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Landolt-Börnstein Numerical Data and Functional Relationships in Science and Technology New Series / Editor in Chief: W. Martienssen

Group IV: Physical Chemistry Volume 11

Ternary Alloy Systems Phase Diagrams, Crystallographic and Thermodynamic Data critically evaluated by MSIT® Subvolume C Non-Ferrous Metal Systems Part 3 Selected Soldering and Brazing Systems

Editors G. Effenberg and S. Ilyenko Authors Materials Science International Team, MSIT®

ISSN 1615-2018 (Physical Chemistry) ISBN 978-3-540-25777-6

Springer Berlin Heidelberg New York

Library of Congress Cataloging in Publication Data Zahlenwerte und Funktionen aus Naturwissenschaften und Technik, Neue Serie Editor in Chief: W. Martienssen Vol. IV/11C3: Editors: G. Effenberg, S. Ilyenko At head of title: Landolt-Börnstein. Added t.p.: Numerical data and functional relationships in science and technology. Tables chiefly in English. Intended to supersede the Physikalisch-chemische Tabellen by H. Landolt and R. Börnstein of which the 6th ed. began publication in 1950 under title: Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik. Vols. published after v. 1 of group I have imprint: Berlin, New York, Springer-Verlag Includes bibliographies. 1. Physics--Tables. 2. Chemistry--Tables. 3. Engineering--Tables. I. Börnstein, R. (Richard), 1852-1913. II. Landolt, H. (Hans), 1831-1910. III. Physikalisch-chemische Tabellen. IV. Title: Numerical data and functional relationships in science and technology. QC61.23 502'.12 62-53136 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in other ways, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution act under German Copyright Law. Springer is a part of Springer Science+Business Media springeronline.com © Springer-Verlag Berlin Heidelberg 2007 Printed in Germany The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Product Liability: The data and other information in this handbook have been carefully extracted and evaluated by experts from the original literature. Furthermore, they have been checked for correctness by authors and the editorial staff before printing. Nevertheless, the publisher can give no guarantee for the correctness of the data and information provided. In any individual case of application, the respective user must check the correctness by consulting other relevant sources of information. Cover layout: Erich Kirchner, Heidelberg Typesetting: Materials Science International Services GmbH, Stuttgart Printing and Binding: AZ Druck, Kempten/Allgäu

SPIN: 10916025

63/3020 - 5 4 3 2 1 0 – Printed on acid-free paper

Editors:

Günter Effenberg Svitlana Ilyenko

MSI, Materials Science International Services GmbH Postfach 800749, D-70507, Stuttgart, Germany http://www.matport.com

Authors:

Materials Science International Team, MSIT®

The present series of books results from collaborative evaluation programs performed by MSI and authored by MSIT®. In this program data and knowledge are contributed by many individuals and accumulated over almost twenty years, now. The content of this volume is a subset of the ongoing MSIT® Evaluation Programs. Authors of this volume are: Nataliya Bochvar, Moscow, Russia

Evgenia Lysova, Moscow, Russia

Anatoliy Bondar, Kyiv, Ukraine

Pierre Perrot, Lille, France

Tatyana Dobatkina, Moscow, Russia

Alan Prince †, Harpenden, U.K.

Olga Fabrichnaya, Stuttgart, Germany

Qingsheng Ran, Stuttgart, Germany

Gautam Ghosh, Evanston, USA

Peter Rogl, Wien, Austria

Joachim Gröbner, Clausthal-Zellerfeld, Germany

Lazar Rokhlin, Moscow, Russia

Katharina Haußmann, Stuttgart, Germany

Myriam Sacerdote-Peronnet, Lyon, France

Volodymyr Ivanchenko, Kyiv, Ukraine

Stephan Schittny, Hanau, Germany

Yan Jialin, Guangxi, China

Rainer Schmid-Fetzer, Clausthal-Zellerfeld, Germany

Jozefien De Keyzer, Leuven, Belgium

Elena L. Semenova, Kyiv, Ukraine

Ulrich E. Klotz, Dübendorf, Switzerland

Oleh Shcherban, L'viv, Ukraine

Kostyantyn Korniyenko, Kyiv, Ukraine

Nuri Solak, Stuttgart, Germany

Tatiana Kosorukova, Kyiv, Ukraine

Vasyl Tomashik, Kyiv, Ukraine

Ortrud Kubashewski, Aachen, Germany

Ludmila Tretyachenko, Kyiv, Ukraine

K.C. Hari Kumar, Chennai, India

Mikhail Turchanin, Kramatorsk, Ukraine

Viktor Kuznetsov, Moscow, Russia

Tamara Velikanova, Kyiv, Ukraine

Nathalie Lebrun, Lille, France

Sigrid Wagner, Stuttgart, Germany

Yurii Liberov, Moscow, Russia

Andy Watson, Leeds, U.K.

Chunlei Liu, Dübendorf, Switzerland

Viktor Witusiewicz, Aachen, Germany

Jörg F. Löffler, Dübendorf, Switzerland

Matvei Zinkevich, Stuttgart, Germany

Hans Leo Lukas, Stuttgart, Germany

Institutions The content of this volume is produced by Materials Science International Services GmbH and the international team of materials scientists, MSIT®. Contributions to this volume have been made from the following institutions: Access, Aachen, Germany

Laboratoire des Multimatériaux et Interfaces, Université Claude Bernard Lyon I

The Baikov Institute of Metallurgy, Academy of Sciences, Moscow, Russia

Max-Planck Institut für Metallforschung, Institut für Werkstoffwissenschaft, Pulvermetallurgisches Laboratorium, Stuttgart, Germany

Donbass State Mechanical Engineering Academy, Kramatorsk, Ukraine

Moscow State University, Department of General Chemistry, Moscow, Russia

EMPA, Materials Science and Technology Laboratory of Joining and Interface Technology, Dübendorf, Switzerland

National University of L'viv, Cathedra of Inorganic Chemistry, L'viv, Ukraine

I.M. Frantsevich Institute for Problems of Materials Science, National Academy of Sciences, Kyiv, Ukraine

Northwestern University, Department of Materials Science and Engineering, Evanston, USA

Heraeus GmbH, Hanau, Germany

RWTH Aachen, Germany

Indian Institute of Technology Madras, Department of Metallurgical Engineering, Chennai, India

Technische Universität Clausthal, Metallurgisches Zentrum, Clausthal-Zellerfeld, Germany

Institute of Materials Science, Guangxi University, Nanning, China

Université de Lille I, Laboratoire de Métallurgie Physique, Villeneuve d’ASCQ, Cedex, France

Institute for Semiconductor Physics, National Academy of Sciences, Kyiv, Ukraine

Universität Wien, Institut für Physikalische Chemie, Wien, Austria

Katholieke Universiteit Leuven, Department Metaalkunde en Toegepaste Materiaalkunde, Heverlee, Belgium

University of Leeds, Department of Materials, School of Process, Environmental and Materials Engineering, Leeds, UK

G.V. Kurdyumov Institute for Metal Physics, National Academy of Sciences, Kyiv, Ukraine

Preface The growing need to develop Pb free solder alloys less damaging for the environment is causing increased research into candidate materials systems, such as those evaluated in this volume. However the lead-tin solder alloys are still commonly used and dominate the industrial market by far. A candidate lead free solder alloy must fulfill many requirements: wettability of the substrate, ability to form a strong chemical bond with the substrate, suitable melting and solidification behavior, good mechanical properties, corrosion resistance, electrical conductivity and it must not be harmful to health and environment. We included in this volume ternary systems from which one may arrive at alloys that satisfy the above requirements and are therefore promising candidates for the development of such soldering and brazing materials. But also other important solder or braze systems which are presently in use are included in this volume. The sub-series Ternary Alloy Systems of the Landolt-Börnstein New Series provides reliable and comprehensive descriptions of the materials constitution, based on critical intellectual evaluations of all data available at the time, and it critically weights the different findings, also with respect to their compatibility with today’s edge binary phase diagrams. Selected are ternary systems of importance to industrial alloy development and systems which gained scientific interest in the recent years otherwise. In a ternary materials system, however, one may find alloys for various applications, depending on the chosen composition. Reliable phase diagrams provide scientists and engineers with basic information of eminent importance for fundamental research and for the development and optimization of materials. So collections of such diagrams are extremely useful, if the data on which they are based have been subjected to critical evaluation, like in these volumes. Critical evaluation means: where contradictory information is published data and conclusions are being analyzed, broken down to the firm facts and reinterpreted in the light of all present knowledge. Depending on the information available this can be a very difficult task to achieve. Critical evaluations establish descriptions of reliably known phase configurations and related data. The evaluations are performed by MSIT®, Materials Science International Team, a group which has been working together for 20 years now. Within this team skilled expertise is available for a broad range of methods, materials and applications. This joint competence is employed in the critical evaluation of the often conflicting literature data. Particularly helpful in this are targeted thermodynamic calculations for individual equilibria, driving forces or complete phase diagram sections. Insight in materials constitution and phase reactions is gained from many distinctly different types of experiments, calculation and observations. Intellectual evaluations which interpret all data simultaneously reveal the chemistry of a materials system best. The conclusions on the phase equilibria may be drawn from direct observations e.g. by microscope, from monitoring caloric or thermal effects or measuring properties such as electric resistivity, electro-magnetic or mechanical properties. Other examples of useful methods in materials chemistry are mass-spectrometry, thermo-gravimetry, measurement of electro-motive forces, X-ray and microprobe analyses. In each published case the applicability of the chosen method has to be validated, the way of actually performing the experiment or computer modeling has to be validated and the interpretation of the results with regard to the material’s chemistry has to be verified. An additional degree of complexity is introduced by the material itself, as the state of the material under test depends heavily on its history, in particular on the way of homogenization, thermal and mechanical treatments. All this is taken into account in an MSIT® expert evaluation. To include binary data in the ternary evaluation is mandatory. Each of the three-dimensional ternary phase diagrams has edge binary systems as boundary planes; their data have to match the ternary data smoothly. At the same time each of the edge binary systems A-B is a boundary plane for many ternary A-

