Principles of Corrosion Engineering and Corrosion Control

• ISBN: 0750659246 • Pub. Date: September 2006 • Publisher: Elsevier Science & Technology Books

PREFACE

The phenomenon of corrosion is as old as the history of metals and it has been looked on as a menace which destroys metals and structures and turns beauty into a beast. Our human civilization cannot exist without metals and yet corrosion is their Achilles heel. Although familiarity with corrosion is ancient, it has been taken very passively by scientists and engineers in the past. Surprisingly, it is only during the last six decades that corrosion science has gradually evolved to a well-defined discipline. Corrosion Science and Engineering is now an integral part of engineering curriculum in leading universities throughout the world. With the rapid advances in materials in the new millennium, the demand for corrosion engineering courses has dramatically increased. This has necessitated the need for the publication of new books. Professor U. R. Evans, Prof. H. H. Uhlig and Prof. M. Fontana wrote a classical generation of basic text books covering the fundamentals of corrosion science and engineering. These books served as texts for decades and some of them are still being used. Several new books in corrosion have been published in recent years to cater to the needs of corrosion science and engineering students. As a teacher of corrosion engineering for the last twenty-five years, I found the material to be deficient in corrosion engineering content. However, sufficient coverage was given to the understanding of corrosion science. In this book, chapters on cathodic protection, materials selection, concrete corrosion and coatings have been written to cater to the needs of corrosion engineering students as well as corrosion engineers. These chapters contain simple and sufficient information to enable students to design corrosion preventive measures. A large number of illustrative problems are given in the chapter on cathodic protection to show how simple cathodic protective systems may be designed. The chapter

on material selection is devoted to an understanding of the art of selection of materials for corrosive environment and applying the knowledge of corrosion prevention - the objective of corrosion engineering students. Concrete corrosion is a global problem and of particular interest to civil, chemical and mechanical engineering students. The chapter on boiler corrosion would be of specific interest to corrosion engineering students and corrosion engineers who desire to refresh their knowledge of the fundamentals of boiler corrosion and water treatment. The chapter on concrete corrosion has been added in view of the global interest in concrete corrosion. It presents the mechanism of rebar corrosion, preventive measures and evaluation methods in a simplified form with eye-catching illustrations. And the unique feature of the book is the follow-up of each chapter by keywords, definitions, multiple-choice questions, conceptual questions and review questions. A solution manual will soon be available to students containing solutions of problems and answers to multiple-choice questions. These are intended to test the readers comprehension of the principles covered in the text. I have put all my lifetime teaching experience into writing this book for corrosion engineering students in the sophomore or junior year. Graduate students lacking background in corrosion will also benefit from the book. It is expected that the students would be able to understand the principles of corrosion science and engineering in a simple and logical manner and apply them for solutions to corrosion engineering problems. This book is written with a new approach and new philosophy and it is hoped that it will fulfill their aspirations. While writing this book, I passed through the most turbulent period of my life with the loss of my most beloved son Intekhab Ahmad who passed away suddenly on April 20, 2004 leaving

Preface

a sea of unending tears and sadness in my life. It was followed by my own sickness, operation and desertions of some of my closest ones. I am grateful to Almighty Allah that I passed through this traumatic period and am able to complete the book. The success of my efforts will depend

XV

on how well this book is received by the students and the corrosion community. This book will not only be found very useful by corrosion engineering students but also by corrosion scientists and engineers in their problems in their professional capacity and those interested in corrosion.

Table of Contents 1. Introduction 2. Basic concepts 3. Corrosion kinetics 4. Types of corrosion materials and environments 5. Cathodic protection 6. Corrosion control by inhibition 7. Coatings 8. Corrosion prevention by design 9. Selection of materials for corrosive environments 10. Atmospheric corrosion 11. Boiler corrosion 12. Concrete corrosion

Index

I N T R O D U C T I O N TO CORROSION

1.1

HISTORICAL

Thenard (1819) suggested that corrosion is an electrochemical phenomenon. BACKGROUND • Hall (1829) established that iron does not rust 'Lay not up for yourselves treasures upon earth wherein the absence of oxygen. • Davy (1824) proposed a method for sacrificial moth and rust doth corrupt and where thieves breakprotection of iron by zinc. through and steal' (Mathew6:14) • De la Rive (1830) suggested the existence of microcells on the surface of zinc. he word corrosion is as old as the earth, but it has been known by different names. The most important contributions were later Corrosion is known commonly as rust, an unde- made by Faraday (1791-1867) [1] who estabsirable phenomena which destroys the luster and lished a quantitative relationship between chembeauty of objects and shortens their life. A Roman ical action and electric current. Faraday's first philosopher, Pliny (AD 23-79) wrote about the and second laws are the basis for calculation of destruction of iron in his essay 'Ferrum Cor- corrosion rates of metals. Ideas on corrosion rumpitar.> Corrosion since ancient times has control started to be generated at the beginaffected not only the quality of daily lives of ning of nineteenth century. Whitney (1903) people, but also their technical progress. There provided a scientific basis for corrosion control is a historical record of observation of corrosion based on electrochemical observation. As early by several writers, philosophers and scientists, but as in eighteenth century it was observed that there was little curiosity regarding the causes and iron corrodes rapidly in dilute nitric acid but mechanism of corrosion until Robert Boyle wrote remains unattacked in concentrated nitric acid. his 'Mechanical Origin of Corrosiveness.' Schonbein in 1836 showed that iron could be Philosophers, writers and scientists observed made passive [2]. It was left to U. R. Evans to procorrosion and mentioned it in their writings: vide a modern understanding of the causes and control of corrosion based on his classical electro• Pliny the elder (AD 23-79) wrote about chemical theory in 1923. Considerable progress towards the modern understanding of corrosion spoiled iron. • Herodotus (fifth century BC) suggested the was made by the contributions of Evans [3], Uhlig [4] and Fontana [5]. The above pioneers use of tin for protection of iron. of modern corrosion have been identified with • Lomonosov (1743-1756). • Austin (1788) noticed that neutral water their well known books in the references given at the end of the chapter. Corrosion laboratories becomes alkaline when it acts on iron.

