ANODIC

PROTECTION

Theory and Practice in

the Prevention of Corrosion

ANODIC
PROTECTION

Theory and Practice in

the Prevention of Corrosion

OLEN L. RIGGS, JR.

Kerr - McGee Technical Center
Oklahoma City, Oklahoma

and

CARL E. LOCKE
University of Oklahoma
Norman, Oklahoma

Consulting editor
NORMAN E. HAMNER

WEST BROMWICH COLLEGE OF CO:'v1MERCE .-.,~D TECHNOLOGY

LIBRARY

PLENUM PRESS NEW YORK AND LONDON

Library of Congress Cataloging in Publication Data

Riggs, Olen L
Anodic protection.
Bibliography: p.
Includes index.
1. Metals-Anodic oxidation. l. Locke, Carl E., joint author. II. Hamner, Norman E.
Ill. Title.
TA462.R46
620.1'623
80-20412
ISBN-13: 978-1-4684-3874-1
e-ISBN-13: 978-1-4684-3872-7
DOl: lO.lO07/978-1-4684-3872-7

Although data and information included in this book have been checked carefully to
insure accuracy, application or use of the data and systems discussed is solely at the
risk of the user. There is no warranty, implied or otherwise, related to the use of the
information herein and no permission is extended covering the application and use of
patented equipment or systems.
Information herein credited to the Russian journal Protection of Metals (Zashchita
Metallov) is reprinted with permission of Plenum Publishing Corp., 227 W. 17th St.,
New York, N.Y. 10011 and is copyrighted by Plenum. Information herein credited to
the Journal of The Electrochemical Society is reprinted by permission of the publisher, The Electrochemical Society, Inc., P.O. Box 2071, Princeton, N.J. 08540.

1981 Plenum Press, New York

Softcover reprint of the hardcover 1st edition 1981

A Division of Plenum Publishing Corporation

227 West 17th Street, New York, N.Y. 10011
All righ ts reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted,
in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher

In appreciation for the thoughtful support,

we dedicate this book to
our understanding wives: Ann and Sammie

Preface

The objectives of this book are to give technical information about anodic protection, explain how economic analyses are made to determine whether or not
it should be used, and describe some of the applications and equipment. Limitations of the technique will be pointed out.
Technological changes that have resulted in higher temperatures, pressures, and velocities increase corrosion rates and markedly influence materials
selection and design decisions. Continuous cycle systems impose increased
demands on system reliability. New processes require more sophisticated
equipment made of costlier metals which are often in short supply and subject
to the vagaries of international commerce. The impact of continuing inflation
influences decisions related to capital expenditures and maintenance costs.
Some problems caused by these considerations can be solved, or solutions
simplified, by the use of anodic protection. Technical and scientific information
is presented on applications to industrial equipment, economics, design and
installation, operation and maintenance, electrochemical principles, laboratory
tests and procedures. A historical summary, patent list, glossary of terms, and
a subject index are included.
It is important to acknowledge that much of the information has been
from the original work of others, including the publications of many friends.
Many of the applications come from developments pioneered by scientists in
Russia, whose innovative work involves corrosive solutions to which anodic protection has not been applied elsewhere. Results of original research and engineering applications by the authors are also included. Manufacturers of equipment and system engineers have cooperated in supplying information and their
cooperation is gratefully acknowledged.
There is every reason to believe that an increasing number of anodic-protection installations will be made in environments where it has been successful
in the past, as well as in others in which it is not commonly used now. Better
understanding of reactions accumulated from actual working equipment and
from laboratory and pilot plant experimentation will permit its use in systems
where it has not been employed frequently so far.
vii

viii

Preface

Techniques and applications described in this book may encourage

increased applications of anodic protection. When this happens, the authors
will appreciate information about new installations and techniques that may
be used in revisions of this book.
Particular thanks is due to the Kerr-McGee Corporation for its continued
support and to the University of Oklahoma for its cooperation in making time
available to prepare the book. The authors also appreciate the cooperation of
publishers who have authorized use of many excerpts from their books. Without this cooperation, preparation of the book would have been much more
difficult.
The ready cooperation of industry, authors, and publishers that characterizes the technical and scientific community in the United States has been
instrumental in helping to make available information about ways to do things
better, easier, and more economically.
Olen Riggs, Jr.,
Kerr-McGee Corporation
Carl E. Locke,
University of Oklahoma
Norman E. Hamner,
Editorial Consultant

Contents
1 Anodic Protection of Metals-A Technique Whose Time Has Come.
Many Protective Methods Are Used. . . . . . . . . . . .
Anodic Protection Used Effectively.
Protection of Alloy Steel Important
Strategic and Absolute Factors Bearing on Materials. .
Substitute Alloys for Chromium
Prices of Substitute Alloys Increase.
Corrosion Protection Is Necessary
Contamination Control Important
Ecological Considerations Are Important.
Energy-Conservation Values
Applications and Limitations.
Limitations Can Be Anticipated . .
Installation Expense Factors
Rapid Development Anticipated.
References.