B-X systems. Therefore combining systematically binary and ternary evaluations can lead to a level of increased confidence and reliability in both ternary and binary phase diagrams. This has started systematically for the first time here, by the MSIT® Evaluation Programs applied to the LandoltBörnstein New Series. The multitude of correlated or inter-dependant data requires special care. Within MSIT® an evaluation routine has been established that proceeds knowledge driven and applies both human based expertise and electronically formatted data and software tools. MSIT® internal discussions take place in almost all evaluation works and on many different specific questions, adding the competence of a team to the work of individual authors. In some cases the authors of earlier published work contributed to the knowledge base by making their original data records available for re-interpretation. All evaluation reports published here have undergone a thorough review process in which the reviewers had access to all the original data. In publishing we have adopted a standard format that provides the reader with the data for each ternary system in a concise and consistent manner, as applied in the MSIT® Workplace: Phase Diagrams Online. The standard format and special features of the Landolt-Börnstein compendium are explained in the Introduction to the volume. In spite of the skill and labor that have been put into this volume, it will not be faultless. All criticisms and suggestions that can help us to improve our work are very welcome. Please contact us via [email protected]. We hope that this volume will prove to be an as useful tool for the materials scientist and engineer as the other volumes of Landolt-Börnstein New Series and the previous works of MSIT® have been. We hope that the Landolt-Börnstein Sub-series Ternary Alloy Systems will be well received by our colleagues in research and industry. On behalf of the participating authors we want to thank all those who contributed their comments and insight during the evaluation process. In particular we thank the reviewers – Andy Watson, Pierre Perrot, Rainer Schmid-Fetzer, Olga Fabrichnaya, Hari Kumar, Gabriele Cacciamani, Matvei Zinkevich, Artem Kozlov, Ludmila Tretyachenko, Joachim Gröbner, Hans Leo Lukas, Yong Du, Marina Bulanova. Special thanks go to Oleksandr Dovbenko who very competently helped the editors to supervise the review and helped the authors in discussing questionable matters. We all gratefully acknowledge the dedicated desk editing by Oleksandra Berezhnytska, Oleksandr Rogovtsov, and Vyacheslav Saltykov.

Günter Effenberg and Svitlana Ilyenko

Stuttgart, March 2006

Contents IV/11 Ternary Alloy Systems Phase Diagrams, Crystallographic and Thermodynamic Data Subvolume C: Non-Ferrous Metal Systems Part 3: Selected Soldering and Brazing Systems

Introduction Data Covered ..................................................................................................................................XI General............................................................................................................................................XI Structure of a System Report ..........................................................................................................XI Introduction..........................................................................................................................XI Binary Systems ....................................................................................................................XI Solid Phases ....................................................................................................................... XII Quasibinary Systems......................................................................................................... XIII Invariant Equilibria ........................................................................................................... XIII Liquidus, Solidus, Solvus Surfaces................................................................................... XIII Isothermal Sections........................................................................................................... XIII Temperature – Composition Sections ............................................................................... XIII Thermodynamics .............................................................................................................. XIII Notes on Materials Properties and Applications............................................................... XIII Miscellaneous ................................................................................................................... XIII References.........................................................................................................................XVI General References .................................................................................................................... XVII

Ternary Systems Ag – Bi – Cu (Silver – Bismuth – Copper).......................................................................................1 Ag – Bi – Sn (Silver – Bismuth – Tin)..............................................................................................4 Ag – Cu – In (Silver – Copper – Indium) .......................................................................................18 Ag – Cu – Mn (Silver – Copper – Manganese) ..............................................................................26 Ag – Cu – Ni (Silver – Copper – Nickel) .......................................................................................30 Ag – Cu – P (Silver – Copper – Phosphorus) .................................................................................38 Ag – Cu – Sn (Silver – Copper – Tin) ............................................................................................47 Ag – Cu – Ti (Silver – Copper – Titanium) ....................................................................................63 Ag – Cu – Zn (Silver – Copper – Zinc) ..........................................................................................75 Ag – In – Sb (Silver – Indium – Antimony) ...................................................................................86 Ag – In – Sn (Silver – Indium – Tin)..............................................................................................96 Ag – Pb – Sn (Silver – Lead – Tin)...............................................................................................113 Ag – Sn – Zn (Silver – Tin – Zinc) ...............................................................................................121 Au – Bi – Sn (Gold – Bismuth – Tin) ...........................................................................................131 Au – Cu – Sn (Gold – Copper – Tin)............................................................................................138 Au – In – Sn (Gold – Indium – Tin) .............................................................................................149 B – Cr – Ni (Boron – Chromium – Nickel) ..................................................................................153 Bi – In – Sb (Bismuth – Indium – Antimony)...............................................................................168

Bi – In – Sn (Bismuth – Indium – Tin) .........................................................................................191 Bi – Sn – Zn (Bismuth – Tin – Zinc) ............................................................................................202 Co – Cu – Mn (Cobalt – Copper – Manganese)............................................................................212 Cr – Ni – P (Chromium – Nickel – Phosphorus) ..........................................................................222 Cr – Ni – Si (Chromium – Nickel – Silicon).................................................................................229 Cu – In – Sn (Copper – Indium – Tin)..........................................................................................249 Cu – Mn – Ni (Copper – Manganese – Nickel) ............................................................................274 Cu – Mn – Sn (Copper – Manganese – Tin) .................................................................................286 Cu – Ni – Sn (Copper – Nickel– Tin) ...........................................................................................303 Cu – Ni – Zn (Copper – Nickel – Zinc) ........................................................................................338 Cu – P – Sn (Copper – Phosphorus – Tin)....................................................................................355 Cu – Pb – Sn (Copper – Lead – Tin).............................................................................................368 Cu – Pd – Sn (Copper – Palladium – Tin) ....................................................................................390 Cu – Si – Zn (Copper – Silicon – Zinc) ........................................................................................393 Cu – Sn – Ti (Copper – Tin – Titanium).......................................................................................409 Cu – Sn – Zn (Copper – Tin – Zinc) .............................................................................................422 Cu – Ti – Zr (Copper – Titanium – Zirconium)............................................................................436 In – Ti – Zn (Indium – Tin – Zinc) ...............................................................................................465 Mn– Ti – Zr (Manganese – Titanium – Zirconium)......................................................................475 Ni – Pd – Si (Nickel – Palladium – Silicon) .................................................................................486

Free WEB Access to update information and more. Content updates of the Landolt-Börnstein sub-series IV/11 plus supplementary information are available from MSI, including: • • • •

Links to Literature (up-to-date bibliographic data base) Diagrams as Published (not MSIT®-evaluated diagrams) Research Results (published and proprietary data) Ternary Evaluations: These are LB IV/11 contents and their updates (if any) as interactive live diagrams & documents.

This service is free of charge for Landolt-Börnstein subscribers and applies for material systems included in the sub-series IV/11. As eligible Springer customer, please contact MSI for access at [email protected] . Contents and supplementary information to the Landolt-Boernstein sub-series IV/11 are made by MSI, Materials Science International Services, GmbH, Stuttgart and its global team MSIT®, as part of their ongoing Phase Diagram Evaluation Programs. For details on “MSIT® Workplace, Phase Diagrams Online” see: http://www.matport.com .

Introduction

XI

Introduction Data Covered The series focuses on light metal ternary systems and includes phase equilibria of importance for alloy development, processing or application, reporting on selected ternary systems of importance to industrial light alloy development and systems which gained otherwise scientific interest in the recent years.

General The series provides consistent phase diagram descriptions for individual ternary systems. The representation of the equilibria of ternary systems as a function of temperature results in spacial diagrams whose sections and projections are generally published in the literature. Phase equilibria are described in terms of liquidus, solidus and solvus projections, isothermal and pseudobinary sections; data on invariant equilibria are generally given in the form of tables. The world literature is thoroughly and systematically searched back to the year 1900. Then, the published data are critically evaluated by experts in materials science and reviewed. Conflicting information is commented upon and errors and inconsistencies removed wherever possible. It considers those, and only those data, which are firmly established, comments on questionable findings and justifies re-interpretations made by the authors of the evaluation reports. In general, the approach used to discuss the phase relationships is to consider changes in state and phase reactions which occur with decreasing temperature. This has influenced the terminology employed and is reflected in the tables and the reaction schemes presented. The system reports present concise descriptions and hence do not repeat in the text facts which can clearly be read from the diagrams. For most purposes the use of the compendium is expected to be selfsufficient. However, a detailed bibliography of all cited references is given to enable original sources of information to be studied if required.

Structure of a System Report The constitutional description of an alloy system consists of text and a table/diagram section which are separated by the bibliography referring to the original literature (see Fig. 1). The tables and diagrams carry the essential constitutional information and are commented on in the text if necessary. Where published data allow, the following sections are provided in each report: Introduction The opening text reviews briefly the status of knowledge published on the system and outlines the experimental methods that have been applied. Furthermore, attention may be drawn to questions which are still open or to cases where conclusions from the evaluation work modified the published phase diagram. Binary Systems Where binary systems are accepted from standard compilations reference is made to these compilations. In other cases the accepted binary phase diagrams are reproduced for the convenience of the reader. The selection of the binary systems used as a basis for the evaluation of the ternary system was at the discretion of the assessor.

