ C 1% Cloud point, ◦ Ca

1600

a Inverse solubility temperature.


132 26 1.05 Complete 50

A 25% solution of this PAG in water with a small amount of corrosion inhibitor was used to replace a petroleum oil based lubricant in a blanking and a drawing operation. The two applications are summarized in Table 36.13. While the good lubricity of the PAGs is evident from the increased tool life, their cleanliness and water washability was also important. 36.5.4.6 Cold forming A chemical MWF formulation for use in cold-forging operations was patented by Felton [48]. The formulation is shown in Table 36.14. This MWF was used neat to successfully form 3/4 in hexagonal nut blanks from a 3/4 in rod of AISI 1038 steel. The nuts were formed at a rate of 2 blanks each second. This operation took five separate

TABLE 36.13 Applications of Aqueous PAG Solutions Operation

Workpiece material

MWF

Number of pieces per die refinishing

Blanking and pressing

Annealed spring steel

Drawing shells

Nickel-plated steel

Oil PAG solutiona Oil PAG solutiona

35,000–50,000 100,000–120,000 25,000–30,000 >65,000

a Solutions contained 25% PAG.

TABLE 36.14 Cold-Forming Lubricant Formulation Component PAG

Sulfurized fatty acid Chlorinated fatty acid Glycerin Potassium nitrite Potassium hydroxide Silicone defoamer Water

Amount (vol %) 32

5 5 3 2 1.75 0.10 51.5

Component description Molecular weight, 2200 40 wt % ethylene oxide (EO) 60 wt % ethylene oxide (EO) 14 wt % sulfur 35 wt % chlorine

steps. The die used in each step was flooded with lubricant between hits. The trial was run without problems for 5 h, indicating good lubrication. The finished blanks were bright and shiny when the PAG based MWF was used, as opposed to the dull, scorched appearance that was achieved when employing a straight oil forming lubricant. Also, the smoke generated during this operation was greatly reduced when the forming lubricant was switched from the oil to the PAG based product.

36.5.4.7 Drawing and forming The use of a PAG based chemical MWF in a number of drawing and forming operations was described by Brown [58]. The formulation used is shown in Table 36.15. This formulation was used at various dilutions with water depending upon the severity of the operation. Up to 5% of a sulfurized fatty acid was added for additional extreme pressure lubrication when needed. The operations in which this formulation was used are summarized in Table 36.16. The first three operations are described in more detail in the following sections.


TABLE 36.15 PAG Based drawing and Forming Lubricant Component PAG Phosphate acid ester Corrosion inhibitor (nonnitrite) TEA Sulfurized fatty acid Water

Amount (wt %) 15 6 15 10 0–5 49–54

36.5.4.7.1 Trailer hitches Trailer hitches were being drawn from HRPO AKDQ C 1008 (0.141 to 0.151 in. thick) drawing-quality steel using an 800 t press. Ten hitches were drawn each minute. Using a straight-oil metalworking lubricant that was fortified with a chlorinated paraffin, the dies had to be refinished every 15,000 to 20,000 parts. While the lubricity provided by the chlorinated oil was good, it was very difficult to completely remove the lubricant from the formed pieces. Also, the operators complained of skin irritation while using the chlorinated product. The straight oil was therefore replaced by the PAG based MWF shown in Table 36.15. This formulation was fortified with 5% of the sulfurized fatty acid and was used without further dilution with water. Die life remained unchanged at 15,000 to 20,000 hitches per refinishing. However, the PAG based lubricant provided excellent corrosion protection while the formed parts were stored and could be easily removed with aqueous cleaning systems prior to subsequent operations. More importantly, the operators found the product to be benign. 36.5.4.7.2 Water heater tops and bottoms A soluble-oil MWF formulated with rust inhibitors and diluted 20 times with water was being used to form water heater tops and bottoms. The operation involved a 4 in. draw of 9 to 10 gauge mild cold-rolled steel. The pieces were produced at a rate of ten per minute. The problem with

TABLE 36.16 Applications of PAG Based Forming Lubricant PAG/fluid dilution ratio, H2 O:lube

Previous producta

Application

Process description

Trailer hitches

Severe draw

Neat

Chlorinated paraffin

Water heater tops and bottoms

Blanking and one 2 in. draw

20:1

R&O sol oil (dil 20:1)

Water heater jacket tops Oven liners

Cone spinning, 40% elongation Five-stage operation (four 0.5 in. draw, one shear/punch) Blanking operation and one 4 in. draw

20:1

Chlorinated sol oil (dil 10–20:1)

2:1

Chlorinated sol oil (dil 2:1)

2:1

Chlorinated sol oil (dil 2:1)

Lawnmower bodies

Observations Nonstaining, nonirritating; good die life Water washable; good rust protection Good cooling and lubrication Water washable; no staining Excellent rust protection; good die life

a Rust and oxidation soluble-oil MWF.

the soluble oil was that it was very difficult to completely remove it from the formed pieces. The presence of residual oil caused defects in the enamel coating, which in turn led to the premature corrosion of the water heater. The chemical MWF shown in Table 36.15 with no sulfurized fatty acid was diluted 20 to 1 with water and used to replace the soluble oil. The PAG based MWF provided equivalent lubricity when compared to the soluble oil. More importantly, this chemical MWF was easily washed off of the formed parts, virtually eliminating defects in the enamel coatings.

both soluble oils and straight-oil MWFs. The PAG containing products have all of the beneficial properties of chemical MWFs including excellent cooling, ease of maintenance, and cleanliness. In addition, they exhibit enhanced lubricity that enables them to compete with heavy-duty soluble oils and, in some cases, straight-oil MWFs. The properties of polyalkylene based chemical MWFs make them especially desirable in applications where workpiece staining or water solubility are important.

36.5.4.7.3 Cone spinning of water heater jacket tops Tops for water heater jackets were made in a cone spinning operation. A 16 in. diameter disk made from mild cold-rolled steel was blanked in a separate step. During the cone-spinning operation, this disk was spun at 1500 to 1700 rpm and made to undergo a 40% elongation. The wheel of the cone spinning machine was flooded with a 20 to 1 dilution of a chlorinated soluble oil. This MWF provided insufficient cooling and lubricity, which resulted in the discoloration of the workpiece. The chlorinated soluble oil was replaced with the chemical MWF shown in Table 36.15 fortified with the sulfurized fatty acid. This product was also used as a 5% solution in water. The lubricity and cooling properties of this product were excellent. Also, this chemical MWF provided the spun workpiece with corrosion protection during storage for even more than 60 days. To summarize, PAG fortified chemical MWFs are effective coolants and lubricants in a wide range of metal removal and deformation operations. They have replaced

Semichemical MWFs are, as their name implies, a hybrid of soluble oils and chemical solutions. Their main advantage is that they are cleaner and better coolants than soluble oils but still contain emulsified hydrocarbons that provide good corrosion protection and lubricity to both the tool or die and the machinery. These advantages are pushing semichemical MWFs growth at the expense of soluble oils and to a lesser extent true synthetic MWFs. A typical formulation for a semichemical MWF concentrate is shown in Table 36.17. This concentrate will then be diluted 10:1 to 30:1 with water for most cutting or grinding operations. For more severe metalworking operations, higher concentrations are employed.


36.6 SYNTHETIC LUBRICANTS IN SEMICHEMICAL MWFS

36.6.1 Polyalkylene Glycol Esters in Semichemical MWFs Synthetic lubricants in semichemical MWFs are used primarily as water-soluble lubricity additives. Canter et al. [36] described the use of PAG esters in semichemical MWF

Self-Emulsifying Esters

TABLE 36.17 Typical Semichemical Concentrate Formulation Component

H3C

Amount (wt %)

Mineral oil Emulsifiers Couplers Corrosion inhibitors EP additives Water-soluble lubricity additives Biocides Water

Hard water stability

5–20 5–20 0–5 5–10 0–10 0–20

EO

H3C COO–C8H17

—a

COOH

40–70

FIGURE 36.11 Generalized structure of self-emulsifying esters

TABLE 36.18 Semichemical Test and Reference Formulations Test formulation (% component)

Reference fluid (% component)

3–13 9–20 10 6 2 1.5

8 12 — 5 2 1.5

60.5

70.5

Naphthenic oil Emulsifier base PAG ester Amine borate Triazine Propylene glycol methyl ether Water

formulations. A number of esters were made up by reacting PAGs with either one or two equivalents of a fatty methyl ester. The PAGs used had ethylene oxide to propylene oxide ratios of 5:1, 3:1, and 1:1. The fatty groups evaluated were pelargonate, laurate, oleate, and stearate. Many of these compounds displayed inverse solubility properties in water. The PAG esters were incorporated into the base formulation shown in Table 36.18. The oil to emulsifier base ratios were adjusted to enable the formation of a stable microemulsion for each PAG ester tested. The reference semichemical fluid formulation is also shown in Table 36.18. All of the semichemical MWF formulations containing PAG esters provided significantly better lubricity on a pin and V-block wear test at a 10 to 1 dilution with water than the reference fluid at the same concentration. Two of the formulations containing dioleate esters as well as the product made with the dipelargonate ester were also low foaming and provided better corrosion protection than the reference fluid.


Lubricity

Emulsification and waste treatability

a As recommended by the manufacturer.

Component

CH3

Another growing use for PAGs in semichemical MWFs is as coupling agents to help solubilize the corrosion inhibitor packages [34].

36.6.2 Self-Emulsifying Esters in Semichemical MWFs Two types of synthetic lubricants find use as chlorinated paraffin replacements. The first, self-emulsifying esters (SEE) are based upon a polymerized fatty acid backbone reacted with ethylene oxide forming polyethylene glycol esters. These polyethylene glycol (PEG) esters are further reacted with monoalcohols and carboxylic acids. The resulting SSE has a structure shown in Figure 36.11. Because SEE are large complex molecules containing ester, carboxylic acid and PEG ester functionality, they act as both emulsifiers and lubricants. As emulsifiers, they have been shown to decrease MWF consumption by up to 50% compared to a control MWF lacking SEE [83]. The carboxylic acid group on the SEE molecule can be reacted with both caustic and amines yielding versitile emulsifying soaps. Yet, their combination of nonionic (PEG) and anionic (acid) groups allows SEE to be both hardwater resistant and waste treatable. The nonionic (PEG) portion allows the carboxylic acid groups to form soaps with divalent cations such as calcium yet remain soluble in water. However, the carboxyl groups are not so stable as to be resistant to common waste-water treatment cationic coagulants like aluminum sulfate. After reacting with waste-treatment coagulants, SEEs migrate to the oil phase and lose the ability to hold a used MWF emulsion together. As lubricants, SEEs have a combination of a bulky polymerized fatty acid and ester functionality. They benefit from branched alkyl groups in the polymerized fatty acid backbone that provide steric hinderence. The hindered

Pentaerythritol

TABLE 36.19 SEE Micro-Tapping Evaluation Summary % Efficiency Formulation Control (average of 11 different coolants) 3% SEE 1% SSE

1018 Steel

6061 Aluminum

100

100

113 —

— 184

All tests run 300 ppm water.

structure provides biostability and helps prevent breakdown by water (hydrolysis).

36.6.3 Laboratory Studies on SEEs in Semichemical MWFs On ferrous materials such as 1018 steel, the addition of three percent SEE in moderately hard water improves the percent tapping efficiency on a micro-tapping test. The percent torque efficiency improvement was 113% compared to an average of 11 different metal working fluids. For 6061 aluminum the advantages of SEE are more substantial. Only one percent SSE in 300 ppm water shows significant micro-tapping efficiency gains compared to the same eleven fluids. The micro-tapping efficiency improvement ranged from a high of 225 to low of 140%. The average micro-tapping efficiency improvement was 184%. The results are summarized in Table 36.19. Other bench tests including Falex, tapping torque and Reichert Wear show the benefits of SEE lubricity [83]. SEEs dual roles as chlorine replacements and waste treatable emulsifiers prolonging coolant lifetimes can contribute to more environmentally friendly fluids.

36.6.4 Complex Polymeric Esters in Semichemical MWFs The second type of synthetic lubricants that are finding use in semichemical fluids as a chlorine replacement are complex polymeric synthetic esters. These complex polymeric esters (CPE) are both soluble in mineral oil and emulsifiable in water. In Figure 36.12, the pentaeythritol backbone of CPE is illustrated. Up to four different species may be reacted at each terminal hydroxyl group. Many different possiblities for forming different CPE are possible. Three major types are commercially availible; complex polymeric vegetable esters (CPVE), complex polymeric sulfurized esters (CPSE) and another form SSE based upon a pentaerythritol center.


HO

HO O

H

OH Each-OH group is available to react with an acid, EO, PO, or another polymer

FIGURE 36.12 Structure of pentaerythritol that is used as a base for forming complex polymeric ester synthetic lubricants

Complex polymeric esters have molecular weight range typically between 15,000 and 50,000. The large size of CPE gives them the ability to hold up well under boundary conditions. They all exhibit high viscosity indexes and show good thermal stability. CPSE have sulfur levels between 10 and 20%. These light colored, low odor CPSE are synergistic with overbased calcium sulfonates and CPVE. The moderate sulfur levels in CPSE are considered inactive sulfurized additives. They do not give greater than a 1b ASTM D-130 copper corrosion stain [84]. Complex polymeric vegetable esters have inherent corrosion inhibition on ferrous materials. As shown in Figure 36.13, a cast iron chip test of at 5% concentration of CPVE in 200 ppm hardness water demonstrates almost no corrosion. On 6061 aluminum, a comparision of 5% CPVE and 5% SSE showed approximately equal tapping torque efficiency in semichemical fluids. However, CPVE had larger improvements over SSE in soluble-oil tapping torque comparisions [84].

36.6.5 Synthetic Hydrocarbons in Semichemical MWFs In theory, synthetic hydrocarbons like polyalphaolefins (PAOs) could be used in place of the emulsified mineral oil in a semichemical formulation. The cost of this substitution usually outweighs the benefits in most applications. However, there are a small number of cases where such formulations are marketed for use in operations where no mineral oils are allowed yet an emulsified lubricant phase is still desired. Polyalphaolefins are used more often as partial mineral oil replacement in semichemical fluids. The blending of more polar PAOs with mineral oil in a semichemical formulation provides some lubrication improvement and foam reduction while keeping the cost more reasonable. Other synthetic hydrocarbons such as polyisobutylenes and mineral oil blends are more difficult to work with in semichemical formulations and are less frequently used.

Complex polymeric vegetable ester IP 287: cast iron rust test Dilution in 200 ppm CaCO3 water

3%

4%

5%

FIGURE 36.13 Corrosion protection of CPVE

TABLE 36.20 Typical Soluble-Oil Concentrate Formulation Component Mineral Oil Emulsifiers Coupling agents Corrosion inhibitors EP additives Biocide Water

Amount (wt %) 70–80 10–20 1–5 5–10 0–10 —a 0–5

a As recommended by the manufacturer.

36.7 SYNTHETIC LUBRICANTS IN SOLUBLE-OIL MWFS Soluble-oil MWFs still make up a major portion of the water based lubricants used today. They are well accepted and the presence of a hydrocarbon oil provides many operators and machinists with a significant degree of comfort. A typical soluble-oil concentrate formulation is shown in Table 36.20. The use of synthetic lubricants in soluble-oil MWFs as oil replacements is very small. Water-soluble synthetic lubricants are not used in soluble-oil formulations. Synthetic hydrocarbons or esters could be emulsified along with or in place of the mineral oil, but the cost of such substitutions usually outweighs the benefits. However, as with semichemical MWFs, there are specialty applications where synthetic hydrocarbons are emulsified to make “synthetic” soluble oils. This is usually done to satisfy customers who require oil-free MWFs but still need an emulsified product. Such formulations can also be used in applications where the workpiece is susceptible to staining.


Another application for synthetic lubricants is in rolling oils for steel. These products are usually soluble oils containing mineral oils and tallow fats. These natural fats are being replaced in some cases by synthetic esters made from the reaction between pentaerythritol or trimethylolpropane and C-12 to C-18 fatty acids [34]. Double-comb polymeric esters, made by reacting butanol with alpha-olefin dicarboxylic acid copolymers [39], have been used to formulate high-performance soluble-oil MWFs. The “double comb” structure is illustrated in Figure 36.14. Several concentrates were made up to determine the effectiveness of the double-comb polymeric esters as lubricity additives. The concentrates were diluted with water to give 10% solutions and then evaluated using a Reichert frictional wear tester, which is believed to correlate well with a number of metalworking operations [39]. The results of this work are shown in Table 36.21. The addition of the double-comb polymeric ester greatly improves the performance of soluble-oil formulations containing a variety of traditional phosphorus and sulfur containing extreme pressure lubricity additives. The development of lubricity additives that can replace chlorinated and sulfurized compounds is a goal of the metalworking industry. The elimination of chlorine is becoming increasingly desirable as the disposal of halogenated wastes becomes more difficult and costly. Sulfurized additives can promote microbial growth in the active MWF. Complex polymeric esters based on pentaerythritol have been used in soluble-oil formulations as lubricity additives to enable the replacement of chlorine and inactive sulfur in some applications [38]. Figure 36.15 shows how various lubricants compare under machining conditions. Several soluble-oil concentrates were blended using the complex polymeric ester in place of a sulfurized fat and a chlorinated paraffin that were used in the control formulation. All of the products were then diluted with

Double-comb polymer ester

Ester groups

Hydrophilic

Carbon “back bone”

Hydrophobic

Hydrocarbon side chains

FIGURE 36.14 Idealized structure of a double-comb polymer ester

TABLE 36.21 Lubricity of Soluble Oils Containing Complex Polymeric Ester Formulation Components

A

B

C

D

E

F

Double-comb polymeric ester, 357 cSt at 100◦ C Mineral oil Emulsifiera Dibutyl phosphite Sulfurized fat, 16% sulfur TPPTb Reichert Test results, % relative abrasionc

—

10

—

10

—

10

75 25 — —

65 25 — —

70 20 3 2

60 25 3 2

72 25 — —

62 25 — —

— 97

— 94

— 91

— 56

3 96

3 73

a Alkylbenzenesulfonate, soap, fatty acid alkanolamide. b Triphenylphosphorothionate. c Deionized water = 100% abrasion.

distilled water to form 5% solutions by weight. The diluted soluble-oil MWFs were then evaluated using the tapping torque test, ASTM D-5619. The evaluations were performed using high-speed taps and 1215 steel nuts at 400 rpm. The control sample containing the chlorinated paraffin and sulfurized fat was assumed to have a tapping efficiency of 100%. Higher tapping efficiencies mean better performance. Formulations A and C performed as well as or better than the control sample. The soluble-oil formulations and tapping torque test results are shown in Table 36.22 [38].


36.8 SYNTHETIC LUBRICANTS IN STRAIGHT-OIL MWFS Straight-oil metalworking lubricants continue to be the products of choice in a large number of metalworking operations, particularly those involving drawing and forming or low speed, high severity metal removal. A typical straight-oil formulation is shown in Table 36.23. Straight-oil MWFs can be formulated with synthetic lubricants instead of mineral oils. The predominant synthetic lubricants used in straight-oil MWFs are PAGs, polyisobutylenes, and esters. The major advantages of these products is their low staining and clean burn-off characteristics. Several applications of straight-oil MWFs based on synthetic lubricants are described below. The use of neat PAGs in two drawing operations is described by Sweatt and Langer [37]. Their work is summarized in Table 36.24. In both operations die life was significantly increased by switching from an oil based product to a PAG. When using an oil soluble PAG to draw 85 to 15 brass, they also found that there was a significant reduction in tarnish. More importantly, it was possible to solder the brass pieces after drawing without first having to remove the lubricant. The use of a water-soluble PAG to draw sheet iron not only increased die life by a factor of five but also enabled the parts to be thoroughly cleaned using a water wash. Similar observations were noted by Russ (1951, private communication, Union Carbide Corp.) while making 3 in. bubble caps. The caps were made from 0.064 in. thick copper sheet. The operation involved a 2.5 in. draw of the copper blanks. The original lubricant was lard oil. The use of the lard oil led to the lubricant sticking between the die and the workpiece and discoloration of the finished caps. The lard oil was replaced by an 80 cSt (40◦ C)

Efficacy at operating temeratures

Lubricant type

Metal sulfides

Metal phosphides Metal chlorides Complex polymeric esters

Metal soaps

0

200

400

600 Temperature,°C

800

1200

1000

FIGURE 36.15 Activation temperatures for various lubricant additives formed at the tool–workpiece interface during machining

water-soluble PAG. The use of this synthetic lubricant eliminated workpiece sticking and discoloration and also improved the surface finish of the drawn caps. The addition of oil soluble PAGs to aluminum sheet and foil-rolling lubricants has also been explored. Whetzel et al. [31] described how the addition of PAGs to light mineral oils resulted in an increase in fluid performance. The percent reduction in thickness achieved when rolling 1100 aluminum alloy under a rolling load of 5500 lb/in. of strip width increased 10 to 15% when 4% PAG was added to the mineral oil base. Another application for oil-soluble PAGs is in vanishing oils. The PAGs are dissolved in low molecular hydrocarbons having flash points of less than 140◦ F. The vanishing oil is then applied to the workpiece where the volatile carrier evaporates, leaving a thin, uniform PAG film. This film provides excellent lubricity and is easy to remove from workpiece. In many cases the workpiece does not have to be cleaned. Polyalkylene glycols, polyisobutylenes, and alkyl benzenes are all finding use in wire drawing compounds as carriers of dispersed solid lubricants. The major advantage of these synthetic lubricants in wire drawing operations is their clean burn-off characteristics during annealing [32,34]. Polyisobutylenes are also used as mineral oil thickeners in a wide variety of metalworking applications. Their high molecular weight, low staining characteristics, and tendency to volatilize completely at high temperatures without leaving varnishes make them well suited for this use [32]. There is little indication that straight oils containing synthetic lubricants are being used in cutting applications. The benefits associated with synthetic lubricants do


TABLE 36.22 Lubricity of Soluble Oils Containing Complex Polymeric Ester Formulation Components

Control

A

B

C

D

Soluble base Complex polymeric ester Amine phosphate TEA Sulfurized fat (10% inactive sulfur) Chlorinated paraffin (60% chlorine) Pale oil, 100 SUS

21 — — — 10

15 5 — 0.75 —

15 2 — 0.30 —

15 3.5 0.5 0.90 —

15 — — — —

4

—

—

—

—

65

79

83

79

85

Tapping torque test, % efficiency

100

106

96.8

100

93.5

TABLE 36.23 Typical Formulation of a Straight-Oil MWF Component Mineral oil Corrosion inhibitors EP additives Boundary lubricity additives Antioxidants

Amount (wt %) 75–100 0–5 5–20 0–10 0–2

not make up for the added cost in this segment of the metalworking industry. However, it is possible that PAOs could be used as cutting-oil base stocks in some specialty operations [34].

TABLE 36.24 Applications of Neat Polyalkylene Glycols as Forming Lubricants Workpiece material

Operation Drawing

85–15 Brass

Drawing

Sheet iron

Metalworking Lubricant

Number of pieces per die refinishing

Oil PAGa Oil PAGb

5,000 17,000 50 250

a Oil soluble; viscosity at 40◦ C, 27 cSt. b Water soluble; viscosity at 40◦ C, 130 cSt.

TABLE 36.25 Cutting Fluid Formulations Based on α-Olefins Amount of component in formulation (wt %) Component

Formulation A (control)

Formulation B (α-Olefin)

Paraffinsa α-Olefin 1-Dodecanol Butyl stearate

93 0 6 1

46.5 46.5 6 1

a Equal amounts of C and C components were used. 18 16

A relatively recent example of the use of synthetic lubricants in straight-oil cutting fluids is the application of alpha olefins containing 16 to 18 carbons as replacements for paraffin base stocks. Work has been done that shows that the replacement of 50% of the paraffinic base stock with an alpha olefin can increase the surface force of attraction to the metal surface by 10 to 40% [59,60]. This high surface attraction results in better surface finish and reduced tool wear. In some cases it has also enabled the reduction of sulfur containing extreme pressure lubricity additives [59]. In sheet and foil-rolling applications, increased thickness reductions, better surface finishes, and reductions in rolling force of up to 22% have been documented [59,61]. To demonstrate the advantages of using alpha olefins in conjunction with paraffins in straight-oil cutting fluids, the two test formulations shown in Table 36.25 were made up [60]. Formulations A and B were first evaluated by tapping predrilled holes in a piece of 1020 steel. The taps were then cleaned and examined for welding spots using a scanning electron microscope. The tap used with the paraffin based formulation A showed 207 weld spots. The tap used with Formulation B, where 50% of the paraffin base stock had been replaced with alpha olefins, exhibited only 76 weld


TABLE 36.26 Surface Finishes of Milled Aluminum Alloys Cutting fluid

Aluminum alloy

Torn area (%)

Formulation A Formulation B Formulation A Formulation B

356 356 380 380

69.4 53.4 83.7 58.7

spots, a 63% reduction [62]. This reduction in welding results in longer tool life and better surface finish. These same two formulations were then used to mill 356 and 380 aluminum alloys. The alloys were milled at a feed rate of 0.38 m/min. The cutting depth was set at 3.56 × 10−4 m. After milling, the surfaces were examined for surface tares. The results are shown in Table 36.26 [60]. With both alloys, the use of Formulation B containing the alpha olefins resulted in significantly smoother surfaces that exhibited 20 to 30% less taring. Formulations A and B were also used to turn 304 stainless steel rods on a lathe. Three different cutting tools were used. The cutting conditions and test results are shown in Table 36.27 [60]. In all three cases, the use of the alpha olefins in Formulation B resulted in reduced surface roughness. A second example of the use of synthetic lubricants in straight-oil cutting fluids is the incorporation of the doublecomb polymeric esters has been shown to improve the lubricity off metal cutting fluids, thereby improving tool life and surface finish [39]. Several formulations were made to determine the effectiveness of the double-comb polymeric esters in cutting fluids. These straight-oil cutting fluids were evaluated using a tapping torque test machine. The effectiveness of the fluid can be determined by measuring the torque required to tap predrilled holes. The fluids were compared to a chloroparaffin based reference oil. A “torque difference” was then calculated. A positive torque difference means that the test fluid outperformed the chloroparaffin standard by requiring less torque to tap a given hole. A negative torque difference indicates poorer fluid performance relative to the standard. The results, summarized in Table 36.28, show the benefits achieved through the use of the double-comb polymeric ester [39].

36.9 MARKET OUTLOOK 36.9.1 Market Size The total annual consumption of MWFs in the United States is currently estimated to be between 100 and

TABLE 36.27 Surface Roughness of Turned 304 Stainless Steel Rod

Cutting fluid Formulation A Formulation B Formulation A Formulation B Formulation A Formulation B

Tool typea

Tool speed (m/sec)

Chip (µm)

Surface roughness (µm)

Standard deviation (nm)

0.172 0.172 2.34 2.34 2.24 2.24

178 178 152 152 152 152

41.5 21.9 63.3 46.4 32.9 25.4

19.5 7.0 26.4 13.7 13.7 18.4

HSS HSS CER CER CTD CTD

a HSS, high speed steel; CER, cermet; CTD, carbide insert coated with Ti nitride and Ti

carbonnitride.

TABLE 36.28 Cutting fluid Formulationsa Containing Double-Comb Polymeric Esters Formulation Chloroparaffin (reference) Formulation Q Formulation R Formulation S Formulation T Formulation U

Mineral oil (ISO VG 46)

TNPS∗

Polymeric ester

TMP ester∗∗

Torque difference

—

—

—

—

—

100 98 75 73 73

— 2

— — 25 25 —

— — — — 25

−3 −0.50 −0.25 +0.30 −1.15

2 2

a TNPS, di-tert-nonyl polysulfide (extreme pressure additives); TMP ester, C fatty acid ester of 9

trimethylolpropane.

140 million gallons of straight oils and water-dilutable concentrates [63,64]. Taking the dilution of the soluble oil, chemical, and semichemical concentrates into account, the total annual consumption of MWFs in the United States has been estimated to be 3.2 billion gallons [65]. Approximately 60 to 70% of the MWFs sold in the United States are used in metal removal operations, while the remaining MWFs and concentrates are employed in forming applications [66,67]. It is estimated that 30 to 40% of these MWFs sold in the United States are straight oils, while soluble oils, chemical, and semichemical fluid concentrates make up the remaining 60% [67]. The water-dilutable MWFs can be subdivided further. Approximately 60% of these products are soluble oils, while the remaining 40% are divided between chemical and semichemical MWF concentrates [67]. Over the last several years, semisynthetic MWFs have taken a greater share of this remaining 40% at the expense of true chemical solutions. The growth rate of the MWF market in the United States has been slow over the last decade. Depending upon the source, this market has grown at a rate of between


0.1 and 1.3% per year [63,64,68]. It is expected that over the next five years the amount of MWFs consumed in the United States will remain constant or even decrease slightly [64]. Environmental concerns will lead to the formulation of longer life fluids, improved fluid maintenance, and increased recycling. All of these trends will contribute to decreased MWF consumption. While the growth of the MWF market in the USA is slow or flat, the global use of metalworking lubricants appears to be growing significantly faster. Over the last six years the total global consumption of straightoil MWFs and water-dilutable concentrates has grown from an estimated 474 million to 638 million gallons [67, unpublished data from Lubrizol Corp., 1996]. This represents a growth of 35%, or a growth rate of roughly 5% per year. Approximately 40 to 50% of this 638 million gallons is straight-oil MWFs. Two thirds of the remaining material is soluble oils, with semichemical fluids representing 10 to 20% of the total MWF market and chemical solutions only accounting for approximately 5% (unpublished data from Lubrizol Corp., 1996).

It is very difficult to determine the number of pounds of synthetic lubricants that go into each of the four segments of MWFs. There are two major reasons for this. First, formulators are hesitant to give out information regarding the amount of synthetic lubricants they use in order to protect their formulation strategies. Second, the producers of synthetic lubricants do not know what percent of their products sold to formulators go into MWFs. This is because the formulators of MWFs are also likely to compound and sell other products like hydraulic fluids, gear lubricants, quenchants, and compressor lubricants. All of these products can be formulated with synthetic lubricants, and it is therefore very difficult for the polymer suppliers to know in what applications their products are being used.

36.9.2 Future of Synthetic Lubricants in MWFs There are three major factors that will influence the shape of the MWF market over the next decade. The first involves waste minimization, disposal, and environmental impact. The second factor is workpiece quality. The third is MWF toxicity. 36.9.2.1 Waste minimization and disposal The most important factor influencing the MWF market today is waste minimization and disposal. Waste disposal regulations are regional and may vary considerably between different municipalities. The appropriate choice of MWF may be greatly affected by these local regulations. The advantages and disadvantages of the four classes of MWFs with respect to waste minimization and disposal are summarized below. Straight-oil MWFs are relatively easy to maintain. With the absence of water, and assuming the product does not contain large amounts of fatty compounds, bacterial activity is minimal when compared to water based products. Once the useful life of the straight-oil MWF is over, the used product can be burned for fuel value or recycled [69]. However, the disposal of straight-oil products can be made significantly more difficult by the presence of chlorinated paraffin lubricity additives. Also, stricter air quality standards are in some cases making it more difficult to use oil based MWFs because of mist formation, smoke generation, and the evolution of volatile hydrocarbons. Of the water based MWFs, soluble oils are the most difficult to maintain. They are very susceptible to attack from microorganisms. They also tend to emulsify tramp oils and can be sensitive to water quality. Because they are two phase systems, they are not always amenable to commonly used fluid maintenance techniques such as ion exchange, ultrafiltration, and centrifugation. From a disposal point of view, soluble oils are relatively easy to treat. Soluble oils can be split rather easily into an oil phase, which can be incinerated or reclaimed, and a


water phase. Often this water phase can be sent directly to the local publicly owned treatment works (POTW). However, as water regulations become increasingly strict, the cases where this aqueous phase does not meet disposal regulations are increasing. In these cases, secondary treatment is required. Soluble oils that contain chlorinated paraffins are becoming more difficult to get rid of. It is becoming harder to incinerate chlorine containing compounds, and local POTWs are starting to closely regulate the amount of chlorinated organic products that they will accept in a waste stream. Chemical fluids are the easiest MWFs to maintain. They are much more resistant to biological attack than soluble oils. Because they form true solutions in water, they are amenable to a wide variety of treatment techniques. They can be ion exchanged to keep the water hardness under control, centrifuged to remove metal fines and tramp oils, and filtered to remove solids and emulsified oils. Large central systems containing chemical MWFs have been maintained for periods of several years. Because chemical MWFs are easier to maintain than soluble oils, they generally last longer. This significantly reduces the volume of waste MWF that is generated. However, because all of the components are water soluble, removing the organic components from the water is difficult. Whether or not this is a problem depends upon the local regulations. Often a POTW will accept a spent chemical MWF if it is found to be compatible with their treatment system. Sometimes a surcharge is levied. Semichemical MWFs fall somewhere between soluble oils and chemical products. They are usually easier to maintain than soluble oils. However, for disposal purposes, semichemical products often take on the worst characteristics of soluble-oil and chemical MWFs. Much of the development work currently being done in the field of metalworking involves minimizing the environmental impact of the lubricants and coolants used to aid in the processing of the metal workpiece. Minimizing the environmental impact of a MWF can be done by making formulation changes that extend its useful life or that aid in the product’s disposal. A technology that may enable the formulation of soluble oils and semisynthetic MWFs that exhibit both extended service life and cleaner, more efficient posttreatment and disposal has recently been commercialized. This technology is based on the development of a destructible, nonionic surfactant. Under basic conditions, this family of surfactants is stable and provides all of the advantages of conventional nonionic surfactants. However, under acidic conditions, these surfactants readily and irreversibly split into their hydrophobic and hydrophilic constituents [70]. Once split, the surfactant can no longer effectively emulsify the oil phase of the MWF. The hydrophobic component of the splittable surfactant then separates out along with the hydrocarbon portion of the MWF. Once separated, the

hydrophobic constituents of the MWF can be removed, resulting in a greatly reduced FOG (fats, oils, greases) content. The hydrophilic portion of the surfactant remains in the aqueous phase, which can be more easily handled due to the removal of the hydrophobic components. Additionally, the treated aqueous phase has less environmental impact because the hydrophilic portion of the surfactant has faster biodegradation and lower aquatic toxicity than most common nonionic surfactants. These splittable surfactants contain a pH-sensitive functionality [71,72] that serves to link the hydrophobic alkyl part of the surfactant to the hydrophilic alkoxylated portion. In a basic aqueous environment, such as that which exists in MWFs, these surfactants are stable. However, if the solution is acidified, the pH-sensitive link becomes unstable and the surfactant breaks down into a hydrophobic compound and hydrophilic alkoxylate. Since the surfactant is now destroyed, the emulsion separates. The hydrophobic segment of the surfactant separates out with the rest of the oil where it can be removed from the aqueous portion of the MWF. Surfactants are needed in soluble-oil and semisynthetic MWFs to emulsify hydrocarbon oils that help to increase lubricity and corrosion protection. Anionic surfactants such as soaps and petroleum sulfonates are often used. This class of surfactant bears a negatively charged ion that makes up the hydrophilic portion of the molecule. A commonly used treatment technology for used MWFs based on anionic surfactants involves the addition of acid and alum or a polyelectrolyte that neutralize the charge and thus remove the emulsifying properties of the surfactant [71]. The oil portion of the MWF then separates out and can be readily removed. The problem with anionic surfactants is that they are prone to foaming and are sensitive to hard water. Nonionic surfactants are often chosen over anionics for use in MWFs because they have better wetting properties and are less sensitive to hard water [73]. Nonionic surfactants also allow the creation of tighter emulsions and are lower foaming that anionic surfactants [71]. The major problem with nonionic surfactants is that they are not amenable to treatment techniques commonly used to separate emulsions made with anionic surfactants. The splittable nonionic surfactants provide the benefits of traditional nonionic surfactants while allowing the formulation of a soluble-oil or semisynthetic metalworking, which can be easily treated to enable the reduction of the FOG content prior to disposal. Treatment involves acidification of the MWF with sulfuric or hydrochloric acid to a pH of between 3 and 5. The splitting of the acetal based surfactant will increase in efficiency as the pH of the system decreases. The temperature of the system being treated should be between 20 and 50◦ C. Splitting efficiency will increase with increasing temperature. Deactivation time typically will range from 30 to 120 min, depending on the


system and process conditions. Also, since the purpose of the splittable surfactant is to permit the coalescence of the FOGs into a readily removable form, the incorporation of other products which act as surfactants or dispersants into the MWF should be avoided. Products which could impede the separation of the oil component of the MWF include polyacrylates, some phosphates, and conventional nonionic surfactants [71]. The splittable surfactants, like conventional nonionic surfactants, biodegrade at a moderate rate before being split. However, after being split in an acidic environment, the hydrophilic and hydrophobic components both exhibit much higher biodegradation rates [73]. The aquatic toxicity of the splittable surfactants before destruction is also similar to other nonionic surfactants. After splitting, the resulting hydrophilic component of the surfactant is essentially nontoxic to aquatic life. Most of the hydrophobe should be removed with the hydrocarbon phase of the acid treatment. Bacterial inhibition tests indicate that neither the surfactant nor its associated hydrophilic and hydrophobic components should negatively impact conventional biological waste-water treatment facilities when discharged at normally expected concentrations [73]. The aquatic toxicity of a splittable surfactant before and after acid treatment is shown in Table 36.29 [73]. 36.9.2.2 Workpiece quality Product quality is becoming extremely important. As a result, tolerance of workpiece corrosion, staining, and coating defects is decreasing. Two major causes of staining and coating defects are the presence of corrosive additives in the MWF and the incomplete removal of the lubricant prior to the coating process. Chlorinated hydrocarbons are one of the most commonly used EP lubricity additives in straight-oil and soluble-oil MWFs. However, during storage, the residual chlorine can cause significant staining of the metal workpieces. Because of their staining tendencies and the fact that their disposal is becoming increasingly difficult, much work is underway to develop replacements. This work is providing significant opportunities for the use of synthetic lubricants in MWFs. The complete removal of residual MWFs from the workpiece can be difficult when either straight-oil or soluble-oil products are used. Residual lubricant can prevent the adherence of coatings, like paint or enamel, causing unacceptable defects. These problems are becoming more widespread as the use of vapor degreasers and solvent-cleaning processes are coming under pressure for various environmental reasons. The need for water washable MWFs should result in the increased use of chemical and semichemical products. It will also favor the use of neat PAGs in straight-oil applications where solvent-cleaning

TABLE 36.29 Aquatic Toxicitya of a Splittable Acetal Based Nonionic Surfactant (9 mol Ethoxylate)

Surfactant Before acid treatment After acid treatment Hydrophobe Hydrophile

Acute Daphnia magna, 48 h LC50 (mg/L)

Acute fathead minnow, 96 h LC50 (mg/L)

Bacterial inhibition, 16 h IC50 (mg/L)

Selenastrum algal, 96 h EC50 (mg/L)

15

5

>10,000

6

0.3 10,000

2 >10,000

970 >10,000

0.5 >20,000

a LC , median lethal concentration; IC , inhibition concentration; EC , calculated concentration with expected 50 50 50

algal cell counts at 50% of control cell counts.

operations can be omitted because of the polymer’s water solubility. The complete burn-off characteristics of PAGs, polyisobutylenes, and alkyl benzenes will become more important since they sometimes enable the elimination of a cleaning operation prior to various high-temperature operations. As the need for improved workpiece quality grows, the production of defective parts will become unacceptable. The resistance to the higher cost of synthetic lubricants should therefore decrease as the price of seconds due to inadequate cleaning increases.

36.9.2.3 Toxicity Health concerns are a major concern in the metalworking industry because of the high exposure of the operator to the MWFs. Potential carcinogens such as polycyclic aromatic hydrocarbons [74], nitrosamines, and specific short-chain chlorinated paraffins have been successfully eliminated from use in MWF formulations [75]. Studies are currently underway to better understand the health effects of other chemicals commonly used in MWFs, including biocides [76,77], formaldehyde [78], diethanolamine, o-phenylphenol, and oil mists [79]. Bacterial growth in MWFs and the resulting endotoxin production is also receiving attention, especially the role mycobacteria endotoxin concentrations in respiratory distress [75]. In general, synthetic lubricant base stocks are very pure relative to petroleum-oil base stocks and are therefore less likely to contain potentially undesirable impurities. Also, synthetic lubricant base stocks such as polyalphaolefins [80], PAGs [81], and polyolesters (82) exhibit low orders of toxicity via skin absorption or ingestion. Some polyalphaolefins and PAGs have FDA status for various applications [81]. The high purity and low toxicity of these synthetic lubricant base stocks could lead to the increased usage of these products as the effort to understand the health effects of MWFs is increased. However, it is difficult to foresee the next toxicity issue or to predict


how it will affect the use of synthetic lubricants in the metalworking industry.

36.10 CONCLUSIONS Synthetic lubricants will continue to play a major role as water-soluble lubricity additives in chemical and semichemical MWFs. The synthetic lubricants most commonly used in these MWFs are PAGs and their ester or acid derivatives. MWFs based on these products are excellent coolants and lubricants. They are in general easy to maintain, low in toxicity and environmental impact, nonstaining, and easy to remove from the finished workpiece. As environmental issues become more important, the use of this class of synthetic lubricants in MWFs is likely to increase. In straight-oil MWFs, due to cost considerations, the use of synthetic lubricants is basically limited to specialty applications. Synthetic esters, polyisobutylenes, and PAGs are all used in applications where clean burn-off or nonstaining characteristics are important. In conclusion, the use of synthetic lubricants in MWFs will grow. Increasingly strict environmental regulations affecting the workplace and air and water quality will favor the use of water based products and therefore PAG lubricants. Environmental and disposal related concerns will also reduce the use of solvent cleaning systems and chlorinated lubricity additives. Both of these factors should also favor the use of synthetic lubricants. The emphasis on product quality and the increasing cost of seconds will also increase the consumption of synthetic lubricants. As the costs associated with waste disposal, fluid maintenance, and workpiece quality all increase, the performance advantages of synthetic lubricants will outweigh their higher initial costs and lead to their increased application in metalworking lubricants.

REFERENCES 1. Shaw, M.C., Metal Cutting Principles, 3rd ed., MIT Press, Cambridge, MA, 1957.

2. Schey, J.A., Tribology in Metalworking, American Society for Metals, Metals Park, OH, 1983. 3. Ellis, E.G., Fundamentals of Lubrication, Scientific Publications (G.B.) Ltd., Broseley, Shropshire, 1968. 4. Booser, R.E., Handbook of Lubrication, Vol. II, CRC Press, Boca Raton, FL, 1988. 5. Springborn, R.K., Cutting and Grinding Fluids: Selection and Application, American Society of Tool and Manufacturing Engineers, Dearborn, MI, 1967. 6. Kajdas, C., Additives for metalworking lubricants — a review, Lubr. Sci., 1, 385–409 (1989). 7. Robin, M., Forming with water base lubricants, Manuf. Eng., 81, 53–55 (1978). 8. Barber, S.J. and Millett, W.H., Water: “New” metalworking solution? Am. Mach., 118, 95–100 (1974). 9. Evans, E.A., Lubricating and Allied Oils, Chapman & Hall Ltd., London, 1963. 10. Biringuccio, V., The Pirotechnia of Vannoccio Biringuccio (1540) (C.L. Smith and M.T. Gnidi, transl.), Basic Books, New York, 1959. 11. Northcott, W.H., A Treatise on Lathes and Turning, Longmans, Green & Co., London, 1868. 12. Edwards, J. and Jones, E., Synthetic cutting fluids, Tribol, Int., 10, 29–31 (1977). 13. Kelly, R., Synthetic can-drawing fluids for D & I operations, Lubr. Eng., 38, 675–680 (1982). 14. Morton, I.S., Water base cutting fluids still a ?, Ind. Lubr. Tribol., 23, 57–62 (1971). 15. Taylor, F.W., On the art of cutting metals, Trans. ASME, 28, 31–58 (1907). 16. Beaton, J., Tims, J.M., and Tourret, R., Function of metalcutting fluids and their mode of action, Proc. Inst. Mech. Eng., 170, 193–214 (1964–1965). 17. Sluhan, C.A., Cutting fluids, Am. Soc. Tool Manuf. Eng., 62, 399, (1963). 18. Thornhill, F.H., Synthetic cutting oils, Ind. Lubr. Tribol., 23, 70–72 (1971). 19. Langer, T.W. and Blake, F.M., Inhibited polyoxyalkylene glycol fluids, U.S. Patent 2,624,708 (1953). 20. Mould, R.W., Silver, H.B., and Syrett, R.J., Investigations of the activity of cutting oil additives: V. The EP activity of some water-based fluids, Lubr. Eng., 33, 291–298 (1977). 21. Sluhan, C.A., Some considerations in the selection and use of water soluble cutting and grinding fluids, Lubr. Eng., 16, 110–118 (1960). 22. Hunz, R.P., Water-based metalworking lubricants, Lubr. Eng., 40, 549–553 (1984). 23. American Machinist, Manufacturing Research Institute, Data Sheet MRI-12. 24. Mueller, E.R. and Martin, W.H., Polyalkylene glycol lubricants: Uniquely water soluble, Lubr. Eng., 31, 348–356 (1975). 25. Jarvholm, B., Zingmark, P.A., and Osterdahl, B.G., High concentration of n-nitrosodiethanolamine in a diluted commercial cutting fluid, Am. J. Ind. Med., 19, 237–239 (1991). 26. U.S. Environmental Protection Agency, Notice to formulators of metalworking fluids? Potential risk from nitrosamines, EPA Chemical Advisory, TS-799, September 1984.


27. Ladov, E.N., Evaluating and communicating the carcinogenic hazards of petroleum derived lubricant base oils and products, Lubr. Eng., 42, 272–277 (1986). 28. Klamann, D., Lubricants and Related Properties, Verlag Chemie, Deerfield Beach, FL, 1984. 29. Mullins, R.M., Miller, P.R., and Bucko, R.J., A comparison of matrix and nonmatrix tapping torque test procedures in the evaluation of experimental cutting fluids, ASLE Preprint 84-AM-3C-1 (1984). 30. Brown, W.L., The role of polyalkylene glycols in synthetic metalworking fluids, Lubr. Eng., 44, 168–171 (1988). 31. Whetzel, J.C., Jr., Chapel, F., and Rodman, S., Metal working lubricant, U.S. Patent 3,124,531 (1964). 32. Singh, R.V., Synthetic metal working lubricants, Proceeedings of the 3rd Internationales Kolloquium, Schmierstoffe in der Metallbearbeitung, 1, pp. 32.1–32.7 (1982). 33. Prybylinski, J.L., Diethanol disulfide as an extreme pressure and anti-wear additive in water soluble metalworking fluids, U.S. Patent 4,250,046 (1981). 34. Williamson, E.I., Commercial developments in synthetic lubricants — a European overview, part 2, J. Synth, Lubr., 3, 45–53 (1986). 35. Russ, J.M., Jr., “UCON” synthetic lubricants and hydraulic fluids, ASTM Technical paper 77:3-11, American Society for Testing and Materials, Philadelphia, 1947. 36. Canter, N.M., Chaloupka, J.J., and Fischesser, G.J., The use of ethylene oxide/propylene oxide (EO/PO) esters as additives in semisynthetic metalworking formulations, Lubr. Eng., 44, 257–261 (1988). 37. Sweatt, C.H. and Langer, T.W., Some industrial experiences with synthetic lubricants, Mech. Eng., 73, 469–476 (1951). 38. Miller, P.R. and Patel, H., Using complex polymeric esters as multifunctional replacements for chlorine and other additives in metalworking, Lubr. Eng., 53, 31–33 (1997). 39. Akzo, Ketjenlube 115, 135, and 165 — a new and proven approach to wear reduction, Technical literature 89.08.10034, Akzo Chemicals, Chicago, 1989. 40. Hobson, P.D., Industrial Lubrication Practice, Industrial Press, New York, 1955. 41. Beiswanger, J.P.G., Katzenstein, W., and Krupin, F., Phosphate ester acids as load-carrying additives and rust inhibitors for metalworking fluids, ASLE Trans., 7, 398–405 (1964). 42. Smith, G.F. and Budd, M.K., Lubricants for cold working of aluminum, U.S. Patent 3,966,619 (1976). 43. Mateeva, S. and Glavchev, I., Some operational characteristics of a hydrolysed polyacrylonitrile-based cutting fluid, Tribol. Int., 13, 69–71 (1980). 44. Stram, M.A., Lubricant compositions, U.S. Patent 3,657,123 (1972). 45. Grower, H.D., Grower, B.G., and Young, D., Aqueous lubricating compositions containing salts of styrene–maleic anhydride copolymers and an inorganic boron compound, U.S. Patent 3,629,112 (1971). 46. Janatka, V. and Kirwan, E.P., Lubricant-coolant, U.S. Patent 3,563,859 (1971). 47. Marx, J., Synthetic lubricant for machining and chipless deformation of metals, U.S. Patent 3,980,571 (1976). 48. Felton, G.F., Jr., Low smoking lubricating composition for cold heading operations, U.S. Patent 3,983,044 (1976).

49. Guminski, R.D. and Willis, J.J., Development of cold-rolling lubricants for aluminum alloys, J. Inst. Met., 88, 481–492 (1960). 50. Richter, J.P., Cutting oil performance — a significant new machining test, ASLE preprint 77-LC-2C-3 (1977). 51. DeChiffre, L., Lubrication in cutting — critical review and experiments with restricted contact tools, ASLE Trans., 24, 340–344 (1980). 52. Ham, I., Fundamentals of tool wear,American Society of Tool and Manufacturing Engineers, MR68-617 (1968). 53. Brown, W.L., Notebook 12811, Union Carbide Chemicals and Plastics Company, Inc., unpublished (1987). 54. Nash, J.C. and Colakovic, N., Effect of synthetic additives on the performance of aluminum tapping fluids, Lubr. Eng., 41, 721–724 (1985). 55. Levesque, A. and McCabe, M., Improved synthetic coolants using a modified polyalkylene glycol, Lubr. Eng., 40, 664–666 (1984). 56. Faville, W.A. and Voitik, R.M., The Falex tapping torque test machine, Lubr. Eng., 34, 193–197 (1978). 57. Katsuki, A., Ueno, T., Matsuoka, H., and Kohara, M., Research on soluble cutting fluids for gear cutting — the influence of dilution ratio and the effect of synthetic fluids, Jpn. Soc. Mech. Eng., 28, 735–743 (1985). 58. Brown, W.L., The use of polyalkylene glycols in metal forming and drawing lubricants, STLE Annual Meeting, Denver, 1990. 59. Shell, NEODENE alpha olefins for metalworking lubricants, Technical literature SC:1927-954R, Shell Chemical Company, Houston, TX, 1994. 60. Denley, D.R., York, G., and Haberman, L.M., Olefinic versus paraffinic based in metalworking applications probed by three different microscopic techniques, Technical bulletin SC:2208-94, Shell Chemical Company, Houston, TX, 1994. 61. Koyama, S., Shido, S., Onodera, X., Hara, S., Tomari, Y., Saito, T., and Nara, T., Lubricating oil composition, U.S. Patent 5,171,903 (1992). 62. Shell, NEODENE additives for metalworking fluids, Technical literature SC:2222-95, Shell Chemical Company, Houston, TX 1995. 63. ILMA, Report on the Volume of Lubricants Manufactured in the United States and Canada by Independent Lubricant Manufacturers in 1995, Independent Lubricant Manufacturers Association, Alexandria, VA, 1996. 64. The Fredonia Group, Inc., Marketing news — Demand for industrial lubricants reach 1.3 billion gallons in 2000, Lubr. Ing., 52, 391 (1996). 65. Anon., HWB fluid market seen ready for sharp growth, Chem. Marketing Rep. 227, 27 (1985). 66. National Petroleum Refiners Association, 1989 Report on U.S. Lubricating Oil Sales, NPRA, Washington, DC, 1989.


67. The Lubrizol Corp.Metalworking Fluid Trends, Lubrizol document 491 404-7 (1991). 68. Steigerwald, J.C., Report on the Volume of Lubricants Manufactured by the Independent Lubricant Manufacturers in 1989, Independent Lubricant Manufacturers Association, Alexandria, VA, 1989. 69. Childers, J.C., Metalworking fluids — A geographical industry analysis, Metalwork. Topi., 1, 1–4 (1989). 70. Anon., Product report, EPA endorses Union Carbide surfactant, Chem. Eng. News, 75, 44 (1997). 71. Galante, D.C., Hoy, R.C., Joseph, A.F., King, S.W., Smith, C.A., and Wizda, C.M., Aldehyde-based surfactant and method for treating industrial, commercial, and institutional waste-water, European Patent Application EP 0742177-A1 (1996). 72. Galante, D.C., Hoy, R.C., Joseph, A.F., King, S.W., Smith, C.A., and Wizda, C.M., Ketone-based surfactant and method for treating industrial, commercial, and institutional wastewater, European Patent Application EP 0742178-A1 (1996). 73. Union Carbide, Triton®SP-series surfactants, Technical Literature UC-1492, Union Carbide Corp., Danbury, ST, 1996. 74. McKee, R.H. and O’Connor, D.J., Dermal carcinogenicity studies of metalworking fluids, Lubr. Eng., 52, 97–102 (1996). 75. Rossmore, H.W., Health and environment, Lubr. Eng., 52, 94–96 (1996). 76. Passman, F.J., Formaldehyde risk in perspective: A toxicological comparison of twelve biocides, Lubr. Eng., 52, 69–80 (1996). 77. Rossmore, H.W. and Rossmore, L.A., Factors affecting selection of metalworking fluid biocides, Lubr. Eng., 52, 23–28 (1996). 78. Brutto, P.E., Pohlman, J.L., Ryan, A.M., and Smith, R., Formaldehyde control in metalworking fluids preserved with triazine biocide, Lubr. Eng., 52, 8–14 (1996). 79. Lucke, W.E., Health and safety of metalworking fluids, Lubr. Eng., 52, 596–604 (1996). 80. Booser, R.E., CRC Handbook of Lubrication and Tribology, Vol. III, CRC Press, Boca Raton, FL, 1994. 81. Rudnick, L.R. and Shubkin, R.L., Ed., Synthetic Lubricants and High-Performance Functional Fluids, 2nd ed., Dekker, New York, 1999. 82. Henkel, Emery 2941-B ISO 46 synthetic lubricant (basestock), Material Safety Data Sheet (MSDS) 2941-B, Henkel Corp.-Emery Group, Cincinnati, OH, 1994. 83. Anon, Self-Emulsifying Esters for Metalworking Fluids, Tribology and Lubrication Technology, 44–46, (2004). 84. Ollinger, C., Self-Emulsifying, Bio-based Lubricant — Naturally Better, Tribology and Lubrication Technology, 40–42 (2004).

37

Lubricants for Near Dry Machining Robert Silverstein CONTENTS 37.1 Introduction 37.2 Friction and Wear 37.3 Metalworking Operations 37.4 Near Dry Machining References

37.1 INTRODUCTION Metalworking may be man’s earliest known technological occupation as gold, silver, and copper were hammered into thin sheets and shaped into jewelry and household utensils as early as 5000 b.c. [1]. Processes involving metal removal can be dated back into antiquity as hammered or cast objects were polished with a stone to a finish; whereas a process such as metal cutting may have been developed in the middle ages [2]. The onset of the industrial revolution, and with it the demand for greater machining accuracy, new machine tools, higher cutting speeds, and more widespread use of grinding saw the development of coolants [2]. The advantage of employing a coolant was first discovered in 1883 when F.W. Taylor directed a stream of water on the tool in a turning operation. The cutting speed and hence, production, could be increased as much as 40% by the cooling effect of the stream of water [3]. Because water has a higher specific heat and heat of vaporization compared to hydrocarbon oils, cutting speeds could be increased because of the excellent cooling properties of water [4]. As a result increased cutting speeds and decreased production time started the metalworking industry on the path to higher output at lower cost. With the evolution of metalworking fluid technology from its earliest beginnings, greater output, longer tool life, and better surface finish have occurred, all of which are of great economic importance. The basic functions of cutting fluid are: • Direct cooling and control of the heat generated in the

metal cutting operation • Lubrication and friction reduction • Prevent welding or adhesion of the tool and workpiece

at metal contacts


There are other important requirements that a cutting fluid provides: • Move chips away from the work area • Protect finished workpieces, tools and machinery against

rust and corrosion Since it has been well documented that the use of metal removal fluid increases cutting tool life by friction reduction and heat removal, various forms of metal removal fluid have been used in the machining process by the metalworking industry. Metal removal fluids help increase the quantity of parts that can be produced before a tool needs to be replaced, or enable a machine tool to produce parts faster with the same cutting tool life increasing productivity [4]. According to survey results from the 2002 National Petrochemical & Refiners Association (NPRA) Lubricating Oil & Wax Sales Report, total reported U.S. sales of metalworking oils were 80 MM gal in 1999, 83 MM gal in 2000, 60 MM gal in 2001, and 55 MM gal in 2002 (Figure 37.1). Furthermore, from the same survey, total reported sales of metal removing oils were 22 MM gal in 1999, 21 MM gal in 2000, 13 MM gal in 2001, and 13 MM gal in 2002 (Figure 37.2) [5]. The main metalworking fluid types primarily manufactured include: straight oils, soluble oils, semi-synthetic fluids, and synthetic fluids. Straight or neat oils are nonaqueous lubricants used as is. Soluble oils contain mineral oil and emulsifiers enabling them to be mixed in water. Semi-synthetic fluids contain a lesser percentage of mineral oil with a larger percentage of emulsifiers blended with water to form a microemulsion. Synthetic fluids are true chemical solutions that contain a large percentage of water and no mineral oil.

Metalworking oils 100 1999

2000

80 MM gal

2001 60

2002

40 20 0

FIGURE 37.1 Total reported U.S. sales metalworking oils 1999 to 2002 Metal removing oils 25

1999

2000

MM gal

20 2001

15

2002

10 5 0

FIGURE 37.2 Total reported U.S. sales metal removing oils 1999 to 2002

37.2 FRICTION AND WEAR A metalworking fluid should impart sufficient lubricity between the tool and the workpiece to cause a significant reduction in friction to occur [6]. Friction is the resistance to the motion of one surface over another. Lubricants are used to reduce the frictional forces. High friction results in heat and because more force or power is necessary to move the parts relative to one another, this friction reduces operating efficiency, and in the case of metalworking, shortens tool life, affects surface finish, and increases production time. When the lubricant film is insufficient to protect the metal surfaces, there is wear on one or both components. Wear is material loss directly caused by the interaction of asperities on the two surfaces while in relative motion to each other. Thus, wear will directly affect tool life and the finish and quality of the workpiece. When a lubricant is applied between the contacting surfaces, the friction and wear can be minimized. Three lubrication regimes are defined depending on the amount of lubricant film separating the surfaces. These are: • Boundary lubrication • Elasto-hydrodynamic (mixed lubrication) • Hydrodynamic lubrication

Hydrodynamic lubrication is a regime where the moving surfaces are essentially separated from each other. In this regime the viscosity of the oil in combination with the movement of the tool can produce a fluid pressure high enough to completely separate the two surfaces.


Elasto-hydrodynamic lubrication is a regime where the film thickness is insufficient to completely separate the surfaces. In this regime the surface asperities make contact, which leads to wear. Lubricant in the contact area is continually replenished at the front of the contact [7]. The film thickness in the elasto-hydrodynamic regime is larger than in boundary lubrication but smaller than the film thickness in the hydrodynamic regime. Boundary lubrication is a regime where film thickness between the moving surfaces is only a few molecules thick. In this regime, because of the closeness of the moving surfaces, friction and wear are determined by properties of both the surfaces and the lubricant. Boundary films form because they reduce the surface energy and, therefore, are thermodynamically favored [8]. These films are formed by molecules that contain polar functional groups. Because of this, they orient onto the surface by either chemical or physical adsorption. Boundary lubrication can range from mild to severe conditions. Physical adsorption is a reversible process where molecules adsorb and desorb from a surface without chemical change. Additives that provide protection by physical adsorption are polar structures. This is because at least two phenomena must occur: the molecule must have a preferential affinity for the surface and it should have a preferred orientation on the surface so that a more closely packed arrangement can be achieved. Alcohols, acids, and amines are examples of long-chain molecules with functional groups at the end. Molecules that can pack tightly and orient in a close packed arrangement relative to the surface provide improved film strength. Because the forces

involved in physical adsorption are relatively weak, these films are effective at low to moderate temperatures. New molecules from the bulk lubricant are constantly available to replace those that physically desorb or are mechanically removed from the surface. Chemical adsorption, however, is an irreversible process where a lubricant fluid molecule or additive component reacts with the surface to form a low shear strength protective layer. As this new low shear strength material is worn away, additional additive reacts to form a new protective layer. Protection from chemical adsorption occurs at higher temperatures because chemical reactions are required to generate the actual species that form the surface films. Wear protection and friction reduction over a wide temperature range can be achieved by combining additives that function by physical adsorption and chemical adsorption. Between the low-temperature physically adsorbed layer and the high-temperature chemically adsorbed layer can be a temperature range over which there is poorer wear protection. This has been experimentally demonstrated where oleic acid was used as the normal wear additive and a chlorinated additive provided extreme pressure protection at the higher temperatures [9].

37.3 METALWORKING OPERATIONS Metal machining involves the removal of metal to produce an item of precise form and dimension from its initial rough form. A machine tool removes material by using power to force one or more precisely shaped tools against the workpiece, moving the two in one or more directions relative to each other [10]. Drilling is one of the most widely used machining processes to produce circular holes in metallic and nonmetallic materials. A drill is a rotary end-cutting tool, with the most common type being the twist drill. The drill, attached to either a stationary machine or hand held, is used to originate or enlarge a hole in a solid material. A drill will have cutting edges and straight or helical grooves or flutes, which allow for movement of chips and cutting fluids/coolants. Drill wear is not proportional to the number of holes drilled, but occurs at an accelerated rate. A reamer is a rotary cutting tool (similar to a drill) with one or more cutting elements, used to enlarge to an exact size and impart a smooth finish to, a previously drilled hole. Drilling can be characterized as in a rough form, whereas reaming is the exact form. Tapping is a procedure by which a thread is formed (machined) on the interior of the metal. An example would be a bolt hole. This process is also called thread tapping. On the exterior part of the metal it is called threading. The threading tools are called dies and can be held in a stationary holder used in a drill press or lathe.


Turning is a machining process for producing external cylindrical or tapered forms by removing metal, typically with a single-point cutting tool. The single-point tool is moved parallel to the machine spindle for straight or contour turning of the outside diameter and turning or boring of an internal surface. The most common turning machines include lathes, automatic screw machines, automatic bar and chucking machines, and CNC automatic turning centers. Boring is for the most part internal turning, in that usually a single-point cutting tool forms internal shapes. Most machines that will perform turning operations will also perform boring operations, although there are boring machines available that instead of turning, will do drilling, reaming, and other related processes. The simplicity of operations and of cutting tool design and application makes planers and shapers the most universal of all machine tools. Flat surfaces can be produced in horizontal, vertical, and angular planes; odd and irregular shapes as well as internal surfaces can be machined. By the use of special tools, these machines can form flat or curved surfaces, and surfaces located in deep pockets and other not readily accessible places. Planning and shaping operations involve a single-point cutting tool fed into a moving workpiece making parallel cuts to remove metal from flat surfaces. Shapers are generally used for smaller operations. Milling produces machined surfaces by removing a material from the workpiece using a rotating cutter containing a certain number of teeth, which is dependent on the application. A characteristic feature of the milling process is that each tooth of the cutting tool takes a portion of material in the form of small, individual chips [11]. Broaching is a precision machining operation where a broach can be pulled or pushed through a workpiece opening or over its surface to produce an exact shape. A broach can finish an entire surface in a single pass as opposed to milling. Internal or External shapes can be cut using broaches. Grinding is an abrasive machining operation, whether rough or precise, whereby material is removed from a workpiece by the mechanical action of abrasive particles of irregular shape, size, and hardness producing smooth surfaces, flat, cylindrical, or irregularly shaped.

37.4 NEAR DRY MACHINING Historically, the metalworking industry has used metal removal fluids by flood application in machining operations. But because the costs associated with use, management, and disposal of flood coolants has risen over the years, in part due to increasing federal, state, and local regulations aimed at worker safety and fluid disposal, there has been a growing trend to utilize methods requiring less

metalworking fluid to reduce cost, protect the environment, and improve and protect worker health, without sacrificing productivity and quality. The basic functions of a flood coolant are:

• Cool the tool and workpiece • Flush away chips • Lubricate the cutting tool

Guerbet alcohols have high molecular weight, low irritation properties, and low volatility. Since they are saturated they exhibit excellent oxidative stability at elevated temperatures, in addition to excellent color initially and at elevated temperatures [13]. They are clear, water white, essentially odor free, oily biodegradable liquids. R1 CH2 CH2 | R2 CH2 CH2 OH

Near dry machining can be described as a process by which a minimum quantity of lubricant mixed with air is continuously applied to the tool/workpiece interface during the machining operation. Thus, the application of near dry machining lubricants, which are for the most part consumed in the machining process, yields desirable economic, employee, and environmental benefits. One of the earlier examples of near dry machining lubrication could be seen in aircraft manufacturing. Freon® gas was used as a lubricant and coolant in three distinct areas of the riveting process — drilling, rivet insertion, and rivet-head milling. Because of the undesirable effects of Freon® gas on the ozone layer, manufacturing research and development engineers introduced an alternate method to cooling tools, using fatty alcohol lubricant compositions to efficiently lubricate tools preventing heat buildup while greatly reducing the reworking after drilling that had been necessary with Freon® because of exit burrs, oversized holes, and a rough finish on the inside surface of the holes. These lubricants were used in drilling, reaming, and coldworking of fastener holes in aircraft wing skins; installation of wedge-head lock bolts; lubrication of hand drills; and on machinery that automatically drill rivet holes and install rivets on large sections of airplanes. It was shown that the application of minimal quantities of lubricant could reduce friction, speed production, increase tool life, and improve surface finish and hole quality in a number of machining applications. Near dry machining lubricant compositions tend to be more expensive on a per unit basis compared to flood coolants, but when overall costs are calculated, they can cost considerably less. Near dry machining lubricant compositions may contain the following chemistries:

1. Guerbet alcohols via the Guerbet reaction are products of the condensation of alcohols at high temperature and pressure in the presence of sodium alkoxide or copper by a dehydrogenation, aldol condensation, and hydrogenation sequence [12]. Both natural and synthetic alcohols may be used as raw materials for Guerbet alcohol synthesis. The end products (2-alkyl alkanols) are linear straight chain alcohols with defined, not random branching. Because they are branched, they remain liquid at very low temperatures.


where R1 and R2 are alkyls. 2. Fatty alcohols are long chain aliphatic or linear alcohols. Monohydric aliphatic alcohols of six or more carbon atoms are generally referred to as higher or fatty alcohols. Higher alcohols are generally nontoxic and cause no primary skin irritation. Hexadecanol and octadecanol are used extensively in the cosmetics and pharmaceuticals industries and in lubricants [14]. Cetyl alcohol (1-hexadecanol) is a waxy, white solid produced from natural feedstocks such as coconut and palm kernel oil. The refined oil is first converted to methyl ester, which is fractionated then hydrogenated to alcohol, which is further fractionally distilled [15]. RCH2 OH where R = C5 alkyl and higher. 3. Synthetic esters are chemical compounds typically derived from the reaction of an organic acid with an alcohol. The ester group is responsible for physical properties such as volatility and flash point, as well as other properties such as thermal stability, hydrolytic stability, solvency, lubricity, and biodegradability [16]. The main types of esters are acid/anhydride centered as exemplified by monoesters, diesters, phthalates, and trimellitates; alcohol centered such as polyols; and polymeric esters such as polyalkylene glycol esters [17]. R1 COOR2 4. Vegetable oils such as rapeseed, canola, or soybean oil, or the methyl esters of fatty acids from vegetable oil such as rape or soy methyl ester. The process of extracting and refining vegetable oils involves a number of steps [18]. Rapeseed oil contains a large percentage of unsaturated carbon chain lengths greater than C-18, while canola and soybean oil are composed predominantly of C-18 unsaturated carbon chain lengths. Vegetable oils are predominantly triglycerides, which are tri-esters where three fatty acid groups are esterified to a glycerol backbone [19]. The fatty acid groups in a triacylglycerol are mostly responsible for the physical and performance properties of a purified vegetable oil [20]. Most vegetable oils are mixed triglycerides because of the presence of more than one type

of fatty acid [21]. Additionally, triglycerides can be converted to methyl esters and glycerine via transesterification utilizing methanol [22]. The glycerine is concentrated and refined. The methyl esters are purified and separated into individual esters by fractional distillation.

TABLE 37.1 Examples of Commercially Available Near Dry Machining Lubricants Product

H2 COOCR1

Acculube Boelube® Coolube Tri-cool

| HCOOCR2 | H2 COOCR3

where R1 , R2 , R3 are fatty acids. In the near dry machining process, the liquid lubricant can be delivered as fine droplets or oil fog through one or more nozzles positioned accordingly around the cutting tool or through a rotating spindle and tool with internal channels, as with oil hole tools. Delivering the lubricant as fine droplets to the cutting edge is necessary in order to reduce friction between the chip, tool, and workpiece, and prevent the chips from adhering to the tool cutting edge. Because the chips have less contact with the tool, a larger percentage of the heat is transferred and carried away with the chip, allowing the tool to stay cooler [23]. The near dry machining process requires continual reapplication of lubricant to the tool cutting edge and wear surfaces. This can be accomplished externally on band and circular saws, milling cutters, broaches, etc., as well as on shallow drilling and tapping operations. Using a coaxial supply of compressed air and lubricant to the nozzle, the nozzle directs lubricant droplets in the compressed air directly to the cutting edge. The compressed air will help move chips from the tool cutting edge as the fine lubricant droplets form a thin film at the point of contact to reduce friction. Lubricant can also be delivered continually through tools with internal channels directly to the cutting edge in drilling, reaming, tapping, boring, gun drilling, etc. In near dry machining the goal is high efficiency, which is achieved as a result of using as little lubricant as possible. Although the lubricant generally has high film strength, it must be continually reapplied to the cutting edges of tools and wear surfaces. Typically, lubricants used in near dry machining are non water-soluble; they may comprise mineral or synthetic oils, ester or fatty alcohol, with ester or fatty alcohol being more common. Depending on the type of machining operation, tool, workpiece composition, etc., the amount of lubricant usage can range from less than 50 ml/h to more often less than 10 ml/hour. Because minimal amounts of lubricant are used, the near dry machining process yields nearly dry workpieces and dry chips [24].


Supplier Illinois Tool Works Inc. The Orelube Corporation Unist, Inc. Trico Mfg. Corp.

Traditional metal removal fluids (oil and water miscible) can also be applied at reduced levels (0.08 l/min or 0.02 gal/min) in a process described by the authors as microlubrication, eliminating the need for a required collection system for the applied fluid [25]. Near dry machining lubricants, the majority of which are in liquid form, can be formulated into solid and paste forms too. Pastes are extremely cost effective in singlepoint work such as tapping, drilling, or reaming. A minimal amount of paste can be brushed on to the tool, or the tool can be dipped into the paste, in order to obtain highquality finish and increased tool life with little or no cleanup required. Solids come in a variety of shapes and sizes to accommodate ease of application in drilling, tapping, reaming, abrasive belts, files, deburring tools, grinding wheels, awls, chisels, band, circular and hand saw blades. They can improve tool life by reducing heat buildup in belt, disc, or wheel-grinding operations. Typically the solid form is applied to the tool before start-up. In a block form, it can be hand held and a drill bit can be touched to the block before drilling or the block may be swiped across the surface to be drilled. Only a minimal amount is required when drilling through thin material. There are a number of near dry machining lubricants of different composition in the marketplace, not all are priced similarly or perform equally (Table 37.1). But in principle, they all share common goals — improvement in tool life and surface finish, reduction in lubricant usage and subsequent cleaning and disposal costs, reduced environmental impact, improved housekeeping, and easier chip handling and recycling.

REFERENCES 1. John A. Schey, Tribology in Metalworking, American Society for Metals, Metals Park, Ohio, 1983, p. 1. 2. John A. Schey, Tribology in Metalworking, American Society for Metals, Metals Park, Ohio, 1983, p. 5. 3. William L. Brown, Synthetic Lubricants and HighPerformance Functional Fluids, 2nd ed., Leslie R. Rudnick and Ronald L. Shubkin (Eds.), Marcel Dekker, New York, 1999, p. 628.

4. T. McClure and M. Gugger, Microlubrication in metal machining operations. Lubr. Eng., Vol. 58, 2002, p. 15. 5. The National Petrochemical & Refiners Association 2002 Report on U.S. Lubricating Oil Sales (used by permission of NPRA). 6. Robert Silverstein and Leslie R. Rudnick, Lubricant Additives, Leslie R. Rudnick (Ed.), Marcel Dekker, New York, 2003, pp. 525–527. 7. J. Pemberton and A. Cameron, A mechanism of fluid replenishment in elastohydrodynamic contacts. Wear, Vol. 37, 1976, pp. 185–190. 8. Boundary Lubrication (Texaco Inc.), Vol. 57, 1971. 9. D.D. Fuller, Theory and Practice of Lubrication for Engineers, John Wiley & Sons, Inc., New York, 1984. 10. The Petro-Canada Guide to Metalworking. Petro-Canada, 1986, p. 2. 11. Ronald A. Walsh, McGraw-Hill Machining and Metalworking Handbook. McGraw-Hill, New York, 1994, pp. 580–596. 12. Hawley’s Condensed Chemical Dictionary, 13th ed., Revised by Richard J. Lewis, Sr. Van Nostrand Reinhold, 1997, p. 555. 13. Anthony J. O’Lenick Jr. and Raymond E. Bilbo, Guerbet Alcohols A Versatile Hydrophobe. Soap/Cosmetics/Chemical Specialties for April 1987, pp. 52–54. 14. Kirk-Othmer, Concise Encyclopedia of Chemical Technology, John Wiley & Sons, Inc., New York, 1985, pp. 52–53. 15. Procter & Gamble Chemicals Technical Data Sheet, CO1695 Cetyl Alcohol, 2001.


16. Steven James Randles, Synthetic Lubricants and HighPerformance Functional Fluids, 2nd ed., Leslie R. Rudnick and Ronald L. Shubkin (Eds.), Marcel Dekker, New York, 1999, p. 63. 17. Steven James Randles, Synthetic Lubricants and HighPerformance Functional Fluids, 2nd ed., Leslie R. Rudnick and Ronald L. Shubkin (Eds.), Marcel Dekker, New York, 1999, p. 64. 18. Vegetable Oils and Fats, Goran Magnusson, Gunilla Hermansson, and Rita Leissner (Eds.), Karlshamns Oils and Fats AB, Halls Offset, Vaxjo, Sweden, 1989, p. 68. 19. S. Lawate, K. Lal, and C. Huang, Tribology Data Handbook, E.R. Booser (Ed.), CRC Press, Boca Raton, FL, 1997, p. 103. 20. S. Lawate, K. Lal, and C. Huang, Tribology Data Handbook, E.R. Booser (Ed.), CRC Press, Boca Raton, FL, 1997, p. 104. 21. Douglas M. Considine (Editor-In-Chief), Chemical and Process Technology Encyclopedia, McGraw-Hill Book Company, New York, 1974, p. 1129. 22. Morrison and Boyd, Organic Chemistry 3rd ed., Allyn and Bacon, Inc., Boston, 1973, p. 682. 23. Dierk Stabler, Basics of Minimal Lubrication Technology. Fraunhofer Institut ICT, Pfinztal, Germany, p. 1. 24. Dierk Stabler, Basics of Minimal Lubrication Technology. Fraunhofer Institut ICT, Pfinztal, Germany, p. 2. 25. T. McClure and M. Gugger, Microlubrication in metal machining operations. Lubr. Eng., Vol. 58, 2002, p. 16.

38

Lubricants for the Disk Drive Industry Tom E. Karis CONTENTS 38.1 Introduction 38.2 Recording Disk Lubricants 38.2.1 Properties 38.2.1.1 Viscoelastic (Rheological) 38.2.1.2 Dielectric 38.2.1.3 Thin Film Viscosity 38.2.1.4 Vapor Pressure 38.3 Spindle Motor Lubricants 38.3.1 Ball Bearing Spindle Motor Bearing Grease 38.3.1.1 Yield Stress at Temperature 38.3.1.2 Hydrodynamic Film Thickness 38.3.1.3 Grease Electrochemistry 38.3.2 Ball Bearing Spindle Motor Ferrofluid Seal 38.3.3 Fluid Bearing Motor Oil 38.3.3.1 Viscosity and Vapor Pressure 38.4 Conclusions and Future Outlook Acknowledgment References

38.1 INTRODUCTION When thinking of a disk drive, one picture that comes to mind is that of digital data bits stored on a spinning disk housed inside a device such as a computer, digital video recorder, or MP3 jukebox. The precision and reliability of these high speed rotating devices is, perhaps, one of the leading examples of micro electromechanical systems and nanotechnology at work today. For example, the magnetic recording read/write head floats on an air lubricated bearing just 10 nm away from the disk surface with a relative velocity, which is often about 10 m/sec. That is a shear rate of 1 billion m/sec, and, occasionally, the recording head contacts asperities on the disk surface. With the data track width decreasing below 200 nm, the tolerance of the spindle motor on which the disks are mounted must have increasing stiffness with vibration amplitudes that are well below the track width to minimize servo seek time and track following. Ball bearing spindle motors used in the past have reached their limit, and future high performance products are incorporating fluid dynamic bearing spindle motors. In addition, when there is a high relative velocity between metallic and insulating components, electrostatic charge generation and dissipation must be


controlled. Lubricants play a key enabling role in all of the above vital requirements for the disk drive industry, and fundamental understanding of the lubrication requirements and the detailed physical chemistry of their performance are essential to the advancement of the technology. This chapter focuses on lubricants for the magnetic recording disk, and the spindle bearing motor. Throughout the chapter, much emphasis is placed on the analytical tools that are common to all of the lubricants. Similar techniques are applied to characterize the physical properties of lubricants that influence their performance. Rheological measurements are employed not only to characterize the viscosity, but to estimate the short time dynamic response of disk lubricants through time–temperature superposition. Shear rheometry is exploited to characterize the yield stress of grease, as well as the effect of blending on fluid dynamic bearing motor oils. Dielectric spectroscopy is widely utilized to explore the dipole relaxation of disk lubricant end groups. Dielectric permittivity and conductivity measurement are used for development of conductivity additives for ferrofluid used in motor seals, and to investigate the effects of contamination on ball bearing grease electrochemistry.

Another powerful technique that is highlighted in this chapter is Fourier transform infrared spectroscopy. This powerful technique can be used to study thin films in reflection or bulk samples in transmission. Examples are shown in which infrared spectroscopy is also applied to identify the reaction product formed during electrochemical oxidation of ball bearing grease. Thermal analysis is employed to measure the vapor pressure of disk lubricants, and a model is described that simulates evaporation of polydispersed lubricants based on molecular weight distributions measured by gel permeation chromatography. Surface energy from measured contact angles is combined with the chemical kinetic model for viscous flow and evaporation to predict the viscosity of molecularly thin films and to understand factors that limit lubricant spin-off from rotating disks. The chemical kinetic model is also employed to combine vapor pressure and viscosity data in the quest for the molecular structure of a fluid bearing motor oil that has both low viscosity and vapor pressure. Not only are the techniques illustrated here with examples from the disk drive industry applicable to the lubrication industry in general, but they also will be particularly useful in adapting these methodologies to the tribology of micro and nano electromechanical systems.

38.2 RECORDING DISK LUBRICANTS The soft magnetic layers on the magnetic recording disk substrate are typically overcoated with about 5 nm of amorphous carbon. Since the carbon has a relatively high surface energy, a low surface energy lubricant is applied on top of the overcoat. The most widely used perfluoropolyethers (PFPEs) are those having the Z type backbone chain. These are random copolymers with the linear backbone chain structure

TABLE 38.1 Molecular Structure for Some of PFPE End Groups on the Z Type PFPE Chain A20H has one Zdolend group. Name

Structure

Z

CF3

Zdol

CF2CH2OH OH CF2CH2OCH2CHCH2OH

Ztetraol Zdiac

CF2COOH

Zdeal

CF2COOCH3 CF2CH2(OCH2CH2)1.5OH

Zdol TX

O AM-3001

A20H

CH2

CF2CH2OCH2

P CF2CH2O N

ZDPA

N P

O CF3

P N

CF2CH2N

O 5 CH2CH2CH3 CH2CH2CH3

The molecular structures of the D and K series of PFPEs, also considered for magnetic recording disk lubricants, are shown in Table 38.2. The repeat unit of the D chain is perfluoro n-propylene oxide. The D series includes Demnum with nonpolar end groups, Demnum SA with a hydroxyl end group, and Demnum SH with a carboxylic acid end group. The repeat unit of the K chain is perfluoro isopropylene oxide. The K series includes Krytox with nonpolar end groups and Krytox COOH with a carboxylic acid end group.

X–[(O CF2 )m –(O CF2 CF2 )n –(O CF2 CF2 CF2 )p –(O CF2 CF2 CF2 CF2 )q ]x0 –O X, where X is the end group. A wide range of end groups is available to tailor the lubricant for optimum lubrication properties. The end groups for some of the commercially available lubricants are shown in Table 38.1. The adsorption energy of end groups (other than –CF3 ) on the carbon overcoat surface is higher than that of the backbone chain [1,2]. The X1P type end group on A20H [3,4] is sterically large in comparison to the chain monomers [5], and the X1P end group molecular weight of about 1000 Da is a significant contribution to the molecular weight of commonly used backbone chains of 2000 to 4000 Da [6]. Lower molecular weight end groups, also intended to passivate Lewis acid sites, are derived from Zdol with dipropylamine [7], and referred to as ZDPA.


38.2.1 Properties Perfluoropolyethers are attractive as magnetic recording disk lubricants because of their low surface energy, low vapor pressure, wide liquid range, transparency, and lack of odor. PFPEs are related to polytetrafluoroethylene, but they have lower glass transition temperatures [8–10]. The first commercially available PFPEs had perfluoromethyl end groups, and are referred to as nonpolar PFPEs. More recently, polar PFPEs with hydroxyl, carboxylic acid, and other polar end groups have come into widespread use. The polar end group provides an additional means to adjust the fluid properties and the interaction with surfaces. PFPEs with polar end groups are predominantly used to lubricate present day rigid magnetic recording media. Their versatility has motivated considerably the detailed study of PFPEs. The bulk viscosity and glass

TABLE 38.2 Molecular Structure for D and K Type PFPEs Name

Structure CF3CF2CF2O

Demnum S100

CF3CF2CF2O

Demnum SA

Demnum DPA

CF3CF2CF2O

CF2CF2CF2O

CF2CF2CF2O

CF2CF2CF2O

xo

xo

CF2CF3

CF2CF2CH2

CF2CF2CH2N xo

OH

CH2CH2CH3 CH2CH2CH3 O

Demnum SH

CF3CF2CF2O

CF2CF2CF2O

xo

CF2CF2C OH

CF3 Krytox 143AD

CF3CF2CF2O

CF

CF2O

xo

CF3 O

CF3 Krytox COOH

CF3CF2CF2O

transition temperature of the nonpolar PFPEs have been extensively characterized by Sianesi et al. [8], Ouano et al. [11], Cantow et al. [12], Marchionni et al. [13–16], Cotts [17], and Ajroldi et al. [18]. Subsequent investigations have begun reporting the properties of PFPEs with polar end groups, for example, Danusso et al. [19], Tieghi et al. [20], Ajroldi et al. [21], and Kono et al. [22]. The composition and molecular weight of several PFPE lubricants, measured by nuclear magnetic resonance (NMR) spectroscopy [23] is given in Table 38.3. 38.2.1.1 Viscoelastic (rheological) Oscillatory shear and creep measurements were done with a Carri-Med CSL 500 (now TA Instruments) Stress Rheometer with the extended temperature module and a 40 mm diameter parallel plate fixture. The dynamic strain amplitude was 5%, and this was within the range of linear viscoelasticity for these materials. The storage G and loss modulus, G , were measured between 1 and 100 rad/sec at each temperature. Typically, measurements were done each 20◦ C from −20 to −100◦ C. Low temperature measurements were performed to provide the high frequency properties that are required for calculations at the short timescales encountered in asperity contacts. The data measured at low temperature is transformed to high frequency through time–temperature superposition with Williams Landel Ferry (WLF) coefficients [24] that


CF

CF2CF3

CF2O

CF

C OH

xo

are derived from the rheological measurement data. The PFPEs were linearly viscoelastic at these test conditions. The dynamic properties were independent of strain amplitude, and no harmonic distortion of the sinusoidal angular displacement waveform was observed even at the lowest measurement temperatures. Time–temperature superposition was employed to obtain the master curves [25]. Viscosities for the lubricants at each temperature were calculated from the steady state creep compliance. The glass transition temperatures, Tg , were measured using a modulated differential scanning calorimeter manufactured by TA Instruments model number 2920 MDSC V2.5F. The samples were cooled to −150◦ C and heated to 20◦ C at 4◦ C/min with a 1.5◦ modulation over a period of 80 sec. The differential heat flow and temperature phase shift were measured to determine the reversible and nonreversible components of the heat flow. The glass transition temperatures of several PFPE lubricants are listed in Table 38.4. The temperature dependence of the viscosity is shown in Figures 38.1 through 38.3 as the ratio of the viscosity to the molecular weight η/Mn plotted as a function of distance from the glass transition temperature T − Tg . The ratio η/Mn is proportional to the segmental friction coefficient [25], and shifting the temperature by Tg takes into account the effect of Tg on the relaxation times. The smooth curves are from the regression fit of the shift factors in the WLF equation. A subset of the Z series showing the effects of different end groups are shown in Figure 38.1. Most

TABLE 38.3 The Composition of Several PFPEs Lubricant Z03 Zdiac Zdeal Ztetraol 2000 Ztetraol 1000 Ztx Zdol4KL819 Zdol4KL492 Zdol4KL990 Zdol4KBL598 Zdol4KL905 Zdol 2500 Demnum S100 Demnum SA2000 Demnum SA2 Demnum DPA Demnum SH Krytox 143 AD Krytox COOH

m

n

p

q

m/n

O/C

x

Mn (Da)

0.530 0.508 0.567 0.485 0.523 0.475 0.612 0.568 0.515 0.492 0.469 0.456 — — — — — — —

0.405 0.435 0.426 0.515 0.477 0.517 0.383 0.425 0.475 0.508 0.526 0.544 — — — — — — —

0.057 0.048 0.003 0 0 0.007 0.003 0.005 0.005 0 0.0025 0 — — — — — — —

0.008 0.008 0.004 0 0 0.001 0.0025 0.002 0.005 0 0.0025 0 — — — — — — —

1.31 1.17 1.33 0.94 1.10 0.92 1.60 1.34 1.08 0.97 0.89 0.84 — — — — — — —

0.754 0.744 0.782 0.743 0.762 0.736 0.720 0.693 0.666 0.658 0.650 0.728 0.333 0.333 0.333 0.333 0.333 0.333 0.333

73.4 24.4 22.8 23.2 14.2 22.7 46.5 39.1 39.2 47.2 41.5 26.1 31.7 12.6 18.6 48.4 18.3 39.8 32.3

6810 2310 2070 2300 1270 2230 4000 3600 3600 4300 3900 2420 5230 2080 3080 8100 3040 6580 5370

The degree of polymerization x = xo + 2. The Zdol4K series are different batches of Zdol 4000 from the manufacturer.

Z03 Zdiac Zdeal Ztetraol 2000 Ztx Zdol4KL 905 Zdol 2500

1.E+04

Lubricant Z03 Zdiac Zdeal Ztetraol 2000 Ztx Zdol4KL819 Zdol4KL492 Zdol4KL990 Zdol4KBL598 Zdol4KL905 Zdol 2500 Demnum S100 Demnum SA2000 Demnum SA2 Demnum DPA Demnum SH Krytox 143 AD Krytox COOH

Tg

C1

C2

−131.8 −118.4 −120.2 −112.2 −109.9 −126.7 −123.3 −119.7 −117.2 −115.6 −113.6 −111.2 −114.1 −110.2 −110.7 −110.1 −66.1 −61.4

14.13 18.14 17.25 23.22 15.67 11.73 16.27 15.98 16.66 10.54 13.62 13.06 13.75 13.77 12.13 13.27 12.22 11.97

24.51 25.90 23.64 45.81 42.75 38.46 49.82 52.22 37.14 38.05 59.72 62.76 43.89 62.11 78.52 63.56 31.65 40.79

The reference temperature for C1 and C2 is Tg .


1.E+02 h/Mn(Pa-sec/Da)

TABLE 38.4 The Glass Transition Temperature and the WLF Coefficients of Several PFPEs

1.E+00

1.E–02

1.E–04

1.E–06

0

25

50

75 T –Tgo

100

125

150

FIGURE 38.1 The ratio of viscosity to molecular weight as a function of distance from the glass transition temperature for the PFPE Z series

of the PFPEs shown in Figure 38.1 had an oxygen to carbon (O/C) ratio of about 0.65, except for the Zdeal, which had an O/C ratio of 0.694. The segmental friction coefficient was the lowest for nonpolar Z03 and the Zdol4KL905 (and Zdol4KL819 shown in Figure 38.2), and highest for

Zdol4KL819 Zdol4KL492 Zdol4KL990 Zdol4KL598 Zdol4KL905

1.E+04

1.E+02 h/Mn(Pa-sec/Da)

h/Mn(Pa-sec/Da)

1.E+02

1.E+00

1.E–02

Demnum S100 Demnum SA2000 Demnum SA2 Demnum DPA Demnum SH Krytox 143AD Krytox COOH

1.E+04

1.E+00

1.E–02

1.E–04 1.E–04 1.E–06

0

25

50

75 T–Tgo

100

125

150

FIGURE 38.2 The ratio of viscosity to molecular weight as a function of distance from the glass transition temperature for the PFPE Zdol4K series, showing the effect of O/C ratio. The smooth curves are from the WLF equation

the Ztetraol, with two hydroxyls on each end group. The segmental friction coefficients for Z chains with other types of end groups were in between the Z03 and Ztetraol. The friction coefficient for the Zdeal was slightly lower than the Zdiac, because the methyl ester probably blocks some of the hydrogen bonding. The Ztx, Zdiac, and Zdol2500 had nearly the same segmental friction coefficient as one another. The effect of the O/C ratio on the segmental friction coefficient for the Zdol 4K series is shown in Figure 38.2. The lots with intermediate O/C ratio, Zdol4K L492, 990, and 598, were above Zdol4K L819 with (high) O/C = 0.72 and Zdol4KL905 with (low) O/C = 0.65, which were about the same as one another, even though their Tg are 11◦ apart. This surprising relationship may arise from a dependence of the segmental friction coefficient on the chain flexibility and the cohesive energy density that is different from the dependence of Tg on these properties. The segmental friction coefficient for the D and K series, shown in Figure 38.3, was within the range of that observed for the Zdol4K series in Figure 38.2. The nonpolar Krytox and the Krytox COOH were nearly the same as one another, and were below the Demnum for most of the Demnum series. All of the Demnum series were nearly the same as one another. The addition of polar end groups had little effect on the segmental friction coefficient of the D and K. The storage and shear moduli, G and G , were measured and shifted along the temperature axis to obtain the master curves. The WLF coefficients [24] were calculated from the shift factors aTo (T ) by nonlinear regression


1.E–06 0

25

50

75 T–Tgo

100

125

150

FIGURE 38.3 The ratio of viscosity to molecular weight as a function of distance from the glass transition temperature for the PFPE Demnum and Krytox series. The smooth curves are from the WLF equation

analysis using the functional form log(aTo ) =

−C1 (T − To ) C2 + (T − To )

(38.1)

where the reference temperature To = Tg , and C1 and C2 are the WLF coefficients with respect to Tg . The WLF coefficients are listed in Table 38.4. Our 10.5 < C1 < 23.5, and 23.5 < C2 < 79 are consistent with those for nonpolar PFPEs Y and Z reported by Marchionni et al. [13]. Up to three Maxwell elements were derived from the master curves by nonlinear regression analysis from the linearly viscoelastic shear storage modulus, G , and loss modulus, G : G =

Gi (ωaT τi )2 o 1 + (ωaTo τi )2

(38.2)

i

and G =

i

Gi ωaTo τi 1 + (ωaTo τi )2

(38.3)

where ω is the shear strain sinusoidal oscillation frequency. The shear rigidities Gi and corresponding relaxation times τi are listed in Table 38.5. The WLF coefficients, the shear rigidities, and the relaxation times provide the solid curves in Figures 38.4 to 38.6. The dynamic response for the Z series with different end groups is shown in Figure 38.4. The polar end group increases the relaxation times. Two relaxation times are observed in the Zdiac, Zdeal, and Zdol4KL905. Three relaxation times are

TABLE 38.5 The Coefficients of the Maxwell Elements from the Master Curves at Reference Temperature Tg η(−20◦ C ) (Pa-sec) Lubricant

G1 (kPa)

τ1 (sec)

G2 (kPa)

τ2 (sec)

G3 (kPa)

τ3 (sec)

From creep

From dynamic

Z03 Zdiac Zdeal Ztetraol 2000 Ztx Zdol4KL819 Zdol4KL492 Zdol4KL990 Zdol4KBL598 Zdol4KL905 Zdol 2500 Demnum S100 Demnum SA2000 Demnum SA2 Demnum DPA Demnum SH Krytox 143 AD Krytox COOH

49.3 28.4 31.1 36.6 55.6 4.0 43.4 49.7 48.4 19.3 51.9 11.8 54.0 35.1 42.0 47.5 55.3 44.9

1.11E + 07 5.17E + 10 6.31E + 09 4.02E + 13 7.42E + 06 3.56E + 05 1.51E + 07 5.77E + 06 2.10E + 08 2.40E + 03 5.03E + 04 4.52E + 04 4.09E + 05 5.49E + 04 1.87E + 08 2.28E + 04 1.35E + 05 3.08E + 04

— 5.6 4.0 8.9 — 5.2 — — — 19.7 — 38.0 — 10.4 3.38 6.8 3.1 4.7

— 3.09E + 09 1.44E + 08 3.86E + 12 — 7.91E + 04 — — — 2.21E + 02 — 9.91E + 03 — 6.43E + 03 1.22E + 07 1.60E + 03 4.30E + 03 1.21E + 03

— — — 5.5 — 14.3 — — — — — 3.4 — — — — 1.0 2.3

— — — 3.16E + 11 — 8.13E + 03 — — — — — 2.84E + 02 — — — — 1.16E + 02 7.17E + 01

0.2 1.0 0.4 83 2.0 0.2 1.3 1.3 2.3 0.3 2.2 3.7 1.1 2.8 3.6 2.9 81 220

0.2 1.0 0.4 70 1.6 0.5 1.1 1.5 1.4 0.2 2.0 1.5 1.5 2.1 2.5 2.8 69 200

The steady shear viscosity measured in creep, and the zero shear viscosity calculated from the dynamic data at −20◦ C.

observed in the Ztetraol and Zdol4KLl819. At ambient temperature the Z03 has nearly the shortest characteristic time, τ1 , of all the PFPEs, even though it has the highest Mn . Ztetraol had the longest τ1 within the Z series. The response of the Zdol with a range of O/C ratio is shown in Figure 38.5. The O/C ratio had a significant effect on the dynamic response of the Zdol 4K series. The dynamic response of the Demnum and Krytox are shown in Figure 38.6. The τ1 for the Krytox is much longer than that for the Demnum. The linear viscoelastic properties, zero shear viscosity η = G1 τ1 and the equilibrium recoverable compliance Je0 = τ1 /η may be calculated from the dynamic properties listed in Table 38.5. The viscosity or relaxation time can be calculated at an arbitrary temperature T with the ratio of the shift factors from the WLF equation. For example, τ1 (T ) or η(T ) = η(Tg )aTg (T ). The relaxation times for the Z series of lubricants calculated at 50◦ C is shown in Figure 38.7.

dielectric analyzer (DEA) model 2970 with a single surface ceramic sensor. Measurements were taken at an applied voltage of 1 V. The frequency sweep ranged from 0.1 to 10,000 Hz. Measurements were done at temperatures ranging from −100 to 100◦ C. The data at the various temperatures were shifted relative to reference temperature T0 = 50◦ C to provide the dielectric master curves for several magnetic recording disk lubricants, shown in Figure 38.8. The dielectric properties are derived from the master curves with a discrete relaxation time (Debye) model [26] for the dielectric loss factor, ε , and the dielectric permittivity, ε : ε =

(εs,i − ε∞ )ωaT τi σ 0 + ε0 ωaT0 1 + (ωaT0 τi )2

and ε = ε∞ +

i

38.2.1.2 Dielectric The lubricant dielectric properties provide complementary information to the rheological data. The concept is similar in that both energy storage and dissipation are characterized in response to a sinusoidal application of an electric field. The permittivity and loss factor of the different lubricant samples were measured using a TA instruments


(38.4)

i

εs,i − ε∞ 1 + (ωaT0 τi )2

(38.5)

where ω is the sinusoidal oscillation frequency of the applied voltage, τi are the dielectric relaxation times, and ε0 is the absolute permittivity of free space (8.85 × 10−12 F/m). The parameters in the discrete relaxation time series determined by a regression fit to the dielectric master curves. There are multiple dielectric relaxation times for the Zdol and Ztetraol. Four were employed to

(a) 1.E+06 Ztx

Ztetraol

G (Pa)

1.E+04 1.E+02 Zdiac 1.E+00 Zdol 2500 Zdeal 1.E–02 Z 03 1.E–04 1.E–16 1.E–14 1.E–12 1.E–10 1.E–08 1.E–06 1.E–04 1.E–02 1.E+00 vaTg(rad/sec) (b) 1.E+06 Ztetraol 1.E+04

G (Pa)

1.E+02 1.E+00 1.E–02

Zdiac

Z03

Zdol 2500 Ztx

Zdeal

1.E–04 1.E–16 1.E–14 1.E–12 1.E–10 1.E–08 1.E–06 1.E–04 1.E–02 1.E+00 vaTg(rad/sec)

FIGURE 38.4 Shear loss (a) and storage (b) modulus master curves for the Z series. The smooth curves are from the discrete relaxation time series fit to the frequency temperature shifted data. Reference temperature Tg

approximately fit the data in Figure 38.8. These provide estimates for theconductivity, σ , the dc relative permittivity, ε (0) = i εs,i , and the limiting high frequency permittivity, ε∞ . Note that the capacitive energy storage is proportional to the dc relative permittivity, and the refractive index n is related to the high frequency relative √ permittivity by the Maxwell relation n ≈ ε∞ . For PFPEs, n ≈ 1.3 [23], which gives ε∞ ≈ 1.7. The dielectric properties, and the four relaxation times, and static relaxation amplitudes are listed in Table 38.6. 38.2.1.3 Thin film viscosity The above results have shown that in bulk PFPEs disk lubricants viscosity increases exponentially as the measurement temperature approaches the glass transition temperature. This is because chain motions are progressively “frozen out” as the thermal energy becomes less than their activation energy. The lubricant viscosity also increases as the lubricant film thickness decreases, which helps to prevent the lubricant from flowing completely off of the magnetic recording disks in the air shear [27].


Viscosity enhancement of thin films arises from a different mechanism than that found with decreasing temperature. Dispersive interaction has a dramatic effect on the viscosity of the molecular layers closest to the surface, and can be explained in terms of the rate theory for viscous flow. Within the rate theory, a flow event comprises the transition of a flow unit from its normal or quiescent state, through a flow-activated state, to a region of lower free energy in an external stress field. For small molecules, the flow unit is the whole molecule, while for longer chains, the flow unit is a segment of the whole molecule. By analogy with chemical reaction rate theory, there is a flow-activation enthalpy, Hvis , and entropy, Svis , for transition into the flow-activated state. A flow unit is approximated by a particle in a box, with the energy being partitioned among rotational and translational degrees of freedom, which govern the transition probability. On this basis, the viscosity η = (Nhp /Vl ) exp( Gvis /RT ), where N is the Avogadro’s number, hp is the Planck constant, Vl is the molar volume, R is the universal gas constant, T is temperature, and

Gvis = Hvis − T Svis is the flow-activation Gibbs free

(a)) 1.E+06

Zdol4KL990

1.E+04

G (Pa)

Zdol4KBL598 1.E+02 1.E+00 1.E–02

Zdol4KL905

Zdol4KL492 Zdol4KL819

1.E–04 1.E–16 1.E–14 1.E–12 1.E–10 1.E–08 1.E–06 1.E–04 1.E–02 1.E+00 vaTg (rad/sec) (b) 1.E+06 1.E+04

G (Pa)

Zdol4KBL598 1.E+02 1.E+00 1.E–02

Zdol4KL492

Zdol4KL819

Zdol4KL905

Zdol4KL990 1.E–04 1.E–16 1.E–14 1.E–12 1.E–10 1.E–08 1.E–06 1.E–04 1.E–02 1.E+00 vaTg (rad/sec)

FIGURE 38.5 Shear loss (a) and storage (b) modulus master curves for the Zdol4K series. The smooth curves are from the discrete relaxation time series fit to the frequency temperature shifted data. Reference temperature Tg

energy. The flow-activation enthalpy Hvis = Evis +

(pV )vis , where Evis is the flow-activation energy and

(pV )vis is the pressure–volume work. At constant pressure, (pV ) = p Vvis . For PFPE Z, the flow-activation volume Vvis ≈ 0.1 nm3 [12], which is equivalent to a spherical region ≈0.6 nm in diameter. At ambient pressure (100 kPa), (pV )vis ≈ 6.2 J/mol, so that near ambient conditions, Hvis ≈ Evis . Therefore, the viscosity is given by: Nhp ( Evis − T Svis ) exp (38.6) η= Vl RT A regression fit to the bulk viscosity as a function of temperature [27], provided Evis = 34.7 kJ/mol and

Svis = 9.87 J/mol ◦ K. The flow-activation energy is close to that reported for bulk Zdol with a molecular weight of 3100 Da in References 28 and 29. A positive value for the flow-activation entropy of bulk Zdol means that the entropy of the flow unit increases on going into the flow-activated state. Changes in the lubricant flow-activation energy and entropy near the solid surface cause changes in the viscosity


with decreasing film thickness. The flow-activation energy near a solid surface is estimated from the thin film vaporization energy as follows: In an ideal gas, the chemical potential µ (or partial molar Gibbs free energy) is given by: dµ = RTd ln P

(38.7)

where P is the partial pressure of the lubricant in the vapor phase. The chemical potential energy per unit volume in the lubricant film µ/Vl = . The ratio of the film surface vapor pressure to the vapor pressure of the bulk lubricant, Po (h)/Po (∞), is derived by integrating Equation (38.7).

Po (h) µ(h) − µ(∞) = RT ln o P (∞)

(38.8)

The reference state is taken to be the chemical potential and vapor pressure of the bulk lubricant: u(∞) = 0 and Po (∞) is the vapor pressure of the bulk liquid. In general, since the surface energy is defined as the free energy per unit area, the total disjoining pressure ( ) for these fluids can be derived from the experimental surface

(a) 1.E+06 Demnum S100 1.E+04

Krytox 143AD

G (Pa)

1.E+02 1.E+00

Demnum SA2 Krytox COOH

1.E–02

1.E–04 1.E–16 1.E–14 1.E–12 1.E–10 1.E–08 1.E–06 1.E–04 1.E–02 1.E+00 vaTg(rad/sec) (b) 1.E+06 1.E+04

Krytox 143AD Demnum S100

G (Pa)

1.E+02 1.E+00 1.E–02

Demnum SA2 Krtox COOH

1.E–04 1.E–16 1.E–14 1.E–12 1.E–10 1.E–08 1.E–06 1.E–04 1.E–02 1.E+00 vaTg(rad/sec)

FIGURE 38.6 Shear loss (a) and storage (b) modulus master curves for the Demnum and Krytox series. The smooth curves are from the discrete relaxation time series fit to the frequency temperature shifted data. Reference temperature Tg

energy (contact angle) data by: =−

∂ d (γ + γ p ) ∂h

(38.9)

Here, γ d and γ p are the dispersive and polar components of the surface energy, respectively, and h is the film thickness. The regression fit to the surface energy data, shown as the smooth curves in Figure 38.9(a) and Figure 38.9(b), were numerically differentiated to obtain the disjoining pressure [30]. The total disjoining pressure, as well as the individual contributions from the dispersive and polar components, is shown in Figure 38.10(a). Notice that γ d decreases monotonically with h, which is consistent with Equation (38.10). Below film thicknesses of approximately 0.5 nm, at each molecular weight is dominated by γ d , which increases rapidly with decreasing film thickness and is largely independent of molecular weight. The γ p , however, oscillates with film thickness and becomes larger in magnitude than γ d as h increases. Oscillations in γ p provide an additional contribution to for PFPE Zdol that produces alternating regions of stable and unstable film thickness [31]. The sum of the two contributions gives rise to oscillations in


the total disjoining pressure. It may seem surprising, but given the disjoining pressure from the surface energies as a function of film thickness, and Equation (38.9) relating the disjoining pressure to the degree of saturation provides the adsorption isotherms for low molecular weight Zdols, according to P/P0 = exp(− Vl /RT ), which are shown in Figure 38.10(b). There are two thermodynamically stable regions of film thickness for degrees of saturation corresponding to regions where > 0 and ∂ /∂h < 0. For thicknesses in between these regions, condensing Zdol molecules will either reevaporate, or form islands at the next higher stable film thickness. For the purpose of explaining the viscosity increase of thin films, surface chemical potential is approximated by the unretarded atom–slab dispersive interaction energy: Vl A (38.10) 6π h3 The dispersive interaction coefficient A is also referred to as the Hamaker constant, and A = 10−19 J for Zdol. As mentioned, the vaporization energy is the energy required to remove a molecule from the liquid without leaving behind a hole and the flow-activation energy, which µ=−

Relaxation time (sec)

(a) 1.E-04

1.E-05

50

Zt e

t ra

Zd o

ol

l2

20

0

Zt x

00

al Zd e

ac Zd i

Z0 3

1.E-06

Relaxation time (sec)

(b) 1.E-04

1.E-05

1.E-06 0.8

1

1.2

1.4

1.6

1.8

m/n

FIGURE 38.7 Longest relaxation time at 50◦ C for the Z series of lubricants (a) and Z series with a range of monomer chain composition (b) calculated from the dynamic rheological measurements with time–temperature superposition

is the energy needed to form a hole of the size of a molecule in the liquid. The free volume needed for a flow unit to transition into the flow-activated state is less than the size of the entire molecule. It is found that the ratio n ≡ Evap,∞ / Evis,∞ > 3, where Evap,∞ and Evis,∞ are the vaporization and flow-activation energy of the bulk liquid, respectively. Thus, the flow-activation energy near the surface is approximately given by:

Evis = Evis,∞ −

µ n

(38.11)

For linear chains longer than 5 or 10 carbon atoms, n increases due to the onset of segmental flow. In practice, n is experimentally determined from the measured values of the vaporization and flow-activation energy. For PFPE Zdol 4000, Evap,∞ = 166 kJ/mol, giving n ≈ 4.8. This is consistent with segmental flow. In order to calculate the thin film viscosity with Equation (38.6), the flow-activation entropy near the surface is also needed. Experimental flow-activation entropy is calculated from the spin-off data [27] with Equations (38.6) and (38.11) as follows: The experimental η vs. h is determined from the dh/dt during air shear induced flow on a rotating disk. Equation (38.6) is then solved for Svis vs. h using Equation (38.11) for Evis .


