Electrocorrosion and Protection of Metals: General Approach with Particular Consideration to Electrochemical Plants
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A new approach to the problem of electrocorrosion protection of passive structural metals is considered in this book, keeping the metals attacked by external currents in the boundaries of their passive field. The systems, developed in accordance with this approach, are based on the modification of existing and elaboration of new methods of electrocorrosion protection. These systems take into account corrosion and electrochemical characteristics of the aggressive media (redox potential, conductivity etc.) and of the passive metal (corrosion and activation potentials, current density in a passive state, etc) as well as the sizes and distribution character of the external currents.
The book covers analysis of leakage current distributions in electrochemical plants, their influence, methods to estimate corrosion stability of metallic structures subject to external currents and presents many concrete examples of the successful introduction of corrosion protection systems in operating plants.
- A new approach to protection from electrocorrosion, taking into account the passive state of the metal in aggressive media
- Newly developed and modifications of well known methods of electrocorrosion protection are presented
- Systematized data on electrocorrosion and protection of metals, especially in electrochemical plants, allow corrosion engineers, researchers and personnel maintaining the equipment of electrochemical plants to analyze the corrosion state of metallic equipment and prevent electrocorrosion
Joseph Riskin
Dr. Riskin has his M.Sc. in Chemical Engineering and Ph.D. in Corrosion and Protection of Metals, Consulting on corrosion protection of metals and failure analysis. Dr J. Riskin during 15 years was a head of laboratory “Protection of metals against electrocorrosion in Moscow Corrosion Institute, Russia. In Israel (Haifa) his activity also included this field.
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Electrocorrosion and Protection of Metals - Joseph Riskin
Riskin
Brief Table of Contents
Copyright Page
Dedication
Preface
Introduction
Chapter 1. Dependence of the Corrosion Behavior of Metals Attacked by an External Current on Their Initial State
Chapter 2. Corrosion and Protection of Underground and Underwater Structures Attacked by Stray Currents
Chapter 3. Operating Features of Electrochemical Plants
Chapter 4. Using Structures of Metallic Materials in Electrochemical Plants without Taking into Account Attack by Leakage Currents
Chapter 5. Corrosion Behavior Investigations of Traditional Structural Metallic Materials in Electrochemical Plant Media, Taking Into Account Attack by Leakage Currents
Chapter 6. Corrosion Behavior Investigations of Titanium and its Alloys in the Media of Electrochemical Plants, Taking into Account the Attack by Anodic Leakage Currents
Chapter 7. Hydrogenation and Corrosion Investigations of Titanium Under Attack by an External Cathodic Current
Chapter 8. Estimation of Corrosion Stability of Structures Made of Passive Metals in Aggressive Media, in the Field of an External Current
Chapter 9. Electrocorrosion Protection of Metals in Electrochemical Plants Based on Existing Methods
Chapter 10. New Principles of Protection of Passive Metals Against Electrocorrosion in Electrochemical Plants
Chapter 11. Electrodes for Metal Protection Against Corrosion Attack by Leakage Currents in Electrochemical Plants
Chapter 12. Industrial Tests and the Introduction Into Electrochemical Plants of the Developed Methods for the Protection of Metals Against Corrosion Attack by Leakage Currents
Table of Contents
Copyright Page
Dedication
Preface
Introduction
Chapter 1. Dependence of the Corrosion Behavior of Metals Attacked by an External Current on Their Initial State
1.1. State of Metals in Aggressive Media in the Absence of Attack by External Currents
1.2. Polarization of Metals
1.3. Attack of External Anodic Current on Actively Corroding Metals
1.4. Attack of External Anodic Current on Passive Metals
1.5. Attack of External Anodic Current on Thermodynamically Stable Metals
1.6. Attack of External Cathodic Current on Metals