T

•

2

Principles of Corrosion Engineering and Corrosion Control

established in M.I.T., USA and University of Cambridge, UK, contributed significantly to the growth and development of corrosion science and technology as a multi disciplinary subject. In recent years, corrosion science and engineering has become an integral part of engineering education globally.

1.2

DEFINITIONS

Corrosion is a natural and costly process of destruction like earthquakes, tornados, floods and volcanic eruptions, with one major difference. Whereas we can be only a silent spectator to the above processes of destruction, corrosion can be prevented or at least controlled. Several definitions of corrosion have been given and some of them are reproduced below:

(C) Corrosion is an aspect of the decay of materials by chemical or biological agents. (D) Corrosion is an extractive metallurgy in reverse. For instance, iron is made from hematite by heating with carbon. Iron corrodes and reverts to rust, thus completing its life cycle. The hematite and rust have the same composition (Fig. 1.1). (E) Corrosion is the deterioration of materials as a result of reaction with its environment (Fontana). (F) Corrosion is the destructive attack of a metal by chemical or electrochemical reaction with the environment (Uhlig).

Despite different definitions, it can be observed that corrosion is basically the result of interaction between materials and their environment. Up to the 1960s, the term corrosion was restricted only to metals and their alloys and it did not incorporate ceramics, polymers, composites and semiconductors in its regime. The term cor(A) Corrosion is the surface wastage that occurs rosion now encompasses all types of natural and when metals are exposed to reactive envi- man-made materials including biomaterials and nanomaterials, and it is not confined to metals ronments. (B) Corrosion is the result of interaction and alloys alone. The scope of corrosion is consisbetween a metal and environments which tent with the revolutionary changes in materials development witnessed in recent years. results in its gradual destruction.

Corrosion Process

Sted ft * C (Si, etc)

Alloying

Pmamf

PV*]

Pe

Added (Heat)

Figure 1.1 Refining-corrosion cycle

3

ftiOs (Hematite) tan Ore

< ^

Released

Introduction to corrosion

i .3

CORROSIVE

ENVIRONMENT Corrosion cannot be defined without a reference to environment. All environments are corrosive to some degree. Following is the list of typical corrosive environments: (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11)

•

3

dyes, packaged goods, etc. with dire consequences to the consumers. Nuclear hazards. The Chernobyl disaster is a continuing example of transport of radioactive corrosion products in water, fatal to human, animal and biological life.

The magnitude of corrosion would depend upon the sensitivity of a particular metal or Air and humidity. alloy to a specific environment. For instance, Fresh, distilled, salt and marine water. Natural, urban, marine and industrial copper corrodes rapidly in the presence of ammonia and it is a serious problem in agriatmospheres. cultural areas. Many historical statues made Steam and gases, like chlorine. from bronze have been destroyed by ammonia Ammonia. released from fertilizers. Environmental condiHydrogen sulfide. tioning offers one method of controlling corSulfur dioxide and oxides of nitrogen. rosion, such as the use of inhibitors and oil Fuel gases. Acids. transmission pipelines. Alkalies. Soils.

It may, therefore, be observed that corrosion 1.5 C O S T OF CORROSION is a potent force which destroys economy, depletes resources and causes costly and untimely failures In a study of corrosion cost conducted jointly of plants, equipment and components. by C. C. Technologies Inc., USA [6], Federal Highway Agencies (FHWA), USA [7] and National Association of Corrosion Engineers [8], the direct corrosion cost was estimated to be 1.4 C O N S E Q U E N C E S OF around 276 billion US dollars, approximately 3.1% of the national gross domestic product. CORROSION Based on an extensive survey conducted by Some important consequences of corrosion are Battelle Columbus Laboratories, Columbus, summarized below: Ohio, USA and National Institute of Standards and Technology (NIST), in 1975, the cost was esti• Plant shutdowns. Shutdown of nuclear mated to be 82 billion US dollars, which would plants, process plants, power plants and have exceeded 350 billion US dollars in view of refineries may cause severe problems to price inflation over the last twenty-five years. industry and consumers. Because of the long time involved in conduct• Loss of products, leaking containers, storage ing cost structure, it is not possible to update tanks, water and oil transportation lines and the information every year. However, both studfuel tanks cause significant loss of product and ies show that corrosion costs are staggering and may generate severe accidents and hazards. a figure of about 350 billion US dollars appears It is well-known that at least 25% of water is to be a reasonable estimate for another two to three years. At least 35% of the above amount lost by leakage. • Loss of efficiency. Insulation of heat could have been saved by taking appropriate corexchanger tubings and pipelines by corrosion rosion control measures. In UK, the corrosion products reduces heat transfer and piping cost is estimated to be 4-5% of the GNP [4]. In Japan, the cost of corrosion is estimated to be capacity. • Contamination. Corrosion products may 5258 trillion Yen per year. For most industrialized contaminate chemicals, pharmaceuticals, nations, the average corrosion cost is 3.5-4.5%

