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Library of Congress Cataloging-in-Publication Data:

Uhlig's corrosion handbook / edited by R. Winston Revie–3rd ed.

p. cm. –(The ECS series of texts and monographs)

Includes index.

ISBN 978-0-470-08032-0

eBook ISBN: 978-0-470-87285-7

oBook ISBN: 978-0-470-87286-4

Herbert H. Uhlig
March 3, 1907–July 3, 1993
This Handbook is dedicated to the memory of Herbert H. Uhlig.

Herbert Uhlig began his career at MIT in 1936 where, with the exception of the interruption caused by World War II, he remained until his retirement nearly 40 years later, bringing the MIT Corrosion Laboratory to a level of international prominence that it retains to this day as a major center of excellence. He helped to establish the Corrosion Division of The Electrochemical Society in 1942 and served as President of the Society in 1955–1956. His characteristics as an uncompromising innovator and meticulous scientist who insisted on reliable data and on achieving results led to the success of his many endeavors as educator and mentor, including the Corrosion Handbook, published in 1948, that he conceived, organized, and edited.

Editorial Advisory Board

Foreword

In the roughly 10 years since the appearance of the second edition of the Corrosion Handbook, new technologies and new engineering systems have found their way into the global marketplace at an increasing rate. It is no wonder now that a third edition would be timely and appropriate. It is also no surprise that the third edition would expand the scope of the previous editions to include chapters on composites such as are used in airframes, shape memory alloys which find application in medical devices, and electrodeposited nanocrystals as well as application-specific chapters which address the materials of construction of the engineered barriers for nuclear waste containment, ethanol-induced stress corrosion cracking of carbon steels, and other such topics. An entirely new section on corrosion monitoring also appears in the third edition.

Corrosion is ubiquitous: All engineering systems are subject to environmental degradation in service environments, whether these systems are used to meet the energy needs of the inhabitants of this planet; to provide clean air; to treat and transport water, food, and other products typical of our commercial world; to both save and improve the quality of our lives; and to ensure the readiness of those engineering systems that are of importance in terms of national defense and homeland security as well as many others. From heart stents to nuclear electric generating stations, corrosion is part of our world.

The Corrosion Handbook continues today, as it has since its first appearance over 60 years ago, to serve as a trusted resource to generations of corrosion engineers. There are many reasons to believe that its presence in the libraries of engineering practitioners of all kinds is greater now than ever before. First, it appears that much of the expertise in this area of technology, which resided for decades in the staff and laboratories of metal producers, has retired and is not being replaced as many of the metal producers have responded to the global economy of the past decade and more. Second, the interest of young people in engineering education, including corrosion engineering, is also in decline. Third, as the global economy recovers from the meltdown of the recent past, nations with a strong manufacturing base that creates products of value to the market will respond most quickly. But this will require an educated and informed engineering workforce. It is a concern to me that industrialized nations all over the world are on the brink of losing this technological infrastructure through retirement, the decline of traditional manufacturing industries, and declining student interest. Without a means of capturing this expertise in a useful form the next generation of engineers are going to find a gap in their knowledge base. I am confident that this volume will be of value in that context. Every industrialized nation must have the capacity and intellectual strength necessary to design, manufacture, and maintain either contemporary engineering systems or emerging engineering systems that may find their way into the marketplace of the future. The Corrosion Handbook remains an invaluable resource in that regard, and once again Winston Revie has assembled a world-class group of authors in producing a comprehensive volume covering the entire field of contemporary corrosion engineering.

R. M. Latanision
February 2010

Director (Emeritus)
The H. H. Uhlig Corrosion Laboratory, MIT, and
Corporate Vice President
Exponent–Failure Analysis Associates, Inc.
Natick, Massachusetts

Foreword to the Second Edition

The first and, prior to the current volume, only edition of the Corrosion Handbook was published in 1948. It represented a heroic effort by Professor Herbert Uhlig and the leadership of the relatively newly established Corrosion Division of the Electrochemical Society. It was intended, as Professor Uhlig recorded in the Preface to the 1948 edition, to serve as “. . . a convenient reference volume covering the entire field of corrosion, to bring together, in effect, much of the information scattered broadly throughout the scientific and engineering literature.” Its success was equally heroic: the Corrosion Handbook has served generation after generation of corrosion engineer and today, more than a one-half of a century since its first appearance, the volume remains a trusted resource in the personal libraries of many of those who populate the world's engineering community.