1.7. Attack of External Alternating Current on Metals
1.8. External Current as a Factor of the Aggressiveness of the Environment
Chapter 2. Corrosion and Protection of Underground and Underwater Structures Attacked by Stray Currents
2.1. Main Media, Sources of Stray Currents and Objects of Their Corrosive Attack
2.2. Methods of Detection and Control of Stray Currents
2.3. Metal Corrosion by Stray Currents
2.4. Protection of Metals Against Corrosion Attack by Stray Currents
2.4.1. Measures for reducing stray currents
2.4.2. Protection of underground structures by electrodrainage
2.4.3. Cathodic protection
Chapter 3. Operating Features of Electrochemical Plants
3.1. General Characteristics of Electrochemical Plants
3.2. Leakage Currents in Electrochemical Plants
3.2.1. Sources of leakage currents, concepts and problems connected with them
3.2.2. Methods of measuring and controlling leakage currents
3.2.3. Magnitudes and distribution regularity of leakage currents along the lines of electrochemical cells
3.3. Aggressive Media
Chapter 4. Using Structures of Metallic Materials in Electrochemical Plants without Taking into Account Attack by Leakage Currents
4.1. Non-Metallic Materials
4.2. Traditional Metallic Materials
4.3. Experience in the Field of Titanium Application
4.3.1. Preconditions for the application of titanium in electrochemical plants
4.3.2. Attempts at titanium application in the zones of attack by leakage currents
4.3.3. Preconditions and experience of titanium application in wet chlorine lines of electrochemical plants
4.3.4. Laboratory and industrial tests of titanium resistance against crevice corrosion in wet chlorine and in chlorine-saturated water: Comparison of results
Chapter 5. Corrosion Behavior Investigations of Traditional Structural Metallic Materials in Electrochemical Plant Media, Taking Into Account Attack by Leakage Currents
5.1. Carbon Steel in Neutral, Alkaline and Chloride-Alkali Media
5.1.1. Neutral solutions of salts
5.1.2. Alkaline solutions
5.1.3. Chloride-alkali solutions
5.2. Stainless Steel 18-10 in Alkaline and Acid Media
5.2.1. Solution of 50% NaOH at 120°C; comparison of corrosion behavior of stainless steel 18-10 and of nickel
5.2.2. Technological solution for producing sodium perborate
5.2.3. Acid sulfate containing electrolyte for copper electrorefining
Chapter 6. Corrosion Behavior Investigations of Titanium and its Alloys in the Media of Electrochemical Plants, Taking into Account the Attack by Anodic Leakage Currents
6.1. Corrosion and Electrochemical Characteristics of Titanium
6.2. Chloride and Chloride-Alkali Media of Chlorine-Producing Electrochemical Plants
6.3. Electrolyte for Copper Electrorefining
6.4. Media of Nickel Electrorefining
6.5. Influence of Welding Seams and Crevices
6.5.1. Welding seams
6.5.2. Artificial crevices
6.6. Titanium Alloys
Chapter 7. Hydrogenation and Corrosion Investigations of Titanium Under Attack by an External Cathodic Current
7.1. Conditions of Hydrogenation and Corrosion of Titanium. Methodological Features of Experiments
7.2. Investigations in Non-Stirred NaCl Solutions
7.3. Investigations Under Conditions of Electrolyte Stirring and Flowing
7.3.1. Relation between the corrosion rate of titanium and the accumulation of oxygen–chlorine compounds in the solution
7.3.2. Two corrosion mechanisms of hydrogenated titanium
7.4. Welding Seams
7.5. Hydrogenation of Cathode Blanks in Solution of Nickel Electrorefining
7.5.1. Electrochemical investigations of combined discharge of nickel and hydrogen ions on titanium
7.5.2. Radiochemical investigations of titanium hydrogenation in the process of nickel deposition
Chapter 8. Estimation of Corrosion Stability of Structures Made of Passive Metals in Aggressive Media, in the Field of an External Current
8.1. Estimation Based on the Potential Value
8.1.1. Activation potential as an estimation criterion of the passive metal state in the field of an external current
8.1.2. Types of structural elements in the form of tubes in the field of an external current
8.1.3. Potential and current distribution along structural elements in the form of tubes
8.1.4. Procedure for computation of the potential distribution along the internal tube surface with the help of a computer