4

Principles of Corrosion Engineering and Corrosion Control

of the GNP. Below are some startling figures of corrosion losses: •

•

•

•

•

•

• •

The corrosion cost of gas and liquid transmission pipelines in USA exceeds seven billion US dollars. The figure for the major oil producing countries in the Gulf region are not known, however the cost expected to be very high because of highly corrosive environment in the region [8]. The corrosion-free life of automobiles in the coastal regions of Arabian Gulf is about six months only [9]. Nearly 95% of concrete damage in the Arabian Gulf coastal region is caused by reinforcement corrosion and consequent spalling of concrete [10]. It is estimated that 10% of all aircraft maintenance in USA is spent on corrosion remediation [11]. Major annual corrosion losses to the tune of £350 million in transport, £280 million in marine, £250 million in buildings and construction and £180 million in oil and chemical industries, have been reported in UK [12]. These are uncorrected 1971 figures. About $120 billion is spent on maintenance of aging and deteriorating infrastructures in USA [13]. Automotive corrosion costs 23.4 billion US dollars annually in USA [8]. Every new born baby in the world now has an annual corrosion debt of $40.

1.6

B R E A K D O W N OF

S P E N D I N G ON C O R R O S I O N

and petrochemical industries are the largest contributor to corrosion expenditure. The highway sector in USA alone includes 4 000 000 miles of highways, 583 000 bridges, which need corrosion remediation maintenance [8]. The annual direct corrosion cost estimated to be 8.3 billion US dollars. The direct corrosion of transportation sector is estimated to be 29.7 billion US dollars. It includes the corrosion cost of aircraft, hazardous materials transport, motor vehicles, railroad car and ships [8]. In the oil sector, drilling poses severe hazards to equipment in the form of stress corrosion cracking, hydrogen induced cracking and hydrogen sulfide cracking [6]. In USA alone this sector costs more than 1.2 billion US dollars. The cost is very staggering in major oil producing countries, like Saudi Arabia, Iran, Iraq and Kuwait. The direct cost of corrosion to aircraft industry exceeds 2.2 billion US dollars [8]. Corrosion has a serious impact on defense equipment. In the Gulf War, a serious problem of rotor blade damage in helicopter was caused by the desert sand. The thickness of the blade was reduced to 2-3 mm in some instances. The desert erosion-corrosion offered a new challenge to corrosion scientists and engineers. The storage of defense equipment is a serious matter for countries with corrosive environments, such as Saudi Arabia, Malaysia and Southeast Asia. Humidity is the biggest killer of defense hardware. Storage of defense equipment demands minimum humidity, scanty rainfall, alkaline soil, no dust storms, no marine environment and minimal dust particles. From the above summary, it is observed that corrosion exists everywhere and there is no industry or house where it does not penetrate and it demands a state of readiness for engineers and scientists to combat this problem.

The petroleum, chemical, petrochemical, construction, manufacturing, pulp and paper and transportation (railroad, automotive and 1.7 CORROSION SCIENCE aerospace) industries are the largest contributors AND CORROSION to corrosion expenditure. The cost of corrosion differs from country to country. For instance E N G I N E E R I N G in USA, the transportation sector is the largest sector contributing to corrosion after public util- The term science covers theories, laws and ities, whereas in the oil producing countries, explanation of phenomena confirmed by intersuch as the Arabian Gulf countries, petroleum subjective observation or experiments. For

Introduction to corrosion instance, the explanation of different forms of corrosion, rates of corrosion and mechanism of corrosion is provided by corrosion science. Corrosion science is a l o w i n g why' of corrosion. The term engineering, contrary to science, is directed towards an action for a particular purpose under a set of directions and rules for action and in a well-known phrase it is 'knowing how.' Corrosion engineering is the application of the principles evolved from corrosion science to minimize or prevent corrosion. Corrosion engineering involves designing of corrosion prevention schemes and implementation of specific codes and practices. Corrosion prevention measures, like cathodic protection, designing to prevent corrosion and coating of structures fall within the regime of corrosion engineering. However, corrosion science and engineering go hand-in-hand and they cannot be separated: it is a permanent marriage to produce new and better methods of protection from time to time.

1.8

INTER-DISCIPLINARY

N A T U R E OF CORROSION The subject of corrosion is inter-disciplinary and it involves all basic sciences, such as physics, chemistry, biology and all disciplines of engineering, such as civil, mechanical, electrical and metallurgical engineering.