The flow-activation entropy and entropy are shown in Figure 38.11(a). The flow- activation energy suddenly increases below about 0.8 nm due to the strong film thickness dependence of the dispersion force. The retarding effect of this increase on flow is compounded by the apparent effect of confinement on restricting the degrees of freedom in the flow transition state, as seen by the negative entropic contribution in Figure 38.11(a). Below 2.3 nm, T Svis ≈ −1.9 kJ/mol, which corresponds to the critical configurational entropy change for flow (−R ln 2 ≈ −5.76 J/mol ◦ K). The combined effects give rise to the observed increase in viscosity with film thickness shown in Figure 38.11(b), and enables extrapolation of the viscosity to even thinner films where the spin-off is so slow that it takes years to measure. The viscosity increases by a large amount with film thickness, which is much greater than the increase with temperatures that might normally be encountered in the disk drive. The bulk viscosity for several PE lubricants is shown in Figure 38.12. Since the increase in viscosity with thickness below about 0.8 nm is so much more than the increase with temperature between 0 and 60◦ C, the operating temperature of disk drives should have no significant effect on lubricant spin-off from the disk by air shear. That is, excluding air shear force due to the head suspension assembly and the air bearing. 38.2.1.4 Vapor pressure The vapor pressure of PFPE lubricants should be low to prevent evaporation from the disk. One method to measure the vapor pressure was developed as follows: A model was derived to calculate the vapor pressure from the measured Zdol molecular weight distribution and evaporation rate. Molecular weight distributions were measured by gel permeation chromatography (GPC), as described in Karis et al. [23]. The vapor pressure of discrete molecular masses was calculated from the evaporation rate measured by isothermal thermogravimetric analysis (TGA) with a stagnant film diffusion model as in Karis and Nagaraj, [32]. Polymers such as Zdol differ from the low molecular weight synthetic hydrocarbon oils in that polymers comprise a variety of different molecular weights. Further considerations must be taken into account in modeling the evaporation of polymers, as described below: A numerical model was developed to simulate the evaporation of a polymer from an initial molecular weight distribution measured by GPC. The evaporation simulation is written in terms of mass flux and the discrete form of the molecular weight distribution wi (t) as: A + wi (t ) = wi (t) − fluxi (t)

t (38.12) m0 where A is the surface area of the evaporating lubricant, m0 is the initial mass of lubricant, and t is the time step

(a) 1.E+08 Ztetraol 1000

1.E+06 1.E+04

Ztetraol 2000

1.E+02

Zdol 4000

1.E+00 1.E–02 1.E–04 1.E–05

1.E–01

1.E+03

1.E+07

1.E+11

1.E+15

vaTo(rad/sec) (b) 1.E+08 Ztetraol 1000

1.E+06 Ztetraol 2000

1.E+04 1.E+02 Zdol 4000 1.E+00 1.E–02 1.E–05

1.E–01

1.E+03

1.E+07

1.E+11

1.E+15

vaTo(rad/sec)

FIGURE 38.8 Dielectric loss factor (a) and relative permittivity (b) master curves for the Ztetraol 1000, Ztetraol 2000, and Zdol 4000. The smooth curves are from the discrete relaxation time series fit to the frequency temperature shifted data. Reference temperature T0 = 50◦ C

TABLE 38.6 The Coefficients of the Debye Equation from the Dielectric Master Curves at Reference Temperature T0 = 50◦ C Lubricant Parameter ε (0) σ (S/m) εs,1 τ1 (sec) εs,2 τ2 (sec) εs,3 τ3 (sec) εs,4 τ4 (sec)

Zdol 4000

Ztetraol 2000

Ztetraol 1000

3,330 1E-11 3,000 500 300 50 30 5 2 1E-8

11,100 4E-8 10,000 50 1,000 5 100 0.5 4 1E-8

11,100,000 6E-7 10,000,000 8 1,000,000 0.8 100,000 0.06 5 1E-8

The high frequency ε∞ ≈ 1.7 from the index of refraction.


in the simulation. The mass flux of the ith molecular weight fraction Mi is given by stagnant film diffusion: Di Mi (38.13) Pi , fluxi (t) = δ RT where, Di is the vapor phase diffusion coefficient and δ is the diffusion length (calculated or measured with a liquid of known vapor pressure). The mass flux divided by the mass density yields the rate of film thickness change. The solution vapor pressure for the ith molecular fraction was approximated assuming an ideal solution according to Raoult’s law Pi = xi Pi0 where xi is the mole fraction of the ith molecular fraction. The Hirschfelder Approximation [33] is used for the vapor phase diffusion coefficient: Di = 1.858 × 10−4

1 1 + Mi Mgas

1/2

T 3/2 Pσi2

(38.14)

where Mgas is the molecular weight of the ambient atmosphere (air or nitrogen to suppress oxidation), P is the

Dispersive (mN/m)

(a) 25 20 15 10 Zdol

5 0 0.0

Z

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

4.0

4.5

Thickness (nm) (b) 25

Polar (mN/m)

20 15 10 5 1100 Da 0 0.0

0.5

1.0

1600 Da

1.5

2.0

2.5

3100 Da 3.0

3.5

Zdol thickness (nm)

FIGURE 38.9 The components of the surface energy measured on CHx overcoated thin film magnetic recording media with fractionated Zdol of narrow polydispersity index. (a) The dispersive component of the surface energy for PFPE Z and Zdol, and (b) the polar component of the surface energy for PFPE Zdol [30] i i )/2 is the colambient pressure, and σi = (σlube + σgas i lision diameter. For nitrogen, σgas = 0.315 nm. The vapor phase molecular diameter of the ith molecular weight component employed in estimating the binary mass diffusion i coefficient √ is approximately given by σlube = 2 × Rg,i ≈ 0.05 × Mi , where the molecular weight Mi is in Da, and the radius of gyration Rg,i is in nanometer. This expression was derived from the radius of gyration for Zdol measured in Freon [34]. The molecular diameters from this approximation for a range of ideal monodisperse Zdol molecular weights are listed in Table 38.7. By analogy to hydrocarbon oils, the collision integral for collision between molecules in the gas phase is a function of their binary Lennard–Jones interaction potential. The collision integral between Zdol molecules and nitrogen molecules was taken to be the same as that for collision between hydrocarbon molecules and nitrogen, = 1.2. The Clapeyron equation is employed to calculate the pure component vapor pressure:

i

i − Evap

Svap 0 Pi = P exp exp{−1} exp (38.15) R RT i i − S is the = Svap where the vaporization entropy Svap liq difference between the entropy in the vapor state and that


in the liquid state. The Zdol liquid entropy is assumed to be independent of molecular weight. It was determined along with the activation energy by comparison of the simulated evaporation with isothermal TGA evaporation weight loss data. The liquid entropy for Zdol, Sliq = 107 J/mol ◦ K, is within the range obtained for the synthetic hydrocarbon oils. The vapor phase translational entropy for oils is approximated with the Sackur–Tetrode equation:

3 (2π )3/2 (RT )5/2 5 i + ln(Mi ) + ln Svap,trans = R 2 2 hp3 N 4P (38.16) The vapor phase rotational entropy is given by [35]:     1 8π 3 IRT a/2  i  (38.17) = R 1 + ln Svap,rot πq  hp2 where a is the number of independent rotation axes, q is the degeneracy, and I is the moment of inertia. A useful i approximation for Svap,rot is given in Reference 32. The vaporization entropy also includes the vibrational entropy. The available vibrational states are comparable between liquid and vapor for these high molecular weight

(a) 80 60

50 ∆Evis

40 30

40 kJ/mol

Π(Mpa)

(a)

1100 Da 1600 Da 3100 Da

20

20 10

T∆Svis

0 0 –20

0

1

2

3

4

–10

5

0.1

Zdol thickness (nm) 5

1100 Da 1600 Da 3100 Da

4

1.0

100.0

(b) 1000

3

100

2 1 0

100.0

h/h`

Zdol thickness (nm)

(b)

1.0 10.0 Zdol thickness (nm)

10

0

0.2

0.4

0.6

0.8

1

P/P0

hydrocarbons, or polymeric oil, molecules, while the translational and rotational states are much more restricted in the liquid phase. Note that the ideal gas law is employed in deriving Equation (38.15) as follows: The vaporization enthalpy i i + (PV ) . The pressure volume expan Hvap = Evap i sion work term has been replaced by (PV )i = RT . The i , also depends on vaporization activation energy, Evap molecular weight because a longer molecule requires more energy to overcome the intermolecular interaction force between itself and its neighbors in the surrounding liquid. Polar end groups contribute a fixed contribution to the vaporization energy, which gives rise to the intercept in the plot of vaporization energy as a function of molecular weight. As one might expect, there seems to be a linear relation between the activation energy and molecui lar weight for Zdol [36], Evap ≈ Eint + Eslope × Mi . The slope, Eslope = 0.029 kJ/mol/Da, and intercept,

Eint = 50 kJ/mol, of the vaporization activation energy dependence on molecular weight for Zdol were determined by comparing of the simulated evaporation data with that measured by isothermal TGA. The thermodynamic properties, vapor phase diffusion coefficient, and vapor pressure for a range of ideal monodisperse Zdol molecular weights calculated as described above are listed in Table 38.8. The numerical values in Table 38.8 can be


10.0

Zdol thickness (nm)

FIGURE 38.11 (a) Flow-activation energy and the entropic component of the flow-activation free energy, and (b) dispersionenhanced viscosity as a function of film thickness. The filled symbols are from the spin-off measurements, and the dashed region of the curve was calculated with constant flow-activation entropy below 2.3 nm. Fractionated Zdol molecular weight 4500 Da, temperature 50◦ C [27] 0.5

0.4

h` (Pa–sec)

FIGURE 38.10 The disjoining pressure from the fractionated Zdol surface energies in Figure 38.9(a) and the corresponding Zdol adsorption isotherms at 60◦ C (b)

1 0.1

0.3 Ztetraol 2000 0.2 Zdol 4000 0.1 Z03 0.0 0

20

40

60

80

100

T (°C)

FIGURE 38.12 Bulk viscosity and flow-activation energy of several PFPE lubricants as a function of temperature

TABLE 38.7 The Gas Phase Molecular Diameter for Ideal Monodisperse Zdol Fractions Calculated from the Radius of Gyration in Theta Solvent √ d(nm) = 0.05 M(Da) Gas phase molecular diameter M (Da) 500 750 1000 1350 1500 2000 3000 4000 4300 5400

d (nm)

Degree of polymerization

Contour length (nm)

Equilibrium thickness (nm)

1.12 1.37 1.58 1.84 1.94 2.24 2.74 3.16 3.28 3.67

3.54 6.29 9.03 12.88 14.53 20.02 31.01 42.00 45.30 57.38

2.71 4.06 5.41 7.29 8.10 10.79 16.18 21.56 23.18 29.10

0.66 0.74 0.82 0.93 0.98 1.14 1.46 1.79 1.88 2.24

The degree of polymerization, the contour length measured along the chain from one end to the other, and the equilibrium thickness are also included. The equilibrium thickness is the maximum stable film thickness, or dewettting thickness, determined from the first zero crossing of the disjoining pressure with increasing film thickness.

used in Equation (38.15) to calculate the vapor pressure of perfectly monodispersed molecular weight fractions. Actual samples of commercial PFPE lubricant such as Zdol are polydisperse. Consequently, there is a wide range of partial pressures for a given sample, and the lowest molecular weight species in the distribution have the highest vapor pressure. In the case of Zdol 2000, since it is a copolymer of perfluoromethylene and perfluoroethylene oxide, the lowest molecular weight oligomers group together with similar molecular weights, hence similar vapor pressures. Figure 38.13(a) shows the molecular weight distribution of Zdol 2000 measured by GPC. The oscillations in the molecular weight distribution are visible up through 1000 Da. The mole fraction distribution is also shown, since it plays a key role in determining the actual vapor pressure. Qualitatively, the vapor pressure is increasing with decreasing molecular weight, but as the molecular weight becomes lower, there are fewer of these molecules in the solution, so Raoults’ law acts to partly offset the increase in vapor pressure, causing the vapor pressure to decrease in the limit of low molecular weight. Hence, the shape of the partial pressure distribution superimposed on the distribution in Figure 38.13(a), calculated at 50◦ C. The partial pressure distribution for Zdol is shown with units on an expanded scale in Figure 38.13(b). This shows the great detail provided by the GPC method, and also, the partial pressure peaks show the molecular weights that will evaporate with the highest rate, or distill out of the distribution. The total vapor pressure of polydisperse Zdol 2000 at 50◦ C is the sum of the partial pressures of each component, in this case, 0.2 Pa.


There are some other important properties of magnetic recording disk lubricants that will not be covered in this chapter, and several references on these are provided below. Lubricant spin-off and transfer to the slider is minimized by chemisorption to the overcoat [37]. Chemisorption [38], also referred to as bonding, is well described by Tyndall et al. [39]. Disk lubricants also serve to inhibit corrosion. The corrosion protection ability of Zol lubricants was related to surface energy by Tyndall et al. [39] The most successful disk lubricant additive has been cyclic phosphazines. However, cyclic phosphazine increases the lubricant mobility [40] and dewetting thickness [31]. More recently, an effort has been made to combine the desirable properties of both by incorporating cyclotrophosphazine end groups onto Zdol. This lubricant is referred to as A20H, and it is well described in a recent paper by Waltman et al. [4]. The A20H end group is shown in Table 38.1.

38.3 SPINDLE MOTOR LUBRICANTS There are ball bearing and fluid dynamic bearing spindle motors, see Reference 41 for a good overview. The arrangement of the spindle motor and types of spindle motor bearing are shown in Figure 38.14.

38.3.1 Ball Bearing Spindle Motor Bearing Grease Ball bearing spindle motor bearings are typically lubricated with an NLGI grade 2 lithium grease. The grease

TABLE 38.8 i , Binary Diffusion CoefVaporization Entropy Svap

(a)

i for Perficient Di , and Vapor Pressure Pvap fectly Monodispersed Zdol Fractions Evaporating into Nitrogen at Ambient Pressure (105 Pa) at Three Different Temperatures, Sliq = 107 J/mol ◦ K, i (kJ/mol) = 50 (kJ/mol) + 0.029 (kJ/mol) × Evap Mi (Da) i (J / mol ◦ K) Svap

Temperature 35◦ C 500 750 1000 1350 1500 2000 3000 4000 4300 5400 Temperature 45◦ C 500 750 1000 1350 1500 2000 3000 4000 4300 5400 Temperature 60◦ C 500 750 1000 1350 1500 2000 3000 4000 4300 5400

D (m2 /sec)

100

i Pvap (Pa)

1000 10,000 Molecular weight (Da)

100,000

(b) 0.0020 123 133 140 147 150 157 167 174 176 182

3.16E−06 2.27E−06 1.78E−06 1.38E−06 1.26E−06 9.79E−07 6.82E−07 5.25E−07 4.91E−07 3.98E−07

1.13E+00 2.26E−01 3.17E−02 1.48E−03 3.72E−04 3.07E−06 1.25E−10 3.61E−15 1.50E−16 1.16E−21

123 133 141 148 151 158 168 175 177 183

3.32E−06 2.38E−06 1.87E−06 1.44E−06 1.32E−06 1.02E−06 7.15E−07 5.51E−07 5.15E−07 4.18E−07

2.76E+00 6.01E−01 9.19E−02 4.87E−03 1.29E−03 1.27E−05 7.44E−10 3.05E−14 1.41E−15 1.61E−20

124 135 142 149 152 159 169 176 178 184

3.56E−06 2.55E−06 2.00E−06 1.55E−06 1.41E−06 1.10E−06 7.66E−07 5.90E−07 5.52E−07 4.48E−07

9.51E+00 2.34E+00 4.05E−01 2.55E−02 7.28E−03 9.19E−05 8.80E−09 5.91E−13 3.17E−14 6.26E−19

Partial pressure (Pa)

Mi (Da)

Weight fraction Mole fraction Partial pressure

0.0015

0.0010

0.0005

0.0000 0

Other parameters used are given in the text.

composition, referred to as SRL, is a lithium grease comprising approximately 10% Li 12-hydroxy stearate, 17% di 2-ethylhexyl sebacate, 70% pentaerythritol tetraesters, and the rest is a sulfonate rust inhibitor and an amine antioxidant. Lithium soap gel fibers thicken the grease [42]. The grease base oil viscosity at 40◦ C is 22 mPa-sec, and the worked penetration is 245. A great variety of greases could potentially be used in these bearings, but in practice, the


500

1000

1500

2000

Molecular weight (Da)

FIGURE 38.13 The molecular weight distribution, mole fraction distribution, and the calculated partial pressure distribution (a) and the partial pressure distribution on an expanded scale with units (b) for Zdol 2000 at 50◦ C

grease is limited by stringent requirements of low volatility, yield stress at temperature, low torque noise, and good thermal stability. 38.3.1.1 Yield stress at temperature Typical ball bearing spindle motor grease rheological properties and yield stress are described by Karis et al. [43]. For practical purposes, the yield stress is measured by gradually increasing the stress in a stress rheometer with a cone-plate fixture. The yield stress is detected when the cone begins to rotate. For example, the yield stress as a function of temperature for several grease candidates for use in ball bearing spindle motors is shown in Figure 38.15. There is a general trend of decrease with temperature, but all the greases maintain a measurable yield stress up through at least 80◦ C. The decrease of the yield stress with temperature is much less than that of the grease base oil, as will be shown later. Diluting the grease with additional base oil, or incorporation of contaminants in the grease, also affects the yield stress. Additional oil is often added to prelubricate the new bearing once it has been filled with grease. This is done to provide a lubrication film during initial startup of the new bearing, before the base oil from the gel thickener of the grease has had time to diffuse throughout the surfaces

Slider Suspension

(a)

Base grease +0.6% Zn (diacrylate) +12.5% Base oil +16% Prelube A +16% Prelube B +36% Prelube B + 0.03% Zn (diacrylate) + 0.01% Fe (octanoate)

Disk Spindle motor

800 700

Base casting

600

Ball bearing spindle motor Ferrofluid seal

Yield stress ( Pa)

(b)

Rotor

Ball Bearings

Stator

400 300 200

Fluid bearing spindle motor

(c)

500

Fluid

Rotor

bearings

Stator

100 0 0

FIGURE 38.14 The arrangement of the magnetic recording disks and head suspension assembly on the spindle motor (a), schematic ball bearing spindle motor (b), and schematic fluid bearing spindle motor (c) 800 F4 SRL L252 BQ 72-72 LY 716R

700

Yield stress (Pa)

600 500 400 300 200 100 0 0

20

40 60 Temperature (°C)

80

100

FIGURE 38.15 The yield stress of various candidate greases for ball bearing spindle motors as a function of temperature

of the balls and raceways. The prelube can either be the grease base oil itself, or specially formulated prelube oil. Results with two types of prelube are also described here. Prelube oil A is diester oil with a sulfonate rust inhibitor and a hindered phenol antioxidant. Prelube oil B is mostly


20

40 60 Temperature (°C)

80

100

FIGURE 38.16 The yield stress of base grease SRL showing the effect of additional base oil, prelube oils, and organometallic salt contamination on yield stress as a function of temperature

diester oil with several percent of a polyalphaolefin oil (PAO), a sulfonate rust inhibitor, and a Zn dialkyl dithiocarbamate antiwear additive. Grease may also be exposed to organometallic salts formed from various components within the bearing, bearing shields, or motor. Zn was incorporated as Zn(diacrylate), and Fe was incorporated as iron (III) 2-ethylhexanoate. The Zn(diacrylate) contaminant was intended to model products of bearing corrosion by the incomplete curing of a motor bearing adhesive [44]. Model grease containing prelube or contaminants was prepared in the laboratory by thoroughly mixing them in a custom-built lab scale grease mill. The grease mill capacity was about 10 g of grease. The mill comprised two 32 mm diameter disks perforated with 35 circular holes, each 460 µm in diameter, inside a stainless steel tube. The perforated disks were separated by a 3.8-mm wide cavity. Grease was forced back and forth through the holes in the perforated disks by the reciprocating action of two opposing pneumatic cylinders driving Teflon pistons against the perforated plate within the steel tube. Air pressure was alternately applied to the cylinders using a cam and follower arrangement driven by a variable speed gear motor. The yield stress of these model greases is shown in Figure 38.16. The yield stress was increased by Zn(diacrylate), while prelube oils decreased the yield stress. For comparison with the yield stress vs. temperature, the viscosity and density of the SRL grease base oil and

100.00 Base oil Prelube A Prelube B

1.0E+00 1.0E–01 1.0E–02

(b)

1000

Density (kg/m3)

1.0E–03 –40 –20

950

0

20 40 60 80 Temperature (°C)

100 120

Film thickness (nm)

Viscosity (Pa-sec)

(a) 1.0E+01

10.00

1.00 Base oil Prelube A Prelube B 0.10 0.001

0.010

0.100

1.000

Mean rolling speed (m/sec)

900

FIGURE 38.18 The film thickness as a function of rolling speed measured by ultrathin film interferometry (courtesy of H.A. Spikes, Imperial College, London)

850 800 –40 –20

0

20 40 60 80 Temperature (°C)

100 120

FIGURE 38.17 The viscosity (a) and density (b) of SRL grease base oil base grease and two prelube oils as a function of temperature

two prelube oils are shown as a function of temperature in Figure 38.17. The viscosity and density of the base oil are somewhat higher than that of the prelube oils. Blends between the base oil and the prelube oils A or B will have intermediate viscosities. The oil viscosities decrease much more than the yield stress with temperature. This implies that most of the yield stress change with temperature, Figure 38.16, is due to the gel network of the thickener. The reduction in yield stress on blending grease with prelube oil is probably due to dilution of a transient network in the gel thickener. 38.3.1.2 Hydrodynamic film thickness The hydrodynamic film thickness of the oil provided by the grease must be sufficient to clear the asperities on the balls and race during operation at the specified load and velocity. The hydrodynamic film thickness is given by: h = k(Uη0 )0.67 (αp )0.53

(38.18)

where h is the film thickness, k is a materials and geometry parameter, U is the entrainment velocity, η0 is the viscosity at atmospheric pressure, and αp is the pressure viscosity coefficient [45]. The film thickness between a steel ball and a plate by ultrathin film interferometry [46] was measured by Prof. H.A. Spikes, and his students, at Imperial College in London. The film thickness as a function of sliding speed for the grease base oil, and the prelube oils A and B,


is shown in Figure 38.18. There is some variation in the power law slope between the oils, which slightly varies from the coefficients used in Equation (38.18). By comparison of a fluid with a known pressure–viscosity coefficient, they estimated the pressure–viscosity coefficients over a limited speed range between 0.1 and 1 m/sec to be approximately 15 l/GPa for the base oil, 12 l/GPa for prelube oil A, and 10.5 l/GPa for prelube oil B. The difference between prelube oils A and B is probably due to the minor fraction of PAO in prelube oil B. 38.3.1.3 Grease electrochemistry Some types of high performance disk drive spindle motors incorporate ball bearings with silicon nitride ceramic balls for higher stiffness and lower vibration. It is critical that the bearings and grease provide smooth rotation so as not to excite resonances of the disk pack, Figure 38.14(a). Electrostatic potential generated by bearings can induce a small current flow through, with a return path through the ferrofluid seal, Figure 38.14(b). In order to investigate the effect of electrochemistry, grease containing various types of contaminants was sandwiched between two steel electrode plates. The plates were 25-mm diameter mirror polished 304 stainless steel electrode plates on 160-µm thick filter paper. The plates were subjected to 25 V to simulate the passage of electrical current through the grease in the bearing. After several hundred hours, the plate were separated and examined for degraded grease as deposits on the plates. Film deposits were characterized by optical microscopy, Fourier Transform Infrared (FTIR) spectroscopy in reflection, and x-ray photoelectron spectroscopy (XPS). Figure 38.19 shows the current through the electrode plates plotted as a function of the voltage applied across the

SRL grease alone 16% Prelube A 16% Prelube B 12.5% Base oil

300 ppm Zn 16% Prelube A+300 pm Zn 16% Prelube B+300 ppm Zn 12.5% Base oil+300 ppm Zn

10,000

Current (nA)

1000

Sample

100

10

1 0.1

TABLE 38.9 Grease Electrochemical Cell Test Results for Grease on 160 µm Thick Filter Paper between 1 in. Diameter Electrode Plates

1

10

100

Voltage

FIGURE 38.19 Initial current–voltage plot for SRL grease alone, and SRL grease with the indicated additives and contaminants measured in the electrochemical cells

grease film with fresh grease between the plates. The conductance of the ferrofluid seal in the motor was about 77 nS (13 M), so that the current through the bearing is typically 30 to 80 nA. In steady state, the electrochemical cells were operated at 25 V, or between 100 and 3000 nA, depending on the type of grease contamination. Higher voltage was employed in the electrochemical cells to increase the rate of any electrochemical reactions that might take place. The initial conductance of the electrochemical cells, calculated from the linear region of the current–voltage plot, is listed in the second column of Table 38.9. The lowest conductance was obtained with the SRL grease alone, and SRL grease combined only with an additional 12.5% more of its own base oil. The highest conductances were found with the grease containing 16% prelube oil B and 300 ppm Zn, and grease containing 16% prelube oil B. The grease conductance gradually varied with time during voltage application, as shown for several greases with and without contaminants in Figure 38.20. Pure grease, with no diluents or contaminants, maintained the lowest conductance. After several hundred hours, the plates were separated and washed with chloroform by squirting from a pipette. When present, films were observed on the negative electrode plate. Although there was sometimes minor film formation or slight pitting on the positive plate, there was too little to quantify. Micrographs of the film deposits on several of the negative electrode plates are shown in Figure 38.21. These show the fibrous appearance. The film


SRL Grease alone SRL grease +36% Prelube A +300 ppm Zn +100 ppm Fe SRL grease +300 ppm Zn, SRL grease +16% Prelube A SRL grease +16% Prelube A +300 ppm Zn SRL grease +16% Prelube B SRL grease +16% Prelube B +300 ppm Zn SRL grease +12.5% SRL base oil SRL grease +12.5% SRL base oil +300 ppm Zn

Initial conductance (ns)

Time (h)

Film deposit

4 28

960 336

light medium

7

336

heavy

8

576

heavy

20

336

light

52

576

light

93

336

heavy

9

336

light

16

336

heavy

The initial conductance was calculated from the linear region of the current–voltage data measured between 1 and 25 V (Figure 38.19). Prelube is defined in the text. The right-hand column gives the appearance of the film deposit on the negative electrode plate after application of 25 V for the amount of time listed in the third column.

deposits were highly viscous. Film deposits were qualitatively ranked in terms of their severity, which is referred to as light, medium, and heavy, after the indicated electrolysis time, in Table 38.9. The lightest deposits were observed with the virgin grease, and the grease diluted with its own base oil. The heaviest deposit coincided with the highest conductance. However, even though they had nearly the lowest conductance, grease contaminated by 300 ppm of Zn as acrylate, or with 16% of the prelube oil A, also formed heavy deposits. Reflection FTIR was performed on the residue on the plates after each test. Typical FTIR spectra are shown in Figure 38.22. The IR peaks were assigned to chemical groups according to the peak assignments in Table 38.10. The peak assignments, in conjunction with XPS measurements on the residue in Table 38.11 clearly show electrochemical oxidation of the grease. The ratio of carbonyl groups has clearly increased following the

SRL grease alone 36% Prelube A + 300 ppm Zn + 100ppm Fe 300 ppm Zn 16% Prelube A 16% Prelube B

Conductance (nS)

100

10

electrochemistry. For the pure thickener, the ratio of carbonyl to Li is 1.07, while aged grease and electrochemically oxidized grease have increased carbonyl due to oxidation. For black grease from a failed bearing, residue in a noisy bearing and a pin on disk wear test track also show increased carbonyl relative to the original thickener. In summary, for the longest lifetime and best performance under all conditions, lithium grease should be kept free of metallic impurities and diluents. When electrochemical oxidation does occur, it forms a residue from the soap thickener on the raceway.

38.3.2 Ball Bearing Spindle Motor Ferrofluid Seal

1 0

200

400 600 Time (h)

800

1000

FIGURE 38.20 Conductance-time plot for SRL grease alone, and SRL grease with additives and contaminants measured in the electrochemical cells

Composition

As mentioned above, the return path from the rotor to the stator for charge generated by the ball bearings is through the ferrofluid seal, Figure 38.14(b). The ferrofluid is held in place by magnets in the seal housing, and the primary function of the ferrofluid seal is to prevent airflow through the motor into the disk drive enclosure. The typical ferrofluid is a suspension of 10 to 30 wt% subdomain magnetite particles 10 nm in diameter in a trimellitic/trimethylolpropane

10 × Lens

20 × Lens

(a)

(b)

100 µm scale bar

FIGURE 38.21 Optical micrographs showing the film deposits on the negative electrode plate following electrochemical oxidation of contaminated grease at two different levels of magnification. The residue was insoluble in chloroform and isopropanol, while the initial grease was easily removed from the plates by rinsing with chloroform. SRL grease +300 ppm Zn for 336 h (a), and SRL grease +16% Prelube A for 576 h (b)


(a) Absorbance

1581

2921

4000

3500

1736

3000

2500

2000

1451

1500

1000

500

1000

500

1000

500

Wave numbers (cm–1)

(b) Absorbance

1587 2922 1456 1712

4000

3500

3000

2500

2000

1500


(c) Absorbance

1587 2922

1718

4000

3500

3000

2500

2000

1456

1500


FIGURE 38.22 Reflection FTIR spectra of residue deposited on the negative electrode plates from grease containing various contaminants (a) Prelube A, Zn, and Fe, (b) Zn, and (c) Prelube A. Oil was removed by washing with solvent before measurement

TABLE 38.10 FTIR Peak Assignments Absorbance Broad dimer hydrogen bonded carbonyl O–H stretch in 12-hydroxy stearic acid Hydrogen bonded O–H stretch in alcohol Asymmetrical methylene C–H stretch Aliphatic aldehyde or ester C=O stretch Aliphatic methyl ketone C=O stretch Aliphatic internal ketone C=O stretch carboxylic acid dimer C=O stretch in 12-hydroxy stearic acid C–O–H in-plane bend in 2-hydroxy stearic acid Carboxylate anion, asymmetrical stretch Carboxylate anion, symmetrical stretch Ester C–C(=O)–O in base oil

Wavenumber (cm−1 ) 3500–2500 3500–3200 2928–2917 1740 1730 1725 1695 1470 1589–1581 1456–1442 1166

The carboxylate anion is formed with Li or Zn and 12-hydroxy stearic acid. The ratio (C=O)salt /C(–H)2 was measured using the carboxylate anion, asymmetrical stretching, and the asymmetrical methylene C–H stretching.


ester oil with 10 to 20 wt% dispersing agent and up to 10 wt% antioxidant. Ferrofluid is a mature technology, and these fluids are highly stable. The most recent effort to modify the properties of the ferrofluid was intended to increase the electrical conductivity so as to reduce the electrical potential between the rotor and stator of the spindle motor. The development of conductivity additives for ferrofluids is described below. Additives to increase the conductivity of the carrier oil were investigated. A number of conductivity enhancing compounds were incorporated in a model carrier oil, trioctyltrimellitate (TOTM), and the conductivity was measured by DEA, as described in Section 38.2.1.2. The results of the initial screening are given in Table 38.12. Most of the additives reduced the conductivity. This probably indicates that the additives were associating with impurities, which were the primary charge carriers in the oil. The most promising initial results were obtained with a micellar solution of succinimide and dodecylbenzenesulfonic acid [47]. Variations of the organic acid, and the succinimide/acid ratio were explored to optimize the conductivity of the TOTM carrier oil. The results are shown in Table 38.13. The mixtures of succinimide and acid provided the highest conductivity to the oil. The most promising conductivity additives based on the tests in the model oil are shown in Figure 38.23. Even the best combination of conductivity additives TOTM still had lower conductivity than any of the ferrofluids. Dielectric spectroscopy was performed to determine the conductivity mechanism of the ferrofluid. The ferrofluid has three dielectric relaxation times, 260, 43, and 6.3 msec. These relaxation modes probably comprise the phoretic motion of the magnetite particles, phoretic motion of ions, and electronic hopping, respectively. The activation energy for conductivity is close to the viscous flow-activation energy, so the conductivity of the ferrofluid is mostly due to the phoretic motion of the magnetite particles. The relaxation times were unchanged by the conductivity additives. Since it became apparent that conventional additives used to enhance the conductivity of the carrier oil are of no benefit, or reduce the conductivity of the ferrofluid, a different approach was needed. Ferrofluid is significantly more conductive than the carrier oil, due to the presence of the magnetic particles. The conductivity of a ferrofluid can only be enhanced by improving the efficiency of charge transfer between the suspended magnetite particles. This may be done by incorporating particles coated with conducting polymer, conducting polymer oligomers, or nano-wires in the form of multiwall carbon nanotubes. Conducting polymer coated carbon black particles (Eeonomer, Eeonyx Corp., 750 Belmont Way, Pinole, CA 94564, USA [48]) and multiwall nanotubes (BU200, Bucky USA, 9402 Alberene Dr., Houston,

TABLE 38.11 The Ratio of Carboxylic Acid to Methylene from FTIR, the Ratio of Total Carbonyl Carbon to Methylene Carbon and to Li, and Atomic per cent of Li and Zn from XPS, in Model Compounds, Electrochemically Deposited Films, Inner Race Deposits, and Black Grease from Failed Motor Bearings FTIR Film

XPS

hydrogen bonded OH

(C=O)salt /C(–H)2

(C=O)total /C(–H)2

(C=O)total /Li

Li (at %)

Zn (at %)

Yes

0.067 (exact)

0.067

1.07

4.3

0.09

Yes —

0.035 —

0.079 0.063

1.5 —

3.6 5,000 >15,380 “Relatively Harmless” >15,700 “Relatively Harmless”

— >3,0 “Practically non-toxic” n/a

a N. Irving Sax, “Dangerous Properties of Industrial Materials.”

Sludge,mg TAN change

PAO, 204°C

Vis. change, %

Mineral oil,190°C

0

2

4

6

8

10

FIGURE 39.1 Oxidation–corrosion stability (24 h). Mineral oil vs. polyalphaolefin base food grade compressor lubricants (ISO 46) (By federal Test Method 5308)

1.4 billion Muslims worldwide, such laws have wide influence in the food-processing industry [22]. Under both religions strict rules cover all aspects of food processing. The following paragraphs list only the portions of those dietary laws applicable to lubricants. In both religions, the lubricant manufacturing plant is subject to supervision of the applicable organization. The Jewish dietary laws are generally termed “Kosher for Pareve” or simply Kosher. Approval under Kosher law is done by one of several rabbinic orders. In the United States, the Orthodox Union and the Organized Kashrus Laboratories, both in New York, are two major approval organizations known to this author to be active in the approval of food-grade lubricants. Essentially, Kosher laws prohibit the use of pork, pork by-products, and control or exclude various other materials and processes. This limitation precludes the use of lard oils and derivatives in lubricants intended for use in Kosher food processing. Kosher laws also prohibit contamination of meats with dairy and eggs. All equipment must be properly cleaned, “kosherized” and left idle for 24 h before and after making Kosher products. The Muslim faiths impose “Halal” laws (an Arabic term meaning lawful or permitted for Muslims) on their food products. In the Unitde States, the Islamic Food and Nutrition Council of America (Chicago) issues Halal Certificates. While differing in many aspects from Kosher, the practical implications on lubricant formulation and


Sludge, mg TAN change Vis. change,%

PAO

Mineral oil

0

1

2

3

4

FIGURE 39.2 Oxidation stability comparison 160◦ C (24 h) (By Federal Test Method 5308)

production of Halal are similar. Halal excludes the use of alcohol in its products, a potential limitation for the manufacturing of some additives.

39.7 OPPORTUNITIES FOR SYNTHETIC-BASED FOOD-GRADE LUBRICANTS The toxicological properties of various base fluids (meeting the requirements as given in Section 39.2) available for the formulation of synthetic-based food-grade lubricants are superior to technical mineral oils, as illustrated in Table 39.2. Synthetic-based food grade lubricants offer improved oxidative stability as well as improved operating temperature properties as shown in Figures 39.1–39.3. Synthetic-based food-grade lubricants can be formulated to

Pour point,°C

TABLE 39.4 Typical Physical Properties of Fully Formulated Food-Grade (H1) ISO 320 Gear Lubricants Property

PAO PAG M/O

–40

–30

–20

–10

0

FIGURE 39.3 Comparison of low temperature properties ISO 320 gear lubricants, food grade

TABLE 39.3 Typical Physical Properties of Food-Grade (H1) ISO 46 Hydraulic Fluids Property Viscosity 40◦ C, cSt

Viscosity 100◦ C, cSt

Viscosity index Flash point, ◦ C Pour point, ◦ C Pump Test, 104◦ C

Mineral oil

PAO

PAG

47.8 6.67 85 204 −20 Pass

42.3 7.21 133 254 −50 Pass

46 6.8 102 185 −15 Pass

Source: ANDEROL Inc. published literature

exceed the performance capabilities of comparable mineral oil-based lubricants. As with other synthetic lubricants, food-grade synthetics offer extended maintenance intervals, high and wide temperature application, and operating cost reduction. To date, synthetic-based lubricants and greases tend to be used as “problem solvers” in food-processing applications; they remain a relatively minor player in the overall lubrication of equipment employed in the food and beverage industry. However, as original equipment manufacturers (OEM) and food processors struggle to meet the myriad regulatory and technical challenges, synthetic lubricants are likely to grow to satisfy critical applications in the food industry. Such areas are likely to include: baking chains in ovens; high temperature bearings and gears, including worm gears; conveyor systems that a wide temperature operating envelop; high performance hydraulic systems; and, sealed for life components.

Viscosity, 40◦ C, cSt Viscosity, 100◦ C, cSt Viscosity index Flash point, ◦ C Pour point, ◦ C FZG Gear test, pass

Mineral oil

PAO

PAG

327 24.8 98 220 −12 12

295 28 127 230 −35 12

285 40.7 198 221 −26 12

3. Third-party certifiers such as NSF International have replaced USDA in order to provide industry with needed documentation regarding the toxicity of proprietary substances for incidental contact of food. 4. Numerous international efforts are underway that will affect the food-grade lubricant of the future: • Efforts in Germany and the United States to develop

an ISO standard governing food-grade lubricants. • Efforts by the World Health Organization, Pan

American Health Organization, and Food and Agriculture Organization of the United Nations to develop and implement national and international food safety systems based on HACCP. 5. Food supply is undergoing rapid globalization. With that shift comes a myriad of national and international regulations and customs. 6. As the food supply continues to globalize, religious laws will have an even greater impact on the lubricants markets. 7. Synthetic-based lubricants offer performance advantage over conventional mineral oil-based products: • Additive systems are limited in both constituents and

dosage rates. • The inherent properties of synthetic base stocks,

such as superior oxidative stability, offer the lubricant formulator a unique opportunity to differentiate performance. The market for food products is operating under an increasingly global business environment. The regulatory and quasi-regulatory surroundings under which food-grade lubricants are controlled are changing rapidly.

39.8 CONCLUSIONS 1. The USDA has abandoned its former command and control programs in favor of HACCP. 2. Food-grade lubricants are no longer “pre-authorized” for incidental food contact.


REFERENCES 1. 2002 Economic Census: Table 1, Advance Summary Statistics for the United States, 2002 NAICS Basis. http://www.census.gov/econ/census02/advance/ table1.htm.

2. Food Safety and Inspection Service, U.S. Department of Agriculture, Washington, D.C. 20250-3700: “Recall Information Center,” http://www.fsis.usda.gov/OA/recalls/. 3. “Comprehensive Intercountry Food Surveillance. A Guarantee of Quality and Hygiene for Imports,” By Dr. Catherine E. Woteki, Under Secretary for Food Safety, USDA (RIMSA 11/18, 9 April, 1999). 4. “Food Safety — Report by the Secretariat”: 108th Session of the Executive Board of the World Health Organization. EB108/7 dated 27 April, 2001. 5. “Health Ministers Seek Improved Food Protection Programs,” Press Release by the Pan American Health Organization, dated 27 September, 2000. 6. “Free Trade Area of the Americas: What are the Benefits to U.S. Agriculture?” Economic Research Service/USDA, Agricultural Outlook, April, 2000. 7. USDA, FSIS Miscellaneous Publication 1419 (updated yearly until 1998), “List of Proprietary Substances and Nonfood Compounds.” 8. Code of Federal Regulations, Vol. 21, Parts 170 to 199, revised annually, U.S. Government Printing Office, Washington, D.C. or on the WWW at //frwebgate.access.gpo.gov. 9. Code of Federal Regulations, Vol. 21, Parts 170 to 199, revised annually, U.S. Government Printing Office, Washington, D.C. or on the WWW at //frwebgate.access.gpo.gov. 10. A Private correspondence with USP. In it, USP traces the monogram of petrolatum, mineral oil, white mineral oil, and other items. 6 April, 2001. 11. Morawek, R., Tietze, P.G., and Rhodes, R.K., “Food Grade Lubricants and Their Applications.” Presented to American Society of Lubrication Engineers (now STLE), 33rd Annual Meeting in Dearborn, MI, 17–20 April, 1978. 12. Morawek, R., Tietze, P.G., and Rhodes, R.K., “Food Grade Lubricants and Their Applications.” Presented to American


13. 14.

15.

16.

17.

18.

19.

20.

21.

22.

Society of Lubrication Engineers (now STLE), 33rd Annual Meeting in Dearborn, MI, 17–20 April, 1978. A Private Correspondence Between Dow Corning (D. Como and J. McCourt) and the author, April 23, 2001. Galli, R.D., Cupples, B.L., and Rutherford, R.E., “A New Synthetic Food Grade White Oil.” Presented at the 36th Annual Meeting of the Society of Tribologists and Lubrication Engineers (STLE) in Pittsburgh, PA, 11–14 May, 1981. USDA, Food Safety and Quality Service, Agriculture Handbook No. 562, September 1979. “Guidelines for Obtaining Authorization of Compounds to be used in Meat and Poultry Plants.” USDA, Food Safety and Quality Service, Agriculture Handbook No. 562, September 1979. “Guidelines for Obtaining Authorization of Compounds to be used in Meat and Poultry Plants.” Raab, M.J., “Assuring Food Safety in Food Processing: The Future Regulatory Environment for Food-Grade Lubricants.” Presented at the 55th Annual Meeting of STLE on 8 May, 2000. NSF Registration Program for Proprietary Substances and Nonfood Compounds used in USDA Meat and Poultry Facilities. Version 1.0, January 24, 2000. Elimination of Prior Approval for Proprietary Substances and Nonfood Compounds (Docket 91-007N), Fed. Regis., 63, (February 13, 1998), 7319–7322. XII Inter-American Meeting, at the Ministerial Level, on Health and Agriculture (Provisional Agenda Item 4.1 — RIMSA12/4 [eng.]). Understanding The Codex Alimentarius, Food And Agriculture Organization of the United Nations, World Health Organization, http://www.fao.org/. The Islamic Food and Nutrition Council of America, “Kosher vs. Halal — A Simplified Comparison for the Food Professionals,” (undated).

40

Critical Cleaning of Advanced Lubricants from Surfaces Ronald L. Shubkin and Barbara F. Kanegsberg CONTENTS 40.1

40.2

40.3

Introduction 40.1.1 Historical Perspective 40.1.2 Why is Cleaning Necessary? Overview of Cleaning Agents 40.2.1 Organic Solvents 40.2.1.1 Hydrocarbons and Oxygenated Hydrocarbons 40.2.1.2 Classic Chlorinated Solvents 40.2.1.3 trans-1,2-Dichloroethylene (Trans) 40.2.1.4 Chlorofluorocarbon Solvents (CFCs) 40.2.1.5 Hydrochlorofluorocarbons (HCFCs) 40.2.1.6 normal-Propyl Bromide (nPB) 40.2.1.7 Perfluorinated Compounds (PFCs) 40.2.1.8 Hydrofluoroethers (HFEs) and Hydrofluorocarbons (HFCs) 40.2.1.9 n-Methylpyrollidone (NMP) 40.2.1.10 Biobased Cleaning Agents 40.2.1.11 Volatile Methyl Siloxanes (VMSs) 40.2.1.12 Solvent Blends 40.2.2 Aqueous and Aqueous Blends 40.2.2.1 Cleaning Action 40.2.2.2 Temperature 40.2.2.3 Time of Exposure 40.2.2.4 Rinsing 40.2.2.5 Drying 40.2.2.6 Soils 40.2.2.7 Materials of Construction and Product Configuration 40.2.2.8 Holistic Process Design 40.2.2.9 Additives to Aqueous Cleaners 40.2.2.10 What is an Aqueous Cleaning Agent? 40.2.2.11 On-Board Cleaning Agent Recovery and Bioremediation 40.2.2.12 Process Change to Aqueous 40.2.3 Semi-Aqueous Systems 40.2.4 Co-Solvent Systems 40.2.5 “Nonchemical” or Limited Chemical Processes Physical and Chemical Properties of Cleaning Agents 40.3.1 Solubility 40.3.1.1 Kauri–Butanol Number 40.3.1.2 Hildebrand Parameters 40.3.1.3 Hansen Parameters 40.3.1.4 TEAS Diagram 40.3.2 Wetting Index 40.3.3 Boiling Point


40.3.4 40.3.5 40.3.6 40.3.7

Flammability Hydrolytic Stability Specific Gravity Compatibility 40.3.7.1 Metals 40.3.7.2 Plastics Compatibility 40.4 Cleaning Processes 40.4.1 Vapor Degreasing 40.4.2 Aqueous Cleaning Lines 40.4.3 Ultrasonics 40.4.4 Hand Wipes 40.4.5 Aerosols 40.4.6 Sprays 40.4.7 Specialized Cleaning Systems 40.5 Comparison of Cleaning Efficiency for Selected Solvents 40.6 Benefiting from Case Studies 40.7 Environmental Considerations and Regulations 40.7.1 SNAP — Significant New Alternatives Policy 40.7.2 VOC — Volatile Organic Compound 40.7.3 ODP — Ozone Depleting Potential 40.7.4 GWP — Global Warming Potential 40.7.5 AL — Atmospheric Lifetimes 40.7.6 SARA — Superfund Amendments and Reauthorization Act 40.7.7 HAP — Hazardous Air Pollutant 40.7.8 NESHAP — National Emission Standard for HAP 40.7.9 RCRA — Resource Conservation Recovery Act 40.8 Conclusion References

40.1 INTRODUCTION Several recent volumes have been devoted to the use of, and advances in, synthetic and mineral oil based lubricants [1,2]. In addition, a comprehensive treatment of critical cleaning has recently been published [3]. This chapter, however, is the first time that the interdependent relationship of these two important areas of practical technology has been addressed as an independent topic.

40.1.1 Historical Perspective The utilization of fluids to perform functional tasks dates to antiquity. The earliest of these applications involved the use of natural oils for lubrication. Art decorations on the inner wall of the Egyptian tomb of Tehuti-Hetep (ca. 1650 b.c.) indicate that olive oil on wooden planks was used to facilitate the sliding of large stones, statues, and building materials. Egyptian chariots dating to 1400 b.c. have been uncovered that have small amounts of greasy materials, presumed to be beef or mutton tallow, on the axles. A millennium later, Herodotus (484 to 424 b.c.) described methods of producing bitumen and


lighter oils from petroleum. It was not until the Industrial Revolution, however, that serious demands began to develop for stable fluids that could maintain their physical characteristics and chemical integrity over a wide range of temperatures and operating conditions. Charles Friedel and James Mason Crafts produced the first synthetic hydrocarbon oils in 1877, and an unsuccessful synthetic hydrocarbon was briefly commercialized in 1929. However, it was the German disaster at the Battle of Stalingrad in 1942 that showed the world that conventional petroleumbased products were inadequate to lubricate the modern machines of war in the sub-zero temperatures of the Russian winter. Since the mid-twentieth century, there has been a proliferation of advanced fluids. Some of these are highly refined mineral oils or other natural products, but many are synthetic fluids. Each of these fluids has been devised to meet rigorous performance criteria for specialized applications, including lubrication, heat transfer, power transmission, electrical insulation, corrosion inhibition, and others. As more and more chemically diverse functional fluids were introduced, a new problem began to surface. How do you remove these fluids in a rigorous fashion?

40.1.2 Why is Cleaning Necessary? Critical cleaning of parts contaminated with lubricants or other functional fluids is an essential part of many technologically advanced processes. There are several aspects of cleaning in relation to lubricants. All involve a consideration of both the individual process step and overall impact on the product. One aspect is appropriate surface preparation prior to the application of lubricants. Critical cleaning may be required to prepare surfaces for the next step in fabrication or for the application of a paint or coating. Preexisting contaminants on a surface have the potential to modify the lubricant and compromise immediate and/or long-term performance. Soil has been defined as matter out of place [4]. A lubricant or other metalworking fluid may perform a critical function at one stage of the build process, but it may have to be removed at subsequent steps. One issue is the question of exactly what constitutes a soil. Certainly, if surface material interferes with a subsequent operation, it would be considered soil. While critical cleaning or precision cleaning is often thought of as the removal of all extraneous materials from the surface, this is not necessarily the case. For example, in certain thermal spray and PVD applications, it is necessary to remove all organic lubricants. However, a visible fingerprint, if it is composed of inorganic material, is readily removed by aluminum oxide blast and does not interfere with the engineered coating [5]. Complex, multistep assembly processes are often conducted at multiple sites; sometimes job-shops or subvendors are involved. An assortment of oils, lubricants, and other metalworking fluids, as well as associated cleaning steps (or lack of cleaning steps), are permitted. Each option may have been evaluated in terms of appropriate physical, chemical, and overall performance properties. However, the fit in the overall process may not have been considered. For example, a series of metalworking fluids may be used — some classic, others synthetic, still others semi-synthetic. Each may be carefully formulated and subject to rigorous quality control requirements; each may meet exacting performance specifications. However, after a series of eight to ten assembly operations with as many metalworking fluids, some accompanied by heating, other by long-term storage, a complex, ill-defined residue is deposited. If the residue has been found to interfere with a subsequent processing operation, the application of a final coating or the end-use application, multiple and often complex cleaning steps are added. The argument could be made that a higher-quality surface with less total cleaning time and effort could be obtained were cleaning conducted at several steps in the fabrication process. The problem of contamination and soil residue is exacerbated by process changes. For example, an assembly operation may include specification-required solvent


cleaning based on traditional usage of a petroleum-based lubricant. Other lubricants used in the same process might be more effectively removed with a different solvent or with water-based cleaning chemistries. Studies may have to be performed to qualify a replacement of the petroleumbased lubricant with a synthetic product. In such cases, it is not unknown to discover that the solvent-based cleaning is left in place. With a bit of planning in such cases cleaning steps could be reduced. Eliminating unnecessary cleaning is important. With cleaning, more is not necessarily better. Aside from increased time, labor, and capital costs, cleaning has the potential to do damage to the product. Rigorous cleaning may also be needed prior to a repair operation, especially if the contaminating lubricant is flammable or can be degraded to a baked on residue during the repair procedure. In fact, burnt-on, caramelized lubricant is a major issue in recovering or restoring parts. Lubricant stabilizers are helpful, but may not prevent all cases of field-related aging. Where additional soils are introduced during use, the problem of removal becomes even more complex. Sometimes a part is coated with a lubricant, grease, or wax to protect it during manufacture, shipping, or storage, but the coating must be removed before the part is used in the final application. Coating of optical lenses is an example of this practice. Cutting oils and other machine oils often contaminate parts during manufacture and must be removed prior to final use. Electronic assemblies and advanced aerospace equipment may be rendered inoperable by mere traces of contamination, and a final cleaning operation is critical to their successful operation.

40.2 OVERVIEW OF CLEANING AGENTS It is fallacious (and expensive) to assume that any arbitrarily selected cleaning agent will be effective for removing a particular lubricant. Both the cleaning agent and the cleaning process require careful, thoughtful selection. Choosing the appropriate cleaning process is an exacting, often traumatic experience. One could write a book about cleaning [3] and still not cover the entire topic. Some ascribe to the theory of first selecting the cleaning equipment and then choosing a cleaning agent that will work in the selected equipment. There is some logic to this approach. Such factors as temperature, cleaning action (spray in air, spray under immersion, agitation, rotation, and ultrasonics), rinsing, water preparation, recycling/waste management, drying, sizing, safety features, environmental controls, and throughput are all equipment-dependent. Others prefer to test various cleaning chemistries and then design cleaning equipment around the optimal chemistry. There is also some logic to this approach. The solvency properties must match the soils in question; the cleaning agent must not damage the part

or leave a significant residues. Physical properties must be such that adequate wetting is achieved to reach tightly spaced components and blind holes. To achieve optimal cleaning, both the cleaning agent and cleaning action must be considered. The cleaning agent and cleaning process have to be developed in parallel. As chemists, we will take the liberty to begin with an overview of cleaning chemistries. Where appropriate, we will also allude to the cleaning process. Some cleaning agents have been in use for a very long time, but a host of new cleaning agents and cleaning agent blends have been introduced in recent years to meet the challenges presented by today’s industrial cleaning requirements. Requirements can be broadly thought of as efficacy of cleaning and drying, compatibility with materials of construction, contamination issues, costs (including both cleaning agent cost and cleaning process cost), employee exposure considerations, and environmental/regulatory issues. The following is meant to provide a general, nonexhaustive overview of cleaning agents and cleaning agent blends, some new, others recently developed. In general, reference is made to aqueous, solvent, and so-called nonchemical or specialty approaches. While water is a solvent in the global sense, most industrial and governmental people, when discussing cleaning, use the term solvent to mean organic solvents and the term aqueous to refer to those systems based primarily on water (“primarily” being a somewhat loosely defined concept). Both aqueous and solvent-based chemistries (as well as advanced or “nonchemical” cleaning) offer advantages in specified niche applications. However, none are universally applicable. The question arises as to whether a water-based system or an organic chemical should be used. One might imagine that the answer would be based on technical considerations. Just as there are people oriented to cleaning equipment vs. cleaning agents, so are there hydrophilic vs. hydrophobic chemists, engineers, and employees of environmental regulatory agencies. In recent years, there has been intense polarization based less on technical considerations than on the judgment of environmental regulatory agencies. Those who actually need to prepare a highquality surface understand that selection of the cleaning agent involves technical, cost, and safety considerations as well as environmental concerns. Most, if not all, cleaning agents and cleaning processes can be managed safely, and with respect for the environment.

40.2.1 Organic Solvents 40.2.1.1 Hydrocarbons and oxygenated hydrocarbons Hydrocarbons and oxygenated hydrocarbons became readily available with the advent of petroleum refining in the mid-nineteenth century. They are very effective for the


removal of hydrocarbon-based mineral oils, and they have the obvious historical advantage of low cost. The use of hydrocarbons and oxygenated hydrocarbons as cleaning solvents is very wide spread, but there are associated safety and environmental issues. Many are flammable and therefore dangerous when used in cleaning operations that are carried out in equipment that is not specifically designed for handling flammable liquids and vapors. Examples of hydrocarbons in use as solvents today include heptane, toluene, and mineral spirits. Examples of common oxygenated hydrocarbons include acetone, methyl ethyl ketone (MEK), isopropyl alcohol, and diethyl ether. Most hydrocarbons and oxygenated hydrocarbons are also listed as Volatile Organic Compounds (VOCs). The use of VOCs may be sharply restricted in areas of poor air quality. Some hydrocarbons also have toxicological problems. Benzene, which was once widely used, has been associated with certain cancers. Acetone deserves special consideration in that it is environmentally favored (and, in many cases effective) but requires careful management because it is flammable. Acetone has recently come into wider use as a cleaning solvent because it has been exempted at the Federal level as a VOC. The use of acetone is therefore favored or at least less regulated in many areas of poor air quality. This situation has led to the unfortunate proliferation in the use of acetone-based aerosols. Typically, the aerosol is primarily acetone with a small amount of a VOC solvent. Because acetone evaporates very rapidly and because it is an exceedingly aggressive solvent, there can be cleaning issues and/or compatibility problems. The use of acetone aerosols has led to the practice of continued spraying of parts until enough of a puddle of the VOC accumulates on the part so that cleaning can be accomplished. Properly contained and managed, acetone can be a useful cleaning agent. There are even liquid/vapor (degreaser) systems for low flashpoint solvents that can be used for acetone and various alcohols. While the initial capital costs are high and the solvent cost is typically low, the investment in a low flashpoint system may be recovered rapidly in solvent savings for some operations [6]. In addition, availability of such systems expands the range of solvent options. 40.2.1.2 Classic chlorinated solvents Chlorinated solvents were developed to overcome the flammability issues associated with hydrocarbons and oxygenated hydrocarbons. Most chlorinated solvents are nonflammable and are extremely effective cleaning agents. Perchloroethylene (PCE), trichloroethylene (TCE), methylene chloride (MC), and 1,1,1-trichloroethane (TCA) have a broad solvency range for an array of lubricants. They can be used in the liquid or vapor phase. Final cleaning in the vapor phase allows self-rinsing in freshly

distilled solvent. They do not leave significant residues. They were relatively low-cost and could be obtained at high levels of purity. However, the first three have relatively unfavorable worker exposure profiles. In addition, past inappropriate chemical management has resulted in groundwater problems and in worker and community health issues. 1,1,1-TCA was introduced as a replacement for TCE, but it was later found to be an Ozone Depleting Chemical (please see Section 4.2.1.3). Existing stockpiles are still in use for critical applications, primarily military. Chlorinated solvents must be used in relatively well-contained liquid/vapor cleaning systems (vapor degreasers) as specified in the Federal NESHAP (National Emission Standard for Hazardous Air Pollutants) rules. These solvents are useful for removal of many organic lubricants, and, even with the current restrictions, they can be used in a relatively nonemissive manner, particularly with some of the newer airless or airtight cleaning systems. Such systems, while requiring a high initial capital input, allow these very powerful solvents to be used in a manner that is responsible to both workers and to the surrounding community. 40.2.1.3 trans-1,2-Dichloroethylene (Trans) Trans is one of the few current chlorinated solvents that are relatively free of regulatory encumbrances. Trans is a chlorinated compound with moderate to aggressive solvency. Although it has a low flashpoint and has not been exempt as a VOC, it is not a hazardous air pollutant (HAP) and has a relatively favorable worker exposure profile. Until recently, Trans was not used neat for cleaning because it is flammable. It can be used in low flashpoint systems, albeit with a substantial initial capital outlay. It has, however, grown in importance recently because it is being used to blend with hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs). The blends are typically azeotropic and thus suitable for use in vapor degreasers. The Trans provides enhanced solvency for the blends while the HFCs or HFEs provide flashpoint suppression and lower VOC content. 40.2.1.4 Chlorofluorocarbon solvents (CFCs) 1,1,2-Trichloro-1,2,2-trifluoroethane (CFC-113) was a popular cleaning agent with a relatively favorable worker safety profile. CFC-113 and 1,1,1-TCA (see Classic Chlorinated Solvents) were widely used because they are nonflammable, self-rinsing, and are effective cleaning agents. They are low in both particulate and in thin-film residue. Cleaning agent residue is an important concern in contamination control. Both evaporate rapidly, and they can be used in both the liquid and vapor phase. Vapor phase cleaning and rinsing is important industrially in that such processes


usually assure clean, uncontaminated solvent. By the midtwentieth century they had come into widespread use for critical cleaning. During the 1970s and 1980s, there was an increasing awareness of the role that many chlorocarbon and hydrochlorocarbon solvents play in the depletion of ozone in the upper atmosphere. In addition, 1,1,1-TCA was included in the list of NESHAP solvents, so that even where it is available, it must be used in relatively contained systems (please refer to Section 4.2.1.5). The phaseout of ozone depleting chemicals has prompted development of a host of new cleaning agents and cleaning processes. None possess the exact attributes of CFC-113 and 1,1,1-TCA. Many process engineers harbor the unrealistic expectation that new products with similar attributes will appear. This expectation is exceedingly unlikely for several reasons. For one thing, increasing technical specificity, stringent cleaning requirements, and a plethora of location-specific environmental regulations have produced a splintered market. In addition, regulatory scrutiny of potential new compounds has increased markedly. With a relatively small potential return, the costs of product development (including technical and regulatory approval) are so high that further development of new cleaning compounds is not likely. 40.2.1.5 Hydrochlorofluorocarbons (HCFCs) HCFCs were developed as cleaning agents to be replacements for CFCs (or, more realistically, adapted from other products that had wider uses in industry such as in foam blowing or refrigerants). The most widely used members of this class include HCFC-141b and HCFC-225. 40.2.1.5.1 HCFC-141b Unfortunately, the most popular and promising HCFC (HCFC-141b) was found to have not only similar performance properties to 1,1,1-TCA but also similar ozone depletion potential. In the United States, the potential for global environmental impact lead to a series of complex regulations at the Federal level restricting both the sale and allowable uses of the compound. However, because HCFC-141b was relatively inexpensive, showed moderate solvency, and reasonable performance properties, and most importantly because it was federally exempt as a VOC, it continued to be used and even to be favored by some local regulatory agencies in areas of poor air quality. In many instances, issues of smog (local air quality) superseded those of ozone depletion potential (global air quality). A Federal production ban was instituted at the beginning of 2003. The material is still used, and will continue to be used as long as sufficient stockpiles are available. One problem is that HCFC-141b is often blended with other solvents, in part to lower the VOC content, so those in industry are often not aware that they are managing

the process on borrowed time, perhaps without an appropriate replacement. The chemical may be described as CAS# 1717-00-6 or as 1,1-dichloro-1-fluoroethane or as dichlorofluoroethane. The challenge will be to find a product that is not too expensive, cleans, and evaporates in an acceptable manner, does not have a flashpoint, and is not too costly. Finding replacement processes for HCFC-141b promises to be challenging for some critical applications. In addition, in aerosol applications there have been trends toward accepting low flashpoint or flammable solvents as well as solvents with less favorable or even unknown worker exposure profiles [7]. Another approach to replacing HCFC-141b has been to develop blends of aggressive cleaners, such as nPB, with mild cleaners such as hydrofluorocarbons [8]. 40.2.1.5.2 HCFC-225 HCFC-225 has moderate solvency (similar to CFC-113). It will eventually be phased out of production because it is an Ozone Depleting Substance (ODS). However, it is used in the United States and throughout the world and is another valuable tool for removal of lubricants. HCFC-225 has a number of favorable properties. It does not have a flashpoint; it is VOC exempt; and it has a relatively favorable worker safety profile. It is available as blends and as constant boiling azeotropes. While these blends tend to increase the VOC content, the addition of stronger solvents serves to increase the solvency range for soils of interest. Less aggressive blends are useful where the substrate to be cleaned may be impacted by the solvents. For cost-effective use, products based on HCFC-225 are often most judiciously employed in relatively contained cleaning systems, with recycling to extend the life of the product. However, the products are sometimes used in bench top or even aerosol processes, particularly for high-value applications. 40.2.1.6 normal-Propyl bromide (nPB) nPB was introduced in the early 1990s as a direct replacement for TCA, which was being phased out. It has nearly identical physical properties to TCA, but it has a very low Ozone Depletion Potential (ODP). It is nonflammable and has proven to be a very effective cleaning solvent with a broad solvency range. It is an attractive option where organic lubricants must be removed. Because it can be obtained both in unblended (neat) and in blends and constant boiling azeotropes, it can be used with a range of substrates and in a number of different applications. Cleaning agents designed to replace CFCs must be deemed acceptable by the Significant New Alternatives Policy (SNAP) Program of the U.S. Environmental Protection Agency (EPA). After an unusually long and comprehensive evaluation period, the U.S. EPA published a


Proposed SNAP Rule for nPB in the Federal Register on June 3, 2003. A SNAP Ruling is required for any solvent introduced to replace an ODS, and the EPA has made it clear that nPB should not be considered as an ozone depleting chemical when it is used within the continental United States. The ODP has been determined to be somewhat higher at equatorial latitudes. Controversy remains concerning the Allowable Exposure Limits (AEL) for personnel handling nPB. The EPA has recommended an AEL of 25 ppm for an 8-h time-weighted average. OSHA has not yet established a legally enforceable exposure limit. 40.2.1.7 Perfluorinated compounds (PFCs) PFCs are nontoxic, nonflammable, and tend to have very favorable worker exposure profiles. However, they tend to be expensive and have poor solvency for most soils, including most lubricants. The notable exception is their ability to solubilize highly fluorinated oils and greases. PFCs are exceedingly stable. Because of their long atmospheric lifetimes, there is regulatory concern about their contribution to global warming. In the United States, the Federal regulatory position is that PFCs should be used only where other approaches are not technically feasible. Development of HFCs and HFEs were in part prompted by expected restrictions on HCFCs. 40.2.1.8 Hydrofluoroethers (HFEs) and hydrofluorocarbons (HFCs) HFCs and HFEs include a range of compounds with variable solvency properties and variable costs. Some, such as HFC-43-10mee (2,3-dihydrodecafluoropentane) and nonafluorobutyl methyl ether (an HFE) have favorable employee exposure profiles, are not ODSs, have relatively short atmospheric lifetimes, and do not have a flashpoint. Perhaps most important for many manufacturing facilities, they are VOC exempt at the Federal level. HFEs and HFCs have limited solvency for most soils of interest. The VOC exemption and the absence of a flashpoint have contributed to their adoption in blends and azeotropes with more aggressive solvents. The above HFCs and HFEs are often blended with varying amounts of trans-1,2-dichloroethylene and/or alcohols. Specific performance properties and environmental attributes vary with the compound. For example, HFC-365mfc (1,1,1,3,3-pentafluorobutane) has a flash point. However, it can be blended with nonflammable solvents such as n-propyl bromide to moderate the solvency, increase wettability (desirable with ornate or closely spaced components), and decrease the VOC content [9]. 40.2.1.9 n-Methylpyrollidone (NMP) NMP has the advantage of removing polar and some nonpolar soils and has found utility in removing certain

lubricants. NMP is a high boiling (295◦ C), high flash point (91◦ C) solvent. NMP is not exempt as a VOC. It is miscible with water at elevated temperatures. At ambient temperatures it forms a distinct phase when mixed with water. This property, properly used, is economically and ecologically advantageous in industrial processes because the solvent can be recovered and reused. Because NMP is miscible in many organic solvents as well as in heated water, it can be used in multistep cleaning processes. Sometimes it must be rinsed off with a lower boiling solvent in order to reduce residues. It is also used in hand-wipe applications. 40.2.1.10 Biobased cleaning agents Biobased products, as the name implies, are derived from currently available plants or animals as opposed to fossil fuels. Such products are more likely to come from renewable resources. In fact many of them represent agricultural waste streams, including portions of plants that would be otherwise unusable. Support for biobased products includes agriculture and environmental regulatory organizations. A consequence of recent Federal legislation is that purchase of biobased products by U.S. federal agencies will be mandated with some exemptions (such as performance and cost issues) [10]. Increased use of biobased products, including biobased lubricants and biobased cleaning agents is also likely in the consumer market. Methyl soyate and d-limonene are two examples of biobased products that are described in more detail below. They are used alone or in blends. Additives can alter the cleaning capabilities and may also modify the worker exposure and environmental profile. Many of the biobased products are unknown quantities in terms of cleaning and toxicity. There is a perception that products derived from plants are inherently safe. However, in most cases, long-term toxicity studies have not been performed. As with all chemicals, prudent handling, including minimizing employee and environmental exposure, are appropriate. Other biobased products are based on palm oil and ethyl lactate. Ethyl lactate is promising in that it is fairly aggressive and has a broad solvency range. Assuming an ongoing emphasis on the reduction of dependence on fossil-based material, it seems likely that designed biobased products, perhaps based on lesser-known crops or other organisms, could be developed. 40.2.1.10.1 Methyl soyate Methyl soyate is an esterified soy product with reasonable solvency (KB value of about 60), similar to many hydrocarbon blends. Methyl soyate has not been exempted as a VOC. However, because it may not be detected in analytical determinations of VOC content, it is considered environmentally preferable in some areas of poor air quality (SCAQMD website [11]). Methyl soyate boils at


over 600◦ F and leaves a residue that must be rinsed off for most applications. Blends containing surfactants can be rinsed with water in semi-aqueous processes. Other blends are more appropriately rinsed with an organic solvent (co-solvent processes). 40.2.1.10.2 d-Limonene d-Limonene is a cyclic hydrocarbon derived from citrus. It is flammable, but it is environmentally friendly. Like NMP, it has a high boiling point (178◦ C) and is therefore slow drying. d-Limonene has a moderately high KB value (in the mid-50s), and has a high solvency for some soils of interest. As with methyl soyate, d-limonene can be used alone, blended, and in semi-aqueous, and co-solvent applications. d-Limonene has been successfully used in removing heavy waxes in optics applications. It is promising for the removal of mixed lubricants and other soil mixtures. 40.2.1.11 Volatile methyl siloxanes (VMSs) VMSs, such as hexamethyldisiloxane, are low in toxicity and contain no halogen atoms. They are chemically very stable. On the other hand, they have flash points and only moderate solvency. They are useful for silicon-based materials and have unexpected solvency for some mixed soils. 40.2.1.12 Solvent blends An important thing to note about blends is that some are azeotropes and some are not. An azeotrope is a blend where the relative concentrations of the components are the same in the boiling liquid and the vapor. When two or more compounds are blended in the correct proportions to form an azeotrope, the resulting blend can be distilled at a constant temperature and the relative concentrations in the distillate will be the same as in the distillation pot. In an operation using a vapor degreaser, it is important to use an azeotropic blend. If a nonazeotropic blend is used, the vapor degreaser will act like a distillation unit. The higher boiling component will be concentrated in the boil-up sump while the lower boiling solvent will concentrate in the rinse sump. In cold cleaning operations, hand wipes, and aerosols, azeotropic performance is not needed. Blended cleaning agents have found applicability in bench-top cleaning as well as for larger batch, automated processes. Blends can increase the solvency range. At the same time, there is the problem of undisclosed composition and undefined toxicological properties of either the individual components or the blend as a whole. Very little is known about possible synergistic or antagonistic impacts of blends. Given the difficulties of conducting toxicological studies of blends, the assumption is that health effects are additive. This may or may not be accurate. The judicious approach is to obtain as much information as possible from the supplier and other sources and then handle the product in a conservative manner.

40.2.2 Aqueous and Aqueous Blends Water is an excellent solvent for inorganic materials. With additives, aqueous-based cleaning systems have also been adopted for removal of lubricants, including synthetic and semi-synthetic lubricants. Particularly with aqueous systems, it is not necessarily productive to consider the cleaning agent apart from the process context. The following are some important aspects of the process context to consider in addition to the cleaning chemistry. It must be emphasized that these factors are important for all systems, solvent and aqueous. They are introduced here because, in part for environmental reasons, aqueous systems are being adopted for removal of soils where solvency parameters are not favorable.

compatibility issues are exacerbated by longer exposure times. In addition, the process must be short enough to be economically feasible. 40.2.2.4 Rinsing

Examples of cleaning action (sometimes called cleaning force) include mechanical agitation (including elbow grease in hand-wipe applications), spray, spray under immersion, ultrasonics, and megasonics. Many techniques are line-of-site (spray and megasonics) whereas ultrasonics is not. Ultrasonics is therefore particularly useful for ornate components with blind holes. It should be emphasized that quantifiable metrics for ultrasonic performance have not been established, certainly not universally accepted. Exposure of standard (not heavy duty) aluminum foil to the ultrasonic system and noting the presence of a characteristic orange peel pattern remains the favored approach for assessing ultrasonic performance. The force of action must be moderated not only to maximize soil removal but also to avoid product damage. Further, particularly with ultrasonics, the cleaning technique can markedly contribute to the aggressiveness of the cleaning agent. On the positive side, this promotes soil removal. On the negative side, materials compatibility issues may be exacerbated.

Rinsing requirements depend on process requirements. For some general metals cleaning requirements and maintenance operations, it is not necessary to avoid cleaning agent residue. For more critical applications, cleaning agent residue itself can have a catastrophic impact on the product. In addition, the rinsing step may serve as an additional cleaning step. For example, in systems employing sequential use of organic solvents, termed co-solvent systems, a high-boiling solvent such as d-limonene may be rinsed with isopropyl alcohol (obviously, in a system designed for low flashpoint cleaning agents). Because the two have very different solvency parameters, such a system is useful for exceedingly adherent soils. Particularly with aqueous systems, it is important to take steps to avoid metal corrosion. Many aqueous cleaning agents contain rust preventatives (often referred to as RPs). RPs may be required at the rinse stage. The longevity of the corrosion protection, from hours to weeks or even months, varies with the RP. In addition, the RP itself leaves a residue. The significance for the specific process must be considered. When water is used to rinse aqueous cleaning agents (certainly a logical choice), it must be remembered that the rinsing agent has a higher surface tension than does the cleaning agent. For complex components, the consequence is that cleaning agent residue may be trapped, only to interfere in subsequent steps. This problem is exacerbated when the components are allowed to dry between steps. The problem may arise during the time it takes to move the component from the washing bath to the rinsing bath. To lessen the problem, some aqueous systems include a water spray between baths.

40.2.2.2 Temperature

40.2.2.5 Drying

In general, the rate of reaction doubles with each ten degrees increase in temperature. Aqueous systems often use heating to simply melt the soil from the surface. However, some substrates are temperature-sensitive. In addition, many aqueous cleaning agents that are designed for use in spray systems contain solvents that must be brought to an adequately high temperature to minimize excess foaming. However, cleaning agents, particularly in systems with ultrasonic action, show an optimal temperature beyond which efficacy of cleaning decreases.

It is amazing that production engineers purchase an aqueous cleaning system with a good design for the wash and rinse stages, neglect to include a drying stage, and then complain that the cleaned component is wet. Where corrosion is a concern, it is crucial to consider the drying step. There are a number of types of drying systems including centrifugal drying and forced air drying. Considerations include temperature optimization to maximize efficiency and avoid product damage as well as filtration and pump selection to avoid recontamination. In specialized applications, organic chemical drying is also used, both with aqueous and solvent systems. One might initially wonder why solvent cleaning is not adopted in these cases. Sometimes, the cleaning agent selected better removes the soil. In addition, chemical drying can

40.2.2.1 Cleaning action

40.2.2.3 Time of exposure Again a balance must be struck. Longer exposure times tend to result in greater soil removal. However, materials


minimize the use of costly solvents. The chemical of choice depends on how dry the part needs to be. Alcohol drying is popular, and it probably also serves as a vapor phase rinse. Where extremely thorough drying is required, fluorinated materials have been used.

agent solely on the basis of coupon testing is often as not unsuccessful. Far from being unsophisticated, aqueous cleaning agents that are successful for critical applications are carefully formulated, sophisticated products containing a number of organic and inorganic additives [12–14].

40.2.2.6 Soils Soils can be particulate or thin film, organic compounds, inorganic compounds, living organisms, or cell debris. Mixtures of soils change the picture for soil removal in terms of both cleaning agents and cleaning action. In general, aqueous cleaning agents have a more narrow solvency range, or, more positively, more soil specificity than do organic solvents. Therefore, when the lubricant is changed or when any other soil is changed, it is prudent to reevaluate the cleaning process. 40.2.2.7 Materials of construction and product configuration There is no universal solvent. If you had one, how would you store it? Everyone would like to optimize cleaning. However, the more aggressive the solvent, the more likely is the occurrence of compatibility problems. Further, just as contamination control or cleaning is related to process, so is compatibility. With aqueous systems, corrosion is a particular materials compatibility issue both at the cleaning and the rinsing stage. Finally, because materials can interact as they degrade, materials of construction must be tested together, not separately. Static dip tests in a cleaning agent at ambient or even at elevated temperature does not tell the whole story. The product must be tested in the cleaning and drying sequence. With increasing miniaturization and greater sophistication of CAD/CAM programs, product configuration and product complexity add to the potential problems in cleaning and process control. It may be observed that many designers have the attitude that if the computer program indicates that the components will fit together, there is the assumption that the product can be successfully built. Potential problems of chemistries involved in the build, cleaning, and ultimate surface quality are not always considered. Therefore a change in product design may cascade into an array of changes in lubricants and metalworking fluids and therefore in cleaning. The tighter the spacing, the more difficult it is for cleaning agents to penetrate. 40.2.2.8 Holistic process design The above factors are important in both solvent and aqueous cleaning. However, traditional solvent cleaning is sometimes more forgiving. A nonoptimized process, therefore, may give at least marginally effective results. With aqueous cleaning, process optimization is far more critical. Attempting to simply adopt an aqueous cleaning


40.2.2.9 Additives to aqueous cleaners The acidity or alkalinity of an aqueous cleaning agent is important for soil removal. Aqueous cleaning agents generally operate at pH ranges away from neutral (pH of 7). In general, acidic (low pH) cleaners are useful as brighteners and for removal of scale. Alkaline cleaners are useful for many soils of interest, including lubricants. As a guideline, acid cleaners have a pH range of 1–5; neutral, pH 7; low alkaline, pH 8–10; high alkaline, pH 10–13; and caustic, pH 12–14. Occasionally, water with either an acid or base is used as the cleaning agent. More often, additional additives are employed to increase efficacy of cleaning, extend the solvency range, control foaming, and protect the product. Surfactants reduce the surface tension or interfacial tension between water and the soil or substrate. Surfactants allow water to get into the smaller spaces and blind holes of ornate parts. Surfactants are classed as nonionic, anionic, cationic, or amphoteric (Zwitterionic). Neutral surfactants such as glycol esters are a frequent choice for industrial cleaning. They are bio-resistant, promote wetting, and many are low foaming. Negatively charged surfactants such as amine/metal salts and sulfonates are more common in high-foaming cleaners and in emulsified coolants. Positively charged surfactants such as ammonium salts serve as emulsifiers. Amphoterics such as sultaines and betaines, once rarely used industrially, are increasingly finding their way into high-performance cleaners. Of course, one must remove the cleaning agent by rinsing, and that generally involves water, which has the higher surface tension you were trying to get away from in the first place. Aqueous cleaning agents contain an array of additives referred to as builders. Builders help to establish the pH of alkaline cleaners, but they may also be multifunctional. For example, amines are used in high alkaline cleaners to promote detergency and to inhibit corrosion. Builders have their positives and negatives. For example, amines contribute to corrosion protection, but many are costly; and there may be odor issues. Phosphates were traditionally used for their detergency and sequestration properties; but there are increasing environmental restrictions and some compatibility problems. Silicates contribute to detergency and corrosion inhibition; but may leave an adherent residue and may mask the presence of cracks during nondestructive testing. Carbonates are low in cost and contribute to detergency and corrosion inhibition, but they are consumed during use.

Cleaning agents may also contain chemicals referred to as sequestrants, chelators, or water conditioners to prevent soap scum and avoid residue buildup on the component. Specific organic chemicals that liquefy at particular temperatures to assist in defoaming may also be added where the product will be used in a spray system. Corrosion inhibitors are important both in the wash and rinse chemistries. They act as barriers to oxidation or they may be sacrificial. Many may be used in a single product. The extent of corrosion protection required will influence the chemistry that is chosen, and this involves working with the cleaning agent vendor. Choosing a reliable vendor who offers good product support is crucial [15]. Because aqueous cleaning agents may have complex formulations, it is important to assure that the additives are safe for workers and for the environment. One issue is that if the toxic is below 1%, it does not have to be listed. If “families” of toxics having related toxicity issues are used, even if each is under 1%, they do have to be listed. However, because there could be a temptation to declare various additives as being at best distant cousins, it is very important to work with reliable cleaning agent suppliers [16].

40.2.2.10 What is an aqueous cleaning agent? Sometimes, the additives in the concentrate result in what is basically a blend of organic solvents with some inorganics. Depending on how dilute the mixture is when employed, one may still have basically an organic blend (perhaps of high boilers) that is then marketed as an aqueous product. One problem is that some U.S. regulations sharply restrict the level of organic compounds that are VOCs. A few organic compounds with low reactivity have been classed as VOC-exempt. In many areas, they can be used with few if any environmental restrictions. Relatively few of these, however, are useful in aqueous blends. To further complicate the situation, some regulatory agencies have programs to determine the VOC content by analytical detection rather than by actual content [17]. Even with gas chromatography/mass spectroscopy (GC/MS), depending on the sample preparation and transfer technique used in the test laboratory, high-boiling organics and complex mixtures may not show up. To maximize available options, it is necessary to consider all applicable environmental regulations, not just the complete list of components as provided by the manufacturer.

40.2.2.11 On-board cleaning agent recovery and bioremediation Maintaining the cleaning agent bath is crucial for ecological, economic, and performance considerations. With


lower boiling organic solvents and azeotropic blends, on-board recovery by distillation is often feasible. With aqueous cleaners and higher boiling blends, filtration and oil separation are required to maintain the cleaning agent. Skimmers are often added to baths to remove oils and particulates and prevent redeposition on the part. Selection of the appropriate filter can be problematic. With aqueous cleaners, any filter will alter the chemistry. Formulators often strive to design the product so that it can be filtered with minimal impact on cleaning agent composition. Some aqueous systems use “oil-eating” bacteria to achieve on-board bioremediation. Such systems are typically “sink on a drum” or remote reservoir cleaners. There is a misconception that the bacteria are promoting the cleaning process. In a sense they are, but they are doing so indirectly by keeping the cleaning bath free of soil. With bacteria remediation systems, the bath temperature, type of soil, and soil loading must be considered. The cleaning chemistry is specific for the bacteria chosen. Because such systems are nearly neutral for appropriate applications, there has been good employee acceptance. 40.2.2.12 Process change to aqueous Success in conversion to aqueous cleaning has been mixed. Aqueous systems are very inexpensive in terms of detergent cost, but they are not suitable for all applications. Unfortunately, zealous, albeit well-intentioned, environmental restrictions have led some companies and locales to mandate adoption of a subset of aqueous technologies without consideration of process design, process cost, or required optimization. High capital investment, multistep processing, a large equipment footprint, and high-energy costs are often reported. Residuals on the clean parts and difficult drying are also problems. Corrosion of metal parts may become a factor. Finally, some critical components such as electrical and electronic applications often cannot tolerate the presence of remaining traces of water. At the same time, for the appropriate lubricants and other soils, aqueous cleaning can be the best approach.

40.2.3 Semi-Aqueous Systems A semi-aqueous system consists primarily of a solvent or solvent blend containing additives that allow rinsing with water. For example, a blend of esters combined with surfactants might be followed with a water rinse. Problems with semi-aqueous processes are typically associated with inadequate attention to process design. One problem with semi-aqueous systems is carryover; that is, the cleaning agent is trapped in the product and carried into the rinse tank. This makes rinsing and disposal more difficult. The problem of proper disposal of semi-aqueous systems is often overlooked. Because of the high organic content, it is not appropriate (or legal in many cases) to

dispose of these systems down the drain. In addition, an RP may be needed in the rinse tank to avoid corrosion. With good process design and ongoing process control, semi-aqueous systems are valid options.

40.2.4 Co-Solvent Systems In co-solvent systems, solvents are used sequentially, often with a high boiler used for washing and a lower boiler for rinsing and perhaps drying. A co-solvent process is particularly attractive where several metalworking fluids with varying solvency properties are used. A similar ester blend to the one described for semi-aqueous cleaning might be supplied without surfactants. The blend would then be rinsed with an HFC or with an alcohol depending on the soil mix, the environmental requirements, and the availability of low flashpoint cleaning systems. Aqueous, semi-aqueous, and co-solvent processes all share similar advantages as well as many of the same potential problems. Again, process control is the key to success.

40.2.5 “Nonchemical” or Limited Chemical Processes Processes such as CO2 snow, CO2 pellets, steam, and a vast array of abrasive materials alone or with liquids have been used for surface finishing or cleaning. CO2 snow is actually a combination of physical and chemical cleaning. Most are appropriate for final spot cleaning rather than removal of appreciable levels of lubricants. All are essentially line-of-sight techniques [18]. In addition, liquid and supercritical CO2 have been used for cleaning. The process time is typically significant as is the initial capital outlay. In addition, cleaning chamber size restricts the parts being cleaned to relatively small objects.

40.3 PHYSICAL AND CHEMICAL PROPERTIES OF CLEANING AGENTS The choice of a solvent for critical cleaning depends on a variety of physical and chemical properties. The most important of these characteristics are described below.

40.3.1 Solubility The underlying principle in both aqueous and solvent cleaning is that the contaminant to be removed must dissolve to some extent in the cleaning agent. Aqueous systems, however, tend to depend less on solvency and more on cleaning action, time of exposure, and temperature than do solvent systems. It is well-established conventional


wisdom that “like dissolves like,” and that is a good starting point for choosing a cleaning solvent. This concept simply means that compounds of similar chemical structure are more likely to be miscible with each other than compounds whose molecules are very different. However, the average person facing a cleaning decision (engineer, shop foreman, etc.) needs a more straightforward way of ranking the solubilizing performance of candidate cleaning solvents toward the soil to be removed. For this reason, several different systems of assigning solubility parameters have come into common use. 40.3.1.1 Kauri–Butanol number The Kauri–Butanol number, or KB number, is widely quoted in reference to cleaning solvents. It is a measure of the ability of a solvent to dissolve a mixture of Kauri resin in butanol. As a practical guide, it is useful in predicting the ability of a solvent to dissolve heavy hydrocarbon oils and greases. The higher the KB number, the more effective the solvent will be. The test was designed for evaluating hydrocarbon solvents, but the range of use has been expanded to include halogenated solvents. It is not used for oxygenated solvents. Table 40.1 contains some representative KB numbers along with the corresponding boiling points. A relatively high boiling point can compensate for a somewhat lower KB number. Sometimes, materials are blended to enhance the KB number. In looking at HFEs alone and blended, it should be noted that blending increases the KB number fivefold but decreases the boiling point. In this case, the azeotrope, HFE-72DE, is desirable in that some of the solvency properties of trans-1,2-dichloroethylene are maintained, but the flashpoint of trans (36◦ F) is suppressed by the HFE. 40.3.1.2 Hildebrand Parameters Unlike the KB number, which is experimentally determined, the Hildebrand Parameters are calculated from several physical constants. Substances with similar Hildebrand solubility parameters tend to be soluble in each other. 40.3.1.3 Hansen Parameters The Hansen Parameters were developed to overcome certain inconsistencies in the Hildebrand Parameters. The Hansen Parameters are broken down into polar, nonpolar, and hydrogen bonding components. These are the three main types of intermolecular attraction. The more closely the three parameters for the solvent compare to the parameters for the lubricant to be removed, the more effective the solvent will be. Table 40.2 presents Hansen Parameters for a variety of solvents.

TABLE 40.1 KB Values and Boiling Points of Selected Solventsa Cleaning agent

KB number

CFC-113 1,1,1-Trichloroethane Methylene chloride Perchloroethylene Trichloroethylene HCFC-141b HCFC-225 HCFC-225 ATEb n-Propyl bromide (nPB) Blend, 1:1 nPB/HFC-365mfc trans-1,2-Dichloroethylene HFC 43-10 HFE-7100 HFE-7200 HFE-72DEc Methyl soyate Alkyl C16 –C18 methyl esters, soybean oil (CAS# 67784-80-9) Parachlorobenzotrifluoride d-Limonene Benzene Toluene Xylene Stoddard solvent (CAS# 8052-41-3)

TABLE 40.2 Hansen Parameters for Selected Solventsa,b

Boiling point, ◦ C

32 124 136 90 129 56 31 115 125 30 117 9 10 10 52 61

48 74 40 121 87 32 54 45 71 45 47 55 61 76 43 315

64 76 107 105 98 33

139 178 80 111 139 188

a KB values obtained from a variety of sources. Validation from suppliers

or by experiment may be advisable.

Compound CFC-113 1,1,1-Trichloroethane HCFC-141bc C6F14 (a perfluorocarbon) Trichloroethylene Methylene chloride Perchloroethylene n-Propyl bromide HFC 43-10mee C7-11 Hydrocarbons, 25% aromatics Parachlorobenzotrifluoride Isopropyl alcohol Acetone Butyl acetate Methyl acetate Ethyl acetate Methyl ethyl ketone Methyl isobutyl ketone Methyl propyl ketone n-Methylpyrollidone d-Limonene Water

Nonpolar (dispersive)

Polar

Hydrogen bonding

14.7 17.0 15.1 11.5 18.0 18.2 19.0 16.0 12.9 15.8

1.6 4.3 5.1 0 3.1 6.3 6.5 6.5 4.5 0

0 2.0 2.0 0 5.3 6.1 2.9 4.7 5.3 0

13.9 15.8 15.5 15.8 15.5 15.7 16.0 15.3 16.0 18.0 16.6 8.6

9.9 6.1 10.5 3.7 7.2 5.3 9.0 6.1 7.6 12.2 0.6 13.4

4.7 16.4 7.0 6.3 7.6 7.2 5.1 4.1 4.7 7.2 0 25.8

a Hansen Parameters obtained from a variety of sources. Validation may be advisable. b Data presented as δ/(MPa)1/2 . c HCFC-141b parameters estimated by Dr Ken Dishart.

b HCFC-225 blended with 55% trans-1,2-dichloroethylene, 3.3% ethyl

alcohol, and 5% nitromethane. c 10% HFE-7100, 20% HFE-7200, 70% trans-1,2-dichloroethylene.

physical properties of the solvent: Wetting Index = density × 1000/(surface tension

40.3.1.4 TEAS diagram The TEAS diagram, which is a measure of the ratios of the polar, hydrogen bonding, and nonpolar forces, provides an indication of solvency characteristics without indicating solvency strength. Thus, many HFCs have a similar solvency style to chlorinated solvents. However chlorinated solvents are more aggressive solvents. For a more comprehensive discussion of solvents and solubility, the reader is referred to a recent review of the topic [19].

40.3.2 Wetting Index The Wetting Index is sometimes used as an indication of the ability of a cleaning or rinsing agent to penetrate tightly spaced components or to reach into blind holes. The concept of the Wetting Index was originally proposed by W.G. Kenyon (Global Centre Consulting) as a guidance or teaching tool [20]. It is derived from three fundamental


× viscosity) The Wetting Index has pragmatic value in understanding the behavior of cleaning and rinsing agents. In general, cleaning agents with a higher Wetting Index are favored for cleaning complex components and for rinsing any residue from complex or tightly spaced components. A few examples of the Wetting Index are provided in Table 40.3. The Wetting Index provides a guideline only; pragmatic testing with the substrates, soils, and product configuration are required. The Wetting Index does not indicate aggressiveness of a particular cleaning agent for the soil of interest. For example, HFE-7200 has a high Wetting Index but is an exceedingly mild solvent. In addition, both the Wetting Index and the component physical properties (density, surface tension, and viscosity) must be considered in evaluating potential cleaning agents. While such physical properties should be readily available, they are not always readily available, particularly for some of the newer biobased materials and for blended products. It should also

TABLE 40.3 Wetting Index of Selected Solvents Cleaning agents (source) HCFC-225a n-Propyl bromidea 1,1,1-Trichloroethanea HCFC-141ba Trichloroethylenea CFC-113a Parchlorobenzotrifluoridea HFC-43-10a HFE-7200b (HFE-569sf2) Acetonea Isopropyl alcohola Hexanea Volatile methyl siloxane (VMS OS-10)a d-Limoneneb H2 0a Saponifier solution, 6% ethanolamine-based saponifierc

Density, g/cm3 (25◦ C)

Surface tension, Dyn/cm3 (25◦ C)

Viscosity centipoises, (25◦ C)

Wetting Index

1.55 1.35 1.32 1.24 1.46 1.57 1.34 1.58 1.43 0.79 (20◦ C) 0.78 0.66 (20◦ C) 0.82

16.2 25.9 25.6 19.3 26.4 17.3 25.0 14.1 13.6 23.3 (20◦ C) 21.8 (15◦ C) 18 (25◦ C) 16.5

0.59 0.49 0.79 0.43 0.54 0.65 0.79 0.67 0.61 0.36 (20◦ C) 2.4 (20◦ C) 0.31 (20◦ C) 0.82

162 106 65 149 102 140 68 167 172 94 15 118 61

0.84 1.00 1.00

25 72.8 29.7

1.28 1.00 1.08

26 14 31

Sources: a Handbook for Critical Cleaning. b MSDS. c Estimates, W.G. Kenyon.

be noted that the wetting properties of water and of other organic solvents can be improved by blending. However, chemicals used for blending, particularly high-boilers, can leave a residue. For many applications, surfactants and other adherent additives must be removed by rinsing; care must be taken that the rinsing agent (water or organic solvent) has sufficient wetting capability to adequately remove the additives. A word of caution should be noted. The calculated Wetting Index has been found to be inconsistent with experimental drop spreading experiments with some blends of solvents. In particular, a 50:50 blend of n-propyl bromide and HFC-365 mfc has a calculated Wetting Index of 135. This is somewhat lower than HCFC-225 (162) or HCFC-141b (149). When several drops of the solvent are dropped on a smooth metal plate, however, the nPB/HFC-365 blend spreads over an area approximately 6.5 times that of either of the other two solvents [21]. In this case, the referenced authors believe that the large difference in the vapor pressures of the two solvents is responsible for the spreading behavior.

temperature, a high boiling solvent may evaporate from the cleaned surface too slowly. A low boiling solvent, on the other hand, may evaporate from the cleaning bath at an unacceptably high rate. The vapors from a solvent that boils at too low a temperature may also pose a worker safety hazard by increasing the risk of inhalation. The boiling temperature of the cleaning agent is also important in cleaning operations that are carried out hot, typically at the boiling point. The solubility of a substance in a cleaning agent (aqueous or solvent-based) is temperature-dependent, with solubility approximately doubling with every 10◦ C increase in temperature. However, higher temperatures are also more likely to damage sensitive substrate materials. In addition, significantly higher energy costs may be associated with maintaining a refluxing solvent bath or an aqueous system at a higher temperature. A solvent with too low a boiling temperature, on the other hand, may be too difficult to efficiently condense and recycle in an open vapor degreaser.

40.3.4 Flammability 40.3.3 Boiling Point The boiling point temperature is very important in choosing a cleaning agent. In cleaning operations performed at room


The flammability of a cleaning solvent is a very important safety concern. Many hydrocarbons and oxygenated hydrocarbons are excellent solvents, but they are highly

flammable and therefore dangerous to use. Some chlorinated solvents and CFCs were developed to overcome this shortcoming. Some of these chlorinated materials have been banned or restricted as ODSs, and other nonflammable compounds have been developed to take their place. These include normal-propyl bromide (nPB), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), and hydrofluoroethers (HFEs). There are a variety of definitions of flammable liquids, and a variety of tests for determining flammability [22]. The most common test for flammability is the Flash Point Test. This may be carried out using the Tag Closed Cup apparatus (ASTM D56, low viscosity fluids), the Tag Open Cup apparatus, the Cleveland Open Cup apparatus, or the Pensky-Martens Closed Cup apparatus (ASTM D93, high viscosity fluids). Solvents tend to have very low viscosities, so ASTM D56 is usually the method of choice. If a solvent fails to show a flash point under the test conditions, it means that it is incapable of maintaining combustion on its own. Some solvents have no flash point, but they will burn in an external source of ignition. This is characteristic of nPB, most chlorinated solvents, and most HCFCs. These solvents should not be used in areas where the vapors may contact the flame from a welding torch or other source of ignition. Another aspect of flammability is the flammability limits of a solvent. Some solvents that do not have a flash point will burn within narrow concentration limits in air. The limits of flammability are reported as the Lower Explosive Limit (LEL) and the Upper Explosive Limit (UEL). The LEL and UEL are usually reported as the volume percent of the solvent vapor in the air. A solvent that has no flash point but does have flammability limits is still considered to be nonflammable. Once ignition takes place, the concentration of the solvent in the air rapidly goes outside the flammable range, and the combustion self extinguishes. Many chlorine containing solvents and nPB have no flash point but do have flammability limits. These solvents generally are not suitable for use where there may be direct contact with liquid or pure oxygen. HFCs and HFEs that have a sufficiently high ratio of fluorine to hydrogen will have no flash point or flammability limits. They are generally safe to use in the presence of oxygen.

40.3.5 Hydrolytic Stability Most chlorinated solvents and nPB hydrolyze to some extent in the presence of water. The result is the formation of hydrochloric acid in the case of the chlorinated solvents and hydrobromic acid for nPB. For this reason, formulations of these solvents for cleaning applications usually include a few percent of an acid acceptor, a compound that is added to neutralize any acid that is formed. Butylene oxide is the most commonly used acid


acceptor. Hydrocarbons, HFCs, and HFEs are generally not susceptible to hydrolysis.

40.3.6 Specific Gravity During the operation of an open vapor degreaser, a certain amount of water is condensed on the cooling coils that are used to capture the solvent vapors. Water has very low solubility in most solvents used for cleaning with an open vapor degreaser. Oxygenated solvents such as low-boiling alcohols and ketones (acetone, for instance) are miscible with water, but these can be used only in closed vapor degreasers because they are also flammable. Hydrocarbons and oxygenated hydrocarbons have specific gravities (or densities) less than water. If they are used in a vapor degreaser, any water that separates from the solvent must be removed from the bottom of the water separator. Halogenated solvents, however, have specific gravities that are greater than water, and the water will float to the top. The design of the water separator must be consistent with the density of the cleaning solvent.

40.3.7 Compatibility Compatibility of cleaning agents with both the parts to be cleaned and the materials of construction of the cleaning equipment is a complex issue. The following sections cover compatibility issues of solvents with metals and with plastics and elastomers. Additional information may be found in the Aqueous section. 40.3.7.1 Metals Some metals chemically react with certain cleaning solvents. Aluminum is a very common material of construction, but it is also very reactive. Normally, a thin layer of inert aluminum oxide forms on the surface and protects the aluminum metal from chemical attack. An aluminum part that is freshly machined, however, may have surfaces that are not yet protected by an oxide coating. 1,1,1-TCA is an example of a solvent that reacts immediately with aluminum. If an aluminum coupon is scratched below the surface of liquid TCA at room temperature, an immediate reaction is visible to the eye. The entire coupon may be consumed in a very short period of time. Other metals, like silver and copper, are easily stained by a variety of solvents. Even carbon steel will react slowly with some solvents. Metal compatibility problems are most typical with chlorinated solvents and nPB. These solvents are formulated for cleaning applications with two or more metal passivators. Metal passivators commonly used include: 1,4-dioxane; 1,3dioxolane; 2,2-dimethoxypropane; acetonitrile, alcohols; and nitromethane.

As discussed earlier, metals compatibility may also be an issue with aqueous cleaning systems. This may be particularly true with iron or carbon steel parts where drying is inadequate to remove the water from blind holes or interior sections of a complex part. 40.3.7.2 Plastics compatibility The most aggressive cleaning agents are also the ones most likely to run into compatibility problems with plastic or elastomeric substrates on the materials being cleaned. The most common problem is absorption of the solvent with subsequent swelling of the plastic or elastomer. A more serious problem is encountered when the solvent actually dissolves part of the substrate. Polycarbonates are particularly vulnerable to dissolution by strong solvents. Among plastics, low-density polyethylene and polyether imides are marginal for use with aggressive solvents at elevated temperature. Among elastomers, butyl rubber and NBR nitrile rubber show marginal performance while EPDM-60 and silicones are unacceptable at elevated temperatures. Sometimes it is possible to solve compatibility problems by shortening the cleaning cycle. Other times, it may be necessary to switch to a less aggressive solvent. Many solvent manufacturers and formulators have solved compatibility problems by blending an aggressive solvent with a mild solvent. Several blends of nPB (a very aggressive solvent) with HFCs or HFEs have appeared on the market in an effort to address the compatibility issue.

40.4 CLEANING PROCESSES The cleaning process is an integration of the cleaning agent with the appropriate cleaning, rinsing, and drying equipment, sometimes referred to as the cleaning system. The process may also include devices for transporting and orienting parts and components. The cleaning process is sometimes incorporated directly into other aspects of the build process. For example, critical applications such as ion vapor deposition (IVD) may include plasma cleaning as an integral part of the IVD system. In addition, the cleaning system may include in-line process monitoring. For example, where particulate contamination is of critical concern, a particle counter may be linked to the process bath. The surface of the product may be monitored in-line. Water or solvent quality may also be continuously tested as an integral part of the process. Finally, the system may include on-board devices for achieving and maintaining appropriate qualities of the cleaning chemistry. Examples include filtration and distillation. Achieving and maintaining appropriate cleaning agent quality is important in order to minimize the costs and ecological consequences of waste generation. It is also crucial to assure that the cleaning and rinsing agents show minimal soil loading and do not themselves become sources of contamination.


Given the number of possible variables, there are a wide array of cleaning methods and equipment available for critical cleaning. The choice of the appropriate cleaning system is application-specific and site-specific. A complete and detailed description of each is beyond the scope of this chapter, but a brief overview of the more important industrial processes follows.

40.4.1 Vapor Degreasing Vapor degreasing with an appropriate solvent or solvent blend is carried out in a specially designed piece of equipment called a vapor degreaser. A vapor degreaser shows some similarities to a reflux condenser, albeit on a larger scale. A vapor degreaser generally consists of a boil-up sump, a rinse sump, and a water separator. The solvent is heated to reflux in the boil-up sump and forms a vapor zone above the sump. The vapors are condensed on cooling coils and the condensate is sent to a water separator to remove any water that may have condensed. The clean solvent flows to the rinse sump. From the rinse sump, it flows back to the boil-up sump. One typical cleaning process is as follows. The parts to be cleaned are lowered into the hot vapor zone above the boiling solvent in the boil-up sump. The solvent vapors condense on the cold surfaces of the part being cleaned. The solvent dissolves the soils and drips back into the boilup sump where the nonvolatile soils remain. For stubborn soils, the parts may be lowered into the boil-up sump. Next the parts are placed in the rinse sump to remove any dirty solvent that may be adhering to the part. Finally, the parts are moved back to the vapor zone. When the parts reach the temperature of the hot vapor, they are dry (free of solvent) and are removed. The entire cleaning process may take as little as five to ten minutes. A number of types of cleaning are possible including vapor phase, hot or cold solvent spray in vapor, immersion, spray under immersion, and ultrasonics. Vapor degreasing is typically self-rinsing (a second cleaning chemistry is not needed). In most cleaning processes, the bath is contaminated as soon as the first part is cleaned. However, vapor phase cleaning provides cleaning in truly uncontaminated solvent. Vapor degreasers vary in size from small bench top models with a solvent capacity of a few gallons to large automated machines that may hold hundreds of gallons. Some are open top models, but there is a trend toward closed systems. The latter reduces solvent emissions into the air, and that may be important for both environmental and economic reasons. Some vapor degreasers are used for batch operations while others are set up for continuous operation as part of an assembly line situation. In addition, where costly or regulated solvents are the best choice, airless or airtight systems are becoming increasingly popular. In some locales, airless systems are considered to be the standard for solvent containment.

The parts to be cleaned are placed in the cleaning container, which is then sealed. Air is removed; and the cleaning and drying activities take place under vacuum. Such systems typically are capital-intensive. Because the chamber is sealed, the option of having large parts partly extending from the chamber is not possible; the equipment must be sized carefully. Airless processes are typically slower than classic vapor degreasing. However, airless provide superior process control with miniscule solvent loss; and they can be adopted successfully [5]. Low-flashpoint systems are specifically designed for use with flammable solvents. Such systems allow cleaning with heated solvent, vapor phase cleaning, and ultrasonics. The initial capital cost is high. However, where isopropyl alcohol, cyclohexane, or acetone is the preferred choice, investment in a low flashpoint systems is imperative. Further, although solvent containment typically does not match that of airless systems, the increased cleaning efficiency and reduction in solvent loss over benchtop cleaning very often results in sufficient savings to justify the initial capital expense.

40.4.2 Aqueous Cleaning Lines Even though aqueous cleaning dates to antiquity, modern critical cleaning with aqueous agents requires specialized equipment [23]. As indicated in the section describing aqueous cleaning agents, matching the appropriate cleaning system with the cleaning agent is crucial for optimizing aqueous performance. The actual cleaning operation may be carried out using a spray or by immersion in a tank. In the case of immersion, several methods of agitation may be employed. These may include ultrasonics, spray-under immersion or turbulation. Temperature is also a critical parameter in the cleaning operation. Foaming of aqueous agents can be a problem, and sometimes this can be controlled with the proper choice of cleaning agent. Sometimes two cleaning tanks are used in series. The first bath removes the bulk of the soil and then the second, cleaner, bath removes the rest. Rinsing is very important in cleaning with aqueous agents. Often, spray rinsing is more effective than immersion rinsing. Multiple rinsing steps are usually required, and care must be taken concerning the purity of the rinse water. Ordinary tap water may leave behind undesirable residues. Finally, the cleaned part must be dried. Water has a high surface tension, a high boiling point, and a high heat of vaporization. Parts wet with water dry slowly. Many aqueous cleaning lines use air knives to dry parts after they are rinsed. Many localities and organizations promote the use of aqueous cleaning over solvent cleaning on the basis that there are no emissions into the atmosphere. A problem with aqueous cleaning that is sometimes overlooked, however, is that while the aqueous cleaning agent itself may present


few disposal problems, once the cleaning agent is contaminated with soils and traces of metal, local ordinances often prohibit disposal of the used streams into sewers. Issues involving disposal of rinse water may be overcome by closed cycle systems for water treatment, but a careful cost analysis should be done before implementing such a system. Because disposal of spent cleaning agent can be significant and because high soil-loading adversely impacts cleaning, oil-splitting chemistries and a filtration system that allows regeneration of the cleaning agent are highly desirable. Filtration that is appropriate for soil removal also tends to retain components of the cleaning chemistry. However, some formulations show minimal impact after filtration. Therefore, ability to be refiltered is yet another consideration in choosing the aqueous cleaning agent. Finally, oil and particles often float to the surface of the bath, only to resettle on the part during transfer. To minimize recontamination, such devices as weirs and carousel oil skimmers are often employed. Choices in configuration, size, and design of aqueous cleaning equipment are so numerous as to be overwhelming. Choices for small-scale applications include a remote reservoir (sink-on-a-drum), a dip tank with agitation (or with ultrasonics for critical processes), or a spray chamber. Such units often do not provide rinsing action and are used where some residue of cleaning agent is acceptable. A spray chamber with a glove box is often selected for low-throughput, high-diversity applications where parts must be individually cleaned and where line-of-sight cleaning is acceptable. Such semi-enclosed systems also have the advantage of minimizing employee exposure to both the cleaning agent and the soils. Aqueous systems that minimize employee involvement are preferable. Even though the cleaning agent may be environmentally preferred, minimizing employee exposure to any industrial process is preferable; and more automated systems allow use of higher temperatures, stronger cleaning forces, and provide better cleaning consistency. With enclosed cabinet washers, the part is placed on a turntable and sprayed with heated cleaning agent, and sometimes with heated rinse agent. Other systems look and act like industrial versions of home dishwashers. For more sophisticated processes, batch cleaning or in-line cleaning are preferable. In-line cleaning involves placing the product on a conveyor belt that then passes through chambers (typically spray chambers) that deliver the cleaning chemistry and rinsing agent. Such processes are therefore also line-ofsight cleaning and often depend on high-pressure spray for the cleaning action. Drying is usually accomplished with air knives. In most batch cleaning processes, the product is placed in baskets or fixtures, which are then transferred to various wash, rinse, and drying baths or chambers. Batch

processes, by the way, are also used with organic chemicals in co-solvent processes. Such chambers are typically heated. Cleaning action may include rotation of the basket as well as other typical cleaning forces. Consistent, acceptable process control is difficult to achieve without automation, usually overhead robotics. A fine spray of water is often introduced between the rinsing and drying tanks to prevent soils and cleaning agent from baking onto the surface. Batch processes are more flexible than in-line processes in that with in-line cleaning, the variables are the conveyor belt length and the conveyor belt speed. With batch processes, it is possible to custom-program the wash, rinse, and dry times to specific product requirements. Sometimes, several of the cleaning or rinsing agents may be sequentially introduced into a single tank to save space or conserve water. The importance of purchasing high-quality equipment cannot be overemphasized, particularly for aqueous applications. Given required heating and agitation, less costly but poorly insulated equipment costs money in the long run. Cutting costs in a way that results in inadequate exposure of the product to the cleaning chemistry can result in unacceptable performance. For example, in estimating equipment size and configuration for spray systems, it is important to remember that the product cannot be jumbled into a basket but must instead be arranged in “monolayers” that are exposed to the spray. It is worth investing the time and money up-front to achieve a consistent process.

40.4.3 Ultrasonics Ultrasonic cleaning may be employed in combination with either solvent or aqueous cleaning agents. In the case of solvent cleaning, the ultrasonic unit may be built into the boil-up sump of a vapor degreaser. Ultrasonic cavitation and implosion effectively displaces a saturated layer of cleaning agent on the surface of the part being cleaned, thus allowing fresh cleaning agent to come in contact with the contaminant being removed from the surface. An excellent review on the theory and application of ultrasonics for cleaning is available [24].

a repair being made in the field. As an example, aerosol cleaners are used for cleaning electronic parts that must be repaired on site and quickly placed back into service.

40.4.6 Sprays Spray cleaning can be carried out with either solvent or aqueous cleaning systems. In addition to the solvating effects of the cleaning agent, a spray provides a gentle agitation that helps to loosen and dissolve the soil. Sprays are sometimes used in combination with vapor degreasers. When a solvent is used in the spray, care should be taken to recover as much of the solvent as is possible and to provide proper ventilation. Spray cleaning is sometimes done in spray cabinets that are specifically designed for this application.

40.4.7 Specialized Cleaning Systems Additional specialized cleaning systems are utilized. Examples include abrasive cleaning with a variety of solid materials from bicarbonate to metal pellets, CO2 (steam, snow, liquid, and supercritical), steam, and plasma. Most are not used for the initial removal of lubricants. Many are used as a final or finishing cleaning, often before coating.

40.5 COMPARISON OF CLEANING EFFICIENCY FOR SELECTED SOLVENTS It is not possible in the limited space available to compare all cleaning agents for all types of cleaning applications. Instead, we have selected a limited number of solvents and will compare their solvency and cleaning efficiency in a very difficult cleaning job. The data presented in this section was obtained experimentally by one of the authors and has been previously published [25]. Figure 40.1 shows the relative solvating ability at room temperature of five halogenated solvents for four common lubricants. The solvents are n-propyl bromide (nPB), 1,1,1trichloroethane (1,1,1-TCA), trichloroethylene (Tric), perchloroethylene (Perc), and methylene chloride (MeCl2 ).

Hand wipe systems for cleaning have been around for a long time. For many applications, nothing is simpler and easier. New innovations in this area have to do with impregnation of the clean agent on a suitable cloth. Most hand wipes should be used with suitable gloves and in areas that are properly ventilated.

40.4.5 Aerosols Aerosols provide a convenient way of cleaning specific areas of otherwise large pieces of equipment. This may be particularly desirable where cleaning is essential prior to


Relative ranking

40.4.4 Hand Wipes

1.4 1.2 1 0.8 0.6 0.4 0.2 0

nPB TCA TCE PCE MC

Mineral oil

Polyol ester

Grease

Silicone oil

Lubricants

FIGURE 40.1 Relative solvating abilities of five halogenated solvents for four lubricants

120 % Soil removed

nPB TCA TCE PCE MC

80 60 40 20

Relative ranking

1.2

100

1 nPB HCFC-225 HFC-43-10 HFE-Me

0.8 0.6 0.4 0.2 0

0 Polyol ester Lubricants

FIGURE 40.2 Cleaning efficiency of five halogenated solvents for difficult cleaning jobs. Metal coupons were coated with soil, heated at 250◦ C for 1 h, and submerged in boiling solvent for 5 min

The four lubricants are a mineral oil, a polyol ester, a mineral oil based grease, and a silicone oil. Thirty percent by weight solutions of each lubricant were prepared in a solvent. Steel wool wedges were weighed and then soaked in the contaminated solvent, drained, and dried at 100◦ C for 30 min. The wedges were reweighed and the weight of the retained lubricant recorded. The impregnated wedges were then placed in short glass tubes and washed with 3 mL of the test solvent. The wedges were then drained, dried, and weighed as before. The grams of soil lost per milliliter of test solvent gives a measure of the solvating power. The final data was normalized to nPB = 1.0. Figure 40.2 compares the same solvents in a much more difficult cleaning task. In this experiment, metal coupons were coated with approximately 0.1 g of the test soil. The soil was then baked on by placing the coupon in an oven at 250◦ C for 1 h. The coupon was then immersed in the boiling test solvent for 5 min, removed, dried, and weighed. The percent soil removal was recorded. Each experiment was run in triplicate and the results averaged. Similar tests were carried out in an effort to compare a halogenated solvent (nPB) to the three leading fluorinated solvent types. The three fluorinated solvents were dichloropentafluoropropane (HCFC-225), heptafluorodecane (HFC-43-10mee), and nonafluorobutyl methyl ether (HFE-Me). The test soils were mineral oil, silicone oil, and a standard soil designated ASTM 448. ASTM 448 contains kerosene (30.7%), mineral spirits (30.7%), mineral oil (2.6%), SAE 10 motor oil (2.6%), vegetable shortening (7.7%), olive oil (7.7%), linoleic oil (7.7%), and C16 /C18 olefin (7.7%). Figure 40.3 is a solvating test of the fluorinated solvents at ambient temperature as described for Figure 40.1. nPB is clearly superior for this task, while HCFC-225 is second best. These results are not surprising when one compares the KB values of the solvents. Figure 40.4 is a tough cleaning job for fluorinated solvents and was carried out in the same manner as the experiment in Figure 40.2. The HFC-43-10mee and the


Mineral oil

Rosin flux

Silicone oil Lubricants

ASTM 448

FIGURE 40.3 Relating solvating ability of a halogenated solvent (nPB) compared to three fluorinated solvents

Wt% soil removed

Mineral oil

100 90 80 70 60 50 40 30 20 10 0

nPB HCFC-225 HFC-43-10 HFE-Me

Mineral oil

Polyol ester

Rosin solder flux

Lubricants

FIGURE 40.4 Cleaning efficiency of one halogenated solvent (nPB) and three fluorinated solvents for difficult cleaning jobs. Metal coupons were coated with soil, heated at 250◦ C for 1 h, and submerged in boiling solvent for 5 min

HFE-Me are somewhat effective on the baked on mineral oil and polyol ester, but are incapable of removing the rosin solder flux. The HCFC-225 did poorly on all three soils.

40.6 BENEFITING FROM CASE STUDIES A study recently published by the University of Dayton Research Institute in conjunction with the Materials Directorate of the U.S. Air Force Laboratory at Wright-Patterson Air Force Base looks at solvency and compatibility issues for a variety of solvents and aqueous cleaning agents under consideration as replacements for HCFC-141b and CFC-113 [26]. The Dayton study is an example of a published study that is valuable, not necessarily in terms of findings that might be copied in detail, but rather as food for thought for one’s own process considerations. A valuable study includes the underlying conditions and motivations for solvent and process selection. This includes such factors as solvency, process time, convenience, costs (capital and ongoing), worker safety, environmental concerns, and customer constraints. While this study is very disclosive in terms of motivations of the participants and in evaluating and comparing studies from a number of sources, given the number of possible variables, it is important to discern the basic motivation of the study. One might immediately see vendor-sponsored studies as requiring

extra consideration. However, even governmentally sponsored studies may in fact effectively represent advocacy for a particular subset of cleaning processes deemed to be environmentally preferred.

United States to have negligible impact on ozone depletion [27]. On the other hand, HCFC-225 with an ODP of 0.03 is scheduled for phase-out.

40.7.4 GWP — Global Warming Potential 40.7 ENVIRONMENTAL CONSIDERATIONS AND REGULATIONS There are many federal, state, and local regulations dealing with the use and disposal of industrial cleaning agents. All cleaning agents are not regulated by the same rules. All regulations do not apply to all applications. And, all rules do not apply in all localities. Suppliers of cleaning agents are usually able to supply information regarding which regulations may apply to their particular product, especially in regard to federal regulations and specific applications. It is always a good idea to check with local authorities to determine if additional regulations apply in your area. In addition to government-mandated rules and regulations, there are several health and environmental considerations when choosing a new cleaning agent. There follows a partial listing of the most important rules, regulations, and related issues.