Over the years that I knew Professor Uhlig personally, he often mentioned to me his concern for the need to produce a revised edition of the Handbook. I am confident that he would have been very pleased that one of his doctoral students at MIT, Winston Revie, had taken up this challenge. Winston, just as his mentor, is a meticulous and innovative corrosion scientist. This truly monumental revision of the Corrosion Handbook is certain to serve the engineering community well as we enter the new millennium. Much has happened in corrosion science and engineering since 1948, and the contributors to this volume, an assembly of the international leaders in the field, have captured these changes wonderfully well. The breadth of corrosion and corrosion control is made clear by the inclusion of ceramics, polymers, glass, concrete and other materials as well as of metals, the focus of the first edition. The introduction of standards into corrosion science and engineering is emphasized as is life prediction, and economic and risk analyses associated with environmental degradation of materials.

While the introduction of new technologies has dramatically changed virtually every aspect of life on the Earth in the fifty years since the appearance of the Corrosion Handbook, what remains a persistent reality in the engineering enterprise is that engineering systems are built of materials. Whether an airframe, integrated circuit, bridge, prosthetic device or, perhaps as we shall see in the not too distant future, implantable drug delivery systems—the chemical stability of the materials of construction of such systems continues to be a key element in determining their useful life. This new edition of the Corrosion Handbook will serve, among others, designers, inspectors, owners and operators of engineering systems of all kinds, many of which are unknown today, for generations to come. Dr. Revie has succeeded, just as did his mentor in 1948, in producing a convenient reference volume covering the entire field of corrosion.

R. M. Latanision

H. H. Uhlig Corrosion Laboratory
Massachusetts Institute of Technology
Cambridge, Massachusetts

Preface

The objective in preparing this third edition of Uhlig's Corrosion Handbook has been to provide an updated book—one affordable volume—in which the current state of knowledge on corrosion is summarized. The fundamental scientific aspects and engineering applications of new and traditional materials and corrosion control methods are discussed, along with indications of future trends. The book is intended to meet the needs of scientists, engineers, technologists, students, and all those who require an up-to-date source of corrosion knowledge. This new edition contains a total of 88 chapters divided among six parts:

Topics discussed in chapters that are new in this edition include failure analysis (Chapter 1), principles of accelerated corrosion testing (Chapter 73), metal–matrix composites (Chapter 35), nanocrystals (Chapter 37), ethanol stress corrosion cracking (Chapter 50), computation of Pourbaix diagrams at elevated temperature (Chapter 9), high-temperature oxidation (Chapters 20 and 74), dealloying (Chapter 11), and diagnosing, measuring, and monitoring microbiologically influenced corrosion (MIC) (Chapter 88). Dr. Tomomi Murata has provided some very insightful introductory notes on the effects of climate change, life-cycle design, and corrosion of steel under changing atmospheric conditions.

Throughout the book, extensive reference lists are included to help readers identify sources of information beyond what could be included in this one-volume handbook.

It is a pleasure to acknowledge the authors who wrote the chapters of this edition as well as the reviewers, who, in anonymity, carried out their work in the spirit of continuous improvement. I would also like to acknowledge the members of the Editorial Advisory Committee, who made many constructive suggestions to help define, focus, and clarify the discussions in this new edition. I would like to acknowledge Mary Yess and her staff at The Electrochemical Society Headquarters in Pennington, New Jersey, for their support during the preparation of this book. I greatly appreciate the encouragement and support of Bob Esposito and his staff at John Wiley & Sons, Inc. in Hoboken, New Jersey.

Finally, I would like to thank my many friends and colleagues at the CANMET Materials Technology Laboratory, where it has been my privilege to work for the past 32 years.

R. Winston Revie

Ottawa, Ontario, Canada

Contributors

^aAgarwal, D. C., DNV Columbus, Inc., Dublin, Ohio, USA

Bale, C. W., Département de génie physique et de génie des matériaux, Ecole Polytechnique, Montréal, Québec, Canada

Beavers, J, A., DNV Columbus, Inc., Dublin, Ohio, USA

Been, J., Alberta Innovates Technology Futures, Calgary, Alberta, Canada

Böhni, H., Institute of Materials Chemistry and Corrosion, Swiss Federal Institute of Technology, Zürich, Switzerland (Retired)

Broomfield, J. P., Corrosion Consultant, London, UK

Campion, R. P., MERL Ltd., Wilbury Way, Hitchin, UK

Cox, B., Centre for Nuclear Engineering, University of Toronto, Toronto, Ontario, Canada (Retired)

Crook, P., Haynes International, Kokomo, Indiana, USA (Retired)

^a Eden, D. A., Honeywell Process Solutions, Houston, Texas, USA

Eiselstein, L. E., Exponent-Failure Analysis Associates, Inc., Menlo Park, California, USA

Efird, K. D., Efird Corrosion International, Inc., The Woodlands, Texas, USA

Elboujdaini, M., CANMET Materials Technology Laboratory, Ottawa, Ontario, Canada

Erb, U., Department of Materials Science and Engineering, University of Toronto, Toronto, Ontario, Canada

