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0765162_FM_Roberge 9/1/99 2:36 Page iii

Handbook of

Pierre R. Roberge

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
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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


Copyright © 2000 by The McGraw-Hill Companies, Inc. All rights

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ISBN 0-07-076516-2

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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 326

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 383
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
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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
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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
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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
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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-
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
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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.