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XII

Introduction

Heading Introduction Binary Systems Solid Phases Quasibinary Systems Invariant Equilibria Text

Liquidus, Solidus, Solvus Surfaces Isothermal Sections Temperature-Composition Sections Thermodynamics Notes on Materials Properties and Applications Miscellaneous

References Miscellaneous Notes on Materials Properties and Applications Thermodynamics Temperature-Composition Sections Tables and diagrams

Isothermal Sections Liquidus, Solidus, Solvus Surfaces Invariant Equilibria Quasibinary Systems Solid Phases Binary Systems

Fig. 1: Structure of a system report

Solid Phases The tabular listing of solid phases incorporates knowledge of the phases which is necessary or helpful for understanding the text and diagrams. Throughout a system report a unique phase name and abbreviation is allocated to each phase. Phases with the same formulae but different space lattices (e.g. allotropic transformation) are distinguished by: – small letters (h), high temperature modification (h2 > h1) (r), room temperature modification (1), low temperature modification (l1 > l2) – Greek letters, e.g., J, J' – Roman numerals, e.g., (I) and (II) for different pressure modifications. In the table “Solid Phases” ternary phases are denoted by * and different phases are separated by horizontal lines.

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Introduction

XIII

Quasibinary Systems Quasibinary (pseudobinary) sections describe equilibria and can be read in the same way as binary diagrams. The notation used in quasibinary systems is the same as that of vertical sections, which are reported under “Temperature – Composition Sections”. Invariant Equilibria The invariant equilibria of a system are listed in the table “Invariant Equilibria” and, where possible, are described by a constitutional “Reaction Scheme” (Fig. 2). The sequential numbering of invariant equilibria increases with decreasing temperature, one numbering for all binaries together and one for the ternary system. Equilibria notations are used to indicate the reactions by which phases will be – decomposed (e- and E-type reactions) – formed (p- and P-type reactions) – transformed (U-type reactions) For transition reactions the letter U (Übergangsreaktion) is used in order to reserve the letter T to denote temperature. The letters d and D indicate degenerate equilibria which do not allow a distinction according to the above classes. Liquidus, Solidus, Solvus Surfaces The phase equilibria are commonly shown in triangular coordinates which allow a reading of the concentration of the constituents in at.%. In some cases mass% scaling is used for better data readability (see Figs. 3 and 4). In the polythermal projection of the liquidus surface, monovariant liquidus grooves separate phase regions of primary crystallization and, where available, isothermal lines contour the liquidus surface (see Fig. 3). Isothermal Sections Phase equilibria at constant temperatures are plotted in the form of isothermal sections (see Fig. 4). Temperature – Composition Sections Non-quasibinary T-x sections (or vertical sections, isopleths, polythermal sections) show the phase fields where generally the tie lines are not in the same plane as the section. The notation employed for the latter (see Fig. 5) is the same as that used for binary and pseudobinary phase diagrams. Thermodynamics Experimental ternary data are reported in some system reports and reference to thermodynamic modelling is made. Notes on Materials Properties and Applications Noteworthy physical and chemical materials properties and application areas are briefly reported if they were given in the original constitutional and phase diagram literature. Miscellaneous In this section noteworthy features are reported which are not described in preceding paragraphs. These include graphical data not covered by the general report format, such as lattice spacing – composition data, p-T-x diagrams, etc.


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MSIT®

Ag-Tl

Tl-Bi

144 e9 (Tl)(h) Tl3Bi+(Tl)(r)

192 e8 l Tl3Bi+Tl2Bi3

202 e7 l (Bi)+Tl2Bi3

294 e2 (max) L (Ag) + Tl3Bi

Ag-Tl-Bi

144 (Tl)(h) Tl3Bi + (Tl)(r),(Ag)

equation of eutectoid reaction at 144°C

(Ag)+(Tl)(r)+Tl3Bi

E2

D1

(Ag)+Tl3Bi+Tl2Bi3

188 L (Ag)+Tl3Bi+Tl2Bi3

(Ag)+(Bi)+Tl2Bi3

197 L (Ag)+(Bi)+Tl2Bi3

207 e6 (max) L (Ag) + Tl2Bi3

(Ag) + (Tl)(h) + Tl3Bi

E1

ternary maximum

289 L + Tl3Bi (Ag) + (Tl)(h) U1 289 e4 (min) L (Ag) + (Tl)(h)

first binary eutectic reaction (highest temperature)

303 e1 l (Tl)(h)+Tl3Bi

Fig 2: Typical reaction scheme

234 d1 (Tl)(h) (Tl)(r),(Ag)

291 e3 l (Ag)+(Tl)(h)

second binary eutectic reaction

261 e5 l (Ag) + (Bi)

Bi-Ag

second ternary eutectic reaction

monovariant equilibrium stable down to low temperatures

reaction temperature of 261°C

XIV Introduction


Introduction

XV

C

Data / Grid: at.% Axes: at.%

δ

p1

700

20

80

500°C isotherm, temperature is usually in °C primary γ -crystallization

γ

40

400°C

300

estimated 400°C isotherm

e2

U

e1

40

300

300

400

α

0 40

80

β (h)

E

50 0

60

liquidus groove to decreasing temperatures

60

0 40

binary invariant reaction ternary invariant reaction

50 0

0 70

20

limit of known region

20

A

40

60

80

B

Fig. 3: Hypothetical liquidus surface showing notation employed

C

Data / Grid: mass% Axes: mass%

phase field notation estimated phase boundary

20

γ

80

γ +β (h)

40

phase boundary

60

three phase field (partially estimated) experimental points (occasionally reported)

L+γ 60

40

tie line

L+γ +β (h)

β (h)

L

80

L+β (h)

L+α

20

limit of known region

α

Al

20

40

60

80

B

Fig. 4: Hypothetical isothermal section showing notation employed Landolt-Börnstein New Series IV/11C3

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XVI

Introduction

750

phase field notation

Temperature, °C

L 500

L+β (h)

L+α

concentration of abscissa element

32.5%

250

β (h)

L+α +β (h)

temperature, °C β (h) - high temperature modification β (r) - room temperature modification β (r) alloy composition in at.%

188

α α +β (h) 0

A B C

80.00 0.00 20.00

60

40

Al, at.%

20

A B C

0.00 80.00 20.00

Fig. 5: Hypothetical vertical section showing notation employed

References The publications which form the bases of the assessments are listed in the following manner: [1974Hay] Hayashi, M., Azakami, T., Kamed, M., “Effects of Third Elements on the Activity of Lead in Liquid Copper Base Alloys” (in Japanese), Nippon Kogyo Kaishi, 90, 51-56 (1974) (Experimental, Thermodyn., 16) This paper, for example, whose title is given in English, is actually written in Japanese. It was published in 1974 on pages 51- 56, volume 90 of Nippon Kogyo Kaishi, the Journal of the Mining and Metallurgical Institute of Japan. It reports on experimental work that leads to thermodynamic data and it refers to 16 crossreferences. Additional conventions used in citing are: # to indicate the source of accepted phase diagrams * to indicate key papers that significantly contributed to the understanding of the system. Standard reference works given in the list “General References” are cited using their abbreviations and are not included in the reference list of each individual system.

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Introduction

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General References [C.A.] [Curr.Cont.] [E] [G] [H] [L-B]

[Mas] [Mas2] [P] [S] [V-C] [V-C2]


Chemical Abstracts - pathways to published research in the world's journal and patent literature - http://www.cas.org/ Current Contents - bibliographic multidisciplinary current awareness Web resource http://www.isinet.com/products/cap/ccc/ Elliott, R.P., Constitution of Binary Alloys, First Supplement, McGraw-Hill, New York (1965) Gmelin Handbook of Inorganic Chemistry, 8th ed., Springer-Verlag, Berlin Hansen, M. and Anderko, K., Constitution of Binary Alloys, McGraw-Hill, New York (1958) Landolt-Boernstein, Numerical Data and Functional Relationships in Science and Technology (New Series). Group 3 (Crystal and Solid State Physics), Vol. 6, Eckerlin, P., Kandler, H. and Stegherr, A., Structure Data of Elements and Intermetallic Phases (1971); Vol. 7, Pies, W. and Weiss, A., Crystal Structure of Inorganic Compounds, Part c, Key Elements: N, P, As, Sb, Bi, C (1979); Group 4: Macroscopic and Technical Properties of Matter, Vol. 5, Predel, B., Phase Equilibria, Crystallographic and Thermodynamic Data of Binary Alloys, Subvol. a: Ac-Au ... Au-Zr (1991); Springer-Verlag, Berlin. Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, ASM, Metals Park, Ohio (1986) Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio (1990) Pearson, W.B., A Handbook of Lattice Spacings and Structures of Metals and Alloys, Pergamon Press, New York, Vol. 1 (1958), Vol. 2 (1967) Shunk, F.A., Constitution of Binary Alloys, Second Supplement, McGraw-Hill, New York (1969) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, ASM, Metals Park, Ohio (1985) Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

MSIT®

IV/11 Ternary Alloy Systems Phase Diagrams, Crystallographic and Thermodynamic Data Subvolume C: Non-Ferrous Metal Systems Part 3: Selected Soldering and Brazing Systems Ag - …

Au - …

B-…

Bi - …

Co - …

Ag - Bi - Cu Ag - Bi - Sn Ag - Cu - In Ag - Cu - Mn Ag - Cu - Ni Ag - Cu - P Ag - Cu - Sn Ag - Cu - Ti Ag - Cu - Zn Ag - In - Sb Ag - In - Sn Ag - Pb - Sn Ag - Sn - Zn

Au - Bi - Sn Au - Cu - Sn Au - In - Sn

B - Cr - Ni

Bi - In - Sb Bi - In - Sn Bi - Sn - Zn

Co - Cu - Mn

Cr - …

Cu - …

In - …

Mn - …

Ni - …

Cr - Ni - P Cr - Ni - Si

Cu - In - Sn Cu - Mn - Ni Cu - Mn - Sn Cu - Ni - Sn Cu - Ni - Zn Cu - P - Sn Cu - Pb - Sn Cu - Pd - Sn Cu - Si - Zn Cu - Sn - Ti Cu - Sn - Zn Cu - Ti - Zr