8.2. Estimation Based on the External Current Value
8.2.1. Estimation based on the external current value for tube-shaped structural elements
8.3. Practical Steps and Examples of Corrosion Stability Estimation of Structures in the Form of Tubes of Different Types
8.4. Significance of the Electrochemical Characteristics of Passive Metals for the Estimation and Provision of Corrosion Stability of Metal Structures
Chapter 9. Electrocorrosion Protection of Metals in Electrochemical Plants Based on Existing Methods
9.1. Insulating Coatings
9.2. Reduction of Leakage Currents Coming From Electrochemical Cells
9.2.1. Reduction of leakage currents along electrolyte piping and prevention of current oscillations
9.2.2. Reduction of leakage currents along piping of wet gases
9.3. Sectionalization of Piping Made of Passive Metals
9.4. Possibilities of Applying Traditional
Methods of Electrochemical Protection and Their Modifications for Electrochemical Plants
9.4.1. Electrodrainage protection
9.4.2. Protection by sacrificial anodes for current drainage in chloride electrolysis plants
9.4.3. Protection by sacrificial anodes for current drainage in electrolysis plants with metal deposition
Chapter 10. New Principles of Protection of Passive Metals Against Electrocorrosion in Electrochemical Plants
10.1. Protection of Metals With the Relationship Δ = Eox − EA < 0, Against Corrosion Attack by an External Anodic Current, With the Help of Dimensionally Stable – Current Leak-Off Anodes
10.1.1. Theoretical basis
10.1.2. Experimental verification of the protection principle
10.2. Corrosion Protection With the Help of Dimensionally Stable Anodes, Oriented Along the Field of the External Current
10.2.1. Theoretical basis
10.2.2. Investigation of the protection principle
10.3. Protection of Metals Against Corrosion Attack by an External Cathodic Current
10.4. Protection of Metals Against Corrosion Attack by Leakage Currents That Periodically Change Their Direction
10.5. Protection of Metals Against Corrosion Attack by External Currents at the Design Stage
Chapter 11. Electrodes for Metal Protection Against Corrosion Attack by Leakage Currents in Electrochemical Plants
11.1. Requirements Upon Materials of Electrodes That are Used for Protection Against Corrosion Attack by External Currents
11.2. Application of Anodes of Commercial Electrolysis Processes for Protection Against Electrocorrosion
11.2.1. Neutral and acid chloride-containing media
11.2.2. Chloride-sulfate media
11.3. Anodes for Media Containing Sulfuric Acid
11.4. Dimensionally Stable Anodes With a Coating Obtained on the Basis of Intermetallic Compounds Produced in an Electric Spark
11.4.1. Preconditions for the choice of materials and methods of producing the anodes: Test conditions
11.4.2. Investigations in chloride solutions
11.4.3. Investigations in chloride-alkali solutions
11.5. Stable Cathodes
11.5.1. Cathodes for media containing dissolved chlorine and for chloride media
11.5.2. Titanium cathodes for other aggressive media
11.5.3. Possibilities of increasing the stability of titanium cathode blanks
Chapter 12. Industrial Tests and the Introduction Into Electrochemical Plants of the Developed Methods for the Protection of Metals Against Corrosion Attack by Leakage Currents
12.1. Protection by Sacrificial Anodes in Electrorefining Plants
12.1.1. Industrial tests
12.1.2. Introduction of the protection in a copper electrorefining plant
12.2. Industrial Tests and the Introduction of Corrosion Protection to Titanium Structures by Current Leak-Off Anodes
12.2.1. Industrial tests
12.2.2. Introduction of protection
12.3. Industrial Tests and the Introduction of Corrosion Protection by Anodes Oriented Along the Field of the External Current in Electrochemical Plants
12.3.1. Industrial tests
12.3.2. Introduction of protection
12.4. Industrial Tests of Titanium Protection Against Corrosion Attack by Cathodic Leakage Currents With the Help of Stable Cathodes
12.5. Combined Protection of Metals Against Corrosion Attack by Leakage Currents
12.6. Effectiveness and Possibilities of Using the Developed Methods of Metal Protection Against Electrocorrosion
Copyright Page
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Library of Congress Cataloging-in-Publication Data
Riskin, Joseph.