40.7.1 SNAP — Significant New Alternatives Policy The U.S. EPA is charged under the Clean Air Act with evaluating all solvents introduced as replacements for ODSs. Once a substance has been submitted to the EPA for evaluation, it may be used commercially until the EPA promulgates a final rule. The primary basis for approval is the ODP of the substance, but worker exposure and toxicity issues also play a large role. The EPA may grant broad approval or they may grant approval only for certain applications.

40.7.2 VOC — Volatile Organic Compound All volatile organic compounds are classified as VOCs until the EPA specifically exempts a compound based on experimental evidence that it does not contribute to the formation of smog. The use of VOC exempt solvents is required in certain “nonattainment” areas where air pollution exceeds mandated federal or state levels.

GWP is a measure of the ability to a substance to contribute to global warming. This value is often linked to persistence in the atmosphere, or atmospheric lifetimes. Most HFCs and HFEs have very high GWPs.

40.7.5 AL — Atmospheric Lifetimes Some solvents decompose rapidly (a few weeks) in the atmosphere, while others are very stable and persist for years. Both the ODP and the GWP values are dependent on the atmospheric lifetime.

40.7.6 SARA — Superfund Amendments and Reauthorization Act This act requires reporting of inventories and emissions of listed chemicals and groups. SARA 313 is specific for cleaning solvents. Choosing a cleaning solvent listed in SARA 313 results in additional paperwork to meet the reporting requirements.

40.7.7 HAP — Hazardous Air Pollutant This is a listing of chemicals that the EPA has declared as hazardous.

40.7.8 NESHAP — National Emission Standard for HAP NESHAP sets standards for the use of materials listed as HAPs. Again, the choice of a solvent that is not on the HAP list will result in having fewer regulations that must be followed.

40.7.9 RCRA — Resource Conservation Recovery Act This act defines hazardous wastes and how to manage them. Once more, the choice of a cleaning agent that is not listed in RCRA allows a wider range of options in how to handle and dispose the waste materials produced by the cleaning operation.

40.7.3 ODP — Ozone Depleting Potential

40.8 CONCLUSION

ODP is a measure of the ability of a substance to deplete the ozone in the upper atmosphere. While no specific maximum ODP has been established, some guidance may be gleaned from rulings and statements by the EPA. The EPA, in their Proposed SNAP Rule for normal-propyl bromide, finds the ODP level of 0.013 to 0.018 in the continental

Critical cleaning of parts and assemblies is an essential element in the fabrication, repair, and/or operation of many products. One type of contaminant that may have to be removed is a functional or lubricating fluid. The necessity for critical cleaning has been confounded by the proliferation of new types of fluids, including synthetics, biobased,


and highly refined mineral oils. Fortunately, many options for cleaning do exist. In this chapter we have attempted to present a broad view of the cleaning agents and methods available today. In addition, we have pointed out a variety of conditions that one must be aware of in making a satisfactory selection. Cleaning efficiency is only one aspect of the cleaning problem. Worker safety, regulatory compliance, and cost-effective performance must all be taken into consideration.

REFERENCES 1. Synthetic Lubricants and High-Performance Functional Fluids (R.L. Shubkin, Ed.), Dekker, New York, 1993. Synthetic Lubricants and High-Performance Functional Fluids, 2nd ed. (L.R. Rudnick and R.L. Shubkin, Eds.), Dekker, New York, 1999. 2. Lubricants and Related Products (D. Klamann, Ed.), Verlag Chemie, 1984. Chemistry and Technology of Lubricants, (R.M. Mortier and S.T. Orszulik, Eds.), Blackie Academic and Professional, 1997. 3. Handbook of Critical Cleaning (B.F. Kanegsberg and E. Kanegsberg, Eds.), CRC Press, Boca Raton, FL, 2001. 4. Petrulio, R., private communication. 5. Kanegsberg, B.F., B. Dowell, S. Norris, and J. Unmack, Compliance and performance: selecting and optimizing a contained cleaning system, Presented at the International Thermal Spray Association, Las Vegas, NV, October 31, 2003. 6. Kanegsberg, B.F., Impact on manufacturing and assembly resulting from exemption of acetone as a VOC, Study for Chemical Manufacturers Association, December, 1999. 7. Kanegsberg, B., Your workday without HCFC 141b, Presentation and Proceedings, Fourteenth Annual International Workshop on Alternative to Toxic Materials in Industrial Processes, Scottsdale, AZ, December 8–11, 2003. 8. Shubkin, R.L. and R.J. DeGroot, New SNAP favored azeotropic blends, Presentation and Proceedings, Fourteenth Annual International Workshop on Alternative to Toxic Materials in Industrial Processes, Scottsdale, AZ, December 8–11, 2003. 9. Shubkin, R.L. and R.J. DeGroot, Solvent Trends for 2003, CleanTech Mag., 3, 27–31, January 2003. 10. Duncan, M., Biobased products as hazardous material alternatives, Presentation and Proceedings, Fourteenth Annual International Workshop on Alternative to Toxic Materials in Industrial Processes, Scottsdale, AZ, December 8–11, 2003. 11. www.aqmd.gov.


12. Kanegsberg, B., Cleaning is more than dipping and scrubbing, Presentation and Proceedings, CleanTech 2003, Chicago, IL, March 2003. 13. Quitmeyer, J., Cleaning challenges: chemistry, process, testing, and waste treatment, Proceedings, CleanTech 2002, pp. 353–360. 14. Bockhorst, R., M. Beeks, and D. Keller, Aqueous cleaning essentials, Chap. 1.3 in CRC Handbook of Critical Cleaning (B.F. Kanegsberg and E. Kanegsberg, Eds.), CRC Press, Boca Raton, FL, 2001, pp. 37–58. 15. Maluso, P. and B. Kanegsberg, Hydrostatic pump rebuild: implementing aqueous, steam and solvent free processes, Proceedings of the Tenth Annual Conference on Solvent Substitution and the Elimination of Toxic Substances and Emissions, Scottsdale, AZ, September 13–19, 1999. 16. O’Neill, E., A. Miremadi, R. Romo, A. Guzman, M. Shub, and B. Kanegsberg, Simplifying aqueous cleaning, IPAX, Products Finishing Magazine, August, 2000. 17. AQMD CAS Program, 2003, South Coast Air Quality Management District, Clean Air Solvent (CAS) Certification Program, http://www.aqmd.gov/rules/cas/cas.html. 18. Kanegsberg, E. and B. Kanegsberg, Critical cleaning by abrasive impact, A2C2 Mag., May, 2000. 19. Burke, J., Solvents and solubility, Chap. 1.2 in CRC Handbook of Critical Cleaning (B.F. Kanegsberg and E. Kanegsberg, Eds.), CRC Press, Boca Raton, FL, 2001. 20. Kenyon, W.G., New ways to select and use defluxing solvents, NEPCON West Proceedings, 1979, pp. 55–71. 21. Shubkin, R.L. and R.J. DeGroot, Newly Developed Advanced Solvent Systems for Critical Cleaning, Presented at CleanTech 2004, Chicago, IL, February 23, 2004. 22. Shubkin, R.L. and B.F. Kanegsberg, Solvent Flammability Basics, CleanTech Mag., 3, 17, October/November, 2003. 23. See Reference 13. 24. Fuchs, R. John, The fundamental theory and application of ultrasonics for cleaning, Chap. 2.2 in CRC Handbook of Critical Cleaning (B.F. Kanegsberg and E. Kanegsberg, Eds.), CRC Press, Boca Raton, FL, 2001. 25. Shubkin, Ronald L., normal-Propyl bromide, Chap. 1.7 in CRC Handbook of Critical Cleaning (B.F. Kanegsberg and E. Kanegsberg, Eds.), CRC Press, Boca Raton, FL, 2001. 26. Roberts, M.B., C.E. Snyder, Jr., L.J. Gschwender, J. Di Cocco, and S. Bryant, Lubricant cleaning and compatibility study for candidate chlorofluorocarbon and hydrochlorofluorocarbon solvent replacements, Tribol. Lubr. Technol., 60, 35–41, February, 2004. 27. U.S. Environmental Protection Agency, 40 CFR Part 82, “Protection of Statospheric Ozone: Listing of Substitutes for Ozone-Depleting Substances-n-Propyl Bromide; Proponed Rule”, Fed. Regist., 68, 33284–33316, June 3, 2003.

Part IV Trends


41

Automotive Trends in Europe R. David Whitby CONTENTS 41.1 Introduction 41.2 Trends in the Automotive Industry in Europe 41.2.1 A Manufacturers and Competitive Forces 41.2.1.1 Production of Vehicles in Western Europe 41.2.1.2 Production of Vehicles in Central and Eastern Europe 41.2.1.3 Imports and Exports 41.2.1.4 European Vehicle Manufacturers’ Trends and Prospects 41.2.1.5 Suppliers of components to the European Automotive Industry 41.2.1.6 Consolidation of Vehicle Manufacturing in Europe 41.2.2 European Automotive Design and Engineering 41.2.3 European Automotive Vehicle Regulations 41.2.3.1 Safety 41.2.3.2 Environment 41.2.4 European Automotive Lubricant Specifications and Tests 41.2.4.1 ACEA 41.2.4.2 CEC 41.2.4.3 Vehicle Manufacturers Lubricant Specifications and Tests 41.3 Current Status of Automotive Fluids in Europe 41.3.1 Engine Oils 41.3.1.1 Gasoline Engine Oils 41.3.1.2 Passenger Car Diesel Engine Oils 41.3.1.3 Heavy Duty Diesel Engine Oils 41.3.1.4 Two-Stroke Engine Oils 41.3.1.5 Automotive Gears and Automatic Transmissions 41.3.1.6 Other Automotive Oils 41.4 Development of Markets for Synthetic and High Performance Automotive Fluids in Europe

41.1 INTRODUCTION Emissions legislation, fuel economy, and vehicle performance have continued to be the major driving forces behind the design and choice of automotive engines and transmissions in Europe. The regulations and market forces that affect vehicle manufacturers have major effects on oil and additive companies. As a result, fuel and lubricants suppliers continue to strive to meet the requirements of existing and advanced technologies emerging from the motor and transport industries. These forces look set to continue to dominate Europe in the foreseeable future.


Current engine oils are required to function effectively for much longer and under more severe operating conditions than ever before. Engines have become more complex, with a larger number of working parts engineered to finer tolerances and a greater mix of different materials. The aerodynamic styling of many car designs, with very few cars having appreciable radiator grilles, for example, has reduced sharply the amount air cooling around the engine. Front wheel drive and the increased use of powered equipment, such as power steering, servo-assisted

braking, and air conditioning, all driven from the engine, have also reduced free space under the bonnet to a minimum. As a result, engines typically run at higher temperatures. Engines are also required to run for much longer, due to extended maintenance intervals, so lubricants must keep engines clean and efficient for longer. As an environmental improvement, engine oils are required to volatilize (evaporate) less at higher temperatures, thereby contributing less to the quantity of part-burned hydrocarbons (from the fuel) emitted to the atmosphere through the exhaust system. The pressures driving the overall performance demands on engine lubricants will continue to grow in the foreseeable future. Some of these pressures for passenger car engines include smaller or flatter oil sumps, improved oil ring efficiency, and lower oil consumption levels and use of on-board oil sensors to give extended oil drain intervals. Pressures for commercial and off-highway diesel engines include use of on-board oil sensors and computers, again to allow extended oil drain intervals. The changes in the last 15 to 20 yr have been dramatic. In Europe, around 19,200 km (12,000 mi) is now a commonplace service interval for family cars and over 80,000 km (50,000 mi for trucks), compared with as little as 6,400 km (4,000 mi) for cars and 30,000 km (18,800 mi) for trucks in the early 1980s. At that time new oil was continually being added, to top-up the lubricant and partially replenish its properties. Nowadays, many car engines do not need to be topped-up with oil between services. Lubricant stress has therefore become much more of an issue. New baseoils, many of them synthetic or severely hydrocracked mineral oils, and additives have been developed to counter this problem and to ensure that lubricants can continue to function effectively under much more demanding operating conditions. During the last few years, the internal combustion engine has been singled out for a great deal of attention and regulation on environmental performance. While emissions from gasoline engines have been reduced by around 95% compared with 20 yr ago, the trend is likely to continue and more attention is now being paid to reducing emissions from diesel engines. There has been a general move by all the organizations concerned with automotive development to improve environmental performance. In the case of engine oils, this has been either accompanied or created by increased efficiency and economic performance. For example, the generation of waste oil has been reduced by the use of smaller sump sizes and extended drain intervals. The amount of lubricant consumed during use has been reduced by improved sealing, which eliminates leakage, and tighter engineering design and tolerances that reduce the amount of oil being burnt in the combustion chamber. Increased fuel efficiency is another area of improved environmental performance, achieved through the use of lower viscosity lubricants.


41.2 TRENDS IN THE AUTOMOTIVE INDUSTRY IN EUROPE 41.2.1 A Manufacturers and Competitive Forces 41.2.1.1 Production of vehicles in Western Europe Western Europe is the world’s largest car market, ahead of North America, and is the third largest truck and bus market in the world, as indicated by the global vehicle population data shown in Table 41.1. In terms of the total numbers of vehicles on the road, Western Europe had 33.6% of the world’s cars and 13.1% of the world’s trucks and buses in 2002. In addition, Central and Eastern Europe (including the former CIS) had 10.1% of the world’s cars and 7.6% of the world’s trucks and buses in 2002.

TABLE 41.1 World Vehicle Population, 1998 to 2002 Number of vehicles in use (million) Region

1998

1999

2000

2001

2002

Cars W Europe C & E Europe N America C & S America Middle East Asia Africa Oceania

169.0 49.2 147.9 26.4 12.6 74.1 10.1 9.8

171.4 51.4 148.4 26.4 12.6 78.8 10.2 10.1

176.9 54.6 150.1 26.9 13.0 81.6 10.2 10.3

181.9 55.7 156.7 27.1 13.2 84.9 10.4 10.4

187.0 56.8 163.1 27.7 13.7 87.7 10.5 10.5

Total cars

499.1

509.3

523.5

540.3

557.0

23.1 15.2 86.6 8.6 5.2 36.6 4.4 2.7

23.4 15.1 86.7 8.7 5.3 39.8 4.4 2.8

24.0 14.3 90.6 8.8 5.4 40.5 4.4 2.9

25.3 14.9 94.1 8.9 5.5 41.2 4.5 2.9

26.6 15.6 97.5 9.0 5.6 41.8 4.6 3.0

Total trucks and buses

182.42

186.2

190.9

197.3

203.6

All vehicles W Europe C & E Europe N America C & S America Middle East Asia Africa Oceania

192.1 64.4 234.5 35.1 17.76 110.63 14.5 12.6

194.8 66.5 235.1 35.1 17.9 118.6 14.6 12.9

200.9 68.9 240.6 35.7 18.4 122.2 14.6 13.1

207.2 70.6 250.8 35.9 18.7 126.1 14.9 13.3

213.7 72.4 260.6 36.7 19.2 129.6 15.0 13.5

Total vehicles

681.5

695.4

714.4

737.6

760.6

Trucks and buses W Europe C & E Europe N America C & S America Middle East Asia Africa Oceania

Source: Pathmaster Marketing, from various industry sources.

TABLE 41.2 Western European Vehicle Population, 1998 to 2002 Number of vehicles in use (million) 1998

2000

2002

Total

Cars

Trucks and buses

Country

Cars

Trucks and buses

Austria Belgium Denmark Finland France Germany Greece Ireland Italy Netherlands Norway Portugal Spain Sweden Switzerland UK Others

3.89 4.42 1.84 2.02 26.30 41.37 2.44 1.06 31.37 5.47 1.69 3.08 14.75 3.70 3.32 21.88 0.39

0.74 0.53 0.30 0.29 5.38 3.22 0.98 0.16 2.79 0.60 0.40 1.01 3.01 0.34 0.22 3.10 0.04

4.63 4.96 2.14 2.31 31.68 44.59 3.41 1.22 34.16 6.07 2.09 4.09 17.76 4.04 3.54 24.98 0.43

4.01 4.49 1.78 2.07 27.48 42.42 2.68 1.27 31.37 6.34 1.81 3.20 17.45 3.89 3.47 22.76 0.43

168.99

23.10

192.09

176.92

Total

Total

Cars

Trucks and buses

0.33 0.45 0.35 0.30 5.61 3.40 1.01 0.19 2.93 0.83 0.45 1.10 3.84 0.35 0.31 2.51 0.04

4.34 4.95 2.13 2.37 33.09 45.82 3.69 1.46 34.30 7.17 2.26 4.30 21.28 4.24 3.78 25.27 0.48

4.18 4.68 1.88 2.15 28.70 44.38 3.42 1.31 33.24 6.54 1.87 3.59 18.15 4.02 3.63 24.85 0.44

0.40 0.62 0.40 0.34 5.90 3.59 1.08 0.22 3.31 0.85 0.46 1.37 4.16 0.41 0.33 3.16 0.05

4.58 5.30 2.28 2.48 34.60 47.98 4.49 1.53 36.55 7.39 2.34 4.96 22.31 4.43 3.96 28.01 0.49

24.00

200.92

187.03

26.63

213.66

Total


The largest markets for vehicles in Western Europe are, not surprisingly, Germany, France, Italy, Spain, and the United Kingdom. Numbers of cars, trucks, and buses for each country in Western Europe are shown in Table 41.2. A number of surprising statistics are evident from the data. In 2002, Italy had 15.8% more cars than France, even though the respective populations of France and Italy were 59.4 and 58.4 million. Germany, the largest country in Western Europe with a population of 82.5 million in 2002, had fewer trucks and buses than either France or Spain, and only slightly more than either Italy or the United Kingdom. Both Greece and Portugal, which are highly agricultural economies, have relatively large numbers of trucks and buses compared to the numbers of cars in each country. Most countries in Western Europe have vehicle manufacturing plants, although the biggest manufacturers of cars, trucks, and buses are located in the five main markets for vehicles. Data for the production of cars in Western Europe is shown in Table 41.3, while the production of trucks and buses is shown in Table 41.4. In total, 14.8 million passenger cars and 2.1 million trucks and buses were manufactured in Western Europe in 2002. It is evident from both Tables that manufacturing of vehicles in Western Europe has been relatively static, or even declining slightly, over the past five or so years. This


TABLE 41.3 Production of Passenger Cars in Western Europe, 1998 to 2002 Number of vehicles manufactured (thousand) Country a Austriab Belgiumb Finland France Germanyb Italy Netherlands Portugal Spain Sweden UK Total

1998

1999

2000

2001

91.5 951.2 31.1 2582.3 5348.1 1402.4 243.0 181.4 2216.4 368.3 1748.3 15164.0

123.8 917.5 34.0 2784.5 5309.2 1410.3 262.2 187.0 2208.7 434.5 1786.6 15458.3

126.0 912.2 38.5 2879.8 5131.9 1422.3 215.1 190.9 2366.4 260.0 1628.5 15171.6

121.2 884.2 41.9 3181.5 5116.8 1271.8 189.3 177.4 2211.1 251.0 1492.4 14938.6

2002 120.4 786.7 39.0 3283.8 4960.9 1125.8 182.4 182.6 2266.9 234.0 1628.0 14810.5

a Cars are not manufactured or assembled in Denmark, Norway, or

Switzerland. b Figures may be slightly inaccurate, due to some double counting

between Germany and Austria and between Germany and Belgium, but the total figure is accurate. Source: Pathmaster Marketing, from various industry sources.

TABLE 41.4 Production of Vans, Trucks, and Buses in Western Europe, 1998 to 2002 Number of vehicles manufactured (thousand) Country a

1998

1999

2000

2001

2002

Austria Belgium Finland France Germany Italy Netherlands Portugal Spain Sweden UK

11.7 114.0 0.5 341.1 378.7 290.4 27.5 89.6 609.7 114.5 227.4

15.5 98.9 0.5 395.7 378.3 290.8 25.1 65.3 643.7 59.1 185.9

25.0 121.1 0.5 468.6 394.7 316.0 30.5 55.8 666.5 35.7 185.3

24.3 128.6 0.4 446.9 390.5 307.9 49.7 62.4 638.7 38.1 192.9

19.9 119.7 0.4 409.0 346.1 301.2 48.9 68.3 588.4 38.5 193.1

2205.1

2158.8

2299.7

2280.3

2133.2

Total

is despite the overall increase in the numbers of vehicles sold in all countries in Western Europe during the same period. The main reason for this is the increase in sales of vehicles in Western Europe that were manufactured in the new and upgraded plants in Central Europe, particularly the Czech Republic, Poland, Slovakia, and Slovenia. These plants have been established mainly as a result of the lower labor costs in these countries and their close proximity to the large markets for vehicles in Western Europe.

41.2.1.2 Production of vehicles in Central and Eastern Europe

a Vans, trucks, and buses are not manufactured or assembled in Denmark, Norway, or Switzerland.


Central and Eastern Europe is the world’s fourth largest market for cars, as well as trucks and buses, well behind Western Europe, North America, and Asia, as shown in Table 41.1. Numbers of vehicles for the larger countries in the region are summarized in Table 41.5. The largest market for vehicles in the region is Russia, which has about the same number of vehicles as the United Kingdom. Other important markets for vehicles are Poland, the Ukraine, and the Czech Republic. Most

TABLE 41.5 Central and Eastern European Vehicle Population, 1998 to 2002 Number of vehicles in use (million) 1998

2000

2002

Total

Cars

Trucks and buses

Total

Cars

Trucks and buses

Total

Country

Cars

Trucks and buses

Bulgaria Croatia Czech Rep Estonia Hungary Kazakhstan Latvia Lithuania Poland Romania Russia Slovakia Slovenia Ukraine Uzbekistan Yugoslavia Others

1.73 0.99 3.62 0.45 2.28 1.00 0.48 0.98 8.78 2.65 14.00 1.18 0.80 4.69 0.90 1.86 2.79

0.25 0.12 0.41 0.09 0.32 0.30 0.10 0.11 1.68 0.44 9.95 0.11 0.06 0.94 0.01 0.16 0.20

1.98 1.11 4.03 0.54 2.60 1.30 0.58 1.09 10.46 3.09 23.95 1.29 0.86 5.63 0.91 2.02 2.99

2.04 1.13 3.72 0.48 2.35 1.02 0.57 1.15 9.28 2.74 17.05 1.27 0.86 4.93 0.90 1.98 3.12

0.31 0.12 0.44 0.10 0.33 0.30 0.11 0.11 1.85 0.46 8.60 0.12 0.07 0.96 0.01 0.17 0.26

2.35 1.24 4.16 0.58 2.68 1.32 0.68 1.26 11.13 3.20 25.65 1.40 0.93 5.89 0.91 2.15 3.38

2.24 1.26 3.70 0.52 2.48 1.04 0.64 1.25 9.39 2.84 17.82 1.25 0.92 5.18 0.90 2.10 3.26

0.33 0.13 0.61 0.11 0.40 0.31 0.13 0.13 1.78 0.48 9.40 0.17 0.08 0.98 0.01 0.19 0.32

2.57 1.39 4.31 0.63 2.88 1.35 0.77 1.38 11.17 3.32 27.22 1.42 1.00 6.16 0.91 2.29 3.58

Total

49.19

15.24

64.42

54.59

14.32

68.91

56.79

15.56

72.35



of the other countries in the region have relatively small numbers of vehicles. The ratio of trucks and buses to cars is much higher in Central and Eastern Europe compared with Western Europe, reflecting the greater importance of commercial and public transport over private transport. Production of passenger cars in Central and Eastern Europe, summarized in Tables 41.6, has been increasing steadily over the past five years. Conversely, production of trucks and buses, summarized in Table 41.7, has been declining steadily. Car production has increased due to steadily reviving economies, which translates to increasing consumer wealth, and as a result of major investment in

TABLE 41.6 Production of Passenger Cars in Central and Eastern Europe, 1998 to 2002 Number of vehicles manufactured (thousand) Country

1998

1999

2000

2001

Belarus Bulgaria Czech Republic Hungary Poland Romania Russia Slovakia Slovenia Ukraine

— — 368.6 83.5 543.9 103.9 830.8 125.1 126.4 25.5

— — 349.2 119.9 474.9 88.3 954.8 126.5 118.2 8.7

— — 428.1 134.7 290.9 64.1 968.1 181.3 122.9 14.4

— — 456.9 140.4 376.1 56.8 1022.0 181.6 126.7 14.8

— — 441.3 138.2 298.1 65.3 980.7 225.4 125.9 36.7

2207.7

2240.5

2204.5

2375.3

2311.6

Total

2002


TABLE 41.7 Production of Vans, Trucks, and Buses in Central and Eastern Europe, 1998 to 2002 Number of vehicles manufactured (thousand) Country

1998

1999

2000

2001

2002

Belarus Bulgaria Czech Republic Hungary Poland Romania Russia Slovakia Slovenia Ukraine

12.7 0.4 44.2 9.3 46.5 23.0 188.6 0.8 — 5.8

12.8 0.5 28.5 8.3 36.9 18.6 221.4 0.3 — 7.4

14.7 0.5 29.5 5.5 23.7 14.0 233.3 0.4 — 2.5

16.8 — 9.5 3.9 19.8 12.0 235.3 0.4 — 2.6

16.5 — 7.2 3.3 18.6 14.1 177.2 0.3 — 1.5

Total

331.3

334.7

324.1

300.3

238.7



new and upgraded plants by international manufacturers. During the last ten years, Volkswagen has acquired Skoda and invested in plants in the Czech Republic, Hungary, and Poland, PSA Peugeot Citroen has built plants in the Czech Republic and Slovakia, Renault has invested in a plant in Slovenia and acquired Dacia in Romania, Daewoo built a plant in Poland (although production has been severely cut back recently), General Motors acquired a plant in Poland, and Suzuki invested in a plant in Hungary. The acquisition of production facilities in Central Europe by a number of international manufacturers has led to the closure of many old, inefficient, formerly stateowned plants. This means, for example, that all cars made now in the Czech Republic are either VW Skodas or PSA Peugeot Citroens, which are being exported all over Europe in addition to being purchased by Czech motorists. All other makes of cars sold in the Czech Republic are imported. Similarly, all cars made currently in Slovakia are VWs or PSA Peugeot Citroens and all cars made in Slovenia are Renaults. In Hungary, only VW Audi and Suzuki make cars. At the same time, production of trucks and buses has declined in Central and Eastern Europe over the last five years. International manufacturers have not yet acquired production facilities in the region and the comparatively poor quality and performance of locally manufactured vehicles has become increasingly evident. This has meant that more trucks and buses are being imported into the region, mainly from Western Europe (see next section). 41.2.1.3 Imports and exports The main vehicle producing countries in Western Europe are large importers as well as large exporters of cars, trucks, and buses. Data for 2001 and 2002 is shown in Table 41.8. The primary reason for this is the concentration of manufacturing by OEMs in each country, with Europe-wide sales of vehicles. For example, all BMW and MercedesBenz cars sold in Europe (Western, Central, and Eastern) are made in Germany. All Renault cars sold in Europe are made in France, Spain, Slovenia, or Turkey, while all PSA Peugeot Citroen cars are made in France, Spain, Italy, the United Kingdom, the Czech Republic, or Slovakia. All this leads to a huge trade in vehicles between countries in Western Europe. Of specific note are the large numbers of cars and trucks that are imported into and exported from Belgium. In 2002, 1.42 million cars were imported into Belgium, 787,000 were manufactured there, and 1.74 million were exported, compared with total sales of cars in Belgium of only 468,000 cars. Belgium appears to be the only country in Western Europe where the import/export/production/sales ratios are so large, suggesting that the country is a major transfer location for vehicles bought and sold throughout Europe.

TABLE 41.8 Import and Export of Vehicles in Western Europe, 2001 and 2002 Numbers of vehicles (thousand) Imports Cars

Exports

Trucks and buses

Cars

Trucks and buses

Country

2001

2002

2001

2002

2001

2002

2001

2002

Austria Belgium Denmark Finland France Germany Greece Ireland Italy Netherlands Norway Portugal Spain Sweden Switzerland UK

437.7 1447.4 96.2 67.6 2376.6 1864.8 280.2 164.7 1737.8 726.8 91.9 345.9 1005.8 349.1 316.6 1851.5

382.9 1417.7 116.6 77.9 2344.6 1915.3 268.5 156.1 1693.4 693.5 88.7 287.3 888.7 363.9 295.1 1999.4

100.3 343.1 36.4 17.8 528.8 182.0 22.8 42.9 182.9 102.6 37.4 112.4 233.0 102.8 31.6 224.1

79.0 291.5 40.7 20.3 529.1 224.4 21.1 40.6 237.7 107.4 31.3 84.3 248.1 104.8 30.2 354.6

265.4 1842.9 — — 3303.4 3639.9 — — 596.1 385.9 — 268.1 1791.3 353.3 — 885.1

223.8 1736.8 — — 3483.3 3623.3 — — 539.6 365.2 — 243.8 1823.7 343.5 — 1063.8

162.5 423.4 — — 479.4 275.9 — — 217.4 50.8 — 68.5 546.1 105.7 — 100.9

62.5 343.2 — — 433.3 251.8 — — 193.4 48.5 — 64.3 503.5 104.0 — 189.6


In 2002, 47% by value of exports of vehicles from Western Europe went to North America, 13% went to Central and Eastern Europe, and 19% went to Asia, of which Japan accounted for 7%. At the same time, 32% of the value of imports into Western Europe came from Japan, 10% came from South Korea, and 30% came from Central Europe. Imports into and exports from selected Central and Eastern European countries are shown in Table 41.9. The data confirms the increasing numbers of cars being exported from the Czech Republic, Hungary, Poland, Slovakia, and Slovenia and the increasing numbers of trucks and buses being imported into many countries in the region. It is also notable that Russia is importing increasing numbers of cars, trucks, and buses, but no longer appears to be exporting vehicles, even to former CIS states. 41.2.1.4 European vehicle manufacturers’ trends and prospects During 2002 and 2003, many European vehicle manufacturers reported falling profits (or increased losses) and generally gloomy prospects. The despondency was caused by falling sales, persistent overcapacity of 30% in manufacturing vehicles, and a dash to cut prices and offer special deals (such as free finance, insurance and/or servicing) just to “move metal.” Some dealers were offering discounts of


as much as 30% in 2003. Discounting on this scale can be a real problem, since it is almost impossible to stop once consumers perceive that future prices might be lower than current ones. Manufacturers of cars in Europe are now under such huge financial pressures that they have begun to realize over the last few years that more profits can be made by selling finance, insurance, parts, servicing, and even mobile “infotainment” than by making and selling cars. They have also been able to make significant savings in the costs of marketing, sales, and distribution of cars. Industry analysts have calculated that the cost of marketing support, advertising, and distribution of vehicles can account for 30% of the pre-tax retail price of a car in Europe. The percentage is higher for small cars and lower for bigger ones. Many European car manufacturers are seeking to rationalize their dealer networks in favor of larger, better-funded groups. Internet sales are now seen as a way of providing information about specific models and their availability to prospective customers and then directing them toward the most appropriate local dealer. In this way, the manufacturer does not by-pass its dealers and consequently does not upset them. Recent surveys have suggested that 50% of U.K. motorists and 39% of French motorists would consider buying a car through the Internet, compared with 49% in the United States and 29% in Japan.

TABLE 41.9 Imports and Exports of Vehicles in Central and Eastern Europe, 2000 and 2001 Numbers of vehicles (thousand) Imports Cars

Exports

Trucks and buses

Cars

Trucks and buses

Country

2001

2002

2001

2002

2001

2002

2001

2002

Czech Republic Hungary Poland Romania Russia Slovakia Slovenia

131.9 129.8 436.3 15.0 81.0 62.5 69.0

139.1 175.4 459.8 36.6 139.9 84.2 67.1

36.9 71.9 125.4 17.2 66.3 16.6 19.7

45.4 82.4 101.0 30.5 136.7 24.8 21.0

365.7 123.6 246.4 9.2 — 184.7 115.0

416.4 122.1 218.8 13.3 — 188.3 118.6

45.1 — 45.4 — — — —

23.8 — 33.1 — — — —


Car manufacturers and their franchised dealers are continuing to pay a high price for the widespread public perception, and in some cases reality, that servicing and repair charges, for both parts and labor, are higher at franchised dealerships. The perceptions vary from country to country in Europe, with German motorists being the least skeptical and U.K. motorists the most skeptical. French and Spanish motorists are somewhere in between. In practice, though, once a car’s three-year warranty expires or it is sold by its company fleet manager, it is not likely to be serviced in a franchised dealer’s service center again. A few car manufacturers in Europe, notably Ford, experimented with either buying or setting-up fast-fit service centers in an attempt to capture some of the lost profits. However, in most cases, the independent service centers tended to continue to offer quicker and better service at lower prices. Some industry analysts forecast that sales of cars in Europe in 2003 would be between 3 and 4% lower than in 2002, and another 2 to 3% lower in 2004. The decline has been biggest in France and Germany, where economic weakness has coincided with a cyclical pause in buying cars. In addition to these problems, DaimlerChrysler, BMW, and Volkswagen are heavily exposed to the U.S. market. PSA Peugeot Citroen and Renault have not been affected as badly, the former due to a number of successful new models and the latter due to a revival with Nissan, now 44% owned by Renault. But two of the biggest casualties in Europe have been General Motors and Ford, both of which have been forced to cut capacity and improve productivity to try to reduce losses. Europe’s weakest car manufacturer in 2002 and 2003 was Fiat, in which GM now has a 20% shareholding. European motorist’s demands for smaller vehicles will also reduce profitability. More motorists are buying smaller cars as a result of the tax benefits of better fuel efficiency.


Small cars are less profitable to make than larger cars. At the same time, European car manufacturers are becoming more frustrated, because climate change is a global issue, not just a European one. In addition, less polluting cars cost more to manufacture. Direct injection gasoline engines (Mitsubishi) are 15% more efficient, but are 10% more expensive. Diesel engines are 20% more fuel efficient, but cost twice as much. Hybrid cars can do 60 mpg, but these cars are 8% more expensive. Car manufacturers also have gloomy prospects about countering low-cost competition from Asia, particularly China. European vehicle manufacturers believe that European governments are not sufficiently committed to manufacturing as a fundamental part of the economy. They forecast that there will be no growth in the European market beyond the current 45–£50 bn total sales. 70% of European vehicle manufacturers believe they can compete effectively within Europe, partly as a result of productivity and efficiency gains. But only 25% believe they are competitive with companies outside Europe. To become more competitive, more products will need to be imported and more manufacturing moved to lower-cost countries. During the last three, there has also been much debate in the United Kingdom about the effect of the £:e exchange rate on the production of vehicles and components in the United Kingdom vs. European countries in the “euro-zone.” For example, Nissan’s plant in Sunderland, United Kingdom, which makes more than 330,000 cars per year, is acknowledged to be the most efficient car plant in Europe. But its profitability has been severely undermined by the relative strength of the £ against the e from 2000 to 2003. Around 70% of the cars made in Sunderland are sold in the euro-zone. Nissan had planned to increase output from Sunderland to 500,000 cars per year, but has

postponed these plans until the £ is “stable” against the e. By “stability,” Nissan appears to mean “when the UK has joined the euro-zone countries.” At some time in the near future, Nissan may decide to expand production of cars in one of the Renault plants in France or Spain, since the French and Japanese companies have merged their operations in Europe. European and U.S. car manufacturers narrowed the productivity gap with leading Japanese manufacturers in Europe in 2002, as a new round of cost reductions improved worker productivity. Toyota, Honda, and Nissan increased labor efficiency in Europe by 5.4% in 2002, while European companies by 7%. This reversed the 2001 trend, when non-Japanese car plants saw productivity fall. However, an annual industry study found that the productivity lead of Toyota, Honda, and Nissan remained unassailable. The Japanese carmakers made an average 87.5 cars per worker at their European factories, against just 58.6 at rival European manufacturers’ plants. Industry observers believe the Japanese method of manufacturing is still viewed as the benchmark. Much of the productivity improvements at companies like General Motors and Ford was due to the adoption of “lean manufacturing” techniques pioneered by the Japanese. But, even the Japanese-owned factories in Europe lagged behind those in Japan itself, where productivity can reach almost double the best level in Europe. All four of the Japanese plants in Europe were in the top eight. However, the factories with the single biggest improvements in 2002 were IBC, the General Motors-owned van plant at Luton, United Kingdom, and Fiat’s Cassino plant in Italy. Toyota’s factory in Burnaston, Derbyshire, was the worst performer among the Japanese, dropping from third to eighth place. Burnaston’s productivity decline fits with accusations made this year by Kosuke Shiramizu, the company’s board member in charge of global production, that French workers work harder than British ones. Toyota’s new Valenciennes plant in Spain took third place, despite of only being one year old, when factories are usually struggling to overcome set-up problems. GM, Fiat, Honda, and PSA Peugeot Citroen all increased productivity by more than 10%. In mid-2002, DaimlerChrysler began a ten-year plan for closer integration of the company’s car brands, including Mercedes-Benz, Chrysler, and Mitsubishi Motors. The aim of the plan is to integrate parts distribution, dealer services, logistics, and salary payments across the group. It is the latest cost-cutting exercise and is being coordinated by the group’s “Executive automotive committee” that was created in 2001 to improve cooperation between brands. The committee had already agreed a ten-year plan to reduce the group’s number of different engines and transmissions, and is aiming to combine such activities as spare parts procurement and distribution and service workshops,


while protecting the identities of DaimlerChrysler’s different marques. In July 2003, MG Rover, which was bought for £10 from BMW in 2000 by a venture capital-backed management team, began selling a new “small” Rover, built entirely by Tata Corporation in India; at least 100,000 “Roverized” versions of the Indica small car from 2003 to 2008. Rover hopes to sell between 35,000 and 40,000 of these cars per year. Selling price is below the Rover 25, due to Tata’s low-cost production base in India. Later in the year, however, a potential manufacturing alliance with China Brilliance, collapsed. Fiat’s share of the Italian car market fell to 27.0% in June 2003, from 34.2% in June 2001. In Italy, PSA Peugeot Citroen had a 10.9% market share in 2003, VW had 10.4%, Ford had 8.6%, GM had 8.1%, Renault had 7.7%, and other manufacturers had 27.3%. Fiat cut 12,300 jobs worldwide in June 2003 in an attempt to reduce losses, which were e4.3 bn in 2002. These job cuts were partially offset by the simultaneous creation of 5,400 new jobs. Fiat aims to increase operating income by e4.7 bn by 2006, allowing the group to break even at the operating level in 2004. Much of the cost savings are intended to come from a turnaround project for Fiat, accelerated restructurings for CNH (the U.S. farm and construction equipment manufacturer), and the Iveco truck division and stronger coordination of purchasing for Fiat Auto, CNH, and Iveco. Only one small plant was closed in Italy, where Fiat suffers from overcapacity, and only 12 of its 138 plants worldwide were closed. 2,800 job cuts in Italy were offset by 1,600 new jobs. Nissan, the Japanese carmaker approached PSA Peugeot Citroen in June 2003 about using its large diesel engine to power U.S. light trucks and to support a possible launch of luxury cars in Europe. The approach came despite Nissan being controlled by Renault, PSA’s main rival. Nissan is also considering developing its own diesel engine, working either with Renault or using a Suzuki diesel currently used by Renault. Nissan wants access to a large diesel engine for pick-up trucks and sports utility vehicles, in case U.S. motorists begin to switch from gasoline after new regulations helping diesel come into effect in 2006. Nissan is mainly interested in having access to a large diesel for the U.S. market. But Nissan also requires a large diesel engine for the launch of luxury vehicles in Europe, either under the Infiniti brand the company uses in the United States, or as Nissans or Renaults. Diesels make up around 40% of all car sales in Europe and sales have been held back at brands such as Honda and Jaguar, which lacked the more efficient engines. If Nissan uses a PSA diesel engine, it would be further confirmation for the French group’s partnership strategy. Unlike many car manufacturers, PSA did not join the rush to merge with another company, but sought to share costs through joint development projects. The company, which is

the world’s biggest manufacturer of diesel engines, already has a joint venture with Ford, to develop and produce 3m diesel engines. A new V6 engine, the one of interest to Nissan, was unveiled in mid-2003 to be used in the latest Jaguar S-type car. Separately, GM’s European subsidiaries, Opel and Vauxhall, are collaborating with Fiat and Isuzu (part of GM’s Japanese affiliate) to develop and use diesel engines in European cars. In July 2003, Toyota began selling cars in Japan that were made in the United Kingdom. The company aims to ship 20,000 Avensis cars and estates from the plant in Burnaston, Derbyshire. The plant manufactured 220,000 Avensis and Corolla models in 2003 and aims to make 270,000 in 2004, with three-shift working. Toyota’s engine plant in Deeside, North Wales made 450,000 engines in 2003, for plants in the United Kingdom, France, Turkey, and South Africa. A number of Western European vehicle manufacturers have either built new plants or completely upgraded old plants in Central European countries during the last six years. Volkswagen acquired a 70% share in the Skoda plant in Mlada Boleslav, the Czech Republic in 1991 and increased this stake to 100% in 2000, having expanded the operations and added an engine plant in 1998. The company also built a new engine plant in Lower Silesia, Poland in 1999 and expanded car manufacturing capacity at its plant in Bratislava, Slovakia, to 250,000 cars per year. Renault has a plant in Romania, following the acquisition of Romania’s biggest car manufacturer, Dacia, in 1999. In January 2003, PSA Peugeot Citroen decided to build a new e700m plant in Trnava, Slovakia, to manufacture up to 300,000 cars per year in 2006. However, the investment in new and upgraded facilities is expected to slow down once the Central European countries begin to join the EU in 2004, as tax benefits and incentives become smaller and workers’ wages grow. In September 2002, DaimlerChrysler paid $700m for a 43% stake in Fuso, the truck unit of Mitsubishi Motors, its Japanese partner, in which it has a 37.7% stake. Prior to the acquisition, DaimlerChrysler had only a 1% share of the Asian truck market, which accounts for 20.5% of the world’s trucks. Separately, DaimlerChrysler announced aggressive plans in December 2002, to share at least 75% of the cost of engines and axles between its truck manufacturing operations in Europe, the United States, and Asia. Analysts believe the company could save $500m to $l bn per year if it can make the plan work. Little effort has been made in the past to share parts among the company’s disparate truck businesses. An attempt to introduce Mercedes-Benz engines to the Freightliner business in North America in 2000 had little success as U.S. truck drivers proved reluctant to abandon traditional Detroit engine brands. The company is now pushing Freightliner to work more closely with Mercedes, the largest European heavy truck


maker, and with Fuso and Hyundai, the company’s new partners in Japan and South Korea. DaimlerChrysler is the largest heavy truck maker, with a 21% share of the world market. But after 20 yr of owning Freightliner, DaimlerChrysler has been forced to find cost savings to stem heavy losses caused by promises to buy back trucks for too high a price in the United States. The company does not plan to build identical “world trucks” for sale everywhere, but intends to try to share more of the parts that buyers do not see. This could mean that at least 75% by value of the engine, axles, and gearbox, which comprise more than half the total cost of a truck, could be identical in all the company’s trucks. DaimlerChrysler is still identifying savings in truck chassis, with internal estimates ranging from 35 to 80% sharing. Very little of the cab is likely to use common parts, because of the different tastes of truck drivers in different regions. Scania and MAN announced a long-term collaboration on component parts in April 2003. The main parts involve gearboxes and axles, for which the companies claim to have substantial synergies. As a result of the announcement, industry observers began speculating about a possible merger of the two companies. MAN and Scania expect the Western European market for heavy trucks to decline by between 5 and 10%, to about 200,000 trucks in 2003. This compares with the North American market of about 172,000 trucks in 2003. However, in July 2003, Volkswagen began discussions to acquire MAN. The German insurance group Allianz holds a 14% stake in MAN and Commerzbank and Munich Re each hold 7%. VW and MAN together would be the world’s third largest truck maker. Currently, MAN is the third largest manufacturer of trucks in Europe, VW only has a light van business. Simultaneously, a European Commission ruling requires Volvo to sell its 31% voting stake (45% capital stake) in Scania before April 2004. VW has a 34% voting stake (18% capital stake) in Scania, so if VW acquired MAN, it may be forced by the European Commission to sell its stake in Scania.

41.2.1.5 Suppliers of components to the European Automotive Industry Vehicle manufacturers demand great commitment and involvement from suppliers, so suppliers are having to invest in high-quality staff, new production processes, and new technologies in order to compete. The more innovative or complex the component, the more closely the supplier and the manufacturer will have to cooperate. Suppliers have become increasingly involved at the earliest stages in the design of a new vehicle and are now required to run computer simulations of how their components will function in conjunction with parts from other suppliers. These simulations also need to model the efficiency

and cost-effectiveness of components in the complete new vehicle. Component suppliers are also doing more of the manufacturing and assembly work that was done previously by vehicle manufacturers. They are also having to exchange information constantly with their customers. The Internet has made the sharing of designs, computer simulations, and parts integration between suppliers and manufacturers and among suppliers, significantly easier and faster. These Internet links are expected to grow, not least because vehicle manufacturers are trying to shift more of the development work and costs to component suppliers. At the same time, European suppliers can reduce their cost bases by shifting some of the design and development work to engineering centers in places like India, again, using the Internet. For example, Valeo, the largest French manufacturer of car components, makes everything from clutch systems to windscreen wipers, supplies parts worldwide, has around 180 production sites and over 100 operating divisions. All the company’s sites are now linked to each other and to customers and suppliers via the Internet. The company now uses the Internet to provide web-catalogs to customers, to run online reverse auctions with its suppliers (using requests for quotation), to manage purchasing decisions, and for customer and supplier relationship management. Hundreds of companies supply parts and components to the main European vehicle manufacturers. Many more companies are subsuppliers. The larger European manufacturers of major components for vehicles include Bosch, Brose, Delphi, Denso, Doga, Dura Automotive, Getrag, GKN, Lear Automotive, Magna, Magneti Marelli, Meritor, TRW, TVR Engineering, and ZF. In another example of the increasing closeness of relationships between manufacturers and suppliers, Magna Kansei in the United Kingdom supplies BMW, Nissan, General Motors, Rover, Land Rover, and Jaguar with automotive interior parts. To boost manufacturing quality and productivity, Magna Kansei uses Six Sigma processimprovement statistical tools. The company is a synchronous supplier to Nissan, in that it has built a factory just a few minutes away from Nissan’s plant in Sunderland. This gives Magna Kansei a huge competitive advantage, because it can adjust production and delivery to match Nissan’s requirements precisely. Despite all this, suppliers remain under relentless cost pressures. Nissan, having completed a 30% cost reduction drive, now intends to reduce production costs by a further 15% by 2005. Faced with exchange rate variations caused by making vehicles outside the euro-zone for sale within it, Nissan’s Sunderland plant has placed only 30% of its components spend for the 2003 Micra with U.K. suppliers compared with 80% for the old model. To cut costs and raise quality and efficiency even further, Nissan is beginning to give suppliers the complex task of producing


entire modules. Magna Kansei needs to build a new plant, because it will make the entire cockpit assembly for the new Micra. 41.2.1.6 Consolidation of vehicle manufacturing in Europe As a result of the cost pressures faced by manufacturers of vehicles in Europe, a significant number of alliances, joint ventures, and even mergers have occurred during the last five years. European vehicle manufacturers have begun to collaborate as never before. In March 1999, Renault acquired a 36.8% shareholding in Nissan. The deal suited both companies, as the cash boost enabled Nissan to overcome the severe financial difficulties experienced in 1998 and continue manufacturing cars, while Renault expanded from its mainly European market into Asia. The alliance between the two companies enabled both to achieve benefits without the costs of a full merger. The alliance was further strengthened in March 2002, when Nissan acquired a 15% stake in Renault and Renault increased its shareholding to 44.4%. At the same time, the French government reduced its shareholding in Renault to 25.9%. The alliance between Renault and Nissan has led to major benefits for both companies, including reduced purchasing costs, sharing of engineering designs, powertrains (engines and gearboxes) and vehicle platforms, cross-utilization of manufacturing sites, and a common European distribution policy. One result is that Renault cars and vans are now being manufactured at Nissan sites in Spain and Mexico and Nissan pick-up trucks are being made at Renault’s plant in Brazil. In March 2002, Nissan began selling Interstar, an adapted version of Renault’s Master van. In July 2002, BMW and PSA Peugeot Citroen initiated a e750m alliance to develop and assemble up to 1 million new engines per year. A common project team designs the engines at BMW’s research center in Munich and PSA oversees parts procurement and engineering. The engine production capacity is planned to meet the future needs of both companies’ small cars, including BMW’s new Mini. New gasoline engines produced under the alliance will reduce BMW’s reliance on its engine joint venture with DaimlerChrysler at Curitiba in southern Brazil. Initially, BMW sourced all engines for its Mini small cars from Brazil. However, the plant’s future was in doubt following a sharp reduction in output for Chrysler, which uses engines from there for its PT Cruiser and Neon models. Chrysler cut engines sourced from Curitiba to just 3,000 in 2002, compared with 100,000 for BMW’s Minis. The plant has a capacity of 250,000 engines a year. The new engines developed with PSA will be used in BMW’s next-generation Mini vehicles, due to be launched after 2007. With current Mini production running at about

250,000 per year, most of the engines from the alliance will initially go to PSA, although the costs of the plant are being split on a 50:50 basis. The alliance follows several other technical alliances by both BMW and PSA, which regard limited cooperation with other carmakers as one way to safeguard their future independence. PSA has a joint venture in diesel engines with Ford and is also developing a new small car with Toyota, to be produced at a new plant in the Czech Republic. BMW has also signed a deal with Toyota for the supply of diesel engines for the Mini. In April 2000, Renault and Volvo trucks announced plans to merge the two companies’ truck activities and, following clearance from the EU Commission competition authorities and the U.S. Federal Trade Commission, Renault became the main shareholder in Volvo Trucks, with a 20% stake, in January 2001. The two companies combined their truck manufacturing, to become Europe’s largest maker of trucks and the world’s second largest truck maker. Following the sale of Volvo cars to Ford in 1999, Volvo has focused on truck manufacturing. Volvo, Renault, and Mack have an alliance, Global Trucks, which now accounts for more than two-thirds of Volvo’s net revenues. Volvo’s other activities include construction equipment, buses, marine and industrial engines, and aerospace engine components.

41.2.2 European Automotive Design and Engineering Europe has always been at the forefront of automotive vehicle design and engineering, and this has continued during the 1990s. Much of the successful automotive engineering carried out in Europe stems from the very heavy involvement in the United Kingdom, Germany, France, Italy, and other countries in the world’s racing car industry, particularly Formula 1 and Indy 500 racing. While these areas are highly specialized and involve comparatively few companies and people, the commercial spin-off from their innovations and developments cannot be overemphasized. European OEMs are currently doing a significant amount of engineering design and development work on gasoline engines. The aim of the work is to make significant further improvements in engine efficiency, to give enhanced fuel economy, and reduced exhaust emissions. Ford introduced a new series of Jaguar XJ cars with aluminum bodies toward the end of 2002. If the new cars prove popular and successful, Ford will consider using aluminum bodies for all its premium cars. Aluminum is becoming increasingly popular as a replacement for steel in cars, to reduce weight and hence gain better performance from the same engine and gearbox assembly. Its use in Europe is being encouraged by tax reductions for low emission cars. The aluminum body Jaguar XJ cars have a 10% better fuel efficiency compared with their previous


steel body equivalents. However, aluminum is more difficult and expensive to work with than steel, so aluminum is likely to be used only for more expensive cars. Cars made by VW’s Audi division have been using aluminum bodies for several years. In June 2003, Ford and PSA Peugeot Citroen announced the introduction of compacted graphite iron (CGI) for the blocks of turbo-charged diesel engines. CGI will replace conventional cast iron in a new 2.7 L V6 diesel engine to be used in Jaguar S-type cars in mid-2004. The strength of CGI means that less material is needed than for a conventional cast iron block, allowing the engine to have a relatively light weight of 202 kg and to occupy less space. This boosts its power-to-weight ratio and fuel economy characteristics. The use of CGI has required advances in manufacturing processes, including the development of machine tools to handle the material. The new engine is the first to be developed under the Ford/PSA collaboration agreement. It is aimed at the rapidly growing premium end of the diesel market, where customers are reluctant to compromise in areas such as performance, noise, and efficiency. Ford and PSA hope the V6 will allow them to compete with BMW and Mercedes, both of which have diesel engines designed for larger cars. After initial use in the Jaguar, the engine will appear in other premium models across the two companies’ ranges. The engine includes a number of technical innovations developed by Ford and PSA during their five-year collaboration. It has a compression ratio of 17.3:1, which is low for a diesel engine, giving quieter combustion and helping to reduce emissions. It also uses state-of-the-art common-rail fuel injection technology capable of achieving an operating pressure of 1650 bar, higher than previous systems. The quantity of fuel injected is controlled by a piezo actuator, while the injectors themselves deliver fuel from a hole 145 µm in diameter, providing a spray of fuel fine enough to achieve maximum uniformity of fuel/air mixture. Ford and PSA have also developed an advanced electronic control unit (ECU) to monitor and manage the new engine. The ECU draws data from 23 sensors and sends out instructions to 20 actuators. Most European car manufacturers currently provide three-year warranties on their vehicles, despite the introduction of five-year warranties by Hyundai in 2002. The change to longer warranties may have been prompted by changes in EU rules that govern car sales and repairs. From the end of 2003, independent service centers have been allowed to carry out service work within a car’s warranty period, without affecting the warranty, provided the service center demonstrates it meets the servicing standards set by the car manufacturer. Car manufacturers are also required to provide independent service centers with all relevant information required to service their cars. A five-year warranty appears to be a marketing plan to tempt car owners to have the servicing done by franchised Hyundai dealers.

However, other European car manufacturers have decided that three-year warranties are more appropriate, since many motorists buy a new car about every three years. One innovation is the use of electromagnetic inlet and exhaust valves. These use the force of a small springloaded armature to change the position of each valve and a magnetic field to hold the valve in the selected open or closed position. A very short electrical impulse switches the spring from one position to the other. These “digital binary valves” will be controlled by an electronic engine management system and will operate significantly faster than valves opened and closed by a mechanical camshaft and springs. Their operation can also be varied depending on the output torque required from the engine. Both developments are claimed to result in fuel savings of up to 20%. Another very important advantage of electronic engine valves is the resulting ability to separate the valve operation from the mechanics of the crankshaft and piston assembly. This, in turn, allows the lubrication of the crankshaft and piston rings to be separated from the lubrication of the valves, since there is no camshaft and tappets to be lubricated. The importance of this innovation lies in the significantly reduced antiwear requirements for engine oils used in these engines, allowing greatly reduced levels of zinc dialkyl dithiophosphate (ZDDP) antiwear additives. European OEMs are seeking engine oils with low (or even no) zinc (Zn) and phosphorous (P) contents, as these elements are accumulative poisons of exhaust system catalysts. OEMs believe that low Zn and P engine oils are likely to assist in maintaining exhaust emissions system durability for the 50,000 km required by European Auto Oil IV regulations due to be implemented in 2005. Another set of technologies that has been developed, and is now being introduced, by European (and Japanese) OEMs is gasoline direct injection (GDI). GDI was developed and implemented first by Mitsubishi in Japan, but requires the use of very low (1760

CO HC + NOx HC NOx

6.90 1.70 — —

5.00 0.80 — —

5.22 — 0.29 0.21

2.27 — 0.16 0.11

CO HC + NOx NOx PM

2.72 0.97 — 0.14

1.00 0.90 — 0.10

0.64 0.56 0.50 0.05

0.50 0.30 0.25 0.025

1305–1760

CO HC + NOx NOx PM

5.17 1.40 — 0.19

1.25 1.30 — 0.14

0.80 0.72 0.65 0.07

0.63 0.39 0.33 0.04

>1760

CO HC + NOx NOx PM

6.90 1.70 — 0.25

1.50 1.60 — 0.20

0.95 0.86 0.78 0.10

0.74 0.46 0.39 0.06

Gasoline 3750 lbs Tier 1 0.32 TLEV 0.160 LEV 0.100 ULEV 0.050

100,000 miles/10 yr

CO

NOx

PM

HCHO

NMOGa

3.4 3.4 3.4 1.7

0.4 0.4 0.2 0.2

0.08 — — —

— 0.015 0.015 0.008

0.31 0.156 0.090 0.055

4.2 4.2 4.2 2.1

0.6 0.6 0.3 0.3

— 0.08 0.08 0.04

— 0.018 0.018 0.011

3.4 3.4 3.4 1.7

0.4 0.4 0.2 0.2

0.08 — — —

— 0.015 0.015 0.008

0.31 0.156 0.090 0.055

4.2 4.2 4.2 2.1

0.6 0.6 0.3 0.3

— 0.08 0.08 0.04

— 0.018 0.018 0.011

4.4 4.4 4.4 2.2

0.7 0.7 0.4 0.4

0.08 — — —

— 0.018 0.018 0.009

0.40 0.200 0.130 0.070

5.5 5.5 5.5 2.8

0.97 0.9 0.5 0.5

— 0.10 0.10 0.05

— 0.023 0.023 0.013

CO

NOx

PM

HCHO

a NMHC for all Tier 1 standards.

Abbreviations: LVW — loaded vehicle weight (curb weight + 300 lbs), LDT — light-duty truck, NMOG — nonmethane organic gases, HCHO — formaldehyde.

Low Emission Vehicles (LEV), Ultra Low Emission Vehicles (ULEV), Super Ultra Low Emission Vehicles (SULEV), and Zero Emission Vehicles (ZEV). Table 43.10 and Table 43.11 summarize the Tier 1/LEV standards applicable through year 2003. Future California emission standards LEV II will extend from 2004 to 2010 and are listed in Table 43.12 (passenger cars, light-duty vehicles) and Table 43.13 (medium-duty vehicles).

43.4.4 Future Perspective Diesels can have a future as mainstream power train technologies for light-duty vehicles in the United States. However, in order to do so, diesels will need to meet Tier 2 Bin 5 emissions standards to capture up to 7% of the U.S. light-duty vehicle market by 2008 and 15% by 2010 [17]. Currently diesel vehicles can be sold in only 45 states, with the exception of California, New York, Massachusetts, Connecticut, and Vermont. In addition, California, New York, Massachusetts and Vermont have stricter emission regulations than federally mandated guidelines. In 2003 only one vehicle manufacturer, Volkswagen, offered diesel passenger cars to the U.S. market. This situation will change in the near future as diesel passenger cars are offered by Daimler Chrysler, Toyota, and


Volkswagen. Currently, all of these vehicles are undergoing testing to show that they can meet the 2007 emission standards [18,19]. Aftertreatment technologies needed to meet new emission regulations are also available. Current testing is being conducted using a low sulfur diesel fuel that is used in Europe, but is not yet widely available in the United States. This fuel will be made available starting in August of 2006. The sulfur content of this fuel is 15 parts per million (ppm), which is down from the current level of 300 ppm. The emissions systems of these prototype aftertreatment technologies must also show that they can maintain the emissions levels for 10 yr or 150,000 miles before they can be certified. A comparison of the newest diesel vs. gasoline counterparts’ vehicles introduced in the United States is shown in Table 43.14. The cost comparison between 2007 diesel technology and current U.S. gasoline technology is not encouraging [21,22]. Diesel engine production might even increase to several thousands dollars higher if aftertreatment systems need to be incorporated. However, if fuel consumption reduction becomes mandated for the gasoline engine, because of future CAFÉ or CO2 standard’s the equation may become a little more palatable. The addition of variable valve train (VVT), gasoline direct injection (GDI), and turbocharging technology to gasoline engines to improve fuel consumption will increase the base engine cost considerably. Perhaps in its ultimate form, with fully flexible

TABLE 43.11 California Emission Standards for Medium-Duty Vehicles, FTP 75, g/miles 50,000 miles/5 yr Category

NMOGa

MDV1, 0–3,750 lbs Tier 1 0.25 LEV 0.125 ULEV 0.075 MDV2, 3,751–5,750 lbs Tier 1 0.32 LEV 0.160 ULEV 0.100 SULEV 0.050 MDV3, 5,751–8,500 lbs Tier 1 0.39 LEV 0.195 ULEV 0.117 SULEV 0.059 MDV4, 8,501–10,000 lbs Tier 1 0.46 LEV 0.230 ULEV 0.138 SULEV 0.069 MDV5, 10,001–14,000 lbs Tier 1 0.60 LEV 0.300 ULEV 0.180 SULEV 0.090

120,000 miles/11 yr

CO

NOx

PM

HCHO

NMOGa

3.4 3.4 1.7

0.4 0.4 0.2

— — —

— 0.015 0.008

0.36 0.180 0.107

5.0 5.0 2.5

0.55 0.6 0.3

0.08 0.08 0.04

— 0.022 0.012

4.4 4.4 4.4 2.2

0.7 0.4 0.4 0.2

— — — —

— 0.018 0.009 0.004

0.46 0.230 0.143 0.072

6.4 6.4 6.4 3.2

0.98 0.6 0.6 0.3

0.10 0.10 0.05 0.05

— 0.027 0.013 0.006

5.0 5.0 5.0 2.5

1.1 0.6 0.6 0.3

— — — —

— 0.022 0.011 0.006

0.56 0.280 0.167 0.084

7.3 7.3 7.3 3.7

1.53 0.9 0.9 0.45

0.12 0.12 0.06 0.06

— 0.032 0.016 0.008

5.5 5.5 5.5 2.8

1.3 0.7 0.7 0.35

— — — —

0.028 0.028 0.014 0.007

0.66 0.330 0.197 0.100

8.1 8.1 8.1 4.1

1.81 1.0 1.0 0.5

0.12 0.12 0.06 0.06

— 0.040 0.021 0.010

7.0 7.0 7.0 3.5

2.0 1.0 1.0 0.5

— — — —

— 0.036 0.018 0.009

0.86 0.430 0.257 0.130

10.3 10.3 10.3 5.2

2.77 1.5 1.5 0.7

0.12 0.12 0.06 0.06

— 0.052 0.026 0.013

CO

NOx

PM

HCHO

a NMHC for all Tier 1 standards.

Abbreviations: MDV — medium-duty vehicle (the maximum GVWR from 8,500 to 14,000 lbs). The MDV category is divided into five classes, MDV1 . . . MDV5, based on vehicle test weight. The definition of “test weight” in California is identical to the Federal ALVW, NMOG — nonmethane organic gases, HCHO — formaldehyde.

TABLE 43.12 California LEV II Emission Standards, Passenger Cars, and LDVs < 8500 lbs, g/miles 50,000 miles/5 yr Category LEV ULEV SULEV

120,000 miles/11 yr

NMOG

CO

NOx

PM

HCHO

NMOG

CO

NOx

PM

HCHO

0.075 0.040 —

3.4 1.7 —

0.05 0.05 —

— — —

0.015 0.008 —

0.090 0.055 0.010

4.2 2.1 1.0

0.07 0.07 0.02

0.01 0.01 0.01

0.018 0.011 0.004

valve train system, the gasoline engine may be able to compete with a light-duty diesel engine, but the cost and complexity are significant and the diesel then becomes an attractive option. The challenge is reducing the cost of the powertrain to a reasonable level that will meet the needs of the customer. The majority of the diesel engines in the United States are currently fitted into pick-up trucks where the market


penetration is expected to be nearly 6%. In these applications, consumers clearly appreciate the added utility of diesel and are willing to pay premiums of up to $5000 for the diesel-powered vehicles. Hence, in order to fully exploit the potential for diesels in the United States, particularly for the very significant SUV and light truck market, the diesel engines are likely to be custom designs for the United States, rather than

transplanted European technology. These custom designs will allow the cost gap to be narrowed between gasoline and diesel while still offering all the benefits of drivability, reduced fuel consumption, low noise, etc. For smaller passenger car applications where four cylinder engines are likely to dominate, applying European engines into U.S. vehicles is considered more feasible. The additional volume for this class of engine will also reduce the cost of the European engines.

43.5 DIESEL BARRIERS IN NORTH AMERICA There are several reasons for the currently limited diesel growth in the United States. They are as follows: 1. Emission legislation. Future Tier 2 and US 2007/2010 emissions legislation presents a technical challenge to diesel engines, which will require the use of advanced combustion and durable aftertreatment systems. While this required technology will be available in the required timeframe, cost issues will remain. 2. Product cost. The level of technology required to meet the future emissions legislation may result in engines that are significantly more expensive to produce than gasoline engines of today. The major cost contributors of the advanced diesel engine are the fuel injection, turbo machinery, exhaust gas recirculation (EGR), and aftertreatment systems.

TABLE 43.13 California LEV II Emission Standards, Medium-Duty Vehicles, Durability 120,000 miles, g/miles Weight (GVWR), lbs. 8,500–10,000

10,001–14,000

3. Diesel perception. Many consumers still regard diesel as “dirty, noisy, smelly, and slow” even though advanced diesel technologies available today are very different from engines in the early 1980s. The main challenge is to educate the consumer and to convince them to test drive a modern diesel-powered vehicle. The diesel engine’s performance benefits would rapidly win over these skeptics. 4. Fuel economy pressure. There is currently little pressure to improve fuel consumption of passenger car motor vehicles. CAFÉ legislation has been relatively ineffective at promoting a reduction in fuel consumption; in fact, average fuel consumption has actually increased in the United States which is in large contrast to the trend in many European countries [23,24]. The cost of fuel is a large driver for the reduction of fuel consumption in Europe where typical fuel costs can be three times that of the United States. All car companies are also committed to the voluntary reduction of CO2 emissions under the ACEA agreement. The situation in the United States may change in the near future due to the government’s stated desire to reduce the U.S. dependency on foreign oil. This may either promote more interest in the reduction of foreign oil consumption or a change to alternative fuels such as hydrogen. 5. Fuel infrastructure. Only around 30% of filling stations in the United States currently offer diesel fuel [25]. Many of these locations are truck stops, where the pumps are located in nonuser friendly locations. However, the investment required to increase the availability is probably relatively low and this process could be completed quickly, should diesel market penetration increase significantly.

43.6 SUMMARY Category

NMOG

CO

NOx

PM

HCHO

0.195 0.143 0.100 0.230 0.167 0.117

6.4 6.4 3.2 7.3 7.3 3.7

0.2 0.2 0.1 0.4 0.4 0.2

0.12 0.06 0.06 0.12 0.06 0.06

0.032 0.016 0.008 0.040 0.021 0.010

LEV ULEV SULEV LEV ULEV SULEV

The biggest factors determining the fate of diesel engines in the U.S. passenger car motor vehicle market is not technical, but more a blend of economic, regulatory, and social. Currently, there is no significant driver to reduce fuel consumption and until this situation changes, there is correspondingly little consumer pressure to change this.

TABLE 43.14 Side-by-side Comparison — Gasoline /Diesel N. American vehicles [20]

Fuel delivery system EPA (mpg) city/hwy Horsepower/torque (lbs. ft.) Price ($)


VW Golf GL, 1.9L (gasoline)

VW Golf GLTDI, 1.9L (diesel)

VW Touareg, 5L, V8 (gasoline)

VW Touareg 5L, V-10 TDI (diesel)

Mercedes-Benz E 320 (gasoline)

Mercedes-Benz E 320 CDI (diesel)

24/31 115/122 16,355

Unit injectors 38/46 100/177 17,775

14/18 310/302 43,255

Unit injectors 17/23 310/553 58,415

19/27 221/232 48,795

Common rail 27/37 201/369 49,795

The desire by the U.S. government to reduce foreign oil dependency may stimulate a change in this direction, but legislation will probably be required. Whether taxation on fuel is a politically acceptable means to drive down fuel consumption is still an unanswered question. Technology is available today to achieve light-duty Tier 2 Bin 5 emissions levels in vehicles up to at least 6000 lb of inertia test weight. The approach required to meet these levels includes increased engine flexibility via the use of advanced air and fuel systems. These systems allow the optimization of low engine out NOx and soot, as well as the flexibility to control aftertreatment devices. From an aftertreatment DPFs will be mandatory for all engine classes. DPF application is now commonplace in Europe and the technology is relatively mature. NOx aftertreatment is much less mature and will still present many technical challenges. For passenger cars under ∼4000 lbs the achievement of Tier 2 Bin 5 appears feasible without the need for NOx aftertreatment. This approach is possible due to the reduced emissions of the lighter vehicles and the fact that alternative combustion can be applied for a wider range of the emission relevant speeds and loads. For heavier vehicles NOx aftertreatment is required and the development of suitable systems is still underway. However, it is likely that suitable NOx aftertreatment devices will be available in the Tier 2 timeframe. Future DPF and NOx aftertreatment devices are likely to be integrated into “4 way catalysts” such as the Toyota DPNR system, which may have the added benefit of reducing overall costs and improved performance. From a larger displacement passenger car motor vehicle perspective, the 2007 emissions levels appear achievable without the need for NOx aftertreatment, but with the application of a DPF. These engines will have a similar cylinder displacement to the light-duty engines, although displacements in the 5.5 to 6.5 L range are expected. However the 2010 regulations are a different matter and at present these will require significant developments in both NOx aftertreatment and combustion technology to ensure emissions compliance. The consumers’ perception of diesel engine technology is also an issue, since perceptions are often not based on facts, but rather feelings. Modern diesels are fuel efficient, clean, quiet, and offer the end user improved drivability over the gasoline engine. Once end users experience these engines, their negative perceptions should quickly be eliminated. The major challenge will be in getting consumers to test drive the vehicles in the first place. This then represents a marketing, rather than a technical challenge, which must be addressed by the auto manufacturers. Lastly, and very significantly, the increased cost of the diesel engine must be considered. Unless the OEMs can convince the end user of the added benefits of diesel technology, it will be difficult to charge a premium for these vehicles and even more difficult to retain a profit from their


sale. As aftertreatment system development and production volumes increase, the overall costs to implement these systems should be reduced. In addition, fuel system costs, which account for around 40% of the total diesel cost, should also be reduced as competitive forces and production volumes increase. If value is placed on fuel economy, either via fuel taxation or future legislation, then gasoline production costs will climb based on the added technology needed to achieve fuel savings. Under this scenario it is possible that the cost associated with diesel technology will become acceptable. In addition to the fuel economy benefit, it is important that the performance aspect be highlighted, which would then allow further justification for any price premiums. With the amount of miles driven by the average U.S. consumer rising, coupled with a decrease in vehicle fuel economy, the usage of fossil fuels is at an all time high in North America. A number of alternative propulsion systems are being evaluated by vehicle OEMs, Government bodies, and research establishments. Fuel cells, Hybrid Electric Vehicles, and Hydrogen IC engines are all being presented as possible solutions to help reduce U.S. dependency on oil. In Europe, where reductions in fuel consumption have been accepted voluntarily by the car companies, the diesel engine is currently the main solution to the fuel equation. In the United States, one or more major drivers will be needed to pull (or push) this technology through, in order for it to become more readily adopted for use in passenger car motor vehicles.

REFERENCES 1. Diesel, R. German Patent No. 67207,“Working Method and Design for Combustion Engines,” February 23, 1893. 2. 10th Diesel Engine Emissions Reduction Conference, August 2004. 3. Heywood, J.B. Internal Combustion Engine Fundamentals McGraw-Hill, New York, 1988. 4. Holt, D.J. “The Diesel Engine,” Society of Automotive Engineers, Warrendale, PA, 2004. 5. Greene, D.L. and Liu, J.T. “Automotive Fuel Economy and Consumers’ Surplus,” Transportation Research A, 22A, 203–218, 1998. 6. Burke, A. and Abeles, E. “Feasible CAFE Standard Increases Using Emerging Diesel and Hybrid-Electric Technologies for Light-Duty Vehicles in the United States,” UCD-ITSRR-04-9, Institute of Transportation Studies, University of California at Davis, Davis, CA, April, 2004. 7. Birch, S. “Ricardo’s Diesel Future,” Automotive Engineering International, 111, 78–79, 2003. 8. Ricardo, “Diesel Passenger Car & Light Commercial Vehicle Markets in Western Europe,” 2004. 9. Brown, W. “Europe’s diesel vehicle market is healthy, growing,” The Washington Post, 2 April 2004. 10. Hart R. “Two more for the road; VW’s take on ‘alternative vehicles increases,’ ” Auto Week, 28 June 2004.

11. Incantalupo, T. Stepping on the diesel with gasoline prices soaring, the economy of this alternative fuel sparks renewed interest among carmakers and the public. Newsday, 30 May 2004. 12. Caravan, “ORC Study #713228” conducted for National Renewable Energy Laboratory by Opinion Research Corporation, Princeton, NJ, May 27, 2004. 13. Duleep, K.G. “Diesel Technology and Product Plan Review,” presentation to the U.S. Department of Energy, Office of Policy, prepared by Energy and Environmental Analysis, Inc., Arlington, Virginia, April 2004. 14. McManus, W. “Hybrids and Clean Diesels: If You Build It, Will They Come?” J.D. Power and Associates, Detroit, Michigan, 2004. 15. www.epa.gov 16. www.dieselnet.com 17. Davis, S.C. and Diegel, S.W. Transportation Energy Data Book, ed 23, ORNL-6970, Oak Ridge National Laboratory, Oak Ridge, Tennessee, October 2003. 18. White, J.B. A New Crop of Diesel Cars Hits the Market Amid Rising Gas Prices, Dow Jones & Co., 27 May 2004.


19. Volkswagen, Mercedes, Jeep Roll Out Fuel-Efficient Models. Wall Street Journal, 27 May 2004. 20. Kranz, R. Gasoline price spike will boost sales of diesel cars, VW predicts; Passat, Touareg join diesel lineup. Automotive News, 26. June 2004 21. Energy Information Administration. Annual Energy Outlook 2004,DOE/EIA-0383-04, U.S. Department of Energy, Washington, DC, January 2004. 22. Diesel Car Perspectives to 2009, May 17, 2003, www.eagleaid.com/dsltext.htm. 23. Kleit, A.N. “The Effect of Annual Changes in Automobile Fuel Economy Standards,” Journal of Regulatory Economics, 2, 515–572, 1990. 24. Motor News — National Research Council (NRC). Effectiveness and Impact of Corporate Average Fuel Economy (CAFÉ) Standards, National Academy Press, Washington, DC, 2002. 25. Hadder, G.R. “High Quality Diesel Fuel Production, Logistics and Consumer Costs,” Engineering Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, May 2004.

44

Automotive Trends in Asia R. David Whitby CONTENTS 44.1 Introduction 44.2 Trends in the Automotive Industry in Asia 44.2.1 A Manufacturers and Competitive Forces 44.2.1.1 Production of Vehicles in Asia 44.2.1.2 Exports and Imports 44.2.1.3 Asian Vehicle Manufacturers’ Trends and Prospects 44.2.1.4 Suppliers of Components to the Asian Automotive Industry 44.2.2 Asian Automotive Design and Engineering 44.2.3 Asian Automotive Vehicle Regulations 44.2.3.1 Safety 44.2.3.2 Environment 44.3 Current Status of Automotive Fluids in Asia 44.3.1 Engine Oils 44.3.1.1 Gasoline Engine Oils 44.3.1.2 Diesel Engine Oils 44.3.1.3 Two-Stroke Engine Oils 44.3.2 Transmission and Gear Oils 44.3.3 Other Automotive Oils 44.4 Development of Markets for Synthetic Automotive Fluids in Asia

44.1 INTRODUCTION Asia is the most populous region on earth, with more than half the world’s people. Asia contains the world’s two most populated countries, China and India, together with Japan, Indonesia, Bangladesh, and Pakistan, all of which have large populations. During most of the 20th century, the population of Asia grew at a faster rate than the world average. Asia was the fastest growing region in the world for more than 10 yr prior to the 1997/1998 financial crisis, with an average annual growth rate of over 7%, compared with around 2% in Europe, 2.5% in the United States, 1.5% in Japan, and a global average of close to 2.5%. Many of the countries that experienced low or even negative growth rates in 1998 and 1999 have now recovered, despite countries such as Hong Kong, Singapore, and Thailand facing further problems in 2001. However, average growth rates in 2002 and 2003 were slightly lower than before, at around 5% per year. Asian countries have experienced widely differing economic circumstances over the last ten years. Japan began to


emerge in mid-2003 from one of the longest recessionary periods in its history. The growth in GDP that began in the second quarter resulted from stronger exports, mainly to the United States, China, South Korea, and Taiwan. Export growth countered the ongoing deflation in the Japanese economy, although some inflation is now starting to reappear. The growth in Japanese GDP is forecast to be 17% in 2005 and the same in 2006. Meanwhile, the economies of China and India have continued to steam ahead. China was finally admitted to the World Trade Organization (WTO) in September 2001, and a new era in Chinese politics and economics began in 2003 with the transfer of the post of state president from Jiang Zemin to Hu Jintao. Chinese GDP growth was 7.9% in 2002 and 9.2% in 2003, following a period of similar annual increases from 1996 onwards. Many analysts believe that this inexorable rate of growth is unsustainable and that the rate will have to slow to around 5 or 6% per year. This is the kind of growth that India has experienced from 1997 onwards, with increases in GDP of 4.8% in 2002 and 6.1% in 2003. Singapore and South Korea struggled a little in 2003, with increases in GDP of 0.8 and 2.5%

respectively, although 2004 was better, with increases of 8.2 and 4.6% respectively. Malaysia, Indonesia, Thailand, and Taiwan experienced respectable increases in GDP of between 3.8 and 7.1% per year during 2003 and 2004. Forecast increase in GDP for 2005 are between 4.4 and 5.1%. Three billion people live in Asia. Half of these people are under 25 yr of age. By 2010, it has been forecast that there could be 120 million cars on the road in Asia, compared with around 62 million in 1996. There could be almost 180 million motorcycles, of which China will account for 40%. Asia is now the largest market for lubricants, having consumed around 11.15 million mt in 2003 and overtaken North America. The growth rate for lubricant demand in the region as a whole has averaged about 3.8% per year for the last 20 yr. In 1997, when consumption was 9.22 million tonnes, Asia looked set to start challenging North America as the largest total market for lubricants, but this changed in 1998 as the economic turmoil in the region spread. Since then, growth in both GDP and lubricants consumption has resumed, although at slightly lower rates. Both China and Japan are not only large consumers of lubricants in their own rights, but are also large producers. Japan is a net exporter of lubricants, mainly to other countries in Asia. China is a large importer of lubricants, as are many of the other countries in the region, with the exception of Singapore, which produces more than it consumes. South Korea is also an exporter of lubricants.

44.2 TRENDS IN THE AUTOMOTIVE INDUSTRY IN ASIA 44.2.1 A Manufacturers and Competitive Forces 44.2.1.1 Production of vehicles in Asia Asia is not only the world’s third largest market for cars after Western Europe and North America, but is also the second largest market for trucks and buses after North America. This is shown by the data in Table 44.1. Asia accounts for 16.1% of the world’s cars and 20.5% of its trucks and buses. As indicated in the Introduction (Section 44.1) to this chapter, the market for cars in Asia has been the fastest growing in the world over the last ten years and is set to keep growing, as more people acquire the finance to purchase a car. From 1998 to 2002, the number of cars in Asia increased by 18%, compared with increases of 11% in Western Europe and 10% in North America. The number of trucks and buses in Asia increased by 14% in the same period, slightly lower than in Western Europe (15%) and slightly higher than in North America (12%). The largest markets for cars in Asia are in Japan, China, Taiwan, and India, as shown by the numbers of vehicles in


TABLE 44.1 World Vehicle Population, 1998 to 2002 Number of vehicles in use (million) Region

1998

1999

2000

2001

2002

Cars W Europe C and E Europe N America C and S America Middle East Asia Africa Oceania

169.0 49.2 147.9 26.4 12.6 74.1 10.1 9.8

171.4 51.4 148.4 26.4 12.6 78.8 10.2 10.1

176.9 54.6 150.1 26.9 13.0 81.6 10.2 10.3

181.9 55.7 156.7 27.1 13.2 84.9 10.4 10.4

187.0 56.8 163.1 27.7 13.7 87.7 10.5 10.5

Total cars

499.1

509.3

523.5

540.3

557.0

23.1 15.2 86.6 8.6 5.2 36.6 4.4 2.7

23.4 15.1 86.7 8.7 5.3 39.8 4.4 2.8

24.0 14.3 90.6 8.8 5.4 40.5 4.4 2.9

25.3 14.9 94.1 8.9 5.5 41.2 4.5 2.9

26.6 15.6 97.5 9.0 5.6 41.8 4.6 3.0

Trucks and buses W Europe C and E Europe N America C and S America Middle East Asia Africa Oceania Total trucks and buses

182.42

186.2

190.9

197.3

203.6

All vehicles W Europe C and E Europe N America C and S America Middle East Asia Africa Oceania

192.1 64.4 234.5 35.1 17.76 110.63 14.5 12.6

194.8 66.5 235.1 35.1 17.9 118.6 14.6 12.9

200.9 68.9 240.6 35.7 18.4 122.2 14.6 13.1

207.2 70.6 250.8 35.9 18.7 126.1 14.9 13.3

213.7 72.4 260.6 36.7 19.2 129.6 15.0 13.5

Total vehicles

681.5

695.4

714.4

737.6

760.6


the main countries in the region, in Table 44.2. The largest markets for trucks and buses are in Japan, China, Thailand, and South Korea. There are more cars, trucks, and buses in Japan than in the rest of the Asian countries put together. The fastest growing vehicle market in Asia, by far, is China. The number of vehicles in other countries in the region has been increasing steadily over the last 20 yr. Passenger cars still account for less than half the Chinese market for vehicles, which is still dominated by trucks and buses. The total number of cars that was sold in China in 2002 was 1.2 million. VW/SAIC had a 23% share, VW/FAW had an 18% share, and GM/SAIC had a 9% share, as did Toyota/TAIC. The Chinese vehicle market has maintained its pace of growth in 2003. In the nine months to September, total vehicle sales were 1,454,522, up 69% for the same period in 2002.

TABLE 44.2 Asia-Pacific Vehicle Population, 1998 to 2002 Number of vehicles in use (million) 1998

2000

2002

Total

Cars

Trucks and buses

Total

Cars

Trucks and buses

Total

Country

Cars

Trucks and buses

Asia China India Indonesia Japan S Korea Malaysia Pakistan Philippines Singapore Taiwan Thailand Others

3.33 4.70 2.73 45.86 6.69 2.30 0.80 0.67 0.37 4.20 1.51 0.91

5.34 2.79 1.74 18.62 2.52 0.61 0.37 0.26 0.13 0.70 3.10 0.36

8.67 7.49 4.48 64.49 9.22 2.91 1.17 0.93 0.50 4.90 4.60 1.27

3.49 4.79 2.85 51.16 7.58 2.57 0.88 0.76 0.40 4.67 1.53 0.94

5.98 2.98 2.28 20.56 2.95 0.65 0.36 0.28 0.14 0.83 3.14 0.38

9.47 7.77 5.13 71.72 10.53 3.22 1.24 1.04 0.54 5.50 4.67 1.32

7.12 4.98 2.95 53.45 8.61 2.65 0.97 0.81 0.41 4.70 2.19 0.96

6.36 3.12 2.32 19.87 3.65 0.71 0.40 0.31 0.15 0.89 3.66 0.40

13.48 8.10 5.27 73.32 12.26 3.36 1.37 1.12 0.56 5.59 5.85 1.36

Total Asia

74.08

36.55

110.63

81.62

40.53

122.15

89.80

41.83

131.63

Pacific Australia New Zealand Others

7.79 1.79 0.27

2.07 0.46 0.20

9.86 2.25 0.47

8.26 1.78 0.24

2.21 0.45 0.20

10.47 2.23 0.44

8.45 1.84 0.24

2.30 0.48 0.20

10.75 2.32 0.44

Total Pacific

9.84

2.73

12.57

10.27

2.86

13.13

10.53

2.98

13.51

83.92

39.28

123.20

91.89

43.39

135.28

100.33

44.81

145.14

Total


Production of cars in Asia from 1998 to 2002 is shown in Table 44.3. Production of trucks and buses is shown in Table 44.4. Data for the Pacific region (Australia and New Zealand) has been included for completeness, since some of the cars manufactured in Japan, South Korea, Malaysia, and most recently China are being sold in the Pacific region. As with vehicle sales, China has experienced the fastest growth in the production of vehicles, particularly cars, over the last decade. In 1995, 290,000 cars and 1.05 million trucks and buses were manufactured in China. By 2002, these figures had increased to 1.10 million and 2.16 million respectively, a total of 3.26 million vehicles. China’s vehicle production was 4.4 million in 2003, with cars reaching 1.9 million, 70% more than in 2002. By 2004, China became the world’s third largest market for vehicles, after the United States and Japan. Some planners expect the Chinese vehicle market to overtake that of United States, to become the world’s biggest in 2025. China has a draft policy for automotive manufacturing, which aims to ensure that local car manufacturers, with their own intellectual property rights (IPR), account for more than half of domestic sales by 2010. Some


TABLE 44.3 Production of Passenger Cars in Asia-Pacific, 1998 to 2002 Number of vehicles manufactured (thousand) Country

1998

1999

2000

2001

2002

Australia China India Indonesia Japan Malaysia New Zealand South Korea Taiwan Thailand

298.2 507.1 498.4 8.4 8,055.8 132.7 8.2 1,625.1 292.1 32.0

322.6 565.4 646.6 5.9 8,100.1 241.4 — 2,361.7 246.0 72.7

329.7 604.7 645.6 37.3 8,363.5 275.3 — 2,602.0 263.0 97.1

304.1 703.5 676.2 32.2 8,117.6 329.0 — 2,471.4 195.1 288.9

328.6 1,090.8 706.1 23.8 8,618.7 350.5 — 2,651.3 231.5 270.1

11,458.0

12,562.4

13,218.2

13,118.0

14,271.4

Total


international manufacturers have expressed concern about this, but others are not so worried. Independent Chinese vehicle companies currently have a share of less than 10% of the market for cars, but dominate sales of trucks and buses.

and smaller numbers of Malaysian and Indian cars being exported to North America and Europe. The scale of the imports and exports is highlighted in Table 44.5. All developing countries in Asia import cars, trucks, and buses, many from Japan and South Korea. A comparatively small number of luxury cars are imported into Japan, Hong Kong, Singapore, Taiwan, and China from Germany, France, the United Kingdom, and Sweden. Japan exported 4.01 million cars and 686,000 trucks in 2002. The United States imported 1.82 million cars and another 233,000 were sent to Canada. Another major destination for Japanese cars was Australia, which imported 268,000 in 2002. Germany imported 193,000 Japanese cars and China imported 78,000 in 2002. South Korea exported 1.41 million cars and 94,000 trucks in 2002. As with Japan, the majority of cars were sent to the United States (629,000) and Canada (98,000), with 76,000 being exported to Italy and 58,000 to the United Kingdom. Conversely, comparatively few cars and almost no trucks and buses are imported into Asia from other regions. These cars that are imported tend to be limited to higher priced luxury cars such as Mercedes-Benz, BMW, Jaguar, and Rolls Royce. There is also a large regional internal trade in cars, trucks, and buses within Asia, with the principal producing countries, particularly Japan, South Korea, and Malaysia exporting relatively small numbers of vehicles of all types to the nonproducing countries of Singapore, Hong Kong, the Philippines, Vietnam, Myanmar, and Cambodia. How the current patterns of exports and regional trade will change in the next few years remains unclear at the time

44.2.1.2 Exports and imports Asia is the world’s largest regional exporter of cars, with huge numbers of Japanese and South Korean cars

TABLE 44.4 Production of Vans, Trucks, and Buses in Asia-Pacific, 1998 to 2002 Number of vehicles manufactured (thousand) Country

1998

1999

2000

2001

2002

Australia China India Indonesia Japan Malaysia New Zealand South Korea Taiwan Thailand

22.0 1120.7 129.3 49.7 1994.0 — — 329.4 109.6 125.5

23.5 1259.3 169.8 117.3 1795.3 — — 481.4 104.3 132.1

25.0 1464.4 155.8 308.1 1781.4 14.9 — 513.0 109.6 242.0

33.4 1630.9 148.7 296.0 1659.6 20.0 — 474.9 76.6 244.1

34.3 2160.4 186.2 275.1 1639.0 14.4 — 496.3 102.2 253.6

Total

3880.2

4083.0

4614.2

4584.2

5161.5


TABLE 44.5 Import and Export of Vehicles in Asia, 2000 and 2001 Number of vehicles (thousand) Imports

Exports Trucks and buses

Cars

Trucks and buses

Cars

Country

2000

2001

2000

2001

2000

2001

2000

2001

Australia China Hong Kong India Indonesia Japan Malaysia Singapore South Korea Taiwan Thailand

294.7 101.7 25.9 35.8 25.6 283.6 26.2 53.9 2.0 45.1 111.4

302.3 116.2 26.8 27.9 28.1 287.1 28.4 54.6 2.2 48.2 74.5

112.7 46.7 17.9 0.6 52.3 14.5 21.2 28.9 0.4 22.4 —

88.9 49.1 18.8 0.5 64.2 15.2 23.8 29.2 0.5 24.4 —

169.2 217.4 — 103.2 — 3737.0 252.5 — 1437.2 ND 94.0

204.7 185.6 — 131.8 — 3568.7 299.8 — 1397.0 ND 278.9

— 913.1 — 25.5 81.4 697.5 — — 265.3 ND 242.0

— 949.2 — 27.6 79.2 597.4 — — 251.2 ND 214.1

ND = No data. Source: Pathmaster Marketing, from various industry sources.


of writing. Many Japanese and Korean car makers have been building production plants in Europe and North America during the last decade in an effort to minimize trade disputes and exchange rate fluctuations. Although these facilities were intended to reduce exports from Asia, recent economic turmoil could prompt a possible return to exporting as a way of countering reduced domestic demand and maximizing foreign currency inflows. 44.2.1.3 Asian vehicle manufacturers’ trends and prospects The alliance between Nissan and Renault, which was agreed in March 1999 has given both companies the benefits of a merger without having to create a merged company. When Nissan experienced severe financial difficulties in 1998, Renault agreed to take a 36.8% shareholding as part of a deal to inject the much needed interim cash. The alliance was further strengthened in March 2002, when Nissan acquired a 15% stake in Renault and Renault increased its shareholding to 44.4%. At the same time, the French government reduced its shareholding in Renault to 25.9%. The deal in 1999 suited both companies, as the cash boost enabled Nissan to continue manufacturing cars and Renault expanded from its mainly European market into Asia. Nissan has had three successive years of increasing profits and has almost eliminated its debt. The company achieved a dramatic turnaround between mid2000 and mid-2003, turning a net debt of ¥2100 billion ($17.4 billion), which threatened the company with bankruptcy, into a net cash position of ¥8 billion ($7 million). (The company’s operating profit in 2002 was ¥737 billion.) The recovery has been due to a combination of severe cost reductions, new and improved models, and increases in market share in all Nissan’s main markets. Renault and Nissan each own 50% of Renault– Nissan BV, a Dutch based strategic management company, which in turn owns Renault–Nissan Purchasing Organisation (RNPO) and Renault–Nissan Information Services (RNIS). Most of the purchasing of components for both companies is supposed to go through RNPO, as in Europe and South America, although the regional Nissan teams in Japan and North America are still very independent. Nissan and Renault have also adopted a common quality system for suppliers. RNPO was created in 2001 to maximize the benefits of developing common platforms and sharing engineering costs for new vehicle development. The new Nissan Almera and Renault Megane/Scenic models share around 60% of their components. Toyota has now become an established competitor to Mercedes-Benz, BMW, and Jaguar in the luxury segment of the car market through the company’s Lexus brand, which was introduced first in North America and has proved to be a strong seller. Lexus cars have been available


in Western Europe for a number of years and Toyota is planning to introduce the brand into the Japanese market in 2005. The aim is to make Lexus a truly global, top-class brand. At the same time, Toyota has recognized that the Japanese car market has changed in recent years, with economic stagnation leading to a shift in market demand toward smaller cars. The company has acknowledged that it cannot rely on bigger production volumes or higher market shares to increase revenues. As a result, Toyota is planning to build “a balanced, global operating platform that enhances our ability to respond quickly and flexibly to changes in the business climate.” This means increasing product development and production capabilities outside Japan. The company has established a joint venture with PSA Peugeot Citroen to manufacture cars in Central and Eastern Europe. A new plant is being built in the Czech Republic, to manufacture up to 300,000 small cars per year for sale throughout Europe, and production is scheduled to start towards the end of 2005. In April 2002, Toyota’s plant in Poland began producing manual transmissions (MTs) for Toyota vehicles manufactured in the United Kingdom and France. Toward the end of 2004, the Polish plant will begin producing gasoline engines for use in the new Czech small car plant. Another plant in Poland will begin producing up to 150,000 diesel engines a year, to be used in cars manufactured in the United Kingdom and France. Mitsubishi and Mazda are two of Japan’s car manufacturers that have struggled in recent years. Mitsubishi Motors (MMC) had DaimlerChrysler as a 37% shareholder until April 2004, when the German company decided that it could not provide any further financial aid to its loss making Japanese affiliate. DaimlerChrysler had been expected to buy several billion euros worth of new shares in addition to the e2.5 billion ($2.95 billion) it had already spent since 1999 to build up the 37% stake. However, the company decided it could not justify further investments in MMC. Following the decision, the Mitsubishi Group (which includes financial, engineering, and shipbuilding companies) indicated it would support MMC’s bail-out plan. DaimlerChrysler is now seeking to sell its shareholding in MMC, although industry analysts have cautioned that, even if MMC survives, it faces severe operational problems as a result of its damaged reputation, ageing models, slow sales, and lack of profitability. As part of the refinancing plans, MMC was forced early in 2004 to sell its 42% shareholding in truck maker Mitsubishi Fuso, which has a 20% share of the southeast Asian market for commercial vehicles. The shareholding was bought by DaimlerChrysler. MMC’s problems in the U.S. market may be due to its “zero, zero, zero” marketing campaign in 2003. A new range of smaller cars, targeted at young, low income buyers, were sold on the basis of no deposit, no interest, and

no repayments for the first year. The company accumulated large losses when a number of the young buyers failed to start making payments after the first year; a problem that DaimlerChrysler might have prevented in a market that Chrysler should have understood. In other markets, including Japan, MMC was forced in 2000 to recall 2.5 million faulty vehicles and admit that it had covered up customer complaints during the previous three decades. Mazda, which is 33% owned by Ford, raised profits by a little in 2003 after several tough years both in Japan and North America. However, industry analysts believe that it is likely to be mid-2005 before new Mazda models will have had a chance to revive the company’s position. Intense competition means that Mazda has lost money in Japan. Although Mazda’s rotary engines and sporty cars sell well in Europe, the company struggles in North America, mainly due to a lack of global integration. To compete on both cost and marketing, car manufacturers have to build a range of models using ever fewer basic chassis and engine designs. Coordinating design, manufacturing, and marketing profitably is a huge challenge. While Mazda’s excellent product development and manufacturing skills have helped Ford, the bigger company has provided little help with marketing to its affiliate in North America. The main theme of vehicle manufacturing in Asia during the last five years has been China. It appears likely that China will continue to be the dominant theme of vehicle manufacturing in Asia for the next five years, since China looks set to overtake Japan as the world’s second largest market for cars. Toyota agreed to establish a joint venture with First Automotive Works (FAW), China’s largest car manufacturer in August 2002 to make up to 400,000 cars per year by 2010. As part of the deal, FAW will acquire a controlling stake in Tainjin Automotive Xiali, Toyota’s other Chinese partner, which manufactures buses. The joint venture started making small cars in FAW’s Tianjin plant in mid-2003, with an annual production target of 100,000 vehicles. Manufacture of between 10,000 and 20,000 sports utility vehicles (SUVs) also started in 2003, at FAW’s Changchun plant. The joint venture plans to start making medium and luxury cars in 2005, with an annual target of 50,000. Toyota’s overall aim is to achieve a 10% share of the Chinese market by around 2010. One difficulty for the new joint venture could be FAW’s relationship with its other partner in China, Volkswagen (VW). Because Toyota and VW will be in direct competition, FAW’s loyalty to one or both of them could be tested at some time in the next few years. Another complication is VW’s partnership with SIAC. Indigenous Chinese vehicle manufacturers are allowed to form joint ventures with more than one foreign partner. China’s top four main car manufacturers (First Automotive Works [FAW], Shanghai Automotive Industry Corp [SAIC], Guangzhou Auto, and Dongfeng Automobile)


have links with at least two international partners. This is a potential source of friction in an industry in which technology and design innovations are guarded closely. To try to counteract this potential conflict, international car manufacturers are starting to form alliances with more than one Chinese partner. Toyota has also initiated discussions with Guangzhou Auto. In mid-2003, Honda and Dongfeng agreed to make a small off-road vehicle, even though Honda already had a joint venture with Guangzhou. Dongfeng also has a joint venture with Nissan and FAW has a technical agreement with Mazda. Volkswagen, the market leader in China with about 35% share of the car market in 2003, is also planning to double its capacity to 1.36 million vehicles per year by 2007, to try to protect its dominant position. The cost of the e6 billion project will be financed entirely from the revenues of the current Chinese plants. VW has a joint venture with FAW in Changchun, northeast China. Production of FAW vehicles will be increased to 33,000 per year, as will the production of VW Golf, Bora, and Jetta models and Audi A4 and A6 models. At the same time, Shanghai Volkswagen Automotive, will increase capacity to 700,000 cars by 2007. VW sold around 600,000 cars in China in 2003, an increase of 17% over 2002. However, VW has experienced a rapid decline in its share of the Chinese car market in recent years. Its share of the car market was over 50% in 2002, declined to around 35% in 2003 and is forecast to be below 20% in 2004. While VW has continued to sell about the same number of cars per year, other manufacturers, particularly Toyota/FAW, GM/SAIC, Nissan, Hyundai, and BMW, have all begun to sell cars in even bigger numbers. VW has responded by announcing the plans to expand capacity still further, by shifting some office jobs from Germany to China, to be closer to customers, and by increasing the local sourcing of components, including engines and transmissions, to cut costs. The company is also considering making Skoda branded cars in China, as recent sales of the VW Polo have been only 65% of planned sales. The Skoda Octavia is a low-cost large family car, while the VW Polo is a complex small car. BMW signed an agreement in March 2003 to establish its first car manufacturing plant in China, as a 50:50 joint venture with Brilliance China Automotive Holdings. The plant started to manufacture 3-series cars towards the end of 2003 and 5-series cars towards the end of 2004. BMW hope to use the joint venture to increase its sales of cars in Asia from about 80,000 in 2003 to more than 150,000 in 2008. Already, China is BMW’s second largest market for 7-series cars, after the United States. Total sales of BMWs in China in 2003 were 15,260 cars. General Motors (GM) announced a further expansion of vehicle manufacturing in China in November 2003, including an extension of its main Shanghai plant and

plans to make and import cars bearing the Cadillac brand. The company is planning to expand capacity from just above 500,000 vehicles per year to about 760,000 by 2006. GM is increasing capacity to meet the demand in the fastest growing car market and to prepare for the fully fledged entry into the market over the next two years of Toyota and Nissan. The company’s Shanghai plant, a joint venture with state-owned SAIC, which went to three-shift production in August 2003, will increase capacity from 200,000 to 300,000 units by the end of 2005. GM’s joint venture in Guangxi making light trucks will increase capacity by 150,000 units to 336,000 by 2006. GM’s joint ventures, which manufacture cars, SUVs, and small trucks, have a market share in China of about 9.1%, having sold a total of 386,710 vehicles in China in 2003. MG Rover, the United Kingdom’s last indigenous volume manufacturer of cars, has been considering a strategic collaboration with SAIC for most of 2004. MG Rover has been struggling to sell cars since it was sold by BMW to a management buy-in team in 2000, so it has had difficulties in developing new models. It is expected that nearly all of MG Rover’s new models would be developed and manufactured under the new venture, which is currently in the final stages of being approved by the Chinese government. The new models would be built in both the United Kingdom and China and the deal is reported to allow SAIC access to MG Rover’s dealer networks in Europe and other countries. This would fit with the Chinese government’s goal of creating a fully integrated car industry capable of exporting to the world’s highly competitive markets. Ford announced at the end of 2003 that it is considering building Land Rovers or Volvos in China, to participate in the growing market for luxury vehicles. The company is currently studying which brand would be most suited to the Chinese market, although the study is unlikely to be completed before the end of 2004 and Ford might still decide not to proceed. Ford believes that Land Rover could benefit from its off-road image, as China still has a lot of rough roads. Theft or abuse of IPR, a problem that is endemic in many Chinese industries, is another source of tension for international vehicle manufacturers. In 2001, VW (which has a partnership with SAIC) found that the main car produced by Chery (a Chinese company part-owned by SAIC) was a direct copy of the Jetta and used original VW parts. The dispute was resolved amicably through discussions, to VW’s satisfaction, even though it had not been possible for VW to sue Chery, because of the difficulty of proving culpability. However, Toyota sued Geely in August 2003, alleging that it had copied Toyota’s logo on its Merrie saloon. Later in 2003, GM began an investigation of Chery’s QQ small car, claiming that its design was copied from the Chevrolet Spark, which is a rebranded version of Daewoo’s Matiz small car. (GM now owns Daewoo.) Although GM has


found solid evidence that Chery copied the design, it faces formidable legal and political obstacles if it decides to try to sue Chery. GM has taken the case to the Chinese government to seek a resolution. Now that China has joined the WTO, all manufacturers expect copyright and trademark laws to be strengthened and counterfeiting to be reduced. In November 2003, VW announced that it will make cars in China for sale in Australia and aiming to make the company’s manufacturing costs low enough to use China as an export base. The initial production run for export to Australia will consist of right-hand drive versions of VW’s Polo model and will be tiny, at about 600 cars in 2004. The symbolic significance is not in the number of cars but in the hoped for political benefits from the export decision. VW made the announcement to reporters brought to one of its Shanghai joint venture plants from around the country to ensure it received wide publicity domestically. Exporting cars from China had not been considered much until recently because costs and quality levels were not internationally competitive and the local market was growing so quickly. VW now believes that some of its Chinese point venture plants, which initially had higher costs than even the company’s German plants, could now manufacture competitively enough to sell in Australia. The Polo sells for Rmb120,000 ($14,498) in China and will be priced similarly in Australia, where import tariff for cars have reduced significantly over the last decade. Of the 43,000 “vehicles” exported from China in 2002, half were leisure vehicles, such as golf carts and snowmobiles. With so many companies either having increased or planning to increase vehicle production in China, some analysts are concerned that international manufacturers could be creating a large over-capacity problem, similar to those that exist now in Europe and the United States. Consensus estimates suggest that total manufacturing capacity for cars, with both local and international companies, could be 7 million by 2008, compared with a projected demand of 5.7 million cars. Although car manufacturers appear to be aware of the potential dangers, similar to the recent problems in Brazil, the severe competition between the global car makers combined with the apparently huge longterm potential of the Chinese market is likely to ensure that the industry marches inexorably toward a short- to medium-term over-capacity position. To complicate the situation even further, the Chinese government is currently trying to engineer a slowdown in the overheated economy. Such a slowdown will affect demand for all goods and services, including cars, vans, trucks, and buses. Indeed, there was a significant reduction in the rate of increase of car production in the first eight months of 2004 compared with 2003. The Chinese car market grew at annualized rates of between 40 and 80% during 2002 and 2003, but is now growing at rates of around 20%. The government put new restrictions on

loans to buy cars, which require consumers to post substantial collateral in order to qualify for a loan, thereby cooling demand. Another factor contributing to slowing demand is the expectation of further price cuts, as some car manufacturers have reduced prices in a battle for market share. Volvo Trucks has signed a joint venture agreement with China National Heavy Truck Corporation (CNHTC) in July 2003 to manufacture Volvo FL, FM9, and FM12 models. The new company, called Jinan Huawo Truck Company, started production toward the end of 2003 in CNHTC’s plant in Jinan. The initial capacity of 2,000 trucks per year is planned to be raised to 10,000 per year by 2010. Later, in March 2004, Volvo Trucks announced plans for a $200 million joint venture with CNHTC and FAW to manufacture engines for trucks, buses, construction equipments, and boats. At the same time, Caterpillar disclosed that it is considering taking stakes in several state-owned Chinese construction equipment companies that could eventually lead to full acquisitions. This is part of a plan to raise Caterpillar’s sales in China from $500 million in 2003 to more than $2 billion by 2010. It has been reported that the Chinese government would like to see some consolidation among national construction equipment manufacturers, because many are inefficient and unprofitable. Caterpillar already has four Chinese joint ventures in excavators, tractors, castings, and small diesel engines, in addition to two wholly owned projects in compactors and generator sets. The South Korean market for passenger cars expanded by 16% in 2002, as a result of government tax incentives for car purchases that continued until September 2002, to boost the indigenous production of vehicles following the financial problems with Daewoo. In October 2002, GM finally acquired a 42% stake in Daewoo, the bankrupt South Korean vehicle manufacturer, after two years of difficult negotiations with the company, union representatives, and the South Korean government. Before Daewoo’s bankruptcy, it had a 26% share of car sales in South Korea, but by the time of the creation of GM Daewoo, this share had fallen to less than 10%. Shortly after the launch of GM Daewoo, it was announced that GM would begin selling Daewoo cars in China and that SAIC would take a 10% stake in GM Daewoo. In 2000, Renault acquired Samsung Motors in South Korea. Initially, the new company, called Renault Samsung Motors, manufactured only one model of car, the “SM5,” which gained popularity steadily. The car was derived from the Nissan “Maxima.” In September 2002, the “SM3” that was developed using the Renault–Nissan alliance was introduced. The second car shares the platform of Nissan’s “Bluebird Sylphy.” In addition to its problems with MMC, DaimlerChrysler has also had problems with its South Korean affiliate Hyundai, in which it had a 10% shareholding, which


it decided to sell in May 2004. Following four years of rapid growth and the improving quality and popularity of Hyundai cars throughout the world, the South Korean company decided it no longer needed the support of the European–U.S. partner. The two companies found that they were increasingly competing with each other, particularly in the United States. When DaimlerChrysler purchased the stake in 2000, Hyundai was going through an upheaval resulting from the break-up of its parent Hyundai Group following the Asian financial crisis of 1997/1998. Since then, exports have grown to 61% of sales in 2003 and net profits have quadrupled. The growth is due, in part, to heavy investment in overseas production, including a plant in the United States, coupled with improvements in quality, design, and branding. At the same time, DaimlerChrysler’s activities in Asia, particularly in China, began to clash with Hyundai’s plans. The two companies’ strategic objectives began to diverge, so the rationale behind the alliance became more tenuous. However, both companies have agreed to continue working together on a project-by-project basis, including the three-way passenger car alliance with MMC. Tata Motors, India’s second largest vehicle manufacturer and a subsidiary of India’s second largest private sector group of companies, returned to profitability in 2003 by reducing its workforce from 26,500 to 21,500 and by intensely focusing on operational cost-efficiency. The company is also negotiating to purchase a Daewoo truck manufacturing plant in South Korea, for US$118 million. Tata is investigating building or acquiring vehicle manufacturing facilities in China, Russia, and South Africa. In addition, the company is exporting its Indica small car to the United Kingdom, to be sold throughout Europe by MG Rover. However, in September 2004, Tata announced that it could consider ending its agreement with MG Rover if current talks fail to resolve differences over the price and positioning of the Indica/CityRover car. MG Rover wants to reduce the price of the car or add free equipment to make it more competitive and has proposed that Tata should bear some of the cost. Sales of the CityRover have been so poor that Tata suspended exports earlier in 2004, when it had planned to sell 100,000 cars over five years. Superficial changes for the U.K. market, such as trim, make the cars unsuitable for sale in India. Tata’s suspicions about MG Rover’s intentions have been heightened by the U.K. company’s ambitions in China. Tata has indicated that it is committed to expansion in South Africa, as a stepping-stone to other markets in Southern Africa. Tata already builds buses and light trucks in Johannesburg with Imperial Holdings, would like to sell its Indigo and Indica cars there too, and is bidding to become one of the main suppliers of minibus taxis. Nissan announced in July 2004 that it plans to invest $246 million in its car plant in Thailand over the next

five years, to increase production of an expanded product range, some of which will be exported to Australia, South America, and Africa. Thailand is Nissan’s third largest manufacturing base in Asia, after Japan and China, and the company views Thailand as an important expanding market and a base to export to other countries in the ASEAN (Association of South East Asian Nations) free trade area. While the current capacity of the plant is 130,000 units a year, production was only slightly over 40,000 in 2003. Nissan plans to expand the capacity to 200,000 units a year by 2008 and to double the workforce. Surprisingly, Thailand is the world’s second largest manufacturer of pick-up trucks, after the United States. Toyota, Isuzu, Mitsubishi, Nissan, Mazda, Ford, and GM all manufacture pick-up trucks in Thailand; total production in 2003 was 470,000 vehicles, most of which were exported. Ford has announced plans to spend $500 million to expand production of both pick-ups and cars, Toyota is spending $750 million to increase capacity and establish a research and development center and Mitsubishi, although struggling elsewhere, is spending $525 million to expand operations in Thailand. Thailand has attracted this investment as a result of innovative government industrial policy and very supportive excise-tax incentives. The government set excise tax on pick-ups at just 3%, compared with as much as 50% for cars, many years ago, thereby guaranteeing sales of pick-ups. The growing local production has become a natural base for exports throughout Asia and more recently for most other regions. The country hopes to be exporting more than 800,000 vehicles by 2011. BMW, for example, is now making 3-, 5-, and 7- series cars in its Thai plant and is exporting them throughout Asia. During 2004, MG Rover and Proton, Malaysia’s national car manufacturer, briefly explored a collaboration on “a number of projects,” although only an intention to collaborate has been signed so far. Proton has investigated a number of strategic partnerships with several unnamed foreign car manufacturers, to help it face the stiffer competition that will arise when Malaysia is forced to abolish import tariffs on cars made in other ASEAN countries, primarily Thailand. Malaysia had agreed to phase out the tariffs in 2005, but decided to extend the deadline until 2008 and impose excise taxes on cars entering the country. The delay is seen as giving Proton more time to adjust to a more competitive market, as Toyota, Nissan, Honda, and Ford all have car plants in Thailand, so are expected to begin exporting to Malaysia as soon as the import tariffs are abolished. The Malaysian market accounts for more than half the 1 million new cars sold each year in southeast Asia and Proton’s share has already fallen from 49% in 2002 to 39% in 2003, as foreign competitors reduced prices and local consumers delayed purchases in the expectation of the abolition of tariffs in 2005.


Although Proton’s cars can be up to 45% cheaper than similar sized Toyota or Honda cars, they have the worst record on quality and reliability in Malaysia. Proton’s latest model, the “Gen.2,” has a waiting list of more than five months because of a shortage of engine components and has a roof that is too low to allow adults in the rear seats to sit comfortably. Proton has begun a drive to become more competitive, by building an automated car plant, cutting staff, and planning to introduce new models based on technology from Lotus, the company’s U.K. subsidiary. Even so, the company is reported to be seeking to sell a 20% shareholding to a foreign partner, although this could be difficult to achieve. 44.2.1.4 Suppliers of components to the Asian automotive industry Companies that supply components to vehicle manufacturers in Asia include both large multinationals and small local suppliers. Those companies that supply to the major international vehicle manufacturers, such as GM, Ford, VW, Renault, Toyota, Nissan, BMW, and DaimlerChrysler, are required to meet the same specifications and quality levels as in Western Europe and North America. Denso, the world’s third largest components supplier that was originally part of Toyota, now has manufacturing plants in 28 countries outside Japan, including most countries in Asia, the United States, Mexico, Brazil, Argentina, most countries in Western Europe, Hungary, Poland, the Czech Republic, Saudi Arabia, and Turkey. The company supplies engine cooling systems, air-conditioning systems, diesel common rail systems, alternators, starter motors, spark plugs, anti-lock brakes, power steering, and navigation systems. Denso plans to build 15 million vehicle air-conditioning units by 2005, which represents 30% of the world market, as a result of expansion in Europe. Aisin Seiki manufactures a wide range of automotive components, from brakes, chassis, body parts, powertrains to information technology. Drivetrain systems, including automatic transmissions (ATs), accounts for almost half of the company’s sales. Aisin Seiki developed powered sliding door systems for vehicles, in conjunction with Toyota. The company purchased Nissan’s 23% shareholding in Exedy Corporation, the specialist manufacturer of clutches and torque converters. Calsonic Kansei, created by the merger of Calsonic and Kansei in 1999, is Nissan’s largest supplier of components, mainly engine cooling and air-conditioning systems. Although Nissan accounts for 60% of the company’s sales, other buyers of components include Honda, Isuzu, Mazda, Mitsubishi, GM, Ford, and DaimlerChrysler. Stanley Electric focuses on automotive lighting, including headlamp and rear combination lamp assemblies, as well as automotive electronic components.

