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
publication may be reproduced or distributed in any form or by any
means, or stored in a data base or retrieval system, without the prior
written permission of the publisher.
1 2 3 4 5 6 7 8 9 AGM/AGM 9 0 4 3 2 1 0 9
ISBN 0-07-076516-2
The sponsoring editor of this book was Robert Esposito. The editing
supervisor was David E. Fogarty, and the production supervisor was
Sherri Souffrance. This book was set in New Century Schoolbook by

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

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

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
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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-

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.
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1
I.1 The Cost of Corrosion 1
I.2 Examples of Catastrophic Corrosion Damage 3
I.2.1 Sewer explosion, Mexico 3

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
Corrosion of metals cost the U.S. economy almost $300 billion 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 these costs. These
estimates result from a recent update by Battelle scientists of an ear-
lier study reported in 1978.
5
The initial work, based upon an elaborate
model of more than 130 economic sectors, had revealed that metallic
corrosion cost the United States $82 billion in 1975, or 4.9 percent of
its GNP. It was also found that 60 percent of that cost was unavoid-
able. The remaining $33 billion (40 percent) was said to be “avoidable”
and incurred by failure to use the best practices then known.
In the original Battelle study, almost 40 percent of 1975 metallic cor-
rosion costs were attributed to the production, use, and maintenance
of motor vehicles. No other sector accounted for as much as 4 percent
of the total, and most sectors contributed less than 1 percent. The 1995

Avoidable 19% 19%
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I.2 Examples of Catastrophic
Corrosion Damage
I.2.1 Sewer explosion, Mexico
An example of corrosion damages with shared responsibilities was the
sewer explosion that killed over 200 people in Guadalajara, Mexico, in
April 1992.
6
Besides the fatalities, the series of blasts damaged 1600
buildings and injured 1500 people. Damage costs were estimated at 75
million U.S. dollars. The sewer explosion was traced to the installation
of a water pipe by a contractor several years before the explosion that
leaked water on a gasoline line laying underneath. The subsequent
corrosion of the gasoline pipeline, in turn, caused leakage of gasoline
into the sewers. The Mexican attorney general sought negligent homi-
cide charges against four officials of Pemex, the government-owned oil
company. Also cited were three representatives of the regional sewer
system and the city’s mayor.
I.2.2 Loss of USAF F16 fighter aircraft
This example illustrates a case that has recently created problems in
the fleet of USAF F16 fighter aircraft. Graphite-containing grease is a
very common lubricant because graphite is readily available from steel
industries. The alternative, a formulation containing molybdenum
disulphide, is much more expensive. Unfortunately, graphite grease is
well known to cause galvanically induced corrosion in bimetallic cou-
ples. In a fleet of over 3000 F16 USAF single-engine fighter aircraft,
graphite grease was used by a contractor despite a general order from
the Air Force banning its use in aircraft.
7