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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

99-35898 CIP

Library of Congress Cataloging-in-PublicationData

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

McGraw-Hill

Copyright © 2000 by The McGraw-HillCompanies, Inc. All rights reserved. Printed in the United States of America. Except as permitted 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 Joanne Morbit and Paul Scozzari of McGraw-Hill’sProfessional Book Group in Hightstown, N.J.

Printed and bound by Quebecor/Martinsburg.

This book was printed on recycled, acid-freepaper containing a minimum of 50% recycled,de-inkedfiber.

McGraw-Hillbooks are available at special quantity discounts to use as premiums and sales promotions, or for use in corporate training programs. For more information, please write to the Director of Special Sales,McGraw-Hill,11 West 19th Street, New York, NY 10011. Or contact your local bookstore.

Information contained in this work has been obtained by The McGraw-HillCompanies, Inc.(“McGraw-Hill)from sources believed to be reliable. However, neitherMcGraw-Hillnor its authors guarantee the accuracy or completeness of any information published herein and neitherMcGraw-Hillnor its authors shall be responsible for any errors, omissions, or damages arising out of use of this information. This work is published with the understanding thatMcGraw-Hilland its authors are supplying information but are not attempting to render engineering or other professional services. If such services are required, the assistance of an appropriate professional should be sought.

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-pHDiagrams

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-TemperatureCorrosion

221

3.1

Thermodynamic Principles

222

3.2

Kinetic Principles

229

3.3

Practical High-TemperatureCorrosion Problems

237

References

265

Contents

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-BasedTraining 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-destructiveEvaluation (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-PerformanceAlloys

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

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

Contents

Appendix E. Chemical Compositions of Engineering Alloys

1061

Appendix F. Thermodynamic Data and E-pHDiagrams

1101

Appendix G. Densities and Melting Points of Metals

1125

Index

1129

 

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, theHandbook of Corrosion Engineering is the result of an extensive survey ofstate-of-the-artinformation 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 scientists and engineers in understanding and preventing the effects of corrosion, 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 moderninformation-processingtechniques 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 information 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 comprehensive 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 significant. There have been substantial developments in newer stainless steels, high-strengthlow-alloysteels, 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

Preface

Chapters 1 to 3) contains fundamental principles governing aqueous corrosion and high-temperaturecorrosion and covers the main environments 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 prediction and assessment of corrosion damage such as modeling, life prediction, 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 corrosion 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 particularly valuable for its detailed descriptions of the performance and maintenance 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 compensate 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 economics with examples detailing calculations based on straight value depreciation. The fourth appendix provides a detailed introduction to basic electrochemical principles. Many examples of E-pH(Pourbaix) diagrams are provided in a subsequent appendix. The designations and compositions of engineering alloys is the subject of a fifth appendix.

Pierre R. Roberge

Acknowledgments

The Handbook of Corrosion Engineering was designed entirely in collaboration 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 present 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 scientists. 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 damage. 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.