Electrocorrosion and protection of metals : general approach with particular consideration to electrochemical plants / Joseph Riskin. — 1st ed.
p. cm.
Includes bibliographical references.
ISBN 978-0-444-53295-4
1. Corrosion and anti-corrosives. 2. Electrolytic corrosion. I. Title
TA462.R488 2008
620.1’623—dc22 200841789
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library
ISBN: 978-0-444-53295-4
For information on all Elsevier publications visit our website at books.elsevier.com
Printed in the Great Britain
08 09 10 11 10 9 8 7 6 5 4 3 2 1
Dedication
In memory of my father Martin Fruman, who perished in a Soviet concentration camp
Preface
The present book may be considered as a first attempt to regard as a whole the problems of corrosion and protection of metals under the attack of external currents in water-containing environments. Corrosion processes in melted environments are not included in this book, since they are characterized by quite other mechanisms and laws.
Corrosion of metals under the attack of external currents is usually defined by the term electrocorrosion.
This term of generalizing character is given in the title of the book. However in the text it is used not too often, as the specific questions connected with corrosion under the attack of stray currents or of leakage currents are considered. Besides, in the text it was necessary to specify additional current characteristics (anodic, cathodic, variable, etc).
Based on the general approach to the problems of electrocorrosion and protection of metals the main attention was concentrated on the results of the researches of metal electrocorrosion in aggressive media of electrochemical plants, where these problems were most acute and least studied. These results formed the basis for developing methods and means of protection of metallic equipment and pipelines from corrosive attack by external currents in these plants. The well-known problems of corrosion and protection of metals in the field of stray currents are given in the form of a review.
Alongside literary data available on this account, results of long-term work carried out by a specialized division on protection of metals against electrocorrosion, headed by the author, in the Moscow R&D Corrosion Institute are considered. The major weight belongs to these results, since available data on electrocorrosion of metals in aggressive environments are rather limited. It must be noted that all the activities of research and development were carried out in constant close contact and cooperation with different operating electrochemical plants of chemical and non-ferrous metallurgical industries.
The successful solution of many problems connected with design and calculation of models of metallic structures operating in the field of external currents and with researches of corrosion and hydrogenation of metals at cathodic polarization in many respects, is credited to the fruitful cooperation of Dr. J. B. Skuratnik, a brilliant scientist of Moscow Scientific–Research Institute of physico-chemical researches in the name of Karpov.
The author thanks all colleagues with whom he has had the luck to collaborate. Owing to the purposeful teamwork with them only could this book be born.
The author considers as a pleasant duty to express special gratitude to the director of the Moscow R&D Corrosion Institute professor V. A. Timonin, who, for many years, encouraged this work. His benevolent attitude to the work, the qualified professional recommendations and advices given at discussions on the results of the studies promoted successful solution of many problems.
Introduction
Corrosion and Electric Current – 200 Years Together
The first electric current source was invented 200 years ago, at the boundary of the eighteenth and nineteenth centuries. In 1800, Volta built the famous column
pile, the first electric battery: a series of alternating copper and zinc disks, separated by cardboard disks soaked with acid or salt solution. Between the copper–zinc pairs, an electric current was generated as a result of zinc dissolution or, in other words, as a result of zinc corrosion. Since then the two phenomena, corrosion and electric current, are closely allied and achievements in the studies of one of them promoted successes in the development of the other.
Nevertheless, only in the third decade of the twentieth century, after publications by Evans and Hoar, did the idea of the electrochemical nature of the corrosion processes of metals in contact with electrolytes finally become established [1].
