Marine Engineering Series MARINE AND OFFSHORE PUMPING AND PIPING SYSTEMS J Crawford, CEng, FIMarE MARINE AUXILIARY MACHINERY—5th edition E Souchotte, CEng, FIMechE, MIMarE David W Smith, CEng, MIMarE MARINE DIESEL ENGINES—5th edition Edited by C C Pounder MARINE ELECTRICAL PRACTICE—5th edition G O Watson, FIEE, FAIEE, MIMarE MARINE STEAM BOILERS—4th edition J H Milton, CEng, FIMarE, MNECIES R M Leach, CEng, MIMechE, FIMarE MARINE STEAM ENGINES AND TURBINES-4th edition S C McBirnie, EEng, MIMechE Marine and Offshore Corrosion Kenneth A Chandler BSc, CEng, FIM, ARSM, FICorrT BUTTERWORTHS London—Boston—Durban—Singapore—Sydney—Toronto—Wellington All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, including photocopying and recording without the written permission of the copyright holder, application for which should be addressed to the publishers. Such written permission must also be obtained before any part of this publication is stored in a retrieval system of any nature. This book is sold subject to the Standard Conditions of Sale of Net Books and may not be resold in the UK below the net price given by the Publishers in their current price list. First published 1985 © Butterwort h & Co (Publishers) Ltd, 1985 British Library Cataloguing in Publication Data Chandler, Kenneth A. Marine and offshore corrosion. 1. Sea-water corrosion. I. Title 620'.4162 TA462 ISBN 0-408-01175-0 Library of Congress Cataloging in Publication Data Chandler, Kenneth A. Marine and offshore corrosion. Bibliography : Includes index. 1. Sea-water corrosion. 2. Offshore structures— Corrosion. I. Title. TA462.C462 1984 620.Γ1223 84-7009 1 ISBN 0-408-01175-0 (U.S.) Filmset by Mid-County Press Printed by Thetford Press Ltd. Bound by Anchor Brendon Ltd. Preface 'Thy needles—now rust disus'd and shine no more' W Cowper (17th Century) This book was originally intended as a revision of Marine Corrosion written by T Howard Rogers and published fifteen years ago. There have, however, been many developments in the field of marine corrosion in the intervening period. Corrosion control in marine situations has become a matter of increasing importance with discoveries of offshore oil and the greater demands being made on the utilisation of the sea's resources for food, fresh water and for energy requirements, e.g. by wave motion. The original book Marine Corrosion was particularly concerned with shipbuilding and the marine engineering associated with it. To allow for a more detailed treatment of general engineering requirements, particu larly of protective coatings for steelwork, the balance of content places less emphasis on ships although a treatment of this topic is included. Consequently, this is really a new book although elements from the original book have been included. It also has a new title to reflect its purpose. Clearly when preparing a book, the author must have in mind his readership. This particular book has been prepared for engineers and designers who are not corrosion specialists but have to deal with marine corrosion problems as part of their day-to-day professional activities. Although the term 'engineer' covers a wide field, the book is not primarily for those who describe themselves as 'corrosion engineers'. However, because corrosion is becoming very specialised and many experts in, say, cathodic protection do not necessarily have expertise in alloy selection, it is hoped that much will be of interest to them. Because the topic—marine and offshore corrosion—covers such a large field, it would be imprac ticable in a book of this size to provide a detailed treatment of every aspect. The aim has been to cover the major aspects in reasonable detail but where appropriate, having drawn a matter to the attention of the reader, to indicate further sources of information. Although general data is included in the book it is not intended as a data handbook. The aim is to indicate the principles on which good corrosion control treatments are based and to highlight some of the problems that have to be overcome to achieve economic solutions to corrosion. Data is generally provided to illustrate a point or a principle and is not intended for design purposes. Where corrosion data is used by designers it is advisable to refer to the original publication because there may be 'caveats' regarding the use of such information in circumstances different from those in which it was obtained. Materials are often being used to near their engineering limit in marine situations and new materials will be developed to meet the requirements which are bound to increase in the next decade or so. Such materials may well be subject to localised and stress-related forms of corrosion and considerable research efforts will be required to overcome some of these difficulties and some of our present problems. The requirements for adequately protecting steel structures from corrosion by painting will also lead to new developments in coatings, cleaning and application techniques. Those involved in marine corrosion must, therefore, maintain close contact with such developments. The basic principles of corrosion and its control are largely established and they are set out in this book but the solutions to many problems remain to be resolved. It should be borne in mind that the aim of designers is not usually to prevent corrosion but to control it within acceptable economic limits, so they are not necessarily concerned with the most corrosion-resistant materials but the ones that have the overall properties of strength, weldability, formability, corrosion resistance and cost that will provide the most effective economic solutions to engineering problems. Corrosion control is only a part of this overall requirement but often a very important part, and so deserves the attention appropriate to the economic consequences that will arise from its neglect. Finally, in any book there will be some chapters where the reader considers the level of treatment too low and others where it is at a level unnecessarily high for his purposes. This book is essentially practical in concept