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Handbook of
Corrosion
Engineering
Pierre R. Roberge
McGraw-Hill
New York San Francisco Washington, D.C. Auckland Bogotá
Caracas Lisbon London Madrid Mexico City Milan
Montreal New Delhi San Juan Singapore
Sydney Tokyo Toronto
0765162_FM_Roberge 9/1/99 2:36 Page iii
Library of Congress Cataloging-in-Publication Data
Roberge, Pierre R.
Handbook of Corrosion Engineering / Pierre R. Roberge.
p. cm.
Includes bibliographical references.
ISBN 0-07-076516-2 (alk. paper)
1. Corrosion and anti-corrosives. I. Title.
TA418.74.R63 1999
620.1'1223—dc21 99-35898
CIP
Copyright © 2000 by The McGraw-Hill Companies, Inc. All rights
reserved. Printed in the United States of America. Except as permit-
ted under the United States Copyright Act of 1976, no part of this
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1 2 3 4 5 6 7 8 9 AGM/AGM 9 0 4 3 2 1 0 9
ISBN 0-07-076516-2
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Information contained in this work has been obtained by The McGraw-Hill
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0765162_FM_Roberge 9/1/99 2:36 Page iv
Contents
Preface ix
Acknowledgments xi
Introduction 1
1.1 The Cost of Corrosion 1
1.2 Examples of Catastrophic Corrosion Damage 3
1.3 The Influence of People 5
References 12
Chapter 1. Aqueous Corrosion 13
1.1 Introduction 13
1.2 Applications of Potential-pH Diagrams 16
1.3 Kinetic Principles 32
References 54
Chapter 2. Environments 55
2.1 Atmospheric Corrosion 58
2.2 Natural Waters 85
2.3 Seawater 129
2.4 Corrosion in Soils 142
2.5 Reinforced Concrete 154
2.6 Microbes and Biofouling 187
References 216
Chapter 3. High-Temperature Corrosion 221
3.1 Thermodynamic Principles 222
3.2 Kinetic Principles 229
3.3 Practical High-Temperature Corrosion Problems 237
References 265
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Chapter 4. Modeling, Life Prediction and Computer Applications 267
4.1 Introduction 267
4.2 Modeling and Life Prediction 268
4.3 Applications of Artificial Intelligence 303
4.4 Computer-Based Training or Learning 322
4.5 Internet and the Web 324
References
Chapter 5. Corrosion Failures 331
5.1 Introduction 332
5.2 Mechanisms, Forms, and Modes of Corrosion Failures 332
5.3 Guidelines for Investigating Corrosion Failures 359
5.4 Prevention of Corrosion Damage 360
5.5 Case Histories in Corrosion Failure Analysis 368
References 369
Chapter 6. Corrosion Maintenance Through Inspection And Monitoring 371
6.1 Introduction 372
6.2 Inspection 374
6.3 The Maintenance Revolution
6.4 Monitoring and Managing Corrosion Damage 406
6.5 Smart Sensing of Corrosion with Fiber Optics 448
6.6 Non-destructive Evaluation (NDE) 461
References 481
Chapter 7. Acceleration and Amplification of Corrosion Damage 485
7.1 Introduction 486
7.2 Corrosion Testing 488
7.3 Surface Characterization 562
References 574
Chapter 8. Materials Selection 577
8.1 Introduction 578
8.2 Aluminum Alloys 584
8.3 Cast Irons 612
8.4 Copper Alloys 622
8.5 High-Performance Alloys 664
8.6 Refractory Metals 692
8.7 Stainless Steels 710
8.8 Steels 736
8.9 Titanium 748
8.10 Zirconium 769
References 777
Chapter 9. Protective Coatings 781
9.1 Introduction 781
9.2 Coatings and Coating Processes 782
Contents
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326
383
9.3 Supplementary Protection Systems 829
9.4 Surface Preparation 831
References 831
Chapter 10. Corrosion Inhibitors 833
10.1 Introduction 833
10.2 Classification of Inhibitors 834
10.3 Corrosion Inhibition Mechanism 838
10.4 Selection of an Inhibitor System 860
References 861
Chapter 11. Cathodic Protection 863
11.1 Introduction 863
11.2 Sacrificial Anode CP Systems 871
11.3 Impressed Current Systems 878
11.4 Current Distribution and Interference Issues 886
11.5 Monitoring the Performance of CP Systems for Buried Pipelines 904
References 919
Chapter 12. Anodic Protection 921
12.1 Introduction 921
12.2 Passivity of Metals 923
12.3 Equipment Required for Anodic Protection 927
12.4 Design Concerns 930
12.5 Applications 932
12.6 Practical Example: Anodic Protection in the Pulp and Paper Industry 933
References 938
Appendix A. SI Units 939
Appendix B. Glossary 947
Appendix C. Corrosion Economics 1001
C.1 Introduction 1001
C.2 Cash Flows and Capital Budgeting Techniques 1002
C.3 Generalized Equation for Straight Line Depreciation 1004
C.4 Examples 1006
C.5 Summary 1009
References 1009
Appendix D. Electrochemistry Basics 1011
D.1 Principles of Electrochemistry 1011
D.2 Chemical Thermodynamics 1029
D.3 Kinetic Principles 1047
0765162_FM_Roberge 9/1/99 2:36 Page vii