In - Ti - Zn

Mn - Ti - Zr

Ni - Pd - Si

Ag–Bi–Cu

1

Silver – Bismuth – Copper Joachim Gröbner Introduction The first data on the Ag-Bi-Cu system were reported by [1951Ava], who considered microstructure of alloys near the binary Ag-Cu eutectic depending on the cooling rate. [1976Zan] reported results of rapid quench-cooling experiments in the Ag rich part of the system. A eutectic reaction was found to exist at 240 5°C, but the phases in equilibrium were not specified. This work was reviewed by [1980Hen] and [1988Hen]. [1988Liu, 1989Liu] investigated the entire ternary system in 12 vertical sections by thermoanalysis (DTA) in an atmosphere of dry nitrogen. They found that the ternary Ag-Bi-Cu system is a simple eutectic one with the invariant reaction at 258°C. [1998Shu] has calculated the liquidus surface using a model of ideal solution of self-associates and compared the result with that measured by [1989Liu]. [2004Doi] has presented the primary crystallization surfaces and liquidus isotherms calculated using Calphad method and the thermodynamic parameters for the three binary systems. A good agreement was found between the results of calculation and the experimental data by [1989Liu]. Binary Systems The binary systems Ag-Cu and Bi-Cu are accepted from the MSIT Evaluation Program [2002Rom] and [2002Cac], respectively. The Ag-Bi phase diagram is accepted from [Mas2]. Solid Phases No ternary phases were found in this system. The crystallographic data of the phases in the Ag-Cu-Bi system and their ranges of stability are listed in Table 1. Invariant Equilibria One invariant eutectic reaction: L (Ag) + (Cu) + (Bi) at 258°C exists in the ternary system [1989Liu]. The composition of the liquid phase is given in Table 2. Liquidus Surface The liquidus surface after [1989Liu] is given in Fig. 1. Notes on Materials Properties and Applications The Ag-Bi-Cu system is a part of the Ag-Bi-Cu-Sn system which has been enumerated as a strong potential candidate alloy for a lead-free solder [2004Doi]. References [1951Ava] [1976Zan]

[1980Hen] [1988Hen]


Avakyan, S.V., Lashko, N.F., “Crystallization of Binary Eutectics in Ternary Systems” (in Russian), Zh. Fiz. Khim., 25, 1085-1091 (1951) (Experimental, 2) Zanicchi, G., Ferro, R., Marazza, R., Contardi, V., “Some Metastable Ag-Rich Alloys in the Silver-Bismuth-Copper System”, J. Less-Common Met., 50, 151-154 (1976) (Experimental, 6) Henig, E.T., “The Ag-Bi-Cu (Silver-Bismuth-Copper) System”, Bull. Alloy Phase Diagrams, 1(2), 62 (1980) (Abstract, 1) Henig, E.T., “Silver - Bismuth - Copper”, MSIT Ternary Evaluation Program, in MSIT Workplace, Effenberg G. (Ed.), MSI, Materials International Services GmbH, Stuttgart, Document ID: 10.12132.1.20, (1988) (Crys. Structure, Phase Diagram, Assessment, 1)

MSIT®

Ag–Bi–Cu

2 [1988Liu]

[1989Liu] [1994Sub] [1998Shu]

[2002Cac]

[2002Rom]

[2004Doi]

Liu, S., Sun, W., Wenqing, “Liquidus of the Silver-Copper-Bismuth System” (in Chinese), Jinshu Xuebao, 24(5), B376-B378 (1988) (Experimental, Phase Diagram, Phase Relations, #, 1) Liu, S., Sun, W., “Liquidus of Ag-Cu-Bi System”, Acta Metall. Sinica, 2B(2), 151-152 (1989) (Experimental, Phase Diagram, #, 1) Subramanian, P.R., Perepezko, J.H., “Ag-Cu (Silver - Copper)”, J. Phase Equilib., 14, 62-75 (1994) (Crys. Structure, Phase Diagram, Review, Thermodyn., 81) Shunyaev, K.Y., Tkachev, N.C., Vatolin, N.A., “Liquidus Surface and Association in Eutectic Ternary Alloys”, Thermochim. Acta, 314, 299-306 (1998) (Calculation, Phase Relations, Thermodyn., #, 21) Cacciamini, G., Cornish, L., Saltykov, P., “Bi-Cu (Bismuth - Copper)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg G. (Ed.), MSI, Materials International Services GmbH, Stuttgart, Document ID: 20.19587.1.20, (2002) (Crys. Structure, Phase Diagram, Assessment, 13) Rompaey, T. van, Rogl, P., “Ag-Cu (Silver - Copper)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg G. (Ed.), MSI, Materials International Services GmbH, Stuttgart, Document ID: 20.14511.1.20, (2002) (Crys. Structure, Phase Diagram, Assessment, 29) Doi, K., Othani, H., Hasebe, M., “Thermodynamic Study of the Phase Equilibria in the Sn-Ag-Bi-Cu Quaternary System”, Mater. Trans., 45(2), 380-383 (2004) (Calculation, Phase Diagram, Thermodyn., 9)

Table 1: Crystallographic Data of Solid Phases Phase/ Temperature Range [°C]

Pearson Symbol/ Space Group/ Prototype

Lattice Parameters Comments/References [pm]

(Ag) < 961.93

cF4 Fm3m Cu

a = 408.57

(Cu) < 1084.62

cF4 Fm3m Cu

(Bi) < 271.442

pure Ag at 25°C [Mas2] dissolves 14 at.% Cu [Mas2, 2002Rom] dissolves 5 at.% Ag [Mas2, 2002Rom], 0.0193 at.% Bi [Mas2, 2002Cac] at 25°C [Mas2] melting point [1994Sub, 2002Rom]

a = 361.46

hR6 R3m As

a = 363.7

pure Cu at 19°C [Mas2, 2002Rom]

a = 454.613 c = 1186.152

at 31°C [V-C2, 2002Cac]

Table 2: Invariant Equilibria Reaction L (Ag) + (Cu) + (Bi)

MSIT®

T [°C]

258

Type

E

Phase

L

Composition (at.%) Ag

Cu

Bi

5.0

0.5

94.5


Ag–Bi–Cu

3

Bi Fig. 1: Ag-Bi-Cu. Liquidus surface projection


e3 400°C

(Bi) e2 E 20

600 80

650 700 40

60

500 750 60

40

800 850

(Cu)

80

20

900 950 (Ag)

Ag


1000 20

40 e1

60

80

Cu

MSIT®

4

Ag–Bi–Sn

Silver – Bismuth – Tin Andy Watson Introduction The Ag-Bi-Sn system has been the subject of intense scrutiny in recent years owing to its possible application as a lead free solder material. However, the vast majority of the interest has been with respect to physical and mechanical properties rather than phase equilibria. Numerous reviews have appeared in the literature [1997Hua, 1997Lee, 1999Ohn, 2001Kat, 2001Sug, 2003Ohn] covering mechanical and physical property studies but all refer ultimately to the same small body of work conducted on the phase equilibria. Studies of the phase equilibria in the ternary system began with a thermodynamic calculation by [1994Kat] that used thermodynamic descriptions of the associated binary systems to extrapolate into the three component system. Predicted liquidus temperatures agreed well with experimental observations using DTA studies of two alloys (Ag3.32-Bi1.14-Sn94.55 and Ag2.91-Bi42.84-Sn54.25). However, the first extensive study of the chemistry of the system was conducted by [1994Has]. Enthalpies of formation of the ternary liquid was measured by high temperature calorimetry at 783 and 878 K along sections Ag:Bi 1:3 and 1:1, Ag:Sn 1:4 and 1:1 and Bi:Sn 1:3, 1:1 and 3:1. High purity materials were used (Ag 99.998, Bi 99.999, Sn 99.999). The results were interpolated in order to construct isoenthalpic curves using models given in [1965Too, 1984Hoc]. By noting deviations in the enthalpy curves, it was possible to present an approximation of the liquidus surface. To complement the work on thermodynamic properties, [1998Has] made an extensive study of the phase equilibria in the ternary system using X-ray powder diffraction, DSC and DTA. Samples of Ag(4N), Bi(5N) and Sn(5N) were sealed in evacuated silica tubes before melting and cooling to an annealing temperature between 120 and 250°C, where they were held for 15 d. A variety of heating and cooling rates were used in the thermal studies (0.1-2°C#min–1), the lowest of which was used for the determination of the invariant temperatures. Three isoplethal sections were characterized (10 at.% Bi, 40 at.% Ag and 70 at.% Bi) and three ternary invariant reactions were found. The locations of two of these were within approximately 2°C the extrapolations of [1994Kat], the third however, was around 23°C higher. More recently, a complete thermodynamic assessment of the ternary system has been presented by [2001Oht] (which was used subsequently in a calculation of the quaternary Ag-Bi-Sn-Zn by [2004Oht]). Firstly, they performed DSC studies along isoplethal sections with 10, 20, 30, 40, 50, 60, 70 and 80 at.% Bi. Sn(99.999%), Ag(99.99%) and Bi(99.99%) were homogenized at 1100°C in sealed quartz tubes and quenched into iced brine before the DSC studies. Peaks were recorded on heating and cooling at 3°C#min–1. Isothermal sections at 200 and 400°C were produced from EDX studies of alloys which had been sealed in argon filled silica tubes and equilibrated for 14 and 7 d, respectively. Using the experimental data of [1994Has, 1998Has] and the results of their own DSC and EDX studies, they produced a thermodynamic description of the system that is in good agreement with all of the available experimental data. Interaction parameters were introduced for the liquid and the phases, and Bi was allowed to substitute for Sn in the model for the Ag3Sn compound. This latter aspect of the modeling was necessary to make the phase boundaries involving this phase in the ternary system fit the experimental data, despite the fact that little solubility of Bi in this phase has been found experimentally. A reaction scheme is also presented showing three invariant equilibria: 2 transition reactions and a ternary eutectic. However, the reaction given at 263.3°C is higher than the binary eutectic in the Ag-Bi system. In order for the ternary reaction to be a transition then there must be a maximum in the monovariant line from the binary Ag-Bi eutectic. This is suggested in [1998Has]. The assessed temperature of this reaction given by [2001Oht] is 263.6°C. [2001Lee] used thermodynamic data to predict viscosity and surface tension of the Ag-Bi-Sn liquid. However, they did not use the data of [2001Oht] but just the descriptions for the binary systems. Nevertheless, they found reasonable agreement with their experimental data.