The development of direct current sources made it possible to use an electric current as a means of influencing the metal–electrolyte system in further investigations. The laws of electrolysis that were discovered by Faraday as a result of these investigations promoted intensive development of theoretical and applied electrochemistry.
The fact that corrosion processes of metals have an electrochemical nature turned corrosion science into a branch of electrochemistry. Methods that are used for studies of corrosion processes are, to a large extent, similar to the electrochemical methods of investigation. Most of these methods (different kinds of polarization measurements, potentiometry, coulometry, impedance, etc.) are based on the influence of external currents on metals. The results of investigations of metal dissolution or deposition kinetics, adsorption and desorption processes, etc., obtained by electrochemists, are of interest to corrosion specialists and vice versa.
Processes based on electrochemical reactions in which electric current plays a part found widespread application in applied electrochemistry (electrolysis processes). The first electrolysis process was used in electrodepositing, the process that is the opposite of the corrosion process. Further investigations led to the development of electrolysis processes without metal deposition in aqueous electrolytes. Among them are water electrolysis for producing hydrogen and oxygen and electrolysis of sodium salts and other chloride solutions for producing chlorine, alkali and oxygen–chlorine compounds. Not only chlorine and oxygen–chlorine compounds, but many other oxidizers: hydrogen peroxide, manganese compounds, persulfates and other peroxides are also produced by electrolysis.
Processes of electrolytic refining and extraction of copper, nickel, cobalt, zinc, chromium, metals of the platinum group and of many other metals were developed. Some of the metals (aluminum, magnesium, alkali and alkaline-earth metals) are produced by the electrolysis of melted salts.
Electrolysis processes are also applied for organic and inorganic electrosyntheses.
For a number of reasons, including the relative ease of execution and monitoring of electrochemical processes, electrochemical plants are now amongst the leading enterprises in the chemical industry [2].
It was possible to create large-scale and energy-consuming enterprises owing to the appearance of high-power sources of electric current. At some of such plants, current magnitudes attain hundreds of kiloamperes.
The use of electric current in electrochemical plants gave rise to problems connected with corrosion effects of leakage currents penetrating to metallic piping and equipment from electrolytic cells. This became a major problem for many plants, since it hindered the further development of the electrochemical plants. It was very difficult to find corrosion-resistant structural metallic materials for such plants, since these materials were attacked not only by media of high aggressiveness, but also by external currents.
Thus, corrosion phenomena promoted the development of different branches of science and technology connected with the processes stimulated by electric currents. In turn, extensive development of these processes engendered serious problems connected with the corrosion of metals under attack by leakage currents appearing in these processes.
So, we have a two-century long history of studies of the relationship between corrosion and electric current, and there are a huge number of investigations connected with the influence of an electric current on metal–electrolyte systems. It is amazing, but, in spite of these facts, the number of researches devoted to studying the direct corrosion attack of metals by external currents in aggressive environments is rather limited. Even fewer are the number of works devoted to methods and means of metal protection against corrosion by external currents in the aggressive media of electrochemical plants where the action of external currents on the metal structures is unavoidable.
Considered the corrosion problems connected with the attack by stray currents on underground and underwater piping and other structures can be considered an exception. Extensive investigations have been carried out in this field. Methods of control and protection of metals used in the said structures against corrosion attack by stray currents were developed. There is a rich library of books containing chapters on the corrosion of underground structures by stray currents. Therefore, only a limited review on this subject is given in Chapter 2 of this book. Such a review was necessary not only to enlarge the scope of the problems connected with the electrocorrosion of metals, but also to analyze the extent to which the experience that was accumulated in the field of corrosion and protection of metals against the attack by stray currents may be appropriated for solving the problems of electrocorrosion in the aggressive media of electrochemical plants.