Appendix E. Chemical Compositions of Engineering Alloys 1061
Appendix F. Thermodynamic Data and E-pH Diagrams 1101
Appendix G. Densities and Melting Points of Metals 1125
Index 1129
Contents
0765162_FM_Roberge 9/1/99 2:36 Page viii
Preface
The design and production of the Handbook of Corrosion Engineering
are drastically different than other handbooks dealing with the same
subject. While other corrosion handbooks have been generally the
results of collective efforts of many authors, the Handbook of
Corrosion Engineering is the result of an extensive survey of state-of-
the-art information on corrosion engineering by a principal author.
Although only one author appears on the cover, this Handbook is
indeed the result of cumulative efforts of many generations of scien-
tists and engineers in understanding and preventing the effects of cor-
rosion, one of the most constant foes of human endeavors. The design
and construction of this Handbook were made for the new millennium
with the most modern information-processing techniques presently
available. Many references are made to sources of information readily
accessible on the World Wide Web and to software systems that can
simplify the most difficult situation. It also provides elements of infor-
mation management and tools for managing corrosion problems that
are particularly valuable to practicing engineers. Many examples, for
example, describe how various industries and agencies have addressed
corrosion problems. The systems selected as supportive examples have
been chosen from a wide range of applications across various industries,
from aerospace structures to energy carriers and producers.
This Handbook is aimed at the practicing engineer, as a comprehen-
sive guide and reference source for solving material selection problems
and resolving design issues where corrosion is possibly a factor.
During the past decades, progress in the development of materials
capable of resisting corrosion and high temperatures has been signifi-
cant. There have been substantial developments in newer stainless
steels, high-strength low-alloy steels, superalloys, and in protective
coatings. This Handbook should prove to be a key information source
concerning numerous facets of corrosion damage, from detection and
monitoring to prevention and control.
The Handbook is divided into three main sections and is followed by
supporting material in seven appendixes. Each section and its chapters
are relatively independent and can be consulted without having to go
through previous chapters. The first main section (Introduction and
0765162_FM_Roberge 9/1/99 2:36 Page ix
Chapters 1 to 3) contains fundamental principles governing aqueous
corrosion and high-temperature corrosion and covers the main environ-
ments causing corrosion such as atmospheric, natural waters, seawater,
soils, concrete, as well as microbial and biofouling environments.
The second section (Chapters 4 to 7) addresses techniques for the pre-
diction and assessment of corrosion damage such as modeling, life pre-
diction, computer applications, inspection and monitoring and testing
through acceleration and amplification of corrosion damage. The second
section also contains a detailed description of the various types of corro-
sion failures with examples and ways to prevent them. The third section
(Chapters 8 to 12) covers general considerations of corrosion prevention
and control with a focus on materials selection. This chapter is particu-
larly valuable for its detailed descriptions of the performance and main-
tenance considerations for the main families of engineering alloys based
on aluminum, copper, nickel, chrome, refractory metals, titanium and
zirconium, as well as cast irons, stainless steels and other steels. This
section also provides elements for understanding protective coatings,
corrosion inhibitors, cathodic protection and anodic protection.
The first appendix contains a table of appropriate SI units making
references to most other types of units. This table will hopefully com-
pensate for the systematic usage of SI units made in the book. Another
appendix is an extensive glossary of terms often used in the context of
corrosion engineering. A third appendix summarizes corrosion econom-
ics with examples detailing calculations based on straight value depre-
ciation. The fourth appendix provides a detailed introduction to basic
electrochemical principles. Many examples of E-pH (Pourbaix) dia-
grams are provided in a subsequent appendix. The designations and
compositions of engineering alloys is the subject of a fifth appendix.