Falkland, M. L., Outokumpu Stainless AB, Avesta, Sweden

Fitzgerald III, J. H., Grosse Pointe Park, Michigan, USA

Ford, T. E., University of New England, Biddeford, Maine USA

Frankenthal, R. P., Bell Laboratories, Lucent Technologies, Murray Hill, New Jersey, USA (Retired)

Garfias-Mesias, L. F., DNV Columbus, Inc., Dublin, Ohio, USA

Ghali, E., Department of Mining, Metallurgy and Materials, Laval University, Québec, Canada

Glaes, M., Outokumpu Stainless AB, Avesta, Sweden

Goodwin, F. E., International Lead Zinc Research Organization, Inc., Research Triangle Park, North Carolina, USA

Grambow, B., La Chantrerie, Laboratoire SUBATECH (UMR 6457), Ecole des Mines de Nantes, Nantes Cedex 3, France

Grauman, J. S., TIMET, Henderson, Nevada, USA

Grubb, J. F., Technical & Commercial Center, ATI Allegheny Ludlum Corp., Brackenridge, Pennsylvania, USA

Gu, J.-D., School of Biological Science, The University of Hong Kong, Hong Kong, China

Gui, F., DNV Columbus, Inc., Dublin, Ohio, USA

Hare, C. H., Coating System Design Inc., Lakeville, Massachusetts, USA (Retired)

Hashimoto, K., Tohoku Institute of Technology, Sendai, Japan

Heidersbach, R., Dr. Rust, Inc., Cape Canaveral, Florida, USA

Hihara, L. H., Department of Mechanical Engineering, University of Hawaìi at Manoa, Honolulu, Hawaii, USA

Huet, R., Exponent-Failure Analysis Associates, Inc., Menlo Park, California, USA

Jack, T. R., University of Calgary, Calgary, Alberta, Canada

John, R. C., Shell International E&P, Inc., Houston, Texas, USA

Jordan, D. L., Ford Motor Company, Dearborn, Michigan, USA

Kane, R. D., iCorrosion LLC, Houston, Texas, USA

Kaye, M. H., Faculty of Energy Systems and Nuclear Science, University of Ontario Institute of Technology, Oshawa, Ontario, Canada

Khaladkar, P. R., E. I. DuPont de Nemours & Co, Inc., Wilmington, Delaware, USA

King, G. A., CSIRO Building, Construction and Engineering, Highett, Victoria, Australia (Retired)

Kruger, J., Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland, USA (Retired)

Latanision, R. M., Exponent-Failure Analysis Associates, Inc., Natick, Massachusetts, USA

Lee, J. S., Naval Research Laboratory, Stennis Space Center, Mississippi, USA

Lewis, B. J., Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, Ontario, Canada

Liljas, M., Outokumpu Stainless AB, Avesta, Sweden

Little, B. J., Naval Research Laboratory, Stennis Space Center, Mississippi, USA

Malhotra, V. M., Consultant, Ottawa, Ontario, Canada

^aMatsushima, I., Maebashi Institute of Technology, Maebashi, Japan

Mendez, M., Honeywell Corrosion Solutions, Houston,Texas, USA

Meng, Q. J., Honeywell Corrosion Solutions, Houston, Texas, USA

Mitchell, R., Laboratory of Microbial Ecology, Harvard School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts, USA

Mitton, D. B., Gold Standard Corrosion Science Group, LLC, Boston, Massachusetts, USA

Morris, P. I., FPInnovations, Vancouver, BC, Canada

Murata, T., Office of Technology Transfer Innovation Headquarters, Japan Science and Technology Agency, Tokyo, Japan

^aMurphy, T. P., Campion Hall, University of Oxford, Oxford, UK

Neši, S., Institute for Corrosion and Multiphase Flow Technology, Ohio University, Athens, Ohio, USA

Nessim, M., C-FER Technologies Inc., Edmonton, Alberta, Canada

Norsworthy, R., Lone Star Corrosion Services, Lancaster, Texas, USA

Papavinasam, S., CANMET Materials Technology Laboratory, Hamilton, Ontario, Canada

^aParkins, R. N., University of Newcastle upon Tyne, Newcastle upon Tyne, UK

Pelton, A. D., Département de génie physique et de génie des matériaux, Ecole Polytechnique, Montréal, Québec, Canada

Piro, M. H., Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, Ontario, Canada

Postlethwaite, J., Department of Chemical Engineering, University of Saskatchewan, Saskatoon, Saskatchewan, Canada (Retired)