GKN, the U.K. automotive and aerospace company, has been working to expand in Japan for many years. As the world’s largest supplier of constant velocity joints, GKN acquired plants owned by Nissan and formed a joint venture with a Toyota Subsidiary. GKN has also had a long-term alliance with Tochigi Fuji Sangyo (TFS), the world leader in torque management systems, devices that give a smoother and safer ride. GKN acquired a 33% stake in TFS in 2002 and acquired the remaining shares in May 2004. Other major suppliers to vehicle manufacturers in Japan, China, and other countries in Asia include Borg-Warner (gearboxes, transmissions), Bosch (spark plugs, injectors, electronics, wipers), Delphi (brakes, clutches, indicators, controls, sensors, injectors), Federal-Mogul (camshafts, seals, gaskets), Getrag (gearboxes, transmissions), INA (bearings), Magneti Marelli (electronics, injectors), Mahle (pistons), Siemens (motors, relays, sensors, controls), SKF (bearings), Valeo (brakes, clutches, switches), and ZF (gearboxes, transmissions). Many of these companies supply a wide range of components in addition to those listed. Additionally, there are hundreds of other companies that supply all the other components, such as glass, plastic, wiring, hoses, and lights. During 2002, Toyota challenged itself to redouble its cost reduction program, aiming to achieve world-class competitiveness for around 170 major components that account for more than 90% of overall parts purchasing costs. The company has initiated focused collaborations between its component suppliers and engineering, production engineering, production, and purchasing divisions. Toyota claims that it has almost achieved the target, but is continuing to pursue manufacturing innovations aimed at achieving substantial cost reductions. This inevitably squeezes the company’s suppliers. Ford initiated plans at the end of 2003 to source about $1 billion worth of components per year from Chinese suppliers, for use in making vehicles in other countries, including plants in Thailand, Malaysia, and the Philippines. This includes many of the metal castings and plastic moldings supplied by local Chinese manufacturers to car plants, including Ford’s competitors in China. Surprisingly, although labor costs are low in China, vehicle manufacturing costs are among the highest in the world. This is caused by fragmented and expensive supply chains, the comparatively high cost of local components, and the need to import many high-technology components from Europe and North America. The result is total manufacturing costs that can be up to 30% higher than in the United States. Prices for some Chinese made components have been set artificially high, to the benefit of state-owned companies. Fortunately, competitive market pressures and reduced government protection has been forcing prices down over the past couple of years.


Indian manufacturers of automotive parts could export components valued at $100 million per year to Ford’s manufacturing plants worldwide, according to Ford. The company has developed a large supplier base in India because the cost of parts is lower, which helps to boost volumes. Industry analysts indicate that Indian automotive parts are between 15 and 20% cheaper than equivalent quality components from European or U.S. suppliers. Ford makes about 40,000 Ikon cars per year at its plant in Chennai. Bharat Forge, a family-controlled company based in Pune, India, close to Tata Motor’s headquarters, is the world’s third largest forging business. In addition to supplying to Tata Motors, the company supplies to international manufacturers such as Ford and DaimlerChrysler. Bharat Forge acquired Carl Dan Peddinghaus in Germany toward the end of 2003, for US$35 million, giving the company an annual production of almost 300,000 of forgings and forecast sales in 2004 of US$350 million. The company is now pursuing ventures in China and North America, which, if successful, will make it the world’s largest supplier of forging, ahead of ThyssenKrupp of Germany.

44.2.2 Asian Automotive Design and Engineering Toyota launched the world’s first mass-produced hybrid car, the Prius, which featured the Toyota Hybrid System (THS), in 1997. Hybrid vehicles have both a combustion engine and a battery system for providing motive power. Up to the end of 2003, the company had sold a total of 130,000 Prius Mark 1 hybrid cars worldwide. The second generation Prius was launched in Japan in April 2003 and in Europe in November 2003. The Mark 2 car is larger than the Mark 1, with an improved shape to appeal to more mainstream consumers. The electric components remain the same, with a traction motor, separate generator, and Panasonic NiMH (nickel metal-hydride) battery pack, but the traction motor’s voltage has been increased from 274 to 500 V. Since the current is the same, the motor’s power has increased from 33 kW (44 bhp) to 50 kW (67 bhp) between 1040 and 5600 rpm. This makes the car’s performance slightly better than the average 1.0 or 1.2 L gasoline engine. The Panasonic battery pack is 15% smaller and 25% lighter, with 35% higher output density. The traction motor’s torque is 400 Nm from 0 to 1200 rpm, which equates to a 0 to 62 mi/h time of 11 sec. The new Prius was named “Car of the Year” at the 2004 Detroit Motor Show. The earlier version was considered to have comparatively slow acceleration, a bland appearance, and a high price. The new five-door version is faster, better looking, and is highly fuel efficient, averaging 66 mi/gal. The new Prius, with THS II, is fully compliant with California’s Advanced Technology Partial Zero

Emission Vehicle (AT-PZEV) regulations that came into effect in 2003. Toyota has begun to expand production in Japan, after receiving orders for more than 10,000 cars from the United States. Toyota was also the first to introduce a commercial fuel cell hybrid vehicle (FCHV), through a limited sales launch in Japan and the United States in December 2002. The company has also been testing a fuel cell hybrid bus, developed jointly with Hino Motors, on Japanese roads, since October 2002. In January 2003, Toyota and Hino were selected by the Tokyo Metropolitan Government to provide vehicles for a pilot scheme for fuel cell hybrid buses operating in Tokyo. Nissan and Toyota announced in September 2002 that they will collaborate on designing and developing hybrid cars. The collaboration, which is expected to last for ten years, involves Toyota supplying Nissan with hybrid vehicle technology, for vehicles to be sold in the United States in 2006. It is planned that sales of these cars in the United States will reach 100,000 per year by 2011. Nissan’s decision to use Toyota’s technology, first developed for the Prius, appears to be another of the pragmatic tactics used by the company to limit costs and avoid expensive development programs. Industry analysts believe that Toyota continues to incur losses of a few thousand dollars on each Prius it sells. It is understood that Nissan has agreed with Toyota to pay only for the hybrid units it needs, on a royalty basis. This may be an indication that Nissan believes sales of hybrid cars may not grow as rapidly as some observers have forecast. However, sales of hybrid vehicles are expected to grow in the United States, from a small base, as a result of forthcoming emissions limits and favorable tax benefits for environmentally friendly vehicles. Sales of hybrid cars have begun to increase in Japan, North America, and Western Europe, albeit from a low base. The main reason for this is fuel economy in an era of high prices for crude oil, and therefore gasoline. Globally, the Honda and Toyota hybrid cars take the first and second places in a list of the ten most fuel efficient vehicles being sold at present. The Honda Insight has a CO2 emissions value of 80 g/km while the Toyota Prius has a CO2 emissions value of 104 g/km. The list is shown in Table 44.6. It is worth noting that the average CO2 emissions value for all new cars sold in the United Kingdom in 2003 was 174 g/km. Honda’s Insight hybrid was launched in 2000, but has met with only limited sales success as a result of it being a two-seater coupe with minimal luggage capacity. Also, the Insight’s gasoline engine and electric unit always ran together, offering no all-electric mode. Honda introduced the Civic IMA hybrid in December 2003, as a hatchback car with luggage space and comparatively little price premium over a conventional gasoline powered car. Honda’s chief R&D engineer, Kenichi Nagahire, is reported to have said


TABLE 44.6 Top Ten Vehicles for Emissions of CO2 , 2004 Rank

Manufacturer and vehicle model

1 2 3 =4 =4 =6 =6 =6 =9 =9

Honda Insight Toyota Prius Citroen C2 Citroen C3 Renault Clio Peugeot 206 Toyota Yaris Smart Daihatsu Charade Ford Fiesta

Engine type Hybrid Hybrid Diesel Diesel Diesel Diesel Diesel Gasoline Gasoline Diesel

CO2 Emissions, g/km 80 104 108 110 110 113 113 113 114 114

Source: ACEA.

that 40% of the company’s sales are likely to be hybrids by the end of this decade. Ford plans to launch a four-wheel-drive hybrid, the Escape, toward the end of 2004 and Nissan and GM are developing hybrid vehicles. Industry analysts forecast that annual sales of hybrid cars in the United States will be 400,000, or about 1 hybrid for every 40 conventional car. In September 2004, Toyota announced that it plans to join forces with China’s FAW to sell Prius hybrids in China. The cars will be assembled from kits made in Japan and will only be available for sale in China and not for export. However, while environmental protection is high on the agenda for Chinese policymakers, there is little evidence, at present, of a consumer base for products that are environmentally friendly.

44.2.3 Asian Automotive Vehicle Regulations 44.2.3.1 Safety Cars are becoming more complex and sophisticated as a result of stricter safety and environmental laws and increasing demands from customers. Many of the safety features in cars are developed initially in Western Europe, North America, or Japan and are then applied to vehicles made and sold in other regions. The trend toward an increasing use of airbags and side-impact protection bars typifies the emphasis on greater safety. Both concepts were pioneered in Europe, with Mercedes-Benz inventing the original steering wheel airbag and Volvo inventing the side-impact protection system. However, the routine use of airbags was evident first in the United States. These trends are now becoming apparent in Asian markets, particularly on Japanese, South Korean, and Malaysian cars destined for export to the United States and Europe.

In Japan, Toyota has been working on vehicle safety for many years. The company developed the anti-lock braking system (ABS) in 1971 and adopted the traction control (TRC) system in 1987. In 1995, Toyota commercialized the steering-assisted vehicle stability control (VSC) system. Toyota engineers believe that the ultimate goal of achieving no accidents and no deaths involves people, vehicles, and the traffic environment being viewed as three pillars of an interrelated whole in which each pillar should complement and support the others. It is essential that countermeasures toward each of these areas are implemented comprehensively. According to Toyota, preventive safety and collision safety are the two target areas that come into play before and after an accident. Within these target areas, the roles that people, automobiles, and the traffic environment play are ever changing. Toyota’s ambition is to continually effect evolutions in safety technology so that the automobile can continue to play a greater role toward safety regardless of the stage of accident occurrence. The basic theme of preventive safety is ensuring a high level of vehicle stability. Toyota has been engaged in the development of visibility support technology, such as the blind-spot monitor. Toyota uses a rigid process to analyze and evaluate its safety technology, examining and recreating accidents to find their causes and then assessing safety technology by incorporating it into its vehicles and examining and confirming its effectiveness in real circumstances. The company seeks to learn from actual accidents that occur within the marketplace. An important conclusion from Toyota’s analyzes is that, even if car manufacturers were to maximize the incorporation of various safety measures, the reduction in fatalities is expected to reach no higher than 60% by 2030. Toyota believes the “zero injuries and fatalities” target can be achieved only from a combination of driver training and experience, the traffic environment and vehicle safety countermeasures. In March 2004, Toyota announced the development of a radar-based cruise control system that can be used in slowmoving traffic to make driving less stressful. The system is an improved version of one introduced in 1997 for Toyota’s Celsior luxury car. The first system was designed for use at speeds of 25 to 60 mi/h (40 to 100 km/h), but with advances in laser sensors and smoother braking, the new system can be used at much lower speeds. The system keeps track of the vehicle in front at speeds of 20 mi/h (∼30 km/h) or lower. When the vehicle in front stops or slows down, the system gives visual and audio warnings urging the driver to apply the brakes. If the driver does not respond in time, the system slows the vehicle to a complete stop. As a result, it can assist the driver in stop-go traffic by reducing pedal work. Toyota estimates that the system’s low speed and conventional modes cover around 90% of driving speeds during a typical weekday on


the Tokyo Metropolitan Expressway. The system will be fitted to a new vehicle to be launched by Toyota later in 2004. Traffic accident statistics in Japan show that rear-end impacts account for almost 50% of all injury-causing accidents and that over 90% of the injuries sustained by occupants whose vehicles are struck in rear-end collisions are to the neck region. More than 200,000 people suffer such injuries annually. Rear-end collisions, even at relatively low impact speeds, can result in back or neck injuries and in some cases lead to subsequent discomfort such as whiplash injuries. Nissan investigated actual traffic accidents thoroughly and has used the data to develop of a safety system based on actual human body movement. Nissan’s Active Head Restraint system uses the force of the occupant’s body against the seatback in a rear-end collision to move the head restraint forward instantaneously to support the head, thereby helping to reduce the impact to the neck of a front-seat occupant. The mechanism of whiplash injuries closely involves two factors resulting from the impact: the force acting to bend the neck backward and the force that causes the head to tilt rearward. Because the Active Head Restraint is effective in controlling these two factors, it can help reduce the load on the neck at the moment of the collision, reducing the resultant bending force by approximately 45%. Nissan started to provide Active Head Restraints as standard equipment in all its cars, wagons, mini-vans, and SUVs in Japan during 2004. Nissan has also developed a number of safety technologies to help protect occupants in side collisions. Typical examples include the high-strength Zone Body construction, SRS side airbag systems for the driver and front passenger (also available in the rear seat on some models), and interior trim materials with high energy-absorbing capabilities. As a further measure, Nissan is continually expanding the application of SRS curtain airbag systems to help minimize head and neck injuries in side collisions. When the vehicle is impacted from the side, the SRS curtain airbag system instantly inflates the airbags built into the sides of the ceiling to help protect front- and rearseat occupants. These airbags help cushion the impact when an occupant’s head strikes a pillar or a side window. They also help to mitigate neck injuries by helping control excessive twisting of the neck. Though SRS curtain airbag systems are often thought to be safety features found on luxury models, Nissan has adopted these systems also on the new generation of its March small passenger car. Nearly all Nissan cars, wagons, mini-vans, and SUVs for the Japanese market were available with SRS curtain airbag systems from early in 2005. In September 2004, Honda announced plans to introduce an in-car warning system that alerts drivers on dark roads when there is a person or animal is ahead of them. The Intelligent Night Vision System uses two far-infra-red

cameras, mounted on a vehicle’s front bumper, to detect warm objects up to 80 m away. The incoming image data is analyzed using software that recognizes the characteristic shapes of pedestrians and calculates how far they are from the car. The system projects an image of the roadway ahead onto a mirror on the vehicle’s dashboard and adds a glowing orange outline of any pedestrians when they are detected. It also sounds an alarm to alert the driver. Honda plans to launch the system later in 2004 in the new version of its Legend car. The Japanese Institute of Traffic Accident Research and Data Analysis has reported that 70% of pedestrian fatalities occur at night. According to MMC, in the event of a collision, reducing the impact to the occupant and maintaining the available survival space within the body are essential. MMC introduced its Reinforced Impact Safety Evolution (RISE) body construction in the 1996 Galant, claiming to set a new standard for improved collision safety performance. In May 2003, MMC launched the Grandis, which uses further refined RISE technology, such as “straight frame construction,” “octangular front side member,” and “three-way input distribution cross-dash pillar braces” to minimize cabin deformation while effectively absorbing and distributing impact energy. In addition, the Grandis incorporates “tailored blank” technology whereby welds are formed between steel materials of varying thickness for improvements in both impact safety performance and weight reduction due to the optimal allocation of material. In MMC vehicles, special construction is used to reduce contact between the foot and the brake pedal and the foot-actuated parking brake in an impact forward of the vehicle. This reduces injury to the driver’s ankle area. In a frontal impact, the backward movement of the engine may cause the brake booster to get pushed in toward the vehicle interior, but this construction allows the brake pedal to withdraw where it is attached at its upper end, allowing it to move down along the stopper plate, thus reducing pedal interference. This safety system is now being fitted to all MMC eK Wagon, Airtrek, Colt, and Grandis vehicles. 44.2.3.2 Environment While the rapid growth of vehicles in Asia has contributed to economic development and welfare, it has become clear that it presents three main problems: congestion (roads in Asian cities are becoming increasingly congested), pollution (air quality in Asian cities are among the worst in the world), and road safety (the Asia/Pacific region accounts for almost half of all accident deaths in the world). These problems have a negative impact on the economic and social development of countries in Asia as they result in significant costs for medical expenses and lost productivity. Tackling these problems requires a comprehensive approach, involving policies, legislation, enforcement, institutional coordination, monitoring, and training.


With specific regard to pollution, a comprehensive strategy includes increasingly stringent emissions standards for new vehicles, specifications for clean fuels, programs to insure proper maintenance of vehicles, and traffic and demand management. The Asian Development Bank issued a report in May 1997 warning that pollution problems in the region pose an economic as well as an environmental threat. The report noted that 13 of the 15 most polluted cities in the world were in Asia and concluded that the region’s environmental crisis is in large part the result of failed policies and neglect. It also emphasized that economic growth itself is not directly to blame. Estimates of the economic costs of environmental degradation in Asia were as high as 9% of GNP. The ADB believed that continuing rapid urbanization was likely to make the situation worse, so it urged governments in the region to change their environmental policies. The report warned that a “pollute now, pay later, approach to the environment increasingly makes little economic or ecological sense.” It is estimated that road transport contributes about 14% to global CO2 and that about 30% of this is from vehicles in the less developed countries (LDCs). LDC contribution is higher than its vehicle share because of higher fuel consumption of older, poorly maintained vehicles, which also emit more pollutants because few of them are fitted with emission control devices. Although buses and trucks are the main contributors, their shares in terms of passenger km or tonne km are relatively low. Poorly maintained diesel engines in buses and trucks produce almost 50% of the world’s output of particulate matter. A large number of two-stroke engines emit high levels of hydrocarbons and smoke. In India it is estimated that they are responsible for about 33% of emissions. Vehicle emission control began in Japan in 1966 under the administrative guidance of the Ministry of Transport. Carbon monoxide (CO) emissions from gasoline vehicles was the first air pollutant to be regulated. Particulate, unburnt hydrocarbon (HC), and NOx emissions were regulated from 1975 onwards. Japan’s Central Environment Council issued Motor Vehicle Exhaust Emission Regulations, which comprehensively set the standards for NOx, HC, and CO for both gasoline and diesel vehicles in 1976. New emission limits with short-term and long-term targets were further set in December 1989. As in Europe and the United States, Japan developed its own environmental program, called the Japan Clean Air Program (JCAP). Although significant reductions in emissions from individual vehicles were achieved from 1975 to 1995, the increasing number of vehicles, particularly diesels, meant that total emissions were still trending upward. As a result, the Ministry of International Trade and Industry (MITI) started a program in 1996 to study possible future fuel and vehicle technology to improve air quality. The first step was started as a Petroleum Energy Centre

(PEC) project, with invited participation by the Japan Automobile Manufacturers Association (JAMA) and the Petroleum Association of Japan (PAJ). The PEC determined that it would not be possible to simply follow the United States and European leads because of the differing air pollution conditions in Japan, differences in automotive technology and, the prevalence of high quality fuel with low sulfur levels and high cetane numbers. Japan imposed more stringent emissions limits on new cars, trucks, buses, and motorcycles in 1998. The standards, which are shown in Tables 44.7 to 44.9, are similar to those in the United States and the European Union (EU). The Central Environmental Council also introduced emissions regulations for special vehicles such as bulldozers, power shovels, and farm tractors, which are estimated to be responsible for around one third of total transport-related NOx emissions. China first introduced laws on the prevention and control of air pollution in 1988, focusing on stationary sources of emissions. Vehicle emission regulations for all new vehicles were adopted in 1995 and were revised in 2000. In addition to the national standards, local standards that are more stringent can be set by the governments of provinces, autonomous regions, or municipalities, after agreement with the State Council. The latest regulations also contain provisions for testing motor vehicles annually to check whether they continue to comply with emissions limits. During 1997, the Chinese government initiated a technical review of the best method to tackle vehicle emissions. The review concluded that the gradual introduction of EU vehicle emissions limits, starting in the major cities, would be best, so Euro 1 limits for gasoline engines in passenger cars became mandatory in Beijing and Shanghai in January 1999. These limits were extended to the whole of China for new cars manufactured from October 2001 onwards. Euro 2 limits were mandated in the main cities during 2002 and became mandatory for new cars throughout China in July 2004. Dates for the introduction of Euro 3 and Euro 4 limits are shown in Table 44.10. The Chinese vehicle emissions standards are planned to be at the “advanced international level” standards by 2010. While the standards currently cover cars, vans, trucks, buses, and motorcycles, the Chinese government is proposing to add agricultural vehicles and LPG and liquefied natural gas (LNG) vehicles. Liquefied natural gas is being promoted in China as the answer to deteriorating urban air quality. LPG and LNG powered vehicles, particularly buses and taxis, have been introduced progressively in many Chinese cities, including Beijing, Shanghai, Shenzen, and Haikou. Shanghai opened its first LNG refueling facility to serve the city’s growing fleet of LNG-powered taxis in 1998 and by 2004 all mass transit vehicles in the city were operating on the gas. Leaded gasoline was finally replaced by LRP (lead replacement petrol) in China in 2003.


The Chinese government announced early in 2004 that it was about to issue the first standards on car fuel efficiency, but at the time of writing the limits had not been decided. However, it is clear that China plans to catch up to international standards for both fuel efficiency and emissions by 2010. As a result, much cleaner gasoline and diesel fuels will have to be available in China, requiring investment in either upgrading existing or building new refineries to meet both quality levels and increasing volume demands. The Chinese government has forecast that annual gasoline consumption could double to 80 million tonnes between 2003 and 2010. India’s government also took a step toward cleaner fuels when it approved proposals to set up diesel hydrodesulphurization units at nine refineries, at a total cost of $1.56 billion. The units enable lower sulfur diesel fuel to be produced, thereby allowing the fitment of more effective catalytic aftertreatment devices to vehicles. The refineries are in Gujarat, Haldia, Mathura, Panipat, Visakapatnam, and Mumbai. Unleaded gasoline has been available throughout India since the beginning of 2000. Progressively during 2000 and 2001, lower sulfur gasoline and diesel (0.05%) has been mandated, first in the main cities (New Delhi, Mumbai, Kolkata, and Chennai) and then in other cities. 0.05% sulfur fuels will be mandated throughout India during 2005. The effectiveness of vehicle emissions inspection programs in reducing pollution in India was brought into doubt by the initial results, reported during 1997, of a crackdown in the Indian capital New Delhi. More than 200,000 motorists had visited pollution control stations to have their vehicles checked and to obtain the certificate required to continue driving in the city. The limited number of stations available meant a familiar problem for such schemes; delays of up to 3 h for motorists requiring a test. From April 15, 1997 onwards, vehicles without a certificate have been unable to purchase petrol. Regulations to control vehicle emissions in India started in 1991, with the introduction of the “Mass Emission Regulation,” which covered CO and HC emissions from gasoline vehicles. Diesel vehicles were added in 1992. The regulations were tightened in 1996 and NOx, evaporative, and crankcase emissions were added. In 1998, 50% tighter limits were applied to vehicles that are fitted with catalytic converters, which were mandated in 42 major cities for gasoline powered cars. “India 2000” limits (equivalent to Euro I standards) were introduced in 2000. In April 2000, the Society of Indian Automotive Manufacturers (SIAM) proposed skipping the Euro III emissions limits for new trucks and buses and adopting the Euro IV limits for these vehicles in 2006/2007. SIAM proposed adopting Euro III limits for new passenger cars in 2004 and two- and three-wheelers in 2005 and Euro IV limits for these vehicles in 2005/2006 and 2009 respectively.

TABLE 44.7 Japanese Gasoline and LPG Motor Vehicle Emissions Standards Vehicle type Passenger cars

Engine typea 2- and 4-cycle

Test modeb 10.15M (g/km)

11M (g/test)

Trucks and buses

4-Cycle mini-sized

10.15M (g/km)

11M (g/test)

2-Cycle mini-sized

10.15M (g/km)

11M (g/test)

Light-duty, GVW 71.7 t

10.15M (g/km)

11M (g/test)

Medium-duty, 1.7t < GVW 71.7 t

10.15M (g/km)

11M (g/test)

Heavy-duty, 71.7 tGVW > 2.5 t

G13M (g/kWh)

Emission typec

Limite Yeard

Maximum

Average

CO HC NOx CO HC NOx

1975 1975 1978 1975 1975 1978

2.70 0.39 0.48 85.0 9.50 6.00

2.10 0.25 0.25 60.0 7.00 4.40

CO HC NOx CO HC NOx CO HC NOx CO HC NOx CO HC NOx CO HC NOx CO HC NOx CO HC NOx CO HC NOx

1998 1998 1998 1998 1998 1998 1975 1975 1975 1975 1975 1975 1988 1988 1988 1988 1988 1988 1998 1998 1994 1998 1998 1994 1998 1998 1995

8.42 0.39 0.48 104 9.50 6.00 17.0 15.0 0.50 130 70.0 4.00 2.70 0.39 0.48 85.0 9.50 6.00 8.42 0.39 0.63 104 9.50 6.60 68.0f 2.29 5.90

6.50 0.25 0.25 76 7.00 4.40 13.0 12.0 0.30 100 50.0 2.50 2.10 0.25 0.25 60.0 7.00 4.40 6.50 0.25 0.40 76 7.00 5.00 51.0g 1.80 4.50

Notes: a 2-Cycle passenger cars, trucks, and buses are no longer in production. GVW = gross vehicle weight. b 10.15-mode (10.15M) represents a typical driving pattern in urban areas. 11-mode (11M) is a typical driving pattern of a

cold-started vehicle traveling from the suburbs to an urban center. c CO = Carbon monoxide, HC = unburnt hydrocarbons, NOx = nitrogen oxides. d Year of first enforcement. e Maximum is the maximum permissible value for the vehicle type; average is the average value for vehicles of that type. f 105 for LPG vehicles. g 76 for LPG vehicles. Source: Japanese Ministry of the Environment.

Currently, emissions from new cars, trucks, and buses have to meet “Bharat Stage II” air quality standards (equivalent to Euro II limits on NOx and particulate emissions) in all major cities. An Indian Inter-Ministerial Task Force recommended in March 2001 that by April 2005, Bharat Stage II emissions will be mandatory across


India and “Bharat Stage III” requirements will have to be met in eleven major cities, including New Delhi, Mumbai, Chennai, and Kolkata. New two- and threewheeled vehicles have had to meet Euro II standards since April 2005 they will have to meet Euro II limits. Vehicle emissions limits for India are shown in Table 44.11.

TABLE 44.8 Japanese Diesel Motor Vehicle Emissions Standards

Vehicle type

Test modea

Engine type

Passenger cars

Trucks and buses

Emission typeb

Limitd Yearc

Maximum

Average

10.15M (g/km)

CO HC NOx PM

1986 1986 1997e 1997e

2.70 0.62 0.55 0.14

2.10 0.40 0.40 0.08

Light-duty, GVW 71.7 t

10.15M (g/km)

CO HC NOx PM

1988 1988 1997 1997

2.70 0.62 0.55 0.14

2.10 0.40 0.40 0.08

Medium-duty, 1.7 t < GVW 71.7 t

10.15M (g/km)

CO HC NOx PM

1993 1993 1997f 1997f

2.70 0.62 0.97 0.18

2.10 0.40 0.70 0.09

Heavy-duty, GVW > 2.5 t

G13M (g/kWh)

CO HC NOx PM

1994 1994 1997g 1997g

9.20 3.80 5.80 0.49

7.40 2.90 4.50 0.25

Notes: a 10.15-mode (10.15M) represents a typical driving pattern in urban areas. 11-mode (11M) is a typical driving pattern of a cold-started vehicle traveling from the suburbs to an urban center. b CO = carbon monoxide, HC = unburnt hydrocarbons, NOx = nitrogen oxides, PM = particulates. c Year of first enforcement. d Maximum is the maximum permissible value for the vehicle type; average is the average value for vehicles of that type. e 1997 for small cars, EIW 71.25 t, and 1998 for medium cars, EIW > 1.25 t. EIW = equivalent inertia weight. f 6 1997 for MT vehicles, 1998 for AT vehicles. g 1997 for GVW 73.5 t, 1998 for GVW 712 t, and 1999 for GVW > 12 t. Source: Japanese Ministry of the Environment.

TABLE 44.9 Japanese Motor Cycle Emissions Standards Engine type Test mode

Emission typea

Limitc Yearb Maximum Average

4-Cycle

2-Wheel test (g/km)

CO HC NOx

1998 1998 1998

20.0 2.93 0.51

13.0 2.00 0.30

2-Cycle

2-Wheel test (g/km)

CO HC NOx

1998 1998 1998

14.4 5.26 0.14

8.00 3.00 0.10

Notes: a CO = Carbon monoxide, HC = unburnt hydrocarbons, NOx = nitrogen oxides, PM = particulates. b Year of first enforcement. 1998 for small motorcycles (Type I), 1999 for larger motorcycles (Type II). c Maximum is the maximum permissible value for the vehicle type; average is the average value for vehicles of that type. Source: Japanese Ministry of the Environment.


“Bharat Stage IV” standards are currently under discussion. All commercial vehicles (buses, taxis, auto-rickshaws, and trucks) in India now have to pass an annual “fitness” check, for emissions, safety, and roadworthiness. The inspection and certification tests are performed by government authorized agencies (RTOs). PUC centers at fuel stations and repair garages are also authorized to perform periodic (three or six monthly) emissions checks on commercial vehicles. SIAM has recommended that “fitness” tests are extended to include cars and two- and threewheelers, using rigorously accredited private test centers. The number of test centers would need to be expanded significantly, as there were more than 40 million two- and three-wheeled vehicles in India in 2002. However, SIAM has recognized that the current PUC system in India is not achieving the objective of reducing pollution, because the independent centers do not follow rigorous procedures (due to inadequate training), the test equipment is not calibrated periodically by independent

TABLE 44.10 Chinese Emissions Limits for Passenger Car Gasoline Engines Emissiona and limits (g/km)

Mandated byb

Emissions standard

CO

HC + NOx

HC

NOx

Beijing

Shanghai

All China

Euro 1 Euro 2 Euro 3 Euro 4

2.72 2.20 2.30 1.00

0.97 0.5 — —

— — 0.2 0.1

— — 0.15 0.08

Jan 1999 Jan 2002 Jan 2005 Jan 2010

Jan 1999 Mar 2002 TBD Jan 2010

Oct 2001 July 2004 TBD TBD

Notes: a CO = Carbon monoxide, HC = unburnt hydrocarbons, NOx = nitrogen oxides. b TBD = To be decided. Source: Pathmaster Marketing, from various industry contacts.

authorities, a lack of professionalism has led to malpractices, and there is no system to monitor vehicles that have failed the tests. To help overcome these difficulties, SIAM has designed an automated emission test device for gasoline vehicles that is as tamper-proof as possible. Other Asian countries have also been active in introducing vehicle emission standards. EU limits have been in place in Singapore and Hong Kong for some years. Malaysia introduced pollution emissions standards based on EU limits in January 1997, aimed at reducing emissions from cars and trucks. In June 2004, the Thai Ministries of Industry and Finance agreed to offer tax incentives to encourage the production and sale of energy-efficient vehicles in Thailand. At the same time, car makers urged the government to cut tariffs on imported hybrid cars. The tax incentives aim to encourage manufacturers to produce vehicles that consume less fuel under the government’s “Best Little Car” project, formerly known as “Eco Car” and would also be provided for fuel cell or hybrid cars as well as models that use ethanol-blended gasohol. New light-duty diesel vehicles sold in Thailand have been required to meet Euro III standards from July 2004 and heavy-duty diesel vehicles currently have to meet Euro II limits. The timing of adopting Euro III limits for heavy-duty diesels and Euro IV limits for all diesel vehicles is currently being discussed. Low sulfur diesel (350 ppm) is now mandated in Thailand and it is proposed that 50 ppm sulfur diesel should be mandated by 2010. In addition, the Thai government has encouraged initiatives to evaluate LPG, dual-fuel (CNG/gasoline and CNG/diesel), and bio-fuel engines for buses and taxis in Bangkok. Motorcycle manufacturers in Asia reacted to pressure to reduce emissions of pollution and noise. In early 1997, an alliance was formed between Honda, Suzuki, Yamaha, and Kawasaki to examine ways to meet the challenges. The Nippon Motorcycle Association, which coordinates the alliance, also invited membership from motorcycle retailers and distributors, and has organized activities


for motorcycle owners, in addition to the environmental research. Worldwide, as the disproportionate contribution to ground level ozone and hydrocarbon pollution from motorcycles became apparent, ways to curb emissions were investigated and developed. The levels of pollution have encouraged some countries, such as Taiwan, to enforce the sale of low emission scooters. From 1998, 5% of scooters sold in Taiwan must offer zero emissions. It might be difficult to see why two-stroke engines should be encouraged from the perspective of emissions alone. Conventional two-stroke engines must pass the fuel– air mixture through the crankcase then into and (as exhaust) out of the cylinder through fixed ports opened and closed by piston movement. Even at their most efficient, combustion temperature is high and so, consequently, are NOx emissions. Wet sump lubrication is not possible, so oil must be carried in the fuel-air mixture, burning with it and contributing to HC emissions. Because of the fixed porting, the engine is at its most efficient only rarely; at other speeds and loads a proportion of the mixture passes straight through the combustion chamber unburned, so fuel consumption is high and HC emissions are increased further. A measure of the challenge to a lean-burn compact two-stroke is that current EU legislation tolerates around ten times the emissions from a small two-stroke scooter than it does from a car. However, with twice as many power strokes in its operating cycle as a four-stroke engine, a much smaller capacity engine can produce the same power, and even more torque. The two-stroke is cheap and simple to produce and maintain. The more these virtues are preserved while emissions and consumption are brought down, the more environmentally (and commercially) friendly they become through the indirect advantages of low weight and compactness. Asian companies known to be working on the development of improved two-stroke engines include Yamaha-Shansin, Honda, Subaru (which has close links to

TABLE 44.11 Indian Vehicle Emissions Limits Fuel type

Vehicle type

Gasoline

2-Wheelers

3-Wheelers

Passenger cars

Diesel

Passenger cars Light vehicles, GVW 73.5 t

Heavy vehicles, GVW > 3.5 t

Emission and limits (g/km or g/kWh)a

Year mandated

CO

HC

HC + NOx

PM

1991 1996 2000 2005 1991 1996 2000 2005 1991 1996 1998b 2000 2004/05

12–30 4.50 2.00 1.50 12–30 6.75 4.00 3.00 14.3–27.0 8.68–12.4 4.34–6.20 2.72 2.20c

8–12 — — — 8–12 — — — 2.0–2.9 — — — —

— 3.00 2.00 1.50 — 5.40 2.00 1.50 — 3.00–4.36 1.50–2.10 0.97 0.50d

— — — — — — — — — — — — —

2004/05e 2004/05f 1992 1996 2000 2004/05 1992 1996 2000 2004/05

1.0 1.0–1.5 14 11.2 4.5 4.0 17.3–32.6 11.2 4.5 4.0

— — 3.5 2.4 1.1 1.1 2.7–3.7 2.4 1.1 1.1

0.7 0.7–1.2 21.5 16.8 9.1 8.1 — 16.8 9.1 8.1

0.08 0.08–0.17 — — 0.36g 0.15 — — 0.36 0.15

Notes: a CO = carbon monoxide, HC = unburnt hydrocarbons, NOx = nitrogen oxides. Values for 2-wheelers, 3-wheelers, and gasoline and diesel passenger cars are g/km and values for diesel engines are g/kWh. b For cars fitted with catalytic converters. c For vehicles up to six seats and GVW up to 2.5 t. 2.2–5.0 for vehicles with more than six seats and GVW up to 3.5 t. d For vehicles up to six seats and GVW up to 2.5 t. 0.5–0.7 for vehicles with more than six seats and GVW up to 3.5 t. e For vehicles up to six seats and GVW up to 2.5 t. f For vehicles with more than six seats and GVW up to 3.5 t. g For engines exceeding 85 kW power. 0.61 for engines less than 85 kW power. Source: Society of Indian Automobile Manufacturers.

Nissan), Toyota, Suzuki, and Daihatsu. The most active in publishing patents in this field have been Yamaha-Shanshin and Honda.

44.3 CURRENT STATUS OF AUTOMOTIVE FLUIDS IN ASIA 44.3.1 Engine Oils 44.3.1.1 Gasoline engine oils An extremely wide range of gasoline engine oil qualities is available in Asia currently, ranging from low quality


mineral oils to fully synthetic oils. The pattern has begun to change over the past five or more years, as many of the countries in the region become more wealthy and more aware of the value of goods and services. High quality automotive lubricants have been available in Japan, Singapore, Hong Kong, South Korea, Taiwan, and Malaysia for over ten years. Other countries in Asia have started to catch up. Within Japan, OEMs have generally developed proprietary factory fill specifications and then selected oil companies to develop the required engine oils using proprietary engine tests. These oils are also marketed by the OEMs as so-called genuine oils. They are mainly SAE

10w30 viscosity grades. There is reluctance to reformulate these oils until there is an engine change and virtually no formulation modifications are accepted without extensive testing. In other countries, Japanese vehicle manufacturers have relied generally on the API classification system to recommend engine oils for service fill applications in passenger cars. The Japanese Automobile Standards Organisation (JASO) is similar in many ways to the Co-ordinating European Council in Europe, in developing engine test procedures that do not have pass/fail limits. The parallel is not complete, however, because Japanese vehicle manufacturers often do not require these tests for their own in-house specifications. The JASO engine tests have an unofficial parallel with the tests used in the API “S” sequences and are used to evaluate oils of different quality levels. In 1993, JASO modified its previous policy and quoted limits for a Japanese industry standard (JIS K2215), which includes a specification for the minimum quality engine oil for Japanese automotive gasoline engines. Since 1990, the JAMA has worked with the Motor Vehicle Manufacturers Association of the United States (MVMA, now the Alliance of Automobile Manufacturers [AAM]) to develop a new performance standard called ILSAC, the International Lubricants Standardisation and Approvals Committee. It is intended that the ILSAC specifications will eventually include at least one Japanese engine test. As a result the Nissan KA24E low temperature valve train wear test has been developed and round robin testing has been completed by JASO. The result is that, in addition to the OEM “genuine oils,” typical gasoline engine oils available in Japan currently meet the API SL, ACEA A1/A3, and ILSAC GF-3 specifications, with API SM and ILSAC GF-4 quality oils about to be introduced before the end of 2004. Some API SG and SH quality oils are still available, although only recommended for use in older model cars and vans. In China, the typical quality level available currently is API SE or SF, made from lower quality baseoils and additive packages no longer available in North America or Western Europe. However, some API SC and SD quality oils are still sold and API SH and SJ quality oils have been marketed for the past few years. Automotive oils accounted for 54% of all lubricants sold in China in 2003. High quality refers to gasoline engine oils that meet API SG or better. Many oils are still monograde SAE 30 or 40 viscosity, although an increasing number of 20w50 and 15w50 multigrade oils are being sold. PetroChina (“Kunlun,” “Feitian,” and “Qixing” brands) and Sinopec (“Great Wall” brand) are the main indigenous suppliers, although there are hundreds of smaller lubricant blending and marketing companies in China. Most of the major international lubricant marketers, including Shell, Esso (ExxonMobil), BP/Castrol,


and Caltex (ChevronTexaco) are active in China. Together, foreign brands accounted for 78% of the high quality gasoline engine oil market in 2003. China’s import tariffs on lubricants have been reduced from 9 to 6% following the country’s entry into the WTO in 2001. PetroChina aims to capture a 35% share of the high quality automotive engine oil market by 2005 and is working hard to improve the recognition and reputation of its main Kunlun brand. Sinopec is now accredited to ISO 9000 and ISO 14000 quality standards and has lubricants that meet international standards (API, ACEA, SAE, ISO) as well as being “approved” by international OEMs such as VW, BMW, DaimlerChrysler, Renault, Volvo, Cummins, Dennison, and ZF. Sinopec’s Great Wall brand now sells a fully synthetic 5w50 gasoline engine oil that meets the API SJ specification. Great Wall also offers API SE, SF, SG, and SJ mineral oil grades. Toward the end of 2003, Jiffy Lube (Shell) and SAIC announced a $30 million joint venture to build a chain of quick lube centers across China. The plan is to build a number of pilot centers in Shanghai during 2004 and then branch out into other cities in China. The centers will be modeled on the U.S. Jiffy Lube chain, providing oil changes and radiator, transmission, filter, and other services in 15 min. Shell and SAIC believe there will be a strong and growing demand for this type of convenience service in China, as a result of the rapid growth in car ownership. Automotive lubricants account for 65% of the market in India. Of this, only 5% is for passenger car gasoline engine oils. Most products are currently API SF or SG quality and generally 20w40 viscosity grade. Over the next five years, gasoline engine oils available in India are forecast to move toward API SH, SL (GF-3), and even SM (GF-4) quality, with fuel-conserving 15w40 and possibly 10w30 viscosity grades becoming available. These newer oils will have higher viscosity index (VI), lower cold cranking simulator viscosity, and lower NOACK volatility than the current products. From mid-2003 onwards, API Group II baseoils became more widely available in India, as a result of the commissioning of a new 140,000 tonne per year hydroprocessing plant at Indian Oil’s Haldia refinery. These baseoils are being used in the higher performance gasoline engine oils, as well as higher performance diesel engine oils and industrial oils, that will be introduced to the market gradually. Additional supplies of Group II baseoils will become available from the beginning of 2006, when Bharat Petroleum commissions a new 180,000 tonne per year plant at its Mumbai refinery. Although many countries in Asia still have lower quality gasoline engine oils on sale, high quality API SL/ACEA A3/ILSAC GF-3 synthetic 5w40 and part-synthetic 10w40 oils have been available in Singapore, Hong Kong, and South Korea for many years. As more motorists begin to

buy more expensive cars in other countries, the current tiny market share of the premium quality oils will begin to grow. 44.3.1.2 Diesel engine oils The pattern for diesel engine oils, both light-duty and heavy-duty, in Asia mirrors the pattern for gasoline engine oils; wide variations in both quality and viscosity. In Japan, JAMA requested a new API category for heavy-duty oils, for use in diesel engines operated in southeast Asia. JAMA’s concern with the CH-4 and CI-4 requirements is that it could lead to low ash oils, counter to their desires for higher ash oils. The requested category would be PC-8 and would be aimed at diesel engines with lower piston temperatures, greater use of slider followers, and hence greater need for wear protection. This specification was dropped, however, in favor of the new DHD-1 specification. The JAMA, ILSAC, and ACEA worked hard to develop the first global specification for heavy-duty diesel engine oils, DHD-1, which was introduced in 2001. The DHD-1 specification not only includes elements of both API CH-4 and ACEA E5 specifications, but also includes the Mitsubishi 4D34T4 engine test for soot-related valve train wear. This aims to overcome JAMA’s concerns about low ash oils. Inevitably, the DHD-1 is more restrictive that either the API or ACEA specifications, as it is intended to provide a very high performance oil that can be used in any heavy duty diesel engine from any OEM used anywhere in the world. Following the introduction of the API CI-4 specification in 2003 and the revised ACEA E5 specification at the end of 2004, JAMA and ILSAC plan to introduce an updated DHD-2 specification during 2005. Shortly after the introduction of DHD-1, the same OEMs recommended guidelines for the development of a set of global specifications for light-duty diesel engine performance. The DLD-1, DLD-2, and DLD-3 specifications are intended for high-speed, four cycle diesel engines. Unlike DHD-1, there are three performance levels. DLD-1 provides a basic level of quality for markets with highsulfur fuels. DLD-2 provides a higher level of performance, while requiring lower oil viscosities to assist with fuel efficiency. DLD-3 provides the highest level of performance, with both long drain and severe operating condition capabilities, as defined by engine manufacturers. All three specifications contain tests developed by CEC, JAMA, and ASTM. The three specifications were introduced, primarily in Asia, in 2003. Although there have been no Japanese industry diesel specifications developed to date, JAMA has been heavily involved in the development of the new DHD-1 and DLD-1, 2, and 3 specifications. As a result, operators of mixed fleets of diesel vehicles anywhere in the world now have the option of using the same quality of oil in either light-duty


or heavy-duty engines irrespective of the OEMs that built the engines. In China, API CD and CE quality diesel engine oils are the most common products, although API CC oils can still be purchased from many of the smaller, local lubricant blenders and marketers. Great Wall (Sinopec) now markets an API CI-4 quality oil that is claimed to also meet ACEA E3, E5, and B4 specifications as well as MB228.3, MB229.1, Volvo VDS-3, Cummins CES20071/72/76/77/78, MAN 3275, and Mack EOM+MTU specifications. Great Wall also offers API CH-4, CF-4, CF, and CD diesel engine oils. Diesel engine oils account currently for 65% of the automotive lubricants market in India. Many of the oils being sold at present are API CC or CD quality and 20w40 viscosity grade. The main manufacturers of trucks in India, such as Tata Motors and Ashok Leyland, began to recommend API CH-4 or CI-4 quality oils for new vehicles from 2005 onwards. It is forecast that the higher performance oils are also likely to be 15w40 viscosity grade. The market drivers for these changes are reductions in emissions limits (see later), which focus on lower NOx and particulates, together with extended drain intervals and reduced oil consumption. Similar qualities of diesel engine oils are available in all other countries in Asia, including Singapore, Hong Kong, South Korea, Taiwan, Malaysia, Thailand, Indonesia, and the Philippines. 44.3.1.3 Two-stroke engine oils Globally, 70% of all motorcycles have two-stroke engines and a large percentage of these motorcycles are found in Asian countries. It is not surprising, therefore, that the current standards for two-stroke engine oils are based on JASO standards. The current JASO specifications for two-stroke engine oils, FB, and FC, incorporate tests for lubricity, initial engine torque, oil detergency, piston skirt deposits (varnish), exhaust smoke levels, and exhaust system blocking performance. The first four tests use a Honda engine, while the last two tests use a Suzuki engine. The FC performance level is more severe than the older FB performance level, particularly with respect to exhaust smoke and exhaust system blocking. Global performance specifications that are based on the types of performance criteria and tests used in the JASO specifications are now being introduced for two-stroke oils. These newer specifications are aimed at improving the image of two-stroke engines and at allowing for continued improvements in engine performance. The specifications are a response by the engine manufacturers, working with specification setting organization such as JASO, ASTM, and CEC, to the growing environmental pressure to reduce smoke emission from exhaust systems and to standardize the quality of lubricant available for use

TABLE 44.12 Japanese and Global Specifications for Two-Stroke Engine Oils JASO specification Global specification Performance criterion

FB EGB

FC EGC

EGD

Requirements

Lubricity Initial torque Detergency

95 98 85

95 98 95

95 98 125

Piston skirt deposits

85

90

95

Exhaust smoke Exhaust system blocking

45 45

85 90

85 90

Test engine Honda Honda Honda Honda Honda Honda Suzuki Suzuki

Test method JASO M340-92 JASO M340-92 JASO M341-92 3 h test JASO M341-92 3 h test JASO M342-92 JASO M343-92

Source: JASO.

worldwide. The specifications cover oils used for motorcycles, scooters, chainsaws, snowmobiles, and agricultural equipment. A summary of the specifications is shown in Table 44.12. Polybutene synthetic oils, which have the ability to depolymerize cleanly in the two-stroke engine, are increasingly being used in the formulation of oils that meet the smoke, exhaust blocking, and lubricity requirements of the major oil types being specified by engine manufacturers. However, polybutenes are not classed as biodegradable and synthetic esters are chosen to meet biodegradability requirements when this is needed for outboard, two-stroke oils. While two-stroke engines have definite advantages, such as reduced weight and size, higher power to weight ratio, fuel efficiency, fewer parts, and lower cost to manufacture, compared with four-stroke engines, their main disadvantage is higher emissions. While a large number of Japanese engine manufacturers, notably Mazda, Subaru, Nissan, and Toyota, were very interested in developing low emission two-stroke engines in the late 1980s, this interest has declined markedly in recent years, due to the problem of overcoming the high emissions levels. However, the work to lower two-stroke emissions led to the development of direct gasoline injection for four-stroke engines, so the research has had a positive outcome. In 2002, India had more than 42 million two- and three-wheeled vehicles with two-stroke engines, so it is not surprising that 13% of Indian automotive lubricants are two-stroke oils. The increasing severity of emissions limits in India mean that many of these vehicles will need to use EGC or EGD specification two-stroke oils by 2005. Other countries in Asia with large numbers of twostroke motor cycles, notably Thailand, Vietnam, Myanmar, and Cambodia, are likely to have to follow India’s example.


44.3.2 Transmission and Gear Oils The majority of developments with automotive gear and transmission fluids occur in North America, primarily because of the huge use of ATs in this market. These developments have impacted the market in Europe, and are starting to impact the Asian market. The overwhelming majority of transmissions in Asia are manual gearboxes and conventional hypoid rear axles, which use standard API classes of gear lubricants. The majority of conventional automotive gear oils in Asia are API GL-4 or GL-5 quality. Fully synthetic SAE 75w90 and 75w140 viscosity grade gear oils are now being sold in China and India. These products have been available in Japan, Singapore, and South Korea for many years. The Japanese automotive transmission market is markedly different from the rest of Asia, in that 63% of transmissions were ATs in 2001. Continuously variable transmissions (CVTs) accounted for 18% of the market and MTs accounted for the other 19%. The market is forecast to change further by 2010, with ATs declining to 50% of the market, CVTs increasing to 38%, and MTs declining to 10%. The remaining 2% is forecast to be dual clutch transmissions (DCTs). The world’s largest manufacturer of ATs is Aisin Seiki. Most car manufacturers are now promoting the concept of “filled-for-life” ATs, to increase customer satisfaction, and to assist with further improving vehicle fuel economy. This is derived from “shudder-free” torque converter clutches and stable automatic transmission fluid (ATF) friction characteristics. The demand for “filledfor-life” will require significant improvements to ATFs. Anti-wear requirements will need to last for 100,000 to 150,000 mi, the oils will need to have exceptional high temperature viscosity properties combined with good low temperature fluidity properties and high shear stability in pump and clutch tests. Obviously, foaming resistance, air

entrainment, and material compatibility (elastomers, bearing materials, and friction materials) will need to be at least as good or better than how it is currently. As a result, there will be a heavy dependence on baseoil properties, which probably means the use of Group II or III baseoils, PAOs, and esters. Ford’s activities toward a MERCON-V specification have continued. ATFs to meet the requirements were trialed in Europe in 1996 and in 1997 in North America. Primary service fill of MERCON-V began at the end of 1997. Although Chrysler has delayed work to develop a new ATF, they are now recommending against the use of any fluids that do not meet their MS7176D specification. It is possible that Chrysler’s new MS9602 specification will be introduced later this year. Following the expenditure of around $3 million by GM and the additive companies on new DEXRON-IV oils, this development has been suspended due to the cost of the ATFs that met the target performance levels. New, lower performance, targets were prepared in 2001 and GM announced the start of DEXRON-III “H” licensing in April 2003. The new performance limits require ATF formulators to use Group II and/or II+ baseoils in the new fluids. The requirements for the next GM ATF are broadly the same as those demanded by Ford and GM’s main service fill will continue to be DEXRON-III until DEXRON-IV is ready, which may now be quite some time in the future. The AAM and JAMA are working toward the standardization of ATF tests. However, it appears that there will not be an ILSAC ATF specification, due to differing friction properties required by different OEMs. One aspect of the current activities is a program to assure customers that they are using the correct ATF in their transmission. Fluids for use in CVTs were developed using factory fill ATFs as a starting point, although a standardized friction test, for determining traction coefficients, still has to be agreed. Many CVTs now use specialized traction fluids, of which Santotrac and Shell are the main suppliers. In Japan, Honda, Toyota, and Mitsubishi have developed CVTs and fluids for use in them. Advanced CVTs, which usually incorporate a lock-up torque converter, appear to be the favored new transmission system solution in Japan for engine sizes up to 2 L. Nissan also claimed to have made significant progress with a split-path toroidal transmission for more powerful vehicles. Engineering opinion is that a CVT coupled with an integrated engine/transmission electronic control unit will become essential if the engine is to be run at high efficiency most of the time, thus reducing fuel consumption and CO2 emissions.

44.3.3 Other Automotive Oils Developments in Asia with other automotive oils, such as brake fluids, shock absorber oils, and air-conditioning


system oils, are influenced mainly by developments in the United States and Europe. The majority of specifications are those recommended by the SAE and API. Even now, brake fluids that meet the DOT 3 specification tend to be marketed rather than those meeting the newer DOT 4 and DOT 5.1 specifications, although the latter are available in the more progressive markets in Japan, Korea, Hong Kong, Singapore, Australia, and New Zealand. Air-conditioning in cars is relatively rare, but is increasing in Australia and Japan.

44.4 DEVELOPMENT OF MARKETS FOR SYNTHETIC AUTOMOTIVE FLUIDS IN ASIA As in all markets, the growth in lubricant demand in Asia follows the general pattern of economic development. In 1995, lubricant demand growth in Asia averaged 5.0%, but by 1997 it had slowed to 4.1%. It picked up to average 4.5% in 2000, but in 2003 it had slowed again, to an average of 3.8%. Even so, this demand growth was considerably higher in 2003 than in Western Europe and North America, which both recorded declines of 0.1% in lubricant consumption. Asia overtook North America in 1999 to become the largest lubricants market. Asia’s share of the global lubricants market was 29.7% in 2003, compared with North America’s share of 23.8% and Western Europe’s share of 13.3%. At present, although synthetic lubricants represent only around 1% of the total market in Asia, the prospects for synthetic automotive lubricants remain optimistic. There are several reasons for this optimism: • Increasingly stringent emissions regulations and envi-

ronmental concerns will promote the use of greater fuel efficiency and higher equipment performance, particularly with gasoline and diesel engines. Many of the recent improvements seen in Europe and North America have been contingent upon higher performance lubricants, including synthetics, so these are also likely to be required in Asia and other developing regions. • Global competition in all industries is likely to promote the adoption of global standards of best practice in manufacturing and services. In order for Asian companies to continue to compete in global markets, their use of the latest technologies will need to grow. This includes the use of synthetic and part-synthetic lubricants in those applications in which mineral oils have demonstrated performance limitations. • The emerging speciality chemicals industries in Asia are likely to identify and exploit opportunities to produce and export synthetic lubricants to other markets in both developed and developing regions. • Even following the economic turmoil experienced in 1997/1998, the majority of people in Asia still aspire to the living standards and mobility of the developed

countries, so development will continue. As a result, the progressive adoption of European and North American patterns of goods and services, including synthetic lubricants, is likely to continue, albeit possibly at a slower pace than in recent years.


Indeed, the most positive outcome of the events of recent years in Asia has been the increasing realization by governments, companies and individuals of the global nature of the world economy and the need to develop and adopt global standards and practices.

45

Automotive Trends in South America R. David Whitby CONTENTS 45.1 Introduction 45.2 Trends in the Automotive Industry in South America 45.2.1 Manufacturers and Competitive Forces 45.2.1.1 Production of Vehicles in South America 45.2.1.2 Imports and Exports 45.2.1.3 South American Vehicle Manufacturers’ Trends and Prospects 45.2.1.4 Suppliers of Components to the South American Automotive Industry 45.2.2 South American Automotive Design and Engineering 45.2.3 South American Automotive Vehicle Regulations 45.2.3.1 Safety 45.2.3.2 Environment 45.3 Current Status of Automotive Fluids in South America 45.3.1 Gasoline and Diesel Engine Oils 45.3.2 Two-Stroke Oils 45.3.3 Transmission and Gear Oils 45.4 Development of Markets for Synthetic Automotive Fluids in South America

45.1 INTRODUCTION Following a period of good economic stability and growth in the mid-1990s, many countries in Central and South America have experienced relative economic instability and low or negative growth over the last four or five years. The previous growth had been due to much stronger structural foundations, demonstrated by progressive economic growth before the Mexican financial crisis in the early 1990s and relatively rapid stabilization following it. Structural reforms, such as reduced public spending, privatization, increased foreign investment and reduced tariffs, stimulated strong economic growth between 1991 and 1994. The benefits were reduced inflation, increased foreign capital inflows, decreased national debt, and rising value-added exports. Unfortunately, the previous economic growth in many countries in Central and South America had been financed with high, and in some cases unsustainable, levels of foreign debt. In the aftermath of the financial crisis in Asia in 1997 and 1998, attention inevitably turned to debt levels in other countries. The countries most affected in South America were Argentina and Brazil.


Growth started to slow in Argentina in 1998 and unemployment started to rise, mainly due to the effects on export markets following the Asian crisis. The situation worsened in 1999, with deflation around 2%. There were frequent violations of the Mercosur trade rules in 1999 by both Argentina and Brazil, the two largest members of the trading block. In 2000, the Argentinean recession continued and unemployment reached more than 15%. Toward the end of 2001, the government suspended repayments of Argentina’s $132 billion foreign debt and in 2002, the economy collapsed, with unemployment reaching 22%, gross domestic product (GDP) down by 11.5%, inflation at 50%, and the $:Peso exchange rate going from 1 to 0.27. Although debt restructuring talks were held with the International Monetary Fund (IMF), the banking system collapsed and the government and most companies were unable to repay any debts. Personal savings fell by an average of between 30 and 40%. The economic situation was stabilized by the government during 2003, after much political and social upheaval, and the Argentinean economy began to grow again.

While the economic situation in Brazil was not as bad as in Argentina, it was not that much better either. By 1998, the country had built-up a large budget deficit and the danger of a financial meltdown became apparent in 1999. The Real was allowed to float after one of the State governments initiated a moratorium on debt repayment and the resulting currency devaluation required taxes to be raised, expenditure to be cut, credit to be tightened, and interest rates to be increased. The political and economic problems escalated during 2000, with average per capita income falling by 5.5%. Brazil has had much lower growth rates than previously during 2001, 2002, and 2003, although the austerity measures now appear to be working. There was considerable uncertainty among foreign investors in Brazil’s abilities to repay debt and with the volatile exchange rate during most of 2001 and 2002. Central and South America’s problems were compounded further by the ongoing insurgency and war on drugs barons in Colombia, political turmoil in Venezuela, recessions in Chile in 1999 and in Peru in 2000 and 2001, and severe economic problems in Paraguay and Uruguay from 1999 to 2002. Peru also experienced severe political turmoil in 2000, when riots led to the (eventually) peaceful overthrow of the government. Chile largely weathered the economic crises in neighboring Argentina and Brazil, but has had lower than normal growth rates in 2001 and 2002. While several countries were poised to provide growth opportunities for vehicle manufacturers and lubricants suppliers, this did not occur between 1999 and 2003. With economies in recession, uncertainty about employment prospects, higher taxes, and tighter credit, the last thing consumers wanted to do was buy new cars and companies were reluctant to spend money on new trucks. Some of the economic pain was mitigated by the two important trading blocks; Mercosur (Brazil, Argentina, Paraguay, Uruguay, and Chile) and the Andean Pact (Venezuela, Colombia, Bolivia, Peru, and Ecuador) are the major trade alliances. Both blocks offered some support foundation industries and dampened short-term disruptions in a number of countries. The intraregional trade agreements gave way to a more balanced common market structure modeled after Europe and reduced tariffs helped to minimize marketers’ supply costs. With the economic, political, and social problems in Central and South America, it is not very surprising that the region had the slowest growth of all regions from 1998 to 2002 in the numbers of cars, trucks, and buses in use. Data for the region, together with those of other regions for comparison, is shown in Table 45.1. While global growth in the number of cars was 11.6% during the period, in Central and South America it was only 4.9% compared with 18.4% in Asia. Growth in the number of trucks and buses in Central and South America was only 4.7% during the period. The total numbers of cars, trucks, and buses in


TABLE 45.1 World Vehicle Population, 1998 to 2002 Number of vehicles in use (million) Region Cars W. Europe C. & E. Europe N. America C. & S. America Middle East Asia Africa Oceania

1998

1999

2000

2001

2002

169.0 49.2 147.9 26.4 12.6 74.1 10.1 9.8

171.4 51.4 148.4 26.4 12.6 78.8 10.2 10.1

176.9 54.6 150.1 26.9 13.0 81.6 10.2 10.3

181.9 55.7 156.7 27.1 13.2 84.9 10.4 10.4

187.0 56.8 163.1 27.7 13.7 87.7 10.5 10.5

Total cars Trucks and buses W. Europe C. & E. Europe N. America C. & S. America Middle East Asia Africa Oceania

499.1

509.3

523.5

540.3

557.0

23.1 15.2 86.6 8.6 5.2 36.6 4.4 2.7

23.4 15.1 86.7 8.7 5.3 39.8 4.4 2.8

24.0 14.3 90.6 8.8 5.4 40.5 4.4 2.9

25.3 14.9 94.1 8.9 5.5 41.2 4.5 2.9

26.6 15.6 97.5 9.0 5.6 41.8 4.6 3.0

Total trucks and buses All vehicles W. Europe C. & E. Europe N. America C. & S. America Middle East Asia Africa Oceania

182.42

186.2

190.9

197.3

203.6

192.1 64.4 234.5 35.1 17.76 110.63 14.5 12.6

194.8 66.5 235.1 35.1 17.9 118.6 14.6 12.9

200.9 68.9 240.6 35.7 18.4 122.2 14.6 13.1

207.2 70.6 250.8 35.9 18.7 126.1 14.9 13.3

213.7 72.4 260.6 36.7 19.2 129.6 15.0 13.5

Total vehicles

681.5

695.4

714.4

737.6

760.6


each of the major countries in the region, in 1998, 2000, and 2002 are shown in Table 45.2.

45.2 TRENDS IN THE AUTOMOTIVE INDUSTRY IN SOUTH AMERICA 45.2.1 Manufacturers and Competitive Forces 45.2.1.1 Production of vehicles in South America Brazil and Argentina dominate the production of cars, trucks, and buses in Central and South America, as shown by the data summarized in Tables 45.3 and 45.4. Between 1998 and 2002, the production of cars in Central and South America (Table 45.3) changed very little. There was a sharp fall in 1999, followed by a recovery in 2000 and 2001. However, total production in 2002 was again below that in

TABLE 45.2 Central and South American Vehicle Population, 1998 to 2002 Number of vehicles in use (million) 1998

2000

2002

Total

Cars

Trucks and buses

Total

Cars

Trucks and buses

Country

Cars

Trucks and buses

Argentina Brazil Chile Colombia Ecuador Panama Peru Puerto Rico Uruguay Venezuela Others

5.05 12.70 1.28 0.78 0.47 0.21 0.68 0.88 0.50 1.53 2.35

1.50 2.89 0.67 0.66 0.05 0.08 0.39 0.19 0.05 0.55 1.60

6.55 15.59 1.95 1.44 0.52 0.29 1.07 1.07 0.55 2.08 3.95

5.15 12.90 1.34 0.76 0.46 0.22 0.70 0.89 0.51 1.56 2.40

1.55 2.90 0.72 0.67 0.06 0.08 0.41 0.20 0.06 0.56 1.62

6.70 15.80 2.06 1.43 0.52 0.30 1.11 1.09 0.57 2.12 4.02

5.31 13.40 1.40 0.77 0.46 0.23 0.72 0.89 0.51 1.60 2.45

1.59 2.91 0.74 0.68 0.06 0.08 0.42 0.20 0.06 0.58 1.64

6.90 16.31 2.14 1.45 0.52 0.31 1.14 1.09 0.57 2.18 4.09

Total

26.43

8.63

35.06

26.89

8.83

35.73

27.74

8.96

36.70

Total


TABLE 45.3 Production of Passenger Cars in Central and South America, 1998 to 2002

TABLE 45.4 Production of Vans, Trucks, and Buses in Central and South America, 1998 to 2002

Number of vehicles manufactured (thousand)

Number of vehicles manufactured (thousand)

Country

1998

1999

2000

2001

2002

Country

1998

1999

2000

2001

2002

Argentina Brazil Chile Colombia Ecuador Peru Venezuela Total

353.1 1254.0 2.8 17.8 — — 127.8 1755.5

224.7 1109.5 1.5 20.8 3.8 — 74.2 1434.5

238.7 1361.7 5.2 33.4 1.2 — 72.9 1713.1

169.6 1483.5 4.4 50.8 13.4 — 114.4 1836.1

111.3 1521.4 6.3 57.1 12.4 — 81.6 1790.1

Argentina Brazil Chile Colombia Ecuador Peru Venezuela

104.9 331.6 16.2 18.9 — 0.3 58.2

80.1 247.2 12.5 13.1 8.7 0.2 33.0

100.5 329.5 14.0 16.5 16.8 0.3 30.4

66.0 315.5 10.5 24.1 14.9 0.3 22.4

48.1 271.2 11.7 21.6 14.8 — 15.1

Total

530.1

394.8

508.0

453.7

382.5



2001. The pattern for manufacturing trucks and buses was even worse (Table 45.4), with a relatively steady decline from 1998 to 2002. Predictably, production of cars in Argentina fell dramatically during the period, while production of cars in Venezuela also declined, but not by as much. Production of cars in Brazil held up reasonably well, mainly due to a significant devaluation of the Real in 1999. This allowed exports of cars (and trucks) to be maintained from Brazil to other South American countries. The main manufacturers of cars in Argentina in 2003 were General Motors (GM; Chevrolet), Fiat, Ford,

Renault, Peugeot Citroen (PSA), Toyota, and Volkswagen. GM manufactures Chevrolet pickups in Argentina, both for the internal market and for export to other South American Countries. Toyota produces Hilux vans in Argentina, Mercedes-Benz produces light and heavy trucks, Chrysler manufactures pickups and Ford, Iveco and Renault also manufacture vans and trucks. Renault manufactures Clio, Kangoo cars and vans, and Megane cars in Argentina. The main manufacturers of cars in Brazil in 2003 were Volkswagen (VW), Fiat, GM, Renault, Honda, and Toyota. GM manufactures Celta, Corsa, Kadett, Ipanema, Vectra, and Omega cars, Corsa pickups and Crew Cab and Blazer


trucks in Brazil. Most of these are sold within South America, although some are exported to the Middle East, South Africa and, most recently, Russia. The company has an assembly plant in Colombia, which imports complete vehicles and completely knocked down (CKD) kits from Japan, Brazil, Canada, the United States, Venezuela, and Chile. Cars are also assembled in Venezuela, for sale in the local market and for export to Colombia and Ecuador. Toyota sold 161 thousand cars and vans in Central and South America in 2003. The company manufactures Corolla cars and assembles engines in Brazil, manufactures Hilux vans and Land Cruisers in Colombia, and manufactures Corolla and Dyna cars, and Daihatsu Terios and Land Cruisers in Venezuela. PSA sold 108 thousand cars and vans in Central and South America in 2003, down 1% on sales in 2002. PSA is now producing Peugeot the 307 in Argentina and the 206W in Brazil. Honda now manufactures the Civic and the Fit, a new small car, in Brazil. Renault manufactures Clio and Megane cars in Brazil and Twingo, Clio and Megane cars in Colombia. The company also manufactures engines, engine subframes, disc hubs, and rear corner modules in Brazil and gearboxes in Chile, some of which are exported to Europe and Asia. Renault stopped making cars in Chile in 1999, having produced only 1100 vehicles in 1998. Sales of Renault vehicles, including Nissan and Samsung, in Central and South America amounted to 129 thousand in 2003, down from 131 thousand in 2002. Ford currently produces Fiesta and Ka cars in Brazil and Escort cars and Ranger vehicles in Argentina for the South American market. Ford has been struggling in Brazil for some time, having seen its market share decline from over 20% in 1985 to less than 5% in 2002. Until 1994, Ford had a manufacturing alliance, called Autolatina, with VW. The European company was the stronger partner and managed to weather the breakup, but Ford had uncompetitive products and an inferior dealer network. So far, only one vehicle manufacturer has attempted to integrate operations across the region as a whole. Fiat’s Project 178, the “world car” platform for its Palio, Weekend, and Siena models, is produced in Brazil, Argentina, and Venezuela, with assembly in Venezuela from kits exported from Brazil and Argentina. Development was carried out with local suppliers. For example, Cofap, a Brazilian maker of shock absorbers, piston rings, and exhaust systems, helped develop the models’ suspension units. Brazil, with a population of 174.6 million, has only one car per 13.0 people, compared with one car per 2.1 people in the United States. The main reason for the lower ownership level is Brazil’s relative poverty; GDP per head was $3,070 in 2001, compared with $34,280 in the United States. This should mean increasing car ownership as the economy recovers and consumers become wealthier. Argentina is


almost as promising. Although its population is less than a quarter of Brazil’s, GDP per head was $7,460 in 2002 and the number of cars per person is 6.8. The largest truck and bus manufacturing countries in Central and South America are Brazil and Argentina, with smaller numbers of vehicles produced in Colombia, Venezuela, Ecuador, and Chile. Volkswagen, GM, Fiat, and Mercedes-Benz are the main manufacturers of commercial vehicles in Brazil. Scania and Volvo also manufacture heavy trucks in Brazil, for both internal sales and exports throughout South America, but Navistar decided at the end of 2002 to pull out of the Brazilian market, due to poor sales. VW’s newest truck and bus factory at Resende, near Rio de Janeiro, has had a capacity to make 40,000 vehicles a year from its start at the beginning of 1997, but is still not fully utilized. Scania launched its Series 4 range in South America in 1998, following its launch in Europe in 1997. MercedesBenz spent $20 million developing its Brazil Series of four trucks, introduced early in 1997 and designed to replace 14 older models. Production and sales of agricultural equipment in South America, which fell sharply in 1996, has not really recovered since, due to the economic problems that have plagued the region. Looking further ahead, it is possible that growth will be led by the economic stabilization program in Brazil and Argentina and long-term economic expansion. Only ten years ago, Brazil’s automotive market was the great hope of a global car industry experiencing painful downturns in Europe and North America. Sales of cars in Brazil increased by 51% in 1993 and by 24% in 1994. By 1997, 1.57 million cars were sold in Brazil, import tariffs were falling, foreign investment was being encouraged by the government, and many of the biggest car companies were racing to build more manufacturing capacity. According to Brazil’s motor industry trade association, more than $30 billion has been invested in car plants since 1995. In 2003, many Brazilian car plants were operating at less than half capacity and thousands of employees were either on compulsory holidays to keep production down or had been made redundant. In August 2003, VW announced plans to lay off almost one in six of its 25,000 employees in Brazil. GM had earlier laid off 650 of its 18,800 employees. Total car manufacturing capacity in Brazil is currently 3.2 million units, but only 1.52 million were produced in 2002, fewer than in 1997. However, the beginnings of a recovery have started to appear. More than 1.42 million vehicles were produced in Brazil the first 8 months of 2004, up 21.3% on the same period in 2003. The Brazilian National Association of Automotive Manufacturers said August 2004 was also a record month for automotive exports, defined as parts, cars, light trucks, and farm tractors. They totaled more than $773 million for August and $5.14 billion since the beginning of the year, up 54%. Only time will tell whether

these trends continue and spread to other countries in the region. 45.2.1.2 Imports and exports In 1995, members of the Mercosur free trade area set duties of 70% for vehicles imported from outside the area and duties of 2% for imported parts as part of an agreement on policies for the motor industries in Brazil and Argentina. Vehicle manufacturers operating in the two countries, however, are allowed to import vehicles at half the set rate. Since 1995, duties on imported vehicles have fallen to the target of 20% in 2000 and duties on components have risen to the Mercosur common external tariff of about 14%. Dual vehicle manufacturing in Brazil and Argentina has become the industry norm, with Argentina tending to be used for higher value, lower volume products and Brazil for bigger volume, “popular” models. A similar regime was agreed in 1993 between Colombia, Venezuela, and Ecuador. Duties on vehicle imports from outside the three countries were set at 35% for passenger cars and light commercial vehicles and at 15% for trucks. Duties on CKD components and kits were set at 3%. Local content requirements were fixed at an initial 30% for cars and light commercial vehicles, rising to 33% in 1998, and of 13%, rising to 18%, for heavy trucks. Components manufactured inside the bloc are treated as local content in all three countries. Intracountry trade in vehicles and components has become a standard practice throughout South America in the last 5 years. The primary driver is to achieve economies of scale in manufacturing, so as to provide lower cost components despite the higher distribution costs. Fiat’s Palio models produced in Brazil are designed primarily to meet the demand of the markets of Central and South American countries. However, the three-door Palio is also exported from Brazil to Italy. Since the Palio range is part of Fiat’s World Car Program, although Brazil is the initial and major hub of Palio production, specific models and parts belonging to the range are also produced in Argentina, Poland, Turkey, Egypt, Morocco, South Africa, India, and Vietnam. According to Fiat, certain Palio models are also to be manufactured in China and Russia in the near future. While the Betim plant manufactures all models within the Palio range, India’s Palio production, for example, focuses entirely on the hatchback and sedan varieties, while Palio production in Vietnam concentrates on just the sedan model. Since all elements of the Palio range produced in Brazil are interchangeable with those produced in Fiat’s other global Palio plants, there is a continual flow of products between Palio facilities worldwide. This therefore gives Fiat do Brasil the opportunity to expand its export potential by producing additional units of certain Palio elements to be fitted to Palio vehicles produced elsewhere.


For example, extra units of parts belonging to the estate car version of the Palio, known as the Palio Weekend, are produced at Fiat’s Betim plant to then be fitted to the Weekend produced in Poland. From Poland, the model is then exported to Italy, France, Germany, and Spain. General Motor’s Celta model is aimed specifically at the South American market, with its major export destinations being Argentina, Bolivia, and Venezuela. In October 2001, GM began to export the Celta to El Salvador, placing the car on the Central American market for the first time. The car is now being exported to other Central American countries, including Guatemala and Honduras. General Motor imports Isuzu light trucks into South America from Japan. GM also transfers cars, pickups and medium-sized trucks from Brazil to Argentina and Chile and imports CKD kits and cars from the United States, Japan, and Europe. The company imports engine parts and other components from the United States, Germany, and Spain into Brazil, for use in the production of cars, pickups, and trucks. Transmissions are imported from Japan and Austria. The company also exports engines from Brazil to Germany and the United Kingdom. Brazil exported $1.29 billion worth of automotive products, which cover both vehicles and component parts, to the United States in 2002, and another $1.16 billion worth to Mexico. Argentina also exported $270 million of automotive products to Mexico in 2002. In total, Central and South America exported automotive products to other regions of the world to a value of $4.93 billion in 2002. In July 2004, the Argentinean government approved an agreement made between local car manufacturers and automotive parts suppliers to limit the value of imported components used to assemble vehicles in Argentina to no more than 40% of the value of the vehicle. 45.2.1.3 South American vehicle manufacturers’ trends and prospects 1996 was a record year for automotive industry spending in South America. VW, the largest car manufacturer in the region, opened two new car plants in Brazil in the last quarter of the year. The company commenced construction in November 1997 of a new $650 million factory in southern Brazil to produce the Audi A3, the new Golf, and Passat. Production of cars, which started in 1999, was planned to rise to a total of 250,000 units, but has not exceeded even half of that to date. Fiat, the second biggest car manufacturer in South America, invested about $1 billion to increase car production in Brazil and to launch the company’s Palio “world car.” It also spent $600 million on a new car factory in Argentina. General Motor, which ranks third behind VW and Fiat in Brazil, spent $1.25 billion on three new plants for cars, components, and engines. The company built a $600 million plant at Grazatai, in Rio Grande do Sul state.

At the same time, Ford invested about $800 million to manufacture its European Fiesta in Brazil, $300 million on a new engine plant in Brazil, and $150 million to modernize its truck plant. Mercedes-Benz announced in July 1997 a 70,000-unit capacity $400 million plant in the state of Minas Gerais to build its A-class model subcompact car. The plant started production towards the end of 1999. General Motors opened its new Brazilian car manufacturing plant, designed to be a benchmark for GM plants elsewhere, in Gravatai in July 2000. The factory manufactures it’s new compact car, the Chevrolet Celta, which competes against VW’s Polo and Fiat’s Mille Smart in the 1-L-engine car market, which accounts for about 65% of Brazilian-made domestic car sales. The Celta is several inches smaller than the lowest-priced GM model, the Opel Corsa. GM plans to also export the car to Europe, Mexico, and Brazil’s Mercosur trading partners Argentina, Paraguay, and Uruguay. General Motor aims to use the plant and the Celta as guinea pigs to test the new factory model, which cuts expenses through ultraswift deliveries of components and increased automation. The plant, located in a new industrial park in the southernmost state of Rio Grande do Sul, is flanked by 16 car-part suppliers who can move their brake and light fittings, air filters, or security systems to GM’s assembly floor in a matter of minutes, slashing storage and inventory costs. The Gravatai industrial park arrangement reduces the number of suppliers GM needs to put a car together by 60%. Gravatai is also GM’s most automated plant in the world with 120 robots and an installed capacity to produce 120,000 vehicles. If the project is successful, GM plans to take the factory model elsewhere, although the company recognizes that it will be difficult to copy and apply to already-existing manufacturing plants. In May 2000, Renault and Nissan announced a broad cooperation agreement in South America’s Mercosur trade bloc, which includes Nissan vehicle production at Renault’s plant in Brazil. Nissan will invest a total of $300 million in the region by 2005 to manufacture five Nissan models with Renault support. Manufacturing, sales, and purchasing operations in Mercosur will be linked, with hopes of gaining a 15% market share in the world’s third largest trade bloc in the next 10 years. Nissan invested $90 million in the first project involving the production, starting early in 2002, of new Frontier pickups at Renault’s existing plant in southern Parana state. In 2003, Nissan started producing Xterra sports utility vehicles at the Brazilian plant. Three other products to be launched are still in the development stages. The two companies want to sell a minimum 150,000 Nissan vehicles by the year 2010 with Renault support. The Nissan–Renault alliance created 600 jobs directly and another 3,000 indirectly through its new operations, mainly in Brazil. Renault’s plant already had a production capacity of 200,000 vehicles per year, producing Clio and Scenic


models since 1998. The plant also makes 280,000 engines a year. The alliance’s plant also makes Renault’s light commercial vehicles. It should produce 50,000 vehicles a year. In Argentina, Renault is producing a wide range of vehicles at its Santa Isabel plant with an annual capacity of 130,000 units. In Uruguay, Renault makes 10,000 cars a year. As part of Fiat’s global car strategy, it has focused heavily on the development of the small, economy car. Since the Brazilian market is primarily concerned with entry-level passenger cars, and Fiat is one of the main manufacturers in South America, Brazil was chosen by Fiat as the launch pad for the Palio range of vehicles. Fiat has been manufacturing vehicles in Brazil since 1972 and began manufacturing the Palio in 1996, when the company redeveloped its existing factory in Betim. The plant’s programming and logistics computer is central to the way in which the facility is controlled, enabling the plant to be operated on a just-in-time delivery basis. Of the top ten cars sold in Brazil, four of them are of the Fiat brand. Of these, three are from the Palio family; the standard Palio, the Palio Weekend, and the Palio Siena. The range is managing to weather the storm due to the extent of its popularity on the domestic market. Fiat’s Betim plant has the capacity to produce approximately 30,000 units of the Palio range per year. The qualities of the Palio in terms of auto parts, technology, and design, are said to be regarded by Brazilian consumers as superior to those of other models. Fiat was forced to suspend 1300 employees in Argentina in 2000, following a decline in sales of over 25% compared with 1999. Fiat, which had to make the suspensions permanent in 2001, blamed the currency devaluation in Brazil, which is Argentina’s main trading partner and buyer of 90% of its vehicle exports. However, the company announced in March 2004 that it plans to invest heavily in Brazil in 2005 and 2006. Ford’s new assembly plant, Complexo Amazon, started production of its Amazon range of cars in April 2002 and the commercial launch of the five new models started later in the year. The new plant has the capacity to produce 250,000 passenger cars per year. The Amazon range of small, compact cars, is based on Ford’s global Fiesta platform. The cars have a Brazilian content of 90%, with 13 of the 23 major components suppliers working within Ford’s assembly plant itself, and the remaining 10 based in the adjoining supplier park. However, despite the economic problems endured by Brazil toward the end of 2001, GM still managed to increase its production of the Celta and continued to do so during 2002. The Celta model is GM’s best-selling car in Brazil, accounting for approximately 25% of the company’s Brazilian sales. According to GM do Brasil, the company is likely to begin producing another economy-sized car in the country within the next 2 or 3 years. The company is also set to

increase its exporting operations for other economy cars that it produces in Brazil. For example, GM has recently started exporting Corsas from Brazil to Egypt, in the form of CKD kits. The devaluation of the Real in 1999 served to encourage GM and Ford to invest in Brazil. The country’s financial crisis helped to lure investment, as international manufacturers recognized the opportunity to benefit from the relative strength of their currencies. Manufacturers chose Brazil as the major production base for economy models over other countries in the region partly as a result of its comparatively cheap production costs. GM’s Gravatai and Ford’s Camacari plants were established when the Argentine Peso was still pegged to the U.S. dollar, making Argentine production far more expensive. Both Ford and GM appear to be willing to be patient about their investments in South America, prepared to wait several years if necessary for their manufacturing plants to become profitable. However, some industry analysts have begun to question whether Ford may eventually be forced to quit production in Brazil if profitability does not return soon. By the time GM’s Gravatai plant opened in September 2000, Brazil’s economy had made a comeback and, as the largest economy within Mercosur, prospects were excellent for vehicle makers to experiment with new manufacturing techniques. Since Brazil has a much longer history as a vehicle manufacturer than some of the other Latin American countries, such as Chile and Venezuela, it has the infrastructure in place to aid the transportation of vehicles to market, and it also has a ready supply of components suppliers. Moreover, Brazil has remained accessible to car manufacturers looking to test new methods, since its industry has greater freedom to absorb change than the more mature industries of Europe. Union opposition to new working arrangements is, although currently on the increase, still far lower in Brazil than it is in countries such as the United States and Mexico. With Brazilian demand tending toward the small, economy passenger car, Brazil has been a logical place for automakers to test new entries to this segment of the market. Since the rate of auto tax that consumers pay depends on the size of the car, vehicle makers such as Ford, Fiat, and GM have better prospects at the smaller end of the market. While Brazilian vehicle demand does focus heavily on small, compact cars, this may become less noticeable over time, for the fashions of the affluent classes tend to be guided by U.S. and European trends. The number of SUVs purchased for private use in Brazil increased slightly in 2005, but only amongst the rich minority. Volkswagen has been manufacturing cars in Brazil since 1953 and the country is VW’s second largest market, after Germany. Brazil accounts for almost 10% of VW’s worldwide production of cars and trucks. The history of its cars and its industrial plant in São Bernardo do Campo


meshes with Brazil’s modern history, with a good part of the economy of the State of São Paulo over the last decades driven by its presence. In the last decade, VW opened new plants in Brazil and Argentina. In November 1995, the company opened the General Pacheco Industrial Centre in Argentina. A year later, in November 1996, it opened a new truck plant in Resende and an engine plant in São Carlos, the latter being enlarged some months later for the production of engines for the Golf and Audi A3 models. In January 1999, the company opened the plant in São José dos Pinhais, in the State of Paraná, with a total investment of 1.2 billion Reals. Over a history of almost 50 years in Brazil, VW has always pursued technological evolution and improvement of its products. The company’s Product Engineering and Development Department has some 1500 engineers, designers, and specialists capable of designing and producing world-class vehicles. The engineering facilities include a vehicle impact center where all of its vehicles manufactured in Brazil are crash-tested. With a total of around 28,000 employees, VW is one of the largest private companies in Brazil and one of the largest employers. The average production capacity is 3,200 vehicles and 2,850 engines everyday in its five manufacturing plants in Brazil. In 2002, VW entered a new stage of production, with its new Nova Anchieta plant, one of the world’s most modern manufacturing centers. Located in the city of São Bernardo do Campo, the plant has undergone a full refurbishing as a requirement for the production of the new Polo. The manufacturing line has 400 new robots and is fully computerized. However, VW took a charge of e120 million in 2003 to cut 4000 jobs in Brazil. The company had initially indicated that it would retrain the employees, but later decided to offer a voluntary redundancy program. Other car manufacturers have also lost substantial amounts of money after rapid building of car plants left the country with massive overcapacity. Then, in September 2004, VW announced plans to manufacture a van derived from the Fox car, in Argentina, with sales starting in 2006. The Fox van marks VW’s entry into a new market segment, to compete with GM’s Meriva and Fiat’s Idea vans. Honda started production of the Fit, a new subcompact car, in Brazil in 2004. The company is promoting the new car as offering innovative safety and environmental features, in addition to excellent power and fuel consumption, excellent driving performance, and outstanding comfort. Peugeot Citroen is seeking to expand sales in the Mercosur markets, particularly Brazil and Argentina, in addition to plans for expansion in Central Europe, Turkey, and China. The company started manufacturing Peugeot 307 cars in Argentina in 2004 and in September 2004, it announced plans to produce Citroen C4 cars in Argentina by 2007.

Toyota forecasts steady demand for vehicles in Brazil for the foreseeable future. In May 2004, the company announced that it is to start selling the Corolla-based Fielder station wagon in Brazil. The model is produced at the company’s Indaiatuba plant in São Paulo state, where the Corolla sedan has been manufactured since 1998. There is no doubt that the last 5 years have been very tough for all automotive manufacturers in South America. In addition to the economic, political, and social turmoil, the overcapacity to produce both vehicles and components has meant that almost every company has lost money. The next 5 years may prove to be equally tough, until the economies of each of the countries, particularly Brazil and Argentina, continue to stabilize and rebound. The weaknesses in vehicle manufacturing in North America and Western Europe are unlikely to help either. 45.2.1.4 Suppliers of components to the South American automotive industry As manufacturing methods in South America become more similar to those in the rest of the world, factories there can supply parts and vehicles to ever wider markets. Brazil is already the industry’s main, though not only, manufacturing base for South America. Manufacturers already swap some parts between factories in Brazil and Europe, for example. As this trend continues, Brazil’s role in the region should be strengthened. Several vehicle manufacturers believe Brazil is the precise choice for manufacturers setting up in the region, simply because it offers the biggest single market. The development of the Mercosur customs union between Brazil, Argentina, Paraguay, and Uruguay should also strengthen Brazil’s role, although the union will take time to mature. Brazil has been used as an experimental zone by several major vehicle manufacturers in recent years, specifically with regard to the development of small-car manufacturing techniques. GM, Ford, and Fiat Auto have all established notable small-car production facilities in Brazil and all three have promising prospects, despite the country’s economic difficulties. The efficiency of the plants in terms of manufacturing looks set to boost the market share of these three automakers within Brazil, while at the same time giving Brazil the opportunity to expand its export markets. This, in the longer term, should set Brazil up as a specialist in small-car production. Ford’s experimental Amazon project and GM’s Gravatai complex have led major manufacturers of both vehicles and components to look to Brazil with interest. Projects such as these have demonstrated how components suppliers can play a far greater role in the vehicle manufacturing process than they do in traditional assembly arrangements. The proportion of components that can be manufactured on-site has reached unprecedented levels and therefore far fewer suppliers are required now. Meanwhile,


Fiat’s Betim plant, although built some 23 years before the others, has captured the world’s attention in recent years, for the way in which the automaker used Brazil as a test-bed to produce its Palio models in 1996. At each of these plants, the focus is on the cost-effective production of small, entry-level passenger cars. General Motor’s Gravatai plant has changed the relationship between vehicle makers and components suppliers, since the role of the supplier has been wholly integrated into the design of the car plant itself. The model currently produced at Gravatai is the Celta, produced since September 2000, with as much as 85% of its components manufactured on-site. In most assembly plants, only 40% of components (in terms of value) are sourced from within the factory. This gives GM greater flexibility, enabling it to adapt certain features of the Celta according to customer preference. As a result of the close integration between manufacturers and components suppliers and the proximity of major suppliers to the assembly lines, these three plants are highly efficient and have the potential to reduce the cost of manufacturing small cars in Brazil significantly. This in turn enables the cars produced to be competitively priced on the domestic market, giving the car makers the opportunity to boost domestic market share. Through the launch of the Amazon line of cars, for example, Ford intends to increase its market share in Brazil from 9 to 14%. With Brazil’s interest rates being characteristically high, it is expensive for automakers based there to obtain credit and this subsequently pushes up the price charged to the consumer for the finished vehicle. If car manufacturers are able to cut production costs, as they are able to do at these new, innovative plants, their ability to price the cars competitively increases. GM claims that the GM Celta is sold at approximately US$500–1000 cheaper than many other small cars sold on the Brazilian market. Since GM itself covers all freight costs within Brazil with regard to the Celta model, the car can be sold for the same price throughout the country, boosting sales in the northeast, for example, far from the industrial center of Sao Paulo. In a climate of intense global competition, increasing car prices and falling sales, a reduction in output costs also gives these automakers the opportunity to increase their share of the small-car export market. Supported by the availability of a relatively cheap labor force, as well as infrastructure that is sufficiently developed to allow vehicles to be easily exported, these new plants in Brazil are able to stand as major low-cost production centers, from which vehicles can be directed primarily toward the markets of other developing countries. Small-car manufacturing is likely to take off further in Brazil in 2002 and to an even greater extent in the long term, since the country has already gone some way toward gaining a reputation as a global small-car specialist. Not only does Brazil look set to build on this reputation

in the coming year, with the production of the Amazon car, but also some of the manufacturing systems used at plants such as Gravatai are likely to be emulated elsewhere. There are already signs that the less controversial aspects of GM’s Gravatai methods have influenced the style of GM’s new Lansing River Plant in Michigan (US). The T-shaped assembly line of Gravatai is to be replicated and the components produced at the Michigan plant are to be codesigned by GM and the components suppliers. Aside from boosting its position as a small-car expert during 2002, Brazil is likely to witness an increase in the role played by components suppliers in the production of larger vehicles in the long term. VW has already demonstrated that this is possible, through its innovative truck plant in Resende. Although the parts are manufactured offsite, they are installed into the trucks by the components suppliers themselves, rather than by VW. The influence to be had by the small-car test-beds has only just begun. Many of the world’s largest suppliers of automotive components have plants and operations in Brazil, Argentina, Chile, Colombia, and Venezuela. Dana operates a new axle-housing manufacturing plant in Sorocaba, Brazil, which recently received a best in class award for technical innovation from DaimlerChrysler Brazil. The plant also houses Dana’s Traction Technology Group, which produces axles for manufacturers of small and fullsize pickups and light trucks, including GM, Ford, and VW. Dana’s Commercial Vehicle Systems, part of Heavy Vehicle Technology and Systems Group, designs, manufactures, and markets front-steer, rear-drive, trailer, and auxiliary axles; driveshafts; steering shafts; brakes; suspensions; and related systems, modules, and services for the commercial vehicle market. Major components and modules are marketed under the Spicer® brand name. Eaton has three plants in Brazil that supply transmissions, axles, and engine air management systems. The company’s Brazilian Transmission Division resulted from the acquisition of Equipamentos Clark, an automotive transmissions manufacturer with a 90% share of the domestic market, in 1996. Components manufactured by Eaton in Brazil are also exported to the United States, Argentina, Mexico, and Turkey. Denso, the world’s third largest components supplier that was originally part of Toyota, now has manufacturing plants in 28 countries outside Japan, including most countries in Asia, the United States, Mexico, Brazil, Argentina, most countries in Western Europe, Hungary, Poland, the Czech Republic, Saudi Arabia, and Turkey. The company supplies engine cooling systems, air-conditioning systems, diesel common rail systems, alternators, starter motors, spark plugs, antilock brakes, power steering and navigation systems. Denso plans to build 15 million vehicle air-conditioning units by 2005, which represents 30% of the world market, as a result of expansion in Europe.


Delphi has a manufacturing plant in Brazil to supply the South American market with systems and modules. The company is one of the world’s major suppliers of automotive components, with 171 plants located in North America, South America, Europe, Asia, the Middle East, and Africa. Delphi designs, engineers, and manufactures a wide variety of components, integrated systems, and modules on a worldwide basis and claims to be the largest and most diversified supplier of parts for cars, trucks, and buses. The company aims to provide vehicle manufacturers with a global, single-point sourcing capability, tailored to meet specific customer’s needs. Visteon has a total of six manufacturing facilities in Brazil and Argentina, making chassis components, power train components, electronics, heating and air-conditioning systems, glass, and vehicle interior and exterior components. The company has 205 facilities in 25 countries worldwide. Visteon is one of the key suppliers to Ford’s Amazon Project in Brazil, where it supplies electronics systems. Valeo is another global automotive components supplier with manufacturing facilities in Brazil and Argentina, as well as in 23 other countries. The company manufactures electrical and electronic systems (lights, wipers, switches, motors, actuators, connectors, sensors, and security systems) as well as air-conditioning and engine cooling systems, friction materials, and clutch systems. Other major suppliers to vehicle manufacturers in South America include Borg-Warner (gearboxes, transmissions), Bosch (spark plugs, injectors, electronics, wipers), Delphi (brakes, clutches, indicators, controls, sensors, injectors), Federal-Mogul (camshafts, seals, gaskets), Getrag (gearboxes, transmissions), INA (bearings), Magneti Marelli (electronics, injectors), Mahle (pistons), Siemens (motors, relays, sensors, controls), SKF (bearings), Valeo (brakes, clutches, switches), and ZF (gearboxes, transmissions). Several of these companies supply a wide range of components in addition to those listed. Additionally, there are hundreds of other companies that supply all the other components, such as glass, plastic, wiring, hoses, and lights.

45.2.2 South American Automotive Design and Engineering Design and engineering for vehicles manufactured and assembled in Central and South America is supplied primarily by parent companies in the United States, Europe, and Japan. While many car and truck design and engineering centers are located in Detroit, Frankfurt, Munich, Tokyo, and other major cities, the trend toward “global” vehicles by most vehicle manufacturers means that inputs to design and production specifications are also being made by local subsidiaries and component suppliers.

Additionally, because many of the bigger manufacturing plants now make vehicles for export as well as local consumption, there is a great deal of more emphasis than before on common design and engineering practices. Brazil and Argentina are no exception to these trends. When visiting most of the larger cities in Central and South America, it is relatively easy to see that the vehicle populations are a blend of comparatively up-to-date European and North American models, with a smaller proportion of Japanese and Asian models. Designs and engineering standards have become global and interchangeable. Since the South American car market is focused on smaller, entry-level cars, such as Fiat’s Palio and GM’s Celta, it is not surprising that some of the design and engineering concepts for these cars have been conceived and developed in Brazil. The result has been that Brazilian engineers and designers have worked with U.S. and European designers to refine and adapt some of the global influences to meet South American consumers’ needs. Another feature of the Brazilian market for cars is the need for vehicles that can run on either gasoline, diesel, natural gas, or ethanol. The Brazilian gasohol (ethanol fuel) program of the 1970s was dropped, but has recently been revived again. Alcohol-fueled cars conquered the Brazilian market in the 1980s, and represented more than 90% of car manufacturing within a few years. Cheap alcohol and expensive gasoline pushed this trend, but alcohol shortages in 1989 and 1990, together with cheaper gasoline, sharply undermined the popularity of ethanol. Sales of alcoholpowered cars plummeted to less than 1% of total vehicle sales. In 2002, VW and GM developed “bi-fuel” vehicles that can run on either gasoline or ethanol, or a mixture of the two. The bi-fuel car emerged because crude oil prices went up to over $25 per barrel, more than twice that of 1988. Dual fuel vehicles are also aimed at helping consumers to get past their hesitations about alcohol-only cars. Drivers are no longer subject to shortages or high prices of one fuel or the other, because they can always use the cheaper one. Additionally, the use of ethanol as a fuel or fuel component is being promoted as more environmentally responsible, since overall emissions of carbon dioxide are lower with the renewable fuel. There are no major differences in the emissions of unburnt hydrocarbons or nitrogen oxide from either fuel. The bi-fuel car may also allow Brazil opportunities to export vehicles, alcohol, and automotive technology. Several countries, including the United States, China, and Canada, already consume gasoline with alcohol added. There are nearly 2 million “flex fuel” cars in the United States, but they have to use a mix with a maximum of 85% alcohol, which means adding 15% gasoline. The bifuel engineering, which VW started developing in 1998, changes that restriction.


Most recently, in October 2004, VW announced the development of a “tri-fuel” polo for the Brazilian market. This car can run on gasoline, ethanol, a blend of the two, or natural gas. The prototype model was presented to the São Paulo Auto Show at the end of October 2004.

45.2.3 South American Automotive Vehicle Regulations 45.2.3.1 Safety The safety standards applied to vehicles manufactured in South America are derived from those developed in North America, Western Europe, and Japan. The main reason for this arises from the export of vehicles, particularly cars, vans, and light trucks to countries outside South America and the manufacturing cost savings that result from having uniform designs and components irrespective of whether the vehicle is destined for the local or international market. There appear to be few South American government regulations that directly govern vehicle safety. Most governments appear content to follow U.S., Japanese, and Western European vehicle safety standards, assuming that manufacturers will adopt uniform standards for economic and business reasons. This approach gained momentum in October 2003 when executives from the world’s main carmakers agreed, at an automotive industry meeting in Japan, to push for global safety and environmental standards. 45.2.3.2 Environment Many of the countries in Central and South America are adopting either U.S. or European standards on the control of emissions of gases from vehicles, albeit more slowly than in the more developed regions of the world. Brazil and Chile have adopted U.S. regulations, while Argentina has opted for European regulations. The majority of regulations were adopted between 1992 and 1995, with slightly less stringent emissions limits being progressively tightened up to 2000. Since then, there has been little further tightening of the regulations in South America, due to the more pressing needs of stabilizing the regions’ economies, reducing unemployment and encouraging saving and investment. Catalytic converters became mandatory for new cars in Chile in 1992. Currently, well over half of all cars in Santiago, the capital city, are fitted with these emissions control devices. On days with “preemergency” pollution alerts, 40% of all cars without catalytic converters are banned from Santiago roads. It is, however, very unclear how this ban is enforced. Levels of air pollution required to trigger a “preemergency” alert include 285 µg/m3 for particulates. This compares with the current limit of 50 µg/m3 in the United Kingdom. Santiago was the first South American city to join the U.S. Department of the Environment “Clean Cities”

program in April 1997. The city authorities are working with their counterparts in Chicago, which has been a member of the program since 1994, to promote greater environmental responsibility. In Chile, the program, which is voluntary, focuses on increasing the use of alternative fuels such as LPG, LNG, and oxygenates. The Argentinean Secretariat of Natural Resources and Environment started a $4.5 million program in January 1997 to establish the precise nature of the pollution problems in Buenos Aires and other urban areas. The project involves a number of mobile air pollution monitors being used in both the capital and in the provincial cities of Cordoba and Rosario. Data from the monitors, together with data from a number of other sources, has been used to establish a national database on air quality. A local Argentinean environmental group, Fundacion Siglo 21, which has monitored air pollution in Buenos Aires, claims that carbon monoxide levels are double the acceptable WHO levels for more than half the time. These claims are dismissed by the authorities, although they do acknowledge that current controls on industrial and transport emissions are few and far between. The air quality problems of Buenos Aires are undoubtedly fewer than those of many other South American cities, such as Santiago and Sao Paulo, even though levels of emissions appear to be little different from these cities, because Buenos Aires enjoys favorable winds and rains that regularly sweep atmospheric pollutants out to sea. In Colombia, it was a requirement for all new cars to have catalytic converters be fitted to them from the beginning of 1998 onward. Although the government expected the total level of emissions from vehicles to decline rapidly, the reality of North American and European experience demonstrated that it has taken at least 5 years for the increasing number of vehicles fitted with catalytic converters to have a significant impact of total emissions, particularly when diesel engines continue to not be fitted with these devices. However, the Colombian government introduced regulations that require all inspection equipment for monitoring emissions and maintaining vehicles to be equivalent to current U.S. and European equipment from 1999 onward. It was reported at the end of 1996 that, at the time when compelling evidence of the damaging effects of excess lead on human health was being submitted to the first World Congress on Air Pollution in Developing Countries, a number of Central American governments were extending the use of unleaded petrol in their countries. A number of doctors had submitted detailed scientific evidence to the Congress of the deleterious effects of lead in the human body, and the degree to which high lead concentrations are transmitted from pregnant women to their unborn children. The evidence that lead poisoning is transmitted from mother to child was particularly worrying,


because a child’s tolerance of high lead levels is far less than that of an adult. In response to the increasing evidence of the damage done by lead poisoning, most Central American governments introduced a formal prohibition on the use of leaded petrol in vehicles. Guatemala imposed a total ban on the use of leaded petrol in 1991, with the full support of the motor industry. Honduras banned leaded petrol in January 1996, Costa Rica in March 1996, and El Salvador and Nicaragua in July 1996. Evidence collected in the City of Tegucigalpa in Guatemala, indicated that within months of banning leaded petrol the amount of lead in the atmosphere dropped from 1.2 mg to just 0.2 mg/m3 . The small amount of lead still remaining in the atmosphere was attributable to the presence of a smelter. In areas without smelters, lead pollution has fallen almost to zero. Guatemala became the first country in the world to make a total change to unleaded petrol and, according to the government, there has been no evidence that any damage has resulted to vehicles in the country. Everyday in most of the larger cities in South America, millions of motorists are held up for hours in traffic jams caused by too many vehicles trying to squeeze onto too little space on the roads. The World Health Organization estimates that 100 million people in Central and South America have health problems related to the emissions. In response, in 1998, the World Bank established the Clean Air Initiative, creating a forum for politicians, environmental organizations, local businesses, and international companies to discuss the issues, identify the problems and causes of air pollution, decide on measures to combat it, and use money from development loans to implement practical measures. The main reason for the dirty air is that 70% of the air pollution is caused by vehicle emissions, which explains why the primary goals of the Clean Air Initiative include cleaner fuels, environment-friendly engines, and promoting public transportation. In Brazil, DaimlerChrysler has set up a Center of Competence for the production of gas engines. The exhaust emissions from these engines are up to 50% lower than those of the diesel engines currently in use. In addition, over 300 DaimlerChrysler gas-powered buses are being used in São Paulo, the largest city in Brazil. Since the subway network in São Paulo is not very extensive, buses are the most important means of getting around. The fastest route from A to B is via the corredores in the middle of the road, which are allowed for the use of only express buses. To keep all the other 5 million vehicles out, the corredores are fenced off. As a result, the express buses run faster than the city’s average of 9 mi/h, which is why so many of the local people, the Paulistanos, prefer to ride them. The line that connects São Mateus and Jabaquara, for example, carries over 6 million passengers per month.

The problem facing Central and South American cities is more than just a matter of the numbers of vehicles on the road. The average age of the vehicles is also a problem. In São Paulo the average car is 10 years old, the average bus 7, and the average truck has been around for 12 years. Along with São Paulo, other cities that take part in the Clean Air Initiative include Lima-Callao, Rio de Janeiro, Buenos Aires, Santiago, and Bogotá. The cities have also decided to cooperate in controlling emissions and coordinate their activities. Even before the Clean Air Initiative was founded, São Paulo had begun working on ways of managing the chaotic traffic and dangerous emissions levels. Since 1996, a system has been in place that requires cars to take turns staying off the roads. They rotate based on the last number on the license plate. On Mondays, for example, all vehicles with license plates ending with a 1 or 2 may not be used. In the past, the Paulistanos cheerfully ignored this regulation, but now the police have started imposing heavy fines on offenders. Environmental emissions are still being taken seriously by most governments in Central and South America, although current evidence suggests that most attention is being paid to levels of pollution, in both air and water, from large mining, power generation, metal processing, and industrial manufacturing plants, rather than from vehicles. As in many other regions, politicians have probably decided that it is easier and more productive to control business than to upset voters.

45.3 CURRENT STATUS OF AUTOMOTIVE FLUIDS IN SOUTH AMERICA 45.3.1 Gasoline and Diesel Engine Oils Demand for all lubricants in Central and South America totaled 2.70 million metric tons in 2002 and 2.73 million metric tonnes in 2003. Of this, around 72% was for the transportation sector and 28% for the industrial sector. Gasoline and diesel engine oils accounted for 69% of all transportation lubricants. Latin Americans prefer passenger cars and minibuses. Motorcycle lubricant consumption is relatively low, reflecting consumer preference for passenger cars as first affordable vehicles. Demand for natural gas engine oils is relatively high, as is the case for automatic transmission fluids. Demand for transportation lubricants is likely to be constrained by low consumer purchasing power, urban congestion, and underdeveloped infrastructure. Lower quality oils will still account for a substantial part of the Latin American market in 2005. In 2002, about 50% of the market for gasoline engine oil used American Petroleum Institute (API) SF quality oils or lower. Monogrades filled about half of the demand and multigrades the other half. The most popular multigrade oils are 20w40 and 20w50, although 15w40 viscosity oils are available in


most countries. Full and partial synthetics, usually 5w40 viscosity, currently command less than 3% of the market. The highest quality levels available currently are API SJ and SL, which also meet the ACEA A3-98 requirements. Lubrax Sinético from Petrobras, for example is a 5w40 oil that meets API SJ/CF, ACEA A3-98/B3-98, VW 502.00/505/00, and MB 229.1 specifications. Many companies have plans to introduce API SM quality oils in the near future. ILSAC GF-2 and GF-3 quality oils do not appear as being sold in South America yet. For diesel engine oils, the average quality level currently is API CF-4, although monograde SAE 30, 40, and 50 API CC oils are still sold in many countries. The highest quality heavy duty diesel engine oils are API CH-4/ACEA E5-99, although API CI-4 oils are now being introduced in Brazil, Argentina, and Chile. Multigrade diesel engine oils are generally 20w50, although the newer, “top of the range” oils are 15w40 viscosity oils. State oil companies control 30% of the lubricants market in Central and South America. Included in this group are Brazil’s Petrobras and Venezuela’s PDVSA affiliate Maraven, both of which are trying to maintain their domestic share and build a position in nearby countries. (Petrobras has been partially, but not fully, privatized.) In 2002, for example, Petrobras acquired Argentina’s EG3 brand. Multinational oil companies, which now control 55% of the lubricants market, entered Central and South America while state-owned oil companies privatized and relinquished control of retail marketing. In 1996, Petroperu privatized and sold Petrolube to Mobil, Brazil prepared for the partial privatization of Petrobras, Bolivia delayed privatization of YPFB, and Venezuela liberalized its retail market and formed a domestic refining company Deltaven. Argentina’s YPF was privatized in 1994, but was acquired by Spain’s Repsol in 1999. It remains to be seen how much market share or control can be retained by previously state-owned companies after markets are opened and downstream operations are privatized. The remaining 15% of the Central and South American petroleum market is controlled by domestic independents. As a whole, the region is in the relatively early stages of market maturity for automotive engine oils. Gasoline service stations account for between 30 and 50% of transportation lubricant sales, depending on the country. Distributors handle around 50% of transportation and 80% of industrial lubricant sales. Indirect distribution channels, such as franchised workshops and mass merchandisers, have yet to achieve the grow associated with more mature markets. Channel structures differ due to market development and the channel preferences of marketing companies. The Mexican financial crisis led to the rapid growth of the “changarro”, or sidewalk peddler, in Mexico, Venezuela, and other South American countries. The changarro are urban and mobile, purchasing lower quality, branded, and

counterfeit products from distributors and reselling them after a severe discount. This channel accounted for roughly 60% of engine oil sales in Mexico and 35% in Venezuela during the Mexican crisis. As a result, Mexican lubricant quality in 1995 fell due to NAFTA’s removal of minimum quality limits and considerable margin volatility. Governments will need to reduce the activities of changarro significantly and encourage more disciplined markets. In Brazil, Petrobras currently controls around 22% of the lubricants market. Petrobras Distribuidora, is responsible for blending, packaging, distribution, and marketing of Lubrax branded lubricants. Although the company’s countrywide logistics and retail network of about 7200 service stations provided a competitive advantage in a protected market environment, it is unlikely that Petrobras will be able to maintain this position in the face of open market competition. Texaco is the leading multinational lubricant marketer in Brazil, followed closely by Shell. Other majors such as Esso, Mobil, and Castrol each have less than a 10% share. Both Texaco and Shell have benefited from a long-term commitment to the marketplace and strong brand management. Texaco’s corporate image building was achieved by support of municipal-level environmental initiatives and community development issues. Texaco has about 2900 service stations, 40 of which are convenience store Star Shops. Texaco has aggressive plans to build an additional 1250 convenience store stations by 2000. Shell has taken a high profile position in Brazil, leveraging its corporate image as a leading edge technology company with appeal to consumers’ European tastes. Shell opened its first convenience store station in 1987 under the name Express, and now has 4500 service stations across the country. In addition, Shell’s local operating company has been given considerable independence to grow as the Brazilian market permits. Castrol has had a number of difficulties in Brazil. Parallel importing and brand management issues led to a weakening of Castrol’s high-end corporate image. In the mid-1980s, Castrol had 20% share of the consumer automotive segment of the market. By 1995, this had fallen to 8%. Castrol is attempting to rebuild its image through promotions of select products. Brazilian refiner Ipiranga controls 18% of the lubricants market. Ipiranga acquired Atlantic in 1995 and now has three blending and packaging facilities and 5588 service stations throughout the country. It has aggressive objectives to expand its retail network through convenience store stations and quick-lube centers. Ipiranga is in the process of unifying its brands from multiple acquisitions and developing commercial ventures that will provide it with product technology and supply to maintain competitiveness. Quaker State, Pennzoil, and Valvoline also have entered Brazil’s market. As market conditions improve,


these companies are expected to expand distribution and establish manufacturing operations. Others are waiting in the wings. Although this is a large market, low market prices and high costs were a significant hurdle that pushed margin performance into the red during 1996 and 1997. The end of Petrobras monopoly in the Brazilian oil industry during 1997 lead to a drop in lubricant prices of between 6 and 12%, due to the liberation of imports. Prior to 1997, importation of lubricants needed a previous authorization from the fuels agency, DNC. The Argentinean petroleum market, and with it the market for lubricants, was deregulated in 1992, and the process to privatize the state-owned oil company YPF was started in 1993. Following the deregulation of the lubricants market, the number of suppliers has dropped from 128 to 42, because most of them were either too small, too inefficient, or unable to restructure and had to merge or be acquired by bigger competitors. At present, about 85% of the lubricant’s market in Argentina is controlled by four companies; Repsol-YPF, Shell, ExxonMobil, and Petrobras (Eg3). In Chile, the leading suppliers of lubricants are Copec (ExxonMobil), Shell, and Texaco, with Repsol-YPF becoming more active. Copec’s current market share is a little over 50%. In 1996, Copec assumed responsibility for sales of lubricants to industrial customers previously supplied by Lubricants de Chile. In 1997, the company took over the operation of a lubricants blending plant and the distribution of Mobil lubricants. Shell Chile currently has a network of 440 service stations in the country and plans to build a lubricants blending plant in Quinteros during 1998. The plant is scheduled to begin its operations in 2000 or 2001. Although Texaco Chile has only around 40 service stations and a 2% share of the fuels market, the company is reported to have a 10% share of the Chilean lubricants market. Lubricant quality levels are similar to those found in Brazil and Argentina. Castrol reported that the trading environment for lubricants intensified in parts of South America in 1996, as new competitors entered these markets and some old ones returned. Major marketing initiatives by Castrol included the launches of Castrol Formula SLX and GTX Magnatec. Supply chain initiatives brought benefits, while harmonization of brands and advertising are bringing scale efficiencies.

45.3.2 Two-Stroke Oils Motorcycles make up only a tiny fraction of transportation vehicles in Central and South America, so demand for two-stroke engine oils is comparatively small. Specifications and performance levels are similar to those in Japan and North America, with almost all motorcycles being imported into Central and South America from Japan. Although there are no plans at present to adopt the latest ECG global two-stroke engine oil standards, it is likely

that Brazil, Argentina, Chile, and Peru will progressively introduce these oils over the next few years. The JASO FC quality oils are used most generally for motorcycles, although API TC oils are also available in many countries. Multigrade 20w50 API SF and SG oils are also sold for four-stroke motorcycles. For outboard twostroke engines, NMMA TCW-3 oils are sold in Brazil and Argentina.