1.9

CORROSION

EDUCATION The subject of corrosion has undergone an irreversible transformation from a state of isolated and obscurity to a recognized discipline of engineering. From the three universities in USA which offered courses in corrosion in 1946, corrosion courses are now offered by almost all major technical universities and institutions in USA, UK, Europe, Southeast Asia, Africa and Japan. Corrosion is now considered as an essential component of design. Learned societies like National Association of Corrosion Engineers,

5

European Federation of Corrosion, Japan Society of Corrosion Engineers and others are playing leading role in the development of corrosion engineering education. Detailed information on corrosion education, training centers, opportunities in corrosion can be found in various handbooks and websites. Some sources of information are listed in the bibliography. As a consequence of cumulative efforts of corrosion scientists and engineers, corrosion engineering has made quantum leaps and it is actively contributing to technological advancement ranging from building structures to aerospace vehicles.

1.10

FUNCTIONAL

A S P E C T S OF CORROSION Corrosion may severely affect the following functions of metals, plant and equipment: (1) Impermeability: Environmental constituents must not be allowed to enter pipes, process equipment, food containers, tanks, etc. to minimize the possibility of corrosion. (2) Mechanical strength: Corrosion should not affect the capability to withstand specified loads, and its strength should not be undermined by corrosion. (3) Dimensional integrity: Maintaining dimensions is critical to engineering designs and they should not be affected by corrosion. (4) Physical properties: For efficient operation, the physical properties of plants, equipment and materials, such as thermal conductivity and electrical properties, should not be allowed to be adversely affected by corrosion. (5) Contamination: Corrosion, if allowed to build up, can contaminate processing equipment, food products, drugs and pharmaceutical products and endanger health and environmental safety. (6) Damage to equipment: Equipment adjacent to one which has suffered corrosion failure, may be damaged. Realizing that corrosion effectively blocks or impairs the functions of metals, plants

6

Principles of Corrosion Engineering and Corrosion Control

and equipment, appropriate measures must be adopted to minimize loss or efficiency of function.

the product image which is a valuable asset to a corporation. Surface finishing processes, such as electroplating, anodizing, mechanical polishing, electro polishing, painting, coating, etching and texturing all lead to the dual purpose of enhancement of aesthetic 1.10.1 H E A L T H , S A F E T Y , value and surface integrity of the product. ENVIRONMENTAL AND (5) Product life: Corrosion seriously shortens PRODUCT LIFE the predicted design life, a time span after which replacement is anticipated. Cars have, in general, a design life of twelve years, but These can involve the following: several brands survive much longer. A DC-3 aircraft has a design life of twenty years but (1) Safety: Sudden failure can cause exploafter sixty years they are still flying. The sions and fire, release of toxic products and Eiffel Tower had a design life of two years collapse of structures. Several incidents of fire only, and even after one hundred years it is have been reported due to corrosion causing still a grand symbol of Paris. The reason for leakage of gas and oil pipelines. Corrosion their survival is that the engineers made use adversely affects the structural integrity of of imaginative designs, environmental resiscomponents and makes them susceptible tant materials and induction of corrosionto failure and accident. More deaths are free maintenance measures. Distinguished caused by accidents in old cars because of and evocative designs always survive whereas the weakening of components by corrosion designs of a transitory nature deteriorate damage. Corrosion has also been a significant to extinction with time. Design life is a factor in several accidents involving civil and process of imagination, material selection military aircraft and other transportation and corrosion-free maintenance. vehicles. Corrosion failure involving bridges, ships, airports, stadiums are too numerous (6) Restoration of corroded objects: Objects of to be mentioned in detail in this chapter outstanding significance to natural history and recorded in the catalog of engineering need to be preserved. Many historical strucdisasters [11]. tures have been lost through the ravages of (2) Health: Adverse effects on health may be corrosion. One recent example is the call for caused by corroding structures, such as a help to restore the revolutionary iron-hulled plumbing system affecting the quality of steamships Great Britain built in 1843. It has water and escaping of products into the been described as mother of all modern ships, environment from the corroded structures. measuring 3000 feet in length and weighing (3) Depletion of resources: Corrosion puts 1930 tons. A plea for £100 000 has been made a heavy constraint on natural resources for its restoration. of a country because of their wastage by corrosion. The process of depletion outweighs the discovery of new resources which may lead to a future metal crisis similar to the l.ll FIVE GOOD R E A S O N S past oil shortage. (4) Appearance and cleanliness: Whereas anes- TO S T U D Y C O R R O S I O N thetics numb the senses, aesthetics arouse interest, stimulate and appeal to the senses, (1) Materials are precious resources of a country. particularly the sense of beauty. A product Our material resources of iron, aluminum, designed to function properly must have copper, chromium, manganese, titanium, an aesthetic appeal. Corrosion behaves like etc. are dwindling fast. Some day there a beast to a beauty. It destroys the aeswill be an acute shortage of these materials. thetic appeal of the product and damages An impending metal crisis does not seem