Pierre R. Roberge
Preface
0765162_FM_Roberge 9/1/99 2:36 Page x
Acknowledgments
The Handbook of Corrosion Engineering was designed entirely in collab-
oration with Martin Tullmin. In fact, Martin is the sole author of many
sections of the book (corrosion in concrete, soil corrosion and cathodic
protection) as well as an important contributor to many others. My
acknowledgments also go to Robert Klassen who contributed to the
atmospheric corrosion section as well as for his study of the fiber optic
sensors for corrosion monitoring.
As I mentioned in the Preface, this book tries to summarize the pre-
sent state of our knowledge of the corrosion phenomena and their
impact on our societies. Many of the opinions expressed in the
Handbook have come either from my work with collaborators or, more
often, from my study of the work of other corrosion engineers and sci-
entists. Of the first kind I am particularly indebted to Ken Trethewey
with whom I have had many enlightening discussions that sometimes
resulted in published articles. I also have to thank the congenial
experts I interacted with in corrosion standard writing committees
(ISO TC 156 and ASTM G01) for their expert advice and the rigor that
is required in the development of new procedures and test methods.
Of the second kind I have to recognize the science and engineering
pillars responsible for the present state of our knowledge in corrosion.
The names of some of these giants have been mentioned throughout
the book with a particular recognition made in the Introduction in
Table I.4. In this respect, my personal gratitude goes to Professor Roger
Staehle for his pragmatic vision of the quantification of corrosion dam-
age. I have been greatly inspired by the work of this great man.
I would also like to take this occasion to express my love to those
close to me, and particularly to Diane whose endurance of my working
habits is phenomenal.
0765162_FM_Roberge 9/1/99 2:36 Page xi
1
I.1 The Cost of Corrosion 1
I.2 Examples of Catastrophic Corrosion Damage 3
I.2.1 Sewer explosion, Mexico 3
I.2.2 Loss of USAF F16 fighter aircraft 3
I.2.3 The Aloha aircraft incident 3
I.2.4 The MV KIRKI 4
I.2.5 Corrosion of the infrastructure 4
I.3 The Influence of People 5
Introduction
Corrosion is the destructive attack of a material by reaction with its
environment. The serious consequences of the corrosion process have
become a problem of worldwide significance. In addition to our every-
day encounters with this form of degradation, corrosion causes plant
shutdowns, waste of valuable resources, loss or contamination of prod-
uct, reduction in efficiency, costly maintenance, and expensive over-
design; it also jeopardizes safety and inhibits technological progress.
The multidisciplinary aspect of corrosion problems combined with the
distributed responsibilities associated with such problems only
increase the complexity of the subject. Corrosion control is achieved by
recognizing and understanding corrosion mechanisms, by using corro-
sion-resistant materials and designs, and by using protective systems,
devices, and treatments. Major corporations, industries, and govern-
ment agencies have established groups and committees to look after
corrosion-related issues, but in many cases the responsibilities are
spread between the manufacturers or producers of systems and their
users. Such a situation can easily breed negligence and be quite cost-
ly in terms of dollars and human lives.
I.1 The Cost of Corrosion
Although the costs attributed to corrosion damages of all kinds have
been estimated to be of the order of 3 to 5 percent of industrialized
countries’ gross national product (GNP), the responsibilities associat-
ed with these problems are sometimes quite diffuse. Since the first sig-
nificant report by Uhlig
1
in 1949 that the cost of corrosion to nations
is indeed great, the conclusion of all subsequent studies has been that
corrosion represents a constant charge to a nation’s GNP.
2
One conclu-
sion of the 1971 UK government-sponsored report chaired by Hoar
3
was that a good fraction of corrosion failures were avoidable and that
improved education was a good way of tackling corrosion avoidance.