MSIT®


Ag–Bi–Sn

5

Binary Systems The Ag-Sn binary system is accepted from the thermodynamic assessment of [1999Oht] and is presented in Fig. 1 with an amendment to the Ag3Sn phase showing some homogeneity which was ignored in the modeling. The Ag-Bi and Bi-Sn systems are taken from the thermodynamic assessments of [1993Kar] and [1994Oht], respectively. Solid Phases Solid phases in the system are listed in Table 1. There are no ternary compounds and little experimental evidence of extension of binary phases into the ternary. However, [2001Oht] found that allowing substitution of Bi for Sn in Ag3Sn in the modeling of the system resulted in a better fit of the calculated phase boundaries to the experimental data. Invariant Equilibria Three invariant equilibria exist in this system. Details are given in Table 2 and the reaction scheme is given in Fig. 2. The reaction scheme is based on [2001Oht]. Liquidus, Solidus and Solvus Surfaces The liquidus surface is shown in Fig. 3. The primary crystallization fields are given by [2001Oht] whereas the liquidus isothermal lines are experimentally determined from calorimetric (605 and 510°C) and differential thermal analysis (477, 427 ant 377°C) measurements of [1994Has]. The liquidus isothermal lines in the Sn rich corner of the system (< 60 at.% Bi, < 7 at.% Ag), taken from [2001Kat] are given in Fig. 4. The enthalpies of mixing of the liquid phase as measured by [1994Has] are exothermic in the Ag rich corner, and endothermic in the main part of the diagram suggesting, along with the shape of the liquidus curves in the Ag-Bi and Bi-Sn systems, the presence of a metastable miscibility gap. This is shown in Fig. 5, taken from the assessment of [2001Oht]. Isothermal Sections Isothermal sections for temperatures of 400 and 200°C are given in Figs. 6 and 7, taken from [2001Oht]. Slight alterations have been made to the Ag3Sn phase to show a degree of homogeneity in agreement with Fig. 1. The extension of the Ag3Sn phase into the ternary system is a product of the optimization of the system without any supporting experimental evidence, but it was necessary for it to be included as discussed above. Temperature – Composition Sections Calculated temperature-composition sections taken from [2001Oht] are given in Figs. 8-13, and are based on experimental observations. Most of the phase boundaries in the calculations agree well with the experimental data which were used in the optimization. However, no experimental data were available for the Ag rich regions at low temperatures, and hence this part of the diagrams should be treated with a degree of caution. Thermodynamics [1994Has] measured by direct reaction calorimetry the enthalpies of formation of liquid (Ag,Bi) and (Ag,Bi,Sn) alloys at 510 and 605°C along different sections characterized by Ag/Bi = 1 (40 alloys) and 1/3 (38 alloys), Ag/Sn = 1 (35 alloys) and 1/4 (30 alloys), Bi/Sn = 1/3 (30 alloys), 1 (40 alloys) and 3 (29 alloys). Figure 14 shows the experimental isoenthalpic lines drawn at 605°C from [1994Has]. A general expression of the excess Gibbs energy of mixture in the liquid state has been derived by [2001Oht, 2004Oht] as a function of the temperature as part of the assessment of the ternary system. The calculated curves are in excellent agreement with the experimental data of [1994Has]: Landolt-Börnstein New Series IV/11C3

MSIT®

6

Ag–Bi–Sn

mixGxs = xAgxSnLAg,Sn + xBixSnLBi,Sn + xAgxBiLAg,Bi + xAgxBixSnLAg,Bi,Sn LAg,Sn = – 4902.5 + 4.30532T + (– 16 474 + 3.12507T)(xAg – xSn) – 7298.6 (xAg – xSn)2 LBi,Sn = 487 + 0.966T – (32 + 0.235T)(xBi – xSn) LAg,Bi = 4589.8 + 23.73047T – 3.93814TlnT – (5716.6 + 0.91452T)(xAg – xBi) + (– 2630.2 + 0.88522T)(xAg – xBi)2 LAg,Bi,Sn = (1700 + 76.2T)xAg + (11 000 + 4T)xBi + (20 000 – 38.95T)xSn Notes on Materials Properties and Applications Owing to increasing concerns over the use of lead, alloys of the Ag-Bi-Sn system have become of interest as possible replacements for the traditional Pb-Sn solder materials [1994Kat, 1997Hua, 1997Lee]. Consequently, a good deal of research has been conducted on the properties of alloys in this system focusing on Sn rich alloys and of Bi-Sn eutectic alloys with small additions of Ag [2002Kat]. With increasing Bi content, the melting temperature of Ag-Bi-Sn alloys decreases promoting wetting behavior [2002Cho]. When used in conjunction with a copper substrate, this can also be attributed to a reduction in the formation of Cu-Sn compounds owing to the presence of Ag. A small addition of Ag was found to improve significantly the ductility of Bi-Sn eutectic solder [1997McC]. The strength of a solder joint is an important issue; and this increases with increasing strain rate [2004Sho] and increasing Bi content owing to solid solution strengthening [2002Shi], with a corresponding loss in ductility. The bonding strength of Bi-Sn joints near room temperature is higher than that of the Sn-3.5Ag solder, but the ductility is lower [2001Kik]. Creep rate of the materials also increases with increasing Bi content [2002Yu], whereas [1998Kar1, 1998Kar2, 1999Kar, 2001Kar] pointed out than addition of Bi drastically degrades the thermal fatigue resistance of Sn-3.5 at.% Ag solder. The choice of substrate material also affects the strength of the solder joint. Cu increases the strength of the joint whereas Ni/Cu finishes are found to decrease it [2004Hwa]. Rare earth additions can improve the wettability of the liquid solder and increase the strength of the joint by refinement of the (Sn) phase [2002Xia1, 2004Wu]. Although Ag-Bi-Sn solders are superior to other candidates with respect to the melting properties and wettability [2001Bra], they are subject to the fillet-lifting (or lift-off) phenomenon [2001Tak]. Fillet-lifting was shown to occur in alloys (3 to 20 at.% Bi) with insufficient latent heat release near the final solidification temperature for the alleviation of the temperature gradient in the solder joint. Miscellaneous Solder powders can be prepared by mechanical alloying [2003Lai]. Grinding media is very important, ceramic balls providing a stronger impact force. As Ag-Bi-Sn solders have higher melting points (202-225°C) than the most popular eutectic Pb-Sn solder (183°C), [2003Shi] uses indium additions to lower the melting point of the solder alloy and to keep the good wetting performances and good mechanical properties which characterizes Ag-Bi-Sn solders [2002Xia2]. Applying ultrasonic waves to the soldering influences the microstructure [2001Kik] and increases the strength of the bonding interface in the solder joints. The surface tension together with the density was measured for the Ag-Bi-Sn liquid alloys (0 to 80 at.% Bi and 0 to 12 at.% Sn) in the temperature range 225 - 900°C [2001Mos] and for the Ag-Sn eutectic between 230 and 950°C [2004Gas]. A linear dependency with temperature was observed. The addition of Bi to liquid Sn and to Ag-Sn eutectic alloy (3.8 at.% Ag) reduces markedly the surface tension. The wettability of Ag-Bi-Sn solders on Cu was measured by Energy Dispersive X-ray Spectrometry [2002Tan]. The wettability and mechanical properties of solders based on Bi-Sn systems are lower than that of solders based on conventional Pb-Sn systems [1998Her, 1999Via2]. However, it may be enhanced by addition of 1 to

MSIT®


Ag–Bi–Sn

7

4 mass% Ag to the solder. An investigation of the melting properties of the 91.84Sn-3.33Ag-4.83Bi solder [1999Via1] suggested the appearance of a metastable, short-range order as a result of thermal aging at low temperature. The kinetics growth of Cu-Sn layers at the interface solder/Cu was also investigated. References [1965Too] [1984Hoc]

[1993Kar]

[1994Has]

[1994Kat]

[1994Oht]

[1997Hua] [1997Lee] [1997McC]

[1998Has]

[1998Her]

[1998Kar1]

[1998Kar2]

[1999Kar]

[1999Ohn]

[1999Oht]