Ray, R. I., Naval Research Laboratory, Stennis Space Center, Mississippi, USA

Rebak, R. B., GE Global Research, Niskayuna, New York, USA

Reid, M., Stokes Research Institute, University of Limerick, Limerick, Ireland

Revie, R. W., CANMET Materials Technology Laboratory, Ottawa, Ontario, Canada

Rigaud, M., Département de génie physique et de génie des matériaux, Ecole Polytechnique, Montréal, Québec, Canada

Roberge, P. R., Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, Ontario, Canada

Ruddick, J. N. R., Department of Wood Science, Forest Sciences Centre, University of British Columbia, Vancouver, B.C., Canada

Sequeira, C. A. C., Instituto Superior Técnico, Lisboa, Portugal

Shibata, T., Department of Materials Science and Processing, Graduate School of Engineering, Osaka University, Japan (Retired)

Silence, W. L., Consultant, Fairfield Glade, Tennessee, USA

Silverman, D. C., Argentum Solutions, Inc., Chesterfield, Missouri, USA

Sridhar, N., DNV Columbus, Inc., Dublin, Ohio, USA

Srinivasan, S., Advanced Solutions–Americas, Honeywell International, Inc., Houston, Texas, USA

Staehle, R. W., University of Minnesota, Minneapolis and Industrial Consultant, North Oaks, Minnesota, USA

^aStreicher, M. A., E. I. DuPont de Nemours & Co., and the University of Delaware, Newark, Delaware

Thompson, W. T., Centre for Research in Computational Thermochemistry, Royal Military College of Canada, Kingston, Ontario, Canada

Thomson, B., MERL Ltd., Wilbury Way, Hitchin, UK

Verink, Jr., E. D., Department of Materials Science and Engineering, University of Florida, Gainesville, Florida, USA (Retired)

Wang, Y.-Z., Canadian Nuclear Safety Commission, Ottawa, Ontario, Canada

Wilmott, M., Wasco Coatings Ltd., Kuala Lumpur, Malaysia

Young, A. L., Humberside Solutions Ltd., Toronto, Ontario, Canada

Yunovich, M., Honeywell Corrosion Solutions, Houston, Texas, USA

Zhang, X. G., Teck Metals Ltd., Mississauga, Ontario, Canada

a. Deceased.

Introductory Notes on Climate Change, Life-Cycle Design, and Corrosion of Steel

T. Murata

Japan Science & Technology Agency, Saitama, Japan

A. Climate Change

Climate change is attributed mainly to increased CO₂ in our atmosphere because of anthropogenic activities and is expected to increase as much as 50% by 2030 compared to the concentration in 2005, that is, 359 ppm [1, 2]. Such a change will affect the corrosion of carbon steel through acidification due to increased concentration of HCO₃⁻ and Ca²⁺ in waters at temperatures a few degrees Celsius higher than those in 1990. In addition, other influential factors that will arise from climate change include the following:

For these reasons, the corrosivity of environments in the future will be complex, and a simple acidification model will not be adequate. To predict the effects of climate change on corrosion, computational analyses and systematic corrosion studies are required to develop models based on projected climate change.

“Time of wetness” is universally considered to be a key corrosion index for atmospheric corrosion. In recent years, weather instability has led to changes in global rainfall distribution, changes that could lead to new and different predictive indices for atmospheric corrosion. For corrosion in waters, microbiological factors are expected to increase in importance with the changing climate. In contrast to the environmental factors that pertain to corrosion in air and water, the heterogeneous distribution of chemicals in contaminated soils in industrialized areas results in nonuniform soil corrosivity. Dynamic corrosion models are required with on-site monitoring systems.

B. Life-Cycle Design

To minimize the environmental burden and to attain a sustainable society, life-cycle design of steel structures is required to ensure safety, reliability, durability, and the best use of materials and energy throughout the life cycle. The life-cycle concept will be required for future design and construction of social as well as industrial infrastructure. For example, in developing a life-cycle design for weathering steels, discussed in Chapter 48, reliable corrosion data for long-term service and a systematic approach to minimize both corrosion damage and social costs are necessary.

In general, corrosion is studied using a set of parameters under simplified or fixed conditions. In the real world, in response to constantly changing environmental parameters, corrosion behavior also changes. For this reason, an understanding of corrosion dynamics is required, and the corrosion protection models that are implemented must have a capacity to reflect dynamic environmental conditions that are subject to constant change.

References

1. Intergovernmental Panel on Climate Change (IPCC), “Climate and Water,” Technical Paper VI, Geneva, June 2008.

2. Intergovernmental Panel on Climate Change (IPCC), “Implications of Proposed CO₂ Emissions Limitations,” Technical Paper IV, Geneva, Oct. 1997, Figure 6, p. 16.

Part I

Basics of Corrosion Science and Engineering