0765162_Intro_Roberge 9/1/99 2:38 Page 1
[...]... TABLE I.4 Landmarks of Discoveries Related to the Understanding and Management of Corrosion Date Landmark 1675 Mechanical origin of corrosiveness and corrodibility Bimetallic corrosion Water becomes alkaline during corrosion of iron Copper-iron electrolytic galvanic coupling Insight into electrochemical nature of corrosion Cathodic protection of Cu by Zn or Fe Microstructural aspect of corrosion (Zn) Relations... intergranular corrosion High-temperature formation of oxides Galvanic corrosion Subscaling of “internal corrosion Quantitative electrochemical nature of corrosion Anodic and cathodic inhibitors E-pH thermodynamic diagrams Autocatalytic nature of pitting Tafel extrapolation for measurement of kinetic parameters Electrochemical noise signature of corrosion Study of corrosion processes with electrochemical impedance... generation of electric currents Passivity of iron Hydrogen overvoltage as a function of current Carbonic and other acids are not essential for the corrosion of iron Oxygen action as cathodic stimulator Compilation of corrosion rates in different media Inhibitive paint Study of high-temperature oxidation kinetics of tungsten Differential aeration currents Season-cracking of brass ϭ intergranular corrosion. .. produced by filiform corrosion of steel are illustrated in Fig 1.11.7 Essentially, a differential aeration cell is set up under the coating, with the lowest concentration of oxygen at the head Coated alloy Tail Back of head X Front of head Head Direction of propagation Figure 1.10 Illustration of the filament nature of filiform corrosion 0765162_Ch01 _Roberge 9/1/99 2:46 Page 27 Aqueous Corrosion 27 X low... lifetime The types of people that can affect the life and performance of engineering systems have been regrouped in six categories (Table I.2).13 Table I.2 also contains a brief description of the main contributions that each category of people can make to the success or premature failure of a system Table I.3 gives an outline of methods of corrosion control14 with an indication of the associated responsibility... Corrosion Cracking of Stainless Steels, in Shreir, L L., Jarman, R A., and Burstein, G T (eds), Corrosion Control Oxford, UK, Butterworths Heinemann, 1994, pp 8:52–8:83 0765162_Ch01 _Roberge 9/1/99 2:46 Page 13 Chapter 1 Aqueous Corrosion 1.1 Introduction 13 1.2 Applications of Potential-pH Diagrams 16 1.2.1 Corrosion of steel in water at elevated temperatures 17 1.2.2 Filiform corrosion 26 1.2.3 Corrosion. .. application of E-pH diagrams to corrosion, thermodynamic data can be used to map out the occurrence of corrosion, passivity, and nobility of a metal as a function of pH and potential The operating environment can also be specified with the same coordinates, facilitating a thermodynamic prediction of the nature of corrosion damage A particular environmental diagram showing the thermodynamic stability of different... 0765162_Ch01 _Roberge 9/1/99 2:46 Page 17 Aqueous Corrosion Potential 17 Mode definition pH Potential Environment definition pH Potential Superposition Operating region of mode Figure 1.2 Representation of a corrosion mode and the corrosion susceptibility of a metal in a given environment on an E-pH scale pH namic boundaries Some examples of the application of E-pH diagrams to practical corrosion problems... (magnitude and type) and environmental conditions that lead to stresscorrosion cracking, corrosion fatigue, or fretting corrosion: 0765162_Intro _Roberge TABLE I.3 9/1/99 2:38 Page 9 Outline of Methods of Corrosion Control (Continued) Method Selection of Materials Responsibility Direct Managerial For stress corrosion cracking, avoid the use of alloys that are susceptible in the environment under consideration,... 0765162_Intro _Roberge 12 9/1/99 2:38 Page 12 Introduction References 1 Uhlig, H H., The Cost of Corrosion in the United States, Chemical and Engineering News, 27:2764 (1949) 2 Cabrillac, C., Leach, J S L., Marcus P., et al., The Cost of Corrosion in the EEC, Metals and Materials, 3:533–536 (1987) 3 Hoar, T P., Report of the Committee on Corrosion and Protection 1971 London, UK, Her Majesty’s Stationary Office . Singapore Sydney Tokyo Toronto 0765162_FM _Roberge 9/1/99 2:36 Page iii Library of Congress Cataloging-in-Publication Data Roberge, Pierre R. Handbook of Corrosion Engineering / Pierre R. Roberge. p generally the results of collective efforts of many authors, the Handbook of Corrosion Engineering is the result of an extensive survey of state -of- the-art information on corrosion engineering. per year at 1995 prices. 4 Broader application of corrosion- resistant mate- rials and the application of the best corrosion- related technical prac- tices could reduce approximately one-third of
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