Toop, G.W., “Predicting Ternary Activities Using Binary Data”, Trans. Metall. Soc. AIME, 233(5), 850 (1965) (Calculation, 13) Hoch, M., Arpshofen, I., “Aggregation Model for the Calculation of Thermodynamic State Functions of Liquid Alloys” (in German), Z. Metallkd., 75(1), 23-29 (1984) (Calculation, 13) Karayaka, I., Thompson, W.T., “The Ag-Bi (Silver-Bismuth) System”, J. Phase Equlib., 14(4), 525-530 (1993) (Phase Diagram, Phase Relations, Thermodyn., Crys. Structure, Assessment, Review, 24) Hassam, S., Gambino, M., Bros, J.P., “Enthalpy of Formation of Liquid Ag-Bi and Ag-Bi-Sn Alloys”, Z. Metallkd., 85, 460-471 (1994) (Experimental, Phase Relations, Thermodyn., *, 27) Kattner, U.R., Boettinger, W.J., “On the Sn-Bi-Ag Ternary Phase Diagram”, J. Electron. Mater., 23(7), 603-610 (1994) (Phase Diagram, Phase Relations,Thermodyn., Calculation, 53) Ohtani, H., Ishida, K., “A Thermodynamic Study of the Phase Equilibria in the Bi-Sn-Sb System”, J. Electron. Mater., 23(8), 747-755 (1994) (Phase Relations, Thermodyn., Experimental, Assessment, 36) Hua, F., Glazer, J., “Lead-Free Solders For Electronic Assembly”, Des. Reliab. Solders Solder Interconnect., Proc. Symp., 65-73 (1997) (Experimental, 63) Lee, N.C., “Getting Ready for Lead-Free Solders”, Soldering Surf. Mount Technol., 9(2), 65-69 (1997) (Mechan. Prop., Phase Relations, Review, 0) McCormack, M., Chen, H.S., Kammlott, G.W., Jim, S., “Significantly Improved Mechanical Properties of Bi-Sn Solder Alloys by Ag-Doping”, J. Electron. Mater., 26(8), 954-958 (1997) (Experimental, Mechan. Prop., 12) Hassan, S., Dichi, E., Legendre, B., “Experimental Equilibrium Phase Diagram of the Ag-Bi-Sn System”, J. Alloys Compd., 268, 199-206 (1998) (Experimental, Phase Diagram, Phase Relations, *, 13) Hermandez, C.L., Vianco, P.T., Rejent, J.A., “Effect of Interface Microstructure on the Mechanical Properties of Pb-Free Hydrid Microcircuit Solder Joints”, IPC/SMTA Electr. Assem. Expo, S19(2), 1-8 (1998) (Experimental, Interface Phenomena, Morphology, Mechan. Prop., 9) Kariya, Y., Otsuka, M., “Effect of Bismuth on the Isothermal Fatigue Properties of Sn - 3.5 mass% Ag Solder Alloy”, J. Electron. Mater., 27(7), 866-870 (1998) (Experimental, Mechan. Prop., 16) Kariya, Y., Otsuka, M., “Mechanical Fatigue Characteristics of Sn-3.5Ag-X (X = Bi, Cu, Zn and In) Solder Alloys”, J. Electron. Mater., 27(11), 1229-1235 (1998) (Experimental, Mechan. Prop., 14) Kariya, Y., Hirata, Y., Otsuka, M., “Effect of Thermal Cycles on the Mechanical Strength of Quad Flat Pack Leads/Sn3.5Ag-X (X = Bi and Cu) Solder Joints”, J. Electron. Mater., 28(11), 1263-1269 (1999) (Experimental, Mechan. Prop., 15) Ohnuma, I., Liu, X.J., Ohtani, H., Ishida, K., “Thermodynamic Database for Phase Diagrams in Micro-Soldering Alloys”, J. Electron. Mater., 28(11), 1164-1171 (1999) (Phase Diagram, Phase Relations, Thermodyn., Calculation, 16) Ohtani, H., Miyashita, M., Ishida, K., “Thermodynamic Study of the Sn-Ag-Zn System”, J. Jpn. Inst. Met., 63 685-694 (1999) (Phase Relations, Phase Diagram, Thermodyn., Assessment, 68)

MSIT®

8 [1999Via1]

[1999Via2]

[2001Bra]

[2001Kar]

[2001Kat]

[2001Kik]

[2001Lee]

[2001Mos]

[2001Oht]

[2001Sug] [2001Tak]

[2002Cho]

[2002Kat] [2002Shi]

[2002Tan]

[2002Xia1]

[2002Xia2]

MSIT®

Ag–Bi–Sn Vianco, P.T., Rejent, J.A., “Properties of Ternary Sn-Ag-Bi Solder Alloys: Part I - Thermal Properties and Microstructural Analysis”, J. Electron. Mater., 28(10), 1127-1137 (1999) (Experimental, Thermodyn., 17) Vianco, P.T., Rejent, J.A., “Properties of Ternary Sn-Ag-Bi Solder Alloys: Part: II -Wettability and Mechanical Properties Analyses”, J. Electron. Mater., 28(10), 1138-1143 (1999) (Experimental, Mechan. Prop., 6) Bradley, E., III, Hranisavljevic, J., “Characterization of the Melting and Wetting of Sn-Ag-X Solders”, Trans. Electron. Packag. Manuf., 24(4), 255-260 (2001) (Experimental, Phase Relations, 16) Kariya, Y., Morihata, T., Hazawa, E., Otsuka, M., “Assessment of Low-Cycle Fatigue Life of Sn-3.5 mass% Ag-X (X = Bi or Cu) Alloy by Strain Range Partitioning Approach”, J. Electron. Mater., 30(9), 1184-1189 (2001) (Assessment, Mechan. Prop., 8) Kattner, U., Handwerker, C.A., “Calculation of Phase Equilibria in Candidate Solder Alloys”, Z. Metallkd., 92(7), 740-746 (2001) (Phase Relations, Thermodyn., Calculation, Review 26) Kikuchi, S., Nishimura, M., Suetsugu, K., Ikari, T., Matsushige, K., “Strength of Bonding Interface in Lead-Free Sn Alloy Solders”, Mater. Sci. Eng. A, A319-321, 475-479 (2001) (Experimental, Mechan. Prop., 4) Lee, J.H., Lee, D.N., “Use of Thermodynamic Data to Calculate Surface Tension and Viscosity of Sn-Based Soldering Alloy Systems”, J. Electron. Mater., 30(9), 1112-1119 (2001) (Experimental, Calculation, Phys. Prop., Thermodyn., 26) Moser, Z., Gasior, W., Pstrus, J., “Surface Tension Measurements of the Bi-Sn and Sn-Bi-Ag Alloys”, J. Electron. Mater., 30(9), 1104-1111 (2001) (Experimental, Mechan. Prop., Interface Phenomena, 33) Ohtani, H., Satoh, I., Miyashita, M., Ishida, K., “Thermodynamic Analysis of the Sn-Ag-Bi Ternary Phase Diagram”, Mater. Trans., JIM, 42(5), 722-731 (2001) (Phase Diagram, Phase Relations, Thermodyn., Assessment, #, 15) Suganuma, K., “Advances in Lead-Free Electronics Soldering”, Curr. Opin. Solid State Mater. Sci., 5, 55-64 (2001) (Experimental, Mechan. Prop., 75) Takao, H., Hasegawa, H., “Influence of Alloy Composition on Fillet-Lifting Phenomenon in Sn-Ag-Bi”, J. Electron. Mater., 30(9), 1060-1067 (2001) (Calculation, Phase Relations, 9) Choi, J.-W., Cha, H.-S., Oh, T.-S., “Mechanical Properties and Shear Strength of Sn-3.5Ag-Bi Solder Alloys”, Mater. Trans., JIM, 43(8), 1864-1867 (2002) (Experimental, Mechan. Prop., 15) Kattner, U.R., “Phase Diagrams for Lead-Free Solder Alloys”, JOM, 54(12), 45-51 (2002) (Phase Relations, Review, #, 47) Shimokawa, H., Soga, T., Serizawa, K., “Mechanical Properties of Tin-Silver-Bismuth Lead-Free Solder”, Mater. Trans., JIM, 43(8), 1808-1815 (2002) (Experimental, Mechan. Prop., 10) Tanabe, T., Harada, S., “Examination of Compound Formation at Interface of Tin-Bismuth-Silver Solder and Copper Substrate by Using Electron Probe Micro Analysis”, X-Ray Spectrom., 31, 3-6 (2002) (Electronic Structure, Phase Relations, Interface Phenomena, 17) Xia, Z., Chen, Z., Shi, Y., Mu, N., Sun, N., “Effect of Rare Earth Element Additions on the Microstrucutre and Mechanical Properties of Tin-Silver-Bismuth Solder”, J. Electron. Mater., 31(6), 564-567 (2002) (Experimental, Mechan. Prop., Morphology, Interface Phenomena, 9) Xia, Z., Shi, Y., Chen, Z., “Evaluation on the Characteristics of Tin-Silver-Bismuth Solder”, J. Mater. Eng. Perform., 11(1), 107-111 (2002) (Experimental, Review, Phys. Prop., Mechan. Prop., 10)


Ag–Bi–Sn [2002Yu]

[2003Lai]

[2003Ohn]

[2003Shi]

[2004Gas]

[2004Hwa]

[2004Oht]

[2004Sho]

[2004Wu]