Introduction to corrosion

7

anywhere to be a remote possibility but a 3. Which is the most common cause of corrosion damage, corrosion fatigue, stress reality. There is bound to be a metal crisis corrosion cracking or pitting corrosion? and we are getting the signals. To preserve these valuable resources, we need to under- 4. Describe with an example how corroded structures can lead to environmenstand how these resources are destroyed by tal pollution. corrosion and how they must be preserved by 5. Does corrosion affect humans? If so, applying corrosion protection technology. explain how. (2) Engineering knowledge is incomplete without an understanding of corrosion. 6. Describe two engineering disasters in which corrosion played a leading role. Aeroplanes, ships, automobiles and other transport carriers cannot be designed with- 7. State two important corrosion websites. out any recourse to the corrosion behavior of 8. How can corroded structures be injurious to materials used in these structures. human health? (3) Several engineering disasters, such as crash- 9. Name three cities in Southeast Asia and the Middle East which have the most corrosive ing of civil and military aircraft, naval and environment. passenger ships, explosion of oil pipelines and oil storage tanks, collapse of bridges and 10. What is the best way to minimize the corrodecks and failure of drilling platforms and sion of defense equipment during storage? tanker trucks have been witnessed in recent 11. What is the relationship between depletion of years. Corrosion has been a very important natural resources and corrosion? factor in these disasters. Applying the knowledge of corrosion protection can minimize such disasters. In USA, two million miles of pipe need to be corrosion-protected for REFERENCES safety. (4) The designing of artificial implants for the [1] Walsh, F. (1991). Faraday and his laws of electrolysis. Bulletin of Electrochem, 7, 11,481-489. human body requires a complete under[2] Schonbein, C. (1936). Pogg. Ann., 37, 390. standing of the corrosion science and [3] Evans, U.R. (1972). An Introduction to Metallic engineering. Surgical implants must be Corrosion, 2nd ed. London: Arnold. very corrosion-resistant because of corrosive [4] Uhlig, H.H. (1985). Corrosion and Corrosion Control, 3rd ed. New York: John Wiley and nature of human blood. Sons. (5) Corrosion is a threat to the environment. For [5] Fontana, M.G. (1986). Corrosion Engineerinstance, water can become contaminated ing, 3rd ed. New York: McGraw-Hill Book by corrosion products and unsuitable for Company. consumption. Corrosion prevention is inte[6] C. C. Technologies Laboratories, Inc. (2001). Cost of corrosion and prevention strategies in gral to stop contamination of air, water and the United States, Ohio: Dublin, USA. soil. The American Water Works Association [7] Federal Highway Administration (FHWA), needs US$ 325 billion in the next twenty years Office of the Infrastructure and Development to upgrade the water distribution system. (2001). Report FHWA-RD-01-156. [8] National Association of Corrosion Engineers (NACE) (2002). Materials Performance, Special Issue, Houston, Texas, USA, July. Jointly with C. C. Technologies and FHWA. [9] Ahmad, Z. (1996). Corrosion phenomena in QUESTIONS coastal area of Arabian Gulf. British ^Corrosion Journal 31, (2), 191-197. [10] Rashid-uz-Zafar, S., Al-Sulaiman, G.J. and CONCEPTUAL Q U E S T I O N S Al-Gahtani, A.S. (1992). Symp. Corrosion and the Control, Riyadh, Saudi Arabia, May, 110. 1. Explain how corrosion can be considered as [11] Tullmin, M.A.A., Roberge, P.R., Grenier, L. and extractive metallurgy in reverse. Little, M.A. (1990). Canadian Aeronautics and Space Journal, 42, (2), 272-275. 2. Listfiveimportant consequences of corrosion.

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Principles of Corrosion Engineering and Corrosion Control

[12] Hoar,T.P. (1971). Report of the Committee on Corrosion and Protection, London: HMSO. [13] Latanisian, R.M., Leslie, G.G., McBrine, N.J., Eselman, T. etal. (1999). Application of practical ageing management concepts to corrosion engineering, Keynote Address. 14th ICC, Capetown, South Africa, 26 Sep-10 Oct.

WEBSITES [20] [21] [22] [23]

GENERAL REFERENCES

SOFTWARE

[14] Hackerman,N. (1993). A view of the history of corrosion and its control. In: Gundry, R.D. ed. Corrosion 93 Planery and Keynote Lectures, Texas: NACE, Houston, 1-5. [15] Pliny (1938). Natural History of the World. London: Heinemann. [16] Hoare, T.P. (1971). Report of the Committee on Corrosion and Protection. London: HMSO. [17] Uhlig, H.H. (1949). Chemical and Engineering News, 97,27'64. [18] N. B. S. (1978). Corrosion in United States, Standard Special Publication. [19] Bennett, L.H. (1978). Economic Effects of Metallic Corrosion in USA, Special Publication 511-1, Washington, DC.

[24] NACE: Basic Corrosion (National Association of Corrosion Engineers, Houston, Texas), Course on CD-Rom, 2002. [25] Corrosion Survey Data Base (COR.SUR), access via NACE website, NACE, Houston, Texas, 2003. [26] Rover Electronic Data Books™, William Andrew, Inc., New York, USA, 2002. [27] Peabody, A.W. Control of Pipeline Corrosion, 2nd Edition, Ed. R. Bianchette, NACE, Houston, Texas, 2003. [28] Corrosion Damage: A Practical Approach, NACE, Houston, Texas, 2003.

www.intercorrosion.com www.learncorrosion.com www.nace.org www.iom3.org

BASIC CONCEPTS IN CORROSION

F

or corrosion to take place, the formation of a corrosion cell is essential. A corrosion cell is essentially comprised of the following four components (Fig. 2.1). • • • •

Anode Cathode Electrolyte Metallic path.