45.3.3 Transmission and Gear Oils The majority of developments with automotive gear and transmission fluids are occurring in North America, primarily because of the huge use of automatic transmissions in this market. These developments have started to impact the market in Europe, and are slowly starting to filter through to South America. The overwhelming majority of automotive transmissions in South America are manual gearboxes and conventional hypoid rear axles, which use standard API classes of gear lubricants, most usually GL-4 and GL-5, but also GL-1. Monograde SAE 90 and 140 oils are commonly available, although they are being replaced slowly by multigrade 85w140, 80w90, and even 75w90 gear oils. Because the majority of South American cars have manual transmissions, the use of automatic transmission fluids is much lower than it is in North America, although it is growing, particularly in the larger cities in Brazil and Argentina. Most ATFs are marketed with U.S. specification performance levels, most usually GM Dexron III, Ford Mercon, and Allison C4 specifications. Petrobras also markets Lubrax OH-50-TA, an ATF that meets the GM Type A Suffix A specification, for use in automatic transmissions fitted to Mercedes-Benz vehicles.

45.4 DEVELOPMENT OF MARKETS FOR SYNTHETIC AUTOMOTIVE FLUIDS IN SOUTH AMERICA In the mid-1990s, vehicle manufacturers looking for double-digit growth rates, as opposed to the much slower growth found in mature markets, turned to South America, Eastern Europe, and South-East Asia, the three regions where demand appeared to be flourishing. Prospects in Brazil and Argentina, the two biggest South American car markets, looked buoyant after a downturn brought about by government economic tightening. The optimist outlook for both markets, linked via the Mercosur trade bloc, was reflected in the series of decisions to build new car plants. Markets in other Central and South American countries were similarly optimistic. The prospects from 1999 onward took a sharp downward turn in Central and South America. They may have started to brighten again more recently, but still do not appear to be anywhere near as optimistic as they appeared in 1998. As a consequence, sales of new vehicles that would


benefit from using synthetic or part-synthetic lubricants have slowed dramatically over the last few years, and so has the growth in demand for higher performance lubricants. South American consumers generally consider a new passenger car “like a valued member of the family, deserving appropriate treatment.” Strong brand image and service provider recommendations highly influence the consumer’s engine oil purchasing decisions. As a result, South Americans place value on brands when seeking high quality lubricants. Marketers should capitalize on this by enhancing the perceived value of their product, price accordingly, and minimize costs. Achieving profit in Central and South America will depend on a marketer’s perception of the customer in terms of price, performance, brand, service, channel, and market linkage. Lubricant sales channels for market entry will continue to be limited until fuel prices reach international levels. In the transportation sector, about 80% of consumer passenger car sales and 50% of commercial truck sales are through service stations, of which there are more than 60,000 throughout South America, many of which are old. Profits from complementary convenience store operations have effectively subsidized these outlets. These will eventually consolidate. New, high-volume, efficient stations have already been built in Brazil, Argentina, Chile, and Peru. As channels evolve, the presence of dealer service centers, franchise workshops, and quick-lube centers are likely to increase. Hypermarkets may come to urban centers, but generally South American consumers are not accustomed to these points-of-sale for lubricants. Imports of high quality lubricant baseoils and synthetic fluids will continue to grow over the coming years, due to the market’s shift to multigrades and multinational penetration, but at a much slower rate of growth than in the mid-1990s. Major regional baseoil suppliers, such as Petrobras, Maraven, Echopetrol, and Repsol-YPF, have not announced firm plans to upgrade their baseoil production facilities. Consequently, the trade deficit will increase unless the local producers improve the quality of their baseoils. New passenger cars and the original equipment manufacturer (OEM) “push” for higher quality oils are likely to reduce the monograde level further. Brazil accounts for around 38% of the South American lubricants market, representing a necessary keystone for building a regional position. Brazilian lubricant demand has been increasing steadily since 1996 and is now slightly more than 1 million tonnes per year. While the transportation sector contracted, the industrial sector enjoyed modest expansion due to the growth of the automotive production, mining, and agricultural processing industries. Most industry analysts forecast that demand for lubricants in Brazil is likely to grow at around 2% annually until 2008. The largest market segments, automotive engine oils (representing 49% of demand), industrial hydraulic oils (14%), and industrial greases and metalworking fluids

(11%), will be moving toward higher quality standards. If the pace of reform slows, demand growth will be relatively flat, but progress toward higher quality should continue. High operating costs have limited the attractiveness of Brazil compared to other South American countries. Although government price controls for lubricants were removed about 3 years ago, the government has imposed a 53% fund unification price (FUP) tax. In 1996, the import duty for finished lubricants was 12% and for baseoils it was 5%. With the implementation of the new petroleum regulation law, these barriers appear to be falling. Other important South and Central American markets for automotive lubricants include Argentina, Venezuela,


Chile, Colombia, and Puerto Rico. In 2002, the total market for lubricants in Argentina was around 270,000 mt, while in Venezuela it was around 200,000 t. All other individual South American lubricants markets are less than 200,000 t annually, with several less than 100,000 t annually. Forecasting future demand for synthetic and partsynthetic lubricants in Central and South America is fraught with difficulty. The region has always had great promise, but in recent years has suffered political, social, and economic turmoil. Until steady and uninterrupted economic growth and social stability returns, demand for higher value products, including automotive lubricants, is unlikely to resume at earlier rates.

46

Industrial Lubricant Trends Garrett M. Grega, John J. Kurosky, Darren J. Lesinski, Michael J. Raab, and Z. Ahmed Tahir CONTENTS 46.1 46.2 46.3 46.4 46.5 46.6

46.7

46.8

Introduction Future Growth Markets General Market Drivers Biodegradable Lubricants Metalworking Trends Gear Lubricant Trends 46.6.1 Original Equipment Manufacturers Trends 46.6.2 Gear Manufacturing Trends 46.6.2.1 Higher Accuracy Hobbing 46.6.2.2 Gear Grinding 46.6.2.3 Superfinishing 46.6.3 Mechanical Trends in Gear Manufacturing 46.6.3.1 Improving Surface Finish. 46.6.3.2 Surface Modification 46.6.3.3 Failure Mechanisms 46.6.4 New Materials in Gear Manufacturing 46.6.4.1 Powder Metallurgy 46.6.4.2 Ceramics 46.6.4.3 Plastics 46.6.5 Trends in Gear Lubrication 46.6.6 Higher Energy Efficiency with Synthetic Gear Lubricants 46.6.6.1 Lubrication Modeling 46.6.7 Gear Lubricant Formulation Trends 46.6.8 Gear Lubricant Specification Trends 46.6.8.1 Bearing Specification Requirements 46.6.9 Specific Synthetic Gear Lubricant Applications 46.6.9.1 Wind Turbines 46.6.9.2 Pumpjack Gearbox 46.6.9.3 Open Gear Sets 46.6.10 Gear Lubricant Summary Compressor Oil Trends 46.7.1 Air Compression 46.7.2 Industrial Gas Compression 46.7.2.1 Rotary Screw 46.7.2.2 Reciprocating 46.7.2.3 Future Trends 46.7.3 Refrigerant Gas Compression 46.7.4 Compressor Lubricants Summar Hydraulic Oil Trends 46.8.1 Types of Hydraulic Systems 46.8.2 Hydraulic Fluid Classification 46.8.3 OEM and End User Future Trends


46.8.3.1 Ecologically Sensitive Fluids 46.8.3.2 Crop Derived Fluids 46.8.3.3 Synthetic Hydraulic Fluids 46.8.3.4 Improved Cleanliness 46.8.3.5 Improved Fire Resistance 46.8.3.6 Products for Use in Food and Pharmaceutical Plants 46.8.3.7 High Pressure Systems 46.8.3.8 Increased Specifier Sophistication 46.8.3.9 Shrinking Market for Low Pressure Systems 46.8.3.10 Fluid and Supplier Rationalization 46.8.3.11 Multigrade Fluids 46.8.3.12 Elastomer and Material Versatility 46.8.3.13 Fluid Monitoring and Trend Analysis 46.8.3.14 Ashless Formulations 46.9 Grease Trends 46.9.1 Grease Overview 46.9.2 Grease Manufacturing Trends 46.9.2.1 Batch Processing 46.9.2.2 Manufacturing for Low Noise 46.9.3 Application Trends 46.9.4 Environmental Trends 46.9.5 Grease Market Trends 46.10 Effects of Base Oils on Industrial Lubricants 46.11 Summary References

46.1 INTRODUCTION This chapter focuses on general trends in industrial lubricants. Industrial lubricants refer to a broad category of lubricants and the trends cannot all be addressed within a single chapter. Therefore we will narrow our focus to the following topics: • • • • • • • • •

Future growth markets General market drivers Biodegradable lubricants Metalworking trends Gear oil trends Compressor oil trends Hydraulic oil trends Grease trends Effects of base oils on industrial lubricants

Over the last three years industrial lubricant sales have seen flat to no-growth. Sales of lubricating oils and greases totaled 2.46 billion gal in 2002, the lowest since 1992, according to the National Petrochemical and Refiners Association. This follows a 3.3% drop in 2001 and flat sales in 2000 [1]. The third-quarter of 2003 showed a 19% decline in U.S. lubricant sales when compared to the same third-quarter of 1997. Many factors contributed to this decline including the global recession, closure of


steel and paper mills, as well as the increased performance of synthetic lubricants.

46.2 FUTURE GROWTH MARKETS With declines in the United States and European lubricant market, growth will need to come from other geographic areas. Asia, particularly Malaysia and China, as well as India represent prime growth areas for industrial lubricants. Frost & Sullivan estimates that the total synthetic lubricant market for Southeast Asia was worth $819 million in 2001 with a compound annual growth rate of 3.5%. At this rate, the region is forecast to reach $1 billion in synthetic lubricant sales by 2008 [2]. Why is the region so ripe for growth? One primary reason is the increase in the standard of living that has increased the number of consumers of automobiles [3]. Malaysia represents one of the largest automobile markets in Southeast Asia. While much of the synthetic growth will be in automotive engine oils, this author believes that synthetic lubricants will be needed in the industrial sector to maintain the production efficiencies required to grow the automotive market. In general, machinery in this region is considered valuable capital that must be maintained. The timely availability of replacement from other areas of the world increases the emphasis

on preventive maintenance practices. Therefore, synthetic lubricants offer more value to operators who need to keep downtime to a minimum and protect the value of the asset. India is another country with projected increases in industrial demand. At the ICIS-LOR World Base Oils Conference, Ramesh V. Rao, general manger and executive director of Gulf Oil Corp. Ltd. projected a 3% sales growth in 2004 and 5% in 2005. India went through some major declines in lubricant sales between 2000 and 2002. However, the growth in India’s vehicle population will create a rise in sales of both automotive lubricants and industrial lubricants. By 2005 India is expected to have over 59 million vehicles on the road compared with only 44 million in 2000. However, the current tax structure could hamper industrial lubricant sales by requiring storage and billing facilities within each state. Some states may also demand entry permits and lube licenses. Mr. Rao states that some trucks can “go through 21 check points to make a delivery” [4]. China clearly represents the growth engine for industrial lubricants in the world. Currently China’s lubricant demand accounts for nearly 30% of the world’s total, according to Harland Bulow of Tri.Zen International [5]. According to Hugh Peman, president of Shanghai-based research company Research-Works, China is 18 months into an “unprecendented economic growth spurt which may last a total of three to five years.” Peman compares China’s growth spurt to the United States in the 1950s when highways and infrastructure were being built [6]. Clearly, if China maintains this pace, industrial lubricant consumption will increase. Within the established markets of Europe and North America, we can expect to see increases in synthetic and specialty lubricants. As equipment manufacturers tighten specifications and increase equipment performance, more specialty lubricants and greases will be needed to meet the expanding performance levels. We are already seeing this in the United States with a reported jump in synthetic lubricants sold by 5.2% in 2002 while conventional lubricants declined during that same period [7]. In addition, with the recent inclusion of ten more member states into the European Union, Europe should see an increase in industrial lubricant growth as these ten economies benefit from the increased trade that a full member of the European Union offers. Industrial lubricant growth will be directly tied to the economic forces within a given region of the world. As the regional economy improves, so will the sales of industrial lubricants. Specialty lubricants and greases should see an increase as both regulations and equipment specifications force lubricant users to consider the advantages of synthetic lubricants. The following sections of this chapter will address direct trends seen within specific lubricant applications.


46.3 GENERAL MARKET DRIVERS Although there are many applications for industrial lubricants, a few common drivers have significant influence on the growth of synthetic lubricants. • Operational improvements • Efficiency gains • Environmental impact

General industrial facilities are under increased pressure to improve productivity while minimizing the cost of operations. Maintenance budgets are constrained while output targets are increased. Therefore, equipment reliability and capital preservation are critical to the success of any manufacturing business. Utility costs represent a significant portion of any manufacturing budget. Reducing energy consumption, particularly with the volatile trend of energy prices, has become even more critical to the cost competitiveness of an operation. Manufacturing companies must incorporate environmental responsibility into each aspect of their business as a result of consumer awareness and legislative pressures. Synthetic lubricants offer an opportunity to be a solution. Typical applications discussed further in this chapter illustrate the impact that synthetics have in meeting these industrial challenges.

46.4 BIODEGRADABLE LUBRICANTS Biodegradable lubricants are receiving increased attention by consumers, regulators, and equipment manufacturers. While there is increased focus on using biodegradable fluids in construction and mining, only 2% of the hydraulic fluids used in bulldozers, tractors, and heavy equipment are considered biodegradable [8]. This gives room for growth. Cargill in particular would like to capitalize on this potential growth. It has announced plans to double the capacity of its Chicago plant-based esters plant [9]. In a separate announcement, Cargill announced plans with Kaufman Holdings Corporation to construct a renewable base oils esterification facility in Brazil [10]. Industries face a range of environmental risks these days. In recent years, legislation has phased out ozonedepleting gases under the Montreal Protocol and other similar initiatives. Additional environmentally targeted legislation, which will directly affect the lubricant market, is currently being debated and may eventually be mandated. As with any formal legislation this is a slow process. However, once implemented the impact on industry can be substantial. Current activity includes the evolution of the Montreal Protocol to incorporate industrial air conditioning and refrigeration equipment, the Farm Bill for the use of renewable resources, and waterway protection programs amongst others. Tough environmental targets and environmental group pressures in addition to current and

TABLE 46.1 Uses of Typical Biodegradable Chemistries Biodegradable chemistries Vegetable oils PAOs Esters and polyolesters PAGs

Typical applications Sawmill lubricants, chain drive lubricants, hydraulic oils Hydraulic oils (low temperature, high pressure applications) Compressor oils, turbine oils, hydraulic oils, and marine based fluids Compressor oils, gear oils

future legislation have placed greater emphasis on effectively managing the risks associated with lubricant use and application. One result of these pressures was the evolution of International Environmental Standard ISO 14001. A number of certification labels signifying compliance with certain norms have been devised in several countries. These include the German “Blue Angel,” the “White Swan” of Nordic countries and the Canadian “Environmental Choice” maple leaf. Certification activities have also been initiated in China, Thailand, Japan, and India. Discussions among several countries have been initiated to create Global Eco-Labeling Network (GEN) [11]. These and other initiatives are specifically targeted at reducing the potential impact of lubricants on the environment and human health. As Table 46.1 shows, biodegradable oils can be classified by their chemistries: Vegetable oils, Biodegradable polyalphaolefins (PAOs), Diesters, Biodegradable polyolesters, and Polyalkyleneglycol (PAGs). Vegetable oils have shown positive performance as sawmill lubricants and chain drive lubricants where the “once-through” aspect of the applications requires a low toxicity lubricant. (Kržan and Vižintin [12] demonstrate that a formulated vegetable-based, and synthetic esterbased Universal Tractor Transmission Oils have high lubricity, high viscosity index, and provide equivalent or, in some respects, superior gear protection performance compared to a mineral-based UTTO fluid [12].) By contrast, Biodegradable PAOs are used in high-pressure and lowtemperature environments as both hydraulic and engine oils. However, biodegradable PAOs are limited to low viscosity grades. Diesters and Polyolesters have historically been used as lubricants for compressors and turbines. However advances in chemistries have identified uses in hydraulics and marine applications. Finally, although PAGs have been known to be biodegradable, they are still poorly miscible with mineral oils. As a result, one must thoroughly flush a system before using a PAG [13]. One of the more demanding areas for biodegradable lubricants includes the marine and inland waterway industries. Shipbuilders, barge operators, and locks and dam owners are seeking biodegradable lubricants that are


nontoxic to the environment and produce no visible sheen on the waterways. Technology advances in this area will satisfy a latent need of industrial lubricant users. Today’s environmentally friendly lubricants, although biodegradable and nontoxic, still provide a visible sheen when inadvertently released into a waterway. To demonstrate the economic incentive to develop a lubricant to meet the requirements of incorporating biodegradability, low toxicity, and no-sheen properties consider the following example: If one assumes an average sump size of 525 gal (2,000 L) per ocean going vessel and a 10% acceptance rate for 20,000 vessels, the estimated market size for biodegradable lubricants is on the order of $15 to 30 million.

46.5 METALWORKING TRENDS Over the years metalworking fluids have been one of constant changing chemistries. As new worker-safety rules that limit particulates, chlorinated paraffins, and exposure levels have taken effect, lubricant providers have had to significantly modify formulations. Today’s focus in the metalworking industry has been in the area of mist control. In March 2004, a three-judge panel for the U.S. Court of Appeals in Philadelphia unanimously ruled that although oil mist does appear to cause health problems, Occupational Safety and Health Administration (OSHA) could focus on materials that pose bigger health risks [14]. As a result, the United Auto Workers Union and the United Steelworkers of America are unlikely to realize legislation that lowers the permissible level of mist exposure for their workers. The regulation battle is not the full story for mist control. Private industry has focused on this as an opportunity and developed new nozzle designs and new lubricants that reduce misting in the workplace. Misting is caused when the air/lubricant stream exiting a nozzle shears and causes a fog or mist to form. Older nozzle designs have been proven to suspend 70% of the lubricant in the air as fog with only 30% reaching the machining surface [15]. Therefore, it was imperative to develop a nozzle where 90% of the lubricant can reach the surface. By changing the nozzle design so that the air flows around the outside of the nozzle (causing laminar air flow) and the lubricant flows through (inside) the nozzle, one can increase the nozzle velocity without inducing a mist. In addition, to the mechanical design improvements, lubricant formulators have designed new products to increase the lubricity of the lubricants to eliminate components with potential health risks and to decrease the misting tendencies of the lubricant. As a result, operators now have the option of installing a nozzle–lubricant combination that delivers over 90% of the lubricant to the machine surface with reduced health risk impact [16]. This design, although proven, has not been adopted throughout the metalworking industry. As the new

technology is implemented, one can see significant decreases in metalworking fluid demand. With 60% more lubricant hitting the active surface, the total lubricant consumption in a metalworking plant will decrease. One other trend occurring in the metalworking industry is the increase of “Dry” cutting operations. Europe, particularly Germany, has led the revolution in “Dry” cutting operations, where no lubricant or coolant is used. As costs for cutting-fluid disposal increase more metalworking shops will opt to use “Dry” technology that includes ceramic and cermet cutting tools that do not require cutting fluids. Although reaming, broaching, and grinding may be the last subsegments to convert, milling and turning operations may go “Dry” [17].

46.6 GEAR LUBRICANT TRENDS Gears systems are employed widely in industrial applications to transmit power or to change speed, torque, or direction of motion. Gears are renowned for their high mechanical efficiency in power transmission with values exceeding 90% routinely obtained in a single mesh design. Competitive pressure to improve energy efficiency of machinery leads the demand for better gearing. As gear teeth mesh, they roll and slide in relation to oneanother. While rolling is continuous throughout the mesh, sliding varies from a maximum velocity in one direction at the start of the mesh, through zero velocity at the pitch line, and back to maximum velocity in the opposite direction at the end of the mesh. In general, it is friction at the rolling/sliding contact that accounts for the majority of losses. Friction can be reduced through effective lubrication strategies. The manufacturing processes for gears have historically left relatively rough surfaces such that oil films are generally on the same scale as the average roughness. It is generally understood that contact between two such surfaces and the enclosed oil film occurs under elastrohydrodynamic conditions. In this section we will examine the mechanical, manufacturing, and energy efficiency, as well as chemistry trends that may drive future lubrication requirements and formulations. Examples are given of successful synthetic-based gear lubricant applications.

46.6.1 Original Equipment Manufacturers Trends The global market for nonautomotive gear manufacturing is estimated to be $10.0 billion dollar with 54% of that manufacture carried out in Europe, 27% in the USA, and 19% in Japan. Unfortunately, there are no readily available data for market activity in such countries as India, China, Australia, Czech Republic, Poland, etc. Each of these countries has a growing industry that is important to world production and consumption of geared products [18].


In the coming years Gear Manufacturers (Original Equipment Manufacturer, OEM) will face increased worldwide competition. Modern, high-speed communication systems will only exacerbate this pressure. Trade restrictions and customs duty have all but been abolished by political pressure. There is a strong movement toward specialization; bigger companies are reducing the number of their product lines. Gear manufacturing will continue to consolidate and move where there is a strong and vibrant steel industry along with the availability of energy and labor at reasonable costs. Specialization will drive OEMs to increase reliability in order to create product differentiation. Additional forces driving reliability are coming from the insurance industry and from Legislative bodies. For example, in the globalization of the wind energy market, the Insurance Industry coupled with the Danish authority, have pushed the wind turbine OEM, gear box manufacturers, and the lubricants industry to international standardization of manufacturing specs (e.g., AGMA 6006). Gearbox OEM’s are coming together with bearing and seal manufacturers to create cross-functional standards (i.e., gear, bearing, seals, and lubricants). Emerging countries and regions will need power plants, transportation systems, water supply, and medical care. These emerging areas will create new opportunities for gear manufacturers. These developing areas have a ready source of low-priced labor but they have little capital; these areas will need to use this cheap labor to pay for their expansion.

46.6.2 Gear Manufacturing Trends Tighter tolerances for equipment and improved processes and techniques are driving improvements in gear manufacturing. Demands driving gearbox design and manufacturing include: increased power density, lower noise, higher reliability, extended warranty, and lower cost. 46.6.2.1 Higher accuracy hobbing Load-carrying capacity of gears, especially the surface durability, is influenced by tooth surface finish (roughness) and the tooth profile. Smoother tooth surfaces, harder gears, and more accurate tooth profiles are needed in order to achieve high load-carrying capabilities. Ariura and Umezaki [19] tell us of advances in the design and materials involved in hobbing of gears. Included is the use of finished hobs, finished hob process is used to remove distortion following the heat treatment process. Finished hobs are required to give good wear and chip resistance, smooth finishing of tooth surfaces, and high accurate hobbing. 46.6.2.2 Gear grinding Hazelton [20] teaches, “the benefits of ground gears are well known. They create less noise, transmit more power

and have longer lives than non-ground gears. But grinding has always been thought of as an expensive process, one that was necessary only for aerospace or other hightech gear manufacturing.” As gear-grinding machinery has become more productive, the grinding wheels are better and the overall cost of grinding has gone down. Gear grinding is now incorporated in a wide variety of industries including makers of automobiles, trucks and motorcycles. It is also commonly used in textile, printing, power generation, and motion control industries. Many standard gearboxes use ground gears to improve control over backlash and noise. 46.6.2.3 Superfinishing Superfinishing the working surfaces of gears and their root fillet regions results in performance benefits. Initially developed to increase surface durability, it has since been found that superfinishing to a low surface roughness can reduce friction, pitting fatigue, noise, operating temperature, bending fatigue, metal debris, and wear. Superfinishing techniques include grinding and honing, or chemically accelerated vibratory finishing. Such techniques have been used to achieve high quality gears with a roughness average of between 1.0 and 3.0 µin [21].

46.6.3 Mechanical Trends in Gear Manufacturing 46.6.3.1 Improving surface finish Improving the surface finish of gear teeth is a highly profitable way of reducing friction and consequently increasing efficiency. For instance, Britton et al. [22], examined the effect of surface finish in a special four-gear test rig using gear tooth frictional losses at loads and speeds representative of those employed in a gas-turbine engine. He found that superfinishing resulted in reducing friction typically by 30% with correspondingly lower tooth surface temperatures. Further, the behavior of friction-torque with increasing loads and speeds indicates a transition from “mixed” to hydrodynamic gear friction occurred with both when ground to a super finish. AGMA 9006-A94 “Gear Tooth Surface Texture with Functional Considerations” teaches that typical surface roughness (Ra ) can range from 0.3 to 6 µm (12 to 250 µin.) for commercial quality gears with some gears as low as 0.2 µm. In one application — gear boxes for wind turbine AGMA 6006-A03 (Table 7) recommends (Ra ) values of 0.5 µm on the low speed sun and planet gears up to 0.7 µm on intermediate and high speed pinions and gears. Krantz and Kahraman [23] studied the influence of lubricant viscosity and additives on the wear rate of spur gear pairs. Their work demonstrated that wear rate is strongly related to the viscosity of a lubricant. Lubricants with higher viscosity exhibit larger lambda ratios and lower


wear rates. In their testing, doubling lambda decreased wear rate by a factor of 3. Since lambda is the ratio of lubricant viscosity to Ra , it is clear that improving surface finish has a strong influence on wear and fatigue life. It should also be noted that increasing the viscosity under the operating condition has an equivalent effect. 46.6.3.2 Surface modification The use of solid lubricants will likely impact the development and manufacturing of gears in the future. While the use of solid lubricants is not new in itself, recent developments in materials and in application methods offer interesting new possibilities. For instance, lamellar solid lubricants or transition metal dichalcogenides MX2 (where M is Mo, W, Nb, Ta, etc. and X is sulfur, selenium, or tellurium) are among the lowest-friction materials known in dry and vacuum environments. MoS2 and WS2 are standard lubricants for vacuum and aerospace applications. However, by themselves the lubricity of these materials are affected by moisture and other environmental effects. Development is occurring in “smart coatings” and nanocomposite and layered solid lubricants that offer longer wear life and lower friction coupled with less sensitivity to variations in the operating environment. Very low coefficient of friction materials such as boric acid, diamond-like carbon, and other advanced materials for solid lubricant application are also being developed [24]. Modern methods of application — such as physical and chemical vapor deposition by sputtering, ion platting, ionbeam deposition, and ion implantation — enable use of the advanced materials on a practical basis. Work by Weck et al. [25] discusses physical vapor deposition coatings of hard materials such as CrAlN, TiAlN, WC/C (amorphous metal carbon coating) and ZrC on gear flanks, coating thickness being 1 to 4 µm. The basic aim of this study is to transfer the functions of individual lubricant additives to the surface of the material via the application of wear-protection coatings in order to be able to reduce the additive content of gear lubricants. The report shows that the use of metal–carbon layers enables the omission of surfactant additives. One coating showed significant difference, particularly in the FZG scuffing test, with regard to wear on the tooth flanks (2.5 fold less mass loss under the specified test conditions). Engineered or “Textured Surfaces” offers yet another possibility for improving gear teeth friction properties. One technique under development is termed “Laser Surface Texturing” (LST) or “Micro Dimpling.” LST creates micropores on surfaces that act as miniature hydrodynamic bearings, improving mechanical seal performance, reducing friction, lowering wear, and face temperature. In summary, surface modifications such as deposited solid lubricants and LST offers significant improvements

by lower coefficient of friction and in improving surface durability of metals. These or similar developments will likely lead to reduced costs making such techniques viable in high performance gearing. 46.6.3.3 Failure mechanisms As highly loaded, case or through-hardened gears have found their way into industrial application researchers have found a new failure mechanism, namely “micropitting.” Micropitting is a surface fatigue occurring in Hertzian contacts caused by cyclic contact stresses and plastic flow on the asperity scale. It is most often found in the dedendum area of gear teeth and represents a large total damage area that results in loss of the tooth profile. It is manifested as a large number of small, shallow pits with a characteristic length of 10 µm. Micropitting has been identified as a key issue in the operation of highly loaded, case or through-hardened gears such as found in wind turbine application. It can be minimized by proper selection of lubricant, improving surface finish, decrease in the corrosiveness of the lubricant to the metallic surface, and decreasing the boundary friction between the metallic surfaces. While testing by FZG gear test rig is the preferred method, other techniques have been used to replicate micropitting in laboratory equipment. Errichello [26] instructs that micropitting occurs after an initial incubation period from 104 to 106 cycles. Micropits originate at surface asperities where maximum peakto-valley roughness of a ground tooth surface may be about 2 to 4 µm. Micropits occur at peaks of asperities and are typically smaller than 1 µm. Therefore, scanning electron microscopy (SEM) is needed to study micropitting, especially in the early stages. Micropitting occurs under elastrohydrodynamic lubrication (EHL) oil films where the oil film thickness is on the same order as the surface roughness (Ra ), and load is borne by surface asperities and lubricant. When a significant portion of load is carried by asperities, collisions between asperities on opposing surfaces cause elastic or plastic deformation depending on local loads. Li and Devlin et al. [27], present a model based on boundary friction coefficient, oil film thickness, oil corrosiveness (measured as average gray value), and surface roughness of the gear tooth applicable to predicting fatigue pitting life in an FZG test for gear oils. The authors show that surface roughness is the dominant contribute to characteristic micropitting giving a 22% relative contribution. They also found that when a macropit or spall formed, it was always observed on the upper edge of a micropitting band, which had formed earlier in the sequence. From a lubrication point of view, Li and Devlin’s empirical expression says that increasing film thickness and decreasing oil corrosiveness has the potentials of changing the hours to pitting [28]. Incorporating additives capable of


modifying the boundary friction (friction modifiers, antiwear, and EP properties) can have a 2051 times greater impact of hours to pitting. From a mechanical point of view, decreasing surface roughness has a 1224 to one impact. Devlin also shows that temperature has an affect on micropitting. When the test temperature was raised from 90 to 120◦ C, the mode of failure changed from micropitting with mild wear (at 90◦ C) to scuffing wear with essentially no micropitting at 120◦ C. Thus, reducing the oil film thickness in the contact zone promotes asperity-to-asperity interactions. Ueno et al. [29] found that antiscuffing additives or EP additives in a GL-5 type gear lubricant could cause micropitting to increase. Following up on this work, Cardis and Webster [30] investigated the impact on lubricant additives on micropitting. They also demonstrated that gear oils could be formulated using new additive systems balanced to meet the combination of providing antiscuffing performance while reducing the risk of micropitting.

46.6.4 New Materials in Gear Manufacturing 46.6.4.1 Powder metallurgy Powder metallurgy (P/M) is a highly developed method of manufacturing reliable ferrous and nonferrous parts. Made by mixing elemental or alloy powders and compacting the mixture in a die, the resultant shapes are then sintered or heated in a controlled-atmosphere furnace to bond the particles metallurgically. Basically this is a “chip less” metalworking process; P/M typically uses more than 97% of the starting raw material in the finished part. Because of this, P/M is both an energy and a materials conserving process. Many of the early P/M parts, were very simple shapes such as bushings and bearings. Today, complex contours and multiple levels are often produced economically. In recent years processes and techniques, including compaction, have evolved to a point were gears are now manufactured by P/M. For example, the 2003 Metal Powder Industries Federation “Overseas Grand Prize” was awarded for a P/M spiral bevel gear used in a reciprocal power saw. While P/M manufactured gears remain on the small size, use of this technology is expected to increase in the foreseeable future. 46.6.4.2 Ceramics Bearings based on ceramic materials such as Silicon Nitride (Si3 N4 )are being manufactured today for gear applications in aerospace. Silicon nitride, being nearly twice as hard as bearing steels, offers improved wearresistance and reduced damage due to the effects of repeated surface contact. The use of ceramic rolling elements reduces lubricant degradation and significantly

increase bearing life in many applications. Silicon nitride can operate at temperatures up to 980◦ C, exceeding the best high temperature bearing steels by a factor of two. Because it is essentially inert, Si3 N4 represents an advance in the effort to improve bearing performance in corrosive environments [31]. Lightweight Si3 N4 balls have a superfine surface finish and high hardness (Rc78) that can help to extend service life up to five times that of standard steel bearings. Low-friction characteristics enhance operation under minimal lubrication conditions and increase both life and speed capabilities of lubricants. Farther into the future, ceramic materials may be employed in gear manufacturing as well. Researchers have demonstrated that including carbon nanotubes into a ceramic material can nearly triple the resistance to fracturing. “Such durable materials could eventually replace conventional ceramics or even metals in countless products,” says Joshua D. Kuntz [32] of the University of California, Davis. “For instance, engineers might use the toughened ceramic to make gears, bearings, or other parts for everything from racecars to industrial food-processing equipment.” 46.6.4.3 Plastics Plastic gears are a powerful means of reducing drive cost, weight, noise, and wear. Plastic gears also open new opportunities for smaller, more efficient transmissions in many products. Historically, they were limited to very-lowpower transmissions, such as clocks, printers, and lawn sprinklers. Today’s stronger, more consistent engineering polymers, and better control of the molding process, now make it possible to produce larger, more precise gears that are compatible with higher horsepower. Thermoplastic and thermosetting polymers have long provided alternatives to metals in low-powered, nonlubricated gear trains. Gears machined from phenolics and other thermoset plastics can be used at higher operating temperatures and they are more resistant to lubricants that are generally required. However, injection-molded thermoplastic gears have better fatigue performance and, unlike those manufactured from thermoset materials, can cut manufacturing costs significantly compared with metal gears. Thermoplastics are now finding their way into applications demanding lubricated drives, higher horsepower, and higher American Gear Manufacturers Association (AGMA) quality standards [33].

46.6.5 Trends in Gear Lubrication Competitive forces will continue to drive design toward smaller gearboxes. Coupled with smaller gearbox designs is the effort to increase transmitted power. This trend means increased gearbox temperature and less oil in the system. Ultimately this will drive the lubricant requirements for higher thermal and oxidative stability.


The OEMs will continue to move away from maintaining lubricant approvals and are turning instead to national and international bodies such as ASTM, AGMA, ISO, DIN to develop and maintain gearbox standards and specifications. As consolidation and internationalization of gear manufacturers continues, look for global standardization to occur as regional design criteria are accepted worldwide. This all means OEM approval lists in the future may disappear; but this will be at the expense of commoditization of lubricant specifications. Differentiation will need to occur at the end user level whereby product performance attributes that directly effect the consumer (such as increased energy efficiency, reduced wear, and other value-added features) will need to be demonstrated in field operations. There is increasing awareness by the gearbox OEM and by the user community that expected life and performance of the gear set, the associated bearings, and the gear lubricant are highly interrelated. For instance, a roller element test developed by FAG OEM und Handel AG, A company of Kugelfischer Group (FE-8) (DIN 51517 Part III) is required by all gearbox OEMs [34]. Additionally, gearbox approvals now require approval by bearing and seal manufacturers in addition to the gearbox OEM. Acceptance of synthetic gear lubricants has been quite impressive in the heavy-duty truck market. Most notably the Eaton Corporation has driven this acceptance. A flavor for the attraction to synthetics is given in a European Patent Specification [35], which documents that oil change intervals of 80,000 km with a petroleum-based lubricant can be extended five fold to 400,000 km with a synthetic gear lubricant. “Until recently, petroleum based oils were used for lubrication in heavy duty truck transmissions even though they were susceptible to oxidation when operating the transmissions at oil sump temperatures above 110◦ C. Many of the mineral gear oils break down above 110◦ C and oxidize, and thereby deposit carbonaceous coatings onto seals, bearings and gears that may cause premature failures. Consequently, regular oil changes were required in order to minimize oxidation and these deposits, to assure maximum component life and to maintain the warranties with the transmission manufacturers. The lower temperature limit and requirements for a transmission oil cooler restricted the success of the mineral gear oils to milder applications. The new synthetic lubricants which are currently available can be operated at temperatures up to 120◦ C, with intermittent operating temperatures up to 150◦ C, without harming the transmission . . . .” New or improved synthetic lubricant base stocks are coming into the market, including higher viscosity PAO and poly internal olefins (PIO). Certain esters and PAG base stocks are gaining interest due to their biodegradability and eco-friendly properties. These new materials allow the lubricant manufacturer to extend the market reach of synthetic based gear lubricants. These new materials give rise

to the possibility of achieving high viscosity indices (VIs) without the use of polymeric VI improvers. The potential benefits include higher film thickness and little or no viscous shearing.

46.6.6 Higher Energy Efficiency with Synthetic Gear Lubricants The literature is replete with energy saving improvements through the use of synthetic lubricants, but energy improvement claims have had minimal impact in most industrial markets. Perhaps as newer demands are imposed on the gearbox this potential benefit will be more fully realized in the marketplace. As early as 1983, Facchiano and Johnson [36] examined the impact of synthetic vs. mineral oil based gear lubricants for their effect on energy efficiency. There results showed a 1.8 to 2.4% increase in energy efficiency depending upon temperature under prescribed load and test conditions in a double enveloping worm gear. Bronshteyn and Kreiner [37] examine the energy efficiency of industrial lubricants in some detail. They claim “lubricants influence energy efficiency mainly through reducing energy losses, which include churning losses and friction losses in hydrodynamic, elastrohydrodynamic and boundary lubrication regimes. The total energy loss depends on lubricant viscosity and chemical composition. Different sources of lubricant-related power losses in industrial systems are described. The dependence of churning and friction losses on oil properties is analyzed.” Among their conclusions is that “. . . a minimal pressure–viscosity dependence, as shown for PAOs, is most beneficial for energy conservation as well as for antiwear performance.” Naruse et al. [38] examined the influence of chemical structure of various lubricant compositions, based on mineral oils and various synthetics, on friction loss in spur gears. They conclude that: “generally, friction loss decreases with increasing viscosity and with increasing rotational speed at relatively high loads. Furthermore it becomes evident that the values of friction loss in high load range are quite dependent on the kind of lubricating base oil, that is, mineral oil and synthetic oils. The temperature rise of gear teeth has a close relationship with friction power loss of spur gear.” Michaelis and H˝ohn measured the churning losses and showed that by using low viscosity lubricants, reduced mesh power losses of as much as 50% of the power loss of mineral oils could be achieved by using Polyglycol-type lubricants. Besides this energy saving effect, the oil temperature in the gear box was reduced by up to 20◦ C [39]. Moore and his coworkers [40] performed a number of studies in process equipment in use in petrochemical operations and showed improved equipment reliability, energy efficiency, and reduced overall costs. Blahey et al. [41] showed


a 3.7% energy savings vs. a mineral oil using an FZG gear test rig. This study then looked at energy efficiency in gearboxes used in a coal crushing operation. Depending upon load, 8.5 to 9.6% of increases in energy efficiency were obtained vs. a comparable mineral oil-based lubricant. 46.6.6.1 Lubrication modeling In 2003 a large body of information had been assembled in understanding the effect of lubrication and its effects on gear surfaces. AGMA published an information sheet (AGMA 925-A03) “designed to provide currently available tribological information pertaining to oil lubrication of industrial gears for power transmission applications. It is intended to serve as a general guideline and source of information about gear oils, their properties, and their general tribological behavior in gear contacts . . . . The equations provided allow the user to calculate specific film thickness and instantaneous contact (flash) temperatures for gears in service. These two parameters are considered critical in defining areas of operation that may lead to unwanted surface distress. Surface distress may be scuffing (adhesive wear), fatigue (micropitting and macropitting), or excessive abrasive wear (scoring). Each of these forms of surface distress may be influenced by the lubricant; the calculations are offered to help assess the potential risk involved with a given lubricant choice [42].”

46.6.7 Gear Lubricant Formulation Trends PAO manufacturers have improved both quality and product range. For instance in 2001 Hope and Twomey [43] of ChevronPhillips showed that improving the degree of hydrogenation (by modifying the order of processing steps) improved oxidation stability of commercial PAO by 30 to 50% (as measured by ASTM D-2272 and other techniques) depending upon viscosity grade. ExxonMobil has several patents in the field. Wu of that company claims low-viscosity fluids with low volatility compared to commercially available PAO [44]. In a separate patent by Wu, novel PAOs with high VIs and low pour points are disclosed. The resultant materials are C30 to C1300 liquid lubricants [45]. Goze et al. [46] also of ExxonMobil claims lower volatility and low pour points achieved through various catalysts. Several higher viscosity polymeric materials have recently been introduced into the market. These new materials extend upward the range of viscosities now available for gear lubricant formulation. Opportunities of greater film thickness under elastrohydrodynamic conditions are possible, helping to reduce friction, increase efficiency, and reduce wear: • Improved wear protection in many lubricating regimes. • A VI that is 35 to 40 units higher compared to conven-

tional PAO of the same viscosity grade.

• A pour point that is 10 to 20◦ C lower than conventional

PAO of the same viscosity grade. • An increase of synergistic VI when blended with mineral and synthetic base stocks. • A high viscosity with good ambient fluidity. Alkylated napthalene: According to Wu and Trotto [47] Alkylated napthalene offers improved solubility, oxidative stability, hydrolytic stability, and additive efficacy compared to esters. The alkylated naphthalene molecule has a lower affinity to metal surfaces compared to esters; it is less likely to form a lubricant film compared to highly polar esters. Alkylated Naphthalene materials offer superior thermal and oxidative properties.

46.6.8 Gear Lubricant Specification Trends Synthetic-based gear lubricants are coming of age as national and international specifications and standards recognize them as equal to or superior to traditional petroleumbased lubricants. For instance, in 2002 the American Gear Manufacturers Association issued ANSI/AGMA 9005E02. This version of the specification titled “Industrial Gear Lubrication” incorporates several changes compared to AGMA 9005-E94 (1994). For one, the distinction between synthetic (S) and mineral oil-based EP mineral oils was removed. Now, the specification treats all EP oils without exception for base oil type (although there are certain exceptions for water separation properties). Further, the oxidative stability requirement was tightened. Gone are the Timken OK load requirement, and 4 ball and 4-ball EP requirements. The newer version of the spec now requires FZG pass of 10, 12 or 12+ depending upon viscosity. The later spec now requires a determination of the temperature for bulk fluid dynamic viscosity at cold start-up.

TABLE 46.2 Selected Properties of ‘High VI PAO’ ISO VG 320 Synthetic Based Gear Lubricant EP (Synthetic Hydrocarbon Blend, no VI Improver) Property Kinematic viscosity at 40◦ Kinematic viscosity at 100◦ Viscosity index Pour point Shear stability, 20 h Flash point NOACK volatility, procedure ‘B’ Four ball load wear index (LWI) Four ball weld load Oxidation induction time


Method

Unit

ASTM D-445 ASTM D-445 ASTM D-2270 ASTM D-97 CEC-L-45 ASTM D-92 ASTM D-5800 ASTM D-2596 ASTM D-2596 PDSC

cSt cSt — ◦

% ◦

% — kg min

Typical value 330 40 175 700 >180

Finally, the new-E02 eliminates the AGMA viscosity grade requirements in deference to the ISO VG system. 46.6.8.1 Bearing specification requirements Gearbox OEMs are recognizing the importance of the lubricant and its impact on bearing life as a critical requirement. For instance, OEMs require the FAG FE 8 bearing test, which is part of DIN Standard 51517 Part III is required by all gearbox manufacturers in wind turbine applications. Other bearing tests are under evaluation for inclusion in the new oil specification as well. Additionally, the SKF Emcor rust test is being evaluated to include testing with salt water [48].

46.6.9 Specific Synthetic Gear Lubricant Applications This section discusses just some of the many examples of successful applications of synthetics in industrial gear application. 46.6.9.1 Wind turbines Wind turbines are machines that take the energy from wind and translate it into electrical energy. Such turbines range from less than 0.4 to well above 2.5 MW. Rotor blades for newer designs are on the order of 75 to 80 m in diameter. Gears connect a low-speed shaft to a high-speed shaft by increasing the rotational speed from about 30 up to 1800 rpm. Wind turbines are expected to last a minimum of 20 yr. Gears are generally spur, helical, sun and planetary, or combinations in order to achieve minimum weight and physical size. Typically 3 to 4 stages are employed with gear ratios on the order of 4 : 1. The loads on a wind turbine are directly related to the site and the design of the turbine. Load fluctuations may occur as a result of any of the following conditions: • Turbulent wind fluctuations due to terrain, boundary

• • • • • • • • • • • •

layer and atmospheric effects, and wakes from other turbines Vertical and horizontal wind shear Gravity loads on overhung components Yawing motion of the rotor Off-axis yawed operation Unsteady loading due to the blades passing through the tower wake Transient starting loads due to generation controls Loads due to monitoring Transient stopping loads from aerodynamic or mechanical brakes Rotor mass imbalance Buffeting during parked rotor conditions Transportation and assembly Fault-induced control actions [49]

The gearbox is subjected to periodic extreme and shock load conditions. A wind turbine gearbox is susceptible to fretting wear. For instance with the high-speed pinion stopped by a brake and the rotor buffeted by the wind, the mating gear rocks back and forth through small amplitude motion. False brinelling can occur when the wind turbine is parked for a short time under light winds. Fretting corrosion can occur when the wind turbine is parked for an extended period under heavy winds. Moreover, fretting corrosion and false brinelling are not merely restricted to gear tooth damage; roller-element bearings can also suffer these effects when the wind turbine is parked. Fretting corrosion can also occur when a wind turbine is rotating, occurring on components such as splines or blade pitch bearings that are subjected to small-amplitude vibratory motion [50] The gear Lubricant must function in an EHD regime; must cope with high incidence of boundary friction; and deal with the potential for generated debris and wear particles. Film thickness is extremely important. New advances in lubricant technology are going to increase film thickness. Examples include PAG-based fluids and high VI PAO fluids. Bearing failures account for nearly 90% of all wind turbine gearbox breakdowns. Wind turbine gearboxes subjected to wide extremes in ambient temperatures and moisture conditions: for example, High Desert, offshore platform, or North Sea cold temperatures. Its’ efficiency is extremely weight sensitive so that eliminating or downsize lubricant coolers and preheaters can offer a big weight savings and can lower costs to manufacture. Periodic maintenance and oil changes are quite costly and problematical. All these factors drive the demand for very-high-performance gear lubricants. 46.6.9.2 Pumpjack gearbox Oil and Gas industry pumpjacks can be subjected to extreme weather application. While petroleum oils are by far the favored lubricants in this application, in lowtemperature application, a synthetic-based EP gear lubricant offers significant performance advantages compared to petroleum type oils. In a multiyear field trial in Alberta Canada, testing demonstrated reduced start-up torques, an average 14.4% lower input energy, and improved pumpability for critical production applications at temperatures as low as −51◦ C. The synthetic gear lubricant maintained a favorable VI and pour point. Assuming that proper fluid condition monitoring and maintenance practices are employed, and given the lowered wear rates, these pumpjacks will require change-outs only once every five years [51]. 46.6.9.3 Open gear sets A nonasphaltic synthetic open gear lubricant can reduce downtime and scheduled maintenance when performing at


extreme temperatures compared to a traditional asphalticbased, solvent-cutback lubricant. Developed to eliminate the use of solvents, this open gear lubricant allows for rapid set-up on gear teeth helping to prevent metal loss and reduces volatile organic carbon (VOC) emissions. The synthetic lubricant is a transparent amber color that can make clean up, inspection, and maintenance simple [52]. Improvements gained from the synthetic lubricant also included excellent cold-weather pumpability, negligible maintenance, and alleviation of excessive spare-part inventory previously required in anticipation of equipment failure [53].

46.6.10 Gear Lubricant Summary Synthetic gear lubricants will play an increasing role in the future lubrication of high performance gears as new processes, materials, and techniques allow for increased power density while at the same time serving extended periods in demanding environments. Competitive pressures of globalization and consolidation as well as mechanical, manufacturing, and environmental factors including energy efficiency will continue to drive future lubrication requirements and formulations.

46.7 COMPRESSOR OIL TRENDS The compressor lubricant industry can be segmented into three primary categories: industrial air compression, industrial gas compression, and refrigerant gas compression. Contrary to most industrial applications synthetics have been generally accepted and utilized with great success in the compressor industry. The primary reasons for their use and acceptance are directly related to the value-added benefits realized by end users including extended lubricant and equipment life, safer operations, environmental responsibility, and energy efficiency. Building on these attributes in addition to satisfactorily addressing new market requirements will contribute to the continuing use of synthetics in compressor applications. The general equipment/market trends influencing the lubricant utilized in each defined segment will be detailed in the following sections

46.7.1 Air Compression The former industry workhorse reciprocating compressors have been and will continue to be replaced by rotary screw designs for most air compressor applications. The traditional diester-based lubricants utilized in most reciprocating designs will remain the lubricant of choice. As the reciprocating design are replaced a decline in the diester lubricant consumption will follow. Rotary screw compressors enjoy the largest market share of the air compressor segment. PAO, Group III, and PAG/ester blend-based products are the current synthetic

base fluids of choice for many OEM’s. Group III products are gaining ground based on comparable performance to PAO at significantly lower costs. End users demands and local legislations are driving future design considerations, which include smaller, quieter, reduced environmental impact, and lower cost of operation compressors. The lubricant selection amongst other engineering considerations plays a significant role in the design process to satisfactorily address each of these emerging market requirements. The leading OEM’s are gradually upgrading their engineering technologies in addition to employing advanced synthetic lubricant technologies to meet these market challenges. In particular there is a trend toward utilizing Polyolester lubricant technology as part of the solution. The applicability of Polyolesters to meet these market requirements is driven by the following attributes. • • • • • •

Extended drain intervals of 10,000 h or more Excellent thermal-oxidative stability Biodegradability Low order of toxicity Inherent lubricity properties Good elastomer/seal compatibility

At present, polyolester technology is the leading chemistry to address the current trends; however, the current synthetic fluids are expected to continue to hold the majority market share for the immediate future. As the demand increases new performance attributes the trend toward higher performing synthetic fluids will accelerate.

46.7.2 Industrial Gas Compression The preferred lubricants for hydrocarbon gas compressors are generally based on PAGs although any of the common types of mineral oil or synthetic lubricants suffice in many applications. The overriding consideration in selecting which lubricant to use is the degree of solubility of the particular gas being compressed in the compressor lubricant, that is, minimizing gas solubility in the oil results in less oil dilution and subsequent loss of oil viscosity. This is the foremost consideration and the reason that PAG’s have found a niche in this market. As in the compression of air, the two main types of compressors utilized in the process and hydrocarbon gas industry are reciprocating and rotary screw. 46.7.2.1 Rotary screw The trend in the process gas industry is toward achieving ever increasing pressures by means of rotary compression. Formulated PAG compressor oils from ISO 68 to 150 are commonly employed. Since the lubricant in rotary screw compressors is recirculated, it is important that the effects of oil dilution by the gas are minimized. Rotary screw compressors are found mainly in various types of gas gathering operations.


There is also a trend toward multistage rotary screw compressors, which permit greater efficiencies than the typical rotary/reciprocating combination. This makes the choice of lubricant even more critical. 46.7.2.2 Reciprocating Again, the trend is toward very high discharge pressures in reciprocating compressors lubricated with PAG-based fluids. For example, the compression of hydrocarbons, nitrogen, and carbon dioxide by hyper-compressors used in enhanced oil recovery operations typically discharge at 5,000 psi with some multistage compressors approaching discharge pressures of 10,000 psi. The trend toward higher discharge pressures exacerbates the loss of oil viscosity due to dilution, resulting in a lubricant requirement for oils of higher ISO grades, for example, ISO 220 to ISO 460. 46.7.2.3 Future trends Environmental awareness and increasing efficiencies in fuel conservation and ultra low emission vehicles (ULEV) has lead to developments in compression of natural gas and hydrogen for consumer-type-fueling systems. Hybrid and natural gas fueled vehicles will require the use of small natural gas compressors, which must operate under standards of safety and reliability more stringent than current industrial standards. Fuel cell powered engines will require the same standards of safety. These standards are not achievable with traditional mineral oil-based lubricants. PAG-based fluids and other types of synthetic fluids such as silicate esters and polyethers will most likely dominate these applications [54–57]. Experimental research efforts by several lubricant base stock manufacturers are attempting to incorporate multifunctional chemical groups to impart improved antiwear, thermal oxidative resistance, and other desirable enhancements into the synthetic base. If successful, these efforts will result in greatly improved lubricant life, improved compressor performance and reliability, and subsequent reduction in waste oil disposal costs [58].

46.7.3 Refrigerant Gas Compression The refrigeration and air conditioning industry is in the process of experiencing dramatic changes, which will have significant impact on the growth of synthetic lubricants. The Montreal protocol’s initiatives are well documented with regard to the phase out of ozone depleting chlorinated refrigerants principally R-22 [59,60] Over the past ten years or more a conversion of both automotive air-conditioning systems and small appliances have been converted to hydrofluorocarbon (HFC) nonchlorine containing gas (R-134A). PAGs became the product of choice for mobile air-conditioning systems while polyolesters dominated the small appliance market.

The market is now experiencing significant changes in several market segments. Europe and Asia are moving toward the use of hydrocarbons refrigerants such as isobutene (R-600), which utilizes mineral oil as the lubricant in small appliance applications [61]. The primary driver for the change is cost. The system design and associated cost of the refrigerant and lubricant are significantly lower compared to the traditional designs. North America is resisting the change due to flammability/fire concerns. The typical appliances in the North American market are much larger than those found in Europe or Asia. As a result the amount of flammable hydrocarbon gas is larger [62]. The larger industrial air-conditioning systems continue to utilize primarily R-22 type gases. Although not certain, the expected trend is that R-22 refrigerant gases will be replaced by R-407/R-410 (chlorine free materials). Significant pressures are being placed on air-conditioning OEM’s to increase the efficiency of their units by as much as 30% as reflected in the proposed 13 SEER standard [63]. This in itself is not the reason for a change to HFC refrigerants. Legislation requires the phase out of chlorofluorocarbon (CFC) refrigerants in industrial air conditioning systems by 2010. This will positively affect the growth of polyolesters (POEs) as the lubricant of choice for miscibility with the chosen gas. Polyvinylether technology remains a viable technology for select applications; however, it is expected to experience minimal growth relative to the general market [64]. The market for refrigeration lubricants is uncertain and will depend largely on government actions, environmental/health concerns, and cost constraints. The future growth of synthetic lubricants, principally PAGs and POEs in the refrigeration market is directly related to the refrigerant technology employed.

46.7.4 Compressor Lubricants Summary The market for synthetic lubricants in compressor applications is changing with the dynamics of each subsegment. Synthetic lubricants have been widely accepted as superior value-added products in most compressor applications and this will continue. Energy savings, longer life, and environmental considerations will continue to influence the choice of the lubricant employed. Environmental and legislative factors are leading factors that necessitate additional potential changes, which in most cases will require higher performing synthetic technologies to meet emerging market requirements.

46.8 HYDRAULIC OIL TRENDS Hydraulic fluids represent the largest market share of industrial lubricants in the world. A tremendous variety of equipment and applications utilize hydraulic fluids. The next sections briefly define the types of hydraulic


Hydraulic fluids

Hydrostatic applications

Hydrokinetic applications

ATF DIN 51502

Mobile systems

HA HN ISO 6743/4

UTTO STOU

FIGURE 46.1 General classification of hydraulic fluids

pumps and classification of different fluids. The primary focus of this section is to discuss future trends in the hydraulic oil segment.

46.8.1 Types of Hydraulic Systems Hydraulic pumps can be classified into three main categories: Gear pumps: Gear pumps are relative to other pump designs and inexpensive to manufacture. A Design News study [65] in 2002 reported that 71% of engineers specify a fixed displacement gear hydraulic pump in their systems. The main market for this type of pump is within the mobile hydraulic segment such as construction equipment. Vane pumps: Vane pumps are a low cost alternative to piston pumps. Vane pumps operate up to about 4500 psi and thus fall into the mid-performance range. A wide variety of applications use vane pumps. Piston pumps: Piston pumps are gaining increasing importance as they offer significant control at low speeds. Operating pressures approach 6000 psi and several pump manufacturers are pushing for even higher pressures primarily by incorporating superior valve technology. Again a wide variety of application use piston pumps to take advantage of the higher efficiencies.

46.8.2 Hydraulic Fluid Classification Mang and Dresel [66] offer a detailed look at the various classification schemes (Figure 46.1 and Figure 46.2) to enable users to select a suitable fluid. It is interesting to note that along with classic fluid property specifications Mang and Dresel add application-derived classifications as well, such as food grade lubricants.

46.8.3 OEM and End User Future Trends Some of the key trends are listed below: A brief description of each trend follows the list: • Ecologically sensitive fluids • Crop derived fluids

Hydrostatic apps

Food grade

Environmentally friendly ISO 15380

Mineral oil based ISO 6743/4, DIN51502 ISO 6743/4 DIN 51524

Water soluble

ISO 11158

Water insoluble

HEPG

NSFH1 and H2

HETG, HEES, HEPR

Fire resistant 7th Lux, ISO 6743/4. Water containing

Water free

HFAE, HFAS, HFB, HFC

HFDR, HFDS, HFDT, HFDU

HH, HL, HM, HR, HV, HS, HG

DIN 51524

HL, HLP, HLPD, HVLP, HVLPD

FIGURE 46.2 Classification of hydraulic fluids for hydrostatic applications • • • • • • • • • • • •

Synthetic hydraulic fluids Improved cleanliness Improved fire resistance Products for use in food and pharmaceutical plants High-pressure systems Increased specifier sophistication Shrinking market for low-pressure systems Fluid and supplier rationalization Multigrade fluids Elastomer versatility Fluid monitoring and trend analysis Ashless formulations

46.8.3.1 Ecologically sensitive fluids The trend to utilize more ecologically sensitive fluids is set to continue both for novel applications and for replacing mineral oil-based fluids in sensitive applications. It is envisaged that the legislative and consumer focus will change from simply requiring a biodegradable fluid to one that takes account of other factors as well. Norrby [67] suggests that for environmentally acceptable lubricants (EALs) in addition to biodegradability, renewability, toxicity, bioaccumulability, life cycle assessment, and energy savings should be considered to determine the overall impact to the environment. He also reports that future trends in the development of EALs include increasing use of renewable raw materials and re-refined base oils. Denison has published data indicating that some biodegradable fluids perform better than mineral oil in vane pumps. As the costs come down for ecologically sensitive fluids, a significant increase in volume is expected. Norrby et al. [68] report that the European “Environmentally Acceptable Lubricants” (EALs) market is expected to


grow by 15% per annum to 2006 and suggest that the next strong market for EALs is in mobile hydraulics such as off-highway equipment and construction. They also suggest that there is a strong downward pressure on price attributed to the economic downturn and that the legislation and global agreements are not moving at sufficient pace for rapid EAL development. This however is expected to change as the global economy is now beginning to show signs of recovery. 46.8.3.2 Crop derived fluids Bevard [69] reports that hydraulic fluids leaking from Triplex mowers, tractors, and aerators with hydraulic lift cylinders and other machinery utilizing hydraulic systems can kill putting green turf on a golf course. Bevard suggests that the vegetable oil-based fluids are just as damaging to the turf as mineral oil-based fluids as primarily damage occurs due to the high temperature of the oil; however, the recovery of the grass is much faster with vegetable oil-based fluids. 46.8.3.3 Synthetic hydraulic fluids Pressure to deliver services in all climatic conditions is putting pressure on users to choose synthetic fluids that typically offer a wider temperature tolerance. Cullen [70] reports one such application in Montreal, Canada where significant reduction in repair and maintenance was achieved by switching a fleet of garbage collection trucks from mineral to synthetic hydraulic fluids. Ehrenman [71] reports that in the United States the demand for synthetic functional fluids is expected to grow by 5% per year to 2006 to $2.8 billion.

46.8.3.4 Improved cleanliness Improved cleanliness of the hydraulic system is a critical element in extending equipment life. This has implication for formulators, system designers, filter manufacturers, and operators alike. From the formulator’s perspective with some filter manufacturers recommending a 3 µm filtration there are implications for keeping additives such as siliconbased antifoam in solution. Stewart [72] reports that filter manufacturers are concerned about filter fibers breaking away due to ever increasing drain intervals without a filter change. He reports a maximum of 325 to 400 h filter lifetime in mining off-road equipment. Stewart also reports that a change from a 13 to a 2 µm fuel filter resulted in a doubling of pump life. Similarly, Anderson [73], reports that in a trial at the Port of Tacoma, USA, maintenance costs were reduced by up to 97% on a straddle carrier by improving the oil cleanliness. Among “extended service” technologies suggested by Stewart are upgraded cellulose, cellulose–synthetic blends, microglass, and meltblown polyester filter media.

dimensions. Redpath [76] reports that for the earth moving segment current systems are operating above 6,000 psi with fuel system pressures approaching 40,000 psi. 46.8.3.8 Increased specifier sophistication End users are knowledgable about different types of fluids and their use in various applications. This trend is expected to continue with sophisticated selection, purchase, and use criterion established end-users. System designers are also critically evaluating various hydraulic fluids on a range of measures that not only include the traditional fluid properties but also field application demands such as corrosive environments, usage in eco-sensitive areas and logistic and technical support. Technical articles on selection and use of hydraulic fluids are now to be found in virtually all industry publications on a regular basis. As an example, Zink [77] suggests evaluating fluids on safety and environmental concerns along with the performance characteristics such as antiwear performance, oxidation resistance, and elastomer compatibility. 46.8.3.9 Shrinking market for low pressure systems

46.8.3.5 Improved fire resistance Fire resistance of hydraulic fluids has also come under the spotlight with several commentators indicating a rapidly developing market. Hitchcox [74], writes that the mere existence of fire resistant and environmentally friendly hydraulic fluids is a liability for nonusers and suggests that litigation prevention may be an important driving force for the development of such fluids.

46.8.3.6 Products for use in food and pharmaceutical plants In many countries, food processing or preparation areas require the use of “food grade” lubricants [75]. This market segment is expected to enlarge rapidly. Food grade lubricants are generally considered those that have been formulated with approved ingredients found in the Food and Drug Administration (FDA) document 21 CFR178.3570 and the Generally Recognized as Safe (GRAS) list within 21 Code of Federal Regulations (CFR). Development of food grade products became stagnant around 1998 by the departure of U.S. Department of Agriculture (USDA) from approving food grade lubricants. National Sanitory Foundation (NSF) International and the Dutch Nederlandse Organisatie Voor toegepast-natuurwetenschappelijk Onderzoek (TNO) among others have since filled this void.

46.8.3.7 High pressure systems The hydraulic fluid market is steadily moving toward ever increasing pressures and smaller overall system


Electromechanical systems are grabbing market share from low-pressure systems. Gear pump systems are particularly affected. Vehicle assembly robots and injection molding machines are examples of segments where this migration is the strongest [78]. 46.8.3.10 Fluid and supplier rationalization There is an increasing trend among the end users toward consolidating products and suppliers. Economic pressures primarily drive this trend. Although in some market segments, such as food grade lubricants, this is partly to avoid cross contamination mistakes. Several lubricant suppliers now offer “total fluid management” programs, however in most cases it is found that savings are achieved in the first two years after which the program becomes unattractive for the fluid suppliers and the customers. An additional concern with such programs is the heavy reliance on a single source and the potential loss of not capitalizing on new developments by another supplier. 46.8.3.11 Multigrade fluids Placek [79] has documented the benefits of using multigrade hydraulic fluids in the forestry segment and includes purchase, maintenance, downtime, and disposal costs in the economic evaluation. Lost production time and machine life reduction is suggested as additional costs to be assessed. He concludes that the use of multigrade hydraulic fluids was a significant factor in keeping the machinery operating at the optimum level and that these fluids were the preferred option when wide operating temperature ranges are encountered.

46.8.3.12 Elastomer and material versatility The applications using hydraulic fluids are widespread with limitless variations in operating environments and demands on the system. A critical aspect in improving system versatility is in improving the versatility of the elastomers, coatings, and hoses used in the system. This is becoming increasingly important as users switch from one fluid type to another due to legislative or other operating demands. As an example, Wangsgaard [80] reports on new urethane seals that are resistant to hydrolysis and thus are suitable for use in vegetable-based fluids and other esters that have a tendency to absorb water. 46.8.3.13 Fluid monitoring and trend analysis Biamonte [81] calls for a rigorous check of the health of the hydraulic fluid at least on a quarterly basis. He suggests the monitoring of viscosity, water, wear metals, and contaminant levels as a minimum and that trending is an effective technique to avoid field failures. Routine fluid monitoring and trending is expected to grow significantly as pressures on system reliability increase. 46.8.3.14 Ashless formulations Legislation, particularly in Western Europe and environmental concerns in other applications is forcing formulators to deliver ashless formulations that is, not containing any metal containing additives. ZDDPs, which are common antiwear additives used in hydraulic fluids, have seen their use decline and this is expected to continue. Duncan et al. [82], report on ashless additives in synthetic POE fluids that meet the performance of several conventional fluids and exceed the performance of vegetable-based oils.

46.9 GREASE TRENDS 46.9.1 Grease Overview In general, grease provides a better mechanical cushion for extreme conditions, resists the washing action of water while sealing out contaminants, and stays where it has been applied compared to liquid lubricants. Lubricating greases utilized in heavy industrial, food processing, automotive, and automotive after-market applications tend to be based primarily on conventional base oil technology. These market segments have incorporated the use of new thickener technologies almost as soon as the technology has become available. On the other hand, commercial and military aviation applications have and will continue to rely on synthetic base oil technologies for lubricating grease requirements. The military aviation market has not readily incorporated advanced grease thickener compositions. The changing needs of these market segments have resulted in new manufacturing methods and equipment as well as utilization of


components that lubricating grease manufacturers have, as a rule, avoided. Consumer demand, regulatory pressure plus advancements made in materials and mechanical engineering provide machinery and components that require lubricating grease products that conform to more stringent specifications. Grease manufacturing must supply product that consistently meet these stringent quality and performance demands, while providing a greater variety of products at the same time [83].

46.9.2 Grease Manufacturing Trends Understanding grease trends requires basic knowledge of the manufacturing process and associated challenges. Production techniques and chemical nature of the components utilized in lubricating grease formulations dictate the processing equipment that manufacturing facilities employ. Lubricating grease production can be described as the formation of a thickener component in a reaction vessel followed by heat to promote the reaction or gel formation. After the thickener has been properly formed the manufacturer cools the product and then mills the grease while adding more base oil, followed by additive addition and filtration, see Figure 46.3. Lubricating greases of a commodity stature tend to be supplied by major petroleum refining companies. These products tend to be lower cost materials that are made in continuous saponification or grease making units. Continuous grease making units produce about 4,000 to 10,000 lbs of grease an hour and need to make large quantities of the same grease formulation per production run to maintain product consistency and cost efficiency. One of the drawbacks to continuous grease making units is that all the components required to manufacture a particular formulation must be liquid, excepting when product is diverted to finishing vessels for the incorporation of lubricating solids [84]. Noncommodity grease formulations tend to be produced in batch processes, which are capable of producing large quantities of lubricating grease, but batch size is constrained by processing vessel capacity. 46.9.2.1 Batch processing Batch processing methods and equipment are more suited to producing specialty greases, especially those based on synthetic fluids other than the synthetic hydrocarbon types. Batch processing equipment is based on pressure reactors like STRATCO® Contactors and autoclaves or open to the atmosphere vessels with proper mist elimination systems. Stratco contactors are very efficient batch processing equipment due to grease saponification times taking approximately 21 to 23 the amount required with open to atmosphere vessels and autoclaves [85]. Grease manufacturers with batch processing equipment for synthetic oil based greases are becoming more important to supply

the demand of consumers for these specialty lubricants. This demand for specialty greases with synthetic base oils is a result of the longer life, improved performance in applications of extreme thermal or oxidizing conditions, and additional lubricity and film forming ability provided by these types of products. Batch processing techniques lend the lubricating grease manufacturer the ability to produce products with mixed thickener systems. Generally, during application the intermixing of greases with differing thickeners can show compatibility issues. The performance of the intermixed blend may be affected in such a way as to influence the performance of the lubricated part. For example, sodium stearate thickened greases find utility as moderately high temperature lubricants in food machinery applications in the Asian marketplace. Sodium stearate thickeners are not approved components for greases that may have incidental food contact. NSF International, a not-for-profit consumer advocate and public health standards group, has approved some aluminum complex thickened greases with United States Pharmacopeia (USP) white oil or PAO fluids for incidental food contact. Compatibility testing between these two types of grease as per American Society for Testing and Materials (ASTM) D 6185 — Standard Practice for Evaluating Compatibility of Binary Mixtures of Lubricating Greases can provide an indication where potential problems could arise in application upon the change from one grease to another. In the future, the intermixing of different grease thickeners to achieve specific performance enhancements will be employed for the lubrication of critical machines operating in adverse conditions. For example, the intermixing of calcium complex greases with polyurea thickened greases has been described as providing a lubricating grease with improved fretting wear performance and additional loadcarrying capacity for automotive bearings in front wheel drive applications [86]. The polyurea described in the invention would not have exhibited improved load-carrying capability without the calcium complex component nor would the polyurea have had a dropping point in excess of 500◦ F. Reduced wear due to fretting would not have been achieved in the calcium complex grease without the polyurea component. Note that the calcium complex grease typically exhibits dropping points in excess of 550◦ F, but the patent describes the invention with a substantially lower dropping point. The dropping point given for the invention is great enough to provide adequate performance in under-the-hood automotive applications. 46.9.2.2 Manufacturing for low noise The manufacturing procedures employed by grease producers can be modified to further enhance the performance of specialty greases in fulfilling the needs of bearing manufactures, such as “low noise” greases. The result of


performance enhancement made by bearing manufacturers for automotive, precision, and electronic/electrical equipment has shown that the noise arising from these types of applications are attributable to the lubricating grease [87]. Filtration of grease components and the finished product take on additional importance due to the substantial influence associated with contamination of foreign materials such as dirt. Because grease is a semifluid to solid product of a dispersion of finely divided particles (thickener) in a liquid lubricant there is a need to control the particle size of the thickening agent. Some lubricating grease manufacturers have dedicated the time and capital to develop manufacturing processes to utilize “clean” raw materials in modified processing equipment that generate grease thickening particles of less than 500 µm in size. An ingenious method of grease production developed by a major oil company was to incorporate milling during the thickener formation. In particular, during the production of low-noise lithium complex thickened grease (with and without synthetic fluids) the grease components were filtered in liquid form prior to addition to the batch. The lithium complex thickener was milled during the saponification process in a SUPRATON® model S400 milling apparatus (available from Krupp Industrietechnik GmbH) with a gap setting of 100 to 500 µm [88]. Another major oil company known for “low noise” polyurea thickened grease employed a facility with prior filtration of grease components and a clean-room environment dedicated to producing one grease formulation.

46.9.3 Application Trends The commercial and military aviation industry has been designing new aircraft and specifying military qualified lubricating greases that had not been reformulated for decades. Lubricating greases qualified to a military or commercial aviation specification cannot be changed without qualifying the new formulation. The qualification of a lubricating grease product can be time consuming and expensive. The subsequent lack of product innovation by lubricant manufactures is not looked upon as entirely inappropriate. A result of decades without major changes to specifications or lubricant technology upgrades are a plethora of qualified suppliers to a given specification. Many of these specifications have performance overlap and in the mid-1990s resulted in a request from commercial aviation companies for the airframe manufacturers and lubricant industry to develop a single-grease specification that could be used on the entire plane [89]. The product initially developed reduced the number of different grease products specified to lubricate a single aircraft from 99 to less than 10. The Boeing Company issued a material specification designated BMS3-33A in 1995 that dictates the lubricating

grease qualified to this specification will be composed of a lithium complex thickener. Other descriptive requirements of this specification are an operating temperature range for the grease of −73 to 121◦ , high load-carrying capability, must prevent corrosion in harsh environments, and resist the washing action of water. The specific requirements of the Boeing specification are more stringent than any military specification written with similar testing procedures (examples would be MIL-PRF-23827C, MIL-G-21164D). A number of lubricant manufacturers designed a mixed grease thickener system (albeit primarily lithium complex) that would allow the qualified greases to perform at low temperatures, possess high load-carrying capability, and prevent corrosion of iron containing metals exposed to salt water solutions of 3% sodium chloride. This mixed grease thickener system incorporated a significant portion of calcium sulfonate complex that is added to the lithium complex during the manufacturing process. During the manufacturing process of lithium complex grease formulators can incorporate low temperature synthetic diesters, which is needed for low temperature performance. The manufacturing of calcium sulfonate complex cannot incorporate synthetic diesters without hydrolyzing these base oils. The calcium sulfonate complex portion allows the qualified grease to prevent corrosion. This portion of the lubricating grease contributes to reducing water washout tendencies and contributes to the load carrying capability of the product. The significance of utilizing a mixed thickener system is that the aviation industry forced lubricant designers to combine the benefits of one thickener type and incorporate the benefits of another to solve difficult lubricating conditions. Powder metallurgy processing techniques produce micrograin high-speed steels with improved wear resistance. These specialty steels are impregnated with oil or semifluid greases and then expected to function in operating conditions reflective of a starved lubrication regime. Theoretically, impregnation of P/M materials with semifluid grease provides lubricating films with a mixed composition of lubricating oil and thickener. The composition of the lubricating film is dependent upon the grease type and speed of the rolling or sliding contacts. Experimental evidence for the makeup of the mixed composition has been investigated with infrared spectroscopic techniques [90]. Lubricating grease thickeners are thought to form thin residual films on metal surfaces. Under starved conditions the lubricating film thickness will depend on the efficiency of the base oil to flow from the thickener into areas of Hertzian contact [91,92]. In these studies greases with thickeners of lithium 12-hydroxystearate (14% by weight) and tetraurea (7 and 14% by weight) showed that the lubricating film was comprised mostly of base oil. Thickeners at low concentration and of lower shear stability, in this case the tetraurea thickener, provided greater lubricating film thickness [9]. Impregnation of P/M steels


with synthetic diester based lithium 12-hydroxystearate thickened semifluid greases work exceptionally well in prolonging the life of these bearings and tools. Reason being that a shear stable thickener like12-hydroxystearate at low concentration (typically less than 7% by weight) releases the diester base oil at rates sufficient to prolong the life of the part. The polar nature of the diester base oil forms a more stable lubricating film, thus providing a larger film thickness than products based on conventional mineral oils.

46.9.4 Environmental Trends Environmental legislation and consumer awareness are impacting the design of and application of grease. Industries operating in eco-sensitive environments are looking to minimize the risk of adversely impacting the environment. The marine and inland waterways are particularly interested in eco-friendly grease products. Ocean going vessel applications include wire rope dressings and vessel stern tubes. Water treatment facilities and hydroelectric facilities are also under pressure to be more environmentally focused. The offshore oil explorations and drilling industry is moving toward greener grease applications. Grease trends in these applications require biodegradability, low toxicity, and the absence of sheen on the water in the event of a release. Formulators employ ester and vegetable-based products to meet the environmental requirements of these applications. Emphasis on environmentally friendly greases, has influenced formulators to consider calcium sulfonate thickener systems. Depending on the chain length, some calcium sulfonates are considered environmentally friendly. One of the challenges facing grease formulators is to find ecologically sensitive additives for rust inhibition, antiwear, and long operating life (The EC Dangerous Preparations Directive attempts to codify additives and thickener systems into broad categories) [93]. For example, amino-based rust inhibitors do not function effectively in the presence of salts. Therefore, finding additives that will work in salt water, brackish water, or hard water environments is difficult.

46.9.5 Grease Market Trends From the above examples, the direction in developing new lubricating greases can be summarized into several specific aspects. In general, users of lithium thickened greases are moving to lithium complex greases, while users of lithium complex greases see increased need for the performance benefits of calcium sulfonate complex thickeners. Calcium sulfonate complex greases offer some inherent lubricating properties with respect to wear and rust inhibition as well as water resistance. Manufacturing equipment and methodology are evolving to produce products that have measurable differences in grease thickener property, such as particle size needed

to sustain the increasing desire for “low noise” greases. A move is seen from mass producing large quantities of the same grease formulation to fulfill commodity supply and demand rules of major petroleum refining operations to the production of batch quantities of specialty lubricating greases to satisfy the more stringent demands imposed by the lubricant consumer. The demand by industry for higher performance greases continues to increase. To achieve the performance requirements formulators are intermixing thickener systems and incorporating new synthetic base fluids to optimize the final formulation. Environmental pressures are also changing the selection and formulation of greases with the requirement of more eco-friendly solutions to meet local and global legislative requirements. To address these industry trends grease marketers/manufacturers will need to be flexible and provide tailored solutions for specific applications.

46.10 EFFECTS OF BASE OILS ON INDUSTRIAL LUBRICANTS With the expected increases in industrial lubricant demand from Asia, North America, and Europe, one can expect tight base oil supplies. Already, Asia is seeing a shortage of base oil for its projected demand [94]. The advent of Group II and Group III production will create further shortages as refiners meet the demands for these new base oil qualities while sacrificing Group I production. Within the next 10 yr, gas-to-liquids (GTL) technology will enter lubricant oil formulations [95]. GTL technology gives refiners the opportunity to tailor molecules to meet exact specifications such as viscosity, VI, and pour point. The new technology products will come the closest to approaching the performance of PAOs and PIBs. In the short term, one can expect new base oil stocks from Russian refiners. Already, Europe and Asia are importing Russian base stocks for use in finished lubricants [96]. If Russia can supply the world with additional base oils, this will mitigate the global tightening that we are experiencing in Group I stocks as more refiners move to Group II and Group III production. So what does all this mean for finished industrial lubricant marketers? In general, Group II and Group III products are not widely used within industrial lubricants. Group II stocks can be found in gas engine oils, compressor oils, and turbine oils. Over the next few years, industry should see a shift toward more Group II and Group III stocks in hydraulic and gear oils. Industrial users will insist upon the additional quality offered by Group II and III stocks. The automotive sector has already adopted this standard. It is now progressing into commercial vehicle lubricants as well as construction and mining. As Group II and Group III stocks increase industrial market share, conventional Group I stocks will decrease.


Industrial synthetics formulated with PAO, PAG, or Polyolester technology should continue a steady growth [97]. Polyolester technology will continue to develop in compressor and aviation turbine technology. As the biodegradable market expands, polyolester base stocks will play a pivotal role in achieving extended life and high temperature performance. Polyalkylene glycol base oils will offer niche performance attributes particularly within the oil and gas segment where gas and liquid solubility is crucial. Compatibility with PAOs, mineral oils, and POEs, will hinder growth of PAGs. PAOs have already been widely accepted within the industrial lubricant segment. Hydraulic, gear, and circulating oils that require high or low temperature performance will typically use PAOs.

46.11 SUMMARY There are many trends happening within industrial lubricants. Some trends, such as biodegradability, are directly influenced by legislation. Demands for biodegradable lubricants are clearly increasing. Within the gear, compressor, and hydraulic markets, manufacturers are reducing the size of equipment. With smaller sump sizes, there are more thermal and oxidative stresses on the lubricant. As a result, future products will incorporate advanced additive technology and synthetic technology to improve lubricant performance characteristics. Some of the same trends affecting oils are also influencing greases. Specialty greases incorporating the benefits of mixed base oil and thickener technologies will emerge to meet the needs of critical equipment. All of these trends are requiring the development of new advanced products, which in many instances are satisfied by employing synthetic lubricant and grease technologies. The growth of synthetics will be directly related to the requirements for improved industrial productivity, efficiency, and environmental concerns. In addition, the cost/performance ratio compared to conventional technologies will have significant influence on the next generation of synthetic fluids.

REFERENCES 1. Tim Sullivan “U.S. Lubes Dipped in 2002,” Lube Report, 18 September 2003, 25 March 2004, http://www.lubereport. com/e_article000202976.cfm?x=a2mM17t,aW0j1gs, aW0j1gs. 2. Anon “Synthetic Lubricants Market in Asia,” Frost and Sullivan, 12 July 2002, 25 March 2004, http://www.laboratorytalk. com/news/fro/fro120.html. 3. Anon “Synthetic Lubricants Market in Asia,” Frost and Sullivan, 12 July 2002, 25 March 2004, http://www.laboratorytalk. com/news/fro/fro120.html. 4. Nancy De Marco, “India’s Lube Sector Rebounds,” Lube Report, 25 February 2004, 25 March 2004, http://www. lubereport.com/e_article000231779.cfm?x=a2DMhT5, aW0j1gs.

5. Tim Sullivan, “Asia’s Indpendents Face Dim Outlook,” Lube Report, 16 March 2004, 25 March 2004, http://www.lubereport.com/e_article000239251.cfm? x=a2HdhY7,aW0j1gs. 6. Nancy DeMarco “Pent-Up Consumer Demand Drives China’s Growth,” Lube Report, 9 March 2004, 25 March 2004, http://www.lubereport.com/e_article000236836.cfm? x=a2GkRDB,aW0j1gs. 7. Tim Sullivan, “U.S. Lubes Dipped in 2002,” Lube Report, 18 September 2003, 25 March 2004, http://www.lubereport. com/e_article000202976.cfm?x=a2mM17t,aW0j1gs, aW0j1gs. 8. Linda McGraw, “ARS and Industry Test New Vegetable Oils as Industrial Lubricants,” Agricultural Research Service, 26 March 2001, 25 March 2004, http://www.ars.usda.gov/is/ pr/2001/010236.htm?pf=1. 9. Tim Sullivan, “Cargill Expands Bioesters Plant,” Lube Report, 17 February 2004, 25 March 2004, http://www. lubereport.com/e_article000229001.cfm?x=a2Cppj3, aW01gs 10. Bill Brady, Cargil, U.S., Maria Miessva, Cargill Brazil,; David Mason, Kaufman Holdings Corp.; “Cargill, Hatco Joint Venture Breaks Ground on Ester Plant in Brazil,” 17 November 2003 Press Release. 11. Anon, “Going Green,” http://www.etfluidpower.com/ environ2.html. 12. Kržan, B. and Vižintin, J., “Vegetable-Based Oil as a Gear Lubricant,” Gear Technology, July/August 2003, pp. 28–33. 13. Lloyd Leugner Maintenance Technology International Inc., “How to apply and maintain biodegradable lubes,” Machinery Lubrication Magazine. July 2003, 6 April 2004, http://www.machinerylubrication.com/article_detail.asp? articleid=511&relatedbookgroup. 14. Tim Sullivan, “Court Nixes Oil Mist Petition,” Lube Report, 23 March 2004, 25 March 2004, http://www.lubreport.com/ e_article000241687.cfm?x=a2J5SCR,aW0j1gs. 15. Brad Rake, John Pohland, and Trico Mfg. Corp., “Microimprovement: advanced lubricants and nozzles improve fluid-mist systems,” Cutting Tool Engineering Magazine, May 2002, Volume 54, pp. 42–46. 16. Brad Rake, John Pohland, Trico Mfg. Corp., “Microimprovement: advanced lubricants and nozzles improve fluid-mist systems,” Cutting Tool Engineering Magazine, May 2002, Volume 54, pp. 42–46. 17. Christina Dunlap, “Should you try dry,” Cutting Tool Engineering Magazine, February 1997, Volume 49, pp. 42–46. 18. American Gear Manufacturers Association, “Overview of the Gear Industry,” http://www.agma.org. 19. Ariura, Y. and Umerzaki, Y., “High accurate hobbing with specially designed finishing hobs,” Gear Technology, November/December 2003, pp. 20–27. 20. Hazelton, J.L., “Gear Grinding 2003,” Gear Technology, November/December 2003, pp. 13–17. 21. Sroka, G. and Winkelmann, L., “Superfinishing gears — the state of the art,” Gear Technology, November/December 2003, pp. 28–37. 22. Britton, R.D., Elcoate, C.D., Alanou, M.P., Evans H.P., and Snidle, R.W., “Effect of surface finish on gear tooth friction,” Transactions of the ASME, January 2000, Volume 122, pp. 354–360.


23. Krantz, T.L. and Kahraman, A., “An experimental investigation of the influence of the lubricant viscosity and additives on gear wear,” Tribology Transactions, Volume 47, pp. 138–148. 24. Ali Erdemir, “Dry Film Lubrication,” STLE Chicago Section Lube School, 17–18 March, 2004, Argonne National Laboratory. 25. Weck, Hurasky-Schònwerth, and Bugiel, “Service behavior of PVD-coated gearing lubricated with biodegradable synthetic ester oils,” Gear Technology, November/December 2003, pp. 34–40. 26. Errichello, R., “Micropitting of gear teeth-a review of the literature, description of morphology and mechanism, and recommendation for prevention,” Copyright Geartech, 3/26/02. 27. Li, S., Devlin, M., Milner, J., Iyer, R., and Tze-Chi Jao, “Investigation of pitting mechanism in the FZG pitting test,” SAE Technical Paper Series, 2003-01-3233, Powertrain & Fluid Systems Conference Pittsburgh, PA, 27–30 October 2003. 28. Li, S., Devlin, M., et al., “Investigation of pitting mechanism in the FZG Pitting Test,” SAE 2003-01-3233, Powertrain and Fluid Systems Conference and Exhibition, Pittsburgh, PA, 27–30 October 2003. 29. Uneo, T., Ariura, Y., and Nakanishi, T., “Surface durability of case-carburized gears — on a phenomenon of gray-staining of tooth surfaces,” ASME paper, No. 80-C2/DET-27, The American Society of Mechanical Engineers, New York, 1980. 30. Cardis, A.B. and Webster, M.N., “Gear oil micropitting evaluation,” Gear Technology, September/October 2000, pp. 30–33. 31. Anon “Ceramic Bearings-an Engineered Solution”, http://www.timken.com/industries/superprecision/ceramics/. Copyright © 2004 The Timken Company. 32. Jessica Gorman, “Fracture protection: nanotubes toughen up ceramics,” Science News Online, Week, 2003, Volume 163, p. 3, Anon “Ceramic Bearings-an Engineered Solution”, http://www.sciencenews.org/articles/20030104/ fob1.asp. 33. Smith, Z. and Fletcher, M., “Gearing up with plastic,” Mechanical Engineering, Copyright 1998 by The American Society of Mechanical Engineers, http://www.memagazine. org/backissues/september98/. 34. Deirdra Barr and Ethyl Petroleum Additives Ltd., “Modern wind turbines: a lubrication challenge,” Machinery Lubrication Magazine, September 2002. 35. “Procedure for Qualifying Synthetic Base Gear Lubricant,” European Patent No. AU7709191, by Muyskens D.E., Newkirk J.E., Published 1991-11-28. 36. Facchiano, D.L. and Johnson, R.L., “An examination of synthetic and mineral based gear lubricants and their effect on energy efficiency,” Presented at the National Lubricating Grease Institute, 23–26 October 1983. 37. Bronshteyn, Lev A. and Kreiner, Jesa H., “Energy efficiency of industrial oils,” Preprint no. 99-AM-2. Presented at the 54th Annual Meeting, Las Vegas, NV. 23–27 May 1999. 38. Naruse, Chotaro., Nemoto, Ryozo., Haizuka, Shoui., and Yoshizaki, Masatoshi., “Influence of oil viscosity, chemical

39.

40.

41.

42. 43.

44. 45.

46.

47.

48.

49.

50.

51.

52.

53.

54.

55. 56. 57. 58.

oil structure, and chemical additives on friction loss of spur gears (concerning the influence of synthetic oil and mineral oil),” Tribology Transactions, 1994, Volume 37, pp. 358–368. Michaelis, K. and Hohn, B.L., Gear Research Center, and Technical University of Munich. “Influence of lubricants on power loss of cylindrical gears,” Tribology Transactions, 1994, Volume 37, pp. 161–167. Moore, L.D., Fels, D.R., Seay, A.B., Lopez, Harris, and Peck, “PAO-based synthetic lubricants in industrial applications,” Lubrication Engineering, January 2003, pp. 23–30. Alan Blahey, Doug Hakala, Bill Sweet, John Straiton, and Mariam Juves, “Improvements in industrial gearing efficiency through application of synthetic lubricants,” by permission of the authors and Imperial Oil. Ibid, page 1. Hope, K.D., Twomey, D., and Chevron Phillips, “Achieving enhanced oxidative stability for polyalphaolefins,” Presentation created 5 June 2001. United States Patent number US 6,703,356 B1, “Synthetic Hydrocarbon Fluids,” to Margaret M. Wu on 9 March 2004. United States Patent number US 4,827,064, “High Viscosity Index Synthetic Lubricant Compositions,” to Margaret M. Wu on 2 May 1989. United States Patent number US 20020193650A1, “Low NOACK volatility poly alpha-olefins,” to Maria Caridad B. Goze and Norman Yang on 19 December 2002. United States Patent Application Publication number US 2004/0018944A1, “Alkylated naphthalenes as synthetic lubricant base stocks,” to Margaret May-Som Wu and Phillip Trotto, published on 29 January 2004. Deirdra Barr, Ethyl Petroleum Additives Ltd., “Modern wind turbines: a lubrication challenge,” Machinery Lubrication Magazine, September 2002. American Gear Manufacturers Association, “AGMA 6006A03 standard for design and specification of gearboxes for wind turbines.” Errichello, R. “Another perspective: false brinelling and fretting corrosion,” Tribology and Lubrication Technology, 2004, Volume 60, pp. 34–37. Grega, G., “Synthetic-based lubricants provide coldweather protection,” 12 March 2004, Industrial Newsroom, Copyright © 2004 Thomas Publishing Company, http://www.industrialnewsroom.com/news/lubricants. Anon, “Washington mills reaps cost savings with synthetic lubricant,” Plant Engineering, http://www.manufacturing. net/ple/index.asp?doc_id=114162&layout=document. Anon, “Washington mills reaps cost savings with environmentally safe synthetic lubricant,” Canadian Industrial Equipment News, July 2003. Anon, Executive Summary Edited by Garth Harris, version 21 September 2002. “Pathways fro Natural Gas Into Advanced Vehicles” Nils-Olof-Nylund, 2003. Clean Air Power, www.cleanairpower.com. U.S. Dept of Energy, Energy Efficiency and Renewable Energy, www.eere.energy.gov. U.S. Alternative Fuels Data Center, www.afdc.nrel.gov. Edward J. Maginn, Dept of Chemical and Biomolecular Engineering, University of Notre Dame.


59. United Nations Environment Program, “Montreal protocol on substances that deplete the ozone layer,” Final Act, United Nations, 1987. 60. London meeting of the parties to the Montreal Protocol, June 1990. 61. Greg Mazuikiewicz, “Adding up the costs of higher SEER,” The Air Conditioning, Heating & Refrigeration News, 19 November 2001. http://www.achrnews.com/ CDA/ArticleInformation/coverstory/BNPCoverStoryItem/ 0,6152,67439,00.html 62. Richard A. Kelley, Business Manager, Hatco Corporation, Personal Interview, 6 May 2004. 63. Danfoss Compressors, “Practical application of refrigerant R 600a isobutane in domestic refrigerator systems,” Technical Bulletin CN.60.E2.02, November 2000. 64. Richard A. Kelley, Business Manager, Hatco Corporation, Personal Interview, 6 May 2004. 65. “Fluid power,” Design News, 4/7/2003, Volume 58, p. 44. 66. Mang, Theo, Dresel, Wilfried (eds). Lubricants and Lubrication. Vch Verlagsgesellschaft Mbh; 2001. 67. Norrby, Thomas, Environmentally adapted lubricants — where are the opportunities? Industrial Lubrication and Tribology, 2003, Volume 55, pp. 268–274. 68. Norrby Torbacke, T. and Kopp, M., Environmentally adapted lubricants in the Nordic marketplace — recent developments. Industrial Lubrication and Tribology, 2002, Volume 54, pp. 109–126. 69. Bevard, Darin S., “After the spill,” Grounds Maintenance, 2002, Volume 37, pp. G33–G36. 70. Cullen, David, “Cold comfort,” Fleet Owner, 2004, Volume 99, pp. 54–55. 71. Ehrenman, Gayle, “Use of synthetic fluid to spread,” Mechanical Engineering, 2003, Volume 125, pp. 22. 72. Stewart, Larry, “Filter innovations clean today’s fluids,” Construction Equipment, 1999, Volume 100, pp. 72–77. 73. Anderson, B., “Fluid analysis pays big dividends,” Hydraulics and Pneumatics, 2002, Volume 55, pp. 41–43. 74. Hitchcox, A.L., “Fluid formulations continue evolutionary improvements,” Hydraulics and Pneumatics, 1999, Volume 52, pp. 35–38. 75. Rajewski, T., Fokens, J., and Watson, M. “Development and application of synthetic food grade lubricants,” Industrial Lubrication and Tribology, 2000, Volume 52, pp. 110–116. 76. Redpath, Jim, “Keep it clean,” Construction, 2004, Volume 71, pp. 29–32. 77. Zink, M., “Match characteristics to application needs,” Hydraulics and Pneumatics, 2002, Volume 55, pp. 31–36. 78. Anon, Fluid Power “A plan for reliability data,” Design News, 2003, Volume 59, p. 44. 79. Placek, D., “Study examines multi-grade fluids for forestry equipment,” Hydraulics and Pneumatics, 2001, Volume 54, pp. 39–41. 80. Wangsgaard, M.F., “Keeping environmentally safe hydraulic fluids in their place,” Hydraulics and Pneumatics, 1999, Volume 52, pp. 39–44. 81. Biamonte, Jeffrey, “Selecting quality fluids,” Hydraulics and Pneumatics, 2003, Volume 56, pp. 52–54.

82. Duncan, C, Reyes-Gavilan, J, Costantini, D., and Oshode, S.J., “Ashless additives and new polyol ester base oils formulated for use in biodegradable hydraulic fluid applications,” STLE, 2002, pp. 18–29. 83. Duringhof, R., “Grease manufacturing by means of high concentrate saponification,” NLGI Spokesman, 1990, Volume 54, pp. 7–321 to 9–323. 84. Witte, A.C. and Colemann, R.L., “Method for continuous grease manufacture,” U.S. Patent 4,297,227, 18 January 1980. 85. Kay, J., “Stratco® contactor reactor economic analysis,” NLGI Spokesman, 2003, Volume 66, pp. 8–17. 86. Waynick, J.A., “Polyurea and calcium soap lubricating grease thickness system,” U.S. Patent 5,084,193, 28 January 1992. 87. Wunsch, F., “Noise characteristics of lubricating greases used for anti-friction bearings,” NLGI Spokesman, 1992, Volume 56. 88. Moehr, S., “Lubricating grease composition and preparation,” U.S. Patent 6,407,043, 18 June 2002. 89. Sullivan, Tim, “Airframe lubrication fit for service?,” Lubesn-Greases, 2002, Volume 8, pp. 20–23. 90. Hurley, S. and Cann, P.M., “Infrared spectroscopic characterization of grease lubricant films on metal surfaces,” NLGI Spokesman, 7 October 2000, Volume 64, pp. 13–21.


91. Hurley, S. and Cann, P.M., “Infrared spectroscopic analysis of a grease-lubricated rolling contact,” NLGI Spokesman, 2003, Volume 67. 92. Cann, P.M., “Friction properties of grease in elastohydrodynamic lubrication,” NLGI Spokesman, 2002, Volume 66, pp. 6–15. 93. John Eastwood, Martina Williams, Hans Ridderikhoff, and Uniqema Lubricants UK, “EC dangerous preparations directive application to greases and ingredients,” ELGI Eurogrease, July/August 2002, pp. 15–21. 94. Tim Sullivan, “Asia’s indpendents face dim outlook,” Lube Report, 16 March 2004, 25 March 2004, http://www.lubereport.com/e_article000239251.cfm? x=a2HdhY7,aW0j1gs. 95. Nancy DeMarco, “Shell: GTL taps will gush in 5 years,” Lube Report, 24 February 2004, 25 March 2004, http://www.lubereport.com/e_article000231367.cfm? x=a2DjWJL,aW0j1gs. 96. Nancy DeMarco, “Russia earmarks more oils for export,” Lube Report, 24 February 2004, 25 March 2004, http://www.lubereport.com/e_article000231377.cfm?x=a2 DjWJL,aW0j1gs. 97. Tim Sullivan, “U.S. lubes dipped in 2002,” Lube Report, 18 September 2003, 25 March 2004, http://www.lubereport. com/e_article000202976.cfm?x=a2mM17t,aW0j1gs, aW0j1gs.

47

Trends Toward Synthetic Fluids and Lubricants in Aerospace Carl E. Snyder, Jr. and Lois J. Gschwender CONTENTS 47.1 Liquid Lubricants 47.2 Hydraulic Fluids 47.3 Other 47.4 Developmental Synthetic Fluids and Lubricants References

Synthetic fluids and lubricants have been used in aerospace equipment for many years. Aerospace applications are very demanding on fluids and lubricants. The major reason that aerospace applications are so demanding is that there is such a concern about the weight associated with aerospace systems. Since significant costs are incurred with flying every pound of an aerospace system, all elements of every system are the smallest, lightest available. This results in minimum volumes of fluids and lubricants used, the smallest heat exchangers possible, smaller reservoirs, smaller pumps, actuators, etc. The result is that fluids and lubricants in aerospace applications are required to withstand extremely severe levels of stress since small volumes are used and must operate at high temperatures generated in the application as well as at extremely low temperatures in which aerospace equipment is required to operate. In general, the synthetic fluids and lubricants are required for aerospace applications due to the wide temperature range over which they must operate. In comparison, nonaerospace applications, which are generally not so concerned about the amount of fluid used or the overall weight of the system, which permits the use of large heat exchangers, if required, do not put as much demand on fluids and lubricants. However, as nonaerospace applications become more sophisticated and the synthetic fluids and lubricants become less exotic and more readily available at lower costs, synthetics will be more widely used. Different classes of synthetics have been used for different aerospace application areas. To better define the scope of aerospace applications, it must be recognized that the largest volume applications are in aircraft equipment. Although the excellent performance characteristics of synthetic fluids and lubricants have also resulted in their use in spacecraft, missiles, and satellites,


these volumes are significantly smaller and, therefore, not as well known or defined. The arrangement of the fluid classes discussed in this chapter will be based on the larger volume applications of the class of synthetics as a primary method of grouping. Lower volume applications will be mentioned as appropriate as they are being discussed. Most of the classes of synthetic lubricants covered in this chapter have been covered in detail in earlier chapters of this book. Therefore, references will be cited only when a specific class of synthetic lubricants is not covered elsewhere in this book or because the information is extremely important. The two major areas of application of synthetic fluids and lubricants are liquid lubricants, primarily as gas turbine engine lubricants, and hydraulic fluids. Applications involving synthetics that are of lower volume are greases, coolants, and inertial guidance damping fluids. This method of grouping is not meant to indicate that a critical, low volume application where a synthetic lubricant is the only choice is not equally, if not more, important.

47.1 LIQUID LUBRICANTS The application area in which the largest volume of liquid lubricants used in aerospace is gas turbine engine oils. The most widely used class of synthetic lubricants used as gas turbine engine oils is the ester class. Selection of esters is driven by their wide usable temperature range and their excellent thermo-oxidative stability in the presence of metals. The environment in which they are required to operate includes extremely low temperatures (down to −54◦ C), at which their viscosity must be low enough to permit the engines to start, as well as high bulk fluid temperatures (over to 200◦ C), at which they must provide lubrication

for the main shaft bearings in the engine. The ester-based lubricants used for the engine lubrication application are described in military specifications MIL-PRF-7808 [1] and MIL-PRF-23699 [2]. The MIL-PRF-7808 revision K describes Grade 3, a −54 to 177◦ C fluid, and Grade 4, a −51 to 204◦ C fluid [3]. MIL-PRF-23699 contains a 175◦ C standard grade (STD) oil, a 175◦ C corrosion inhibited (CI) oil and a 204◦ C higher temperature (HTS) grade. Materials conforming to these specifications are adequate to meet the lubrication requirements for most current aerospace gas turbine engines. However, in an attempt to improve the fuel efficiency of turbine engines and to meet the more severe operational requirements, higher operational temperatures are predicted for near-term advanced engines. It is anticipated that these requirements can be met by the successful development of improved ester-based lubricant formulations that will increase their upper temperature capability to 230◦ C. An on-going research program is underway to develop that “optimal ester”-based gas turbine engine oil. The term “optimal ester” was coined as it is the consensus of the aerospace fluid and lubricant community that it represents the widest temperature operational lubricant that can be developed from the ester chemistry. It will probably necessitate a relaxation of the lower temperature operational capability from −54 to approximately −40◦ C. This will require a careful balance of ester base stocks and improved additives to achieve the balance of viscosity– temperature properties and excellent thermo-oxidative stability as well as other requirements for a gas turbine engine lubricant. As discussed later, further advanced engine concepts will require utilization of different classes of synthetic lubricants. In addition to turbine engine lubrication, the esters are used in aerospace applications as low temperature greases, for example, MIL-PRF-23827 [4] gear oils, for example, DOD-L-85734 [5], and to some degree as instrument lubricants, for example, MIL-PRF-6085 [6]. When SR-71 aircraft engine operational temperatures exceeded the limits of ester-based lubricants, another class of synthetic lubricants with significantly higher high temperature stability was utilized. This class of synthetic lubricants is the polyphenylethers [7]. The liquid lubricant described in military specification MIL-PRF-87100 [8] has an upper operational temperature of 300◦ C. An improved version of MIL-PRF-87100 with an extension of the upper operational temperature to 320◦ C has been developed but not implemented. In addition, MIL-PRF-87100 has excellent fire resistance as demonstrated by a flash point in excess of 450◦ C and autogenous ignition temperature of 450◦ C. The major deficiency of the polyphenylether class of liquid lubricants is that they have extremely poor low temperature operational capability as they have pour points of +5◦ C and higher, limiting their lower temperature use temperature to +15◦ C. In addition, the current formulation described by the specification of these fluids has relatively poor lubricity characteristics compared with other classes


of liquid lubricants. These limitations, coupled with their high cost ($1000+ per gallon), have limited their use to applications in which no other liquid lubricants would function. As more efficient gas turbine engines operating at higher temperatures are developed, the polyphenylethers, either as MIL-PRF-87100 or as an advanced version of the specification, will find increased applications. When the capabilities of the polyphenylethers are exceeded or when liquid lubricants capable of operating not only at the elevated temperatures at which polyphenylethers operate but also at the more typically required low temperatures of −40◦ C and below, it is anticipated that the liquid lubricant of choice will be based on a perfluoropolyalkylether (PFPAE) [9]. Commercial versions of this class of synthetic lubricants that have the potential for providing a liquid lubricant capable operating over a −55 to 300◦ C temperature range are currently available. Research and development programs are currently underway to increase the upper temperature to at least 330◦ C. The major drawback of this class of synthetic lubricants is the lack of suitable additive technology. The chemical behavior of the PFPAE fluids is so different from other nonperfluorinated lubricants that the additives used to enhance the properties of other lubricants are not even soluble in PFPAE fluids. Up until a few years ago there were very limited examples of additives that are soluble in PFPAE fluids, and these were all specifically synthesized to be soluble in PFPAE fluids [10–12]. Although this class of fluids has very attractive and impressive properties as unformulated fluids, their true potential cannot be realized until a supporting technology base of performance improving additives has been developed. The types of additives required for PFPAE fluids to have properties appropriate for their use as liquid lubricants in aerospace applications are (1) metal deactivator/stability additive; (2) rust inhibitor additive; and (3) lubricity additive. Significant advances in additive technology for PFPAEs have been made in the last few years. A number of soluble, effective performance improving additives have been recently developed that will significantly improve their capabilities in the lubrication of mechanical equipment [13]. The PFPAE synthetics are used in oxidatively stable greases as described in military specification MIL-PRF-27617 [14]. Other potential aerospace applications for formulated PFPAE fluids include long life lubricants for space, instrument lubricants, and high temperature nonflammable hydraulic fluids.

47.2 HYDRAULIC FLUIDS Synthetic-based hydraulic fluids are widely used in aerospace. The nonsynthetic hydraulic fluid that the synthetics replaced in both commercial and military aircraft is described in specification MIL-PRF-5606 [15]. The reason

synthetic hydraulic fluids were developed to replace MILPRF-5606 was to provide increased fire safety. MIL-PRF5606 is a naphthenic mineral-oil-based hydraulic fluid that has proved to be an adequate aerospace hydraulic fluid from an operational aspect. However, the high flammability hazard associated with its use is well known [16]. The commercial aircraft industry recognized this hazard first and, in conjunction with the fluid industry, developed a fire resistant hydraulic system around the phosphate ester class of synthetics. It was necessary to develop an entirely new hydraulic system because the phosphate esters are not compatible with the same seals, paints, wiring insulation, etc. that are used in aircraft using a hydrocarbonbased hydraulic system. In addition, hydraulic system components had to be modified to provide optimum performance with the new phosphate ester-based hydraulic fluids. The phosphate ester hydraulic fluids are described in AS1241 [17]. The military community did not follow the commercial industry in the switch from MIL-PRF-5606 to phosphate esters. This decision was driven primarily by the noncompatibility of the phosphate esters with the aircraft systems and ground service equipment originally designed to use the hydrocarbon-based MIL-PRF-5606. In fact, mixing MIL-PRF-5606 and AS1241 hydraulic fluids resulted in gel formation causing excessive maintenance to correct the problem. In addition, the aggressive solvency of the phosphate esters toward seals, paints, and wiring insulation used in aircraft with hydrocarbon-oilbased hydraulic systems prevented their consideration as a retrofit option. The military conversion from MIL-PRF5606 to a fire resistant synthetic-based hydraulic fluid required that another new class of synthetic fluids be developed, that is, synthetic hydrocarbon fluids based on polyalphaolefins (PAOs). The synthetic hydraulic fluids based on PAOs are described in military specifications MIL-PRF-83282 [18] and MIL-PRF-87257 [19]. MILPRF-83282 was developed to replace MIL-PRF-5606 as a no-retrofit, drain and fill replacement. This required total compatibility with the materials used in MIL-PRF-5606 systems and with the MIL-PRF-5606 system designs. Most military aircraft were converted to MIL-PRF-83282 by the year 1985. The only aircraft for which the conversion was not approved were those for which acceptable operation at −54◦ C would be compromised by the higher viscosity of MIL-PRF-83282 at lower temperatures. MILPRF-83282 is described as a −40 to 204◦ C hydraulic fluid compared with −54 to 135◦ C for MIL-PRF-5606. MIL-PRF-87257, a −54 to 200◦ C PAO-based fire resistant hydraulic fluid with equivalent −54◦ C viscosity to MIL-PRF-5606, was developed to provide a fire resistant hydraulic fluid that would not compromise the low temperature operational use at −54◦ C. The successful validation of MIL-PRF-87257 has led to its use in U.S. Air Force aircraft [20,21] and small commercial aircraft.


MIL-PRF-87257, like MIL-PRF-83282, was designed to serve as a no-retrofit, direct replacement hydraulic fluid for MIL-PRF-5606. It is totally miscible with MIL-PRF-5606 and is compatible with MIL-PRF-5606 hydraulic system materials and design. A similar PAO-based hydraulic fluid containing rust inhibitors has been developed for use in ground vehicles [22]. The improved fire resistant properties of MIL-PRF-83282 and MIL-PRF-87257 over MIL-PRF5606, which have resulted in significant reductions in hydraulic fluid fire damage, include (1) higher flash and fire points; (2) higher autogenous ignition temperature; (3) lower flame propagation rate; and (4) improved resistance to gunfire ignition [16]. The conversion of aircraft from MIL-PRF-5606 to MIL-PRF-83282 was accomplished by both drain and fill and attrition methods, both of which were equally successful and without problem. The conversion of aircraft from MIL-PRF-5606 to MILPRF-87257 has been by attrition. Recent introduction of JP-8 fuel into the military to replace JP-4 has lessened the need for a −54◦ C hydraulic fluid since JP-8 is significantly inferior to JP-4 in low temperature flow characteristics. However a low temperature hydraulic fluid may still be required because of long, small diameter lines used in current aircraft hydraulic systems. Long, small diameter lines require relatively low viscosity fluids to permit flow and circulation, which is needed for hydraulic actuation. Other quite important but smaller volume applications of PAO are as greases, for example, MIL-PRF-81322 [23] and MIL-PRF-3204 [24], instrument lubricants, and liquid coolants [25]. The PAO-based greases provide excellent usable temperature range and good reliability with low maintainability requirements. MIL-PRF-32014 is superior to MIL-PRF-81322 because it is lithium soap thickened rather than clay thickened and has many corrosion resisting additives. The newer, MIL-PRF-32014 was recently developed to meet the operational requirements of the #1 bearing in the F-107 cruise missile engine. This grease is covered by the military specification MIL-PRF-32014. This grease has proven to be an excellent grease that has enabled the overhaul interval for the engine to be extended from 12 months, which was limited primarily by the poor hydrolytic stability of the previously used grease, to 60 months. Additionally, the engine overhaul depot reported that in most cases, at the 60-month overhaul period, the #1 engine bearing is cleaned, inspected, and relubricated with MIL-PRF-32014 and put back into service for an additional 60 months. In response to the excellent overall properties of MIL-PRF-32014, it is being considered as a multipurpose grease, which could potentially replace a number of older, outdated greases in the DoD inventory. This would be a significant improvement in our logistic situation, which now requires the availability of a wide number of greases for aircraft maintenance. It was sucessfully test flown for over two years on a C-5 aircraft and is being evaluated by the Navy for several aircraft with

wear and corrosion problems. Instrument lubricants based on PAO have successfully replaced the difficult to obtain paraffin-based mineral oil instrument lubricants previously used. A PAO-based coolant meeting the properties defined in MIL-PRF-87252 [26] has essentially replaced another class of synthetic fluids, the ortho-silicate esters, described in MIL-C-47220 as dielectric and liquid coolants in military electronic systems. MIL-PRF-87252 is also finding use in cooling mainframe computers and in other applications. In this case, it is replacing water–glycol coolants, eliminating the algae problem, and fluorinated coolants, greatly reducing cost and weight. The PAOs have excellent properties as lubricants and hydraulic fluids. Their compatibility with mineral oils and systems designed to use mineral-oil-based lubricants and fluids makes them excellent candidates for use in newly emerging aerospace systems. Replacing mineral oils is especially important when mineral-oil-based products are either difficult to obtain or no longer provide adequate performance. Both phosphate ester and PAO hydraulic fluids have been excellent hydraulic fluids, which, due to their fire resistant properties, have significantly reduced the hydraulic fluid fire hazards in both commercial and military aircraft. However, they are not nonflammable, but are capable of ignition if sufficient energy (temperature, flame, etc.) is available. With regard to current and future aircraft, high fire hazard areas where hydraulic fluids are used exist in brake systems, in which brake temperatures can approach 1600◦ C on an aborted take-off and around engine nacelles where the temperatures exceed 800◦ C. Both these conditions exceed the autogenous ignition temperatures and flash and fire points of both phosphate ester- and PAObased hydraulic fluids. As the costs of our aircraft and other aerospace systems continue to increase, it becomes even more important to minimize the possibility of losing these aircraft to hydraulic fluid fires. The development and validation of a completely nonflammable hydraulic fluid and compatible seals has been completed [27,28]. The synthetic hydraulic fluid is based on chlorotrifluoroethylene (CTFE) oligomers and is described in military specification MIL-H-53119 [29]. The CTFE-based hydraulic fluid is not compatible with hydraulic systems designed for use with other hydraulic fluids and therefore requires that hydraulic systems be designed around its unique properties. MIL-H-53119 is specified for use from −54 to 175◦ C and is compatible with a number of elastomeric seals. One of the major disadvantages of MIL-H-53119 is that it has significantly higher density, which results in a serious weight penalty for use in aerospace applications. In order to overcome this penalty, higher-pressure hydraulic components were developed and systems were designed and validated. At higher pressures, 55.2 MPa (8000 psi), the penalties associated with the higher density are minimized due to the extremely small volumes of hydraulic fluid required. If the weight penalty were not important,


MIL-H-53119 could be used at lower pressures and provide nonflammable hydraulic systems for a variety of application areas. MIL-H-53119, although fully demonstrated, has not yet been used. However, because it is essentially nonflammable and has been demonstrated to be a good operational hydraulic fluid, it will find applications in the future. Another important, but small volume, application for higher molecular weight versions of CTFE as well as for polymers of bromotrifluororethylene (BTFE) is as high density flotation/damping fluids for inertial guidance systems.