9

Yu, J., Shin, S.W., “Rupture Time Analyses of the Sn-3.5Ag Solder Alloys Containing Cu or Bi”, Acta Mater., 50, 4315-4324 (2002) (Experimental, Mechan. Prop., Interface Phenomena, 23) Lai, H.L., Duh, J.G., “Lead-Free Sn-Ag and Sn-Ag-Bi Solder Powders Preparation by Mechanical Alloying”, J. Electron. Mater., 32(4), 215-220 (2003) (Experimental, Phys. Prop., Phase Relations, 46) Ohnuma, I., Miyashita, M., Liu, X.J., Ohtani, H., Ishida, K., “Phase Equilibria and Thermodynamic Properties of Sn-Ag Based Pb-Free Solder Alloys”, IEEE Trans., Electron. Pack. Manuf., 26(1), 84-89 (2003) (Phase Relations, Thermodyn., Assessment, Review, #, 21) Shiue, R.-K., Tsay, L.-W., Lin, Ch.-L., Ou, J.-L., “A Study of Sn-Bi-Ag-(In) Lead-Free Solders”, J. Mater. Sci., 38(6), 1269-1279 (2003) (Experimental, Interface Phenomena, Morphology, Phase Relations, 38) Gasior, W., Moser, Z., Pstrus, J., Bukat, K., Kisiel, R., Sitek, J., “(Sn-Ag)eut + Cu Soldering Materials, Part I: Wettability Studies”, J. Phase Equilib. Diffus., 25(2), 115-121 (2004) (Crys. Structure, Experimental, Interface Phenomena, Morphology, Phase Relations, Phys. Prop., 17) Hwang, C.-W., Suganuma, K., “Joint Reliability and High Temperature Stability of Sn-Ag-Bi Lead-Free Solder with Cu and Sn-Pb/Ni/Cu Substrates”, Mater. Sci. Eng. A, A373, 187-194 (2004) (Experimental, Mechan.. Prop., 15) Ohtani, H., Ono, S., Doi, K., Hasebe, M., “Thermodynamic Study of Phase Equilibria in the Sn-Ag-Bi-Zn Quaternary System”, Mater. Trans., 45(3), 614-624 (2004) (Thermodyn., Assessment, *, #, 25) Shohji, I., Yoshida, T., Takahashi, T., Hioki, S., “Tensile Properties of Sn-Ag Based Lead-Free Solders and Strain Rate Sensitivity”, Mater. Sci. Eng. A, A366, 50-55 (2004) (Experimental, Mechan. Prop., 17) Wu, C.M.L., Yu, D.Q., Law, C.M.T., Wang, L., “Properties of Lead-Free Solder Alloys with Rare Earth Element Additions”, Mater. Sci. Eng. R, 44, 1-44 (2004) (Mechan. Prop., Interface Phenomena, Review, 100)




(Ag) < 961.93

cF4 Fm3m Cu

a = 408.57

at 25°C [Mas2] Dissolves up to 2.76 at.% Bi [1993Kar], ~11.3 at.% Sn at 722.5°C [1999Oht]

(Bi) < 271.442

hR6 R3m As

a = 454.613 c = 1186.152

at 31°C [V-C2] Dissolves up to 3.8 at.% Sn at 140.2°C [1994Oht]

(Sn) 231.9681 - 13

tI4 I41/amd Sn

a = 583.18 c = 318.18

at 25°C [Mas2] Dissolves ~16 at.% Bi at 140.2°C [1994Oht]

(Sn) < 13

cF8 Fd3m C (diamond)

a = 648.92

[Mas2]


MSIT®

Ag–Bi–Sn

10 Phase/ Temperature Range [°C]



, (Ag-Sn) < 722.5

hP2 P63/mmc Mg

a = 296.58 c = 478.24

[1999Oht], [V-C2]

Ag3Sn < 476.5

oP8 Pmmn Cu3Ti

a = 478.02 b = 596.8 c = 518.43

[1999Oht], [V-C2] 23.5-25 at.% Sn [Mas2] Dissolves ~19 mass% Bi at 200°C (predicted) [2001Oht]

Table 2: Invariant Equilibria T [°C]

Reaction

Type

Phase

Composition (at.%) Ag

Bi

Sn

L (Ag) + (Bi)

264?

e1 (max)

-

-

-

-

L + (Ag) + (Bi)

263.6

U1

L

2.0

97.7

0.3

L + Ag3Sn + (Bi)

262.5

U2

L

2.6

97.3

0.1

L (Bi) + Ag3Sn + (Sn)

139.2

E

L

0.5

53.9

45.6

1000

Fig. 1: Ag-Bi-Sn. The Ag-Sn binary system

L

Temperature, °C

750

722.5

500

476.5

ζ 250

220.5 (β Sn)

0

Sn

(Ag)

Ag3Sn

20

40

60

80

Ag

Ag, at.%

MSIT®



Ag-Bi

Ag-Bi-Sn

A-B-C

Ag-Sn

Bi-Sn

722.5 p1 l + (Ag) ζAg 476.5 p2 l + ζ Ag3Sn

264? e1(max) L (Ag) + (Bi) 263.6

L + (Ag) ζ + (Bi)

U1

(Ag)+ζ+(Bi) 262.3 e2 l (Ag) + (Bi)

262.5

L + ζ Ag 3Sn+(Bi)

U2

Ag–Bi–Sn

ζ+Ag3Sn+(Bi)

220.5 e3 l Ag3Sn + (βSn) 140.2 e4 l (Bi) + (βSn)

139.2 L (Bi) + Ag3Sn+(βSn)

E

(βSn)+Ag3Sn+(Bi)

11

MSIT®

Fig. 2: Ag-Bi-Sn. Reaction scheme

Ag–Bi–Sn

12

Sn Fig. 3: Ag-Bi-Sn. Liquidus surface projection


e3 (β Sn) 20

80

Ag3Sn

40

60

427

377°C

p2

e4

E

60

40

510

80

605

p1

ζ

(Bi) 20

477 (Ag) 20

Ag

Fig. 4: Ag-Bi-Sn. Liquidus lines near the Sn corner

40

60

U2 U1

e2

80

7

Bi

300 290

280

6

270 Ag3Sn

260

5

250

Ag, mass%

240 4

230 220 210

3

200

(βSn) 2

220

1

210

200 190

230

Sn

10

20

30

Bi, mass%

MSIT®

180

40

170 160 50

150 E e4

(Bi) Bi 60.00 Sn 40.00


Ag–Bi–Sn

13

Sn


Fig. 5: Ag-Bi-Sn. Calculated metastable miscibility gap in the liquid at 200 < T < 400°C

L1

20

80

200

40

60

250 300

60

40

400 80

20

L2 20

Ag

40

60

80

Sn

Bi


Fig. 6: Ag-Bi-Sn. Isothermal section at 400°C 20

L

80

40

60

60

40

Ag3Sn 80

20

ζ

L+Ag3Sn+ζ (Ag)+L+ζ

(Ag)

Ag


20

40

60

80

Bi

MSIT®

Ag–Bi–Sn

14

Sn Fig. 7: Ag-Bi-Sn. Isothermal section at 200°C


(β Sn)

20

80

(β Sn)+L+Ag3Sn

L 40

60

60

40

Ag3Sn

(Bi)+L+Ag3Sn

80

20

ζ (Ag)

(Bi) 20

Ag

40

60

80

Bi

Fig. 8: Ag-Bi-Sn. Isopleth at 10 at.% Bi 750

L

Temperature, °C

L+(Ag) L+ζ 500

L+Ag3Sn+ζ 263.6

L+Ag3Sn

Ag3Sn

250

(β Sn)+Ag3Sn+L

L+Ag3Sn+(Bi)

139.2 (Bi)+Ag3Sn+ζ

(Bi)+(Ag) 0

Ag 90.00 Bi 10.00 (Bi)+(Ag)+ζ Sn 0.00

MSIT®

20

40

Sn, at.%

(β Sn)+Ag3Sn+(Bi) 60

80

Ag 0.00 Bi 10.00 Sn 90.00


Ag–Bi–Sn

Fig. 9: Ag-Bi-Sn. Isopleth at 20 mass% Bi, plotted in at.%

15

750

L

Temperature, °C

L+(Ag) L+ζ

500

L+Ag3Sn+ζ 263.6

L+Ag3Sn

Ag3Sn+(Bi)

250

L+Ag3Sn+(Bi)

(β Sn)+Ag3Sn+L 139.2

Ag3Sn+(Bi)+ζ

(Bi)+(Ag) 0

Ag 88.57 Bi 11.43 (Ag)+(Bi)+ζ Sn 0.00

20

(β Sn)+Ag3Sn+(Bi) 40

60

80

Sn, at.%

Ag 0.00 Bi 12.44 Sn 87.56

500

Fig. 10: Ag-Bi-Sn. Isopleth at 10 mass% Ag, plotted in at.%

L L+ζ

Temperature, °C

L+(Ag)

Ag3Sn+L 250

(β Sn)+Ag3Sn+L L+Ag3Sn+(Bi) 139.2 (β Sn)+Ag3Sn

Ag3Sn+(Bi) (β Sn)+Ag3Sn+(Bi)

(Bi)+(Ag) 0

Ag 17.71 Bi 82.29 Sn 0.00


20

40

Sn, at.%

60

80

Ag 10.90 0.00 Bi Sn 89.10

MSIT®

Ag–Bi–Sn

16

Temperature, °C

Fig. 11: Ag-Bi-Sn. Isopleth at 30 mass% Ag, plotted in at.%

L 500

L+ζ

Ag3Sn+L

L+(Ag)

250

(β Sn)+Ag3Sn+L L+Ag3Sn+(Bi) 139.2 Ag3Sn+(Bi)

(β Sn)+Ag3Sn (β Sn)+Ag3Sn+(Bi)

(Bi)+(Ag) 0

Ag 45.36 Bi 54.64 Sn 0.00

20

40

60

Sn, at.%

Ag 32.05 0.00 Bi Sn 67.95

Fig. 12: Ag-Bi-Sn. Isopleth at 70 at.% Bi L

Temperature, °C

500

L+(Ag)

L+ζ L+Ag3Sn

250

Ag3Sn+(Bi) L+Ag3Sn+(Bi) 139.2

0

Ag 30.00 Bi 70.00 Sn 0.00

MSIT®

(β Sn)+Ag3Sn+(Bi)

Ag3Sn+(Bi)+ζ

(Bi)+(Ag)

(Bi)+(Ag)+ζ

20

10

Ag, at.%

Ag 0.00 Bi 70.00 Sn 30.00


Ag–Bi–Sn

17

Fig. 13: Ag-Bi-Sn. Isopleth at 40 at.% Ag

L 500

Temperature, °C

L+ζ

L+(Ag) L+Ag3Sn

250

(β Sn)+Ag3Sn+L

(Bi)+ζ L+Ag3Sn+(Bi) 139.2 Ag3Sn+(Bi) (β Sn)+Ag3Sn+(Bi)