Anode: One of the two dissimilar metal electrodes in an electrolytic cell, represented as the negative terminal of the cell. Electrons are released at the anode, which is the more reactive metal. Electrons are insoluble in aqueous solutions and they only move, through the wire connection into the cathode. For example, in a battery, zinc casing acts as the anode. Also in a Daniel cell, zinc is the anode as oxidation occurs on it and electrons are released (Fig. 2.2). Corrosion nomenclature is the opposite of electroplating nomenclature, where an anode is positive and the cathode is negative. Cathode: One of the two electrodes in an electrolytic cell represented as a positive terminal of a cell. Reduction takes place at the cathode and electrons are consumed. Example, carbon electrode in a battery, copper electrode in a Daniel cell. Figure 2.3 shows the reduction of hydrogen ion. The electron is always a reducing agent. Electrolyte: It is the electrically conductive solution (e.g. salt solution) that must be present

for corrosion to occur. Note that pure water is a bad conductor of electricity. Positive electricity passes from anode to cathode through the electrolyte as cations, e.g. Z n + + ions dissolve from a zinc anode and thus carry positive current away from it, through the aqueous electrolyte. Metallic Path: The two electrodes are connected externally by a metallic conductor. In the metallic conductor, 'conventional' current flows from (+) to (—) which is really electronsflowingfrom (—) to (+). Metals provide a path for the flow of conventional current which is actually passage of electrons in the opposite direction. Current Flow: Conventional current flows from anode (—) to cathode (+) as Z n + + ions through the solution. The current is carried by these positive charged ions. The circuit is completed by passage of electrons from the anode (—) to the cathode (+) through the external metallic wire circuit (outer current). Electron Flow: H + + e -+ H,

2H -* H 2 f

Although the anode (e.g. Fe or Zn) is the most negative of the two metals in the cell, this reaction does not occur there because its surface is emanating Fe + + ions which repel H + ions from discharging there. The circuit is completed by negative ions (—) which migrate from the cathode (+), through the electrolyte, towards the anode (—). They form

10

Principles of Corrosion Engineering and Corrosion Control Current flow in an electrochemical cell is shown in Fig. 2.4.

Current carrying electrolyte

-A-v 2.1

ANODIC AND

CATHODIC REACTIONS Non-corroding area

Corroding area

Figure 2.1 Corrosion cell in action

Fe(OH)2 when they enter the cloud of Fe + + ions coming from the anode.

The anode is the area where metal is lost. At the anode, the reactions which take place are oxidation reactions. It represents the entry of metal ion into the solution, by dissolution, hydration or by complex formation. It also includes precipitation of metal ions at the metal surface. For example Fe 2+ + 20H~ -» Fe(OH)2. Ferrous hydroxide or rust formation on steel surface is a common example. Some more examples are:

Anions'. Migrate towards the anode (OH~) but precipitate as Fe(OH)2 before reaching it. (a) 2A1 + 6HC1 » 2A1C13 + 3H2 t 2+ (b) Fe + 2HC1- FeCl2 + H 2 t Cations'. Migrate towards the cathode (Fe ).

Anode T h ~ (Znrod) I U

-ju+ | + ^ Cathode (Cured)

In I Zn 2 * S04*tact> II Cu2* S & t a q ) ! Cu Chemical reaction — *

Figure 2.2 A galvanic cell (Daniel cell)

>

Basic concepts in corrosion

11

involve oxidation to a higher valence state. Reactions (a-d) can be written in terms of electron transfer as below: Anode —

r

4 " Cathode (a) (b) (c) (d)

Al-> Al 3+ + 3e Fe-+ Fe 2+ + 2e Z n - y Zn 2 + + 2e Z n - > Zn2+ + 2e

Anodic reaction in terms of electron transfer is written as M -> M n + + ne

2.2 Figure 2.3 Figure showing the reduction of hydrogen in an acid electrolyte

The reactions (a-d) involve the release of hydrogen gas. All the reactions shown above

||2e*

Hydrogen picks up an v Q electron and tabbies V ^ off at cathode

CHARACTERISTICS (1) Oxidation of metal to an ion with a charge. (2) Release of electrons. (3) Shift to a higher valence state.

(c) Zn + H 2 S 0 4 -+ Z n S 0 4 + H 2 t (d) Zn + HC1 -> ZnCl2 + H 2 t

Cathode

ANODIC REACTIONS

The process of oxidation in most metals and alloys represents corrosion. Hence, if oxidation is stopped, corrosion is stopped.