47.3 OTHER The only class of synthetic fluids that has been developed for quite some time and has not been discussed in this chapter is the silicones. The silicone class of synthetics has some very interesting properties, which would make it a serious candidate for a wide number of aerospace applications. The most important of those is the extremely good viscosity–temperature properties that silicone fluids possess, especially the polydimethylsiloxanes. However, the silicones also possess two less desirable properties that make them less useful for the two major volume applications in aerospace, that is, gas turbine engine lubricants and hydraulic fluids. The more significant deficiency is their inability to provide lubrication for steel-on-steel rubbing surfaces. Lubricity additives are generally not effective in silicones. This deficiency has limited their use as both liquid lubricants and hydraulic fluids, but in addition, another deficiency that limits their use as hydraulic fluids is their low bulk modulus, or high propensity for compressibility. This requires compensation in hydraulic system design in the form of larger actuators than would be required for less compressible fluids. The larger actuator would compensate for the “sponginess” of the fluid and would provide satisfactory service, but the weight of the hydraulic system would be significantly increased, which is unacceptable for aerospace applications. However, silicones have been used in a variety of greases [30] that are widely used in aerospace applications. Another member of the silicon containing class of synthetic fluids is the silicate ester class [7]. This class of synthetic fluids has had two areas of application, that is, wide temperature range hydraulic fluids and coolants. The original application of the silicate esters as a hydraulic fluid was as described in military specification MIL-PH-8446 [31]. This specification, which has been canceled due to lack of current systems requiring the fluid, described a hydraulic fluid for use over the temperature range of −54 to 204◦ C. The silicate esters were the most acceptable class of hydraulic fluids for that requirement. Silicate ester-based hydraulic fluids were used in the now retired B-58 and in the B-1 test aircraft and in the retired commercial supersonic aircraft, the Concorde. Their major deficiency was

their propensity to hydrolyze with moisture that got into the hydraulic system. The resulting hydrolysis products were an alcohol, which degraded the fire resistance of the fluid, and a gelatinous precipitate, that clogged system filters and the small orifices that exist in hydraulic systems, resulting in the need for high levels of maintenance. Similar hydrolysis problems were experienced with the silicate ester-based coolants, described in military specification MIL-C-47220 [32]. This problem with hydrolysis that resulted in a high level of maintenance has led to the substitution of the PAO-based coolant MIL-PRF-87252 for MIL-C-47220 in nearly all military aerospace applications.

47.4 DEVELOPMENTAL SYNTHETIC FLUIDS AND LUBRICANTS The synthetic fluids and lubricants discussed previously in this chapter have either found significant application in the aerospace industry or there is a significant production capability and potential applications have been identified. In this section, classes of newly emerging synthetic lubricants and fluids will be discussed as well as the properties that make them so promising. The first class of newly emerging synthetics is the silahydrocarbon, or tetralkylsilane, class. While this class of synthetics has been known for quite some time, their potential application in the aerospace industry had not been significantly advanced until recently [33]. The largest volume application for the silahydrocarbons is as wide temperature range, high temperature, and fire resistant hydraulic fluids. Their excellent viscosity–temperature properties make them excellent candidates as they can be used down to −54◦ C while still maintaining adequate viscosity at elevated temperatures to provide adequate film thickness for lubrication. Their excellent stability at temperatures up to 370◦ C permits their extended use at elevated temperatures. Since these fluids contain aliphatic carbon–hydrogen bonds, oxygen must be excluded at these elevated temperatures. Another very important aerospace application is liquid space lubricants [34–36]. Their excellent viscosity–temperature characteristics permit the selection of extremely high molecular weight (1000 to 1500 amu) silahydrocarbon fluids to be used. These fluids have extremely low volatility, which makes them excellent candidates for long life, noncontaminating liquid and grease lubricants for space. A third potential application of the silahydrocarbons is as a cryogenic coolant with a −150◦ C or lower low temperature capability. As with the other potential applications, silahydrocarbons are yet to be used for this application. Another class of synthetic fluids and lubricants, which are still in the stages of development, are the n-alkyl benzenes [37]. These fluids have excellent thermal stability and very good viscosity–temperature properties. One of


the advantages these fluids have over the PAO and silahydrocarbon classes for use at high temperature is their improved solubility for performance improving additives. The benzene ring appears to provide significant solubility enhancement for the typically polar performance improving additives, which are essential to provide the required performance. Their most promising aerospace application is as a wide temperature range, high temperature hydraulic fluid. The major obstacle in reducing them to the application is lowering the cost of production, while maintaining the wide liquid range stability. Future trends in aerospace synthetic fluid and lubricant development will be the development of more environmentally acceptable lubricants and fluids. There is significant interest in biodegradable hydraulic fluids and nontoxic rust inhibited fluids. Aerospace lubricants are generally more stable materials, which is usually contrary to good biodegradability. Because hydraulic fluids especially compose a significant percentage of the waste stream from operational bases and airports, emphasis has been placed on reduction of this waste stream. Fortunately MIL-PRF87252 and MIL-PRF-83282 are biodegradable to some extent. Military systems have long depended on rust inhibited hydraulic fluids for storage of aerospace hydraulic system components and as functional hydraulic fluids in military ground vehicles. MIL-PRF-6083 and MIL-PRF46170 are the rust inhibited versions of MIL-PRF-5606 and MIL-PRF-83282, respectively. Both of these fluids currently use a barium-based rust inhibitor and, since barium is now considered a toxic material, used MIL-PRF-6083 and MIL-PRF-46170 must be disposed of at great expense. Recently a study concluded operational fluid could be used for aircraft component storage in place of rust inhibited versions. Technical documents are being changed to reflect this finding.

REFERENCES 1. MIL-PRF-7808L Military Specification, Lubricating Oil, Aircraft Turbine Engine, Synthetic Base, NATO Code Numbers 0-148 (Grade 3) and 0-163 (Grade 4) (2 May 1997). 2. MIL-PRF-23699F, Military Specification, Lubricating Oil, Aircraft Turbine Engine, Synthetic Base, NATO Code Number 0-156 (21 May 1997). 3. Gschwender, L.J., Snyder, C.E., Jr., and Beane,G.A., IV, “Military Aircraft 4-cSt Gas Turbine Engine Oil Development,” Lubr. Eng., 43, 654–659 (1987). 4. MIL-PRF-23827C(1) Military Specification, Grease, Aircraft and Instrument, Gear and Actuator Screw, NATO Code Number G-354 (19 June 2002). 5. DOD-PRF-85734, Lubricating Oil, Helicopter Transmission System, Synthetic Base (29 June 2004). 6. MIL-PRF-6085D Military Specification, Lubricating Oil: Instrument, Aircraft, Low Volatility (20 February 1998). 7. Gunderson, R.C. and Hart, A.W., Eds., Synthetic Lubricants, Reinhold Publishing Co., New York (1962); Joaquim, M.,

8.

9.

10.

11.

12.

13.

14.

15.

16.

17.

18.

19.

20.

21.

22.

“Polyphenyl Ether Lubricants,” in Synthetic Lubricants and High-Performance Functional Fluids, L.R. Rudnick and R.L. Shubkin, Eds., Marcel Dekker (1999); Hamid, S., “Polyphenyl Ether Lubricants,” in Synthetics, Mineral Oils and Bio-Based Lubricants: Chemistry and Technology, L.R. Rudnick, Ed., Marcel Dekker, 2005 (this volume). MIL-PRF-87100A, Military Specification, Lubricating Oil, Aircraft Turbine Engine, Polyphenyl Ether Base (28 November 1997). Snyder, C.E., Jr. and Gschwender, L.J., “Fluoropolymers in Fluids and Lubricant Applications,” I & EC Prod. R & D, 22, 383–386 (1983). Tamborski, C. and Snyder, C.E., Jr., “Perfluoroalkylether Substituted Aryl Phosphines and Their Synthesis,” U.S. Patent 4,011,267 (8 March 1977). Tamborski, C. and Snyder, C.E., Jr., “Perfluoroalkylether Substituted Phenyl Phosphines,” U.S. Patent 4,454,349 (12 June 1984). Sharma, S.K., Gschwender, L.J., and Snyder, C.E., Jr., “Development of a Soluble Lubricity Additive for Perfluoropolyalkylether Fluids,” J. Synth. Lubr., 7, 15–23 (1990). Gschwender, L.J., Snyder, C.E., and Fultz, G.W., “Soluble Additives for Perfluoropolyalkylether Liquid Lubricants,” Lubr. Eng., 49, 702–708 (1993). MIL-PRF-27617F, Military Specification Grease, Aircraft and Instrument, Fuel and Oxidizer Resistant (17 February 1998). MIL-PRF-5606H(1), Military Specification, Hydraulic Fluid, Petroleum Base; Aircraft, Missile and Ordnance, NATO Code Number H-515 (23 July 2003). Snyder, C.E., Jr., Krawetz, A.A., and Tovrog, T., “Determination of the Flammability Characteristics of Aerospace Hydraulic Fluids,” Lubr. Eng., 37, 705–714 (1981). AS 1241B, “Fire Resistant Phosphate Ester Hydraulic Fluid for Aircraft,” Society of Automotive Engineers, 400 Commonwealth Dr., Warrendale PA 15096 (18 February 1992). MIL-PRF-83282D(1) Military Specification, Hydraulic Fluid, Fire Resistant, Synthetic Hydrocarbon Base, Aircraft, Metric, NATO Code Number H-537 (1 December 1997). MIL-PRF-87257B Military Specification, Hydraulic Fluid, Fire Resistant; Low Temperature, Synthetic Hydrocarbon Base, Aircraft and Missile, NATO Code Number H-538 (22 April 2004). Gschwender, L.J., Snyder, C.E., and Fultz, G.W., “Development of a −54◦ to 135◦ C Synthetic Hydrocarbon-Based, Fire-Resistant Hydraulic Fluid,” Lubr. Eng., 42, 485–490 (1986). Gschwender, L.J., Snyder, C.E., and Sharma, S.K., “Pump Evaluation of Hydrogenated Polyalphaolefin Candidates for a −54◦ C to 135◦ C Fire-Resistant Air Force Aircraft Hydraulic Fluid,” Lubr. Eng., 44, 324–329 (1988). Alvarez, R.A., Wright, B.R., and Phillips, G.L., “Final Report on Technology Demonstration of Single Hydraulic


23.

24. 25.

26.

27.

28.

29.

30.

31. 32. 33.

34.

35.

36.

37.

Fluid for Armored Ground Vehicle Systems,” U.S. Army Interim Report, TFLRF No. 306, AD A312088 (1996). MIL-PRF-81322G Military Specification, Grease, Aircraft, General Purpose, Wide Temperature Range (24 January 2005). MIL-PRF-32014 Grease, Water Resistant, High Speed, Aircraft and Missile (29 September 1997). Gschwender, L.J., Snyder, C.E., Jr., and Conte, A.A., Jr., “Polyalphaolefins as Candidate Replacements for Silicate Ester Dielectric Coolants in Military Applications,” Lubr. Eng., 41, 221–228 (1985). MIL-PRF-87252C Military Specification, Coolant Fluid, Hydrolytically Stable, Dielectric, NATO Code No. S-1748 (24 October 97). Gschwender, L.J., Snyder, C.E., Jr., VanBrocklin, C.H., and Warner, W.E., “Chlorotrifluoroethylene Oligomer Based Nonflammable Hydraulic Fluid, I Fluid, Additive and Elastomer Development,” J. Syn. Lubr., 9, 188–203 (1992). VanBrocklin, C.H., Gschwender, L.J., Snyder, C.E., Sharma, S.K., and Campbell, W.B., “Chlorotrifluoroethylene Oligomer Based Nonflammable Hydraulic Fluid, II Hydraulic Component Development,” J. Syn. Lubr. 9, 299–309 (1992). MIL-H-53119 Military Specification, US Army, Hydraulic Fluid, Nonflammable, Chlorotrifluoroethylene Base (1 March 1991). MIL-G-25013E Military Specification, Grease, Aircraft, Ball and Roller Bearing, NATO Code Number G-372 (28 October 1991). MIL-H-8446B Military Specification, (Canceled) Hydraulic Fluid, Nonpetroleum Base, Aircraft (16 July 1959). MIL-C-47220B Military Specification, (cancelled) USAF, Coolant Fluid, Dielectric (13 January 1995). Snyder, C.E., Gschwender, L.J., Tamborski, C., Chen, G., and Anderson, D.R., “Synthesis and Characterization of Silahydrocarbons — A Class of Thermally Stable Wide Liquid Range Functional Fluids,” ASLE Trans., 25, 299–308 (1982). Paciorek, K.J.L., Shih, J.G., Kratzer, R.H., Randolph, B.B., and Snyder, C.E., Jr., “Polysilahydrocarbon Synthetic Fluids I. Synthesis and Characterization of Trisilahydrocarbons,” I & EC Prod. R & D, 29, 1855–1858 (1990). Snyder, C.E., Jr, Gschwender, L.J., Randolph, B.B., Paciorek, K.J.L., Shih, J.G., and Chen, G.J., “Research and Development of Low Volatility Long Life Silahydrocarbon Based Liquid Lubricants for Space,” Lubr. Eng., 48, 325–328 (1992). Gschwender, L.J., Snyder, C.E., Jr., Massey, M., and Peterangelo, S., “Improved Liquid/Grease Lubrication for Space Mechanisms,” Lubr. Eng., 12, 25–31 (2000). Gschwender, L.J., Snyder, C.E., Jr., and Driscoll, G., “Alkyl Benzenes — Candidate High-Temperature Hydraulic Fluids,” Lubr. Eng., 46, 377–381 (1990).

48

Commercial Developments R. David Whitby CONTENTS 48.1 Introduction 48.2 Demand for Synthetic Lubricants 48.3 Economic Comparison of Synthetic Lubricants 48.3.1 Advantages and Disadvantages of Different Synthetic Oils 48.3.2 Balancing Conflicting Performance Requirements 48.3.3 Costs and Cost Comparisons 48.4 Developments in the Synthetic Lubricants Business 48.5 End-Use Markets for Synthetic Lubricants 48.5.1 Automotive Lubricants 48.5.1.1 Gasoline and Diesel Engine Oils 48.5.1.2 Motorcycles and Outboard Engines 48.5.1.3 Transmissions and Gearboxes 48.5.1.4 Automatic Transmissions 48.5.1.5 Brake Fluids 48.5.1.6 Automotive Air-Conditioning 48.5.1.7 Automotive Greases 48.5.2 Compressor Oils 48.5.2.1 Air and Gas Compressors 48.5.2.2 Natural Gas Compressors 48.5.2.3 Refrigeration Compressors 48.5.3 Turbine and Hydraulic Oils 48.5.3.1 Steam Turbine Oils 48.5.3.2 Gas Turbines Oils 48.5.3.3 Hydraulic Fluids 48.5.4 Gear, Circulating, Process, and Functional Oils 48.5.4.1 Circulation Systems 48.5.4.2 Gears 48.5.4.3 Bearings 48.5.4.4 Heat Transfer Oils and Solar Fluids . 48.5.4.5 Electrical and Insulating Oils 48.5.4.6 Cable Compounds 48.5.4.7 Oil-Based Drilling Fluids 48.5.4.8 Circuit Board Fluxes 48.5.4.9 Mould Release Agents 48.5.5 Metalworking Fluids 48.5.5.1 Water-Miscible Cutting Fluids 48.5.5.2 Neat Cutting Oils 48.5.5.3 Steel, Aluminium, and Copper Rolling Oils 48.5.5.4 Stamping, Pressing, and Forming Oils 48.5.5.5 Wire and Tube Drawing Lubricants 48.5.5.6 Aluminium Can Stock and Can Drawing Fluids 48.5.5.7 Heat Treatment (Quenching) Fluids 48.5.6 Other Industrial Lubricants 48.5.6.1 Textile Lubricants


48.6

48.5.6.2 Wire Rope, Chain, and Chainsaw Lubricants 48.5.6.3 Food Grade Oils 48.5.7 Greases 48.5.8 Aviation Lubricants 48.5.8.1 Civil Aviation Lubricants 48.5.8.2 Military Aviation Lubricants Future Trends

48.1 INTRODUCTION

48.2 DEMAND FOR SYNTHETIC LUBRICANTS

The last 15 yr has witnessed the transition of synthetic lubricants from a niche segment of some industrial applications to a mainstream segment of the whole lubricants industry. It has now become impossible to discuss the international lubricants business without including a discussion of synthetic lubricants. The first commercially used synthetic lubricants were silicones, developed by Dow Corning and General Electric in 1943. Then followed polyalkylene glycols, in 1945, developed by Union Carbide, diesters in 1951, phosphate esters in 1953, and polyol esters in 1963. Many of the early applications for synthetic fluids were in U.S. military equipment, notably gas turbines, hydraulic systems and instruments. Demanding service conditions required higher levels of performance than were possible using conventional mineral oils, even with performance enhancing additives. Amsoil Corporation introduced the first API-rated fully synthetic engine oil in 1972, although Agip had launched a part-synthetic motor oil, Sint 2000, in Italy in 1969. Mobil 1 was launched as the first worldwide fully synthetic engine oil in 1977. When it was launched, Mobil claimed that the oil improved fuel economy, reduced oil consumption, allowed faster cold-weather starting, kept engines cleaner, and provided better engine protection. Synthetic lubricants are now used in more than 70 applications, in gasoline and diesel engines, aviation and industrial gas turbines, gear and transmission systems, compressors, hydraulic systems, heat transfer systems, air conditioning, metalworking fluids, food contact industries, and greases. While the higher cost of synthetic fluids has previously been perceived as a barrier to their wider use, it is now more generally accepted that the performance benefits provided often outweigh the higher cost, particularly in applications for which higher lubricity, lower volatility, better biodegradability, lower toxicity, or wider operating range are important factors. As a result, it is now recognized that, while overall worldwide demand for lubricants is likely to remain relatively static, demand for synthetic lubricants is likely to increase at between 5 and 7% per year. This inevitably means that demand for mineral oil-based lubricants is likely to fall over the next five to ten years.

The conventional definition of a synthetic baseoil is one that has been chemically synthesized from distinct discrete chemical components. It is, therefore, easy to see that polyalphaolefins (PAOs) are synthetic because they have been synthesized from ethylene via 1-decene and that polyalkylene glycols (PAGs) are also synthetic because they have been synthesized from ethylene or propylene and alcohols via ethylene oxide and/or propylene oxide. Mineral baseoils, on the other hand, are made by physically removing or chemically altering the undesirable components present in vacuum distillation residues derived from crude oil. These definitions of synthetic have, however, been thrown into considerable confusion by Shell’s development of the Middle Distillate Synthesis Process, now being used commercially in Bintulu in Malaysia. The process makes paraffin waxes, as part of a process to make very clean diesel, kerosene, and other distillates from natural gas, which Malaysia has in abundance. Some of the paraffin wax is now being shipped to Shell’s lubricants refinery in Yokkaichi, Japan, where it is converted into very high viscosity index (VHVI, API Group III) baseoils using the company’s wax isomerization process. The composition and properties of these VHVI baseoils are identical to those of the VHVI baseoils produced from crude oil by Shell at Petit Courrone. But, according to the conventional definitions, the Yokkaichi VHVI baseoils are synthetic, because they have been synthesized from natural gas. Much discussion between oil, chemical, additive, and lubricant end-user companies, about what is synthetic and what is not, over the last five years has yet to reach a definitive conclusion. However, a consensus is beginning to emerge that, for lubricants, “synthetic” is a marketing term that helps to define a level of lubricant performance. In the United States, the API and the SAE have decided not to technically define the term synthetic, but to define the properties, performance, and manufacturing processes of each type of baseoil. For users of lubricants, what is important is the performance and suitability of the lubricant, not whether it has been made by one process or another. According to some industry analysts, synthetic lubricants, however they are defined, were forecast to account


for more than 5% of the total lubricants market by 2000. In reality, by the beginning of 2003, fully synthetic lubricants accounted for around 7.8% of the market in Western Europe and part-synthetic lubricants accounted for another 21.4%. (Total synthetic baseoil demand was almost 19% of the Western European lubricants market.) Synthetic and VHVI (API Group III)-based lubricants already accounted for almost 5% of the North American lubricants market and around 3% of the lubricants market in other regions of the world. Total worldwide demand for synthetic and VHVI/Group III baseoils amounted to over 1.8 million tonnes in 2002, or around 4.9% of global lubricant demand. Other chapters in this book have described and reviewed the main types of synthetic fluids, and have summarized the volumes of each type of fluid sold each year, so a comprehensive breakdown of the volumes of each type of fluid sold is not attempted in this section. However, the main types of “synthetic” fluids, by market volume, are polyalphaolefins (PAOs), esters (of all types), polyalkylene glycols (PAGs), polybutenes (PIBs) and, of course, VHVI/Group III mineral oils. Pathmaster Marketing’s estimates of the volumes of synthetic baseoils used in lubricants in Western Europe are shown in Table 48.1.

48.3 ECONOMIC COMPARISON OF SYNTHETIC LUBRICANTS 48.3.1 Advantages and Disadvantages of Different Synthetic Oils Each of the different synthetic oils described in this book have their good points and their poor points. Some good

points are better than others, some worse. A number of the more important advantages and disadvantages of each type of synthetic oil are described in their respective chapters. Whether any specific advantage or disadvantage is important will depend on the application for which the lubricant is to be used. In general, highly desirable lubricant properties that are generally advantageous are: • • • • • • •

Good inherent lubrication properties Good low-temperature properties Good high-temperature properties Good viscosity/temperature properties Low volatility Good stability Low toxicity

In some applications, an apparently inferior performance might turn out to be a positive advantage. Examples include: • The incompatibility of some PAGs with mineral hydro-

carbons enables them to be used in natural gas compressors. • The thermal depolymerization of polyisobutenes enables them to be used in clean-burning two-stroke oils. • The chemical structure of diesters that gives them poor hydrolytic stability also means that they are readily biodegradable. The most important consideration in assessing comparative advantages and disadvantages is that, if a specific application does not require a particular performance property, then a synthetic oil that performs well in that

TABLE 48.1 Estimated Consumption of Synthetic Baseoils in Western Europe, 1990 to 2002 Estimated consumption (000 tonnes) Synthetic type Polyalphaolefins Esters Polyisobutenes Polyalkylene glycolsa Phosphate esters Alkyl benzenes Others Total

1990

1996

1998

2000

2001

2002

45 45 22 15 4 8 6

90 55 28 18 4 9 8

125 90 38 23 5 11 9

190 110 46 25 5 11 10

220 120 50 25 5 11 11

220 125 52 26 5 11 11

145

212

301

397

442

450

a PAG content only.

Source: Pathmaster Marketing.


respect will not have any added value for that application. Conversely, if the synthetic oil performs poorly, then, for that application, it will not matter anyway.

Successfully determining the correct level of costeffective performance is usually achieved by obtaining realistic answers to the following questions:

48.3.2 Balancing Conflicting Performance Requirements

• • • • •

The lubrication chemist’s task in formulating a costeffective lubricant to perform a specific function is not easy. In many cases, a large number of performance requirements, some of which may conflict, will need to be satisfied. Previous chapters have described the range of tests available, both standard and specific, under: • • • • •

User specifications Laboratory tests Rig and bench tests Quality control tests Quality assurance and acceptance tests

There are literally hundreds of examples of potentially conflicting requirements that need to be balanced when formulating a lubricant. A few illustrations will suffice to explain the problem: • Blending a diester with a PAO to improve the latter’s

•

•

•

•

seal swell properties in automotive engine oil tests is likely to detract from the excellent hydrolytic stability characteristics. Polyisobutenes are very shear stable and can be used to make very good gear oils, but their low-temperature properties make them unsuitable for use in outdoor gearboxes in cold climates. Using VI improvers in conventional mineral oils can be a cheap way to enhance the viscosity/temperature properties, but at the expense of overall shear stability properties. Water-based hydraulic fluids generally have excellent fire-resistant properties, but cannot be used at operating temperatures much above 60◦ C or much below about 5◦ C. Water-miscible cutting fluids that contain soluble polymer load-carrying and extreme-pressure additives can have lubricating properties close to those of mineral oil cutting fluids, but at the expense of significantly higher monitoring and maintenance costs.

Many users of experience have shown that the task of formulating a finished lubricant is analogous to producing a perfectly round inflated balloon; if you try to push in any small bump on one part of the balloon’s surface, another bump is likely to appear somewhere else on the surface! Push too hard and the result might not be the desired one.


What performance does my customer want? What performance will satisfy my customer’s needs? How much is my customer willing and able to pay? Can this performance be achieved at this cost? What aspects of performance can be sacrificed to meet a cost limit? • Will I still be able to make a profit? Finding these answers is not always easy. Often, it requires a genuine partnership between lubricant supplier and user. Fortunately, with original equipment manufacturers (OEMs), industrial and military users, such partnerships are becoming more usual. It is particularly important to remember at all times that the only true test of a lubricant’s performance is whether it functions satisfactorily for several years in the machinery for which it was formulated. Lubricant specifications, laboratory tests, rig tests, and field trials are only useful as a guide or prediction of likely performance in service. Ultimately, there is no universal short-cut to the dilemma of balancing the conflicting requirements. This is where the expertise, experience, and dedication of the lubricant supplier provides a great deal of added value.

48.3.3 Costs and Cost Comparisons The current costs of various types of mineral and synthetic baseoils are listed in Table 48.2, which also lists their relative costs compared with 150 solvent neutral Group I mineral baseoil. We should emphasize strongly that these prices are averaged list prices in Europe for unformulated baseoils only, and do not reflect the volume discounts that some suppliers are able to offer their long-term customers. Also, the prices and their comparisons change from month to month, particularly with changes in the prices of Group I baseoils. The prices of synthetic oils tend to vary less with time than those of mineral oils, which are more directly dependent on the price of crude oil. When comparing the costs of different fluids, will a user of a PAG get six times the performance compared to a mineral oil? Is a polyol ester about nine times better than a mineral oil or a PAO almost twice as good as a Group III baseoil? Fortunately, these comparisons are highly misleading. First, for many applications, large quantities of additives need to be added to mineral oils to bring their performance to a satisfactory level. This adds significantly to the total cost. Second, there are a number of other costs that need to be considered when attempting to compare performance.

TABLE 48.2 Western European List Prices for Lubricant Baseoils, March 2004 Fluid Group I baseoils Group III (VHVI) baseoils Group III+ (XHVIa ) baseoils Polyalphaolefins Polyalkylene glycols Polybutenes Diesters Polyol esters Phosphate esters Alkyl benzenes

List price ($/ton) 370 600–700 900–1000 1400–1500 2200–2450 950–1750 2300–3500 3000–4000 3750–5250 1350–1450

Price relative to 150 SN 1.0 1.6–1.9 2.4–2.7 3.8–4.1 6.0–6.6 2.6–4.7 6.2–9.5 8.1–10.8 10.1–14.2 3.6–3.9

a XHVI is a registered Shell trademark.

Source: Pathmaster Marketing, from industry discussions.

These include: Immediate costs

Baseoils Additives and components Blending and storage Transportation and distribution Field trials Sales Marketing

Hidden costs

Formulation Laboratory testing Rig and specification testing Monitoring Servicing Collection Disposal

A more realistic comparison of cost as regard performance would be in the price paid by the user. Although this depends on all the factors that we identified earlier, it is likely to be a more accurate guide to comparative performance. In these terms, the most readily obtainable price comparisons are those for retail motor oils sold on garage forecourts and DIY shops. Currently, average price comparisons for a number of automotive oil types on sale from the major oil companies in the United Kingdom and Germany are shown in Table 48.3. Clearly, the U.K. market believes that a fully synthetic 0w40 gasoline engine oil will be able to provide 7.1 times the performance of a 20w50 mineral oil product for certain demanding applications in high-performance cars. Conversely, in Germany, the market is only willing to pay 2.9 times the price for the fully synthetic 0w40 oil, although the basic product is a 15w40 grade in Germany, while it is still a 20w50 grade in the United Kingdom. Many manufacturers of synthetic oils produce tables that attempt to compare the performances of various types of oils in a range of tests. These tables, too, can be misleading. The quoted tests are usually selected very carefully to


TABLE 48.3 Motor Oil Price Comparisons in the United Kingdom and Germany, May 2004 Price ratio compared to lowest cost product Product

UK

Germany

Gasoline engines 20w50 Mineral oil 15w40 Mineral oil 10w40 Part-synthetic 5w40 Synthetic 0w40 Synthetic

1.0 2.6 3.8 5.9 7.1

— 1.0 1.8 2.5 2.9

Diesel engines 15w40 Mineral oil 10w40 Part-synthetic

2.0 4.1

1.2 1.8

Source: Pathmaster Marketing.

show the particular manufacturer’s product(s) in the best possible light. The use of ticks, crosses, plus signs, and minus signs to indicate good or poor performance is an oversimplification that does not provide qualitative comparisons. Even replacing ticks and crosses with relative numbers does not help much. Is a mineral oil’s hydrolytic stability five times better than that of a diester? Does a PAG lubricate 2.5 times better than a silicone oil? The answer usually depends on which test you do and how you measure the result. In any case, the proper answer is the comparative overall performance of each of the lubricants in the practical application. Attention to what the customer needs is the key to assessing comparative performance.

48.4 DEVELOPMENTS IN THE SYNTHETIC LUBRICANTS BUSINESS The synthetic lubricants business has been progressing steadily since the late 1970s and early 1980s, when chemical companies became interested in the commercial potential of speciality products that could command high prices. At that time, it was not well recognized that the costs of most synthetic lubricants are tied to the prices of bulk chemical feedstocks such as ethylene, propylene, and naphtha, which in turn are linked to the price of crude oil and natural gas. It was an unfortunate coincidence that shortages of chemical feedstocks occurred in 1987 and 1988, pushing ethylene and some derivative prices to very high levels and bulk PAOs to nearly $2000 per ton. As a result of pricing swings, the price ratio of PAOs to mineral baseoils, for example, has varied between 3.5 and 7.0 to 1 during the 1990s. The lesson has been that the lubricants industry

need to understand the driving forces in synthetic lubricant production and pricing, while the chemical industry needs to understand the economics of the baseoil industry, which has remained linked to crude pricing for 30 yr. Only the VHVI/Group III baseoils have been able to break this pattern. Automotive lubricants have seen by far the biggest increase in synthetic fluid use in the 1990s. Increased sales of part-synthetic oils has lead to significant increases in demand for both PAOs and diesters from lubricants blenders. Sales of Group III baseoils are booming. The pattern started in Europe in the mid-1980s and has now spread to all regions of the world, as lubricant marketers recognized the commercial gains possible from a “good/better/best” range of automotive engine oils. Although synthetics have been used for many years in the industrial markets, steady growth is still being experienced for PAOs, PIBs, PAGs, and esters, particularly in compressors, bearings, gears, and circulation systems and for fire-resistant hydraulics and metalworking applications. Esters are emerging as the dominant technology for biodegradable lubricants, as used in forestry, waterways, and construction. Phosphate esters are making a comeback against polyol esters in fire-resistant hydraulic fluids, but the long-term position of polyglycols in brake fluids is uncertain, with the introduction of DOT 4 and DOT 5.1 fluids. The technical understanding of the properties of synthetic lubricants has been increasing for some years. Some applications have been lost by one synthetic, but gained by another. Where demonstrable advantages can be assessed, for example, in high-performance compressors, there is a solid acceptance at all levels, from OEMs, lubricant companies, and customers. This is the key to success. If any of the three elements of consensus are missing, there is only disappointment and frustration. The market penetration of synthetic fluids received a major boost in the 1980s from the introduction of the NOACK volatility test and is now receiving a second boost from biodegradability and toxicity issues, generally summarized as environmental benefits. Consolidation and focus has also begun to emerge in the synthetic lubricants business. Hatco purchased the industrial synthetic lubricants business of Hüls, including the Anderol, PQ, and Aosyn brand names, in September 1996. The company then purchased Royal Lubricants, the aviation and military lubricants business of Shell Oil, in November 1996. Hatco, which has manufactured and marketed ester fluids for many years, has announced that it will operate its synthetic industrial lubricants business under the Anderol brand and its aviation and military synthetic lubricants business under the Royal brand, for the foreseeable future. Amoco Chemicals purchased the PAOs business of Albemarle Corporation in January 1996. Albemarle had


decided to focus on its core α-olefins business, while Amoco had recognized that PAOs would be a strategic fit with its lubricants business. In the early 1990s, no oil company that manufactured VHVI oils had a chemical division that made PAOs or esters, while no chemical company that manufactured PAOs or esters was owned by an oil company that made VHVI baseoils. By the end of 1997, this situation had begun to change radically. BP purchased Amoco, then Arco, then Castrol and merged all the lubricants activities under the BP and Castrol brands. ExxonMobil Oil makes Groups II and III baseoils and ExxonMobil Chemical makes PAOs and esters, as does Fortum Oil/Fortum Chemical and ChevronTexaco Oil/ChevronTexaco Chemical. Crompton (previously Uniroyal) also announced a progressive 50% increase in its high viscosity PAO manufacturing capacity in July 1996, in response to increasing market demand. It has become evident that the performance advantages of synthetic lubricants are becoming understood and accepted by the market, and that synthetic fluids are becoming integrated into the strategic business plans of the majority of lubricants manufacturers and marketers. This is a significant commercial advance from the situation only 20 yr ago, and is unlikely to stop now.

48.5 END-USE MARKETS FOR SYNTHETIC LUBRICANTS The range of current and potential applications for synthetic lubricants is huge. In order to cover the subject in some systematic way, we will group the applications into the following areas: • • • • • • • •

Automotive lubricants Compressor oils Turbine and hydraulic oils Gear, circulating, and process oils Metalworking fluids Other industrial lubricants Greases Aviation lubricants

In total, within these sectors, some 70 end uses for synthetic oils have been identified. In some applications, only synthetic fluids are used, primarily due to some performance limitation or other demonstrated by conventional mineral oils. These applications include automotive air conditioning units, brake fluids, a number of different types of gas compressor lubricants, fire-resistant hydraulic fluids, electro-hydraulic fluids, aviation gas turbine oils, electrical cable oils, chain lubricants, and aviation greases. In most other markets, synthetic fluids are used for the demanding, high-performance applications in which the performance of mineral oils is inadequate.

48.5.1 Automotive Lubricants 48.5.1.1 Gasoline and diesel engine oils The drivers for changes to engines are government regulations, on fuel economy, emissions, noise, and recycling, coupled with consumer needs for affordability, performance, driveability, durability, and styling. These drivers lead to changes in engine, fuel, lubricant and other material technologies. Regulatory compliance is now regarded as an entry price for vehicle manufacturers, while meeting consumer’s desires is seen as the way to product differentiation, increased market share, and higher profits. The changes in engine design technology are typified by General Motors’ “World Engine,” introduced in 2000. About 800,000 of these engines are being built in both North America and Europe, in multiple configurations of four cylinder, double overhead camshaft, with 2 and 4 valve per cylinder variants in 1.8, 2.0, and 2.2 L capacities. The development costs were around $1.3 billion. At the same time, the Toyota D-4 engine was engineered for improved performance with ultra-low fuel consumption, higher output, quicker response, and lower emissions. It has high pressure, fuel swirl, direct injection, helical intake ports, variable valve timing, exhaust gas recirculation, and NOx storage reduction catalysts. The replacement of current tests for proof of performance testing and the development of the next engine oil specifications (ILSAC GF-4, API PC-10, and ACEA 04) are the main issues at present. The GF-4 requirements were proposed toward the end of 2001, as a follow-on to the GF-3 specification, to reduce emissions, to protect emission control systems, to further improve fuel economy, and to give protection during extended drain intervals. GF-4 oils are required to be backwards compatible with GF-3 and earlier oils, to have maximum phosphorous and sulfur contents, to have even lower viscosities (5w20) and to provide better wear performance in roller cam followers. GF-4 oils were originally required for 2004 model year cars and the specification definition, tests and test limits were the first trial of a new system of cooperation between OEMs, oil companies and additive manufacturers. Although matrix testing started in June 2002, it was quickly realized that the time schedule was too tight, so the target introduction was revised to 2005 model year cars. Agreement on test limits was achieved in July 2003 and the final GF-4 specification was released in January this year. Product formulation, development, and testing has been done since then and the date for first API licensing has been set for July 31, 2004, so that oils will be available for motorists toward the end of the year. Licensing of GF-3 oils in the United States will cease in June 2005.


In Europe, the ACEA specifications were introduced in January 1996. These replaced the CCMC specifications and included five new tests. ACEA has now replaced the initial specifications with updated ACEA-02 specifications having significant changes and improved product performance. ATEIL and ATC are, however, questioning the need and timing for the changes, as well as the process to be used for the new categories. The new categories are A5 for fuel economy and higher oxidation resistance, B4 for direct injection passenger car diesel engines with 30,000 km oil drain, B5 as the passenger car diesel equivalent of A5, E4 for super high-performance diesel engine oils, to meet the MB 441LA test requirements and E5 for longer drain intervals. Other new ACEA tests could include some of those proposed for GF-4, including fuel economy retention, OPEST (oil protection of emissions system test), BRT (ball rust test), and Cummins M11. The latest North American heavy duty diesel engine specification is CI-4 (developed as provisional classification nine, PC-9), which was introduced in mid-2002. The main reason for the new specification is that mandated reductions on NOx emissions from diesel engines cause an increase in soot in the engine oil. As a result, the CI-4 specification has three new engine tests, Caterpillar 1R for steel and aluminium piston deposits, oil consumption and oil oxidation, Mack T-10 for ring and liner wear and Cummins M11 for crosshead wear, oil sludge and oil filter pressure drop. To these have been added tests for shear stability, low-temperature pumpability, elastomer compatibility, volatility, corrosion, and foaming. The CI-4 category was defined during 1999, when reference oils were also selected. Precision testing was completed in June 2001, as was the ASTM ballot, and test limits were decided in October 2001. API licensing began in December 2001 and the first products began to appear in the North American market in April 2002. The development cost for CI-4 was $5.7 million. In addition to the industry standards, other OEMspecific approvals such as Mack, will continue. Mack plans to issue a new approval list, EO-M, and Cummins is reported to be considering the introduction of a new list of approved premium specification HDD oils. In Japan, JAMA has requested a new API category for HDD oils, for use in diesel engines operated in South-East Asia. JAMA’s concern with the CH-4 and CI-4 requirements is that it could lead to low ash oils, counter to their desires for higher ash oils. The requested category would be PC-8 and would be aimed at diesel engines with lower piston temperatures, greater use of slider followers, and hence greater need for wear protection. This specification has now been dropped, however, in favor of the new DHD-1 specification. The next HDDEO for the North American market is PC-10, which will be required for 2007 model year

trucks equipped with EGR engines and particulate traps and emissions control catalysts. The first request for a PC-10 specification was made in June 2001, although it was only confirmed in September 2002. Development of new engine tests began in October 2002, but the decision to develop the specification was delayed until February 2003. Matrix testing started in May of this year. The API committee responsible for PC-10 plans to issue the final specification by June 2005 and to begin first licensing of the new classification (which will be CJ-4) in July 2006. The performance demands of the current and emerging engine oil specifications means that PAOs, esters, Group III and Group II baseoils feature heavily and are likely to continue to do so in the formulation of many of the higher-performance products. 48.5.1.2 Motorcycles and outboard engines The development of global standards for oils for air-cooled two-stroke (2T) engines continues to progress. At present, 70% of all motorcycles worldwide are 2T and the current standards for oils are based on the JASO FA, FB, and FC specifications. These are now being developed further by ASTM, CEC, and JASO working groups. By the early 1990s, requirements for improved engine durability and reduced maintenance led European OEMs to look for even better detergency and higher-temperature performance than that specified by the JASO FC, now ISO-L-EGC, category. As a result, a higher detergency EGD category has been added, together with a piston skirt deposit index. A draft international standard was issued in 1998 and final approval of the new EGD category was agreed at the beginning of 1999. Because consumers are demanding more performance, better durability, and reduced maintenance, the latest generation of increased complexity two-stroke engines are smaller, lighter, and equipped with refinements such as fuel and oil injection, variable exhaust valves and catalytic converters. As a result, demands on the lubricant are continuing to increase and even higher levels of lubricant performance are being sought. This has led Piaggio in Europe to develop a test method, using their liquid-cooled single-cylinder 150 cc Hexagon engine running at high speed (7000 rpm) and maximum load for 20 h, to really differentiate between the highest-performing oils. At the end of the test, candidate oils are rated for ring sticking and cleanliness of the aluminium piston, together with exhaust port blocking. The Hexagon test proposed by Piaggio is likely to become the basis for the next level of specification, ISO-L-EGE. North American motorcycles are mainly four-stroke (4T), with the oil system common to the engine and transmission. Worldwide, around 30% of motorcycles are 4T, and this percentage is continuing to grow. The main growth


factors are emissions and noise levels. Most 4T motorcycles use conventional PCMOs (passenger car motor oils), but some ILSAC GF-2 oils have been found to cause problems of one-way clutch slipping, due to low viscosity and low friction properties. Transmission gear durability problems have also been observed, so clutch and gear durability tests are being developed. As a result, many motorcycle manufacturers are developing 4T oils specifically for motorcycles. Emissions standards have now been developed for recreational marine 2T engines. These were introduced in the United States and Europe from 1997 onwards, with the aim of being fully implemented by 2006. The emissions levels are 75% lower than those permitted in 1991, and are mainly related to reductions in levels of volatile organic carbons (VOCs). While manufacturers of outboard marine engines would like to continue to sell 2T engines, it is likely that new technologies will need to be introduced to meet increasingly tighter emissions standards. The next stage in the development of outboard engine oils, particularly in the United States, will be in more environmentally friendly oils. This is being built into the revised TC-W3© specification. The biodegradability test for this standard will be based on the ASTM D5864 28-day test method. The proposed minimum level of biodegradability will be 60%, whereas current TC-W3 oils fall mainly between 10 and 25%. In the United States, the current Federal Trade Commission guidelines for environmental claims indicate that to claim biodegradability, “. . . the entire product will completely break down and return to nature . . . .” The need to be able to support such statements may inhibit the marketing of improved outboard engine oils and is almost certain to make them more expensive, since they will have to be based on synthetic or natural esters. 48.5.1.3 Transmissions and gearboxes Automotive manual transmission and axle oils are increasingly multigrade in Western Europe and North America, with SAE 80w140 and 75w90 viscosity grades replacing EP80 and EP90 viscosity grades. The use of SAE 75w90 or 80w140 gear oils is reputed to save between 4 and 10% on fuel consumption. The use of these grades, when based entirely on mineral oils, has reportedly led to rear axle wear problems. This problem has been eliminated by the incorporation of from 20 to 25% of esters into the formulation of 75w90 or the use of combinations of PAOs and PIBs, particularly in fully synthetic 75w90 formulations. Some of the latest formulations also contain up to 20% wt of 4 cSt Group III baseoil. According to Castrol, lubricant oil temperatures at high speeds can be 30◦ C cooler with a synthetic oil. In the United States Eaton Axles issued new “Road-Ranger” specifications for full synthetics in July 1996. In the heavy duty

gear and transmission systems of class 8 trucks, after the first oil change (3,000 to 5,000 mi) the fluids can be run for up to 500,000 mi without changing, giving real cost-benefits to users. Eaton regards these systems as “filled-for-life” and believes that the next improvement will be “sealed-for-life,” which will definitely require synthetic oils. Part-synthetic 80w90 heavy duty gear oils were also introduced in North America. Texaco launched “Multigear SS” early in 1996, followed by Century Lubricants “Unigear SS.” A number of other companies are selling similar products. Peterbilt Motors, a large U.S. builder of trucks, began using fully synthetic gear and transmission oils as factory fill in all its trucks in April 1996. Peterbilt uses mainly Eaton and Rockwell gear and transmission components, and has been a major supporter of Eaton’s extended drain and fill-for-life policies associated with the use of synthetic lubricants. Demand for SAE 75w90 rear axle oils is expected to grow. The attitude of the OEMs is critical, as the majority of vehicles now have filled-for-life transmissions. The market for 75w90 is strong in Scandinavia, with their severe winters. In the past axle oils have been frozen solid, when engines were still able to start. The annual demand in the United States for automotive axle and gearbox fluids is currently around 125,000 t, for both cars and trucks. At present, sales of synthetic gear oils are between 5,000 and 6,000 t per year, mainly 75w90 for trucks, but also cars. In Western Europe, demand for automotive manual transmission gear and axle oils was 189,000 t in 2002, of which around 10,000 t was fully synthetic oils. 48.5.1.4 Automatic transmissions Most car manufacturers are now promoting the concept of “filled-for-life” automatic transmissions, to increase customer satisfaction and to assist with further improving vehicle fuel economy. This is derived from “shudder-free” torque converter clutches and stable ATF friction characteristics. The demand for “filled-for-life” will require significant improvements to ATFs. Antiwear requirements will need to last for 100 to 150 thousand miles, the oils will need to have exceptional high-temperature viscosity properties combined with good low-temperature fluidity properties and high shear stability in pump and clutch tests. Obviously, foaming resistance, air entrainment, and material compatibility (elastomers, bearing materials, and friction materials) will need to be at least as good or better than currently. As a result, there will be a heavy dependence on baseoil properties, which probably means the use of Group II or III baseoils, PAOs, and/or esters. Ford’s activities toward a MERCON-V specification have continued. ATFs to meet the requirements were trialed in Europe in 1996 and in 1997 in North America.


Primary service fill of MERCON-V began at the end of 1997. Although Chrysler has delayed work to develop a new ATF, they are now recommending against the use of any fluids that do not meet their MS7176D specification. It is possible that Chrysler’s new MS9602 specification will be introduced later this year. Following the expenditure of around $3m by General Motors and the additive companies on new DEXRON-IV oils, this development has been suspended, due to the cost of the ATFs that met the target performance levels. New, lower performance, targets were prepared in 2001 and GM announced the start of DEXRON-III “H” licensing in April 2003. The new performance limits require ATF formulators to use Group II and/or II+ baseoils in the new fluids. The requirements for the next GM ATF are broadly the same as those demanded by Ford and GM’s main service fill will continue to be DEXRON-III until DEXRON-IV is ready, which may now be quite some time in the future. 48.5.1.5 Brake fluids Brake fluids used to represent one of the major outlets for PAGs when DOT 3 fluids were used widely. Now, the two main brake fluid formulations in use in Western Europe and North America are based on specifications issued by the U.S. Department of Transportation (DOT). They are DOT 4 and DOT 5.1. The former fluids use comparatively little PAG, which has been replaced by mixed glycol ether borates. The latter fluids are based almost entirely on mixed glycol ethers and mixed glycol ether borates. As a result, the amount of PAGs used in brake fluids has been decreasing for some time. Brake fluids have been continually improved, especially in terms of boiling point, starting from the SAE J 7OR3 specification of the 1960s. However, brake fluid has largely become a filled-for-life fluid and is rarely changed. It is now being widely recognized that brake fluids deteriorate in service after two to three years, due to water absorption. In general, the higher the boiling point of the brake fluid, the more hygroscopic the glycols are. Boiling points are still trending slightly upwards. Typical boiling points in use in Europe are now 220 to 250◦ C. 220◦ C is the minimum requirement to meet DOT 4. DOT 5.1 fluids have typical boiling points of 240 to 260◦ C. The DOT 4 fluids are formulated to give greater “in service” stability, especially as regard water absorption. The formulation of DOT 4 blocks the ether linkage and hydroxyl group, which are vulnerable to moisture pickup. These properties are further improved in the DOT 5.1 fluids. There has been a major swing toward DOT 4 fluids in the last five years in Europe and in the United States. Naturally this has been reflected in lower sales of PAGs to the formulators. This trend will of course continue to work its way through the car “fleet” over the next five to ten years.

At the peak, in the mid-1980s, PAG sales were about 12,000 t for consumption in Europe, but had declined to about 6,000 t by 1996. DOT 5 fluids have also been introduced in Western Europe and North America. These are silicone-based brake fluids, with performance properties comparable to DOT5.1 fluids. However, the two fluids are completely incompatible and severe problems could result if they are inadvertently mixed in an automotive braking system. 48.5.1.6 Automotive air-conditioning This market is much larger in the United States than anywhere else in the world, although there has been a big increase in the number of new vehicles being sold with airconditioning in many countries, notably in Europe. As a result of the chlorofluorocarbon (CFC) controversy and the Montreal Protocol, new hydrofluorocarbon (HFC) refrigerants have been introduced, notably R134A for automotive air-conditioning systems. Air-conditioning (refrigeration) systems that use HFC refrigerants cannot be lubricated with mineral oils or PAOs, because of their higher miscibility with the refrigerant. Consequently, polyol ester or PAG-based refrigerator oils are used with HFC systems. Both fluids have well-defined viscosity/temperature/pressure relationships with each of the most widely used HFCs, including R134a. They provide excellent evaporator cleanliness, reduced compressor wear, excellent low-temperature fluidity, and improved evaporator efficiency. At present, PAGs appear to be more widely used than polyol esters in automotive air-conditioning systems. Recently, a number of suppliers of these fluids have developed “capped PAGs,” which have even better compatibility with HFC refrigerants. 48.5.1.7 Automotive greases PAO and ester-based greases are being used for automotive purposes, but the bulk of the market remains with conventional products, such as lithium-based greases. However, in Western Europe, concern expressed for the environment, with particular emphasis on buses and trucks with automatic grease applicators, is leading to the adoption of polyol ester-based greases, using long chain (such as C18 oleic acid) technology. At present this market for biodegradable greases is in its infancy, having really begun in 1990, but it is growing.

48.5.2 Compressor Oils This is a complex market, because of the wide range of gases and compressors in service. The main gases, types


of compressor, the competing synthetic products being sold into each end-use are described below, or those uses where only one synthetic has proved satisfactory. The total demand for compressor lubricants in Western Europe is around 40,000 tons. As an order of magnitude estimate, it is estimated that total synthetics sales are currently in the range of 20,000 tons. There is now competition from VHVI (API Group III) mineral oils. At least a similar volume is used in the United States, where Group III baseoil competition is not so strong. A volume of 4,000 tons of PAGs is known to be used in chemical, natural gas, and helium compressors. The United States of course has a large network of natural gas pipelines and gas production. 48.5.2.1 Air and gas compressors Stability in the presence of combinations of air and moisture is the most important reason for selecting a synthetic fluid to lubricate an air compressor. Oxygen in the air reacts with hydrocarbon oils (oxidation) to form organic acids, carbon oxides, varnishes, sludge and hard, carbonlike deposits. Water can condense as air is compressed and later cooled. This may cause corrosion, solubilize, or form emulsions. This not only interferes with compressor lubrication but also promotes more rapid deterioration of the oil. These reactions are catalyzed by certain metals such as iron and copper. The acids and sludge formed promote rapid deterioration of the oil. Other considerations for selecting a synthetic lubricant are safety, maintenance, and the potential to reduce energy requirements. Each type of compressor can take advantage of the these properties. VHVI and PAO-based reciprocating compressor oils have been formulated with low volatility and low carbonforming tendency. This has led to cleaner operation and reduction of fires in critical installations. Performance was good, with discharge temperatures at 392◦ F (200◦ C) and pressures at 100 psi (68 kPa) in a 120-hp two-stage reciprocating compressor after 16,000 h of operation. PAOs have to be blended with esters to improve their solvency and seal swell properties, and with oil-soluble silicones to reduce cylinder feed rates. When deposits are formed they are either very sticky (polymers) or hard varnishes (as with paraffinic oils). The major benefit of VHVIs and PAOs is their compatibility with elastomers and paints found in older compressors, which were designed for use with mineral oils. VHVIs and PAOs are used extensively and increasingly in rotary screw air compressors. They are often preferred over esters for use in standard 100 psi (68 kPa), 90◦ C applications. The excellent hydrolytic stability and compatibility, not only with rubber and plastic in the compressor, but also in the compressed air system. They are also compatible with mineral oils and common additives.

This makes compressor conversions from mineral oils simple and helps to prevent problems with materials and equipment used in the compressed air system. The PAOs have very little effect on swelling of rubber or elastomers. It is very common to add from 8 to 15% of a diester (or polyol ester) to increase seal swell and to help solubilize contaminants. PAO-based compressor oils have longer drain intervals than do diesters (usually about 30% longer). Their low water adsorption and rapid water separation result in improved rust and corrosion protection and help water to be easily drained from the oil reservoir during long periods of shut down. A high viscosity index and low volatility allow the use of lower-viscosity grades. This combined with excellent low-temperature fluidity reduces power consumption during start-up in cold environments. 48.5.2.2 Natural gas compressors The problems associated with the compression of gases have been known for a long time but in specific areas these problems have now become critical with the need to compress gases to much higher pressures. These problems are particularly relevant in oil fields where it is now the practice to reinject surplus natural gas into a suitable formation rather than flare off surplus gas, which was the practice in the past. Gas injection pressures, can be in the region of 400 bar and to achieve these high pressures, reciprocating compressors are normally used. The combination of the nature of the gas, its rate of flow, and the high pressures involved have caused problems with these compressors resulting in scoring and high rates of wear of piston rings and pressure packings. There are four basic problems involved when using mineral oil cylinder lubricants. The first problem, reduction in viscosity caused by dissolution of the gas into the oil, can be overcome by increasing the viscosity of the oil used, although with very rich gases the highest viscosity oils could be reduced to an unsatisfactory level. Difficulty could also be experienced with pumping of these heavy oils, particularly in low-temperature installations. The second problem, which can be experienced with low pressure gas as well as with high pressure gas, is high rates of wear resulting from the lubricant being washed off the cylinder surfaces by liquid components in the gas. An investigation into the cause of premature failure of a high pressure natural gas compressor highlighted the third problem, which was an unexpected loss of lubricant into the high pressure gas. To compensate for this loss under typical reinjection conditions, the lubricant supply to the cylinders and packings would have to be increased to at least ten times the manufacturer’s recommended feed rates. This would mean that a typical reinjection compressor might consume a barrel of lubricant per day.


The fourth problem is associated with production rather than lubrication but is still related to the type of cylinder lubricant used. It has been found that certain additives used in the cylinder lubricants, which are necessary to ensure adequate lubrication and to prevent excessive wear, can react with the wellbore fluids being used and can cause well impairment (blocking of the porous rock structure) resulting in reduced gas injection rates, or in some cases, permanent impairment. The cumulative effect of these problems is to severely restrict the operating period of the compressors, often as low as 600 h, before complete stripdown and replacement of piston components and pressure packings is necessary, each overhaul taking approximately two days. In addition to the cost of replacement components, there is also the loss of oil production during the frequent downtime periods. Most gases are soluble in lubricating oils and the degree of solubility will depend on the gas temperature and pressure, gas composition, and the type of lubricating oil. In general the effect of gas solubility is to reduce the viscosity of the oil, thereby reducing the effective oil film thickness and limiting the protection it affords, particularly under boundary conditions. Since absorption or solubility of gas into the oil increases with pressure it could be considered that the viscosity of gas saturated oils decreases with increasing pressure. However, it is also known that oils increase their viscosity with increasing pressure and it is therefore necessary to determine the resultant effect taking these two opposing factors into account. In addition, solubility will decrease with increase in temperature. The way in which these problems have been overcome has been to use oil insoluble PAG-based lubricants in natural gas compressors. The viscosity of a PAG lubricant is approximately double that of a mineral oil when subjected to a pressure of 340 bar and saturated with methane. With an increasingly large gas pipeline transmission network in North America, in Europe, and in South America, the trend toward PAG lubricants is expected to accelerate. 48.5.2.3 Refrigeration compressors Refrigeration lubricants may be required to provide many years of service without makeup and with a minimum of maintenance. Final compression temperatures may reach 160◦ C for some applications, at which temperatures unsuitable oils form carbonaceous deposits. In the special case of hermetic compressors, the motor materials must not be adversely affected by the lubricant/refrigerant mixture or by-products from its deterioration. This requires a lubricant that has excellent thermal and chemical stability and produces a minimum of deposits. The lubricant in compression refrigeration systems has an influence on the operation and efficiency of the entire system. Some lubricant is carried out of the compressor

and into the system. The lubricant must act as a compression sealing aid and reduce wear and friction in the compressor without adversely affecting the operation of the filter dryers, condenser, expansion valve, or evaporator. The behavior of the oil/refrigerant pair is of major importance. Refrigerants can be carbon dioxide (CO2 ), ammonia (NH3 ), chlorofluorocarbons (CFCs; R11, R12, R113, or R502), hydrochlorofluorocarbons (HCFCs; R22, R123, or R124), or hydrochlorocarbons (HFCs; R23, R134a, R404a, R407c, R410a, or R507). The solubility of the refrigerant gas in the lubricant and the miscibility of the liquid refrigerant with the lubricant respectively affect compressor performance and system performance. Dissolved gas has the effect of reducing lubricant viscosity. Miscibility is considered for design of components and piping to promote uniform oil movement through the system and back to the compressor. Heattransfer problems are more significant in systems where the oil is immiscible or partly miscible with the refrigerant. The main differences between screw compressors and reciprocating compressors for refrigerating systems, with respect to the oil system, are that a screw compressor has an oil separator and an oil sump situated on the high-pressure side and the compression chamber is flooded with oil, to seal the threads that are under compression. In refrigerating screw compressors, the lubricant has more effect on performance than it does with the reciprocating compressor. To reach high performance, the screw compressor needs a lubricant with limited solubility of the refrigerant gas at discharge conditions (at the oil separator). Limited solubility will reduce or eliminate by-passing of refrigerant from discharge to suction or to a lower situated thread. External by-pass caused by the refrigerant circulating with the oil is also reduced. This leads to both high volumetric efficiency and low torque. Most lubricants with low solubility also have low miscibility (liquid refrigerant in oil). In some cases a synthetic lubricant can meet the requirement of low solubility while maintaining good miscibility. This, combined with low volatility, reduces oil in the system to improve heat transfer. Mineral oils were used extensively in refrigeration compressors, due to their good miscibility with R-12 refrigerant. Superior chemical and thermal stability of HVI and VHVI oils have reduced the risk of carbonizing at high temperatures in heat pumps with R-12 and R-114. Superior adiabatic efficiency of 3 to 10% is achieved in rotary-screw compressors using these refrigerants when compared to naphthenic refrigeration oils. Further efficiency improvements can be obtained with PAOs, largely due to their higher viscosity at higher temperatures in the presence of the refrigerant. Superior performance and reliability have been achieved in reciprocating, twin-screw, and single-screw compressors. The Montreal Protocol banned the used of CFCs and these refrigerants are now being phased out and replaced


with HFCs. HCFCs are also being phased out progressively, although many marine refrigeration systems still use these refrigerants. Lower evaporator temperatures are permissible with PAOs than with mineral oils because PAOs are wax-free and have good low-temperature fluidity for oil return. Low-temperature fluidity is the major reason why PAOs have been used in the United States for relatively insoluble refrigerants such as R-13 and R-503. The lubricant viscosity, ISO 15 or 32, is selected by considering operating viscosity in the compressor as well as low-temperature fluidity below −73◦ C in the direct expansion dry-type evaporator system. PAOs and VHVI oils have been found to provide several performance advantages in ammonia refrigerating systems. Better thermal and chemical stability with ammonia results in reduced sludge and varnish and has resulted in extended drain intervals. Lower solubility helps improve lubrication and reduces foaming. Lower volatility reduces oil consumption and improves heat transfer by limiting the amount of oil in the system and on heat-exchanger tubing. The excellent low-temperature fluidity and HVI of the PAO fluids allow evaporator temperatures below −46◦ C and maintain viscosity for higher compressor operating temperatures. Good low-temperature fluidity facilitates oil removal in most systems. Refrigeration systems and heat pumps that use CO2 , NH3 , CFCs, or HCFCs as refrigerants can be lubricated with mineral oils or PAOs. In general, refrigerator lubricant suppliers and users have increasingly tended to use PAO-based fluids, because they have better low- and hightemperature properties. As a result, they can be used in compressors operating at high discharge temperatures in refrigeration systems with low evaporator temperatures. Additionally, PAOs have much lower volatilities than mineral oils, so are less prone to “light end stripping,” thus minimizing viscosity buildup and giving lower oil consumption. The solubility of most of the refrigerants in PAOs is low, resulting in higher film thickness in the presence of refrigerants under pressure and lower shaft seal leakage. Refrigeration systems that use HFC refrigerants cannot be lubricated with mineral oils or PAOs, because of their higher miscibility. Consequently, polyol ester and PAGbased refrigerator oils are used with HFC systems. Both fluids have well-defined viscosity–temperature–pressure relationships with each of the most widely used HFCs. They provide excellent evaporator cleanliness, reduced compressor wear, excellent low-temperature fluidity, and improved evaporator efficiency. When changing from a CFC or HCFC refrigerant to an HFC refrigerant, the compressor oil must also be changed. This necessitates a complete clean and flush of the lubrication and refrigeration systems. All refrigerator compressor manufacturers issue recommended procedures for changing both the refrigerant and the lubricant.

48.5.3 Turbine and Hydraulic Oils 48.5.3.1 Steam turbine oils In general, the properties required of a steam turbine lubricant are not extreme, but they need to be maintained for many thousands of hours of continuous service. The oils are expected to remain in service for between 10 and 20 yr without any oil change. These requirements are adequately met by specially refined baseoils from selected crude oils, inhibited with rust and oxidation inhibitors. Regular topping-up of the system with new oil contributes to achieving the long oil life. If improved oil seals are developed, which reduce the oil top-up rate, or if oil system temperatures are increased, the life of the current turbine oils could be considerably reduced. Under these operating conditions there would be a need for a more oxidatively stable oil. This could be achieved by using PAOs but, since the systems are large, the cost could be prohibitive and it is more likely that a blend of PAO and mineral oil would be used. On the smaller steam turbines it is usual to use the main system oil as the fluid for the hydraulically controlled governor systems. Larger turbines now tend to use electro-hydraulic governor control systems that operate at relatively high pressures and this, combined with higher steam temperatures, increases the risk of a fire if a leak develops in a hydraulic line. For this reason the trend is to use phosphate ester fire-resistant hydraulic fluids in these systems, operated from a separate supply. Phosphate esters have also been used successfully as a combined hydraulic fluid and system lubricant in a turbo generator. It is envisaged that the use of these lubricants could be an economical way of reducing the fire risks associated with steam turbines in hazardous environments such as oil refineries, sugar and paper mills, and chemical plants.

48.5.3.2 Gas turbines oils Industrial gas turbines fall into two main types: • The direct use of aero-derived turbines for electricity

generation and mechanical drive applications (compressors and pumps). • Specially developed gas turbines, pioneered by General Electric (GE), but also now developed by ABB, GEC, and Siemens. These are also used for electricity and cogeneration but are now on a much larger scale than the aero engines. For example, while the RollsRoyce RB211 aero-engine generates 25 MW, the latest industrial GE Frame “9 F” produces 210 MW of electricity. Almost all aero-derived engines operating on oil rigs in the North Sea, or on Soviet gas pipelines for pumping,


use aero-engine oils, for example, diesters for Rolls-Royce “Avons” and polyol esters for RB211s. On the other hand, the large industrial gas turbines have tended to use highperformance mineral turbine oils. Now, however, there are examples of some using synthetics, based on PAO/ester mixes. In the 1990s the market outlook for heavy-duty industrial gas turbines was exceptionally good, as natural gas fired combined cycle power stations of high efficiency and moderate capital cost are built in large numbers, in response to environmental pressures. Since privatization, in the United Kingdom alone, about 25 new power stations of 300 to 900 MW each have been either built or proposed, mainly using combinations of at least two industrial gas turbines and one steam turbine. Since 1960, GE, the market leader, has shipped over 5000 units of industrial gas turbines. The current world market for industrial turbine lubricants of all types (steam and gas) is around 285,000 t per year. Of this, only about 20,000 t is represented by the toptier VHVI, ester-, and PAO-based products. Around 5,000 t per year of PAOs are used currently, mainly in PAO/mineral oil blends for larger gas turbines in combined cycle power generation plants. 48.5.3.3 Hydraulic fluids Increasingly, hydraulic systems have become smaller and are required to operate at higher pressures. This has demanded the use of more thermally, oxidatively, and hydrolytically stable oils, particularly in those systems that use high-pressure rotary vane pumps to deliver fluid pressure and flow. Demands for multi-metal compatible, superior antiwear and enhanced corrosion protection fluids has increased since 1980. Fortunately, most of these demand can be achieved using correctly formulated HVI-based oils. Simultaneously, demands for increased workplace safety, especially in places involving hot surfaces or explosion hazards, such as foundries, steel and aluminium rolling mills, casting workshops, and coal mines, has lead to an increase in the use of fire-resistant hydraulic fluids. Most hydraulic fluids are either mineral oils, or one of the four types of fire-resistant fluids, which are oil-inwater emulsions, water-in-oil (invert) emulsions, waterglycol solutions, or phosphate esters. During the 1980s, PAOs and polyol esters were promoted as “fire-resistant” fluids, but it has now been demonstrated clearly that the fire retardancy properties of these synthetics is very limited. In general, VHVI oils do not show any useful performance advantages over HVI oils for hydraulic fluid applications. The one notable exception is in the formulation of “multigrade” hydraulic oils, for use in machines operated outdoors in colder climates. In these applications, the hydraulic oil must be pumpable at low temperatures (from 0 to −30◦ C) when the machines are first started

each morning, but must also have all the required hydraulic fluid attributes of good oxidation, thermal, and hydrolytic stabilities, together with excellent antiwear and corrosioninhibiting properties. Hydraulic oils with the correct viscometric and pour point properties can be formulated from HVI baseoils, by the use of appropriate amounts of viscosity index improvers and pour point depressants, as well as the normal antiwear, oxidation inhibitor, and corrosion inhibitor additives. However, the use of viscosity index improvers does increase the level of shear instability of the hydraulic oil, particularly under the high fluid shear conditions found in many hydraulic pumps and motors. One way of overcoming the shear problem found with some HVI hydraulic oils is to use a VHVI baseoil, so that the amount of viscosity index improver is either eliminated or reduced significantly. Unfortunately, the cost penalty of using this formulation route is quite high. As a result, shear stable “multigrade” hydraulic oils based on VHVI oils are marketed for only a relatively few critical applications in which the high fluid shear conditions or the extremes of temperature experienced in the hydraulic equipment justifies the additional cost. The majority of these applications are found in Scandinavia, northern Europe, Canada, and northern U.S. states, particularly in outdoor timber and construction machinery and agricultural equipment. PAOs have begun to find a small niche as central system hydraulic fluids in a few designs of passenger cars. These central systems combine the suspension, shock absorber, clutch, and brake systems, for which a universal system, preferably mineral oil compatible is required. This is a very small market, which is unlikely to grow much in the next few years. Another recent trend has been an increase in the demand for environmentally friendly or biodegradable hydraulic fluids for use in outdoor and mobile equipment. These systems include those on logging and forestry machinery, excavators and mechanical handling machinery in open-cast mining, hydraulically operated rock-drills, and road construction machinery. Demands for ester-based and vegetable oil-based hydraulic fluids have been greatest in Canada, Sweden, Switzerland, Austria, Germany, Norway, and Finland. Initially, many of these biodegradable hydraulic oils were based on vegetable oils. However, problems were encountered in many applications with oxidation stability, thermal stability, and low-temperature performance, so more of these applications are now using synthetic ester hydraulic oils. In 2002, the International Standards Organisation (ISO) issued a new global standard for biodegradable hydraulic fluids, ISO 15380. This standard contains specifications for four new categories of “environmentally acceptable” hydraulic fluids:

• HEES: Synthetic esters • HEPR: Polyalphaolefins and related hydrocarbons

• HETG: Triglycerides (Vegetable oils) • HEPG: Polyglycols

Gear oils are used to lubricate various types of “gears” designed to transmit power from one point to another


(Specifications for mineral oil [classification H] hydraulic fluids are contained in ISO 11158 and specifications for fire-resistant [classification HF] hydraulic fluids are contained in ISO 12922.) Development of the ISO standard was based on the experiences of suppliers and users of biodegradable hydraulic fluids in a number European countries, including Sweden, Germany, Austria, and Switzerland. In addition to the usual tests for viscosity, pour point, flash point, rust prevention, copper corrosion, oxidation stability, foaming tendency, air release, demulsibility, and antiwear performance, ISO 15380 contains limits for biodegradability, acute fish toxicity, acute daphnia toxicity, and bacterial inhibition, using standard ISO test methods. The technical and marketing approaches to health, safety, and environmental issues are intended to promote lubricants that are more friendly to the general environment, including people. Either they are more compatible, have reduced ecological impact, reduce pollution, or are more environmentally responsive or responsible. The current annual world market for all hydraulic fluids is around 1.35 million metric tons, of which mineral oils represent over 85%. The other 15% are mainly fireresistant products, including oil-in-water emulsion fluids, water-glycol fluids, and synthetic phosphate esters. The Western European market for biodegradable hydraulic oils was around 35,000 t in 2002, of which around 20,000 t was synthetic esters.

48.5.4 Gear, Circulating, Process, and Functional Oils 48.5.4.1 Circulation systems Some circulation systems, such as those feeding lubricant to gearboxes operating paper mill drying cylinders, run at high bulk oil temperatures. Particularly in Scandinavia and the United States, it has been found that PAG lubricants enable the mills to be run faster and at higher temperatures, without deterioration of the lubricant through oxidation. Higher paper output has been achieved. Large paper mill manufacturers are now recommending synthetics at startup. Polypropylene glycol is the most commonly used synthetic base for this application, but PAOs are also being introduced. In low-temperature conditions, found in cold storage applications and occasionally in steel works and opencast mining, alkyl benzenes and PAOs are being used as circulation lubricants. 48.5.4.2 Gears

in order to do work. The primary function of a gear lubricant is to provide a high degree of reliability and durability in the service life of gear equipment. Use of gear lubricants dates back to the early days of the industrial revolution when ways were being sought to generate and transmit more power, more efficiently and at higher loads than could normally be handled. Nowadays, the technology associated with gears, their function, and their lubrication has become very sophisticated. The basic types of gears include spur and helical, bevel, hypoid, and worm, from which all gear “systems” are developed. A system, whether automotive or industrial, may contain only one type of gear or it may involve a combination of gears. However, most automotive applications use hypoid and spur gearing, while most industrial applications use bevel and worm gearing. The speeds may range from very low to very high under both light and heavy loads, depending on the type of work required from the gear system. These gear systems may be enclosed or open and exposed to the atmosphere. Speed, load, and climatic conditions all have an effect on the operating temperature of the particular gear system. Proper lubrication is essential to ensure optimum life of the gears. The gear lubricant should be of the type, grade, and quality to provide proper protection for the gears to function effectively for the intended application. Such lubricants should provide the following general performance characteristics: • • • • • • • • •

Extreme pressure and antiwear protection Thermal and oxidative stability Foam suppression Ability to demulsify water Proper working viscosity Good low-temperature flow properties Seal compatibility Environmental acceptability Cost-effectiveness

Synthetic gear lubricants operate over a different temperature range in terms of viscosity than do conventional mineral oil-based gear lubricants. This range is important to the user, enabling the use of one lubricant for a variety of applications. The viscometrics for a PAO, for example, enable gear lubricants to be formulated for both low- and high-temperature performance without the use of polymeric viscosity index improvers, since the PAOs have a high “natural” viscosity index. PAGs have similar properties. Among the most important factors of synthetics are their low-temperature viscosity properties. When oils are cold their viscosity may be many times higher than at ambient temperature. This changes the lubricity of the lubricant and in extreme cases can cause damage to the gears.


Synthetic gear lubricants have better low-temperature pumpability. In general, PAO-based multigrade gear oils have much greater shear stability than conventional mineral oil-based formulations, since they use less or no viscosity index improver. Also, multigrade mineral oil based gear lubricants tend to shear out of grade, a problem that does not affect fully synthetic formulations. This can be very important to the service life and durability of modern gearboxes and gear oils. Most industrial gear oil specifications are based on performance criteria easily met by conventional gear lubricants. These, mineral oil-based gear oils are very costeffective, so there is little incentive to change. However, there is a growing volume of evidence to suggest that significant energy savings can be made by using synthetic gear lubricants. The use of PAOs and PAGs in industrial gearboxes can lead to important savings in energy consumption, as well decreased down-time and lower maintenance requirements. The wide range of operating temperatures allows the use of less viscous oils, which results in greater energy efficiency. The relatively low coefficient of friction for PAGs and PAOs reduces the amount of internal friction created by the normal shearing of an oil film during operation. 48.5.4.3 Bearings The high pressures encountered on large calender machines producing rubber or plastics, can result in bulk oil temperatures of over 200◦ C. Up to about 150◦ C mineral oils are still used, but for higher temperatures the PAGs have been accepted as the solution. Again, PAOs have also been introduced for this application and even some PAO/ester blends in the United States. 48.5.4.4 Heat transfer oils and solar fluids Heat transfer systems and the fluids used in them are complex and highly specialized. The largest volumes are in major circulation systems at chemical or process plants. This business is usually awarded at the initial-fill stage, with sales thereafter only as top-up or infrequent change. It is important to offer technical support at the design and commissioning stage of these large “one-off” systems. The fluid used is dependent on the heat transfer temperature required. About 45% of the overall heat transfer fluid market is met with mineral oils. The total worldwide market is 50,000 t per annum, and synthetics represent about 9,000 t (20% of the total) per annum. Thus liquids represent 65% of the market. The balance are high-temperature vapor-phase systems (25%) and intermediate temperature systems (10%). The main synthetic fluids are polyglycols, silicones, and specialized hydrocarbons. Mineral oils have a tendency

to foul, and also have a relatively narrow operating range (up to 300◦ C) and poor thermal stability. PAGs also have some problems of thermal stability and narrow operating range (165–250◦ C). However, they are in wide use in smaller systems, such as plastic injection molding machines, mobile heat exchangers (for composites), or small chemical reactors. Silicones have high thermal stability and wide operating range, but poor heat transfer properties. The specialized hydrocarbons, such as hydrogenated polyphenyls (−10–345◦ C), alkyl aromatics (50–300◦ C), or polyphenyls (75–400◦ C) are offered to provide the right balance of properties. Monsanto and Dow Chemical are leaders, with the widest range of specialist products on offer. BP/Castrol, Bayer, Hüls, ChevronTexaco, Nippon Steel, and Wibarco (with alkyl aromatics) are suppliers with narrower ranges of products. These well-established aromatic compounds, phenyls and diphenyl oxide type materials, are coming under increasing government pressure for control and restriction in the United States. Crompton (Uniroyal) and BP have been actively promoting PAOs in this market sector, as potential replacements. Solar fluids for roof-type water heaters are another heat transfer market, which although already in wide use in countries like the United States, Italy, Cyprus, and Israel, is likely to grow, in an energy-conscious and “green” world. Low viscosity PAOs (2 cSt), with metal deactivators, are finding outlets as solar fluids.

dependent on electricity-related properties, where the main function is as a heat transfer medium; whereas high-voltage capacitor uses have required a range of other products. Silicones and other speciality type products have probably gained the biggest share of the PCB replacement market. They are particularly suitable for new equipment, which can be designed around the dielectric. Dow Corning has been marketing a polymethylsiloxane product and silicone-based products are also offered by Bayer and Rhone Poulenc for transformers. Other developments in this field came from GEC Alsthom in the United Kingdom, which completed work on natural fatty acid-based esters, which are marketed under the name of Midel. GEC Alsthom believes the main market is for retrofilling existing equipment, where silicone-based products are less suitable. Another ester product has been developed by Rhone Poulenc, in cooperation with the Swedish cable company, Asea Kabel. The fluid is a nonchlorinated ester, benzyl neocaprate. Further possibilities for PCB replacement exist with PAOs. Crompton introduced a range of high molecular weight PAO fluids, which it claims are less costly than silicones and which have been approved by the fire authorities. The demand for insulating oils of all types, including mineral oils, is estimated at 150,000 t in Western Europe, covering both the initial-fill and top-up and replacement markets. The expected demand for synthetics, of all types, is thought to be in the 2,000 t range.

48.5.4.5 Electrical and insulating oils

48.5.4.6 Cable compounds

Naphthenic baseoils have traditionally been used in transformers and capacitors, for those applications where fire risk was not being considered, that is to say, outdoors. The naphthenics were believed to have higher oxidation stability than paraffinics and, with their lower wax contents, the pour points were suitable, on average, for transformers operating outdoors down to −35◦ C (pour points of −45◦ C). In fact, special naphthenics have been refined with pour points down to −60◦ C, but for applications with potential operating temperatures below −50◦ C, synthetics have generally been used. In the past, transformers operating indoors tended to use fire-resistant insulating fluids, such as polychlorinated biphenyls (PCBs). However, under EU regulations, end users have been prohibited from using PCBs for more than 30 yr. The EU regulations have led to the total replacement of PCBs in all applications. The environmental persistence of PCBs was first recorded in Sweden in the late 1960s. The excellent range of properties exhibited by PCBs as dielectrics is illustrated by the number of products that has been necessary to introduce to cover the same field adequately. In general, silicone-based products have been found satisfactory for those transformer applications less

“Cable compound” is a term concerned with those compounds used for the impregnation of paper-insulated electric power cables and for filling interstitial spaces in plastic-insulated telecommunication cables. It includes blends of oils (which may be mineral oil or synthetic), and formulations of such blends with additives to achieve particular characteristics, such as higher viscosity and a nonmigratory performance during service. Even in this limited and specialized field there is a wide diversity of compound types. The primary differentiation is between power cables and telephone cables, as follows:


• Power cables:

• “Self contained” hollow core cable • “Pipe” type cable • “Solid” cable (mass impregnated; non-draining or viscous liquid) • Telephone cables:

• “Fully filled” plastic-insulated cables • Optical fiber cables

It is important to distinguish between the terms “impregnating,” as applied to power cables, and “filling,” as applied to telephone cables. In a power cable, the compound and the paper together form a composite dielectric, which has greatly superior properties of insulation than could be achieved with either component separately. The compound forms an integral part of the cable insulation, and in the manufacture of the cable every effort is made to ensure that no air or vacuous spaces remain in the dielectric, following the process of impregnation. In a telephone cable it is the extruded plastic around the conductors that forms the primary insulation. The “filling” compound has a secondary insulating function, but is primarily introduced to prevent the penetration of water into and along the length of the cable, in the event of rupture of the cable oversheath. Pockets of air can be tolerated within the interstitial spaces of the cable core, provided a continuous channel does not exist along a significant length of the cable. Nationally or internationally agreed quality control tests are applied to manufactured cable lengths, to ensure compliance with specification requirements. Cables of the hollow fiber type require oils of the lowest possible viscosity, compatible with the need for an acceptably high flash or fire point, to minimize the possibility of fire hazard. Naphthenic mineral oils having a carefully controlled degree of aromaticity are still used for this application, but currently alkyl benzenes are more often specified. Pipe type cables utilize a fairly low viscosity oil to transmit the hydraulic pressure within the pipe, but a considerably higher viscosity compound to impregnate the cable cores. Polybutenes have replaced mineral oils to a very great extent in this design. Solid type cables were traditionally impregnated with blends of viscous oils, to which refined natural resin (colophonium) had been added. This addition resulted in a very greatly increased viscosity at ambient temperature, without unduly increasing the viscosity at cable impregnating temperatures (commonly between 115 and 135◦ C). In this way problems resulting from compound drainage in service were reduced, while processing times during manufacture could be kept down, in the interests of economics. PIBs of approximately 900 to 1200 molecular weight have been widely used in the past two decades for the same purpose; their disadvantage of HVI has been made good by improved cable manufacturing techniques. However, since the 1960s, by far the greater proportion of solid cables have been impregnated with Mass Impregnated Non-Draining (MIND) compounds. These can be based either on mineral oils or on PIBs, to which are added suitable waxes, which result in a high melting point. In optical fiber cables used for telecommunications, the tube or slot filling formulations are based on low viscosity technical white oils/PIBs or high molecular weight


PAOs, gelled with micronized silica. Interstitial spaces are filled with wax/mineral oil or wax/PIBs. Technical white oils and waxes are used to prepare thixotropic gels that are hydrophobic, are stable over a wide range of temperatures and can be pumped into the cable tube at room temperature. They are non-melting, with no phase or structural changes, and have a substantially constant viscosity over a wide range of temperatures. These cable jellies act as water blocking and buffering materials. Metallic (usually copper) conductor telecommunications cables use compounds made from either white oil/wax blends, PIB/wax blends, technical white oils, or block copolymers. Cable compounds for power and telephone usage are usually formulated by specialists such as DussekCampbell, BP Chemicals, ExxonMobil Chemicals, Crompton (previously Witco), or Sasol (previously Schumann). 48.5.4.7 Oil-based drilling fluids Due to high temperatures and pressures, there are significant advantages to the use of oil-based drilling muds, including good lubricity coefficients, easier drilling through salt, potash, or gypsum, reduced drill point torque and drag, plus corrosion protection of the drill pipe. In general, faster drilling, longer bit life, and higher working temperatures are possible. The range of possible viscosities used on drilling fluids is quite wide, and varies from light mineral process oils through nontoxic gas oils to odorless kerosene. Although oil-based muds use less additives and are reusable, there have been concerns about harm to marine life if muds are disposed of at sea. (Muds are not deliberately disposed of, but some fluid adheres to the drill cuttings that are disposed and accumulate on the sea bed.) Hence the development of the shrimp test or Krangen–Krangen test, used in the North Sea, to assess the effects of mud oils on sea life. At its height the North Sea was using about 50,000 t of mineral oil bases for drilling muds annually. In the mid1990s, oil-based muds were banned in the North Sea as a consequence of their poor biodegradability compared to water-based muds. Biodegradable ester-based muds were, however, permitted. As a result, the drilling industry switched to ester or water-based muds in the North Sea, while continuing to use mineral oils and low viscosity PAOs in other offshore regions, as well as for onshore drilling. More recently, the disposal of drill cuttings in the North Sea has also been banned, so all drill cuttings (and thus drilling mud) must be returned onshore for disposal, adding significantly to the costs of drilling. Oil-based muds have begun to make a comeback, although many are mineral oil based.

48.5.4.8 Circuit board fluxes A new end use for synthetics has been developed in printed circuit board fluxes, where clean burn-off is an essential requirement. PAGs dominate this market. Potential sales are around 5000 t per annum worldwide, with of course strong demand from the Pacific Rim.

cutting fluids. The Law on Water sets limits on the concentration of pollutants routed into sewers. Also, the law on the handling of water-polluting substances, Water Pollution Categories and storage and/or volumes define the Water Pollution stages which, in turn, govern the cost-relevant monitoring and investment-intensive protection measures necessary when handling water-polluting fluids.

48.5.4.9 Mould release agents

48.5.5.1 Water-miscible cutting fluids

This is another hard-to-define market. Mineral oil emulsions have been used as concrete mold release agents for many years. The end use identified here is for mold release in the plastics and rubber industries, where clean lift-off and noncompatibility with the rubber or plastic are essential characteristics. PAGs are the most popular product on a price/performance basis, with silicones also competing in this sector, although at much higher prices. Since the early 1990s, the use of environmentally friendly, biodegradable concrete mold release oils has been encouraged in Western Europe, particularly in Scandinavia, Germany, Austria, France, Belgium, and the Netherlands. Many of the products are based on vegetable oils, but some of the products are based on biodegradable synthetic esters. The market for biodegradable mould release oils was estimated to be around 13,000 t in 2002, of which 10,000 t were vegetable oils and 3,000 t were synthetic esters.

With water-mix cutting fluids, change is constant, and the current situation is that the main favored product is semi-synthetic, that is, it retains a mineral oil content, but contains an array of other products, mainly based around a corrosion inhibitor (CI) additive package. Some of the semi-synthetic cutting oils contain up to 20 components and it is very difficult to persuade formulators to confirm what is being used in the final product. In the 1970s polyglycols were introduced as components for cutting fluids, but suffered technical drawbacks from paint stripping and the removal of lubricants from machine slideways. As a result, synthetics received a “poor press” in the cutting oil business. The move to semi-synthetics in the 1980s was an attempt to rebalance the situation, by again adding mineral oils to the formulation. Nevertheless, it appears that cutting oils are still a target for the synthetics suppliers, with primarily PAGs trying and gaining success, especially for very hard or exotic metals. PAGs have also been used by formulators as the lubricity base for water-soluble cutting and grinding fluids. They work by taking advantage of the phenomenon of inverse solubility, which means that a material becomes less soluble in water as the solution temperature increases, as it does at the metalworking workface, between tool and piece. The PAG comes out of solution and coats/protects the metal surfaces at the critical time. A recent development was the introduction of longchain polyol esters as “neo-synthetics.” These are used at high levels (30 to 50%) in the emulsion concentrates, to replace the EP additive, sulfur, or chlorine. Such formulations are used for machining hard alloys, like silicone aluminium, and for deep hole or gun drilling applications. Another development has been the development, by Uniqema, of self-emulsifying esters specifically for watermix fluids. These fluids combine lubrication and emulsification in one molecule that allows a single formulation to be suitable for use in all types of water hardness. Self-emulsifying esters do not suffer problems with the formation of calcium soaps in hard waters or the development of excessive foam in soft waters. Also, no depletion of anionic emulsifiers or corrosion inhibitors occurs. The overall result is more stable emulsions that have longer service lives compared to conventional water-mix emulsions. Self-emulsifying esters can also be used in neat forming oils, to allow water washability after forming, in copper

48.5.5 Metalworking Fluids During the early 1980s, neat (mineral oil-based) cutting oils were increasingly replaced by water-based emulsion and solution cutting fluids, due to problems with faster cutting speeds, generation of oil mists, health and safety issues associated with MVI mineral oils and chlorinated additives and the risk of fires. It was soon recognized, however, that water-based cutting fluids suffered equally serious problems of microbial degradation, shorter operating lifetimes, corrosion, sticky deposits after evaporation from workpieces and machine tool surfaces, and requirements for much greater monitoring and control. In 1995 and 1996, several European initiatives caused machine tool workshop staff to ask for replacements for water-soluble metalworking fluids. Health and disposal issues have exposed these fluids to considerable study and monitoring. Adverse health effects related to watermiscible fluids involve the presence of benzoic acid derivatives, alkaline nitrites, the danger of nitrosamine formation and germicidal contamination. Germany’s Waste Water Levy and Law on Water have considerable influence on the splitting and reconditioning of water-miscible cutting fluid. Waste Water Levy charges for pollutants with high chemical oxygen demand (COD, CSB) that are routed into public sewers are of particular relevance to water-miscible


wire drawing oils, to reduce copper soap formation, and in low-foaming grinding fluids. Overall, however, volumes of synthetics sold into this sector remain small, and the bulk of the market remains either with traditional mineral oil emulsions or the multicomponent “semisynthetics,” which are mainly complex chemicals, rather than the synthetic base fluids under review. 48.5.5.2 Neat cutting oils As a result, neat mineral oils containing replacements for chlorinated additives have been developed to eliminate these concerns, while maintaining the advantages of water-miscible fluids. When making the switch back to neat cutting fluids, the favorable properties that water imparts (good cooling, good chip flushing, and fire resistance) need to be considered. Low viscosity fluids are needed to retain these qualities. Drag-out losses on workpieces and chips is also dependent on viscosity. But low viscosity mineral oils traditionally display relatively high evaporation rates and low flash points, which conflict with worker safety and ecological considerations. Such problems can be solved with low-viscosity, esterbased cutting fluids, which have rapid biodegradability, low evaporation, low misting, and high flash point properties. High-performing synthetic esters are obtained by the chemical/physical modification/refining of either natural vegetable or animal oils (oleochemical products) or mineral oil. In metalworking, the first machining trials with ester-based oils took place in the 1980s. The priorities then were technical requirements for high-speed grinding and the avoidance of additives containing chlorine. Ester oils performed well under high speeds, producing good surface finishes. Since then, and with a view to the “machine tool” system, it has been possible to develop an ester-based fluid family of cutting fluids, gear oils, slideway oil, hydraulic fluids, and greases. These are all compatible with one another, so leakages from machine parts do not, or only slightly, alter the properties of the cutting fluid. This results in longer cutting fluid life and the elimination of tramp oil problems (including costs). 48.5.5.3 Steel, aluminium, and copper rolling oils In steel rolling oils, the move toward long-chain polyol esters has continued and they now have a dominant share of the steel market in Western Europe. These products are based on trimethylol propane (TMP) or pentaerythritol esters. Earlier formulations were based on emulsifiable oils (70% mineral oil, 25% tallow fats, 5% emulsifiers). The TMP esters were originally developed by Quaker Chemical, but this technology has now been adopted by other specialist suppliers in both Europe and the United States.


However, while these esters now have an estimated 90% of the European market, development in the United States has been much slower, and only about 35% of the steel market is currently using long-chain esters. In cold rolling of aluminium foil, where all products used must be nontoxic, because the foil is used for food wrapping, the main fluid used for the rolling process is a nontoxic gas oil, mainly produced by solvents companies. Also in wide use are iso-paraffinic solvents such as Exxon’s “Norpar.” A single large mill can use 3000 t of solvents per year. Rolling is at 200 to 300 meters per minute at 675◦ C. The base solvent has a viscosity of 1.8 cSt at 40◦ C and a boiling range of 200 to 250◦ C. Load carrying and lubricity additives are incorporated, which enable increased reductions to be taken, before breakdown of the lubricants. It is known that PIB is in use as an additive, because of its ability to depolymerize and evaporate. Similarly there is evidence in the United States that PAGs are used as an additive/rolling aid at a ratio of 5% of the total solvent. Additionally, from 1988 to 1991, in foil rolling plants in Europe, PIB-formulated machinery lubricants increased their share of the business, to ensure compatibility and nontoxicity in the event of cross-leakage to the foil. For copper rolling, the annual demand for fluids is about 15,000 t in Western Europe. Emulsifiable mineral oil/fatty acid blends are used, to avoid staining problems due to water, and metal passivators are also added. Fatty acid esters are replacing straight fatty acids. PIBs have been used for hot rolling of copper, but it is not known if the products are yet established. 48.5.5.4 Stamping, pressing, and forming oils In hot stamping the primary products that are used are mixtures of graphite and water, from companies such as Acheson Colloids. The concern of the hot stamping companies is that, if they use any kind of mineral product or chemical product, there will be a “fire-flash,” before the product actually serves its purpose, as a carrier of the graphite to the point of contact. Nevertheless, there is still interest in the possibility of using polyglycols or PIBs for these applications. More technical work is needed before progress will be made, as this is a very conservative industry. In cold pressing lubricants for sheet metal, it is believed that the traditional special semifluid pastes are still the dominant products, coming from organizations such as the Houghton Group. BP confirms that they are selling PIBs for stainless steel pressing, again presumably because of the clean burn-off and non-staining nature of the PIB. PAGs and PIBs are also being used in automatic cold stamping of components, such as spark plug bodies. The clean burn-off of the products during annealing is a major advantage. Several suppliers have been trying synthetics in recent years for these applications.

In the stamping and forging of aluminium in the United States, the industry has recently been replacing chlorinated paraffins, for environmental reasons. Removal of stamping fluid is of course needed, and here PAGs, which can be water-rinsed, are finding an outlet in preference to products needing washing off with 1,1,1-trichloroethane. 48.5.5.5 Wire and tube drawing lubricants In the drawing of wire, the products that were used for many years were based on soaps and fats. Clearly these are now being replaced by more modern and environmentally acceptable products. It has been reported that some 2500 t of polyglycols are being sold into the wire drawing sector in Europe, and this usage for PAGs has also been confirmed in the United States. BP Chemicals also advise that PIBs are being used in stainless steel wire drawing and also in copper tube drawing. On the other hand, in the production of shaped aluminium extrusions, such as for window frames or patio doors, it appears that water-graphite mixtures are still the norm. These are swabbed onto the ram area of the extruder, and not used as a die lubricant. 48.5.5.6 Aluminium can stock and can drawing fluids These are specialized markets, where a number of companies, like ExxonMobil, have strong positions. Additionally, specialized formulators like Nalco and Ferro in the United States compete, and some aluminium companies make up their own formulations on site. Nontoxicity and FDA approval are, of course, mandatory requirements. It is known that PAGs are in use in small amounts, as are PIBs. Similarly, long-chain polyol esters, which are emulsified at consuming plants, are used for aluminium can stock drawing in the United States. 48.5.5.7 Heat treatment (quenching) fluids In the quenching fluids sector, attempts by producers of synthetic quenchants to push up their market share continue without abatement. Union Carbide (now Dow Chemical) was the first company active in this sector, with their “Quenchant A,” and subsequently Uniqema (ICI) and others moved into the market. Polymer quenchants are much better than mineral oils in environmental terms, because of the elimination of fire hazards and the need for less protection equipment. They also improve working conditions, due to the elimination of smoke and fumes. Additionally, because they are diluted with water to an average of 15% (range 10 to 20%), there are lower initial costs and reduced “drag-out.” The main products competing in this market are PAGs, polyvinyl alcohols (PVA), polyvinyl pyrrolidone (PVP), and polyacrylates. The two leaders at present are PAGs and polyacrylates, there having been a number of problems with PVA and PVP.


48.5.6 Other Industrial Lubricants 48.5.6.1 Textile lubricants Synthetic fibers are polymers of very high molecular weight. The nature of polymers is such that they have very little inherent lubricity. In every stage of their manufacture, from polymerization to production of finished consumer articles, it is necessary to provide lubrication to aid the control of friction. This lubrication is provided as a “spin finish” for primary fiber production. Depending on the end use, this finish may be removed and secondary textile mill finishes provided for subsequent processing and even for point-of-sale handling. The demands of the textile industry for processing aids to control the fiber friction at different stages of processing are infinite. This has led to a supporting industry providing the necessary expertise, often integrating chemical manufacture, textile evaluation, and blending facilities. For simplicity the requirements can be classified into two main groups: 1. Spin finishes • Provide the correct balance of fiber-to-fiber and fiber-

to-guide friction. • Provide static control during polymer spinning and

subsequent processing. • Seek to provide a product that has optimal thermal

stability and volatility characteristics. • Give rapid fiber surface wet out; Have good anticor-

rosive properties. • Have good stability at high and low temperatures;

Have minimal effect on the fastness of dyes and pigments. • Are easy to remove in washing off baths. 2. Textile mill finishes • Provide correct frictional and static control as with

spin finishes. • Provide effective control for a full range of natural

and synthetic fibers and blends. • Provide efficient performance in a range of textile

operations. • Are compatible with other processing aids both within

the system and with spin finishes. • Can be easily removed and have no adverse effect on

the dyeing or dye fastness ratings. • Do not leave deposits that are difficult to remove, or

interfere with machine performance. • Are stable over a wide range of temperatures and have

an extended shelf life. Originally white mineral oils were widely used for this application. PAGs have now taken over from white oils

almost completely, due to their controllability (via molecular weight) and water solubility. PAGs are used mainly in nylon and polyester finishes. Probably 90% of PAG consumption is in this area rather than in wool or natural fibers. There are no figures available on actual PAG consumption within the many finish formulations. 48.5.6.2 Wire rope, chain, and chainsaw lubricants Industrial chains are often working under severe conditions of heat, in textile works (stenter chains) in car factories or in pottery and glass kilns. Large chains are mainly used in conveyor systems, but the difficult applications are mainly those involving severe heat from ovens. Such hightemperature conveyor bearings have always been a difficult lubrication problem. Often molybdenum disulphide carrying products have been used. PAOs, PIBs, and trimellitates have proved successful for temperatures up to 200◦ C. Some manufacturers in the United States also market ester-based products for this application, for use up to 280◦ C. One major supplier estimates a total of 1000 t of sales of synthetics into “hot” applications in the United States, such as ovens, glassworks, stenters, and conveyors. Although the PAGs enjoy a broad industrial market, increased usage of synthetic alternatives is expected in future. PAOs and PAO/ester blends are the most likely competitors. It is believed that sales of synthetics into these sectors of the industrial market have increased significantly over the past few years, as a result of major sales efforts, especially by ExxonMobil, and total sales in Western Europe could now be around 10,000 t per annum. Similarly, for forestry chainsaw oils, long-chain esters are used together with diester-based two-stroke oils, for the chainsaw engine. PIB based products are available for “high tackiness” applications on overhead conveyors in car plants, where drip-off would be unacceptable. PIBbased products are also now in use in wire rope lubricant formulations, traditionally bitumen based. Since the late 1990s, vegetable oil-based biodegradable chainsaw oils are being used increasingly in Scandinavia, Germany, Austria, and Switzerland. The total Western European market for chainsaw oils was estimated to be around 40,000 t in 2002, of which about 15,000 t were vegetable oil-based and about 2,000 t were synthetic esters. 48.5.6.3 Food grade oils For many years white mineral oils have been used for direct food contact applications. A high volume example is dough-knife lubricants in bakeries; a large bakery can use 50 to 100 t/yr of white oil. There are numerous applications for medicinal white oils used in direct contact with foods. These include release agent and lubricant for bakery products, release agent for dehydrated fruits,


vegetables, and egg white solids, release agent, binder and lubricant in the manufacture of yeast for bakery and brewing, release agent and as sealing and polishing agent in the manufacture of confectionery and release agent, binder and lubricant in or on capsules or tablets containing concentrates of flavorings, spices, condiments, or nutrients intended for addition to foods, excluding confectionery, and in or on capsules or tablets containing food for special dietary use. Other applications include protective float on fermentation fluids in the manufacture of wine or vinegar, to prevent or retard access of air, evaporation of water or alcohol and wild yeast contamination during fermentation, protective float on brine used in the curing of pickles, protective coating on raw fruits and vegetables, component of hot-melt coating applied when freezing meats, dust control agent for wheat, corn, soybean, barley, rye, oats, sorghum, and rice. Protective coatings applied to fruits and vegetables are also used to provide “glossing,” to give the products a more appealing look for consumers. Antidusting sprays used for grains are used mainly in storage silos, conveyors, and bulk grain transporters (trucks, rail tank cars, and ships) to minimize the risks of explosions associated with static buildup during movement of the grains. In addition to the use of medicinal white oils in or on foods, all lubricants used in machinery for preparation or handling foods must be food (medicinal) grade quality. This applies whether the lubricants are oils or greases. Food machinery lubricants include: • • • • • • • • • • • • •

Hydraulic oils Gear oils Air compressor oils Refrigerator compressor oils Vacuum pump oils Heat transfer oils Rotary cooker and sterilizer oils and greases Dryer and over oils and greases Chain oils and greases Conveyor oils and greases Plastic packaging machine oils and greases Bottle, crate, and keg washing machine oils and greases Bottle filling and capping machine oils and greases

Lubricants based on PAGs, PAO, and PIB can be formulated to pass FDA tests. Dow Chemical offers a range of fully formulated PAG-based extreme pressure lubricants for food machinery, where accidental contact can occur. All components can be identified in the FDA Regulations 21CFR 178.3570(a). In addition to providing nontoxicity, better lubricity, higher VI, oxidation and thermal stability, the lower pour points and viscosities have led to energy saving of up to 8%, compared to white oils or mineral oils, in food machinery gearboxes. As discussed earlier under aluminium rolling, lubricants for machinery rolling foil is

a growing outlet for PIB-formulated lubricants. PAO producers are also selling into the “food-grade” markets at present. Many food grade oils and greases now use either Group III (VHVI), PAO, diester, polyol ester, polyalkylene glycol, or silicone baseoils. Formulations are very similar to those of standard industrial oils, but using only FDA approved additives. A number of newer formulations do not use technical or medicinal mineral white oils, which require higher concentrations of oxidation inhibitors to achieve satisfactory stability.

48.5.7 Greases All lubricating greases, whether mineral oil or synthetic fluid based, consist of two fundamental components: a base fluid representing the principal ingredient in the formulation and a thickening agent that is used to immobilize the fluid. The concentration of thickener determines the consistency of the finished product. However, it is the nature of the oil that determines whether the grease will be classified as a synthetic. Although all greases contain oil and thickener, the possible oil, thickener, antioxidant, antiwear, extreme pressure, and anticorrosion additive combinations that can be used provide manufacturers with a great deal of flexibility in formulating products with many different physical and chemical attributes. The primary advantages of synthetic greases are improved thermo-oxidative stability, wide temperature serviceability, and less change in apparent viscosity as a function of temperature. Since oils used to formulate synthetic greases are virtually free of unsaturation and are synthesized to be resistant to oxidative attack, synthetic greases, as a class, greatly outperform their non-synthetic rivals under severe oxidizing conditions. With selected oils, synthetic grease can be formulated with unsurpassed ability to remain pliable at −54◦ C while not deteriorating or excessively evaporating at temperatures above 177◦ C. Adequate viscosity under operating conditions is the most important property any lubricant can possess. Without it, moving surfaces are destined for self-destruction regardless of how well the grease is fortified with special additives. Greases made from synthetic oils maintain their apparent viscosity as a function of temperature better than non-synthetics. Higher-performance greases, based on synthetics of all types, PAO, PAG, PIB, and polyol esters (all chain lengths), are now being promoted widely. Polyurea greases are ideally suited for rolling bearings operating in hightemperature and high-speed conditions, particularly if the grease is ester based. Kluber has developed both fullsynthetic and part-synthetic ester-based polyurea greases, specifically for bearings operating under arduous conditions. Lithium soaps can also be used for synthetic greases, as can PAOs, PAO/VHVI blends, and PAO/ester blends. Hatco has a polyol ester grease (HATCO 3000) for use


on stenter frames, and other applications with operating temperatures of up to 280◦ C. Many grease manufacturers believe that the total market for greases will remain static, with increasing demand in some industries and regions being offset by the ever expanding use of sealed-for-life bearings and longer life products that substantially decrease relubrication intervals. These trends inevitably mean the use of greater amounts of synthetic fluids in grease manufacture, which has been confirmed in the latest worldwide surveys conducted by the U.S. National Lubricating Grease Institute (NLGI). Synthetic, highly water-resistant greases have also been introduced. Environmental issues are also having an increasing influence on grease users. Biodegradable greases are now being supplied for a number of environmentally sensitive applications, including agriculture, forestry, railroad, mining, and central lubrication systems for trucks and buses. These are applications in which the grease can leak into the environment, be washed off exposed surfaces, or may be spilled accidentally. The trends are most evident in Scandinavia, Germany, Austria, Switzerland, and the Netherlands, although biodegradable greases are also being used in France, the United Kingdom, Belgium, and Italy. In 1998, environmental criteria for lubricating greases were included in the Gothenburg “Ren Smörja” (“Clean Lubrication”) project. These criteria have been further refined and are now a part of the Swedish Standard “Lubricating Grease — Requirements and Test Methods — SS 15 54 70.” Following international consultation, the Standard was issued in 2002 and the official English version will be issued during 2004. The environmental requirements, as given in Section 4.2 in the Standard, are rigorous. They require that a lubricating grease should be biodegradable and have minimal aquatic toxicity. Also, an assessment is required of chemical compounds that have sensitizing properties. A grease conforming to SS 15 54 70 is classified in one of three classes; A, B, or C. These are differentiated by the levels of substances allowed in the product. Class A greases must have a minimum content of components from renewable resources of 65% by weight. The content of renewable resources in Class B greases should be more than 45%. For Class C greases, there is no requirement to include components form renewable resources. Greases are examined by SP (Swedish National Testing and Research Institute), on behalf of the producer or supplier. Each assessment requires access to the formulation, including the chemical composition of the base fluid(s) and the additives. All information about the product and the test results is supplied to SP under a written personal confidentiality agreement. The required performance properties are set by the Standard and the test results are certified by the manufacturer.

As of March 2004, only Class B greases had been assessed. A number of European marketers of greases now supply biodegradable products, including Agro Oil, Binol, BP/Castrol, Cargo Oil, Fortum, Kuwait, Preem, Shell, and Statoil. Automotive greases were covered in Section 4.7.5.1 and aviation greases will be covered in the next section.

48.5.8 Aviation Lubricants 48.5.8.1 Civil aviation lubricants The bulk of civilian aviation lubricant demand is for gas turbines in jet aircraft, followed by aviation piston engine oils. Development costs for jet lubricants are extremely high, as are the costs of flight tests. In 1998, only Castrol, Esso, Mobil, Nyco, and Shell remained in the aviation gas turbine business, even BP having withdrawn in 1980, as others did in the 1970s. Now, following the merger of Exxon and Mobil at the end of 1999, the situation has changed as a consequence of conditions attached to the merger by the U.S. Securities and Exchange Commission (SEC) and the European Commission (EC) Competition Directorate. Exxon’s aviation lubricants business was sold to BP, which is now back in the business as BP/Castrol. Mobil’s activities became the basis for ExxonMobil’s new aviation lubricants business, so there are now only four main suppliers: BP/Castrol, ExxonMobil, Nyco, and Hatco (Royal). The first generation of gas turbine lubricants, known as Type I oils, were of 3 cSt viscosity, mainly based on diesters, principally azealates and sebacates. One other earlier type of lubricant (the Type I, 7.5 cSt oil) was thickened with a PAG. This product was used primarily in turboprops, to combat the heavier loadings. The civil turboprop aircraft that used Type I oils are now mainly phased out, except for a few Viscounts, plus of course HS748s and Fokker F27s, used on regional routes. In Western Europe most aircrafts now use Type II or Type III oils, which are all based on polyol esters and are of 5 cSt viscosity. The accompanying slide shows the various lubricant specifications. Diester-based Type I oils are still in use, at a level of about 1500 t per annum in Europe, for both civil aircraft as mentioned and for aircraft retained by the military (such as the VC10 or Buccaneer). Additionally a good proportion of diesters are used in jet engines for generating, gas pumping, or industrial use, such as the Rolls-Royce Avon. Almost no diesters are in use now in the United States. ExxonMobil have their major blending plant at Bayway (New Jersey) and Shell, Nyco, and BP/Castrol blend in Europe. The leading base ester suppliers in the United States are Hatco and ExxonMobil, followed by Emery (now Henkel), while in Europe, Uniqema, Ciba, and Nyco are the main producers of esters approved for aviation usage. Nyco is a major


supplier to the French Air Force, and also a significant exporter of synthetics to the USSR. In the piston engine aviation market, which is of course dominated by engine lubricants for small light aircraft, high-quality single-grade mineral oils have been the preferred choice for many years. However, Shell introduced a PAO/mineral oil multigrade (Aeroshell Oil W 15w50), and it is understood that this is enjoying increasing popularity. In the field of aircraft hydraulics, civilian aircraft are using specially developed types of fire-resistant phosphate esters in their hydraulic systems. Monsanto and Chevron of the United States are the two suppliers to this market sector on a global basis. The requirement is for phosphate esters capable of operating at very low temperatures. Monsanto makes alkyl-aryl esters “in-house” at Bridgeport, New Jersey, and possibly in St Louis. Chevron offers mixed triaryl/trialkyl esters. Total demand for phosphate esters is believed to be about 3000 to 4000 t. Military aircraft tend not to use fire-resistant hydraulic fluids, but more recently have been switching from naphthenic mineral oils to PAO/ester blends, following losses in action in Vietnam, through fires from hydraulic leakages. The overall demand for “aviation” hydraulic fluids worldwide is estimated at about 15,000 t, including the former CPE countries. About half this demand is mineral oil, and it should also not be overlooked that “aviation quality” or “superclean” and military specification fluids are demanded for ground equipment, and even in earthmoving equipment, by nonmilitary organizations. Aviation greases are of course made to the same stringent standards as other products for the aircraft industry, and have to withstand the same extremes of temperature. A number of companies are offering greases using PAOs or esters as bases, and these are proving to be increasingly successful in this demanding market. Despite its intrinsic appeal, the aviation business does not utilize large volumes of lubricants. The lubricants in gas turbines are rarely changed, but are simply topped up at the end of long flights, so that there is a continual renewal of the charge. Additionally, one company in the United Kingdom has Rolls-Royce approval to recondition gas turbine lubricants. A small but steady business exists in recycling and reconstituting used gas turbine lubricants and returning them to their owners, all over the world. It is estimated that the total consumption for both military and civilian aviation is in the order of 70,000 t per annum, split as follows: 45% for gas turbine oils, 25% for piston engines, 25% for hydraulic fluids, and the balance of 5% for greases, compounds, and miscellaneous uses. 48.5.8.2 Military aviation lubricants Practically all military lubricant applications are covered by specifications, issued by the United States (Mil-L-etc.),

the United Kingdom (DEng), France (AIR), or Russia, with NATO codes also available as a cross-reference. Obviously many synthetic products, such as gas turbine lubricants, are common to both civilian and military uses. However there are differences in specifications and usage, in that, for example, the U.S. Air Force prefers to use a 3 cSt polyol ester, while most civilian aircraft and the U.S. Navy prefer 5 cSt. There are now signs of change here, and a new 4 cSt polyol ester specification is being introduced soon. So far, BP/Castrol (with Castrol 4000) is the only approved supplier. The U.S. Army has a tank, the M1 Abrams, which is the only one in the world with a gas turbine engine. This has a requirement for a polyol ester lubricant meeting the Mil-L-23699D specification. A further long-standing but small U.S. Army requirement has been for an Arctic engine oil (spec. Mil-L-46167). A product meeting this specification was in great demand by oil companies in the Alaskan oil fields, during their development, but since then sales have dropped sharply. The predominant formulation used was a dialkyl benzenebased lubricant, supplied by ConocoPhillips; however, the specification can also be met with a 70% PAO/30% ester formulation. PAO-based formulations have also been in use for several years in military hydraulic fluids for aircraft (MilH-83282) and ground equipment (Mil-H-46170). Sales of these fluids were around 12,000 t in 1996, worldwide. The 83282 specification replaces the naphthenic mineral oil specification. (Mil-H-5606) and is known to be used in F14, F16, and F/A18 fighters of the U.S. Air Force, Navy, and Marines. The formulation is a mixed 65% PAO/35% diester, but it is believed that a polyol ester may be introduced soon. The 46170 specification formulation includes rust inhibitors, for tanks and other ground equipment hydraulics, used when in storage. Additionally, PAO and esters have been introduced for instrument applications, where the recognized specification is Mil-L-6085A. Avionics uses include dielectric heat transfer fluids, used in closed systems for radars and ECM systems. A U.S. Air Force specification Mil-C-87252 calls for a 2 cSt PAO for these applications. A wide range of military greases for aviation has been specified, including those with NATO codes such as G382 based on mineral oils (−40 to 120◦ C operating range), or silicones and perfluorosilicones (G372 and G398). As far as synthetics are concerned, G354 is a diester-based grease (−75 to 120◦ C operating range), G395 is a non-soap PAO-based grease (−55 to 175◦ C operating range), and G363 is a complex ester-based grease that is hydrocarbonresistant. Finally, mention should be made of the CIS, which surprisingly has used large volumes of naphthenic mineral oils for aircraft gas turbine lubrication for many years. However, the CIS also has a polyol ester specification, B-3V for


a 5 Kinematic Viscosity (100◦ C) lubricant, and VNII NP50-1-4-U for a 3.2 KV diester-based lubricant, as well as IPM-10 for a 3 KV diester/synthetic hydrocarbon blended product.