(Bi)+(Ag) 0

Ag 40.00 Bi 60.00 Sn 0.00

20

(β Sn)+Ag3Sn

Ag 40.00 0.00 Bi Sn 60.00

40

Sn, at.%

Sn


Fig. 14: Ag-Bi-Sn. Experimental isoenthalpic lines at 605°C. Full line: liquidus line at 605°C

20

80

500°C 0 40

60

-500 1000 -1500 60

40

-2500 1500 80

20

2000

Ag


20

40

60

80

Bi

MSIT®

18

Ag–Cu–In

Silver – Copper – Indium Ortrud Kubaschewski, Alan Prince†, updated by Joachim Gröbner Introduction [1951Geb] and [1952Geb] investigated phase relationships in the indium poor region of this system by thermal analysis, metallography and electrical conductivity measurements. They established six four-phase equilibrium reactions and represented their findings by constructing three isothermal sections and four isopleths. [1955Val], [1967Mcd] and [1979Dri] reviewed the work of [1951Geb] and [1952Geb]. Later work by [1988Woy] is in substantial disagreement with [1951Geb] and [1952Geb]. The 1 phase occurring at high temperatures in the Cu-In system, forms a solid solution series with the low-temperature 2 phase of the Ag-In system. [1951Geb] and [1952Geb] assumed the bcc high temperature phases of Cu-In(1) and Ag-In(2) both to be stabilized in the ternary and to decompose eutectically at 490 and 475°C, respectively. [1988Woy] found both phases to be already decomposed at 505°C. Since [1951Geb] and [1952Geb] identified the phases by metallography only and not by X-ray diffraction, a partial explanation of the disagreement with [1988Woy] may be a misinterpretation of the phase as ternary solutions of the phases. Nevertheless only part of the micrographs of annealed specimen published by [1952Geb] can be interpreted by the isothermal sections given by [1988Woy]. Binary Systems The binary Ag-Cu system was taken from the recent, published in the MSIT Evaluation Program by [2002Rom]. Ag-In and Cu-In are accepted from [Mas2]. Solid Phases The solid phases of Ag-In and Cu-In are listed in Table 1. No ternary phases have been reported. Invariant Equilibria Almost the entire reaction scheme can be derived from the liquidus surface given by [1988Woy] (Fig. 1) but without temperatures for the four-phase equilibria. This disagrees with the partial reaction scheme given by [1952Geb] in as far the two phases react and disappear before the L + 1 + 2 three-phase field reacts with another three-phase field. Since temperatures of Gebhardt's [1952Geb] scheme are tentatively assigned to the invariant equilibria, which probably explain the thermal analysis effects of Gebhardt's isopleths, it is not possible to reinterpret all measured points of these isopleths to be consistent with the findings of [1988Woy]. Invariant solid-state reactions were not studied by [1988Woy]. The superstructure phases are ignored in the reaction scheme. Liquidus Surface In Fig. 2 the liquidus surface according to [1988Woy] is shown. In the In poor part some isotherms from [1951Geb] are inserted. For comparison the partial liquidus surface published by [1951Geb] is shown in Fig. 3. Isothermal Sections In Fig. 4 and Fig. 5 the 676 and 505°C isothermal sections as published by [1988Woy] are shown. Figure 5 shows the overwhelming influence of the phase on the ternary equilibria. The 676°C isothermal section (Fig. 4) does not correspond with the isopleths at 20 and 25 mass% In (Fig. 7 and Fig. 8). In particular [1952Geb] indicates that the liquid phase occurs at 676°C on the 20 mass% In section. [1988Woy] shows the liquidus isotherm located at higher In contents. It should be noted that the liquid apexes of the four tie triangles in Fig. 4 do not correspond with points on the monovariant curves in Fig. 2. The L + + field in MSIT®


Ag–Cu–In

19

the 505°C isotherm is changed because the original disagrees with the liquidus surface. The L + 2 + 2 field in Fig. 4 fits more closely Gebhardt's liquidus surface (Fig. 3) than to Fig. 2. Gebhardt's 500°C isothermal section is shown in Fig. 6 for comparison. Temperature – Composition Sections Figures 7 and 8 show the isopleths at 20 and 25 mass% In, respectively, according to [1952Geb]. Notes on Materials Properties and Applications The effect of quenching on the stress-strain characteristics of Ag alloy with 2 mass% Cu and 0.5 mass% In was investigated in the temperature range from 500 to 650°C by [2004Nad]. References [1951Geb] [1952Geb] [1955Val] [1967Mcd] [1972Jai]

[1979Dri]

[1988Woy] [1994Sub]

[2002Rom]

[2004Nad]

Gebhardt, E., Dreher, M., “On the Constitution of the Copper-Silver-Indium System” (in German), Z. Metallkd., 42, 230-238 (1951) (Experimental, Phase Relations, 6) Gebhardt, E., Dreher, M., “On the Constitution of the Copper-Silver-Indium System”, Z. Metallkd., 43, 357-363 (1952) (Experimental, Phase Relations, 3) Valentiner, S., “Indium Alloys” (in German), Z. Metallkd., 46, 442-449 (1955) (Review, 86) McDonald, A.S., Price, B.R., Sistare, G.H., “Ternary and Higher-Order Alloys of Silver”, Silver-Economics, Metallurgy and Use, 272-303 (1967) (Phase Diagram, Review, 38) Jain, K.C., Ellner, M., Schubert, K., “On Phases in the Vicinity of the Composition Cu64In36” (in German), Z. Metallkd., 63, 456-461 (1972) (Experimental, Crys. Structure, Phase Relations, 6) Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padezhnova, E.M., Rokhlin, L.L., Turkina, N.I., “Cu-In-Ag” in “Binary and Multicomponent Copper-Base Systems”, Nauka, Moscow, 128-129 (1979) (Phase Diagram, Review, 3) Woychik, C.G., Massalski, T.B., “Phase Stability Relationships and Glass Formation in the System Cu-Ag-In”, Metall. Trans., A19, 13-21 (1988) (Experimental, Phase Relations, 13) Subramanian, P.R., “Cu (Copper)”, in “Phase Diagrams of Binary Copper Alloys”, Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E. (Eds.), ASM International, Materials Park, OH, 1-3 (1994) (Crys. Structure, Review, 16) Van Rompaey, T., Rogl, P., “Ag-Cu (Silver - Copper)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Document ID: 20.14511.1.20, (2002) (Phase Diagram, Crys. Structure, Thermodyn., Assessment, 29) Nada, R.H., “Precipitation Kinetics in Ag-2wt.% Cu and Ag-2wt.% Cu-0.5wt.% In Alloys During Transformation”, Physica B, 349(1-4), 166-173 (2004) (Experimental, Kinetics, Mechan. Prop., Morphology, Phase Relations, 22)




2, (Ag) < 961.93

cF4 Fm3m Cu

a = 408.57

at 25°C [Mas2]

1, (Cu) < 1084.62

cF4 Fm3m Cu

a = 361.46

at 25°C [Mas2] melting point [1994Sub]


MSIT®

Ag–Cu–In

20 Phase/ Temperature Range [°C]



(In) < 156.634

tI2 I4/mmm In

a = 325.3 c = 494.7

at 25°C [Mas2]

2, Ag3In(h2) 695 - 660

cI2 Im3m W

a = 336.82

[V-C2]

, Ag3In(r) < 670

hP2 P63/mmc Mg

a = 295.63 c = 478.57

[Mas2]

’, Ag3In < 187

cP4 Pm3m AuCu3

a = 414.4 0.4

[Mas2]

, (Cu,Ag)9In4

cP52 P43m Cu9Al4

a = 992.2

[V-C2]

a = 925.03

[V-C2]

2, Ag9In4(h) 314 1, Cu9In4(h) 684 - 614 ’, AgIn2 < 166

tI12 I4/mcm Al2Cu

a = 688.1 c = 562

[V-C2]

1, Cu4In(h) 710 - 574

cI2 Im3m W

a = 304.6

[Mas2, V-C]

, Cu7In3(r) < 631

aP40 P1 Cu7In3

a = 1007.1 b = 912.6 c = 672.4 = 90.22° = 82.84° = 106.81°

[V-C2]

, Cu2In(h3) 667 - 440

hP6 P63/mmc Ni2In

a = 412.0 c = 526.3

[V-C2]

Cu7In4(h2) 480 - 350

oP55 P*

a = 2137.5 b = 740.5 c = 521.8

[1972Jai] superstructure of the Ni2In type

Cu7In4(h1) 450 - 298

oP88 P*

a = 3419.4 b = 739.5 c = 526.2

[1972Jai] superstructure of the Ni2In type

Cu7In4(r) < 390

-

-

[1972Jai]

Cu15In8 < 355

-

-

[1972Jai]

Q, Cu11In9 < 310

mC20 C2/m CuAl

a = 1281.4 b = 435.43 c = 735.3 = 54.49°

[V-C2]

MSIT®



Ag-Cu 779.1 e1 l α1 + α2

Ag-In

Ag-Cu-In

Cu-In 710 p1 l + α1 β1

695 p2 l + α2 β2

678 e2 l β1 + γ

670 p4 α2 + β2 ζ 660 e3 β2 ζ + l

β2 L + α2 + ζ

L + α2 γ + ζ

U3

β1 α1 + γ + δ

L+γ+ζ 77.7 ~79.0 ~79.0 >75.2

~22.1 ~19.9 ~20.4 ~24.7

Physical Chemistry)

Physical Chemistry

Physical Chemistry