2e

Cu

art"

Anode

Fe . Current (Fe** tons) leaves surface of iron causing corrosion

m

m

Negative current enters surface of copper and protects copper

€)

!2e1

©

tI

%

© It!f©

Fe(OH)a

Figure 2.4

Current flow in an electrochemical cell

conventional current flow ——-# electron flow

Iron atom loses two electrons and combines with hydroxyl ions to " form ferrous hydroxide precipitate

12

Principles of Corrosion Engineering and Corrosion Control

2.3 CATHODIC REACTIONS CHARACTERISTICS

2.4 T Y P E S OF CORROSION CELLS

Cathodic reactions are reduction reactions which occur at the cathode. Electrons released by the anodic reactions are consumed at the cathode surface. Unlike an anodic reaction, there is a decrease in the valence state. The most common cathodic reactions in terms of electrons transfer are given below:

There are several types of corrosion cells:

(a) 2H + + 2e —>• H2 f ( m ac id solution) (b) 0 2 + 4H+4e -> 2H 2 0 (in acid solution) (c) 2H 2 0 + 0 2 + 4e -+ 4 0 H " (in neutral and alkaline solutions) (d) Fe 3+ + e -» Fe +2 (metal ion reduction in ferric salt solutions) (e) Metal deposition: M 2 + + 2e -> M N i + + + 2e -> Ni Cu2+ + 2e -> Cu (f) Bacterial reduction of sulfate: SO^ - + 8H+ + 8e -> S" + 4H 2 0

(1) (2) (3) (4)

Galvanic cells Concentration cells Electrolytic cell Differential temperature cells.

2.4.1

GALVANIC C E L L S

The galvanic cell may have an anode or cathode of dissimilar metals in an electrolyte or the same metal in dissimilar conditions in a common electrolyte. For example, steel and copper electrodes immersed in an electrolyte (Fig. 2.5), represents a galvanic cell. The more noble metal copper acts as the cathode and the more active iron acts as an anode. Current flows from iron anode to copper cathode in the electrolyte.

Electricity Hows from cathode to the anode through the metallic conductor.

Current

The metal having Ilia lower energy level (in this case Cu), no corrosion occurs at the cathode.

»Cathode

Anode*—

Cu

The metal having the higher level of energy (In this case Fe), corrosion occurs at the anode,

41 I I

Electrolyte - * conventional current flow ~* electron flow

Figure 2.5 Typical galvanic cell

Water and dissolved salts conduct the flw of electricity from steel anode to the copper cathode.

Basic concepts in corrosion

13

2.4.2 CONCENTRATION CELLS External power source

This is similar to galvanic cells except with an anode and cathode of the same metal in a heterogeneous electrolyte. Consider the corrosion of a pipe in the soil. Concentration cells may be set up by: (a) Variation in the amount of oxygen in soils. (b) Differences in moisture content of soils. (c) Differences in compositions of the soil. Concentration cells are commonly observed in underground corroding structures, such as buried pipes or tanks (Fig. 2.6). The inequality of dissolved chemicals causes a potential difference which establishes anode in the more concentrated region and cathode in the less concentrated region.

^JEfectolyle - * conventional current flow ~* electron flow

2.4.3

ELECTROLYTIC C E L L

Figure 2.7 Electrolytic cell. The cathode and anode This type of cell is formed when an external cur- can be any metal rent is introduced into the system. It may consist of all the basic components of galvanic cells and concentration cells plus an external source of electrical energy. 2 . 5 MECHANISM OF Notice that anode has a (+) polarity and cathode has (—) polarity in an electrolytic cell, C O R R O S I O N O F IRON where external current is applied. This is the type of cell set up for electrically protecting the struc- Consider a piece of iron exposed to humid air tures by cathodic protection. The polarity of an which acts as an electrolyte. Fe 2+ ions are released electrolytic cell is opposite to that in a galvanic from the anode by oxidation and OH~ ions from (corrosion) cell (Fig. 2.7). the cathode by reduction on the metal surface.

Air

day (low oxygen)

:^yy^yM>:^^y. V^4L

Loam (High oxygen) Yf///^

Anodic area ^ ^ ^ C a t h o d l c

Figure 2.6 Concentration cell formation in an underground pipeline

a

o

^

W

14

Principles of Corrosion Engineering and Corrosion Control

The negative and positive ions combine Fe + + + 2 0 H " ->Fe(OH) 2 (white green precipitate) Fe(OH)2 is insoluble in water and separates from the electrolyte. A more familiar name of Fe(OH)2 is rust. Details of reactions involved in the corrosion of iron-based materials is given below: (1) Fe + H 2 0 U FeO + 2H+ + 2e~ Forms monolayer of FeO islands (2) Fe + 2H 2 0 - • Fe(OH)2 + 2H+ + 2e (3) 3FeO + H 2 0 -> Fe 3 0 4 + 2H+ + 2e (Black)

(Magnetite)

(4) 2 F e 3 0 4 + H 2 0 - > 3 ( y - F e 2 0 3 ) + 2 H + + 2 e (Brown)

(5) 2[y - Fe 2 0 3 ] + 3HzO -* 6(y - FeOOH) (Brown)

where

and

From the Gibbs-Helmholtz equation:

G=

H-TS

(2.2)

Substituting H = U + PV from the First Law of Thermodynamics F = PV - TS

(2.3)

Differentiating: dG = dU + PdV + VdP - TdS - SdT

(2.4)

But for a reversible process,

(Yellow hydrated oxide)