and, apart from the chapter concerned with principles of corrosion, the treatment of theoretical matters is kept to a minimum, although it is hoped that readers will—where appropriate—study matters in more detail by referring to the publications noted at the end of each chapter. KAC Acknowledgements In this book reference is made to published work by other authors and investigators but because of the practical nature of the book and because it is intended for practising engineers, references have been limited to those papers and books from which data has been extracted or where the original work may, to advantage, be studied. The knowledge of corrosion and its control is, of course, gained in many ways other than by one's own reading, research and experience. Discussions with colleagues, attendance at conferences and meetings are all important means of developing views on matters of interest. Often the original source of the information or concepts that one uses as a basis for published work is no longer clear. I, therefore, take this opportunity to thank all those with whom I have been involved on corrosion and related matters and apologise for any omissions of specific acknowledgements for contributions they may have made to my views on marine corrosion. I wish to thank Dr Lionel Shreir, OBE, for useful comments and for his permission to use material from his many published papers on the principles and theories of corrosion. These and his work for the Department of Industry (UK) form the basis of Chapter 2 'Principles of Corrosion'. I thank Mr Bryan Wyatt who supplied the material for the chapter on cathodic protection and Mr Hector Campbell for his advice on parts of the chapter on non-ferrous metals. Also thanks are due to the late Mr T Howard Rogers who gave permission shortly before his death for the use of material from his book Marine Corrosion (Butterworths, 1968) in the chapters dealing with marine environments. Mr. John Morley is thanked for data on piling. Finally, I wish to express my thanks to my wife, Veronica, who has painstakingly typed and checked the drafts of this book. In tr odu ct ion : The control of corrosion in marine 1 environments This book is concerned with the control of corrosion in marine environments and in this chapter the general causes of corrosion and the various means of controlling it will be considered in broad terms. Other chapters deal with specific areas of corrosion and control in more detail. Corrosion can be defined in a number of ways but ‘the chemical or electrochemical reaction of a metal or an alloy with its environment’ provides a reasonable explanation of the term ‘corrosion’. It is one of the two common causes of metal deterioration, the other being the mechanical loss of the metal by erosion, abrasion or wear. Sometimes there is a joint action of corrosion and erosion. Although corrosion can sometimes be prevented, the aim is usually to control it within economic limits. There are situations where no corrosion at all is acceptable, but these are few. Generally, the choice ofmaterials is based on regular maintenance during the life of the construction. This is a sensible approach provided it is part of the design philosophy. Corrosion can be a very serious problem when it occurs unexpectedly and emergency measures have to be taken to deal with it. Economic considerations are the essence of corrosion control procedures, but not necessarily in a straightforward way. Designers and engineers should be aware of the economics of corrosion but they cannot necessarily make the final decision in these matters. Other personnel are involved, not least accountants, and hopefully the corrosion require- ments will properly be considered in relation to other factors. Never- theless, the deciding factor may be the strength of a structure, time for construction, availability of materials and, of course, capital cost. Therefore corrosion control is a matter ofoptions to fit in with the many other requirements to be taken into account by the design team. Often corrosion problems arise because, due to changes in design that often take place in the early stages of a project, the materials or coatings originally selected may not be suitable at a later stage, where the conditions and environments may have changed. Furthermore, on large structures and 1 2 INTRODUCTION: THE CONTROL OF CORROSION plant, different parts may be designed by different teams. If there is not close contact between them, corrosion and, incidentally, other problems may well occur. Generally, the overall corrosion requirements can be handled in a fairly straightforward way. The solutions may be a compromise but if the materials or coatings chosen are known to have limitations, this can be taken into account in the maintenance or monitoring procedures. More serious problems arise where changes are made, of which those concerned or responsible for the corrosion elements in the design are not aware. A change to a more corrosion-resistant alloy may be advantageous for a particular section of the plant or structure. However, the new alloy may cause problems, e.g. bi-metallic corrosion, in another part of the plant. Designers must take such matters into account. The word 'design' will appear many more times in this book. Corrosion control in marine engineering is basically a design problem, using the term in its widest sense. It is not just a question of choosing resistant materials or very durable coatings, it is a matter of fitting together all the different elements to reduce corrosion to an acceptable and economic level. Additionally it concerns the choice and selection of materials and coatings that will meet the requirements of both performance and cost. The marine environment is a very aggressive one and new materials will be developed to provide improved properties, including corrosion resistance, for the constructions and plant that will be required as more demands are made upon the sea's resources. It is, therefore, necessary to maintain a close contact with such developments. The basic principles of corrosion and its control, however, remain largely unchanged; it is their application to new problems that will result in improvements both of an economic and technical nature. 