48.6 FUTURE TRENDS The market for automotive engine oils has been through a period of unprecedented change in terms of industry specifications, product development, and customer expectations at a time of low overall growth in demand for products. This has caused problems of profitability for additive manufacturers and baseoil producers, in addition to opportunities for companies with marketing and service support skills. The primary observation is that suppliers with higherperformance products, better marketing, and attention to service support are more likely to take market share from suppliers that lack one or more of these customer-driven attributes. Overall growth in markets for industrial lubricants is likely to continue to be relatively slow for the foreseeable future. World GDP and inflation rates are becoming lower, so increases in demand for industrial lubricants in Asia, South America, and Central Europe are likely to be substantially offset by decreases in demand in Western Europe and North America. Quality and performance are likely to be the key to higher prices and product differentiation in industrial lubricants. Unfortunately, higher quality and performance are likely to lead to further increases in product lifetimes, extended drain intervals, lower maintenance, and downtime and reductions in lubricant volumes. The dominant environmental issues for automotive and industrial lubricants over the next five years are likely to be: • • • • •

Fuel efficiency Emissions limits and emissions durability Biodegradability and bioaccumulation Toxicity Waste, disposal, and recyclability

There is likely to be a greater use of PAOs and PAO/mineral oil blends in land-based gas turbines. Larger, heavy-duty power generating gas turbines will be favored in many parts of the world in which natural gas is readily available. This includes large parts of Western and Central Europe, Asia, and South America, particularly Chile and Argentina. The trend toward higher gas temperatures for greater thermal efficiency is likely to continue. In industrial gearboxes, there is likely to be an increasing use of synthetic lubricants, but PAOs are unlikely to grow as fast as PAGs. The main reason for this, despite the favorable reductions in operating temperatures and power consumptions for both types of fluids, is the sludge problems experience by PAO-based fluids in gear systems exposed to moist operating conditions.

With rotary screw air compressors, the use of PAOs is likely to increase, although the competition from VHVI oils is likely to increase. Unfortunately, this is not a large market in total. There is unlikely to be any significant change in the use of PAOs in refrigerating compressors. Last, but by no means least, it is likely that lubricant suppliers will pay more attention in future to customer needs and improved marketing methods. Benefit selling is likely to be a key factor in determining success, whereby genuine partnerships between lubricant suppliers and lubricant users will allow both to share in the financial rewards obtained from using higher-quality and performance industrial lubricants. The synthetic lubricants business is no longer a pioneering industry. However, it remains competitive, tough, and “slow-going.” Some of the promised benefits have not been demonstrated and education of the market has taken much longer than many people anticipated. Expertise, experience, and confidence have grown among users and suppliers throughout the 1980s. Identifying user benefits and technology-oriented marketing remain the key to commercial success. More specifications are being introduced that favor the use of synthetic oils. The situation with U.S. automotive specifications is worth watching. Relationships between price and performance for conventional baseoils, Group III baseoils, and synthetic oils are better understood. Suppliers of all types of lubricants have learnt to adopt user-sensitive pricing strategies. Health, safety, and environmental issues have opened up new opportunities for synthetic lubricants. Some examples are the growth in demand for esters and rapeseed/ester blends in biodegradable lubricants, the substitution of PAGs, or polymer esters for chlorinated paraffins, in the forging and stamping of aluminium, or the increasing use of long-chain polyol esters in plants such as paper converters, where there may be a fire risk. Ease of disposal will grow as an issue in the lubricants business, as it is in the plastics business today, which may help some synthetics. The synthetic lubricants business is entering an exciting new phase of potential development. A growing number of OEMs and customers have begun to accept that synthetics offer improved cost/performance compared to mineral oils. This trend is likely to continue. More specifications are being issued, like VW503, Mercedes-Benz p229.5, or “Road Ranger” from Eaton, which can only be met with synthetics or unconventional baseoils. This opens up wider opportunities. There will be an increased commitment to the use of Group III, synthetics and/or part-synthetics, as know-how is acquired.


However, due to the likely continuing overcapacity in conventional lubricants markets, the market for synthetics is likely to remain competitive. There will be growing inter-product competition, especially in automotive, twostroke, compressor, bearing, circulation, and hydraulic applications. The result is likely to be a constant stream of reformulated, improved, and new products based on cost-benefit analyses of customers’ needs. The dynamism of the synthetics business is reflected in the many sectors that have been opened up in the last decade or so. Examples are two-stroke engine, auto airconditioners, aircraft piston engines, military hydraulics and instruments, extensions in the usage of fire-resistant fluids, offshore compensators, solar fluids, electrostatic precipitator, fiber optic gels, circuit board fluxes, and metalworking applications, especially rolling, drawing, stamping, and pressing operations. Pricing relationships between the synthetics and between mineral oils, unconventional baseoils, and synthetics are now more widely understood, together with product performance advantages or limitations. This is now leading to more careful and accurate formulation choices, especially in those areas where confusion reigned in the early 1980s, such as motor oils, where PAOs, esters, and their new competition from VHVI baseoils are now the preferred blending stocks for advanced formulations, involving 0w/5w-based motor oils with low volatility. However despite all these efforts, synthetic lubricants remain (except perhaps in European motor oils) a conglomeration of niche markets. As a result, the forecasts in the early 1980s are likely to prove to be optimistic, unless there is, in particular, a more rapid swing to 0w motor oils and even lower NOACK volatility limits for U.S. automobile and truck engine oils. Considering that most of the market in the United States is already on 5w/10w oils, this is of significant importance for synthetic lubricant volume, as it has been in Europe. The future for synthetics remains interesting, but not spectacular. Success will come from hard work and the dedication of efforts to meeting real customer needs and solving technical problems. Structurally, the suppliers of synthetic baseoils are particularly chemical companies, whilst the bulk of lubricants are sold by oil companies. To succeed, chemical company know-how about end users and performance, needs to match that of the oil companies. The lubricants business has in general been dominated by engineers, not chemists, and the blending of these two disciplines, or their partnership, is the key to the future of synthetics.

Part V Methods and Resources


49

Lubricant Performance Test Methods and Some Product Specifications Leslie R. Rudnick

This chapter contains a selection of many of the most commonly used test methods and specifications selected from the United States, Europe, and Japanese Lubricant Testing Methods. These include methods, standards, and specifications from ASTM, FTM, MIL, CEC, DIN, JPI, as well as Federal Supply Class 9150 commodities. Some cross-references are also given.

The American Society for Testing and Materials publishes an Annual Book of ASTM Standards: Petroleum Products, Lubricants, and Fossil Fuels, Volumes 5.01–5.04, where a complete list of ASTM methods pertaining to lubricants may be found.

Summary of Standard Test Methods and Specifications ASTM D 86 D 88 D 92 D 93 D 95 D 97 D 130 D 150-98 (2004) D 156 D 189 D 217 D 257-99 D 287 D 445 D 482 D 524 D 525-05 D 566 D 567 D 611 D 664 D 665 D 877-02e1 D 874 D 892

Standard Test Method for Distillation of Petroleum Products Standard Test Method for Viscosity Saybolt Seconds Universal Standard Test Method for Flash and Fire Points by Cleveland Open Cup Standard Test Method for Flash Point by Pensky-Martens Closed Tester Standard Test Method for Water in Petroleum Products and Bituminous Materials by Distillation Standard Test Method for Pour Point of Petroleum Products Standard Test Method for Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test Standard Test Methods for AC Loss Characteristics and Permittivity (Dielectric Constant) of Solid Electrical Insulation Standard Test Method for Saybolt Color of Petroleum Products (Saybolt Chromometer Method) Standard Test Method for Conradson Carbon Residue of Petroleum Products Standard Test Method for Cone Penetration of Lubricating Grease Standard Test Methods for DC Resistance or Conductance of Insulating Materials Standard Test Method for API Gravity of Crude Petroleum and Petroleum Products (Hygrometer Method) Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and the Calculation of Dynamic Viscosity) Standard Test Method for Ash from Petroleum Products Standard Test Method for Ramsbottom Carbon Residue of Petroleum Products Standard Test Method for Oxidation Stability of Gasoline (Induction Period Method) Standard Test Method for Dropping Point of Lubricating Grease Standard Test Method for Calculating Viscosity Index Standard Test Method for (1993)el Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents Standard Test Method for Acid Number of Petroleum Products by Potentiometric Titration Standard Test Method for Rust-Preventing Characteristics of Inhibited Mineral Oil in the Presence of Water Standard Test Method for Dielectric Breakdown Voltage of Insulating Liquids Using Disk Electrodes Standard Test Method for Sulfated Ash from Lubricating Oils and Additives Standard Test Method for Foaming Characteristics of Lubricating Oils


ASTM (Continued) D 893 D 942 D 943 D 972 D 974 D 1091 D 1092 D 1093 D 1159 D 1160 D 1209 D 1238 D 1264 D 1296 D 1298 D 1331 D 1358 D 1401 D 1403 D 1478 D 1500 D 1646 D 1662 D 1742 D 1743 D 1744 D 1748 D 1831 D 2007 D 2070 D 2155 D 2161 D 2265 D 2266 D 2270 D 2272 D 2273 D 2500 D 2509 D 2512-95 (2002)

Standard Test Method for Insolubles in Used Lubricating Oils Standard Test Method for Oxidation Stability of Lubricating Grease by the Oxygen Bomb Method Standard Test Method for Oxidation Characteristics of Inhibited Mineral Oils Standard Test Method for Evaporation Loss of Lubricating Greases and Oils Standard Test Method for Acid and Base Number by Color-Indicator Titration Standard Test Methods for Phosphorus in Lubricating Oils and Additives Standard Test Method for Measuring Apparent Viscosity of Lubricating Greases Standard Test Method for Acidity of Hydrocarbon Liquids and Their Distillation Residues Standard Test Method for Bromine Numbers of Petroleum Distillates and Commercial Aliphatic Olefins by Electrometric Titration Standard Test Method for Distillation of Petroleum Products at Reduced Pressure Standard Test Method for Color of Clear Liquids (Platinum Cobalt Scale) (APHA Color) Standard Test Method for Flow Rates of Thermoplastics by Extrusion Plastimeter (Melt Index) (or ISO 1133–1991) Standard Test Method for Determining the Water Washout Characteristics of Lubricating Greases Standard Test Method for Odor of Volatile Solvents and Diluents Standard Test Method for (1990)el Density, Relative Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method Standard Test Method for Surface and Interfacial Tension of Solutions of Surface Active Agents Standard Test Method for (1995)el Spectrophotometric Diene Value of Dehydrated Castor Oil and Its Derivatives Standard Test Method for Water Separability of Petroleum Oils and Synthetic Fluids Standard Test Methods for Cone Penetration of Lubricating Grease Using One-Quarter and One-Half Scale Cone Equipment Standard Test Methods for Low-Temperature Torque of Ball Bearing Grease Standard Test Method for Color of Petroleum Products (ASTM Color Scale) Standard Test Method for Rubber Viscosity, Stress Relaxation, and Pre-Vulcanization Characteristics (Mooney Viscometer) Standard Test Method for Active Sulfur in Cutting Oils Standard Test Method for Oil Separation from Lubricating Grease During Storage Standard Test Method for Corrosion Preventive Properties of Lubricating Greases Standard Test Method for Determination of Water in Liquid Petroleum Products by Karl Fischer Reagent Standard Test Method for Rust Protection by Metal Preservatives in the Humidity Cabinet Standard Test Method for Roll Stability of Lubricating Grease Standard Test Method for Characteristic Groups in Rubber Extender and Processing Oils and Other Petroleum Derived Oils by the Clay-Gel Absorption Chromatographic Method Standard Test Method for Thermal Stability of Hydraulic Oils (discontinued 1981, replaced by E 659) Standard Practice for Conversion of Kinematic Viscosity to Saybolt Universal Viscosity or to Saybolt Furol Viscosity Standard Test Method for Dropping Point of Lubricating Grease over Wide Temperature Range Standard Test Method for Wear Preventive Characteristics of Lubricating Grease (Four Ball Method) Standard Test Method for Standard Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 and 100◦ C Standard Test Method for Oxidation Stability of Steam Turbine Oils by Rotating Bomb Standard Test Method for Trace Sediment in Lubricating Oils Standard Test Method for Cloud Point of Petroleum Oils Standard Test Method for Measurement of Load Carrying Capacity of Lubricating Grease (Timken Method) Standard Test Method for Compatibility of Materials with Liquid Oxygen (Impact Sensitivity Threshold and Pass-Fail Techniques)


ASTM (Continued) D 2549-02 D 2595 D 2596 D 2602 D 2603-01 D 2619-95 (2002)e1 D 2620 D 2622 D 2625 D 2670 D 2710 D 2711 D 2766 D 2782 D 2783 D 2786-91 (2001)e1 D 2879 D 2882 D 2887 D 2893 D 2896 D 2982 D 2983 D 3120 D 3228 D 3232 D 3233 D 3238 D 3244 D 3336 D 3427-03 D 3525 D 3527 D 3704 D 3705

Standard Test Method for Separation of Representative Aromatics and Nonaromatics Fractions of High-Boiling Oils by Elution Chromatography Standard Test Method for Evaporation Loss of Lubricating Greases over Wide Temperature Range Standard Test Method for Measurement of Extreme-Pressure Properties of Lubricating Grease (Four Ball Method) (replaced by D 5293), Standard Test Method for Apparent Viscosity of Engine Oils at Low Temperature Using the Cold-Cranking Simulator Test Method for Sonic Shear Stability of Polymer-Containing Oils Standard Test Method for Hydrolytic Stability of Hydraulic Fluids (Beverage Bottle Method) (discontinued 1993, replaced by D 5293) Standard Test Method for Sulfur in Petroleum Products by X-Ray Spectrometry Standard Test Method for Determining Endurance Life and Load Carrying Capacity of Dry Solid Film Lubricants (Falex Method) Standard Test Method for Measuring Wear Properties of Fluid Lubricants (Falex Method) Standard Test Method for Bromine Index of Petroleum Hydrocarbons by Electrometric Titration Standard Test Method for Demulsibility Characteristics of Lubricating Oils Standard Test Method for Specific Heat of Liquids and Solids Standard Test Method for Measurement of Extreme-Pressure Properties of Lubricating Fluids (Timken Method) Standard Test Method for Measurement of Extreme-Pressure Properties of Lubricating Fluids (Four-Ball Method) (Load Wear Index) Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry Standard Test Method for Vapor Pressure–Temperature Relationship and Initial Decomposition Temperature of Liquids by Isoteniscope Standard Test Method for Indicating the Wear Characteristics of Petroleum and Non-Petroleum Hydraulic Fluids in a Constant Volume Vane Pump Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography Standard Test Method for Oxidation Characteristics of Extreme-Pressure Lubricating Oils Standard Test Method for Base Number of Petroleum Products by Potentiometric Perchloric Acid Titration Standard Test Method for Detecting Glycol-Base Antifreeze in Used Lubricating Oil Standard Test Method for Low-Temperature Viscosity of Automotive Fluid Lubricants Measured by Brookfield Viscometer Standard Test Method for Trace Quantities of Sulfur in Light Liquid Petroleum Hydrocarbons by Oxidative Microcoulometry Standard Test Method for Total Nitrogen, in Lubricating Oils and Fuel Oils by Modified Kjeldahl Method Standard Test Method for Measurement of Consistency of Lubricating Greases at High Temperatures Standard Test Method for Measurement of Extreme Pressure of Fluid Lubricants (Falex Method) Standard Test Method for Carbon Distribution and Structural Group Analysis of Petroleum Oils by the ndM Method Standard Test Method for Standard Practice for Utilization of Test Data to Determine Conformance with Specifications Standard Test Method for Life of Lubricating Greases in Ball Bearings at Elevated Temperatures Standard Test Method for Air Release Properties of Petroleum Oils Standard Test Method for Gasoline Diluent in Used Gasoline Engine Oils by Gas Chromatography Standard Test Method for Life Performance of Automotive Wheel Bearing Grease Standard Test Method for Wear Preventative Properties of Lubricating Grease Using the (Falex) Block on Ring Test Machine in Oscillating Motion Standard Test Method for Misting Properties of Lubricating Fluids


ASTM (Continued) D 3711 D 3829 D 3850-94 (2000) D 3945 D 4047 D 4048 D 4049 D 4057 D 4172 D 4294 D 4310 D 4485 D 4624 D 4628 D 4629 D 4636 D 4683 D 4684 D 4693 D 4739 D 4741 D 4742 D 4781-03 D 4857 D 4927 D 4950 D 4951 D 5119 D 5133

D 5182 D 5183

Standard Test Method for Deposition Tendencies of Liquids in Thin Films Standard Test Method for Predicting the Borderline Pumping Temperature of Engine Oil Standard Test Method for Rapid Thermal Degradation of Solid Electrical Insulating Materials By Thermogravimetric Method (TGA) Standard Test Method for Shear Stability of Polymer-Containing Fluids Using Diesel Injector Nozzle (Deactivated 1998, replaced by D6278) Standard Test Method for Phosphorus in Lubricating Oils and Additives by Quinoline Phosphomolybdate Method Standard Test Method for Detection of Copper Corrosion from Lubricating Greases Standard Test Method for Determining the Resistance of Lubricating Grease of Water Spray Standard Test Method for Standard Practice for Manual Sampling of Petroleum and Petroleum Products Standard Test Method for Wear Preventive Characteristics of Lubricating Fluid (Four-Ball Method) Standard Test Method for Sulfur in Petroleum Products by Energy-Dispersive X-Ray Fluorescence Spectroscopy Standard Test Method for Determination of the Sludging and Corrosion Tendencies of the Inhibited Mineral Oils Standard Test Method for Standard Specification Performance of Automotive Engine Oils Standard Test Method for Measuring Apparent Viscosity by Capillary Viscometer at High-Temperature and High Shear Rates Standard Test Method for Analysis of Barium, Calcium, Magnesium, and Zinc in Unused Lubricating Oils by Atomic Absorption Spectrometry Standard Test Method for Trace Nitrogen in Liquid Petroleum Hydrocarbons by Syringe/Inlet Oxidative Combustion and Chemiluminescence Detection Standard Test Method for Corrosion and Oxidative Stability of Hydraulic Oils, Aircraft Turbine Engine Lubricants, and Other Highly Refined Oils Standard Test Method for Measuring Viscosity at High Shear Rate and High Temperature by Tapered Bearing Simulator Standard Test Method for Determination of Yield Stress and Apparent Viscosity of Engine Oils at Low Temperature (MRV TP-1 Cycle) Standard Test Method for Low Temperature Torque of Grease-Lubricated Wheel Bearings Standard Test Method for Base Number Determination by Potentiometric Titration Standard Test Method for Measuring Viscosity at High Temperature and High Shear Rate by Tapered-Plug Viscometer Standard Test Method for Oxidation Stability of Gasoline Automotive Engine Oils by Thin-Film Oxygen Uptake (TFOUT) Standard Test Method for Mechanically Tapped Packing Density of Fine Catalyst Particles and Catalyst Carrier Particles Standard Test Method for Determination of Coefficient of Friction of Lubricants Using the Four-Ball Wear Test Machine Standard Test Method for Elemental Analysis of Lubricant and Additive Components, Barium, Calcium, Phosphorus, Sulfur, and Zinc, by Wavelength-Dispersive X-Ray Fluorescence Spectroscopy Standard Classification and Specification for Automotive Service Greases Standard Test Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma Atomic Emission Spectrometry Standard Test Method for Evaluation of Automotive Engine Oils in CRC L-38 Spark Ignition Engine Standard Test Method for Low Temperature, Low Shear Rate, Viscosity/Temperature Dependence of Lubricating Oils Using a Temperature-Scanning Technique (Scanning Brookfield Test with Gelation Index Calculation) Standard Test Method for Evaluating the Scuffing Load Capacity of Oils (FZG Visual Method) Standard Test Method for Evaluating Coefficient of Friction of Lubricants Using the Four-Ball Wear Test Machine


ASTM (Continued) D 5185

D 5293 D 5302 D 5306-92 (2002)e1 D 5480 D 5483 D 5533 D 5570 D 5621 D 5704 D 5706 D 5707 D 5800 D 5862 D 5864 D 5949 D 5968-04 D 5969 D 6006 D 6022 D 6046 D 607904e1 D 608097(2002) D 6081 D 6082 D 6121 D 6138 D 6158 D 6186 D 6278

Standard Test Method for Determination of Additive Elements, Wear Metals, and Contaminants in Used Lubricating Oils and Determination of Selected Elements in Base Oils by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) Standard Test Method for Apparent Viscosity of Engine Oils between −5 and −30◦ C Using the Cold-Cranking Simulator Standard Test Method for Evaluation of Automotive Engine Oils in the Sequence VE Spark Ignition Engine Standard Test Method for Linear Flame Propagation Rate of Lubricating Oils and Hydraulic Fluids Standard Test Method for Engine Oil Volatility by Gas Chromatography Standard Test Method for Oxidation Induction Time of Lubricating Greases by Pressure Differential Scanning Calorimetry Standard Test Method for Evaluation of Automotive Engine Oils in the Sequence IIIE Spark Ignition Engine Standard Test Method for Evaluating the Thermal Stability of Manual Transmission Lubricants in a Cycle Durability Test Standard Test Method for Sonic Shear Stability of Hydraulic Fluids Standard Test Method for Evaluation of Thermal and Oxidative Stability of Lubricating Oils Used for Manual Transmissions and Final Drive Axles Standard Test Method for Determining Extreme-Pressure Properties of Lubricating Greases Using a High-Frequency, Linear-Oscillation (SRV) Test Machine Standard Test Method for Measuring Friction and Wear Properties of Lubricating Grease Using a High Frequency, Linear-Oscillating (SRV) Test Machine Standard Test Method for Evaporation Loss of Lubricating Oils by the NOACK Method Standard Test Method for Evaluation of Engine Oils in Two-Stroke Cycle Turbo-Supercharged 6V92TA Diesel Engine Standard Test Method for Determining the Aerobic Aquatic Biodegradation of Lubricants or Their Components Standard Test Method for Pour Point of Petroleum Products Standard Test Method for Evaluation of Corrosiveness of Diesel Engine Oil at 121◦ C Standard Test Method for Corrosion Preventive Properties of Lubricating Greases in the Presence of Dilute Synthetic Sea Water Environments Standard Guide for Assessing Biodegradability of Hydraulic Fluids Standard Test Method for Calculation of Permanent Shear Stability Index Standard Classification of Hydraulic Fluids for Environmental Impact Standard Test Method for Evaluating Lubricity of Diesel Fuels by the High-Frequency Reciprocating Rig (HFRR) Standard Practice for Defining the Viscosity Characteristics of Hydraulic Fluids Standard Practice for Aquatic Toxicity Testing of Lubricants: Sample Preparation and Results Interpretation Standard Test Method for High Temperature Foaming Characteristics of Lubricating Oils Standard Test Method for Evaluation of Load Carrying Capacity of Lubricants Under Conditions of Low Speed and High Torque Used for Final Hypoid Drive Axles Standard Test Method for Determination of Corrosion Preventive Properties of Lubricating Greases Under Dynamic Wet Conditions (Emcor Test) Standard Specification for Mineral Oil Hydraulic Oils Standard Test Method for Oxidation Induction Time of Lubricating Oils by Pressure Differential Scanning Calorimetry (PDSC) Standard Test Method for Shear Stability of Polymer-Containing Fluids Using a European Diesel Injector Apparatus (see also D 3945)


ASTM (Continued) D 6278

Standard Test Method for Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus D 6417 Standard Test Method for Estimation of Oil Volatility by Capillary Gas Chromatography D 6425 Standard Test Method for Measuring Friction and Wear Properties of Extreme-Pressure (EP) Lubricating Oils Using SRV Test Machine D 6557 Standard Test Method for Evaluation of Rust Preventative Characteristics of Automotive Engine Oils D 6594-04a Standard Test Method for Evaluation of Corrosiveness of Diesel Engine Oil at 135◦ C D 6595 Standard Test Method for Determination of Wear Metals and Contaminants in Used Lubricating Oils or Used Hydraulic Fluids by Rotating Disk Electrode Atomic Emission Spectrometry E 537-02 Standard Test Method for The Thermal Stability Of Chemicals By Differential Scanning Calorimetry E 659 Standard Test Method for (1994)el Autoignition Temperature of Liquid Chemicals E 1064 Standard Test Method for Water in Organic Liquids by Coulometric Karl Fischer Titration G72Standard Test Method for Autogenous Ignition Temperature of Liquids and Solids in a High-Pressure 82(1996)e1 Oxygen-Enriched Environment G133/95 Standard Test Method for Linearly Reciprocating Ball-on-Flat Sliding Wear STP 315H Multicylinder Test Sequence for Evaluating Automotive Engine Oils STP 509A Single Cylinder Engine Test for Evaluating the Performance of Crankcase Lubricants CEC Test Methods L-01-A-79 L-02-A-78 L-07-A-85 L-11-T-72 L-12-A-76 L-14-A-93 L-18-A-80 L-19-T-77 L-20-A-79 L-21-T-77

L-24-A-78 L-25-A-78 L-28-T-79 L-29-T-81 L-30-T-81 L-31-T-81 L-33-A-93 L-33-A-94 L-34-T-82 L-35-T-84 L-36-96 L-36-A-90 L-36-A-97 L-37-T-85

Test for diesel engine crankcase oils using the Petter AVI single cylinder laboratory diesel engine Oil oxidation and bearing corrosion test using the Petter W1 single cylinder gasoline engine Load carrying capacity test for transmission lubricants using the FZG testrig The coefficient of friction of automatic transmission fluids using the DKA friction machine Evaluation of piston cleanliness in the MWM KD 12 E test tengine (Method B more severe) Evaluation of the shear stability of lubricating oils containing polymers using the Bosch diesel fuel injector pump rig Procedure for measurement of low temperature apparent viscosity by means of the Brookfield viscometer (liquid bath method) Evaluation of the lubricity of two-stroke engine oils (using the Motobecane engine AV7L 50 cm3 ) Evaluation of two-stroke engine lubricants with respect to engine deposit formation oils (using the Motobecane engine AV7L 50 cm3 ) The evaluation of two-stroke engine lubricants: Sequence I — Piston antiseizure Seqeunce II — General performance Sequence III — Preignition (using a Piaggio Vespa 180 SS engine) Engine cleanliness under severe conditions using the Petter AVB supercharge diesel engine Engine oil viscosity stability test (using a Peugeot 204 engine) The evaluation of outboard engine lubricant performance (using Johnson and Evinrude marine outboard engines) Ford Kent test procedure for evaluating the influence of the lubricating oil on piston ring sticking and deposit formation (using a Ford Kent engine) Cam and tappet pitting test procedure (using MIRA cam and tappet test machine) Predicting the borderline pumping temperature of engine oils using the Brookfield viscometer Biodegradability of Two-Stroke Cycle Outboard Engine Oils in Water Biodegradability of two-stroke cycle outboard engine oils in water Preignition tendencies of engine lubricants (using a Fiat 132C engine) Motor oil evaluation in a turbocharged passenger car diesel engine (using a VW ATL 1.6 litre). The Evaluation of Oil-Elastomer Compatibility (Laboratory Test) The measurement of lubricant dynamic viscosity under conditions of high shear (using a Ravensfield viscometer) HTHS Shear stability test for polymer-containing oils (using the FZG test rig)


CEC Test Methods (Continued) L-38-A-94 L-39-T-87 L-40-A-93 L-41-T-88 L-42-A-92 L-46-T-93 L-51-T-95 L-51-T-98

L-53-T-95 L-54-T-96 L-55-T-95 L-56-T-95 L-56-T-98

Valve train scuffing (using a PSA TU3 engine) wear test Oil/elastomer compatibility test Lubricating oil evaporative losses (using NOACK evaporative tester). Evaluation of sludge-inhibition qualities of motor oils in a gasoline engine (using a Mercedes-Benz M102E engine) Evaluation of bore polish, piston cleanliness, liner wear, and sludge in a DI turbo-charged diesel engine (using Mercedes-Benz OM364A engine) VW Intercooled turbo-Diesel ring stiching and Piston cleanliness test OM 602A neon test The Evaluation of Engine Crankcase Lubricants with Respect to Low Temperature Lubricant Thickening & Wear under Severe Operating Conditions (MB-OM602A engine) ‘A’ Status granted basis cam-wear only M111 black sludge test Fuel Economy Effects of Engine Lubricants (MB M111 E20) TU3 MH high temperature deposits, ring stiching, and oil thickening test XUD11 ATE medium temperature dispensarity test Oil Dispersion Test at Medium Temperature for Automobile Diesel Engines (XUD11BTE engine)

GM 9099P

Engine Oil Filterability Test (EOFT) (to be modified for GF-3)

SAE J183 J300 J357 J1423

Engine Oil Performance and Engine Service Classification (Other Than "Energy-Conserving") Engine Oil Viscosity Classification Standard Physical and Chemical Properties of Engine Oils Classification of Energy-Conserving Engine Oil for Passenger Cars, Vans, and Light-Duty Trucks

Miscellaneous Test Methods CEM Electric Motor Test (grease) DIN 51350 Part 2 Weld Load DIN 51350 Part 3 Wear Scar DIN 51352-1 Testing of lubricants; determination of ageing characteristics of lubricating oils; increase in Conradson carbon residue after ageing by passing air through the lubricating oil DIN 51554-1 Testing of mineral oils; Test of susceptibility to ageing according to Baader; Purpose, sampling, ageing DIN 51587 Testing of Lubricants; Determination of the Ageing Behaviour of Steam Turbine Oils and Hydraulic Oils Containing Additives DIN 51802 (IP-220) Emcor Rust Test DIN 51851 (ASTM-D 5100 NOACK Volatility) Emcor Rust Test (grease) FE-8 Test (grease) FTM-350 Evaporation Loss FTM-791B Cone Bleed FTM-791C (Method 3470.1) Homogeneity and Miscibility FTM-3009 Contamination, Particulate (oils) FTM-3411 Thermal Stability and Corrosivity FTM-5309 Corrosion, Copper, 24 Hours FTM-5322 Corrosiveness (bimetallic couple) GE Electric Motor Test (grease) JPI-55-55-99 Hot Tube Test MIL-G-22050 Gasket and Packing Material, Rubber, for Use With Polar Fluids, Steam, and Air at Moderately High Temperatures


Miscellaneous Test Methods (Continued) MIL-G-81322 Grease, Aircraft Wide Temperature Range MIL-H-22072C(AS) Hydraulic Fluid Catapult MIL-H-27601B Hydraulic Fluid, Petroleum Base, High Temperature, Flight Vehicle MIL-H-46170, Water Sensitivity MIL-H-46170B Hydraulic Fluid, Rust Inhibited, Fire Resistant, Synthetic Hydrocarbon Base MIL-H-53119 Corrosion Rate Evaluation Procedure (CREP) for CTFE Hydraulic Fluids MIL-H-83282 High-Temperature Stability (sealed ampule) MIL-H-83282 Linear Flame Propagation Rate MIL-H-83282C Hydraulic Fluid, Fire Resistant, Synthetic Hydrocarbon Base, Aircraft MIL-H-83306 Hydraulic Fluid, Fire Resistant, Phosphate Ester Base, Aircraft MIL-H-87257 High Temperature Stability (Purged with Nitrogen) MIL-P-25732 Cold resistant acrylonitrile-butadiene rubber MIL-PRF-2104 Lubricating Oil, Internal Combustion Engine, Combat/Tactical Service MIL-PRF-2105 Lubricating Oil, Gear Multi-purpose MIL-PRF-10924 Grease, Automotive and Atrillery MIL-PRF-46170 Hydraulic Fluid, Rust Inhibited, Fire Resistant, Synthetic Hydrocarbon Base MIL-PRF-63460 Lubricant, Cleaner and Preservative for Weapons and Weapons Systems (Metric) MIL-PRF-81322 Grease, Aircraft, General Purpose, Wide Temperature Range MIL-PRF-83282 Hydraulic Fluid, Fire Resistant, Synthetic Hydrocarbon Base, Metric, NATO CODE NUMBER H-537 MIL-PRF-87252 Coolant Fluid, Hydrolytically Stable, Dielectric MIL-R-83248 Rubber, Fluorocarbon Elastomer, High-Performance Fluid and Compression Set Resistant MIL-STD-1246 Cleanliness Levels SKF R2F Test (simulates paper mill applications) USS Low-Temperature Mobility Test (grease)

Federal Supply Class 9150 Product Commodities Document MIL-PRF-23699F MIL-PRF-23827C MIL-PRF-81322F MIL-PRF-81329D MIL-PRF-83282D MIL-PRF-85336B MIL-L-19701B MIL-G-21164D MIL-L-23398D MIL-G-23549C MIL-G-25013E MIL-G-25537C MIL-H-81019D MIL-S-81087C a MIL-G-81827A MIL-L-81846 MIL-G-81937A DOD-L-85645Aa DOD-G-85733 DOD-L-85734

Summarized title and description Synthetic Aircraft Turbine Engine Oil Aircraft and Instrument Grease Aircraft Wide Temperature Range Grease Solid Film Lubricant Synthetic Fire Resistant Hydraulic Fluid All Weather Lubricant for Weapons Semi-Fluid Lubricant for Weapons Molybdenum Disulfide Grease Solid Film Lubricant, Air-Cure General Purpose Grease Aircraft Bearing Grease Aircraft Helicopter Bearing Grease Hydraulic Fluid for Ultra Low Temperatures Silicone Fluid Anti-Wear Grease Aircraft High Loading and Anti-Wear Grease Instrument Ball Bearing Lubricating Oil Ultra Clean Instrument Grease Dry Thin Film Lubricant High Temperature Catapult Grease Synthetic Helicopter Transmission Lubricant


QPL Yes Yes Yes No (FAT) Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes No Yes No Yes Yes

Custodian Navy/AS

NATO code O-156/O-154 G-354 G-395 S-1737 H-537

G-353 S-748 G-372 G-366 H-536

Federal Supply Class 9150 Product Commodities (Continued) Document VV-D-1078B SAE J1899 SAE J1966 SAE AMS-G-4343 SAE AMS-G-6032 MIL-H-22072C A-A-59290 MIL-PRF-9000H MIL-PRF-17331H MIL-PRF-17672D MIL-PRF-24139A DOD-PRF-24574 MIL-L-15719A MIL-T-17128C MIL-G-18458B MIL-H-19457D MIL-L-24131B MIL-L-24478C DOD-G-24508A DOD-G-24650 DOD-G-24651 VV-L-825C A-A-50433 A-A-50634 A-A-59004A MIL-PRF-6081D MIL-PRF-6085D MIL-PRF-6086E MIL-PRF-7808L MIL-PRF-7870C MIL-PRF-8188D MIL-PRF-27601C MIL-PRF-27617F MIL-PRF-32014 MIL-PRF-83261B MIL-PRF-83363C MIL-PRF-87100A MIL-PRF-87252C MIL-PRF-87257A MIL-H-5606Ga DOD-L-25681D MIL-L-87177A MIL-PRF-2104G MIL-PRF-2105E MIL-PRF-3150D MIL-PRF-6083F MIL-PRF-10924G MIL-PRF-12070E MIL-PRF-21260E

Summarized title and description Silicone Fluid Damping Fluid Aircraft Piston Engine Oil, Ashless Dispersant Aircraft Piston Engine Oil, Non Dispersant Pneumatic Systems Grease Plug Valve Grease Hydraulic Fluid for Catapults Arresting Gear Hydraulic Fluid Diesel Engine Oil Steam Turbine Lubricating Oil Hydraulic Fluid Multipurpose Grease Lubricating Fluid for Oxidizing Mixtures High Temperature Electrical Bearing Grease Transducer Fluid Exposed Gear and Rope Grease Fire Resistant Hydraulic Fluid Graphite and Alcohol Lubricant Molybdenum Disulfide and Alcohol Lubricant Multipurpose Grease Food Processing Equipment Grease Food Processing Equipment Lubricating Oil Lubricating Oil for Refrigerant Compressors Sea Water Resistant Grease Lubricating Oil for Compressors Using HFC-134A Anti-Galling Compound Jet Engine Lubricating Oil Aircraft Instrument Lubricating Oil Aircraft Gear Petroleum Lubricating Oil Aircraft Turbine Synthetic Engine Oil Low Temperature Lubricating Oil Corrosion Preventive Engine Oil [FSC 6850] Hydraulic Fluid Aircraft and Instrument Grease Aircraft and Missile High Speed Grease Aircraft Extreme Pressure Grease Helicopter Transmission Grease Aircraft Turbine Synthetic Engine Oil Dielectric Coolant Fluid [FSC 9160] Synthetic Fire Resistant Hydraulic Fluid Petroleum Hydraulic Fluid for Aircraft/Ordnance Silicone Fluid with Molybdenum Disulfide Synthetic Corrosion Preventive Lubricant Combat/Tactical Diesel Engine Oil Multipurpose Gear Oil Preservative Oil Operational and Preservative Hydraulic Fluid Automotive/Artillery Grease Fog Oil Preservative and Break-in Engine Oil


QPL No Yes Yes No Yes Yes No Yes Yes Yes Yes Yes Yes No Yes No (FAT) Yes No Yes No No No No No No Yes Yes Yes Yes Yes Yes Yes Yes No No No Yes Yes Yes Yes No No (FAT) Yes Yes Yes Yes Yes No Yes

Custodian

Navy/AS2 Navy/AS2 Navy/SH

NATO code S-1714 to 1732 O-123/O-128 O-113/O-117 G-392 G-363 H-579 O-278 O-250 H-573

H-580

O-282/O-290

Air Force/11

O-132/O-133 O-147 O-153/O-155 O-148/O-163 O-142 C-638 G-397-399/-1350

G-396 S-1748 H-538 H-515 Air Force/68 Air Force/70 Army/AT

S-1735 O-236/-237/-1236 O-186/-226/-228 O-192 C-635 G-403 F-62 C-640/C-642

Federal Supply Class 9150 Product Commodities (Continued) Document MIL-PRF-32033 MIL-PRF-46002C MIL-PRF-46010F MIL-PRF-46147C MIL-PRF-46167C MIL-PRF-46170C MIL-PRF-46176B MIL-PRF-53074A MIL-PRF-53131A VV-G-632B VV-G-671F A-A-52039B A-A-52036A A-A-59354 SAE J1703 MIL-PRF-63460D MIL-L-11734C MIL-L-14107C MIL-L-45983 MIL-L-46000C MIL-G-46003A MIL-L-46150 MIL-PRF-3572B MIL-DTL-17111C MIL-PRF-26087C MIL-L-3918Aa MIL-L-46014a MIL-L-83767Ba VV-C-846B A-A-50493A A-A-59113 A-A-59137 A-A-59173 A-A-59197 SAE AS1241C

Summarized title and description

QPL

Preservative and Water-Displacing Oil Vapor Corrosion Inhibitor (VCI) Preservative Oil Solid Film Lubricant Solid Film Lubricant Arctic Engine Oil Synthetic Fire Resistant Hydraulic Fluid Silicon Brake Fluid Steam Cylinder Lubricating Oil Precision Bearing Synthetic Lubricating Oil General Purpose Industrial Grease Graphite Grease Automotive Engine Oil API Service SH Commercial Heavy Duty Diesel Engine Oil Hydraulic Fluid for Machines Conventional Brake Fluid Cleaner-Lubricant-Preservative for Weapons Synthetic Lubricant for Mechanical Fuse Systems Low Temperature Weapons Lubricant Heat-Cured Solid Film Lubricant Semi-Fluid Weapons Lubricant Rifle Grease Semi-Fluid High Loading Weapons Lubricant Colloidal Graphite in Oil Power Transmission Fluid Reciprocating Compressor Lubricating Oil Instrument Lubricating Oil for Jewel Bearings Spindle Lubricating Oil Vacuum Pump Lubricating Oil Emulsifiable Oil Type Cutting Fluids Penetrating Oil Machine Tools/Slideways Lubricating Oil Breech Block Lubricating Oil (Naval Ordnance) Silicone Grease Fatty Oil for Metal Working Lubricants Fire Resistant Phosphate Ester Hydraulic Fluid

Yes No (FAT)

0-190

Yes Yes Yes Yes Yes No Yes No No No No No No Yes No

S-1738

Yes No Yes Yes Yes No No (FAT) No No No No No No No No No No No

Custodian

NATO code

O-183 H-544 H-547 O-258

G-412

Army/AR

H-542 S-758

O-157 O-158

DSCR/GS H-575

a

Those specifications in bold italics had been designated as “Inactive for New Design” and no longer used except for replacement purpose. Their QPLs will be maintained until the products are no longer required. b See Navy/AS2 under Abbreviations used below.

Specifications having Cross-Reference between, JIS, ASTM, and Others ASTM or others

JIS

F 312

B 9930

F 313 D 117 D 923 D 4559

B 9931 C 2101


Title and contents Hydraulic Fluid — Determination of Particulate Contamination by the Particle Count Method Fluid Contamination — Determination of Contaminants by the Gravimetric Method Testing method of electrical insulating oils Sampling Evaporation

Specifications having Cross-Reference between, JIS, ASTM, and Others (Continued) ASTM or others

JIS

D 1218/21807 D 974 D 1275 D 1533 D 2112/2440 D 877/1816 D 924 D 1169 K 2249 D 1298/E100 D 4052/5002 ISO 3833 D 941 D 70 D 1250 D 140/4057/4177 D 1093

K 2251 K 2252 K 2254

D 86, E133 D 1160 D 2287 K 2255 D 3341 D 3237 D 661 D 323 D 381

K 2256 K 2258 K 2261 K 2265

D 56 D 3828/3278 D 93 D 92 K 2269 D 97 D 2500 K 2270 D 189 D 4530 K 2272 D 482 D 874 K 2275 D 95/4006 D 4377/1744 DIN 9114 K 2276 D 873 D 2386


Title and contents Refractive index and specific dispersion Total acid number Corrosive sulfur Water content Oxidation stability Dielectric strength Dielectric loss tangent and relative dielectric constant Volume resistivity Crude petroleum and petroleum products — Determination of the density and petroleum measurement tables based on a reference temperature (15◦ C) I-shaped float method Oscillating method Wardon picnometer method I-shaped picnometer method Hubbard picnometer method Density, mass, and volume conversion table Crude Petroleum and Petroleum Products — Sampling Testing Method for Reaction of Petroleum Products Petroleum products — Determination of distillation characteristics Test method for distillation of petroleum products at atmospheric pressure Test method for distillation of petroleum products at reduced pressure Test method for boiling range distillation of petroleum products by gas chromatography Petroleum products — Gasoline — Determination of lead content Iodine monochloride method Atomic absorption spectroscopy method Testing Methods for Aniline Point and Mixed Aniline Point of Petroleum Products Testing Method for Vapor Pressure of Crude Oil and Petroleum Products (Reid Method) Petroleum products — Motor gasoline and aviation fuels — Determination of existent gum — Jet evaporation method Crude oil and petroleum products — Determination of flash point Tag closed test Small scale closed test Pensky–Martens closed cup test Cleveland open cup test Testing methods for pour point and cloud point of crude oil and petroleum products Pour point Cloud point Crude Petroleum and Petroleum products — Determination of carbon residue Conradson method Micro method Testing methods for ash and sulfated ash of crude oil and petroleum products Ash Sulfated ash Crude oil and petroleum products — Determination of water content Distillation method Karl-Fischer volumetric method Karl-Fischer coulometric method Hydride reaction method Petroleum products — Testing methods for aviation fuels Oxidation stability (potential residue) Freezing point

Specifications having Cross-Reference between, JIS, ASTM, and Others (Continued) ASTM or others

JIS

D 1094 D 235/4952 D 3227 D 1740 D 1840 FS 1151.2 D 3242 D 3948 D 2550 D 3241 D 2276/5452 IP 227 D 2624 D 3343 K 2279 D 4529/4868 D 4868 K 2280 D 2699 D 2700 D 909 D 613 D 4737 D 1368 D 2268 K 2283 D 445/446 D 2270 D 341 D 525 IP 309 D 1145 D 1945/1946 ISO 6326-1 ISO 6326-1 ISO 6327 D 900/1826 D 3588 D 1070 D 3588 D 4057

K 2287 K 2288 K 2301

K 2420 K 2501

D 974 D 664 D 4739 D 2896 K 2503 D 91/2273


Title and contents Water tolerance Doctor test Determination of mercaptan sulfur (potentiometric method) Luminometer number test Determination of naphthalene (ultraviolet spectroscopy) Explosive vapor test Total acid number Water separation index (micro separometer) Water separation index (water separometer) Thermal stability (JFTOT) Particulate contaminant Copper corrosion Electric conductivity Hydrogen content Crude petroleum and petroleum products — Determination and estimation of heat of combustion Net heat of combustion Gloss heat of combustion Petroleum products — Fuels — Determination of octane number, cetane number, and calculation of cetane index Research octane number Motor octane number Supercharge octane number Cetane number Calculation method for cetane index using four variable equation Small amount of lead in n-heptane and isooctane (dithizone method) Purity of n-heptane and isooctane (capillary gas chromatography) Crude petroleum and petroleum products — Determination of kinematic viscosity and calculation of viscosity index from kinematic viscosity Kinematic viscosity Viscosity index Estimated relation between kinematic viscosity and temperature Testing Methods for Oxidation Stability of Gasoline (Induction Period Method) Gas oil — Determination of cold filter plugging point Fuel gas and natural gas — Methods for chemical analysis and testing Sampling of gas sample Chemical analysis (gas chromatography) Analysis of total sulfur Analysis of hydrogen sulfide Analysis of water (dew point method) Heat of combustion (Junkers gas calorimeter) Heat of combustion (calculation method) Specific gravity (picnometer method) Specific gravity (calculation method) Method of Sampling for Aromatic Hydrocarbon and Tar Products Petroleum products and lubricants — Determination of neutralization number Color indicator titration (TAN, strong acid number, strong base number) Potentiometric titration (TAN, strong acid number) Potentiometric titration (TBN, strong base number) Potentiometer titration (TBN, perchloric acid method) Testing method of lubricating oil for aircraft Precipitation number

Specifications having Cross-Reference between, JIS, ASTM, and Others (Continued) ASTM or others D 94 FS 3006.3 FS 204.1 ISO 6617 FS 5308.7 D 665 D 130 ISOTa D 943 D 2272 D 3397 IP 280 D 892

JIS

K 2510 K 2513 K 2514

K 2518 K 2619

D 2619 D 2782 K 2520 D 1401 IP 19 K 2536 D 1319/2001/2427 D 2267/4420/5580 D 1322

K 2537 K 2540 K 2541

D 2785/ISO 4260 D 3120 D 1551 D 4294/ISO 8754 D 129 D 1266 D 2622 K 2580 D 156 D 1500 K 2601 D 3828 D 96/4007/1796 IP 77 D 3230 D 2892 D 1159/2710

K 2605 K 2609

D 3228 D 3431 D 4629/5762

Title and contents Saponification number Contamination Diluted pour point Oxidation stability Corrosiveness and oxidation stability Testing Method for Rust-Preventing Characteristics of Lubricating Oil Petroleum Products — Corrosiveness to Copper — Copper Strip Test Lubricating oils — Determination of oxidation stability Oxidation stability of lubricants for internal combustion engine Turbine oil oxidation stability test (TOST) Rotating pressure vessel oxidation test (RBOT) Total acid number (semimicro method) Turbine oil oxidation stability (oil soluble catalyst method) Petroleum products — Lubricating Oils — Determination of Foaming Characteristics Lubricating oils — Testing methods for load carrying capacity Soda four ball (4 ball test modified by Dr. Soda) Timken Petroleum products — Lubricating oils — Determination of demulsibility characteristics Demulsibility test Steam emulsion number Liquid petroleum products — Testing method of components Fluorescent indicator adsorption analysis (FIA) Determination of aromatics by gas chromatography Petroleum Product — Aviation Turbine Fuels and Kerosene — Determination of Smoke Point Testing method for thermal stability of lubricating oils Crude oil and petroleum products — Determination of sulfur content Oxy-hydrogen combustion method Microcoulometric titration Quartz tube test Energy dispersive x-ray fluoroscence spectroscopy General bomb method Lamp method Wavelength dispersive x-ray fluoroscence spectroscopy Petroleum products — Determination of color Saybolt ASTM Testing methods for crude petroleum Flash point Water and sediment Salt content (titration) Salt content (coulometric) Distillation at atmospheric pressure Petroleum distillates and commercial aliphatic olefins — Determination of bromine number — Electrometric method Crude petroleum and petroleum products — Determination of nitrogen content Macro-Kjerdahl method Microcoulometric titration Chemiluminescence method

Note: a ISOT stands for Indiana Stirring Oxidation Test.


ABBREVIATIONS USED QPL FAT Navy/AS Navy/AS2 Navy/SH Navy/YD Air Force/11 Air Force/68 Air Force/70 Army/AT Army/AR DSCR/GS

Qualified Products Listing No QPL exists, but a First Article Test (FAT) is required or may be optional Naval Air Systems Command (NAVAIR), Patuxent River, MD Naval Air Systems Command (NAVAIR), Lakehurst, NJ Naval Sea Systems Command (NAVSEA), Arlington, VA Naval Facilities Engineering Command (NAVFAC), Alexandria, VA Air Force Aeronautical Systems Center (ASC), Wright-Patterson AFB, OH Air Force San Antonio Air Logistics Center (SAALC), Kelly AFB, TX Hill Air Force Base Logistics Center, UT Army Tank-Automotive and Armaments Command, Tank-Automotive Research Development and Engineering Center (TARDEC), Warren, MI Army Tank-Automotive and Armaments Command, Armaments Research Development and Engineering Center (ARDEC), Picatinny, NJ Defense Logistics Agency’s Defense Supply Center Richmond (DSCR), Richmond, VA

ACKNOWLEDGMENTS This chapter was compiled with the generous help of several colleagues in the lubricant community. The author thanks Piet Purmer (Shell Chemical Company), Dick Kuhlman (Ethyl Corporation), Don Campbell,


Ed Zaweski, and Hiroshi Yamaochi (Amoco Chemicals — retired), Alan Plomer (BP — Belgium), Darryl Spivey (BP — Analytical), Ed Snyder (AFRL/MLBT), and Bob Rhodes.

50

Lubricant Industry Related Terms and Acronyms Leslie R. Rudnick

The plethora of acronyms related to the field of lubrication continues to grow. These acronyms and abbreviations come from a variety of diverse industries and disciplines, including original equipment manufacturers, component suppliers, lubricant additive and fluid suppliers and producers, and professional societies directly and peripherally involved in the lubricants industry. Each class of lubricants, synthetic and conventional, has its set of abbreviations reserved to describe differences in structure or performance characteristics. Terms and acronyms for lubricant

3P2E 4P3E 4T 5P4E 6P5E AAM AAMA AAR AB ABIL ABMA

ABOT ACC ACIL ACEA ACERT ACS AEL AEOT AES AEV A/F AFNOR AFR AFV AGELFI

additives are numerous and generally reflect the chemical structure or type of additive. In some cases the acronym reflects the function of the additive. Acronyms created at different times by different industries have resulted in identical abbreviations that refer to different things. This chapter collects in one place many of the important terms generally used in the lubricants industry. A complete list would require far more space than can be devoted in this book.

three-ring polyphenyl ether four-ring polyphenyl ether A term applied to lubricants for four-cycle engines five-ring polyphenyl ether six-ring polyphenyl ether Alliance of Automobile Manufactures American Automobile Manufactures Association American Association of Railroads alkylbenzene agriculture-based industrial lubricants American Bearing Manufacturers Association — a nonprofit association of American manufacturers of antifriction bearings, spherical plain bearings, or major components thereof. The purpose of ABMA is to define national and international standards for bearing products and maintain bearing industry statistics aluminum beaker oxidation test American Chemistry Council American Council of Independent Laboratories, ACIL is the national trade association representing independent, commercial engineering, and scientific laboratory, testing, consulting, and R&D firms Association des Constructeurs Europeens d‚Automobiles Advanced Combustion Emission Reduction Technology (Caterpillar) American Chemical Society allowable exposure limits Engine Oil Aeration Test Average engine sludge Average engine varnish air to fuel ratio Association Francais de Normalisation Air/fuel ratio alternative fuel vehicle Co-operative Research Organization of AGIP, ELF, and FINA oil companies


AGO AGMA AHEM AIAM AIChE AL ALTNER Anti-oxidant Anti-wear additive ANFAVEA ANIQ ANSI AO AOCA AOCS API ARB ASEAN ASLE ASME ASTM A/T ATF ATIEL AT-PZEV AW BFPA Bhp-hr BHRA BLF Block grease

Automotive gas oil, automotive gear oil American Gear Manufacturers Association Association of Hydraulic Equipment Manufacturers Association of International Automobile Manufacturers American Institute of Chemical Engineers atmospheric lifetimes Alternative Energy Programs of the European Commision A chemical component added to lubricants to reduce the tendency for oxidation-related degradation of the oil Additives that can deposit multilayer films thick enough to supplement marginal hydrodynamic films and prevent asperity contact, or preferentially wear rather than allow contact between asperities that result in wear Associação Nacional dos Fabricantes de Veículos Automotores Asociación Nacional de la Industria Química, AC American National Standards Institute anti-oxidant American Oil Change Association, provides a link between the motoring public and auto maintenance specialists American Oil Chemists Society, a global forum for the science and technology of fats, oils, surfactants, and related materials American Petroleum Institute Air Resources Board (California) Association of South East Asian Nations American Society of Lubrication Engineers American Society of Mechanical Engineers American Society of Testing and Materials Conventional shifting automatic transmission Automatic transmission fluid Association Technique de l‚Industrie Europeenne des Lubrifants Advanced Technology Partial Zero Emission Vehicle anti-wear

BOCLE BOI BOIG BOTD Boundary lubrication BSFC BTU

British Fluid Power Association brake horsepower hour British Hydromechanics Research Association British Lubricants Federation A very firm grease produced as a block that is applied to large open plain bearings that operate at low speed and high temperatures Ball on cylinder lubricity evaluator Base oil interchange Base Oil Interchange Guidelines Ball on three disks A regime of lubrication where there is partial contact between the metal components and partial separation of the surfaces by the lubricant fluid film brake specific fuel consumption British Thermal Units

CAA CAAA CAFÉ CARB CBO CCD CCR CCS CDP

Clean Air Act Clean air act amendment (1990) Corporate average fuel economy California Air Resources Board Conventional base oil Combustion chamber deposits Conradson carbon residue Cold cranking simulator cresyl diphenyl phosphate


CEC CEN CFC CFR CFV CGSB CIDI CMA CMMO CMVO CNG CNHTC CO CO2 CONCAWE Corrosion inhibitor CPPI CRC CVMA CVS CVT b-CVT t-CVT DAP DASMIN DBC DBPP DCT DDC DEC DEER Demulsibility DEO DEOAP DETA DEXTRON DFA DH-1 DHYCA DI DI DI DII DIN DIOC DiPE DMC DME DOA

Co-ordinating European Council Europeen de Normalization Chlorofluorocarbon Coordinating Fuel and Equipment Research Committee clean fuel vehicle Canadian General Standards Board — a consensus organization of producers, users, and general interest groups that develops standards for test methods and products for Canada Compression ignition direct injection (diesel) Chemical Manufacturers Association Chemically modified mineral oil chemically modified vegetable oils Compressed natural gas China National Heavy Truck Corporation Carbon monoxide Carbon dioxide Conservation of Clean Air and Water-Europe A lubricant additive used to protect surfaces against chemical attack from contaminants in the lubricating fluid or grease. These additives generally operate by reacting chemically and forming a film on the metal surfaces Canadian Petroleum Product Institute Co-ordinating Research Council, Incorporated Canadian Vehicle Manufacturers Association Constant volume sampling Continuously variable transmission Belt-CVT Toroidal-CVT Detroit Advisory Panel (API) Deutsche Akkreditierungastelle Mineralol (German) Dibutyl carbonate dibutyl phenyl phosphate dual clutch transmission Detroit Diesel Corporation Diethyl carbonate diesel engine emissions reduction A measure of the ability of an oil to separate from water as measured by the test time required for a specified oil–water emulsion to break using ASTM D-1401 Diesel engine oil Detroit Engine Oil Advisory Panel (API/EMA) Diethylene triamine General Motors ATF specification Diesel fuel additive A JASO diesel engine oil category — a category mainly for Japanese-made heavy duty diesel engines providing wear, soot handling properties, and thermal-oxidative stability Direction des Hydrocarbares et Carburants (French Ministry of Industry) detergent inhibitor direct injection drivability index Diesel injection improver Deutsche Industrie Normung Diisooctyl carbonate dipentaerythritol Dimethyl carbonate Dimethyl ether Dioctyl adipate


DOC DOCP DOD DOE DOHC DOP DOS DOT DPF DPMA Dropping point DSC DTBP

Diesel oxidation catalysts dispersant olefin copolymer Department of Defense Department of Energy Double overhead cam Di 2-ethylhexylphthalate Di 2-ethylhexylsebacate Department of Transport Diesel particulate filters dispersant polymethacrylate The temperature at which a grease changes from a semisolid to a fluid under the test conditions. This temperature can be considered to be a measure of the upper use limit for the grease differential scanning calorimetry Di-tert-butyl phenol

EC ECCC EDC EEC EFI EGR EHDPP EHEDG ELGI ELTC ELV EMA EMPA Emulsion

EPACT EPACT EPDM EPM ESCS ESI ETC EU EUC EUDC EUROPIA EV EVA

European Community Electronically controlled computer clutch Electronic diesel contro European Economic Community Electronic fuel injection Exhaust gas recirculation 2-ethylhexyl diphenyl phosphate European Hygiene and Equipment Design Group European Lubricating grease Institute Engine Lubricant Technical Committee (CEC) end-of-life vehicle Engine Manufacturers Association Swiss Federal Laboratories for Materials Testing and Research A mechanical mixture of two mutually insoluble fluids. Some metalworking fluids are designed to remain as a stable emulsion by incorporation of an emulsifier European Natural Gas Vehicle Association Engine Oil Licensing and Certification System(API) Extreme pressure — an additive designed to prevent metal–metal adhesion or welding when the degree of surface contact is sufficiently high that the normal protective (oxide) films are removed and other surface active species in the oil are not reactive enough to deposit a protective film. EP additives function by reacting with the metal surface to form a metal compound, for example, iron sulfide Environmental Protection Act of 1992 Energy Policy and Conservation Act Ethylenepropylene diene-based elastomeric seal material Ethylene propylene-based elastomeric seal material Engine Service Classification System extended service interval European Transient Test Cycle European Union Elementary Urban Cycle Extra Urban Driving Cycle European Petroleum Industry Association electric vehicle Ethyl vinyl alcohol

FATG FBP FCAAA FCC FDA FE

Fuel Additive Task Group (CMA) final boiling point Federal Clean Air Act Amendments fluid catalytic cracker Food and Drug Administration Fuel economy

ENGVA EOLCS EP additive


FEI FF FFV FIE FIMS FSIS FT FTC FTIR FZG

Fuel economy improvement (fuel efficiency increase) Factory fill flexible fueled vehicle Fuel injection equipment Field ionization mass spectrometry Food Safety Inspection Service Fischer-Trophsch Federal Trade Commision (US) Fourier-transform infrared Forschungstelle fur Zahnrader und Getriebau

GATC GC

Gross additive treat cost In the ASTM D-4950 Standard Classification and Specification for Automotive Service Greases, the letters GC designate service typical of the lubrication of wheel bearings operating in passenger cars, trucks, and other vehicles under mild to severe duty gasoline direct injection Gross delivered treating cost Group des Experts pour la Pollution et l’Energie (group of experts for pollution and energy) Gear service characteristics (API) glycerol monoleate generally recognized as safe Gas-to-liquids global warming potential

GDI GDTC GEPE GL-4/5 GMO GRAS GTL GWP HACCP HAP HC HCB HCCI HCFC HDD HDDEO HDEO HDMO HEUI HFC HFE HOOT HOPOE HRMS HSPOE HTHSRV HVI Hydrodynamic lubrication

Hazard and Critical Control Point implement procedures for USDA regulators requirements hazardous air pollutant Hydrocarbon Hydrocracker bottoms Homogeneous charge combustion ignition Hydrochlorofluorocarbon heavy-duty diesel Heavy duty diesel engine oil Heavy duty engine oil Heavy duty motor oil Hydraulically operated electronically controlled unit injectors Hydrofluorocarbon hydrofluoroethers Hot Oil Oxidation Test highly optimized POE High-resolution mass spectrocopy high-stability POE High-temperature high-shear rate viscosity high viscosity index oil A lubrication regime characterized by a full fluid film between two moving surfaces. As oil is moved between the moving parts the action causes a high pressure in the lubricant fluid and this separates the moving parts

IBP IC IDDPP IDI IEA IENICA IFP ILMA ILSAC IOP

initial boiling point internal combustion isodecyl diphenyl phosphate indirect injection International Energy Agency Interactive Network for Industrial Crops and Applications Institut Franciais du Petrole Independent Lubricant Manufacturers Association Internation Lubricant Standardization and Approval Committee Industries Institute of Physics — Tribology group


IP IPPP IR ISO IVD

Institute of Petroleum (UK) isopropylphenyl phenyl phosphate infrared International Organization for Standardization Intake valve deposit

JALOS JAMA JASO JAST JIS

Japanese Lubricating Oil Society Japan Automobile Manufacturers Association Japanese Automotive Standards Organization Japanese Society of Tribologist Japanese Industrial Standard

KTH KV

Royal Institute of Technology, Sweden Kinematic viscosity

LB

LCO LCST LDV LEV LeRC LMOA LNG LOFI LPG LSC LSD

In the ASTM D-4950 Standard Classification and Specification for Automotive Service Greases, the letters LB designate service typical of lubrication of chassis components and universal joints in passenger cars, trucks, and other vehicles under mild to severe duty light cycle oil lower critical solution temperature Light duty vehicles Low emission vehicles Lewis Research Center — NASA Locomotive Maintenance Officers Association Liquefied natural gas Lubricant Oil Flow Improver Liquid petroleum gas Lubricant Standards Committee Low sulfur diesel

MERCON MIL MITI MOD MOE MON MOT MSDS MT MTAC MTBE MTF MVMA MWF MWT

Ford ATF specification Military Specification Ministry of International Trade and Industry (Japan) Ministry of Defence (British) Ministry of Energy (UK) Motor octane number Ministry of Transport (UK) material safety data sheet manual transmissions Multiple Test Acceptance Criteria Methyl t-butyl ether Manual transmission fluid Motor Vehicle Manufacturer’s Association Metal working fluid(s) maximum workable die temperature

NAFTA NAAQS NATC NDTC NEDO NEFI NESHAP NFPA NI NLGI NMR

North American Free Trade Agreement National Ambient Air Quality Standards Net additive treat rate Net delivered treat rate New Energy and Technology Development Organization (Japan) New England Fuel Institute National Emission Standard for Hazardous Air Pollutants National Fluid Power Association nonpolarity index National Lubricating Grease Institute (US) Nuclear magnetic resonance (spectroscopy)


NOX NPG NPI NPRA NRCC NREL NRL

Nitrogen oxides Neopentylglycol non-polarity index National Petrochemical & Refiners Association National Research Council of Canada National Renewable Energy Laboratory Naval Research Laboratory

OCP ODI ODP ODS OEM OPEC OPEST ORD ORNL OSHA OTA Oxidation

olefin copolymer Oil drain interval ozone depleting potential ozone depleting substance original equipment manufacturer Organization of Petroleum Exporting Countries Oil Protection of Emission Systems Test Octane requirement decrease Oak Ridge National Laboratory Occupational Safety and Health Administration Office of Technology Assessment (DOE) One of several modes of oil degradation. The process generally involves the addition of oxygen to the lubricant structure, followed by cleavage or polymerization resulting in unfavorable oil properties and performance

PAG PAH PAHO PAJ PAO PAPTG PC PCD PCEO PCMO PCTFE PDSC PDVSA PE PEA PEC PFPAE PFPE PIB PIO PM2.5 PM10 PM PMA PMAA PNA PNGV POFA Poise

polyalkylene glycol polycyclic aromatic hydrocarbons Pan American Health Organization Petroleum Association of Japan polyalphaolefin Product Approval Protocol Task Group (CMA) Proposed classification Passenger car diesel passenger car engine oil passenger car motor oil polychlorotrifluoroethylene pressure differential scanning calorimetry Petroleos de Venezuela pentaerythritol Polyether amine Petroleum Energy Centre perfluoropolyalkylether Perfluoropolyether polyisobutylene polyinternalolefins particulate matter less than 2.5 microns diameter particulate matter less than 10 microns diameter Particulate matte polymethacrylate Petroleum Marketers Association of America polynuclear aromatic Partnership for a New Generation of Vehicles (US) polymerized fatty acids The CGS unit of absolute viscosity (dyne-sec/cm2 ) as measured by the shear stress required to move one layer of fluid along another over a total thickness of one centimeter at a shear rate of one centimeter per second. Absolute viscosity values are independent of density and are directly related to the resistance to flow A conventional measure of the lower temperature limit for low-temperature flow of a lubricating fluid

Pour point


PPD PPE ppm PTFE PVC PVE

Pour point depressant polyphenyl ether Parts per million Polytetrafluoroethylene pressure viscosity coefficient polyvinyl ethers

QPL

Qualified Products List (US Military)

RBOT RCRA RME ROCOT RON ROSE RVP

rotary bomb oxidation test Resource Conservation Recovery Act Rapeseed methyl ester rotating compressor oxidation test Research octane number Rose Foundation — Recovery of Oil Saves the Environment Reid vapor pressure

SAE SAIC SAIT SARA SCR Scuffing SF SHC SHPD SIAM SIB SIP SMDS SME SMM&T SMR SMRP SNAP SNCF SOF SOT SSI STLE SULEV SUS SUV SwRI

Society of Automotive Engineers Shanghai Automotive Industry Group South African Institute of Tribologists Superfund Amendments and Reauthorization Act Selective catalyst reduction Wear caused by the localized welding and fracture of rubbing surfaces Service fill Synthetic hydrocarbon Super high-performance diesel Society of Indian Automotive Manufacturers sulfurized isobutylene Styrene-isoprene copolymer Shell Middle Distillate Synthesis Society of Manufacturing Engineers Society of Motor Manufacturers and Traders Ltd. (UK) Svenska Mechanisters Rikssorenings Society for Maintenance and Reliability Professionals Significant New Alternatives Policy Societe Nationale des Chemins de fer Francais soluble organiz fraction Spin orbit tribometer Shear stability index Society of Tribologists and Lubrication Engineers Super ultra low emission vehicle Saybolt Universal Second (same as SSU) Sport utility vehicle Southwest Research Institute

TAN TBEP TBN TBP TBPP TCP TEOST TFMO TFOUT tga ThOD THOT

total acid number tributoxyethyl phosphate total base number tributyl phosphate tert-butylphenyl phenyl phosphate tricresyl phosphate thermal-oxidation engine oil simulation test Thin Film Micro Oxidation Test thin film oxygen uptake test Thermogravimetric analysis Theoretical oxygen demand turbohydrodynamic oxidation test


TiBP TISI TLEV TLTC TMP TOCP TOP TOST TOTM TPP TXP

triisobutyl phosphate Thailand Industrial Standards Institute Transitional low emission vehicles Transmission Lubricants Technical Committee Trimethylolpropane triorthocresyl phosphate trioctyl phosphate turbine oxidation stability test trioctyl trimellitate triphenyl phosphate trixylenyl phosphate

UCBO UCST UEIL UFIP ULEV ULSD USB USCAR USDA UTTO

Unconventional base oil upper critical solution temperature European Union of Independent Lubricant Manufacturers Union Francaise des Industries Petrolieres Ultra low emission vehicles ultra low sulfur diesel United Soybean Board United States Council for Automotive Research United States Department of Agriculture universal tractor transmission oil

VDS, VDS2 VGO VGRA VHVI VI VII VM VOC VOF Volatility VTC VVT

Volvo Long Drain Lubricant Specification Vacuum gas oil viscosity-grade read across very high viscosity index viscosity index viscosity index improver Viscosity modifier volatile organic compound volatile organic fraction A measure of the amount of material evaporated from a sample under a particular set of conditions, usually expressed as a percentage of original sample viscosity-temperature coefficient variable valve train

WAFI WASA WCM WSPA

Wax antisettling flow improver Wax antisettling additive Wax crystal modifier Western States Petroleum Association

XDP

xylenyl diphenyl phosphate

ZDDP ZDP/ZDTP ZEV

zinc dialkyldithiophosphate zinc dithiophosphate Zero emission vehicle


51

Lubricant Industry Internet Resources Leslie R. Rudnick CONTENTS 51.1 Alphabetical Listing 51.2 Internet Listings by Category 51.2.1 Lubricant Fluids (Base Oils, Greases, Biodegradable, Synthetics, Packaged Oils, and Solid Lubricants) 51.2.2 Additives 51.2.3 Oil Companies 51.2.4 University Sites 51.2.5 Government Sites/Industry Sites 51.2.6 Testing Labs/Equipment/Packaging 51.2.7 Car/Truck MFG 51.2.8 Publications/References/Recruiting/Search Tools, etc.

51.1 ALPHABETICAL LISTING 2V Industries Inc., www.2vindustries.com 49 North, www.49northlubricants.com 76 Lubricants Company, www.tosco.com A.W. Chesterton Company, www.chesterton.com A/R Packaging Corporation, www.arpackaging.com Acculube, www.acculube.com Accumetric LLC, www.accumetric.com Accurate Lubricants & Metalworking Fluids Inc. (dba Acculube), www.acculube.com Acheson Colloids Company, www.achesonindustries.com Acme Refining, Division of Mar-Mor Inc., www.acmerefining.com Acme-Hardesty Company, www.acme-hardesty.com Adco Petrol Katkilari San Ve. Tic. AS, www.adco.com.tr Advanced Ceramics Corporation, www.advceramics.com Advanced Lubrication Technology Inc. (ALT), www.altboron.com Aerospace Lubricants Inc., www.aerospacelubricants.com AFD Technologies, www.afdt.com African Lubricants Industry, www.mbendi.co.za/aflu.htm AG Fluoropolymers USA Inc., www.fluoropolymers.com Airflow Systems Inc., www.airflowsystems.com Airosol Company, Inc., www.airosol.com Akzo Nobel, www.akzonobel.com Alco-Metalube Company, www.alco-metalube.com Alfa Laval Separation, www.alfalaval.com Alfa Romeo, www.alfaromeo.com


Alithicon Lubricants, Division of Southeast Oil & Grease Company, Inc., www.alithicon.com Allegheny Petroleum Products Company, www.oils.com Allen Filters Inc., www.allenfilters.com Allen Oil Company, www.allenoil.com Allied Oil & Supply Inc., www.allied-oil.com Allied Washoe, www.alliedwashoe.com Alpha Grease & Oil Inc., www.alphagrease. thomasregister.com/olc/alphagrease/ ALT Inc., www.altboron.com Amalie Oil Company, www.amalie.com Amber Division of Nidera, Inc., www.nidera-us.com Amcar Inc., www.amcarinc.com Amerada Hess Corporation, www.hess.com American Agip Company, Inc., www.americanagip.com American Bearing Manufacturers Association, www.abma-dc.org American Board of Industrial Hygiene, www.abih.org American Carbon Society, www.americancarbonsociety.org American Chemical Society (ACS), www.acs.org American Council of Independent Laboratories (ACIL), www.acil.org American Eagle Technologies Inc., www.frictionrelief.com American Gear Manufacturers Association (AGMA), www.agma.org American International Chemical, Inc., www.aicma.com/ American Lubricants Inc., www.americanlubricantsbflo.com

American Lubricating Company, www.alcooil.com American Machinist, www.penton.com/cgi-bin/ superdirectory/details.pl?id=317 American National Standards Institute (ANSI), www.ansi.org American Oil & Supply Company, www.aosco.com American Oil Chemists Society (AOCS), www.aocs.org American Petroleum Institute (API), www.api.org American Petroleum Products, www.americanpetroleum.com American Refining Group Inc., www.amref.com American Society of Agricultural Engineering (ASAE), www.asae.org American Society of Agronomy (ASA), www.agronomy.org American Society for Horticultural Science (ASHS), www.ashs.org American Society for Testing and Materials (ASTM), www.astm.org American Society of Mechanical Engineers International (ASME), www.asme.org American Synthol Inc., www.americansynthol.com Amoco, www.amoco.com Amptron Corporation, www.superslipperystuff.com/ organisation.htm Amrep Inc., www.amrep.com AMSOIL Inc., www.amsoil.com Ana Laboratories Inc., www.analaboratories.com Analysts Inc., www.analystinc.com Anderol Specialty Lubricants, www.anderol.com Andpak Inc., www.andpak.com ANGUS Chemical Company, www.dowchemical.com Anti Wear 1, www.dynamicdevelopment.com API Links, www.api.org/links Apollo America Corporation, www.apolloamerica.com Applied Energy Company, www.appliedenergyco.com Aral International, www.Aral.com Arch Chemicals, Inc., www.archbiocides.com ARCO, www.arco.com Argonne National Laboratory, www.et.anl.gov Arizona Chemical, www.arizonachemical.com Asbury Carbons, Inc.—Dixon Lubricants, www.asbury.com Asbury Carbons, Inc.—Dixon Lubricants, www.dixonlube.com Asbury Graphite Mills Inc., www.asbury.com Asheville Oil Company, Inc., www.ashevilleoil.com Ashia Denka, www.adk.co.jp/eng.htm Ashland Chemical, www.ashchem.com Ashland Distribution Company, www.ashland.com Asian Oil Company, www.nilagems.com/asianoil/ Aspen Chemical Company, www.aspenchemical.com Aspen Technology, www.aspentech.com/ Associated Petroleum Products, www.associatedpetroleum.com


Associates of Cape Cod Inc., www.acciusa.com ASTM, www.astm.org Atlantis International Inc., www.atlantis-usa.com Atlas Oil Company, www.atlasoil.com ATOFINA Canada Inc., www.atofinacanada.com Audi, www.audi.com Ausimont, www.ausiusa.com Automotive & Industrial Lubricants Guide, www.wearcheck.com Automotive Aftermarket Industry Association (AAIA), www.aftermarket.org Automotive and Industrial Lubricants Guide by David Bradbury, www.escape.ca/∼dbrad/index.htm Automotive and Industrial Lubricants Tutorial, www.escape.ca/∼dbrad/index.htm Automotive News, www.autonews.com Automotive Oil Change Association (AOCA), www.aoca.org Automotive Parts and Accessories Association (APAA), www.apaa.org Automotive Service Industry Association (ASIA), www.aftmkt.com Automotive Services Retailer, www.gcipub.com AutoWeb, www.autoweb.com AutoWeek Online, www.autoweek.com Avatar Corporation, www.avatarcorp.com

Badger Lubrication Technologies Inc., www.badgerlubrication.com Baker Petrolite, www.bakerhughes.com/bakerpetrolite/ BALLISTOL USA, www.ballistol.com Bardahl Manufacturing Corporation, www.bardahl.com Baron USA Inc., www.baronusa.com BASF Corp., www.basf.com Battenfeld Grease and Oil Corporation of New York, www.battenfeld-grease.com Bayer Corp., www.bayer.com Bearing.Net, www.wearcheck.com Behnke Lubricants/JAX, www.jaxusa.com Behnke Lubricants Inc./JAX, www.jax.com Bell Additives Inc., www.belladditives.com Bel-Ray Company Inc., www.belray.com Benz Oil Inc., www.benz.com Berenfield Containers, www.berenfield.com Bericap NA, www.bericap.com Berry Hinckley Industries, www.berry-hinckley.com Bestolife Corporation, www.bestolife.com BF Goodrich, www.bfgoodrich.com BG Products Inc., www.bgprod.com Bharat Petroleum, www.bharatpetroleum.com Bianco Enterprises Inc., www.bianco.net Big East Lubricants Inc., www.bigeastlubricants.com Bijur Lubricating Corporation, www.bijur.com Bio-Rad Laboratories, www.bio-rad.com

BioTech International Inc., [email protected] Bismuth Institute, www.bismuth.be Blackstone Laboratories, www.blackstone-labs.com/ Blaser Swisslube, www.blaser.com BMW (International), www.bmw.com/bmwe BMW (USA), www.bmwusa.com BMW Motorcycles, www.bmw-motorrad.com Bodie-Hoover Petroleum Corporation, www.bodie-hoover.com Boehme Filatex Inc., www.boehmefilatex.com BoMac Lubricant Technologies Inc., www.bomaclubetech.com Boncosky Oil Company, www.boncosky.com Boswell Oil Company, www.boswelloil.com BP, www.bp.com BP, www.bptechchoice.com BP, www.bppetrochemicals.com BP Amoco Chemicals, www.bpamocochemicals.com BP Lubricants, www.bplubricants.com Brascorp North America Ltd., www.brascorp.on.ca Brenntag Northeast, Inc., www.brenntag.com/ Brenntag, www.brenntag.com Briner Oil Company, www.brineroil.com British Lubricants Federation Ltd., www.blf.org.uk British Petroleum (BP), www.bp.com Britsch Inc., www.britschoil.com Brno University of Technology, Faculty of Mechanical Engineering, Elastohydrodynamic Lubrication Research Group, http://fyzika.fme.vutbr.cz/ehd/ Brugarolas SA, www.brugarolas.com/english.htm Buckley Oil Company, www.buckleyoil.com Buckman Laboratories Inc., www.buckman.com Buick (GM), www.buick.com Burlington Chemical, www.burco.com BVA Oils, www.bvaoils.com Cabot Corporation (fumed metal oxides), www.cabot-corp.com/cabosil Cadillac (GM), www.cadillac.com California Air Resources Board, www.arb.ca.gov Callahan Chemical Company, www.calchem.com Caltex Petroleum Corporation, www.caltex.com Calumet Lubricants Company, www.calumetlub.com Calvary Industries Inc., www.calvaryindustries.com CAM2 Oil Products Company, www.cam2.com Cambridge, http://chemfinder.camsoft.com Cambridge Universirty, Department of Materials Science and Metallurgy, Tribology, www.msm.cam.ac.uk/tribo/ tribol.htm Cambridge University, Department of Engineering, Tribology, www-mech.eng.cam.ac.uk/Tribology/ Canner Associates, Inc., www.canner.com Cannon Instrument Company, www.cannon-ins.com Capital Enterprises (Power-Up Lubricants), www.NNL690.com


Car and Driver Magazine Online, www.caranddriver.com Cargill—Industrial Oil & Lubricants, www.techoils. cargill.com Car-Stuff, www.car-stuff.com Cary Company, www.thecarycompany.com CasChem, Inc., www.cambrex.com Castle Products Inc., www.castle-comply.com Castrol Heavy Duty Lubricants, Inc., www.castrolhdl.com Castrol Industrial North America, Inc., www.castrolindustrialna.com Castrol International, www.castrol.com Castrol North America, www.castrolusa.com CAT Products Inc., www.run-rite.com Caterpillar, www.cat.com Caterpillar, www.caterpillar.com Center for Innovation Inc., www.centerforinnovation.com Center for Tribology, Inc. (CETR), www.cetr.com Centurion Lubricants, www.centurionlubes.com CEPSA (Spain), www.cepsa.es Certified Laboratories, www.certifiedlaboratories.com Champion Brands LLC, www.championbrands.com Charles Manufacturing Company, www.tsmoly.com Chart Automotive Group Inc., www.chartauto.com Chattem Chemicals, Inc., www.chattemchemicals.com Chem Connect, www.chemconnect.com Chem-EcoI Ltd., www.chem-ecol.com Chemetall Foote Corporation, www.chemetall.com/ Chemical Abstracts Service, www.cas.org Chemical Resources, www.chemcenter.org Chemical Week Magazine, www.chemweek.com Chemicolloid Laboratories Inc., www.colloidmill.com Chemlube International Inc., www.chemlube.com Chempet Corp., www.rockvalleyoil.com/chempet.htm Chemsearch Lubricants, www.chemsearch.com Chemtool Inc./Metalcote, www.chemtool.com Chevrolet (GM), www.chevrolet.com Chevron Chemical Company, www.chevron.com Chevron Oronite, www.chevron.com Chevron Phillips Chemical Company LP, www.cpchem.com Chevron Phillips Chemical Company, www.chevron.com Chevron Products Co. Lubricants & Specialties Products, www.chevron.com/lubricants Chevron Products Company, www.chevron.com Chevron Texaco, www.chevrontexaco.com Chevron, www.chevron.com Christenson Oil, www.christensonoil.com Chrysler (Mercedes Benz), www.chrysler.com Ciba Specialty Chemicals Corporation, www.cibasc.com CITGO Petroleum Corporation, www.citgo.com Citroen (France), www.citroen.com Citroen (UK), www.citroen.co.uk/fleet Clariant Corporation, www.clariant.com Clark Refining and Marketing, www.clarkusa.com

Clarkson & Ford Company, www.clarkson-ford.com CLC Lubricants Company, www.clclubricants.com Climax Molybdenum Company, www.climaxmolybdenum.com Coastal Corporation, www.elpaso.com Coastal Unilube Inc., www.coastalunilube.com Cognis, www.cognislubechem.com Cognis, www.cognis-us.com Cognis, www.cognis.com Cognis, www.na.cognis.com College of Petroleum and Energy Studies CPS Home Page, www.colpet.ac.uk/index.html College of Petroleum and Energy Studies, www.colpet.ac.uk Colorado Petroleum Products Company, www.colopetro.com Colorado School of Mines Advanced Coating and Surface Engineering Laboratory (ACSEL), www.mines.edu/ research/acsel/acsel.html Commercial Lubricants Inc., www.comlube.com Commercial Oil Company Inc., www.commercialoilcompany.com Commercial Ullman Lubricants Company, www.culc.com Commonwealth Oil Corporation, www.commonwealthoil.com Como Industrial Equipment Inc., www.comoindustrial.com Como Lube & Supplies Inc., www.comolube.com Computational Systems, Inc., www.compsys.com/ index.html Concord Consulting Group Inc., www.concordcg.com Condat Corporation, www.condatcorp.com Conklin Company, Inc., www.conklin.com Conoco, www.conoco.com Containment Solutions Inc., www.containmentsolutions.com Coolants Plus Inc., www.coolantsplus.com Co-ordinating European Council (CEC), www.cectests.org Coordinating Research Council (CRC), www.crcao.com Cortec Corporation, www.cortecvci.com Cosby Oil Company, www.cosbyoil.com Cosmo Oil, www.cosmo-oil.co.jp Country Energy, www.countryenergy.com CPI Engineering Services, www.cpieng.com CRC Industries, Inc., www.crcindustries.com Creanova, Inc., www.creanovainc.com/ Crescent Manufacturing, www.crescentmfg.net Croda Inc., www.croda.com Crompton Corporation, www.cromptoncorp.com Crop Science Society of America (CSSA), www.crops.org Cross Oil Refining and Marketing Inc., www.crossoil.com Crowley Chemical Company Inc., www.crowleychemical.com Crown Chemical Corporation, www.brenntag.com Crystal Inc-PMC, www.pmc-group.com/ CSI, www.compsys.com


Cummings-Moore Graphite Company, www.cumograph.com Cummins Engine Company, www.cummins.com Custom Metalcraft Inc., www.custom-metalcraft.com Cyclo Industries LLC, www.cyclo.com

D & D Oil Company, Inc., www.amref.com D. A. Stuart Company, www.d-a-stuart.com D. B. Becker Company, Inc., www.dbbecker.com D. W. Davies & Company Inc., www.dwdavies.com D-A Lubricant Company, www.dalube.com Daimler Chrysler, www.daimlerchrysler.com Danish Technological Institute (DTI) Tribology Centre, www.tribology.dti.dk/ Darmex Corporation, www.darmex.com Darsey Oil Company Inc., www.darseyoil.com David Weber Oil Company, www.weberoil.com Davison Oil Company, Inc., www.davisonoil.com Dayco Inc., www.dayco.com DeForest Enterprises Inc., www.deforest.net Degen Oil and Chemical Company, www.eclipse. net/∼degen Delkol, www.delkol.co.il Delphi Automotive Systems, www.delphiauto.com Dennis Petroleum Company, Inc., www.dennispetroleum.com Department of Defense (DOD), www.dodssp.daps.mil/ dodssp.htm Departments of Mechanical Engineering Luleå Technical University, Sweden, www.luth.se/depts/mt/me/me.html Des-Case Corporation, www.des-case.com Detroit Diesel, www.detroitdiesel.com Deutsches Institute Fur Normung e. V. (DIN), www.din.de Dexsil Corporation, www.dexsil.com Diagnetics, www.entek.com Dialog, www.dialog.com Diamond Head petroleum Inc., www.diamondheadpetroleum.com Diamond Shamrock Refining Company, LP, www.udscorp.com Diesel Progress, www.dieselpub.com Digilube Systems Inc., www.digilube.com Dingo Maintenance Systems, www.dingos.com/ Dion & Sons Inc., www.dionandsons.com Diversified Petrochemical Services, www.chemhelp.com Division of Machine Elements Home Page Niigata University, Japan, http://tmtribo1.eng.niigata-u.ac.jp/ index_e.html Dixon Lubricants & Special Products Group, Div. of Asbury Carbons, www.dixonlube.com Dodge, www.dodge.com Don Weese Inc., www.schaefferoil.com Dover Chemical, www.doverchem.com Dow Chemical Company, www.dow.com

Dow Corning Corporation, www.dowcorning.com Dryden Oil Company, Inc., www.castrol.com Dyson Oil Company, www.synergynracing.com DSI Fluids, www.dsifluids.com DSP Technology Inc., www.dspt.com Dumas Oil Company, www.esn.net/dumasoil DuPont-Dow Elastomers, www.dupont-dow.com DuPont Krytox Lubricants, www.lubricants.dupont.com DuPont, www.dupont.com/intermediates Duro Manufacturing Inc., www.duromanufacturing.com Dutton-Lainson Company, www.dutton-lainson.com Dylon Industries Inc., www.dylon.com

E. I. DuPont de Nemours and Company, www.dupont.com/intermediates Eagle, www.eaglecars.com Eastech Chemical Inc., www.eastechchemical.com Eastern Oil Company, www.easternoil.com Easy Vac Inc., www.easyvac.com Ecole Centrale de Lyon, France Laboratoire de Tribologie et Dynamique des Systèmes, www.ec-lyon.fr/recherche/ltds/index.html Ecole Polytechnique Federale de Lausanne, Switzerland, http://igahpse.epfl.ch Ecopetrol (Columbian Petroleum Company), www.ecopetrol.com.co Ecotech Div., Blaster Chemical Companies, www.pbblaster.com Edjean Technical Services Inc., www.edjetech.com Eidgenössische Technische Hochschule (ETH), Zurich Laboratory for Surface Science and Technology (LSST), www.surface.mat.ethz.ch/ EKO, www.eko.gr El Paso Corporation, www.elpaso.com Elco Corporation, The, www.elcocorp.com Elementis Specialties-Rheox, www.rheox.com Elf Atochem Canada, www.atofinachemicals.com Elf Lubricants North America Inc., www.keystonelubricants.com Eljay Oil Company, Inc., www.eljayoil.com ELM Environmental Lubricants Manufacturing Company, www.elmusa.com EMERA Fuels Company, Inc., www.emerafuels.com Emerson Oil Company, Inc.www.emersonoil.com Energy Connection, The, www.energyconnect.com Engel Metallurgical Ltd., www.engelmet.com Engen Petroleum Ltd., www.engen.co.za Engineered Composites Inc., www.engineeredcomposites.net ENI, www.eni.it Environmental and Power Technologies Ltd., www.cleanoil.com Environmental Lubricants Manufacturing, Inc. (ELM), www.elmusa.com


Environmental Protection Agency (EPA), www.fedworld.gov Equilon Enterprises LLC, www.equilon.com Equilon Enterprises LLC-Lubricants, www.equilonmotivaequiva.com Equilon Enterprises LLC-Lubricants, www.shellus.com Equilon Enterprises LLC-Lubricants, www.texaco.com Ergon Inc., www.ergon.com Esco Products Inc., www.escopro.com Esslingen, Technische Akademie, www.tae.de Ethyl Corporation, www.ethyl.com Ethyl Petroleum Additives, www.ethyl.com ETNA Products Inc., www.etna.com Etna-Bechem Lubricants Ltd., www.etna.com European Automobile Manufacturers Association (ACEA), www.acea.be European Oil Companies Organization of E. H. and S. (CONCAWE), www.concawe.be European Patent Office, www.epo.co.at/epo/ EV1, www.gmev.com Evans Industries Inc., www.evansind.com Evergreen Oil, www.evergreenoil.com Exxon, www.exxon.com ExxonMobil Chemical Company, www.exxonmobilchemical.com ExxonMobil Corp., www.exxonmobil.com ExxonMobil Lubricants & Petroleum Specialties Company, www.exxonmobil.com

F&R Oil Company, Inc., www.froil.com F. Bacon Industriel Inc., www.f-bacon.com F.L.A.G. (Fuel, Lubricant, Additives, Grease) Recruiting, www.flagsearch.com/ Fachhochschule Hamburg, Germany, www.haw-hamburg. de/fh/forum/f12/indexf.html/tribologie/etribology.html Falex Corporation, www.falex.com Falex Tribology NV, www.falexint.com/ FAMM (Fuel and Marine Marketing), www.fammllc.com Fanning Corporation, The, www.fanncorp.com Far West Oil Company Inc., www.farwestoil.com Farmland Industries Inc., www.farmland.com Federal World, www.fedworld.gov Ferrari, www.ferrari.com Ferro/Keil Chemical, www.ferro.com FEV Engine Technology, Inc., www.fev-et.com/ Fiat, www.fiat.com Fina Oil and Chemical Company, www.fina.com Findett Corporation, www.findett.com Finish Line Technologies Inc., www.finishlineusa.com FINKE Mineralolwerk, www.finke-mineraloel.de Finnish Oil and Gas Federation, www.oil.fi Flamingo Oil Company, www.pinkbird.com Flo Components Ltd., www.flocomponents.com Flowtronex International, www.flowtronex.com

Fluid Life Corporation, www.fluidlife.com Fluid Systems Partners US Inc., www.fsp-us.com Fluid Technologies Inc., www.Fluidtechnologies.com Fluids Analysis Lab, www.butler-machinery.com/oil.html Fluidtec International, www.fluidtec.com Fluitec International, www.fluitec.com/ FMC Blending & Transfer, www.fmcblending-transfer.com FMC Lithium, www.fmclithium.com FMC, www.fmc.com Ford Motor Company, www.ford.com Fortum (Finland), www.fortum.com Forward Corporation, www.forwardcorp.com Freightliner, www.freightliner.com Frontier Performance Lubricants Inc., www.frontierlubricants.com Fuchs Lubricants Company, www.fuchs.com Fuchs, www.fuchs-oil.de Fuels and Lubes Asia Publications, Inc., www.flasia.com.ph Fuki America Corporation, www.fukiamerica.com Functional Products, www.functionalproducts.com

G-C Lubricants Company, www.gclube.com G & G Oil Co. of Indiana Inc., www.ggoil.com G. R. O’Shea Company, www.groshea.com G. T. Autochemilube Ltd., www.gta-oil.co.uk Galactic, www.galactic.com Gamse Lithographing Company, www.gamse.com Gard Corporation, www.gardcorp.com Gas Tops Ltd., www.gastops.com Gasco Energy, www.gascoenergy.com Gateway Additives, www.lubrizol.com Gear Technology Magazine, www.geartechnology.com/ mag/gt-index.html General Motors (GM), www.gm.com Generation Systems Inc., www.generationsystems.com Geo. Pfau’s Sons Company, Inc., www.pfauoil.com Georgia Tech Tribology, www.me.gatech.edu/research/ tribology.html Georgia-Pacific Resins, Inc.—Actrachem Division, www.gapac.com Georgia-Pacific Resins, Inc.—Actrachem Division, www.gp.com Gerhardt Inc., www.gerhardths.com Global Electric Motor Cars, LLC, www.gemcar.com Globetech Services Inc., www.globetech-services.com Glover Oil Company, www.gloversales.com GMC, www.gmc.com GOA Ce., www.goanorthcoastoil.com Gold Eagle Company, www.goldeagle.com Golden Bear Oil Specialties, www.goldenbearoil.com Golden Gate Petroleum, www.ggpetrol.com Goldenwest Lubricants, www.goldenwestlubricants.com


Goldschmidt Chemical Corporation, www.goldschmidt.com Gordon Technical Service Company, www.gtscofpa.com Goulston Technologies, Inc., www.goulston.com Graco Inc., www.graco.com Granitize Products Inc., www.granitize.com Greenland Corporation, www.greenpluslubes.com Grignard Company LLC, www.purelube.com Groeneveld Pacific West, www.groeneveldpacificwest.com Gulf Oil, www.gulfoil.com

H & W Petroleum Company, Inc., www.hwpetro.com H. L. Blachford Ltd., www.blachford.ca H.N. Funkhouser & Company, www.hnfunkhouser.com Haas Corp., www.haascorp.com Hall Technologies Inc., www.halltechinc.com Halocarbon Products Corporation, www.halocarbon.com Halron Oil Company, Inc., www.halron.com Hammonds Fuel Additives, Inc., www.hammondscos.com Hampel Oil Distributors, www.hampeloil.com Hangsterfer’s Laboratories Inc., www.hangsterfers.com Harry Miller Corporation, www.harrymillercorp.com Hasco Oil Company, Inc., www.hascooil.com Hatco Corporation, www.hatcocorporation.com Haynes Manufacturing Company, www.haynesmfg.com HCI/Worth Chemical Corporation, www.hollandchemical.com Hedwin Corporation, www.hedwin.com HEF, France, www.hef.fr/ Henkel Surface Technologies, www.henkel.com Henkel Surface Technologies, www.thomasregister.com/ henkelsurftech Hercules, Inc., Aqualon Division, www.herc.com Herguth Laboratories Inc., www.herguth.com Heveatex, www.heveatex.com Hexol Lubricants, www.hexol.com Hindustan Petroleum Corporation, Ltd., www.hindpetro.com Hino Motor Ltd., www.hino.co.jp Hi-Port Inc., www.hiport.com Hi-Tech Industries, Inc., www.hi-techind.com Holland Applied Technologies, www.hollandapt.com Honda (Japan), www.worldhonda.com Honda (USA), www.honda.com Hoosier Penn Oil Company, www.hpoil.com Hoover Materials Handling Group, Inc., www.hooveribcs.com Horix Manufacturing Company, www.sgi.net/horix Houghton International Inc., www.houghtonintl.com How Stuff Works, www.howstuffworks.com/engine.htm Howes Lubricator, www.howeslube.thomasregister.com Huls America, www.CreanovaInc.com/ Huls America, www.huls.com

Huntsman Corporation, www.huntsman.com Huskey Specialty Lubricants, www.huskey.com Hydraulic Repair & Design, Inc., www.h-r-d.com Hydrocarbon Asia, www.hcasia.safan.com Hydrocarbon Online, www.wearcheck.com/ publications.html Hydrocarbon Processing Magazine, www.hydrocarbonprocessing.com/ Hydrosol Inc., www.hydrosol.com Hydrotex Inc., www.hydrotexlube.com Hy-Per Lube Corporation, www.hyperlube.com Hysitron Incorporated: Nanomechanics, www.hysitron.com/ Hyundai, www.hyundai-motor.com

I.S.E.L. Inc., www.americansynthol.com ICIS-LOR Base Oils Pricing Information, www.icislor.com/ Idemitsu, www.idemitsu.co.jp ILC/Spectro Oils of America, www.spectro-oils.com Illinois Oil Products Inc., www.illinoisoilproducts.com Imperial College, London ME Tribology Section, www.me.ic.ac.uk/tribology/ Imperial Oil Company, Inc., www.imperialoil.com Imperial Oil Ltd., www.imperialoil.ca Imperial Oil Products and Chemicals Division, www.imperialoil.ca Independent Lubricant Manufacturers Association (ILMA), www.ilma.org Indian Institute of Science, Bangalore, India, Department of Mechanical Engineering, www.mecheng.iisc.ernet.in Indian Oil Corporation, www.indianoilcorp.com Indiana Bottle Company, www.indianabottle.com Industrial Lubrication and Tribology Journal, www.mcb.co.uk/ilt.htm Industrial Maintainence and Engineering Links (PLI, LLC), www.memolub.com/link.htm Industrial Maintenance & Plant Operation (IMPO), www.mcb.co.uk/cgi-bin/mcb_serve/ table1.txt&ilt&stanleaf.htm Industrial Packing Inc., www.industrialpacking.com Infineum USA LP, www.infineum.com Infiniti, www.infiniti.com Ingenieria Sales SA de CV, www.isalub.com Inolex Chemical Company, www.inolex.com Innovene, www.innovene.com Insight Services, www.testoil.com/ Institut National des Sciences Appliquees de Lyon, France, Laboratoire de Mechanique des Contacts, www.insa-lyon.fr/Laboratoires/LMC/index.html Institute of Materials Inc. (IOM), www.savantgroup.com Institute of Materials, www.savantgroup.com Institute of Mechanical Engineers (ImechE), www.imeche.org.uk


Institute of Petroleum (IP), http://212.78.70.142 Institute of Physics (IOP), Tribology Group, www.iop.org Instruments for Surface Science, www.omicroninstruments.com/index.html Interline Resources Corporation, www.interlineresources.com Internal Energy Agency (IEA), www.iea.org International Group Inc., The (IGI), www.igiwax.com International Lubricants Inc., www.lubegard.com International Organization for Standardization (ISO), www.iso.ch International Products Corp., www.ipcol.com Intertek Testing Services-Caleb Brett, www.itscb.com Intl. Tribology Conf. Yokohama 1995, www.mep.titech.ac. jp/Nakahara/jast/itc/itc-home.htm Invicta a.s., www.testoil.com/ Iowa State University, Tribology Laboratory, www.eng. iastate.edu/coe/me/research/labs/tribology_lab.html IQA Lube Corporation, www.iqalube.com Irving Oil Corporation, www.irvingoil.com ISO Translated into Plain English, http://connect.ab.ca/ ∼praxiom Israel Institute of Technology (Technion), http://meeng. technion.ac.il/Labs/energy.htm#tribology Isuzu, www.isuzu.com ITW Fluid Products Group, www.itwfpg.com

J & H Oil Company, www.jhoil.com J & S Chemical Corporation, www.jschemical.com J.H. Calo Company, Inc., www.jhcalo.com J.R. Schneider Company, Inc., www.jrschneider.com J.A.M. Distributing Company, www.jamdistributing.com J.A.M.Distributing, www.jamdistributing.com J.B. Chemical Company, Inc., www.jbchemical.com J.B. Dewar Inc., www.jbdewar.com J.D. Streett & Company, Inc., www.jdstreett.com J.N. Abbott Distributor Inc., www.jnabbottdist.com Jack Rich Inc., www.jackrich.com Jaguar, www.jaguarcars.com Japan Association of Petroleum Technology (JAPT), www.japt.org Japan Automobile Manufacturers Association (JAMA), www.japanauto.com Japan Energy Corporation, www.j-energy.co.jp/eng/ index.html Japan Energy, www.j-energy.co.jp Japanese Society of Tribologists (JAST) (in Japanese), www.jast.or.jp Jarchem Industries Inc., www.jarchem.com Jasper Engineering & Equipment, www.jaspereng.com JAX-Behnke Lubricants Inc., www.jax.com Jeep, www.jeep.com Jenkin-Guerin Inc., www.jenkin-guerin.com Jet-Lube (UK) Ltd., www.jetlube.com

John Deere, www.deere.com Johnson Packings & Industrial Products Inc., www.johnsonpackings.com Journal of Fluids Engineering, http://borg.lib.vt.edu/ ejournals/JFE/jfe.html Journal of Tribology, http://engineering.dartmouth.edu/ thayer/research/index.html K.C. Engineering Ltd., www.kceng.com/ K.l.S.S. Packaging Systems, www.kisspkg.com Kafko International Ltd., www.kafkointl.com Kanazawa University, Japan, Tribology Laboratory, http://web.kanazawa-u.ac.jp/∼tribo/labo5e.html Kath Fuel Oil Service, www.kathfuel.com Kawasaki, www.kawasaki.com Kawasaki, www.khi.co.jp Keck Oil Company, www.keckoil.com Keil Chemical, www.ferro.com Kelsan Lubricants USA LLC, www.kelsan.com Kem-A-Trix Specialty Lubricants & Compounds, www.kematrix.com Kendall Motor Oil, www.kendallmotoroil.com Kennedy Group. The, www.kennedygrp.com King Industries Specialty Chemicals, www.kingindustries.com Kittiwake Developments Limited, www.kittiwake.com Kleenoil Filtration Inc., www.kleenoilfiltrationinc.com Kleentek-United Air Specialists Inc., www.uasinc.com Kline & Company Inc., www.klinegroup.com Kluber Lubrication North America LP, www.kluber.com Koehler Instrument Company, www.koehlerinstrument.com KOST Group Inc., www.kostusa.com Kruss USA, www.krussusa.com Kuwait National Petroleum Company, www.knpc.com.kw Kyodo Yushi USA Inc., www.kyodoyushi.co.jp Kyushu University, Japan, Lubrication Engineering Home Page, www.mech.kyushu-u.ac.jp/index.html Lambent Technologies, www.petroferm.com Lambourghini, www.lamborghini.com Laub/Hunt Packaging Systems, www.laubhunt.com Lawler Manufacturing Corporation, www.lawler-mfg.com Leander Lubricants, www.leanderlube.com Leding Lubricants Inc., www.automatic-lubrication.com Lee Helms Inc., www.leehelms.com Leffert Oil Company, www.leffertoil.com Leffler Energy Company, www.leffler.com Legacy Manufacturing, www.legacymfg.com Les Industries Sinto Racing Inc., www.sintoracing.com Lexus, www.lexususa.com Liftomtic Inc., www.liftomatic.com Lilyblad Petroleum, Inc., www.lilyblad.com Lincoln-Mercury, www.lincolnmercury.com Linpac Matls. Handling, www.linpacmh.com


Liqua-Tek Inc., www.hdpluslubricants.com Liqua-Tek/Moraine Packaging, www.globaldialog.com/∼mpi Liquid Controls Inc., A Unit of IDEX Corporation, www.lcmeter.com Liquid Horsepower, www.holeshot.com/chemicals/ additives.html LithChem International, www.lithchem.com Lockhart Chemical Company, www.lockhartchem.com Loos & Dilworth Inc. — Automotive Division, www.loosanddilworth.com Loos & Dilworth Inc. — Chemical Division, www.loosanddilworth.com Lormar Reclamation Service, www.lormar.com Los Alomos National Laboratory, www.lanl.gov/ worldview/ Lowe Oil Co./Champion Brands LLC, www.championbrands.com LPS Laboratories, www.lpslabs.com LSST Tribology and Surface Forces, http://bittburg.ethz. ch/LSST/Tribology/default.html LSST Tribology Letters, http://bittburg.ethz.ch/LSST/ Tribology/letters.html Lube Net, www.lubenet.com LubeCon Systems Inc., www.lubecon.com Lubelink, www.lubelink.com Lubemaster Corporation, www.lubemaster.com LubeNet, www.lubenet.com LubeRos—A Division of Burlington Chemical Company Inc., www.luberos.com Lubes and Greases, www.lngpublishing.com LuBest, Division of Momar Inc., www.momar.com Lubricant Additives Research, www.silverseries.com Lubricant Technologies, www.lubricanttechnologies.com Lubricants Network Inc., www.lubricantsnetwork.com Lubricants USA, www.finalube.com Lubricants World, www.lubricantsworld.com Lubrication Engineering Magazine, www.stle.org/ le_magazine/le_index.htm Lubrication Engineers Inc., www.le-inc.com Lubrication Engineers of Canada, www.lubeng.com Lubrication Systems, www.lsc.com Lubrication Technologies Inc., www.lube-tech.com Lubrication Technology Inc., www.lubricationtechnology.com Lubrichem International Corporation, www.lubrichem.net Lubrifiants Distac Inc., www.inspection.gc.ca/english/ ppc/reference/n2e.shtml Lubri-Lab Inc., www.lubrilab.com LUBRIPLATE Div., Fiske Bros. Refining Company, www.lubriplate.com Lubriport Labs, www.ultralabs.com/lubriport Lubriquip Inc, www.lubriquip.com Lubritec, www.ensenada.net/lubritec/ Lubrizol Corporation, The, www.lubrizol.com

Lubromation Inc., www.lubromation.com Lub-Tek Petroleum Products Corporation, www.lubtek.com Lucas Oil Products Inc., www.lucasoil.com LukOil (Russian Oil Company), www.lukoil.com Lulea University of Technology, Department of Mechanical Engineering, www.luth.se/depts/mt/me/ Lyondell Lubricants, www.lyondelllubricants.com Machines Production Web Site, www.machpro.fr/ Mack Trucks, www.macktrucks.com MagChem Inc., www.magchem.com Magnalube, www.magnalube.com Maine Lubrication Service Inc., www.mainelube.com MaintenanceWorld, www.wearcheck.com Manor Technology, www.manortec.co.uk/ Manor Trade Development Corporation, www.amref.com Mantek Lubricants, www.mantek.com Marathon Ashland Petroleum LLC, www.mapllc.com Marathon Oil Company, www.marathon.com MARC-IV, www.marciv.com Marcus Oil and Chemical, www.marcusoil.com Markee International Corporation, www.markee.com Marly, www.marly.com Maryn International Ltd., www.maryngroup.com Maryn International, www.poweruplubricants.com Master Chemical Corporation, www.masterchemical.com Master Lubricants Company, www.lubriko.com Maxco Lubricants Company, www.maxcolubricants.com Maxim Industrial Metalworking Lubricants, www.maximoil.com Maxima Racing Lubricants, www.maximausa.com Mays Chemical Company, www.mayschem.com Mazda, www.mazda.com McCollister & Company, www.mccollister.com McGean-Rohco Inc., www.mcgean-rohco.com McGee Industries Inc., www.888teammclube.com McIntyre Group Ltd., www.mcintyregroup.com McLube Divisionl/McGee Industries Inc., www.888teammclube.com Mechanical Engineering Magazine, www.memagazine.org/index.html Mechanical Engineering Tribology Web Site, http://widget.ecn.purdue.edu/∼metrib/ Mega Power Inc., www.megapowerinc.com Mercedes-Benz (Germany), www.mercedes-benz.de Metal Forming Lubricants Inc., www.mflube.com Metal Mates Inc., www.metalmates.net Metalcote/Chemtool Inc., www.metalcote.com Metalworking Lubricants Company, www.metalworkinglubricants.com Metalworking Lubricants, www.maximoil.com Metorex Inc., www.metorex.fi Mettler Toledo, www.mt.com MFA Oil Compny, www.mfaoil.com


Michel Murphy Enterprises Inc., www.michelmurphy.com Micro Photonics Inc., www.microphotonics.com/ Mid-Michigan Testing Inc., www.tribologytesting.com Mid-South Sales Inc., www.mid-southsales.com Mid-Town Petroleum Inc., www.midtownoil.com Migdal’s Lubricant Web Page, http://members.aol.com/ sirmigs/lub.htm Milacron Consumable Products Division, www.milacron.com Milatec Corporation, www.militec.com Millennium Lubricants, www.millenniumlubricants.com Miller Oil of Indiana, Inc., www.milleroilinc.com Mitsubishi Motors, www.mitsubishi-motors.co.jp Mobil, www.mobil.com Mohawk Lubricants Ltd., www.mohawklubes.com MOL Hungarian Oil & Gas, www.mol.hu Molyduval, www.molyduval.com Molyslip Atlantic Ltd., www.molyslip.co.uk Monlan Group, www.monlangroup.com Monroe Fluid Technology Inc., www.monroefluid.com Moore Oil Company, www.mooreoil.com Moraine Packaging Inc., www.hdpluslubricants.com Morey’s Oil Products Company, www.moreysonline.com Moroil Technologies, www.moroil.com Motiva Enterprises LLC, www.motivaenterprises.com Motor Fuels/Combustibles Testing, www.empa.ch/ englisch/fachber/abt133/index.htm Motorol Lubricants, www.motorolgroup.com Motul USA Inc., www.motul.com Mozel Inc., www.mozel.com Mr. Good Chem, Inc., www.mrgoodchem.com Murphy Oil Corporation, www.murphyoilcorp.com/ Muscle Products Corporation, www.mpc-home.com Muse, Stancil & Company, www.musestancil.com Nalco Chemical Company, www.nalco.com Nanomechanics and Tribology Swiss Tribology Online, http://dmxwww.epfl.ch/WWWTRIBO/home.html NanoTribometer System, www.ume.maine.edu/LASST Naptec Corporation, www.satec.com NASA Lewis Research Center (LeRC) Tribology & Surface Science Branch, www.lerc.nasa.gov/ Other_Groups/SurfSci National Centre of Tribology, UK, www.aeat.com/nct/ National Fluid Power Association (NFPA), www.nfpa.com National Institute for Occupational Safety and Health, www.cdc.gov/homepage.html National Institute of Standards and Technology, http://webbook.nist.gov/chemistry National Lubricating Grease Institute (NLGI), www.nlgi.org National Metal Finishing Resource Center, www.nmfrc.org National Oil Recyclers Association (NORA), www.recycle.net/Associations/rs000141.html

National Petrochemical & Refiners Association, www.npradc.org National Petrochemical Refiners Association (NPRA) www.npradc.org National Petroleum News, www.petroretail.net/npn National Petroleum Refiners Association (NPRA), www.npra.org National Research Council of Canada Lubrication Tribology Services, http://132.246.196.24/en/fsp/ service/lubrication_trib.htm National Resource for Global Standards, www.nssn.org National Tribology Services, www.natrib.com Naval Research Lab Tribology Section — NRL Code 6176, http://stm2.nrl.navy.mil/∼wahl/6176.htm NCH, www.nch.com Neale Consulting Engineers Limited, www.tribology.co.uk/ Neo Synthetic Oil Company Inc., www.neosyntheticoil.com Newcomb Oil Company, www.newcomboil.com Niagara Lubricant Company, Inc., www.niagaralubricant.com Nissan (Japan), www.nissan.co.jp Nissan (USA), www.nissandriven.com Nissan (USA), www.nissanmotors.com NOCO Energy Corporation, www.noco.com Noco Lubricants, www.noco corn Nordstrom Valves Inc., www.nordstromaudco.com Noria-OilAnalysis.Com, www.oilanalysis.com/ Northern Technologies International Corporation, www.ntic.com Northwestern University, Tribology Lab, http://cset.mech.northwestern.edu/member.htm Nyco SA, www.nyco.fr Nye Lubricants, www.nyelubricants.com Nynas Naphthenics, www.nynas.com

O’Rourke Petroleum, www.orpp.com Oak Ridge National Laboratory (ORNL) Tribology Test Systems, www.ms.ornl.gov/htmlhome Oakite Products, Inc., www.oakite.com OATS (Oil Advisory Technical Services), www.oats.co.uk Occidental Chemical Corporation, www.oxychem.com Occupational Safety and Health Administration (OSHA), www.osha.gov Ocean State Oil Inc., www.oceanstateoil.com Oden Corporation, www.oden.thomasregister.com Oden Corporation, www.odencorp.com Ohio State University, Center for Surface Engineering and Tribology, Gear Dynamics and Gear Noise Research Laboratory, http://gearlab.eng.ohio-state.edu/ Oil Analysis (Noria), www.oilanalysis.com Oil Center Research Inc., www.oilcenter.com Oil Depot, www.oildepot.com


Oil Directory.com, www.oildirectory.com Oil Distributing Company, www.oildistributing.com Oil Online, www.oilonline.com/ Oil-Chem Research Corporation, www.avblend.com Oilkey Corporation, www.oilkey.com Oil-Link Oil & Gas Online, www.oilandgasonline.com Oilpure Technologies Inc., www.oilpure.com Oilspot.com, www.oilspot.com OKS Speciality Lubricants, www.oks-india.com OMGI, www.omgi.com OMICRON Vakuumphysik GmbH, www.omicroninstruments.com/index.html Omni Specialty Packaging, www.nuvo.cc OMO Petroleum Company, Inc., www.omoenergy.com OMS Laboratories, Inc., http://members.aol.com/ labOMS/index.html Opel, www.opel.com Orelube Corporation, www.orelube.com Oronite, www.oronite.com O’Rourke Petroleum Products, www.orpp.com Ottsen Oil Company, Inc., www.ottsen.com Owens-Illinois Inc., www.o-i.com Oxford Instruments Inc., www.oxinst.com Paper Systems Inc., www.paper-systems.com Paramount Products, www.paramountproducts.com PARC Technical Services Inc., www.parctech.com Parent Petroleum, www.parentpetroleum.com PATCO Additives Division — American Ingredients Company, www.patco-additives.com Pathfinder Lubricants, www.pathfinderlubricants.ca/ Patterson Industries Ltd. (Canada), www.pattersonindustries.com PBM Services Company, www.pbmsc.com PdMA Corporation, www.pdma.com PDVSA (Venezuela), www.pdvsa.com PED Inc., www.ped.vianet.ca Pedroni Fuel Company, www.pedronifuel.com PEMEX (Mexico), www.pemex.com Pennine Lubricants, www.penninelubricants.co.uk Pennsylvania State University, The, www.me.psu.edu/ research/tribology.html Pennwell Publications, www.pennwell.com Pennzoil Industrial Lubricants, www.pennzoil.com/ prdsmktg/products/industrial/default.htm Pennzoil, www.pennzoil.com Pennzoil-Quaker State Company, www.pennzoilquakerstate.com PENRECO, www.penreco.com Penta Manufacturing Company/Division of Penta International Corporation, www.pentamfg.com Performance Lubricants & Race Fuels Inc., www.performanceracefuels.com Perkin Elmer Automotive Research, www.perkinelmer.com/ar