2 Anodic Protection of Industrial Equipment

Sulfuric Acid Applications
Sulfuric Acid Corrosion.
Hydrogen Attack Is Also a Problem
Product Purity Is Important
Protection of Sulfuric Acid Storage Equipment
Application Details in Storage Tanks.
Spent Sulfuric Acid.
Heat Exchangers for Sulfuric Acid
Transport of Sulfuric Acid
Protection Provided for Barge.
Nitrate Fertilizer Container Protection
Other Interesting Uses for Fertilizer Solutions
Pulp and Paper Industry Applications.
Miscellaneous Applications.
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Contents
Summary.
References.

3 Equipment for Anodic Protection

Characteristics of Electrodes.
Characteristics of the Cathode .
Platinum-Clad Cathodes .
Hastelloy C Cathodes
Stainless (Cr-Ni) Steel Cathodes.
Reference-Electrode Designs.
Calomel Half-Cell
Silver/Silver Chloride Half-Cell .
Mercury/Mercury Sulfate Half-Cell
Metal Oxide Electrodes.
Metals As Reference Electrodes.
Electronic Control and Power Supplies
Potential Controller .
Power Supplies
Summary.
References ..

4 Design, Operation, and Maintenance of Anodic Protection Systems

Design Requirements.
Electrochemistry
Establishing Electrochemical Parameters
Time Effects on Passivation Currents.
Electrodes .
Electronic-Hardware Selection.
Power-Supply Criteria.
I nstallation and Start-up
Electrode-Installation Modes
Electrical-Wiring Criteria.
Location of Power Supply and Controller
Start-up Procedures .
Operation and Maintenance Parameters
Corrosion-Rate Measurements ..
How to Take Solution Samples.
Commercial Units Reliable.
Summary
References.

5 Economic Evaluation of Anodic Protection.

Known Costs of Anodic Protection.
Costs of Small Tanks.
Data on Larger Tanks

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Contents
Current Costs of Protecting Steel Tanks Against Sulfuric Acid
Why Tanks Require Protection.
Cost of Internally Lining Tanks
Sulfuric Acid Coolers.
Summary.
References ..

6 Principles of Anodic Protection

Electrochemical Description of Passivity
Characteristics of Anodic-Polarization Curves
The Passive Metal Layer.
Proposed Mechanism of Iron Passivity.
Metal Passivity Breakdown .
References.

7 The Potentiostat
Potentiostat Mode.
Development of the Potentiostat .
Potential Control
Control Amplifier.
Current Regulator
Solid-State Potentiostats
Commercial Electronic Potentiostats
Portable/Field Potentiostat ..
Summary Comments on Potentiostatic Mode
The Potentiostat .
References.

8 Laboratory Tests and Procedures .

Wiring Sequence for Potentiostatic Experiments ..
Reproducibility of Potentiostatic and Potentiodynamic Anodic-Polarization
........
. ...... .
Measurements ..
Polarization Cells ..
Elevated-Pressure Polarization Cells.
Proposed Experimental Procedure.
Experimental Procedure.
High-Temperature Polarization Cells.
Crevice Corrosion Testing Polarization Cells ..
Summary.
References.

9 Selected Examples of Anodic Protection ..

Alloy Evaluation.
Alloy Effects. . ........... .

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Contents

xii
Concentration Effects ..
Temperature Effects.
Environmental Effects
Preliminary Investigations Are Necessary ..
Time Effects
References ....

10 Future Uses for Anodic Protection

A Realm of Probability
Cooling-Tower Water
Raney Catalyst.
Prosthetic Implants
Stainless Steel Pickling
Molten Salt-Metal Technology
Metallography
Coolant Systems.
Solution-Potential Concept
Sulfide Minerals.
Enzyme Production
Surface-Area-Ratio Concept
The Sufficiently Real Possibilities.
Potentiostatic Conditioning of Electrodes.
The Cell Cathode ..
The Electrochemical-Conditioning Concept
References

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APPENDIXES

1 Electrochemical Principles of Corrosion

Corrosion.
Electrode Terminology
Potential Series ..
Nernst Equation ..
The Electrical Double Layer
Free Energy.
Polarization Diagrams .
Electrochemical Equivalents of Metals.
Conversion Factors ..
Partial Electrochemical Equivalent.
References.

II Glossary

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Contents

xiii

III Historical Development

233

IV United States Patents Relating to Anodic Protection ..

235

V Bibliography

239

INDEX

281