1.1 THE CORROSION PROCESS Corrosion is an electrochemical process and is discussed in detail in Chapter 2. To assist in the explanation of control methods, a summary of the basic reactions will be considered. The process can be broken down into anodic and cathodic reactions. If one of these reactions is controlled then the overall rate of corrosion is affected. It is important to appreciate the electrochemical nature of corrosion because the control methods are based on altering or stifling one or other, or both, of the electrode processes. If the corrosion of carbon steel is considered in very simple terms it can be explained as follows. The steel is not homogeneous and at the initiation of corrosion anodic and cathodic sites are formed on the surface of the alloy. In the presence of an electrolyte, small corrosion cells are set up on the surface and at the anodic areas iron goes into solution as INTRODUCTION: THE CONTROL OF CORROSION 3 ferrous ions, i.e. the steel corrodes. Various reactions can occur at the cathode. The cathodic reaction under ordinary atmospheric or immersed conditions results in the production of hydroxyl ions and the two reactions can be written as follows: Anode: 2Fe -► 2Fe2+ + 4e~ Cathode: 0 + 2H 0 + 4e" -> 40H" 2 2 The two products Fe2+ and OH~ react together to form ferrous hydroxide which eventually is oxidised further to rust : Fe2+ + 20H- -+ Fe(OH) -+ FeOOH (rust) 2 Either the anodic or cathodic process can be controlled. If rust is formed at the steel surface, it will stifle the process so, despite the availability of moisture and oxygen, the corrosion rate may be reduced. In practice, on carbon steels, the anodic process at one place is stifled and corrosion begins at new sites—hence the general nature of the corrosion. With other alloys, e.g. stainless steel, the anodic reaction may continue for some time at the original site and result in localised pitting. However, under most circumstances, there are many fewer anodic sites on stainless steel than on carbon steel, so the overall corrosion is much less. Most corrosion is of the general type and arises from the rusting of steel, the most widely used constructional alloy. The general methods for controlling it are considered below and, of these, coating the steelwork is the most commonly used. To achieve reasonable standards of protection by coatings does not generally require a very deep knowledge of corrosion. However, particularly in marine environments, an under standing of corrosion processes does assist engineers to appreciate the importance of matters such as surface preparation of steelwork and the choice of suitable coatings. When considering other forms of attack such as pitting and bimetallic corrosion, an appreciation of corrosion processes is important. Many simple general corrosion concepts may turn out to be either incorrect in specific situations or not quite as simple as had been anticipated. For example, it is generally considered that reinforcements in concrete do not corrode because concrete provides an alkaline environment, which is non-corrosive to steel. This is generally true, but if chloride ions—in plentiful supply in marine conditions—reach the steel, they can in fact affect its passivity, causing attack. Again although in theory two metals joined together might be expected to lead to serious bimetallic corrosion of one of them, this may not necessarily happen in practice because of various effects such as the polarisation of the anodic and cathodic sites, the nature of the environment or the relative areas of the two metals. 4 INTRODUCTION: THE CONTROL OF CORROSION 1.2 CORROSION CONTROL As corrosion results from a reaction between an alloy and its environ ment, the basic control methods are concerned with treating the environment or selecting suitable alloys. The methods can be grouped into four main categories, irrespective of which of the two factors— environment or material—are of major importance. (i) Use of coatings. (ii) Selection of materials that will resist a particular environment. (iii) Cathodic protection. (iv) Control or treatment of the environment. A fifth method really covers the proper application of the other methods in practice but may be considered as a method of control, i.e. design. If corrosion control is considered to be more than a technical approach to the problem, then other matters related to the maintenance of the structural integrity or operational efficiency must be considered. This would include requirements for access to carry out maintenance and the overall design in relation to the successful application of the control procedures. Often more than one method of control may be employed and this may be advantageous from the economic standpoint. 1.2.1 Coatings Coatings used to protect carbon steel in marine environments are considered in detail in other parts of the book. A few fundamental points concerning them are, however, worth considering. Coatings are the most common method by far, in terms of steel tonnage, for controlling corrosion. The basic concept is not usually electrochemical in nature, it is simply to insulate the alloy from the corrosive environment. In practice, however, many problems arise and often insufficient attention is paid to them because of the apparently simple nature of coating systems. A range of different types of coating is available, the most common of which are paints although metal coatings, plastics, waxes, greases and other materials are also used. Organic coatings are basically of two types : those that are applied manually, e.g. by spraying or brushing, and those that are applied in works, e.g. plastisols. All organic coatings are permeable to moisture and oxygen to a greater or lesser extent and to overcome this, there has been a growing tendency to specify thicker coatings for marine situations. This has been made possible by the nature of coatings such as epoxies and