Perkins Products Inc., www.perkinsproducts.com Pertamina (Indonesia), www.pertamina.com Petro Star Lubricants, www.petrostar.com PetroBlend Corporation, www.petroblend.com Petrobras (Brazil), www.petrobras.com.br Petro-Canada Lubricants, www.htlubricants.com Petrofind.com, www.petrofind.com Petrogal (Portugal), www.galpenergia.com/ Galp+Energia/home.htm Petrogal (Portugal), www.petrogal.pt Petrolab Corporation, www.petrolab.com Petrolabs Inc., http://pages.prodigy.net/petrolabsinc Petroleum Analyzer Company LP (PAC), www.Petroleum-Analyzer.com Petroleum Marketers Association of America (PMAA), www.pmaa.org Petroleum Packers Inc., www.pepac.com Petroleum Products Research, www.swri.org/4org/ d08/petprod/ PetroleumWorld.com, www.petroleumworld.com Petro-Lubricants Testing Laboratories, Inc., www.pltlab.com PetroMin Magazine, www.petromin.safan.com PetroMoly, Inc., www.petromoly.com Petron Corporation, www.petroncorp.com Petroperu (Peru), www.petroperu.com Petrotest, www.petrotest.net Peugeot, www.peugeot.com Pfaus Sons Company Inc., www.pfauoil.com Pflaumer Brothers Inc., www.pflaumer.com Philips Industrial Electronics Deutschland, www.philips-tkb.com Phillips Petroleum Company/Phillips 66, www.phillips66.com/phi11ips66.asp Phoenix Petroleum Company, www.phoenixpetroleum.com Pico Chemical Corporation, www.picochemical.com Pilot Chemical Company, www.pilotchemical.com Pinnacle Oil Inc., www.pinnoil.com Pipeguard of Texas, www.pipeguard-texas.com Pitt Penn Oil Company, www.pittpenn.com Plastic Bottle Corporation, www.plasticbottle.com Plastican Inc., www.plastican.com Plews/Edelmann Division, Stant Corporation, www.stant.com PLI LLC, www.memolub.com Plint and Partners: Tribology Division, www.plint.co.uk/trib.htm Plymouth, www.plymouthcars.com PMC Specialties Inc., www.pmcsg.com PolimeriEuropa, www.polimerieuropa.com PoIySi Technologies Inc., www.polysi.com Polaris Laboratories, LLC, www.polarislabs.com Polar Company, www.polarcompanies.com Polartech Ltd., www.polartech.co.uk


PolySi Technologies, www.polysi.com Pontiac (GM), www.pontiac.com Power Chemical, www.warcopro.com Power-Up Lubricants, www.mayngroup.com Practicing Oil Analysis Magazine, www.practicingoilanalysis.com Precision Fluids Inc., www.precisionfluids.com Precision Industries, www.precisionind.com Precision Lubricants, www.precisionlubricants.com PREDICT/DLI—Innovative Predictive Maintenance, www.predict-dli.com Predictive Maintenance Corporation, www.pmaint.com/ Predictive Maintenance Corporation: Tribology and the Information Highway, www.pmaint.com/tribo/docs/ oil_anal/tribo_www.html Predictive Maintenance Services, www.theoillab.com Premo Lubricant Technologies, www.premolube.com Prime Materials, www.primematerials.com Primrose Oil Company, Inc., www.primrose.com Probex Corporation, www.probex.com Products Development Manufacturing Company, www.veloil.com ProLab TechnoLub Inc., www.prolab-technologies.com ProLab-Bio Inc., www.prolab-lub.com Prolong Super Lubricants, www.prolong.com ProTec International Inc., www.proteclubricants.com Pulsair Systems Inc., www.pulsair.com Purac America, Inc., www.purac.com Purdue University Materials Processing and Tribology Research Group, www.ecn.purdue.edu/∼farrist/lab.html Pure Power Lubricants, www.gopurepower.com QMI, www.qminet.com Quaker Chemical Corporation, www.quakerchem.com Quaker State, www.qlube.com Quorpak, www.quorpak.com R & D/Fountain Industries, www.fountainindustries.com R.A. Miller & Company, Inc., www.ramiller.on.ca R.T. Vanderbilt Company, Inc., www.rtvanderbilt.com R.E. Carroll Inc., www.recarroll.com R.E.A.L. Services, www.realservices.com R.H. Foster Energy LLC, www.rhfoster.com R.T. Vanderbilt Company, www.rtvanderbilt.com Radian Inc., www.radianinc.com Radio Oil Company, Inc., www.radiooil.com Ramos Oil Company, Inc., www.ramosoil.com Rams-Head Company, www.doall.com Ransome CAT, www.ransome.com Ravenfield Designs Ltd., www.ravenfield.com Reade Advanced Materials, www.reade.com Red Giant Oil Company, www.redgiantoil.com Red Line Oil, www.redlineoil.com Reed Oil Company, www.reedoil.com

Reelcraft Industries Inc., www.realcraft.com Reit Lubricants Company, www.reitlube.com Reitway Enterprises Inc., www.reitway.com Reliability Magazine, www.pmaint.com/tribo/docs/ oil_anal/tribo_www.html Renewable Lubricants, Inc., www.renewablelube.com Renite Company, www.renite.com Renite Company-Lubrication Engineers, www.renite.com Renkert Oil, www.renkertoil.com Rensberger Oil Company, Inc., www.rensbergeroil.com Rexam Closures, www.closures.com Rhein Chemie Corporation, www.bayer.com Rhein Chemie Rheinau GmbH, www.rheinchemie.com Rheotek (PSL SeaMark), www.rheotek.com Rheox Inc., www.rheox.com Rhodia, www.rhodia.com Rhone-Poulenc Surfactants & Specialties, www.rpsurfactants.com Ribelin, www.ribelin.com RiceChem, A Division of Stilling Enterprises Inc., www.ricechem.com RichardsApex Inc., www.richardsapex.com Riley Oil Company, www.rileyoil.com RO-59 Inc., http://members.aol.com/ro59inc Rock Valley Oil & Chemical Company, www.rockvalleyoil.com Rocol Ltd., www.rocol.com Rohm & Haas Company, www.rohmhaas.com RohMax Additives GmbH, www.rohmax.com Ross Chem Inc., www.rosschem.com Rowleys Wholesale, www.rowleys.com Royal Institute of Technology (KTH), Sweden Machine Elements Home Page, www.damek.kth.se/mme Royal Lubricants Inc., www.royallube.com Royal Manufacturing Company, Inc., www.royalube.com Royal Purple, Inc., www.royalpurple.com Russell-Stanley Corportion, www.russell-stanley.com RWE-DEA (Germany), www.rwe-dea.de RyDol Products, www.rydol.com

Saab Cars USA, www.saabusa.com Saab, www.saab.com Safety Information Resources on the Internet, www.siri.org/links1.html Safety-Kleen Corporation, www.safety-kleen.com Safety-Kleen Oil Recovery, www.ac-rerefined.com Saftek: Machinery Maintenance Index, www.saftek.com/boiler/machine/mmain.htm Saitama University, Japan Home Page of Machine Element Laboratory, www.mech.saitama-u.ac.jp/ youso/home.html San Joaquin Refining Company, www.sjr.com Sandia National Laboratories Tribology, www.sandia.gov/ materials/sciences/


Sandstrom Products Company, www.sandstromproducts.com Sandy Brae Laboratories Inc., www.sandy/brae.com Santie Oil Company, www.santiemidwest.com Santotrac Traction Lubricants, www.santotrac.com Santovac Fluids Inc., www.santovac.com Sasol (South Africa), www.sasol.com SATEC Inc., www.satec.com Saturn (GM), www.saturncars.com Savant Group of Companies, www.savantgroup.com Savant Inc., www.savantgroup.com Saxton Industries Inc., www.saxton.thomasregister.com Saxton Industries Inc., www.schaefferoil.com Scania, www.scania.se Schaeffer Manufacturing, www.schaefferoil.com Schaeffer Oil and Grease, www.schaefferoil.com Schaeffer Specialized Lubricants, www.schaefferoil.com Scully Signal Company, www.scully.com Sea-Land Chemical Company, www.sealandchem.com Selco Synthetic Lubricants, www.synthetic-lubes.com Senior Flexonics, www.flexonics-hose.com Sentry Solutions Ltd., www.sentrysolutions.com Service Supply Lubricants LLC, www.servicelubricants.com Sexton & Peake Inc., www.sexton.qpg.com SFR Corporation, www.sfrcorp.com SGS Control Services Inc., www.sgsgroup.com Shamban Tribology Laboratory Kanazawa University, Japan, http://web.kanazawa-u.ac.jp/∼tribo/labo5e.html Shamrock Technologies, Inc., www.shamrocktechnologies.com Share Corp., www.sharecorp.com Shell (USA), www.shellus.com Shell Chemicals, www.shellchemical.com Shell Global Solutions, www.shellglobalsolutions.com Shell International, www.shell.com/royal-en Shell Lubricants (USA), www.shell-lubricants.com Shell Oil Products US, www.shelloilproductsus.com/ Shell, www.shellus.com Shepherd Chemical Company, www.shepchem.com Shrieve Chemical Company, www.shrieve.com Silvas Oil Company, Inc., www.silvasoil.com Silverson Machines Inc., www.silverson.com Simons Petroleum Inc., www.simonspetroleum.com Sinclair Oil Corporation, www.sinclairoil.com Sinopec (China Petrochemical Corporation), www.sinopec.com.cn SK Corporation (Houston Office) www.skcorp.com SKF Quality Technology Centre, www.qtc.skf.com Sleeveco Inc., www.sleeveco.com Slick 50 Corporation, www.slick50.com Smooth Move Company, www.theprojectsthatsave.com Snyder Industries, www.snydernet.com Sobit International, Inc., www.sobitinc.com Society of Automotive Engineers (SAE), www.sae.org

Society of Environmental Toxicology and Chemistry (SETAC), www.setac.org Society of Manufacturing Engineers (SME), www.sme.org Society of Manufacturing Engineers, www.sme.org Society of Tribologists and Lubrication Engineers (STLE), www.stle.org Soltex, www.soltexinc.com Sourdough Fuel, www.petrostar.com Southern Illinois University, Carbondale Center for Advanced Friction Studies, www.frictioncenter.com Southwest Grease Products, www.stant.com/ brochure.cfm?brochure=155&location_id=119 Southwest Research Institute (SwRI) Engine Technology Section, www.swri.org/4org/d03/engres/engtech/ Southwest Research Institute, www.swri.org Southwest Spectro-Chem Labs, www.swsclabs.com Southwestern Graphite, www.asbury.com Southwestern Petroleum Corporation (SWEPCO), www.swepco.com Southwestern Petroleum Corporation, www.swepcousa.com SP Morell & Company, www.spmorell.com Spacekraft Packaging, www.spacekraft.com Spartan Chemical Company Inc. Industrial Products Group Division, www.spartanchemical.com Spartan Oil Company, www.spartanonline.com Specialty Silicone Products Inc., www.sspinc.com Spectro Oils of America, www.goldenspectro.com Spectro Oils of America, www.spectro-oils.com SpectroInc. Industrial Tribology Systems, www.spectroinc.com/ Spectronics Corporation, www.spectroline.com Spectrum Corp., www.spectrumcorporation.com Spencer Oil Company, www.spenceroil.com Spex CertiPrep Inc., www.spexcsp.com SQM North America Corporation, www.sqmna.com St. Lawrence Chemicals, www.stlawrencechem.com Star Brite, www.starbrite.com State University of New York, Binghamton Mechanical Engineering Laboratory, www.me.binghamton.edu/ me_labs.html Statoil (Norway), www.statoil.com Steel Shipping Containers Institute, www.steelcontainers.com Steelco Industrial Lubricants, Inc., www.steelcolubricants.com Steelco Northwest Distributors, www.steelcolubricants.com Stochem, Inc., www.stochem.com STP Products Inc., www.stp.com Stratco Inc., www.stratco.com SubTech (Petroleum Service & Supply Information), www.subtech.no/petrlink.htm Suburban Oil Company, Inc., www.suburbanoil.com Summit Industrial Products Inc., www.klsummit.com


Summit Technical Solutions, www.lubemanagement.com Sunnyside Corporation, www.sunnysidecorp.com Sunoco Inc., www.sunocoinc.com Sunohio, Division of ENSR, www.sunohio.com Superior Graphite Company, www.superiorgraphite.com/ sgc.nsf Superior Lubricants Company, Inc., www.superiorlubricants.com Superior Lubrication Products, www.s-l-p.com Surtec International Inc., www.surtecinternational.com Swiss Federal Laboratories for Materials Testing and Research (EMPA) Centre for Surface Technology and Tribology, www.empa.ch Synco Chemical Corporation, www.super-lube.com SynLube Inc., www.synlube.com Synthetic Lubricants Inc., www.synlube-mi.com Syntroleum Corporation, www.syntroleum.com

T.S. MoIy-Lubricants Inc., www.tsmoly.com T.W. Brown Oil Company, Inc, www.brownoil.com/ soypower.html Taber Industries, www.taberindustries.com TAI Lubricants, www.lubekits.com Tannas Company, www.savantgroup.com Tannis Company, www.savantgroup.com/tannas.sht TCC, www.technicalchemical.com Technical Chemical Company, www.technicalchemical.com Technical University of Delft, Netherlands Laboratory for Tribology, www.ocp.tudelft.nl/tribo/ Technical University, Munich, Germany, www.fzg.mw. tu-muenchen.de Technische Universitat Ilmenau, Faculty of Mathematics and Natural Sciences, www.physik.tu-ilmenau.de/ index_e.html Tek-5 Inc., www.tek-5.com Terrresolve Technologies, www.terresolve.com Test Engineering Inc., www.testeng.com Texaco Inc., www.texaco.com Texas Refinery Corporation, www.texasrefinery.com Texas Tech University, Tribology, www.osci.ttu.edu/ ME_Dept/Research/tribology.htmld/ Textile Chemical Company, Inc., www.textilechem.com Thailand, Petroleum Authority of, www.nectec.or.th/ users/htk/SciAm/12PTT.html Thailand, Petroleum Authority, www.nectec.or.th The Maintenance Council, www.trucking.org Thermal-Lube Inc., www.thermal-lube.com Thermo Elemental, www.thermoelemental.com Thomas Petroleum, www.thomaspetro.com Thornley Company, www.thornleycompany.com Thoughtventions Unlimited Home Page, www.tvu.com/ %7Ethought/ Tiodize Company, Inc., www.tiodize.com

Titan Laboratories, www.titanlab.com TMC, www.truckline.com Tokyo Institute of Technology, Japan Nakahara Lab. Home Page, www.mep.titech.ac.jp/Nakahara/home.html Tomah Products, Inc., www.tomah3.com Tom-Pac Inc., www.tom-pac.com Top Oil Products Company Ltd., www.topoil.com Torco International Corporation, www.torcoracingoils.com Tosco, www.tosco.com Total, www.total.com Total, www.totalfinaelf.com/ho/fr/index.htm Totalfina Oleo Chemicals, www.totalfina.com Tower Oil & Technology Company, www.toweroil.com Toyo Grease Manufacturing (M) SND BHD, www.toyogrease.com Toyota (Japan), www.toyota.co.jp Toyota (USA), www.toyota.com TransMontaigne, www.transmontaigne.com Transmountain Oil Company, www.transmountainoil.com TriboLogic Lubricants Inc., www.dynamaxx.com TriboLogic Lubricants Inc., www.tribologic.com Tribologist.com, www.wearcheck.com/sites.html Tribology Consultant, http://hometown.aol.com/ wearconsul/wear/wear.htm Tribology Group, www.msm.cam.ac.uk/tribo/tribol.htm Tribology International, www.elsevier.nl/inca/ publications/store/3/0/4/7/4/ Tribology Letters, www.kluweronline.com/issn/ 1023-8883 Tribology Research Review 1992-1994, www.me.ic.ac.uk/ department/review94/trib/tribreview.html Tribology Research Review 1995-1997, www.me.ic.ac.uk/ department/review97/trib/tribreview.html Tribology/Tech-Lube, www.tribology.com Tribos Technologies, www.tribostech.com Trico Manufacturing Corporation, www.tricomfg.com Tricon Specialty Lubricants, www.tristrat.com Trilla Steel Drum Corporation, www.trilla.com Trinity College, Dublin Tribology and Surface Engineering, www.mme.tcd.ie/Groups/Tribology/ Troy Corporation, www.troycorp.com Truklink (Truck fleet information), www.truklink.com Tsinghua University, China, State Key Laboratory of Tribology, www.pim.tsinghua.edu.cn/index_cn.html TTi’s Home Page, www.tti-us.com/ Turmo Lubrication Inc., www.lubecon.com TXS Lubricants Inc., www.txsinc.com U.S. Department of Energy (DOE), www.energy.gov U.S. Department of Transportation (DOT), www.dot.gov U.S. Energy Information Administration, www.eia.doe.gov U.S. Patent Office, www.uspto.gov U.S. Data Exchange, www.usde.com U.S. Industrial Lubricants Inc., www.usil.cc


U.S. Oil Company, Inc., www.usoil.com UEC Fuels and Lubrication Laboratories, www.uec-usx.com Ultimate Lubes, www.ultimatelubes.com Ultra Additives, Inc., www.ultraadditives.com Ultrachem Inc., www.ultracheminc.com Unilube Systems Ltd., www.unilube.com Unimark Oil Company, www.gardcorp.com Union Carbide Corporation, www.unioncarbide.com Uniqema, www.uniqema.com Uniroyal Chemical Company Inc., www.uniroyalchemical.com UniSource Energy Inc., www.unisource-energy.com Unist, Inc., www.unist.com Unit Pack Company, Inc., www.unitpack.com United Color Manufacturing Inc., www.unitedcolor.com United Lubricants, www.unitedlubricants.com United Oil Company, Inc., www.duralene.com United Oil Products Ltd., http://ourworld. compuserve.com/homepages/Ferndale_UK United Soybean Board, www.unitedsoybean.org Universal Lubricants Inc., www.universallubes.com University of Akron Tribology Laboratory, www.ecgf. uakron.edu/∼mech University of Applied Sciences (FH-Hamburg), Germany Dept of Mech. Eng Tribology, www.fh-hamburg.de/fh/fb/m/tribologie/e_index.html University of Applied Sciences, Hamburg, Germany, www.haw-hamburg.de/fh/fb/m/tribologie/e_index.html University of California, Berkeley Bogey’s Tribology Group, http://cml.berkeley.edu/tribo.html University of California, San Diego Center for Magnetic Recording Research, http://orpheus.ucsd.edu/cmrr/ University of Florida, Mechanical Engineering Department, Tribology Laboratory, http://grove.ufl.edu/ ∼wgsawyer/ University of Illinois, Urbana-Champaign Tribology Laboratory, www.mie.uiuc.edu University of Kaiserslautern, Germany Sektion Tribologie, www.uni-kl.de/en/ University of Leeds, M.Sc. (Eng.) Course in Surface Engineering and Tribology, http://leva.leeds.ac.uk/ tribology/msc/tribmsc.html University of Leeds, UK Research in Tribology, http://leva.leeds.ac.uk/tribology/research.html University of Ljubljana, Faculty of Mechanical Engineering, Center for Tribology and Technical Diagnostics, www.ctd.uni-lj.si/eng/ctdeng.htm University of Maine Laboratory for Surface Science and Technology (LASST), www.ume.maine.edu/LASST/ University of Newcastle upon Tyne, UK Ceramics Tribology Research Group, www.ncl.ac.uk/materials/ materials/resgrps/certrib.html University of Northern Iowa, www.uni.edu/abil

University of Notre Dame Tribology/Manufacturing Laboratory, www.nd.edu/∼ame University of Pittsburg, School of Engineering, Mechanical Engineering Department, www.engrng.pitt.edu/∼mewww University of Sheffield, UK Tribology Research Group, http://www.shef.ac.uk/mecheng/tribology/ University of Southern Florida. Tribology, www.eng.usf.edu/∼hess/ University of Texas at Austin, Petroleum & Geosystems Engineering, Reading Room, www.pe.utexas.edu/Dept/ Reading/petroleum.html University of Tokyo, Japan, Mechanical Engineering Department, www.mech.t.u-tokyo.ac.jp/english/ index.html University of Twente, Netherlands Tribology Group, http://www.wb.utwente.nl/vakgroep/tr/tribeng.htm University of Western Australia Department of Mechanical and Material Engineering, http://www.mech.uwa.edu.au/tribology/ University of Western Ontario, Canada Tribology Research Centre, http://www.engga.uwo.ca/research/tribology/ Default.htm University of Windsor, Canada Tribology and Wear Research Group, http://zeus.uwindsor.ca/research/wtrg/ index.html University of Windsor, Canada, Tribology Research Group, http://venus.uwindsor.ca/research/wtrg/ index.html Unocal Corporation, www.unocal.com Uppsala University, Sweden Tribology Group, http://www.angstrom.uu.se/materials/index.htm U.S. Department of Agriculture (USDA), www.usda.gov U.S. Department of Energy (DOE), www.energy.gov U.S. Department of Defense (DOD), www.dod.gov USX Engineers & Consultants, www.uec.com/labs/ctns USX Engineers and Consultants: Laboratory Services, www.uec.com/labs/ Vacudyne Inc., www.vacudyne.com Valero Mktg. & Supply, www.valero.com Valhalla Chemical, www.valhallachem.com Valvoline Canada, www.valvoline.com Valvoline, www.valvoline.com Van Horn, Metz & Company, Inc., www.vanhornmetz.com Vauxhall, www.vauxhall.co.uk Vesco Oil Corporation, www.vesco-oil.com Victoria Group Inc., The, www.victoriagroup.com Viking Pump Inc., A Unit of IDEX Corporation, www.vikingpump.com Vikjay Industries Inc., www.vikjay.com Virtual Oil Inc., www.virtualoilinc.com Viswa Lab Corporation, www.viswalab.com Vogel Lubrication System of America, www.vogel-lube.com


Volkswagen (Germany), www.vw-online.de Volkswagen (USA), www.vw.com Volvo (Sweden), www.volvo.se Volvo Cars of North America, www.volvocars.com Volvo Group, www.volvo.com Vortex International LLC, www.vortexfilter.com VP Racing Fuels Inc., www.vpracingfuels.com Vulcan Oil & Chemical Products Inc., www.vulcanoil.com Vulsay Industries Ltd., www.vulsay.com

Wallace, www.wallace.com Wallover Oil Company, www.walloveroil.com Walthall Oil Company, www.walthall-oil.com Warren Distribution, www.wd-wpp.com Waugh Controls Corporation, www.waughcontrols.com WD-40 Company, www.wd40.com Wear Chat: WearCheck Newsletter, www.wearcheck.com/publications.html Wear, www.elsevier.nl/inca/publications/ store/5/0/4/1/0/7/ Wearcheck International, www.wearcheck.com/ Web-Valu Intl.www.webvalu.com Wedeven Associates, Inc., http://members.aol.com/ wedeven/ West Central Soy, www.soypower.net West Penn Oil Company, Inc., www.westpenn.com Western Michigan University Tribology Laboratory, www.mae.wmich.edu/labs/Tribology/Tribology.html Western Michigan University, Department of Mechanical and Aeeronautical Engineering, www.mae.wmich.edu/ Western States Oil, www.lubeoil.com Western States Petroleum Association, www.wspa.org Whitaker Oil Company, Inc., www.whitakeroil.com Whitmore Manufacturing Company, www.whitmores.com Whitmore Manufacturing Company, The, www.whitmore.com Wilcox and FIegel Oil Company, www.wilcoxandflegel.com Wilks Enterprise Inc., www.wilksir.com Winfield Brooks Company, Inc., www.tapfree.com Winzer Corp., www.winzerusa.com Witco (Crompton Corporation), www.witco.com Wolf Lake Terminals Inc., www.wolflakeinc.com Worcester Polytechnic Institute, Department of Mechanical Engineering, www.me.wpi.edu/Research/ labs.html World Tribologists Database, http://greenfield. fortunecity.com/fish/182/tribologists.htm Worldwide PetroMoly, Inc., www.petromoly.com WSI Chemical Inc., www.wsi-chem-sys.com WWW Tribology Information Service, www.shef.ac.uk/ ∼mpe/tribology/

WWW Virtual Library: Mechanical Engineering, www.vlme.com/ Wynn Oil Company, www.wynnsusa.com X-1R Corporation, The, www.x1r.com Yahoo Lubricants, http://dir.yahoo.com/business_ and_economy/shopping_and_services/automotive/ supplies/lubricants/ Yahoo Tribology, http://ca.yahoo.com/Science/ Engineering/Mechanical_Engineering/Tribology/ Yocum Oil Company, Inc., www.yocumoil.com YPF (Argentina), www.ypf.com.ar Yuma Industries Inc., www.yumaind.com Zimmark Inc., www.zimmark.com Zinc Corporation of America, www.zinccorp.com

51.2 INTERNET LISTINGS BY CATEGORY 51.2.1 Lubricant Fluids (Base Oils, Greases, Biodegradable, Synthetics, Packaged Oils, and Solid Lubricants) 2V Industries Inc., www.2vindustries.com 49 North, www.49northlubricants.com 76 Lubricants Company, www.tosco.com A/R Packaging Corporation, www.arpackaging.com Acculube, www.acculube.com Accurate Lubricants & Metalworking Fluids Inc. (dba Acculube), www.acculube.com Acheson Colloids Company, www.achesonindustries.com Acme Refining, Division of Mar-Mor Inc., www.acmerefining.com Acme-Hardesty Company, www.acme-hardesty.com Advanced Ceramics Corporation, www.advceramics.com Advanced Lubrication Specialties Inc., www.advancedlubes.com/ Aerospace Lubricants Inc., www.aerospacelubricants.com African Lubricants Industry, www.mbendi.co.za/aflu.htm AG Fluiropolymers USA Inc., www.fluoropolymers.com Airosol Company Inc., www.airosol.com Akzo Nobel, www.akzonobel.com Alco-Metalube Co., www.alco-metalube.com Alithicon Lubricants, Div: Southeast Oil & Grease Co. Inc., www.alithicon.com Allegheny Petroleum Products Company, www.oils.com Allen Oil Company, www.allenoil.com Allied Oil & Supply Inc., www.allied-oil.com Allied Washoe, www.alliedwashoe.com Alpha Grease & Oil Inc., www.alphagrease. thomasregister.com/olc/alphagrease/


ALT Inc., www.altboron.com Amalie Oil Company, www.amalie.com Amber Division of Nidera, Inc., www.nidera-us.com Amcar Inc., www.amcarinc.com Amerada Hess Corporation, www.hess.com American Agip Company Inc., www.americanagip.com American Eagle Technologies Inc., www.frictionrelief.com American Lubricants Inc., www.americanlubricantsbflo.com American Lubricating Company, www.alcooil.com American Oil & Supply Company, www.aosco.com American Petroleum Products, www.americanpetroleum.com American Refining Group Inc., www.amref.com American Synthol Inc., www.americansynthol.com Amptron Corporation, www.superslipperystuff.com/ organisation.htm Amrep Inc., www.amrep.com AMSOIL Inc., www.amsoil.com Anderol Specialty Lubricants, www.anderol.com Anti Wear 1, www.dynamicdevelopment.com Apollo America Corporation, www.apolloamerica.com Aral International, www.Aral.com Arch Chemicals, Inc., www.archbiocides.com ARCO, www.arco.com Arizona Chemical, www.arizonachemical.com Asbury Carbons, Inc.—Dixon Lubricants, www.asbury.com Asbury Carbons, Inc.—Dixon Lubricants, www.dixonlube.com Asbury Graphite Mills Inc., www.asbury.com Asheville Oil Company Inc., www.ashevilleoil.com Ashia Denka, www.adk.co.jp/eng.htm Ashland Chemical, www.ashchem.com Ashland Distribution Company, www.ashland.com Aspen Chemical Company, www.aspenchemical.com Associated Petroleum products, www.associatedpetroleum.com Atlantis International Inc., www.atlantis-usa.com Atlas Oil Company, www.atlasoil.com ATOFINA Canada Inc., www.atofinacanada.com Ausimont, www.ausiusa.com Avatar Corporation, www.avatarcorp.com

Badger Lubrication Technologies Inc., www.badgerlubrication.com BALLISTOL USA, www.ballistol.com Battenfeld Grease and Oil Corporation of New York, www.battenfeld-grease.com Behnke Lubricants/JAX, www.jaxusa.com Behnke Lubricants Inc./JAX, www.jax.com Bell Additives Inc., www.belladditives.com Bel-Ray Company Inc., www.belray.com

Benz Oil Inc., www.benz.com Berry Hinckley Industries, www.berry-hinckley.com Bestolife Corporation, www.bestolife.com BG Products Inc., www.bgprod.com Big East Lubricants Inc., www.bigeastlubricants.com Blaser Swisslube, www.blaser.com Bodie-Hoover Petroleum Corp., www.bodie-hoover.com Boehme Filatex Inc., www.boehmefilatex.com BoMac Lubricant Technologies Inc., www.bomaclubetech.com Boncosky Oil Company, www.boncosky.com Boswell Oil Company, www.boswelloil.com BP Amoco Chemicals, www.bpamocochemicals.com BP Lubricants, www.bplubricants.com BP, www.bptechchoice.com BP, www.bppetrochemicals.com Brascorp North America Ltd., www.brascorp.on.ca Brenntag Northeast, Inc., www.brenntag.com/ Brenntag, www.brenntag.com Briner Oil Company, www.brineroil.com British Petroleum (BP), www.bp.com Britsch Inc., www.britschoil.com Brugarolas SA, www.brugarolas.com/english.htm Buckley Oil Company, www.buckleyoil.com BVA Oils, www.bvaoils.com

Callahan Chemical Company, www.calchem.com Caltex Petroleum Corporation, www.caltex.com Calumet Lubricants Company, www.calumetlub.com Calvary Industries Inc., www.calvaryindustries.com CAM2 Oil Products Company, www.cam2.com Canner Associates, Inc., www.canner.com Capital Enterprises (Power-Up Lubricants), www.NNL690.com Cargill- Industrial Oil & Lubricants, www.techoils.cargill.com Cary Company, www.thecarycompany.com CasChem, Inc., www.cambrex.com Castle Products Inc., www.castle-comply.com Castrol Heavy Duty Lubricants, Inc., www.castrolhdl.com Castrol Industrial North America Inc., www.castrolindustrialna.com Castrol International, www.castrol.com Castrol North America, www.castrolusa.com CAT Products Inc., www.run-rite.com Centurion Lubricants, www.centurionlubes.com Champion Brands LLC, www.championbrands.com Charles Manufacturing Company, www.tsmoly.com Chart Automotive Group Inc., www.chartauto.com Chem-EcoI Ltd., www.chem-ecol.com Chemlube International Inc., www.chemlube.com Chempet Corporation, www.rockvalleyoil.com/ chempet.htm Chemsearch Lubricants, www.chemsearch.com


Chemtool Inc./Metalcote, www.chemtool.com Chevron Chemical Company, www.chevron.com Chevron Oronite, www.chevron.com Chevron Phillips Chemical Company LP, www.cpchem.com Chevron Phillips Chemical Company, www.chevron.com Chevron Products Company, Lubricants & Specialties Products, www.chevron.com/lubricants Chevron Products Company, www.chevron.com Christenson Oil, www.christensonoil.com Ciba Specialty Chemicals Corporation, www.cibasc.com Clariant Corporation, www.clariant.com Clark Refining and Marketing, www.clarkusa.com Clarkson & Ford Company, www.clarkson-ford.com CLC Lubricants Company, www.clclubricants.com Climax Molybdenum Company, www.climaxmolybdenum.com Coastal Unilube Inc., www.coastalunilube.com Cognis, www.cognislubechem.com Cognis, www.cognis-us.com Cognis, www.cognis.com Cognis, www.na.cognis.com Colorado Petroleum Products Company, www.colopetro.com Commercial Lubricants Inc., www.comlube.com Commercial Oil Company, Inc., www.commercialoilcompany.com Commercial Ullman Lubricants Company, www.culc.com Commonwealth Oil Corporation, swww.commonwealthoil.com Como Lube & Supplies Inc., www.comolube.com Condat Corporation, www.condatcorp.com Conklin Company Inc., www.cnklino.com Coolants Plus Inc., www.coolantsplus.com Cortec Corporation, www.cortecvci.com Cosby Oil Company, www.cosbyoil.com Country Energy, www.countryenergy.com CPI Engineering Services, www.cpieng.com CRC Industries, Inc., www.crcindustries.com Crescent Manufacturing, www.crescentmfg.net Crompton Petroleum Additives Corporation, www.cromptoncorp.com Crown Chemical Corporation, www.brenntag.com Cyclo Industries LLC, www.cyclo.com

D & D Oil Company, Inc., www.amref.com D. A. Stuart Company, www.d-a-stuart.com D. W. Davies & Company, Inc., www.dwdavies.com D-A Lubricant Company, www.dalube.com Darmex Corporation, www.darmex.com Darsey Oil Company Inc., www.darseyoil.com David Weber Oil Company, www.weberoil.com Davison Oil Company, Inc., www.davisonoil.com Dayco Inc., www.dayco.com

DB Becker Co. Inc., www.dbbecker.com Degen Oil and Chemical Company, www.eclipse.net/∼degen Delkol, www.delkol.co.il Dennis Petroleum Company, Inc., www.dennispetroleum.com Diamond Head Petroleum Inc., www.diamondheadpetroleum.com Diamond Shamrock Refining Company LP, www.udscorp.com Digilube Systems Inc., www.digilube.com Dion & Sons Inc., www.dionandsons.com Dixon Lubricants & Special Products Group, Div. of Asbury Carbons, www.dixonlube.com Don Weese Inc., www.schaefferoil.com Dow Chemical Company, www.dow.com Dow Corning Corp., www.dowcorning.com Dryden Oil Company, Inc., www.castrol.com Dryson Oil Company, www.synergynracing.com DSI Fluids, www.dsifluids.com Dumas Oil Company, www.esn.net/dumasoil DuPont Krytox Lubricants, www.lubricants.dupont.com DuPont, www.dupont.com/intermediates

E.I. DuPont de Nemours and Company, www.dupont.com/ intermediates Eastech Chemical Inc., www.eastechchemical.com Eastern Oil Company, www.easternoil.com Ecotech Div., Blaster Chemical Companies, www.pbblaster.com EKO, www.eko.gr El Paso Corporation, www.elpaso.com Elf Lubricants North America Inc., www.keystonelubricants.com Eljay Oil Company, Inc., www.eljayoil.com ELM Environmental Lubricants Manufacturing Company, www.elmusa.com EMERA Fuels Company Inc., www.emerafuels.com Emerson Oil Company, Inc.www.emersonoil.com Engen Petroleum Ltd., www.engen.co.za Enichem Americas, Inc., www.eni.it/english/mondo/ americhe/usa.html Environmental Lubricants Manufacturing, Inc. (ELM), www.elmusa.com Equilon Enterprises LLC, www.equilon.com Equilon Enterprises LLC-Lubricants, www.equilonmotivaequiva.com Equilon Enterprises LLC-Lubricants, www.shellus.com Equilon Enterprises LLC-Lubricants, www.texaco.com Esco Products Inc., www.escopro.com ETNA Products Inc., www.etna.com Etna-Bechem Lubricants Ltd., www.etna.com Evergreen Oil, www.evergreenoil.com Exxon, www.exxon.com


ExxonMobil Chemical Company, www.exxonmobilchemical.com ExxonMobil Lubricants & Petroleum Specialties Company, www.exxonmobil.com F&R Oil Company, Inc., www.froil.com F. Bacon Industriel Inc., www.f-bacon.com FAMM (Fuel and Marine Marketing), www.fammllc.com Far West Oil Company Inc., www.farwestoil.com Fina Oil and Chemical Company, www.fina.com Findett Corp., www.findett.com Finish Line Technologies Inc., www.finishlineusa.com FINKE Mineralolwerk, www.finke-mineraloel.de Finnish Oil and Gas Federation, www.oil.fi Flamingo Oil Company, www.pinkbird.com Forward Corporation, www.forwardcorp.com Frontier Performance Lubricants Inc., www.frontierlubricants.com Fuchs Lubricants Company, www.fuchs.com Fuchs, www.fuchs-oil.de Fuki America Corporation, www.fukiamerica.com G-C Lubricants Company, www.gclube.com G & G Oil Co. of Indiana Inc., www.ggoil.com G.T. Autochemilube Ltd., www.gta-oil.co.uk Gard Corp., www.gardcorp.com Geo. Pfau’s Sons Company, Inc., www.pfauoil.com Georgia-Pacific Pine Chemicals, www.gapac.com Glover Oil Company, www.gloversales.com GOA Company., www.goanorthcoastoil.com Gold Eagle Company, www.goldeagle.com Golden Bear Oil Specialties, www.goldenbearoil.com Golden Gate Petroleum, www.ggpetrol.com Goldenwest Lubricants, www.goldenwestlubricants.com Goldschmidt Chemical Corporation, www.goldschmidt.com Goulston Technologies, Inc., www.goulston.com Great Lakes Chemical Corporation, www.glcc.com Granitize Products Inc., www.granitize.com Greenland Corporation, www.greenpluslubes.com Grignard Company LLC, www.purelube.com Groeneveld Pacific West, www.groeneveldpacificwest.com Gulf Oil, www.gulfoil.com H & W Petroleum Company, Inc., www.hwpetro.com H.L. Blachford Ltd., www.blachford.ca H.N. Funkhouser & Company, www.hnfunkhouser.com Halocarbon Products Corporation, www.halocarbon.com Halron Oil Company, Inc., www.halron.com Hampel Oil Distributors, www.hampeloil.com Hangsterfer’s Laboratories Inc., www.hangsterfers.com Harry Miller Corp., www.harrymillercorp.com Hasco Oil Co. Inc., www.hascooil.com

Hatco Corporation, www.hatcocorporation.com Haynes Manufacturing Company, www.haynesmfg.com HCI/Worth Chemical Corp., www.hollandchemical.com Henkel Surface Technologies, www.henkel.com Henkel Surface Technologies, www.thomasregister.com/ henkelsurftech Hexol Canada Ltd., www.hexol.com Hexol Lubricants, www.hexol.com Holland Applied Technologies, www.hollandapt.com Hoosier Penn Oil Company, www.hpoil.com Houghton International Inc., www.houghtonintl.com Howes Lubricator, www.howeslube.thomasregister.com Huls America, www.CreanovaInc.com/ Huls America, www.huls.com Huskey Specialty Lubricants, www.huskey.com Hydrosol Inc., www.hydrosol.com Hydrotex Inc., www.hydrotexlube.com/ Hy-Per Lube Corporation, www.hyperlube.com I.S.E.L. Inc., www.americansynthol.com ILC/Spectro Oils of America, www.spectro-oils.com Illinois Oil Products, Inc., www.illinoisoilproducts.com Imperial Oil Company, Inc., www.imperialoil.com Imperial Oil Ltd., www.imperialoil.ca Imperial Oil Products and Chemicals Division, www.imperialoil.ca Ingenieria Sales SA de CV, www.isalub.com Innovene, www.innovene.com Inolex Chemical Company, www.inolex.com International Lubricants Inc., www.lubegard.com International Products Corporation, www.ipcol.com IQA Lube Corporation, www.iqalube.com Irving Oil Corp, www.irvingoil.com ITW Fluid Products Group, www.itwfpg.com J & H Oil Company, www.jhoil.com J & S Chemical Corporation, www.jschemical.com J.A.M.Distributing, www.jamdistributing.com J.B. Chemical Company, Inc., www.jbchemical.com J.B. Dewar Inc., www.jbdewar.com J.D. Streett & Company, Inc., www.jdstreett.com J.N. Abbott Distributor Inc., www.jnabbottdist.com Jack Rich Inc., www.jackrich.com Jarchem Industries Inc., www.jarchem.com Jasper Engineering & Equipment, www.jaspereng.com JAX-Behnke Lubricants Inc., www.jax.com Jenkin-Guerin Inc., www.jenkin-guerin.com Jet-Lube (UK) Ltd., www.jetlube.com Johnson Packings & Industrial Products Inc., www.johnsonpackings.com Kath Fuel Oil Service, www.kathfuel.com Keck Oil Company, www.keckoil.com Kelsan Lubricants USA LLC, www.kelsan.com


Kem-A-Trix Specialty Lubricants & Compounds, www.kematrix.com Kendall Motor Oil, www.kendallmotoroil.com Kluber Lubrication North America LP, www.kluber.com KOST Group Inc., www.kostusa.com Kyodo Yushi USA Inc., www.kyodoyushi.co.jp Lambent Technologies, www.petroferm.com LaPorte, www.laporteplc.com Leander Lubricants, www.leanderlube.com Lee Helms Inc., www.leehelms.com Leffert Oil Company, www.leffertoil.com Les Industries Sinto Racing Inc., www.sintoracing.com Lilyblad Petroleum, Inc., www.lilyblad.com Liqua-Tek Inc., www.hdpluslubricants.com Liquid Horsepower, www.holeshot.com/chemicals/ additives.html LithChem International, www.lithchem.com Loos & Dilworth Inc.-Automotive Division, www.loosanddilworth.com Loos & Dilworth Inc.-Chemical Division, www.loosanddilworth.com Lowe Oil Company./Champion Brands LLC, www.championbrands.com LPS Laboratories, www.lpslabs.com LubeCon Systems Inc., www.lubecon.com Lubemaster Corporation, www.lubemaster.com LubeRos — A Division of Burlington Chemical Company, Inc., www.luberos.com LuBest, Division of Momar Inc., www.momar.com Lubricant Technologies, www.lubricanttechnologies.com Lubricants USA, www.finalube.com Lubrication Engineers Inc., www.le-inc.com Lubrication Engineers of Canada, www.lubeng.com Lubrication Technologies Inc., www.lube-tech.com Lubrication Technology Inc., www.lubricationtechnology.com Lubrichem International Corporation, www.lubrichem.net Lubrifiants Distac Inc., www.inspection.gc.ca/english/ ppc/reference/n2e.shtml Lubri-Lab Inc., www.lubrilab.com LUBRIPLATE Div., Fiske Bros. Refining Company, www.lubriplate.com Lubritec, www.ensenada.net/lubritec/ Lucas Oil Products Inc., www.lucasoil.com Lyondell Lubricants, www.lyondelllubricants.com MagChem Inc., www.magchem.com Magnalube, www.magnalube.com Maine Lubrication Service Inc., www.mainelube.com Manor Trade Development Corporation, www.amref.com Mantek Lubricants, www.mantek.com Markee International Corporation, www.markee.com Marly, www.marly.com

Maryn International Ltd., www.maryngroup.com Maryn International, www.poweruplubricants.com Master Chemical Corporation, www.masterchemical.com Master Lubricants Company, www.lubriko.com Maxco Lubricants Company, www.maxcolubricants.com Maxim Industrial Metalworking Lubricants, www.maximoil.com Maxima Racing Lubricants, www.maximausa.com McCollister & Company, www.mccollister.com McGean-Rohco Inc., www.mcgean-rohco.com McGee Industries Inc., www.888teammclube.com McLube Divisionl/McGee Industries Inc., www.888teammclube.com Mega Power Inc., www.megapowerinc.com Metal Forming Lubricants Inc., www.mflbeu.com Metal Mates Inc., www.metalmates.net Metalcote/Chemtool Inc., www.metalcote.com Metalworking Lubricants Company, www.metalworkinglubricants.com Metalworking Lubricants, www.maximoil.com MFA Oil Company, www.mfaoil.com Mid-South Sales Inc., www.mid-southsales.com Mid-Town Petroleum Inc., www.midtownoil.com Milacron Consumable Products Division, www.milacron.com Millennium Lubricants, www.millenniumlubricants.com Miller Oil of Indiana, Inc., www.milleroilinc.com Mohawk Lubricants Ltd., www.mohawklubes.com Molyduval, www.molyduval.com Molyslip Atlantic Ltd., www.molyslip.co.uk Monroe Fluid Technology Inc., www.monroefluid.com Moore Oil Company, www.mooreoil.com Moraine Packaging Inc., www.hdpluslubricants.com Morey’s Oil Products Company, www.moreysonline.com Moroil Technologies, www.moroil.com Motiva Enterprises LLC, www.motivaenterprises.com Motorol Lubricants, www.motorolgroup.com Motul USA Inc., www.motul.com Mr. Good Chem, Inc., www.mrgoodchem.com Muscle Products Corporation, www.mpc-home.com NCH, www.nc.com Neo Synthetic Oil Company, Inc., www.neosyntheticoil.com Niagara Lubricant Company, Inc., www.niagaralubricant.com NOCO Energy Corporation, www.noco.com Noco Lubricants, www.noco.com Nyco SA, www.nyco.fr Nye Lubricants, www.nyelubricants.com Nynas Naphthenics, www.nynas.com O’Rourke Petroleum, www.orpp.com Oakite Products, Inc., www.oakite.com


OATS (Oil Advisory Technical Services), www.oats.co.uk Occidental Chemical Corporation, www.oxychem.com Ocean State Oil Inc., www.oceanstateoil.com Oil Center Research Inc., www.oilcenter.com Oil Center Research International LLC, www.oilcenter.com Oil Depot, www.oildepot.com Oil Distributing Company, www.oildistributing.com Oil-Chem Research Corporation, www.avblend.com Oilkey Corporation, www.oilkey.com Oilpure Technologies Inc., www.oilpure.com OKS Speciality Lubricants, www.oks-india.com Omega Specialties, www.omegachemicalsinc.com Omni Specialty Packaging, www.nuvo.cc OMO Petroleum Company Inc., www.omoenergy.com Orelube Corp., www.orelube.com Oronite, www.oronite.com O’Rourke Petroleum Products, www.orpp.com Ottsen Oil Company, Inc., www.ottsen.com

Paramount Products, www.paramountproducts.com Parent Petroleum, www.parentpetroleum.com PATCO Additives Division-American Ingredients Company, www.patco-additives.com Pathfinder Lubricants, www.pathfinderlubricants.ca/ PBM Services Company, www.pbmsc.com Pedroni Fuel Company, www.pedronifuel.com Pennine Lubricants, www.penninelubricants.co.uk Pennzoil Industrial Lubricants, www.pennzoil.com/ prdsmktg/products/industrial/default.htm Pennzoil, www.pennzoil.com Pennzoil-Quaker State Company, www.pennzoil-quakerstate.com PENRECO, www.penreco.com Penta Manufacturing Company/Division of Penta International Corporation, www.pentamfg.com Performance Lubricants & Race Fuels Inc., www.perforanceracefuelsm.com Perkins Products Inc., www.perkinsproducts.com Petro Star Lubricants, www.petrostar.com PetroBlend Corporation, www.petroblend.com Petro-Canada Lubricants, www.htlubricants.com Petroleum Packers Inc., www.pepac.com PetroMoly, Inc., www.petromoly.com Petron Corp., www.petroncorp.com Pfaus Sons Company Inc., www.pfauoil.com Pflaumer Brothers Inc., www.pflaumer.com Phoenix Petroleum Company, www.phoenixpetroleum.com Pico Chemical Corporation, www.picochemical.com Pinnacle Oil Inc., www.pinnoil.com Pitt Penn Oil Company, www.pittpenn.com Plews/Edelmann Div., Stant Corp., www.stant.com PoIySi Technologies Inc., www.polysi.com

Polar Company, www.polarcompanies.com PolimeriEuropa, www.polimerieuropa.com PolySi Technologies, www.polysi.com Power Chemical, www.warcopro.com Power-Up Lubricants, www.mayngroup.com Precision Fluids Inc., www.precisionfluids.com Precision Industries, www.precisionind.com Precision Lubricants Inc., www.precisionlubricants.com Prime Materials, www.primematerials.com Primrose Oil Company Inc., www.primrose.com Probex Corporation, www.prob.com Products Development Manufacturing Company, www.veloil.com ProLab TechnoLub Inc., www.prolab-technologies.com ProLab-Bio Inc., www.prolab-lub.com Prolong Super Lubricants, www.prolong.com ProTec International Inc., www.proteclubricants.com Pure Power Lubricants, www.gopurepower.com QMI, www.qminet.com Quaker Chemical Corporation, www.quakerchem.com Quaker State, www.qlube.com R.E. Carroll Inc., www.recarroll.com Radio Oil Company Inc., www.radiooil.com Ramos Oil Company, Inc., www.ramosoil.com Rams-Head Company, www.doall.com Ransome CAT, www.ransome.com Red Giant Oil Company, www.rediantoilg.com Red Line Oil, www.redlineoil.com Reed Oil Company, www.reedoil.com Reit Lubricants Company, www.reitlube.com Reitway Enterprises Inc., www.reitway.com Renewable Lubricants, Inc., www.renewablelube.com Renite Company, www.renite.com Renite Company-Lubrication Engineers, www.renite.com Renkert Oil, www.renkertoil.com Rensberger Oil Company, Inc., www.rensbergeroil.com RichardsApex Inc., www.richardsapex.com Riley Oil Company, www.rileyoil.com RO-59 Inc., http://members.aol.com/ro59inc Rock Valley Oil & Chemical Company, www.rockvalleyoil.com Rocol Ltd., www.rocol.com Rowleys Wholesale, www.rowleys.com Royal Lubricants Inc., www.royallube.com Royal Manufacturing Company Inc., www.royalube.com Royal Purple, Inc., www.royalpurple.com RyDol Products, www.rydol.com

Safety-Kleen Oil Recovery, www.ac-rerefined.com Sandstrom Products Company, www.sandstromproducts.com


Santie Oil Company, www.santiemidwest.com Santotrac Traction Lubricants, www.santotrac.com Santovac Fluids Inc., www.santovac.com Saxton Industries Inc., www.saxton.thomasregister.com Saxton Industries Inc., www.schaefferoil.com Schaeffer Manufacturing, www.schaefferoil.com Schaeffer Oil and Grease, www.schaefferoil.com Schaeffer Specialized Lubricants, www.schaefferoil.com Selco Synthetic Lubricants, www.synthetic-lubes.com Sentry Solutions Ltd., www.sentrysolutions.com Service Supply Lubricants LLC, www.servicelubricants.com SFR Corporation, www.sfrcorp.com Share Corporation, www.sharecorp.com Shell Global Solutions, www.shellglobalsolutions.com Shell Lubricants (USA), www.shell-lubricants.com Shrieve Chemical Company, www.shrieve.com Simons Petroleum Inc., www.simonspetroleum.com SK Corporation (Houston Office) www.skcorp.com Slick 50 Corporation, www.slick50.com Smooth Move Company, www.theprojectsthatsave.com Sobit International, Inc., www.sobitinc.com Soltex, www.soltexinc.com Sourdough Fuel, www.petrostar.com Southwest Grease Products, www.stant.com/ brochure.cfm?brochure=155&location_id=119 Southwestern Graphite, www.asbury.com Southwestern Petroleum Corporation, www.swepcousa.com Spartan Chemical Company Inc. Industrial Products Group Division, www.spartanchemical.com Spartan Oil Company, www.spartanonline.com Specialty Silicone Products Inc., www.sspinc.com Spectro Oils of America, www.goldenspectro.com Spectro Oils of America, www.spectro-oils.com Spectrum Corporation, www.spectrumcorporation.com Spencer Oil Company, www.spenceroil.com St. Lawrence Chemicals, www.stlawrencechem.com Steelco Industrial Lubricants Inc., www.steelcolubricants.com Steelco Northwest Distributors, www.steelcolubricants.com STP Products Inc., www.stp.com Suburban Oil Company, Inc., www.suburbanoil.com Summit Industrial Products, Inc., www.klsummit.com Sunnyside Corporation, www.sunnysidecorp.com Superior Graphite Company, www.superiorgraphite.com/sgc.nsf Superior Lubricants Company, Inc., www.superiorlubricants.com Superior Lubrication Products, www.s-l-p.com Surtec International Inc., www.surtecinternational.com Synco Chemical Corporation, www.super-lube.com SynLube Inc., www.synlube.com

Synthetic Lubricants Inc., www.synlube-mi.com Syntroleum Corporation, www.syntroleum.com T.S. MoIy-Lubricants Inc., www.tsmoly.com T.W. Brown Oil Company, Inc, www.brownoil.com/ soypower.html TAI Lubricants, www.lubekits.com TCC, www.technicalchemical.com Technical Chemical Company, www.technicalchemical.com Tek-5 Inc., www.tek-5.com Terrresolve Technologies, www.terresolve.com Texas Refinery Corporation, www.texasrefinery.com Textile Chemical Company, Inc., www.textilechem.com Thermal-Lube Inc., www.thermal-lube.com Thornley Company, www.thonleycompanyr.com Tiodize Co. Inc., www.tiodize.com Tom-Pac Inc., www.tom-pac.com Top Oil Products Company, Ltd., www.topoil.com Torco International Corporation, www.torcoracingoils.com Totalfina Oleo Chemicals, www.totalfina.com Tower Oil & Technology Company, www.toweroil.com Toyo Grease Manufacturing (M) SND BHD, www.toyogrease.com TransMontaigne, www.transmontaigne.com Transmountain Oil Company, www.transmountainoil.com TriboLogic Lubricants Inc., www.dynamaxx.com TriboLogic Lubricants Inc., www.tribologic.com Tribos Technologies, www.tribostech.com Trico Manufacturing Corporation, www.tricomfg.com Tricon Specialty Lubricants, www.tristrat.com Turmo Lubrication Inc., www.lubecon.com TXS Lubricants Inc., www.txsinc.com U.S. Industrial Lubricants Inc., www.usil.cc U.S. Oil Company, Inc., www.usoil.com Ultrachem Inc., www.ultracheminc.com Unimark Oil Company, www.gardcorp.com Union Carbide Corporation, www.unioncarbide.com Uniqema, www.uniqema.com Uniroyal Chemical Company Inc., www.uniroyalchemical.com UniSource Energy Inc., www.unisource-energy.com Unist, Inc., www.unist.com United Lubricants, www.unitedlubricants.com United Oil Company, Inc., www.duralene.com United Oil Products Ltd., http://ourworld. compuserve.com/homepages/Ferndale_UK United Soybean Board, www.unitedsoybean.org Universal Lubricants Inc., www.universallubes.com Unocal Corporation, www.unocal.com Valero Mktg. & Supply, www.valero.com Valvoline Canada, www.valvoline.com


Valvoline, www.valvoline.com Vesco Oil Corporation, www.vesco-oil.com Vikjay Industries Inc., www.vikjay.com Virtual Oil Inc., www.virtualoilinc.com Vogel Lubrication System of America, www.vogel-lube.com VP Racing Fuels Inc., www.vpracingfuels.com Vulcan Oil & Chemical Products Inc., www.vulcanoil.com Wallover Oil Company, www.walloveroil.com Walthall Oil Company, www.walthall-oil.com Warren Distribution, www.wd-wpp.com WD-40 Company, www.wd40.com West Central Soy, www.soypower.net Western States Oil, www.lubeoil.com Whitaker Oil Company, Inc., www.whitakeroil.com Whitmore Manufacturing Company, www.whitmores.com Wilcox and FIegel Oil Company, www.wilcoxandflegel.com Winfield Brooks Company, Inc., www.tapfree.com Winzer Corporation, www.winzerusa.com Witco (Crompton Corporation), www.witco.com Wolf Lake Terminals Inc., www.wolflakeinc.com Worldwide PetroMoly, Inc., www.petromoly.com Wynn Oil Company, www.wynnsusa.com X-1R Corp., The, www.x1r.com Yocum Oil Company, Inc., www.yocumoil.com Yuma Industries Inc., www.yumaind.com

51.2.2 Additives Acheson Colloids Company, www.achesonindustries.com Acme-Hardesty Company, www.acme-hardesty.com Advanced Lubrication Technology Inc (ALT), www.altboron.com AFD Technologies, www.afdt.com AG Fluoropolymers USA Inc., www.fluoropolymers.com Akzo Nobel, www.akzonobel.com Amalie Oil Company, www.amalie.com Amber Division of Nidera, Inc., www.nidera-us.com American International Chemical, www.aicma.com/ Amitech, www.amitech-usa.com ANGUS Chemical Company, www.dowchemical.com Anti Wear 1 www.dynamicdevelopment.com Arch Chemicals, Inc., www.archbiocides.com Arizona Chemical, www.arizonachemical.com Asbury Carbons, Inc.—Dixon Lubricants, www.asbury.com Asbury Carbons, Inc.—Dixon Lubricants, www.dixonlube.com Ashland Distribution Company, www.ashland.com Aspen Chemical Company, www.aspenchemical.com

ATOFINA Chemicals, Inc., www.atofina.com ATOFINA Canada Inc., www.atofinacanada.com

Baker Petrolite, www.bakerhughes.com/bakerpetrolite/ Bardahl Manufacturing Corporation, www.bardahl.com BASF Corporation, www.basf.com Bayer Corporation, www.bayer.com Bismuth Institute, www.bismuth.be BoMac Lubricant Technologies Inc., www.bomaclubetech.com BP, www.bp.com BP Amoco Chemicals, www.bpamocochemicals.com Brascorp North America Ltd., www.brascorp.on.ca Brascorp North America Ltd., www.brascorp.on.ca British Petroleum (BP), www.bp.com Buckman Laboratories Inc., www.buckman.com Burlington Chemical, www.burco.com Cabot Corporation, (fumed metal oxides), www.cabot-corp.com/cabosil Callahan Chemical Company, www.calchem.com Calumet Lubricants Company, www.calumetlub.com Cargill-Industrial Oil & Lubricants, www.techoils. cargill.com Cary Company, www.thecarycompany.com CasChem, Inc., www.cambrex.com Center for Innovation Inc., www.centerforinnovation.com Certified Laboratories, www.certifiedlaboratories.com Chattem Chemicals, Inc., www.chattemchemicals.com Chemetall Foote Corporation, www.chemetall.com/ Chemsearch Lubricants, www.chemsearch.com Chevron Oronite, www.chevron.com Ciba Specialty Chemicals Corporation, www.cibasc.com Clariant Corp., www.clariant.com Climax Molybdenum Company, www.climaxmolybdenum.com Cognis, www.cognislubechem.com Cognis, www.cognis-us.com Cognis, www.cognis.com Cognis, www.na.cognis.com Commonwealth Oil Corporation, www.commonwealthoil.com Cortec Corporation, www.cortecvci.com Creanova, Inc., www.creanovainc.com/ Croda Inc., www.croda.com Crompton Petroleum Additives Corporation, www.cromptoncorp.com Crowley Chemical Company Inc., www.crowleychemical.com Crown Chemical Corporation, www.brenntag.com Crystal Inc.-PMC, www.pmc-group.com Cummings-Moore Graphite Company, www.cumograph.com


D.A. Stuart Company, www.d-a-stuart.com D.B. Becker Company, Inc., www.dbbecker.com DeForest Enterprises Inc., www.deforest.net Degen Oil and Chemical Company, www.eclipse. net/∼degen Dover Chemical, www.doverchem.com Dow Chemical Company, www.dow.com Dow Corning Corporation, www.dowcorning.com DuPont — Dow Elastomers, www.dupont-dow.com Dylon Industries Inc., www.dylon.com E.I. DuPont de Nemours and Company, www.dupont.com/intermediates E.W. Kaufmann Company, www.ewkaufmann.com Elco Corporation, The, www.elcocorp.com Elementis Specialties, www.elementis-na.com Elementis Specialties-Rheox, www.rheox.com Elf Atochem Canada, www.atofinachemicals.com Environmental Lubricants Manufacturing, Inc. (ELM), www.elmusa.com Ethyl Corporation, www.ethyl.com Ethyl Petroleum Additives, www.ethyl.com Fanning Corporation, The, www.fanncorp.com Ferro/Keil Chemical, www.ferro.com FMC Lithium, www.fmclithium.com FMC, www.fmc.com Functional Products, www.functionalproducts.com G.R. O’Shea Company, www.groshea.com Gateway Additives, www.lubrizol.com Geo. Pfau’s Sons Company., Inc., www.pfauoil.com Georgia-Pacific Pine Chemicals, www.gapac.com Georgia-Pacific Resins, Inc.—Actrachem Division, www.gapac.com Georgia-Pacific Resins, Inc.—Actrachem Division, www.gp.com Goldschmidt Chemical Corporation, www.goldschmidt.com Great Lakes Chemical Corporation, www.glcc.com Grignard Company LLC, www.purelube.com Hall Technologies Inc., www.halltechinc.com Hammonds Fuel Additives, Inc., www.hammondscos.com Heveatex, www.heveatex.com Holland Applied Technologies, www.hollandapt.com Huntsman Corporation, www.huntsman.com Infineum USA LP, www.infineum.com International Lubricants Inc., www.lubegard.com J.H. Calo Company, Inc., www.jhcalo.com J.B. Chemical Company, Inc., www.jbchemical.com Jarchem Industries Inc., www.jarchem.com

Keil Chemical Division; Ferro Corporation, www.ferro.com King Industries Specialty Chemicals, www.kingindustries.com Lambent Technologies, www.petroferm.com LaPorte, www.laporteplc.com Lockhart Chemical Company, www.lockhartchem.com Loos & Dilworth Inc.—Chemical Division, www.loosanddilworth.com LubeRos— A Division of Burlington Chemical Company Inc., www.luberos.com Lubricant Additives Research, www.silverseries.com Lubricants Network Inc., www.lubricantsnetwork.com Lubri-Lab Inc., www.lubrilab.com Lubrizol Corporation, The, www.lubrizol.com Lubrizol Metalworking Additive Company, www.lubrizol.com Mantek Lubricants, www.mantek.com Marcus Oil and Chemical, www.marcusoil.com Master Chemical Corporation, www.masterchemical.com Mays Chemical Company, www.mayschem.com McIntyre Group Ltd., www.mcintyregroup.com Mega Power Inc., www.megapowerinc.com Metal Mates Inc., www.metalmates.net Metalworking Lubricants Company, www.metalworkinglubricants.com Milatec Corporation, www.militec.com

R.T. Vanderbilt Company Inc., www.rtvanderbilt.com R.H. Foster Energy LLC, www.rhfoster.com R.T. Vanderbilt Company, www.rtvanderbilt.com Reade Advanced Materials, www.reade.com Rhein Chemie Corporation, www.bayer.com Rhein Chemie Rheinau GmbH., www.rheinchemie.com Rheox Inc., www.rheox.com Rhodia, www.rhodia.com Rhone-Poulenc Surfactants & Specialties, www.rpsurfactants.com RiceChem, A Division of Stilling Enterprises Inc., www.ricechem.com Rohm & Haas Company, www.rohmhaas.com RohMax Additives GmbH, www.rohmax.com Ross Chem Inc., www.rosschem.com Santotrac Traction Lubricants, www.santotrac.com Santovac Fluids Inc., www.santovac.com Sea-Land Chemical Company, www.sealandchem.com Sea-Land Chemical Company, www.sealandchem.com Shamrock Technologies, Inc., www.shamrocktechnologies.com Shell Chemicals, www.shellchemical.com Shepherd Chemical Company, www.shepchem.com Soltex, www.soltexinc.com SP Morell & Company, www.spmorell.com Spartan Chemical Company Inc. Industrial Products Group Division, www.spartanchemical.com SQM North America Corporation, www.sqmna.com St. Lawrence Chemicals, www.stlawrencechem.com Stochem, Inc., www.stochem.com

Nagase America Corporation, www.nagase.com Naptec Corporation, www.satec.com NC’eed Enterprises, www.backtosebacics.com Northern Technologies International Corporation, www.ntic.com

Thornley Company, www.thornleycompany.com Tiodize Company, Inc., www.tiodize.com Tomah Products, Inc., www.tomah3.com Troy Corporation, www.troycorp.com

Oil Center Research Inc., www.oilcenter.com OKS Specialty Lubricants, www.oks-india.com Omega Specialties, www.omegachemicalsinc.com OMG Americas Inc., www.omgi.com OMGI, www.omgi.com Oronite, www.oronite.com

Ultra Additives Inc., www.ultraadditives.com Uniqema, www.uniqema.com Uniroyal Chemical Company Inc., www.uniroyalchemical.com United Color Manufacturing Inc., www.unitedcolor.com United Lubricants, www.unitedlubricants.com

PATCO Additives Division-American Ingredients Company, www.patco-additives.com Pflaumer Brothers Inc., www.pflaumer.com Pilot Chemical Company, www.pilotchemical.com PMC Specialties Inc., www.pmcsg.com Polartech Ltd.., www.polartech.co.uk Precision Fluids Inc., www.precisionfluids.com Purac America, Inc., www.purac.com

Valhalla Chemical, www.valhallachem.com Van Horn, Metz & Company, Inc., www.vanhornmetz.com Virtual Oil Inc., www.virtualoilinc.com


Wynn Oil Company, www.wynnsusa.com Zinc Corporation of America, www.zinccorp.com

51.2.3 Oil Companies Adco Petrol Katkilari San Ve. Tic. AS, www.adco.com.tr Amoco, www.amoco.com Aral International, www.Aral.com/ Asian Oil Company, www.nilagems.com/asianoil/ Bharat Petroleum, www.bharatpetroleum.com BP, www.bp.com CEPSA (Spain), www.cepsa.es Chevron Texaco, www.chevrontexaco.com Chevron, www.chevron.com CITGO Petroleum Corporation, www.citgo.com Coastal Corporation, www.elpaso.com Conoco, www.conoco.com Cosmo Oil, www.cosmo-oil.co.jp Cross Oil Refining and Marketing Inc., www.crossoil.com Ecopetrol (Columbian Petroleum Company), www.ecopetrol.com.co ENI, www.eni.it Ergon Inc., www.ergon.com ExxonMobil Corp., www.exxonmobil.com

MOL Hungarian Oil & Gas, www.mol.hu Murphy Oil Corporation, www.murphyoilcorp.com/ PDVSA (Venezuela), www.pdvsa.com PEMEX (Mexico), www.pemex.com Pertamina (Indonesia), www.pertamina.com Petrobras (Brazil), www.petrobras.com.br Petrogal (Portugal), www.galpenergia.com/ Galp+Energia/home.htm Petrogal (Portugal), www.petrogal.pt Petroperu (Peru), www.petroperu.com Phillips Petroleum Company/Phillips 66, www.phillips66.com/phi11ips66.asp RWE-DEA (Germany), www.rwe-dea.de San Joaquin Refining Company, www.sjr.com Sasol (South Africa), www.sasol.com Shell (USA), www.shellus.com Shell International, www.shell.com/royal-en Shell Oil Products US, www.shelloilproductsus.com/ Sinclair Oil Corp., www.sinclairoil.com Sinopec (China Petrochemical Corporation), www.sinopec.com.cn Statoil (Norway), www.statoil.com Sunoco Inc., www.sunocoinc.com

Fortum (Finland), www.fortum.com Gasco Energy, www.gascoenergy.com Hindustan Petroleum Corporation, Ltd., www.hindpetro.com Idemitsu, www.idemitsu.co.jp Indian Oil Corporation, www.indianoilcorp.com Interline Resources Corporation, www.interlineresources.com/

Texaco Inc., www.texaco.com Thailand, Petroleum Authority, www.nectec.or.th/ users/htk/SciAm/12PTT.html Tosco, www.tosco.com Total, www.total.com Total, www.totalfinaelf.com/ho/fr/index.htm YPF (Argentina), www.ypf.com.ar

51.2.4 University Sites

Japan Energy Corporation, www.j-energy.co.jp/eng/ index.html Japan Energy, www.j-energy.co.jp

Brno University of Technology, Faculty of Mechanical Engineering, Elastohydrodynamic Lubrication Research Group, http://fyzika.fme.vutbr.cz/ehd/

Kuwait National Petroleum Company K. S. C., www.knpc.com.kw/

Cambridge Universirty, Department of Materials Science and Metallurgy, Tribology, www.msm.cam.ac.uk/ tribo/tribol.htm Cambridge University, Department of Engineering, Tribology, www-mech.eng.cam.ac.uk/Tribology/ College of Petroleum and Energy Studies CPS Home Page, www.oxfordprinceton.com College of Petroleum and Energy Studies, www.colpet.ac.uk

LukOil (Russian Oil Company), www.lukoil.com Marathon Ashland Petroleum LLC, www.mapllc.com Marathon Oil Company, www.marathon.com Mobil, www.mobil.com


Colorado School of Mines Advanced Coating and Surface Engineering Laboratory (ACSEL), www.mines.edu/ research/acsel/acsel.html

Ohio State University, Center for Surface Engineering and Tribology, Gear Dynamics and Gear Noise Research Laboratory, http://gearlab.eng.ohio-state.edu/

Danish Technological Institute (DTI) Tribology Centre, www.tribology.dti.dk/ Departments of Mechanical Engineering Luleå Technical University, Sweden, http://www.luth.se/depts/mt/me/ Division of Machine Elements Home Page Niigata University, Japan, http://tmtribo1.eng.niigata-u.ac.jp/ index_e.html

Pennsylvania State University, The, www.me.psu.edu/ research/tribology.html Purdue University, Materials Processing and Tribology Research Group, www.ecn.purdue.edu/∼farrist/lab.html Purdue University, Mechanical Engineering Tribology Web Site, http://widget.ecn.purdue.edu/∼metrib/

Ecole Centrale de Lyon, France Laboratoire de Tribologie et Dynamique des Systèmes, www.ec-lyon.fr/recherche/ltds/index.html Ecole Polytechnique Federale de Lausanne, Switzerland, http://igahpse.epfl.ch Eidgenössische Technische Hochschule (ETH), Zurich Laboratory for Surface Science and Technology (LSST), www.surface.mat.ethz.ch/ Esslingen, Technische Akademie, www.tae.de Fachhochschule Hamburg, Germany, www.haw-hamburg.de/fh/forum/f12/indexf.html/ tribologie/etribology.html Georgia Tech Tribology, www.me.gatech.edu/research/ tribology.html Imperial College, London ME Tribology Section, www.me.ic.ac.uk/tribology/ Indian Institute of Science, Bangalore, India, Department of Mechanical Engineering, www.mecheng.iisc.ernet.in Institut National des Sciences Appliquées de Lyon, France, Laboratoire de Mécanique des Contacts, www.isan-lyon.fr/Laboratoires/LMC/index.html Iowa State University, Tribology Laboratory, www.eng.iastate.edu/coe/me/research/labs/ tribology_lab.html Israel Institute of Technology (Technion), http://meeng. technion.ac.il/Labs/energy.htm#tribology Kanazawa University, Japan, Tribology Laboratory, http://web.kanazawa-u.ac.jp/∼tribo/labo5e.html Kyushu University, Japan, Lubrication Engineering Home Page, www.mech.kyushu-u.ac.jp/index.html Lulea University of Technology, Department of Mechanical Engineering, www.luth.se/depts/mt/me/ Northwestern University, Tribology Lab, http://cset.mech. northwestern.edu/member.htm


Royal Institute of Technology (KTH), Sweden Machine Elements Home Page, www.damek.kth.se/mme Saitama University, Japan Home Page of Machine Element Laboratory, www.mech.saitama-u.ac.jp/ youso/home.html Sandia National Laboratories Tribology, www.sandia.gov/materials/sciences/ Shamban Tribology Laboratory Kanazawa University, Japan, http://web.kanazawa-u.ac.jp/∼tribo/labo5e.html Southern Illinois University, Carbondale Center for Advanced Friction Studies, www.frictioncenter.com State University of New York, Binghamton Mechanical Engineering Laboratory, www.me.binghamton.edu/ me_labs.html Swiss Federal Laboratories for Materials Testing and Research (EMPA) Centre for Surface Technology and Tribology, www.empa.ch Swiss Tribology Online, Nanomechanics and Tribology, http://dmxwww.epfl.ch/WWWTRIBO/home.html Technical University of Delft, Netherlands Laboratory for Tribology, www.ocp.tudelft.nl/tribo/ Technical University, Munich, Germany, www.fzg.mw.tu-muenchen.de Technische Universitat Ilmenau, Faculty of Mathematics and Natural Sciences, www.physik.tu-ilmenau.de/ index_e.html Texas Tech University, Tribology, www.osci.ttu.edu/ ME_Dept/Research/tribology.htmld/ Tokyo Institute of Technology, Japan Nakahara Lab. Home Page, www.mep.titech.ac.jp/Nakahara/home.html Trinity College, Dublin Tribology and Surface Engineering, www.mme.tcd.ie/Groups/Tribology/ Tsinghua University, China, State Key Laboratory of Tribology, www.pim.tsinghua.edu.cn/index_cn.html University of Akron Tribology Laboratory, www.ecgf.uakron.edu/∼mech University of Applied Sciences, Hamburg, Germany Dept of Mech. Eng Tribology, www.fh-hamburg.de/fh/fb/m/tribologie/e_index.html

University of Applied Sciences, Hamburg, Germany, www.haw-hamburg.de/fh/fb/m/tribologie/e_index.html University of California, Berkeley Bogey’s Tribology Group, http://cml.berkeley.edu/tribo.html University of California, San Diego, Center for Magnetic Recording Research, http://orpheus.ucsd.edu/cmrr/ University of Florida, Mechanical Engineering Department, Tribology Laboratory, http://grove.ufl.edu/ ∼wgsawyer/ University of Illinois, Urbana-Champaign Tribology Laboratory, www.mie.uiuc.edu University of Kaiserslautern, Germany Sektion Tribologie, www.uni-kl.de/en/ University of Leeds, M.Sc. (Eng.) Course in Surface Engineering and Tribology, http://leva.leeds.ac.uk/ tribology/msc/tribmsc.html University of Leeds, UK Research in Tribology, http://leva.leeds.ac.uk/tribology/research.html University of Ljubljana, Faculty of Mechanical Engineering, Center for Tribology and Technical Diagnostics, www.ctd.uni-lj.si/eng/ctdeng.htm University of Maine Laboratory for Surface Science and Technology (LASST), www.ume.maine.edu/LASST/ University of Maine, NanoTribometer System, www.ume.maine.edu/LASST University of Newcastle upon Tyne, UK Ceramics Tribology Research Group, www.ncl.ac.uk/materials/ materials/resgrps/certrib.html University of Northern Iowa, www.uni.edu/abil University of Notre Dame Tribology/Manufacturing Laboratory, www.nd.edu/∼ame University of Pittsburg, School of Engineering, Mechanical Engineering Department, www.engrng.pitt. edu/∼mewww University of Sheffield, UK Tribology Research Group, http://www.shef.ac.uk/mecheng/tribology/ University of Southern Florida. Tribology, www.eng.usf.edu/∼hess/ University of Texas at Austin, Petroleum & Geosystems Engineering, Reading Room, www.pe.utexas.edu/Dept/ Reading/petroleum.html University of Tokyo, Japan, Mechanical Engineering Department, www.mech.t.u-tokyo.ac.jp/english/ index.html University of Twente, Netherlands Tribology Group, http://www.wb.utwente.nl/vakgroep/tr/tribeng.htm University of Western Australia Department of Mechanical and Material Engineering, http://www.mech.uwa.edu.au/tribology/ University of Western Ontario, Canada Tribology Research Centre, http://www.engga.uwo.ca/research/tribology/ Default.htm University of Windsor, Canada Tribology and Wear Research Group, http://zeus.uwindsor.ca/research/ wtrg/index.html


University of Windsor, Canada, Tribology Research Group, http://venus.uwindsor.ca/research/wtrg/ index.html Uppsala University, Sweden Tribology Group, http://www.angstrom.uu.se/materials/index.htm Western Michigan University Tribology Laboratory, www.mae.wmich.edu/labs/Tribology/Tribology.html Western Michigan University, Department of Mechanical and Aeeronautical Engineering, www.mae.wmich.edu/ Worcester Polytechnic Institute, Department of Mechanical Engineering, www.me.wpi.edu/ Research/labs.html

51.2.5 Government Sites/Industry Sites American Bearing Manufacturers Association, www.abma-dc.org American Board of Industrial Hygiene, www.abih.org American Carbon Society, www.americancarbonsociety.org American Chemical Society (ACS), www.acs.org American Council of Independent Laboratories (ACIL), www.acil.org American Gear Manufacturers Association (AGMA), www.agma.org American National Standards Institute (ANSI), www.ansi.org American Oil Chemists Society (AOCS), www.aocs.org American Petroleum Institute (API), www.api.org American Society of Agricultural Engineering (ASAE), www.asae.org American Society of Agronomy (ASA), www.agronomy.org American Society for Horticultural Science (ASHS), www.ashs.org American Society for Testing and Materials (ASTM), www.astm.org American Society of Mechanical Engineers International (ASME), www.asme.org Argonne National Laboratory, www.et.anl.gov ASTM, www.astm.org Automotive Aftermarket Industry Association (AAIA), www.aftermarket.org Automotive Oil Change Association (AOCA), www.aoca.org Automotive Parts and Accessories Association (APAA), www.apaa.org Automotive Service Industry Association (ASIA), www.aftmkt.com British Lubricants Federation Ltd., www.blf.org.uk California Air Resources Board, www.arb.ca.gov Center for Tribology, Inc. (CETR), www.cetr.com

Co-ordinating European Council (CEC), www.cectests.org Coordinating Research Council (CRC), www.crcao.com Crop Science Society of America (CSSA), www.crops.org Department of Defense (DOD), www.dodssp.daps. mil/dodssp.htm Deutsches Institute Fur Normung e. V. (DIN), www.din.de Environmental Protection Agency (EPA), www.fedworld.gov European Automobile Manufacturers Association (ACEA), www.acea.be European Oil Companies Organization of E. H. and S. (CONCAWE), www.concawe.be Federal World, www.fedworld.gov Independent Lubricant Manufacturers Association (ILMA), www.ilma.org Industrial Maintenance & Plant Operation (IMPO), www.mcb.co.uk/cgi-bin/mcb_serve/table1. txt&ilt&stanleaf.htm Institute of Materials Inc. (IOM), www.savantgroup.com Institute of Mechanical Engineers (ImechE), www.imeche.org.uk Institute of Petroleum (IP), http://212.78.70.142 Institute of Physics (IOP), Tribology Group, www.iop.org Internal Energy Agency (IEA), www.iea.org International Organization for Standardization (ISO), www.iso.ch Japan Association of Petroleum Technology (JAPT), www.japt.org Japan Automobile Manufacturers Association (JAMA), www.japanauto.com Japanese Society of Tribologists (JAST) (in Japanese), www.jast.or.jp Los Alomos National Laboratory, www.lanl. gov/worldview/ NASA Lewis Research Center (LeRC) Tribology & Surface Science Branch, www.lerc.nasa.gov/ Other_Groups/SurfSci National Centre of Tribology, UK, www.aeat.com/nct/ National Fluid Power Association (NFPA), www.nfpa.com National Institute for Occupational Safety and Health, www.cdc.gov/homepage.html National Institute of Standards and Technology, http://webbook.nist.gov/chemistry National Lubricating Grease Institute (NLGI), www.nlgi.org National Metal Finishing Resource Center, www.nmfrc.org


National Oil Recyclers Association (NORA), www.recycle.net/Associations/rs000141.html National Petrochemical & Refiners Association, www.npradc.org National Petrochemical Refiners Association (NPRA), www.npradc.org National Petroleum Refiners Association (NPRA), www.npra.org National Research Council of Canada Lubrication Tribology Services, http://132.246.196.24/en/fsp/service/ lubrication_trib.htm Naval Research Lab Tribology Section—NRL Code 6176, http://stm2.nrl.navy.mil/∼wahl/6176.htm Oak Ridge National Laboratory (ORNL) Tribology Test Systems, www.ms.ornl.gov/htmlhome Occupational Safety and Health Administration (OSHA), www.osha.gov Petroleum Marketers Association of America (PMAA), www.pmaa.org Society of Automotive Engineers (SAE), www.sae.org Society of Environmental Toxicology and Chemistry (SETAC), www.setac.org Society of Manufacturing Engineers (SME), www.sme.org Society of Tribologists and Lubrication Engineers (STLE), www.stle.org Southwest Research Institute (SwRI) Engine Technology Section, www.swri.org/4org/d03/engres/engtech/ Southwestern Petroleum Corporation (SWEPCO), www.swepco.com Thailand, Petroleum Authority (PTT), www.nectec.or.th U.S. Department of Agriculture (USDA), www.usda.gov U.S. Department of Defense (DOD), www.dod.gov U.S. Department of Energy (DOE), www.energy.gov U.S. Department of Transportation (DOT), www.dot.gov U.S. Energy Information Administration, www.eia.doe.gov U.S. Patent Office, www.uspto.gov U.S. Data Exchange, www.usde.com Western States Petroleum Association, www.wspa.org

51.2.6 Testing Labs/Equipment/Packaging A.W. Chesterton Company, www.chesterton.com A/R Packaging Corporation, www.arpackaging.com Accumetric LLC, www.accumetric.com

Airflow Systems Inc., www.airflowsystems.com Alfa Laval Separation, www.alfalaval.com Allen Filters Inc., www.allenfilters.com Ana Laboratories Inc., www.analaboratories.com Analysts Inc., www.analystinc.com Anatech Ltd., www.anatechltd.com Andpak Inc., www.andpak.com Applied Energy Company, www.appliedenergyco.com Aspen Technology, www.aspentech.com/ Associates of Cape Cod Inc., www.acciusa.com Atico-Internormen-Filter, www.atico-internormen.com Baron USA Inc., www.baronusa.com Berenfield Containers, www.berenfield.com Bericap NA, www.bericap.com BF Goodrich, www.bfgoodrich.com Bianco Enterprises Inc., www.bianco.net Bijur Lubricating Corporation, www.bijur.com Biosan Laboratories, Inc., www.biosan.com Bio-Rad Labroatories, www.bio-rad.com BioTech International Inc., [email protected] Blackstone Laboratories, www.blackstone-labs.com/ Cannon Instrument Company, www.cannon-ins.com Certified Laboratories Lubricants, www.certifiedlaboratories.com Chemicolloid Laboratories Inc., www.colloidmill.com Como Industrial Equipment Inc., www.comoindustrial.com Computational Systems, Inc., www.compsys.com/ index.html Containment Solutions Inc., www.containmentsolutions.com CSI, www.compsys.com Custom Metalcraft Inc., www.custom-metalcraft.com Delphi Automotive Systems, www.delphiauto.com Des-Case Corporation, www.des-case.com Dexsil Corporation, www.dexsil.com Diagnetics, www.entek.com Digilube Systems Inc., www.digilube.com Dingo Maintenance Systems, www.dingos.com/ DSP Technology Inc., www.dspt.com Duro Manufacturing Inc., www.duromanufacturing.com Dutton-Lainson Company, www.dutton-lainson.com Dylon Industries Inc., www.dylon.com Easy Vac Inc., www.easyvac.com Edjean Technical Services Inc., www.edjetech.com Engel Metallurgical Ltd., www.engelmet.com Engineered Composites Inc., www.engineeredcomposites.net


Environmental and Power Technologies Ltd., www.cleanoil.com Evans Industries Inc., www.evansind.com Falex Corporation, www.falex.com Falex Tribology NV, www.falexint.com/ FEV Engine Technology, Inc., www.fev-et.com/ Flo Components Ltd., www.flocomponents.com Flowtronex International, www.flowtronex.com Fluid Life Corporation, www.fluidlife.com Fluid Systems Partners US Inc., www.fsp-us.com Fluid Technologies Inc., www.Fluidtechnologies.com Fluids Analysis Lab, www.butler-machinery.com/oil.html Fluidtec International, www.fluidtec.com Fluitec International, www.fluitec.com/ FMC Blending & Transfer, www.fmcblending-transfer.com Framatome ANP, www.framatech.com Fuel Quality Services Inc., www.fqsgroup.com G.R. O’Shea Company, www.groshea.com G.T. Autochemilube Ltd., www.gta-oil.co.uk Galactic, www.galactic.com Gamse Lithographing Company, www.gamse.com Gas Tops Ltd., www.gastops.com Generation Systems Inc., www.generationsystems.com Georgia-Pacific Resins, Inc.—Actrachem Division, www.gapac.com Gerhardt Inc., www.gerhardths.com Globetech Services Inc., www.globetech-services.com Graco Inc., www.graco.com Gulfgate Equipment, Inc., www.gulfgateequipment.com Hedwin Corporation, www.hedwin.com Hercules, Inc., Aqualon Division, www.herc.com Herguth Laboratories Inc., www.herguth.com Hi-Port Inc., www.hiport.com Hi-Tech Industries, Inc., www.hi-techind.com Hoover Materials Handling Group Inc., www.hooveribcs.com Horix Manufacturing Company, www.sgi.net/horix Hydraulic Repair & Design, Inc., www.h-r-d.com Hysitron Incorporated: Nanomechanics, www.hysitron.com/ Indiana Bottle Company, www.indianabottle.com Industrial Packing Inc., www.industrialpacking.com Insight Services, www.testoil.com/ Instruments for Surface Science, www.omicron-instruments.com/index.html Interline Resources Corporation, www.interlineresources.com International Group Inc., The (IGI), www.igiwax.com

Intertek Testing Services-Caleb Brett, www.itscb.com Invicta a.s., www.testoil.com/ J & S Chemical Corporation, www.jschemical.com J.R. Schneider Company, Inc., www.jrschneider.com JAX-Behnke Lubricants Inc., www.jax.com Johnson Packings & Industrial Products Inc., www.johnsonpackings.com K.C. Engineering, Ltd., www.kceng.com/ K.l.S.S. Packaging Systems, www.kisspkg.com Kafko International Ltd., www.kafkointl.com Kennedy Group, The, www.kennedygrp.com Kittiwake Developments Limited, www.kittiwake.com Kleenoil Filtration Inc., www.kleenoilfiltrationinc.com Kleentek-United Air Specialists Inc., www.uasinc.com Koehler Instrument Company, www.koehlerinstrument.com Koehler Instrument Company, www.koehlerinstrument.com Kruss USA, www.krussusa.com Laub/Hunt Packaging Systems, www.laubhunt.com Lawler Manufacturing Corporation, www.lawler-mfg.com Leding Lubricants Inc., www.automatic-lubrication.com Legacy Manufacturing, www.legacymfg.com Liftomtic Inc., www.liftomatic.com Lilyblad Petroleum, Inc., www.lilyblad.com Linpac Matls. Handling, www.linpacmh.com Liqua-Tek/Moraine Packaging, www.globaldialog.com/∼mpi Liquid Controls Inc., A Unit of IDEX Corporation, www.lcmeter.com Lormar Reclamation Service, www.lormar.com LubeCon Systems Inc., www.lubecon.com Lubricant Technologies, www.lubricanttechnologies.com Lubrication Engineers of Canada, www.lubeng.com Lubrication Systems, www.lsc.com Lubrication Systems, www.lsc.com Lubrication Technologies Inc., www.lube-tech.com Lubriport Labs, www.ultralabs.com/lubriport Lubriquip Inc, www.lubriquip.com Lubrizol Corporation, The, www.lubrizol.com Lubromation Inc., www.lubromation.com Lub-Tek Petroleum Products Corporation, www.lubtek.com Machines Production Web Site, www.machpro.fr/ Manor Technology, www.manortec.co.uk/ Metalcote/Chemtool Inc., www.metalcote.com Metorex Inc., www.metorex.fi Mettler Toledo, www.mt.com Michel Murphy Enterprises Inc., www.michelmurphy.com


Micro Photonics Inc., www.microphotonics.com/ Micro Photonics Inc., www.microphotonics.com/ Mid-Michigan Testing Inc., www.tribologytesting.com Monlan Group, www.monlangroup.com Motor Fuels/Combustibles Testing, www.empa.ch/ englisch/fachber/abt133/index.htm Mozel Inc., www.mozel.com Nalco Chemical Company, www.nalco.com Naptec Corporation, www.satec.com National Tribology Services, www.natrib.com NC’eed Enterprises, www.backtosebacics.com NCH, www.nc.com Newcomb Oil Company, www.newcomboil.com Nordstrom Valves Inc., www.nordstromaudco.com Oden Corporation, www.oden.thomasregister.com Oden Corporation, www.odencorp.com Oil Analysis (Noria), www.oilanalysis.com OMICRON Vakuumphysik GmbH, www.omicron-instruments.com/index.html OMS Laboratories, Inc. http://members.aol.com/ labOMS/index.html Owens-Illinois Inc., www.o-i.com Oxford Instruments Inc., www.oxinst.com Paper Systems Inc., www.paper-systems.com PARC Technical Services Inc., www.parctech.com Patterson Industries Ltd. (Canada), www.pattersonindustries.com PCS Instruments, www.pcs-instruments.com PdMA Corporation, www.pdma.com PED Inc., www.ped.vianet.ca Perkin Elmer Automotive Research, www.perkinelmer.com/ar Perkins Products Inc., www.perkinsproducts.com Perma USA, www.permausa.com Petrolab Corporation, www.petrolab.com Petrolabs Inc., http://pages.prodigy.net/petrolabsinc Petroleum Analyzer Company LP (PAC), www.Petroleum-Analyzer.com Petroleum Products Research, www.swri.org/4org/d08/petprod/ Petro-Lubricants Testing Laboratories, Inc., www.pltlab.com Petrotest, www.petrotest.net Pflaumer Brothers Inc., www.pflaumer.com Philips Industrial Electronics Deutschland, www.philips-tkb.com Pipeguard of Texas, www.pipeguard-texas.com Plastic Bottle Corporation, www.plasticbottle.com Plastican Inc., www.plastican.com Plews/Edelmann Division, Stant Corporation, www.stant.com

PLI LLC, www.memolub.com Plint and Partners: Tribology Division, www.plint.co.uk/trib.htm Polaris Laboratories, LLC, www.polarislabs.com PREDICT/DLI—Innovative Predictive Maintenance, www.predict-dli.com Predictive Maintenance Corporation, www.pmaint.com/ Predictive Maintenance Services, www.theoillab.com Premo Lubricant Technologies, exwww.premolube.com Pulsair Systems Inc., www.pulsair.com Quorpak, www.quorpak.com R & D/Fountain Industries, www.fountainindustries.com R.A. Miller & Company Inc., www.ramiller.on.ca R.E.A.L. Services, www.realservices.com Radian Inc., www.radianinc.com Ramos Oil Co. Inc., www.ramosoil.com Ravenfield Designs Ltd., www.ravenfield.com Ravenfield Designs Ltd., www.ravenfield.com Reelcraft Industries Inc., www.realcraft.com Rexam Closures, www.closures.com Rheotek (PSL SeaMark), www.rheotek.com Ribelin, www.ribelin.com Russell-Stanley Corportion, www.russell-stanley.com Safety-Kleen Corporation, www.safety-kleen.com Saftek: Machinery Maintenance Index, www.saftek.com/ boiler/machine/mmain.htm Sandy Brae Laboratories Inc., www.sandy/brae.com SATEC Inc., www.satec.com Savant Group of Companies, www.savantgroup.com Savant Inc., www.savantgroup.com Saxton Industries, www.saxton.thomasregister.com Scully Signal Company, www.scully.com Senior Flexonics, www.flexonics-hose.com Service Supply Lubricants LLC, www.servicelubricants.com Sexton & Peake Inc., www.sexton.qpg.com Silvas Oil Co. Inc., www.silvasoil.com Silverson Machines Inc., www.silverson.com Sinclair Oil Corporatoin, www.sinclairoil.com SKF Quality Technology Centre, www.qtc.skf.com Sleeveco Inc., www.sleeveco.com Snyder Industries, www.snydernet.com Southwest Research Institute, www.swri.org Southwest Spectro-Chem Labs, www.swsclabs.com Spacekraft Packaging, www.spacekraft.com Specialty Silicone Products Inc., www.sspinc.com SpectroInc. Industrial Tribology Systems, www.spectroinc.com/ Spectronics Corporation, www.spectroline.com


Spex CertiPrep Inc., www.spexcsp.com Star Brite, www.starbrite.com Steel Shipping Containers Institute, www.steelcontainers.com Stratco Inc., www.stratco.com Sunohio, Division of ENSR, www.sunohio.com Superior Lubricants Company, Inc., www.superiorlubricants.com Taber Industries, www.taberindustries.com Tannas Company, www.savantgroup.com Tannis Company, www.savantgroup.com/tannas.sht Thermo Elemental, www.thermoelemental.com Thomas Petroleum, www.thomaspetro.com Thoughtventions Unlimited Home Page, www.tvu.com/ %7Ethought/ Titan Laboratories, www.titanlab.com TriboLogic Lubricants Inc., www.dynamaxx.com TriboLogic Lubricants Inc., www.tribologic.com Trico Manufacturing Corporation, www.tricomfg.com Trilla Steel Drum Corporation, www.trilla.com TTi’s Home Page, www.tti-us.com/ UEC Fuels and Lubrication Laboratories, www.uec-usx.com Ultimate Lubes, www.ultimatelubes.com Unilube Systems Ltd., www.unilube.com Unit Pack Company Inc., www.unitpack.com USX Engineers & Consultants, www.uec.com/labs/ctns USX Engineers and Consultants: Laboratory Services, www.uec.com/labs/ Vacudyne Inc., www.vacudyne.com Van Horn, Metz & Company, Inc., www.vanhornmetz.com Viking Pump Inc., A Unit of IDEX Corporation, www.vikingpump.com Viswa Lab Corporation, www.viswalab.com Vortex International LLC, www.vortexfilter.com Vulsay Industries Ltd., www.vulsay.com

Wallace, www.wallace.com Waugh Controls Corporation, www.waughcontrols.com Wearcheck International, www.wearcheck.com/ Wedeven Associates, Inc., http://members. aol.com/wedeven/ West Penn Oil Company Inc., www.westpenn.com Western States Oil, www.lubeoil.com Wilks Enterprise Inc., www.wilksir.com WSI Chemical Inc., www.wsi-chem-sys.com Zimmark Inc., www.zimmark.com

51.2.7 Car/Truck MFG Alfa Romeo, www.alfaromeo.com Audi, www.audi.com BMW (International), www.bmw.com/bmwe BMW (USA), www.bmwusa.com BMW Motorcycles, www.bmw-motorrad.com Buick (GM), www.buick.com Cadillac (GM), www.cadillac.com Caterpillar, www.cat.com Caterpillar, www.caterpillar.com Chevrolet (GM), www.chevrolet.com Chrysler (Mercedes Benz), www.chrysler.com Citroen (France), www.citroen.com Citroen (UK), www.citroen.co.uk/fleet Cummins Engine Company, www.cummins.com Daimler Chrysler, www.daimlerchrysler.com Detroit Diesel, www.detroitdiesel.com Dodge, www.dodge.com Eagle, www.eaglecars.com EV1, www.gmev.com Ferrari, www.ferrari.com Fiat, www.fiat.com Ford Motor Company, www.ford.com General Motors (GM), www.gm.com Global Electric Motor Cars, LLC, www.gemcar.com Hyundai, www.hyundai-motor.com Infiniti, www.infiniti.com Isuzu, www.isuzu.com Jaguar, www.jaguarcars.com Jeep, www.jeep.com John Deere, www.deere.com Kawasaki, www.kawasaki.com Kawasaki, www.khi.co.jp Lambourghini, www.lamborghini.com Lexus, www.lexususa.com Lincoln-Mercury, www.lincolnmercury.com Mack Trucks, www.macktrucks.com Mazda, www.mazda.com


Mercedes-Benz (Germany), www.mercedes-benz.de Mitsubishi Motors, www.mitsubishi-motors.co.jp Nissan (Japan), www.nissan.co.jp Nissan (USA), www.nissandriven.com Nissan (USA), www.nissanmotors.com Opel, www.opel.com Peugeot, www.peugeot.com Plymouth, www.plymouthcars.com Pontiac (GM), www.pontiac.com Saab Cars USA, www.saabusa.com Saab, www.saab.com Saturn (GM), www.saturncars.com Scania, www.scania.se Toyota (Japan), www.toyota.co.jp Toyota (USA), www.toyota.com Vauxhall, www.vauxhall.co.uk Volkswagen (Germany), www.vw-online.de Volkswagen (USA), www.vw.com Volvo (Sweden), www.volvo.se Volvo Cars of North America, www.volvocars.com Volvo Group, www.volvo.com

51.2.8 Publications/References/Recruiting/ Search Tools, etc. American Machinist, www.penton.com/cgi-bin/ superdirectory/details.pl?id=317 API Links, www.api.org/links Automotive & Industrial Lubricants Guide, www.wearcheck.com Automotive and Industrial Lubricants Guide by David Bradbury, www.escape.ca/∼dbrad/index.htm Automotive and Industrial Lubricants Tutorial, www.escape.ca/∼dbrad/index.htm Automotive News, www.autonews.com Automotive Service Industry Association, www.aftmkt.com/asia Automotive Services Retailer, www.gcipub.com AutoWeb, www.autoweb.com AutoWeek Online, www.autoweek.com Bearing.Net, www.wearcheck.com Cambridge, http://chemfinder.camsoft.com Car and Driver Magazine Online, www.caranddriver.com Car-Stuff, www.car-stuff.com Center for Innovation Inc., www.centerforinnovation.com

Chem Connect, www.chemconnect.com Chemical Abstracts Service, www.cas.org Chemical Resources, www.chemcenter.org Chemical Week Magazine, www.chemweek.com Concord Consulting Group Inc., www.concordcg.com Dialog, www.dialog.com Diesel Progress, www.dieselpub.com Diversified Petrochemical Services, www.chemhelp.com Energy Connection, The, www.energyconnect.com European Patent Office, www.epo.co.at/epo/ F.L.A.G. (Fuel, Lubricant, Additives, Grease) Recruiting, www.flagsearch.com/ Farmland Industries Inc., www.farmland.com Fuel Quest, www.fuelquest.com/cgi-bin/fuelqst/ corporate/fq_index.jsp Fuels and Lubes Asia Publications, Inc., www.flasia.com.ph Gear Technology Magazine, www.geartechnology.com/ mag/gt-index.html Haas Corporation, www.haascorp.com HEF, France, www.hef.fr/ How Stuff Works, www.howstuffworks.com/engine.htm Hydrocarbon Asia, www.hcasia.safan.com Hydrocarbon Online, www.wearcheck.com Hydrocarbon Processing Magazine, www.hydrocarbonprocessing.com/ ICIS-LOR Base Oils Pricing Information, www.icislor.com/ Industrial Lubrication and Tribology Journal, www.mcb.co.uk/ilt.htm Industrial Maintainence and Engineering Links (PLI, LLC), www.memolub.com/link.htm Intl. Tribology Conf. Yokohama 1995, www.mep.titech. ac.jp/Nakahara/jast/itc/itc-home.htm ISO Translated into Plain English, http://connect.ab.ca/∼praxiom Journal of Fluids Engineering, http://borg.lib.vt.edu/ ejournals/JFE/jfe.html Journal of Tribology, http://engineering.dartmouth.edu/ thayer/research/index.html Kline & Comphany Inc., www.klinegroup.com LSST Tribology and Surface Forces, http://bittburg. ethz.ch/LSST/Tribology/default.html


LSST Tribology Letters, http://bittburg.ethz.ch/LSST/ Tribology/letters.html Lube Net, www.lubenet.com Lubelink, www.lubelink.com Lubes and Greases, www.lngpublishing.com Lubricants Network Inc., www.lubricantsnetwork.com Lubricants World, www.lubricantsworld.com Lubrication Engineering Magazine, www.stle.org/ le_magazine/le_index.htm

MaintenanceWorld, www.wearcheck.com MARC-IV, www.marciv.com Mechanical Engineering Magazine, www.memagazine. org/index.html Migdal’s Lubricant Web Page, http://members.aol.com/ sirmigs/lub.htm Muse, Stancil & Company, www.musestancil.com

National Petroleum News, www.petroretail.net/npn National Resource for Global Standards, www.nssn.org Neale Consulting Engineers Limited, www.tribology.co.uk/ Noria—OilAnalysis.Com, www.oilanalysis.com/

Oil Directory.com, www.oildirectory.com Oil Online, www.oilonline.com/ Oil-Link Oil & Gas Online, www.oilandgasonline.com Oilspot.com, www.oilspot.com

Pennwell Publications, www.pennwell.com Petrofind.com, www.petrofind.com PetroleumWorld.com, www.petroleumworld.com PetroMin Magazine, www.petromin.safan.com Practicing Oil Analysis Magazine, www.practicingoilanalysis.com Predictive Maintenance Corporation: Tribology and the Information Highway, www.pmaint.com/tribo/docs/ oil_anal/tribo_www.html ref

Reliability Magazine, www.pmaint.com/tribo/docs/ oil_anal/tribo_www.html Safety Information Resources on the Internet, www.siri.org/links1.html Savant Group of Companies, www.savantgroup.com SGS Control Services Inc., www.sgsgroup.com Shell Global Solutions, www.shellglobalsolutions.com SubTech (Petroleum Service & Supply Information), www.subtech.no/petrlink.htm

Summit Technical Solutions, www.lubemanagement.com Sunohio, Division of ENSR, www.sunohio.com

United Soybean Board, www.unitedsoybean.org Victoria Group Inc., The, www.victoriagroup.com

Tannas Company, www.savantgroup.com Test Engineering Inc., www.testeng.com The Maintenance Council, www.trucking.org TMC, www.truckline.com Tribologist.com, www.wearcheck.com Tribology Consultant, http://hometown.aol.com/ wearconsul/wear/wear.htm Tribology International, www.elsevier.nl/inca/ publications/store/3/0/4/7/4/ Tribology Letters, www.kluweronline.com/ issn/1023-8883 Tribology Research Review 1992-1994, www.me.ic.ac.uk/ department/review94/trib/tribreview.html Tribology Research Review 1995-1997, www.me.ic.ac.uk/ department/review97/trib/tribreview.html Tribology/Tech-Lube, www.tribology.com Truklink (truck fleet information), www.truklink.com


Wear Chat: WearCheck Newsletter, www.wearcheck.com Wear, www.elsevier.nl/inca/publications/ store/5/0/4/1/0/7/ World Tribologists Database, http://greenfield. fortunecity.com/fish/182/tribologists.htm WWW Tribology Information Service, www.shef.ac.uk/ ∼mpe/tribology/ WWW Virtual Library: Mechanical Engineering, www.vlme.com/ Yahoo Lubricants, http://dir.yahoo.com/ business_and_economy/shopping_and_services/ automotive/supplies/lubricants/ Yahoo Tribology, http://ca.yahoo.com/Science/ Engineering/Mechanical_Engineering/Tribology/

Appendix. Publisher’s Note: The Meaning of “Synthetic” This note appeared in the Journal of Synthetic Lubrication, Vol 17, #1, april 2000 and is reprinted by permission of Stephen Godfree, publisher. Readers of this journal, particularly in the United States, will no doubt be aware of the decision by the National Advertising Division (NAD) of the Council of Better Business Bureaux, made in April 1999, concerning the use of the word “synthetic” as a description of certain lubricants on the market. Its attempt to widen the use of the term to cover hydroprocessed oils would seem to have raised more questions than it has solved. The original Castrol–Mobil tussle that led to the NAD’s adjudication was over an advertising claim within the United States. Mobil objected (despite allegedly having itself marketed hydroisomerized base stocks as “synthetic” in Europe and elsewhere∗ ) that Castrol’s hydroprocessed Syntec® was not synthetic. The NAD did not agree, arguing that Castrol’s evidence, although not demonstrating its product’s superiority, constituted a reasonable basis for the claim that Castrol Syntec, as currently formulated, is a synthetic motor oil. Perhaps the first thing to realize is that the NAD is a powerless body outside the USA. Its jurisdiction is advertising claims on its home territory. It would not be unreasonable to say that it was out of its depth here, where the issues would seem to be: (1) what does “synthetic” mean in the context of lubricant make-up? (2) what is the importance of performance? and (3) why does anyone need to define mineral hydroprocessed oils as “synthetic?”

A.1 “SYNTHETIC” AS A TERM The normal scientific or technological definition is of “synthesis,” not of “synthetic.” “Synthesis,” in the context of chemistry, means the “artificial production of compounds from their constituents as distinct from extraction from plants, etc.” (The Concise Oxford Dictionary.) In practice, this involves taking two or more defined molecular species and synthesizing from them a product that is a predictable and defined compound. While Group III base oils are the result not simply of refining but also of a sophisticated process wherein ∗ Katherine Bui, “A defining moment for synthetics, Part 1,” Lubricant’s World, October 1999.


a smaller or larger proportion of the molecules are chemically converted, there remain, in every case, elements of the oil that are unknown and that can only be identified by analysis. This process would seem to be almost the opposite of synthesis. Herein lies the first error in the NAD ruling. It seemingly failed or was unable to define “synthetic,” the adjective from “synthesis,” in terms of its technical use, even ignoring the industry definition found in the base oil groupings in API Publication 1509, where Groups I, II, and III are identified by saturates, VI, and sulfur, while Group IV oils are simply defined as polyalphaolefins. In other words, a distinction is made between refined (I, II, and III) and synthetic (IV) oils. Instead, the NAD concerned itself exclusively with the word in the marketing context. This is intimately connected with the question of performance.

A.2 THE IMPORTANCE OF PERFORMANCE One of the central themes of the Castrol–Mobile dispute was performance. Performance is a concept that has, in a wider context, taken on more importance of late. Certain research and testing establishments are now told to judge products on performance, in a possibly ill-informed, if not downright dangerous, attempt to sweep away old methods and open up competition. As a result, it seems, lubricant and fluid evaluations can no longer relate to chemical class. Thus, when choosing blindly, between fluid A and fluid B, the selector will be unable to take into account the hydrolysis problem associated with fluid A, since hydrolysis tests are not normally used to evaluate fluids in the application in question and so have not hitherto been included in performance tests. This disadvantage will not be apparent until it is too late. Considerations of safety are liable to become secondary to those of price where performance is made the sole criterion. Conversely, in the limited, in terms of performance, popular automotive market, a hydroprocessed oil will easily perform within the specifications of a normal engine oil. These are not very demanding: pour points of −30◦ C, flash points of 225◦ C, and drain intervals of up to 10,000 miles (16,000 km), usually define their use and life.

In some ways, synthetics in this market are unnecessary, an overkill, as the automotive manufacturers have not yet commercialized cars and trucks that are guaranteed to run on the same oil for, say, 500,000 to a million miles (800,000–1.6 m km), that is, in sealed-for-life engines. Instead, automotive engines still usually demand services including oil changes every 4,500 or 6,000 miles, thus never giving synthetic oils a chance to show their real mettle. However, in the extreme conditions imposed by a jet engine or the climate in the Antarctic, for instance, only a synthetic oil has all the properties required. So, here the NAD ruling really falls down. Having concluded from the performance criteria that hydroprocessing produces a synthetic oil, it had to admit that Castrol was unable to show that their enhanced mineral oil was superior to a synthetic and effectively ignored the fact that specific synthetic oils can always outperform mineral oils. Herein lies the second, major, difference concerning performance: since true “synthetics” are chemically designed, their properties can be varied at will — pour points, flash points, VIs, kinematic viscosities, within much greater ranges than enhanced mineral oils — according to their end purpose. This can be done to a certain extent with hydroprocessed mineral oils by additivation. But is “additivation” the same as synthesis? Does additivating an oil make it “synthetic?” Is a vegetable oil that has its properties altered “synthetic?” The risk is that by extending the term to cover any oil that has had its chemistry tampered with, it loses all meaning.


A.3 DEFINING MINERAL HYDROPROCESSED OIL AS “SYNTHETIC” Why does anyone need to define mineral hydroprocessed oil as “Synthetic?” This is, perhaps, one of the most interesting, and unconsidered, aspects of the whole question. If a hydroprocessed mineral oil has certain performance advantages over a normal refined mineral oil, why not define it, marketwise, as “hydroprocessed” and let the products and their performance stand on their merits in that category? Why bother to try to borrow a term previously used for something else? The answer must inevitably be marketing related. It has been perceived, rightly or wrongly, that “synthetic” oils, as normally defined, possess some consumer cachet, some commercial magic, that mineral oils do not. This decision may come back to haunt the advertisers, should they ever have a product that they really want to distinguish as synthetic. The manufacturers and marketers of “real” synthetics could react by saying what their synthetic is, for example, a PAO or an ester. The image creators could surely have a field day with the terminology, the chemical makeup, and the futuristic mystery of these chemically synthesized products. So there it is: “synthetic” as a term has been redefined and watered down by the NAD decision. It obscures questions of the ultimate performance and application of synthetics. And all because of what? A marketing ploy? Perhaps that was all the Castrol–Mobil dispute was about.

Synthetics, Mineral Oils, and Bio-Based Lubricants Chemistry and Technology

Chemistry and Technology of Lubricants

Chemistry and Technology of Lubricants, Third Edition

Chemistry and Technology of Lubricants 3rd Ed

Oils and Fats Authentication: v. 5 (Chemistry and Technology of Oils and Fats)

Biobased Lubricants and Greases: Technology and Products (Tribology in Practice Series)

Process Chemistry of Lubricants

Paper Chemistry and Technology

Pulping Chemistry and Technology

Flavor chemistry and technology

Ozone Chemistry and Technology

Cellulose Chemistry and Technology

Lubricants and Lubrication

Fats and oils

Chemistry and Technology of Surfactants

Resorcinol: Chemistry, Technology and Applications

Chemistry and Technology of Explosives:

Chemistry and Technology of Carbodiimides

Microsystem Technology in Chemistry and

Tobacco: Production, Chemistry, and Technology

Fats and Oils Handbook

Polyurethane and Related Foams: Chemistry and Technology

Textile and Paper Chemistry and Technology

Chemistry And Technology Wines And Liquors

Cotton Fiber Chemistry and Technology (International Fiber Science and Technology)

Lectures Notes for Chemical Students Embracing Mineral and Organic Chemistry

Asphaltenes, Heavy Oils, and Petroleomics

Handbook of Essential Oils: Science, Technology, and Applications

Biobased Industrial Products: Research and Commercialization Priorities

Advances in Potato Chemistry and Technology

Synthetics, Mineral Oils, and Bio-Based Lubricants Chemistry and Technology

Chemistry and Technology of Lubricants

Chemistry and Technology of Lubricants, Third Edition

Chemistry and Technology of Lubricants 3rd Ed

Oils and Fats Authentication: v. 5 (Chemistry and Technology of Oils and Fats)

Biobased Lubricants and Greases: Technology and Products (Tribology in Practice Series)

Process Chemistry of Lubricants

Paper Chemistry and Technology

Pulping Chemistry and Technology

Flavor chemistry and technology

Ozone Chemistry and Technology

Cellulose Chemistry and Technology

Lubricants and Lubrication

Fats and oils

Chemistry and Technology of Surfactants

Resorcinol: Chemistry, Technology and Applications

Chemistry and Technology of Explosives:

Chemistry and Technology of Carbodiimides

Microsystem Technology in Chemistry and

Tobacco: Production, Chemistry, and Technology

Fats and Oils Handbook

Polyurethane and Related Foams: Chemistry and Technology

Textile and Paper Chemistry and Technology

Chemistry And Technology Wines And Liquors

Cotton Fiber Chemistry and Technology (International Fiber Science and Technology)

Lectures Notes for Chemical Students Embracing Mineral and Organic Chemistry

Asphaltenes, Heavy Oils, and Petroleomics

Handbook of Essential Oils: Science, Technology, and Applications

Biobased Industrial Products: Research and Commercialization Priorities

Advances in Potato Chemistry and Technology

Recommend Documents