The formation of rust, Fe(OH)2, is shown in Fig. 2.8.

aA = activity of the substance, T = absolute temperature, R = gas constant.

dU = qTeY — PdV at constant pressure and grev = TdS at constant temperature

(2.5)

So, dG = TdS - PdV + PdV + VdP

2 . 6 C O N C E P T OF F R E E ENERGY

- TdS - SdT i.e.

dG = VdP — SdT, for a reversible process at constant pressure and temperature. (2.6)

In this section the relationship between free energy and equilibrium constant is shown. The contribution made by one mole of any conAt constant pressure, dP vanishes and this stituent, A, to the total free energy, G, of a mixture becomes: is GA> which may be represented by dG GA = Gl + RT In aA (2.1)

Oj+2H20+4e"

Figure 2.8 Formation of rust in seawater

Basic concepts in corrosion and at constant temperature dT vanishes and:

So, for 1 mole of forward reaction a

dG=VdP

PV = RT RT

Integration between the limits G'4, GA and

p, A

p

(Van't Hoff reaction isotherm) (2.11) At equilibrium

, /RT\ , >dG=\— \dP, since dG=VdP \P ) (2.7)

P

a

A^-Ar20^T>T^( C AG = AG° + RTln { =£=%

However, the ideal gas equation for 1 mole is

V=

AG=0 and I acrai\ K where Kis the e uilibrium

\vjr '

ives: °

GA

PA ,

P'A

GA-G'=RT

^

\aAaB/ constant. 0 = AG° + RT\nK

x

/-/(f)* G'A

15

AG° = -RTlnK

-m

(2.8)

(v AG° is always = -RT In K)

2.6.1

If GA is taken to refer for standard conditions,

(2.12)

FREE

ENERGY

(THE

DRIVING F O R C E OF A CHEMICAL REACTION)

GA-G'A

= RTIn

PA

G = G* = #T In P

(2.9)

^ chemical reaction at constant temperature and pressure will only occur if there is an overall . , _ . decrease in the free energy of the system during If activities are used instead of pressures, then as t h e r e a c t i o n > Consider the following two reactions in equation (2.1) for example: or

GA = G°A+RT\naA

(a) ZnO(s) + C(s)^Zn(s)+CO(g) at 1373K A5° = +285JK- 1 mor 1 AH° = +349.9kJ• mol - 1

Applying AG for the reaction

(b) Fe(s) + 2±y 0 2 ( s ) ^ F e O ( s ) AS° = - 7 1 J K ~ 1 m o r 1 FeO AH 0 = +265.5 kj.mol" 1 FeO

aA+bB**cC+dD gives

In example (b), both AH° and AS° work in AG = (cGc + dGd)- (aGA + bGB)

(2.10)

Using expression (2.1) for GA, GB) Gc and GD: AG = c[G£+jRTln ac\ + d[Gp + RT In ap] -a[G°A+RTIn

aA]-b[G0B+RTIn

aB]

°PP o s i t e s i 8 n s t 0 e a c h o t h e r i n t e r m s of direction of energy change, however, both of them proceed spontaneously as indicated. It is important tQ k n o w w h k h o n e w o u l d d e d d e t h e d i r e c t i o n

of the reaction (AH° or A 5°). We must, therefore, introduce a single function expressing the combined effect of change of both AH and A5. of the total enthalpy of the system only a part

16

Principles of Corrosion Engineering and Corrosion Control

is converted to useful work, which is called free Illustrative Example 2.1 energy (AG). It can be defined in terms of AH, A 5 and T. The relationship between the three is Calculate A G° for the following reaction at 500 K. deduced as CuO(s)+H 2 (g)->Cu(s)+H 2 0 AH°-AG° = TAS° (2.13) which is a statement of the Second Law of Thermodynamics and may be rearranged to: AG = AH-TAS

Solution: AH5°00 = - 8 7 k J - m o r 1 AS£00 = +47JK- 1 mor 1

(2.14)

AG = A f f ° - r A 5 °

= -87000-(500x47) J-mol" 1 AG is thus a driving force for a reaction to occur. Reactions at constant temperature and = 110.5kJ-mor 1 pressure proceed in a direction which tends to cause a decrease in free energy. AG can be used to predict the feasibility of a reaction as shown AG° is negative (—ve), hence the reaction is feasible. below. Ever if AG° were positive, a reaction producFor a chemical reaction where the reactants ing gas pressures of products of less than unit (A+B) react to yield the product (C+D) activity (=lbar, for gases) is possible. The sign according to of AG° only predicts spontaneity if all activities A+B-^C+D (2.15) are unity. the free energy change of the reaction can be expressed as

2.6.2

CELL

POTENTIALS

AND E M F AG=GP-GR

(2.16)

AG = (Hp-HR)-T(SP-SR)

(2.17)

AG = A H - T A S

(2.18)

where P = products R = reactants.

Electrochemical cells generate electrical energy due to electrochemical reactions. The electrical energy available is Electrical energy=volts x current x time = volts x coulombs = EQ

(a) If the value of free energy change is negative, the reactions will be spontaneous and take place from left to right (A+B^C+D). (b) If the value of the free energy change is zero, the reaction is at equilibrium (A+B