The relatively low aggressiveness levels of soil, fresh water and seawater enables the application of carbon steel as a major structural material in these media. Extensive and comprehensive investigations of carbon steels that usually have rather similar corrosion and electrochemical characteristics in these media made it possible to unify most methods and means of protection of underground piping and other structures against corrosion by stray currents. For engineers who are designing and carrying out corrosion protection of these objects today and are using existing standards for these purposes, knowledge in the field of electrical engineering is often more important than knowledge in the field of corrosion and protection of metals.
In electrochemical plants, the situation is quite different since aggressive media and applied structural materials are characterized by their great variety. This variety must be taken into account when the corrosion of metals by external currents and methods of protection against their attack are considered.
This approach to the problem means that a profound analysis of the metal state (passive, active, etc.) in the given aggressive environment of corrosion and electrochemical characteristics (corrosion and activation potentials of the metal, oxidation or reduction potentials of medium components on the metal surface, ratio of external current density to the current density of metal in the passive state, polarization characteristics, etc.) has to be carried out. Under such an approach, the external current is considered to be not just one of the factors of environmental aggressiveness, but the most aggressive one.
A very important point in this approach involves the fact that in the majority of cases, the metals that are used in aggressive media are initially in a passive state. Concentrating on this fact enabled the elaboration of fundamentally new very effective methods and means of protection of metals from electrocorrosion in aggressive media. The major concept of these methods consists of retaining by all means the potential of the protected metal within the limits of its passive field.
Further, it will be shown that such an approach turned out to be the most fruitful, particularly for the development of effective methods of metal protection against electrocorrosion in electrochemical plants.
Bibliography
References
1. U.R. Evans, T.P. Hoar, The Velocity of Corrosion from the Electrochemical Standpoint, Proceedings of the Royal Society of London 1932373- No. 137
2. J. O’M Bockris, Electrochemistry for a future society J. O’M. Bockris, D.A.J. Rand, B.J. Welch, Trends in Electrochemistry 1977 Plenum Press New York, London1-23
Chapter 1. Dependence of the Corrosion Behavior of Metals Attacked by an External Current on Their Initial State
1.1. State of Metals in Aggressive Media in the Absence of Attack by External Currents
When a pure metal comes into contact with an aqueous solution of its salt, an equilibrium electrode potential, Eeq, is established on the metal. This potential corresponds to the equality of speeds of metal atom ionization and of metal ion discharge on its surface. The value of the equilibrium potential of a metal in a 1 N solution of its salt at a temperature of 25°C is identified as the standard electrode potential, which is considered an important metal characteristic. To compare the thermodynamic stabilities of various metals, a so-called electrochemical series was established in which the metals are located in ascending order of their stability. In general, the more positive the standard potential of a metal, the higher is its thermodynamic stability. Values of standard electrode potentials are specified with respect to the standard potential of a hydrogen electrode, which is conventionally accepted as equal to zero.
During electrochemical corrosion, the process of metal dissolution in the electrolytes, which proceeds in accordance with the electrochemical mechanism, two conjugated reactions take place: anodic reaction of metal ionization(1.1)Me=Men++ne−,and cathodic reaction of reduction of any solution component on the metal surface(1.2)Ox+ne−=Red.
The spontaneous course of a corrosion process according to reaction (1.1) is possible only if the electrode potential of the metal is more negative than the potential of the cathodic reaction (1.2). Such a relationship between the potentials is a thermodynamic condition for the occurrence of the corrosion process. During the course of an irreversible corrosion process, a compromise potential, Es, is established on the metal. It is called the stationary or corrosion potential.
The hydrogen ion is the component that is most often reduced on the cathode in acid media. The summarizing reaction of cathodic depolarization of a hydrogen ion is characterized by the equation(1.3)2H+H²O+2e−=H²+2H²O.
In many media, particularly in water, dissolved oxygen is reduced on the cathode. The summarizing reaction of this reduction is as follows:(1.4)O²+2H²O+4e−=4OH−.
The reversible potential of this reaction in a neutral solution in an atmosphere of air (i.e., at a partial oxygen pressure of 0.21 atm) is equal to 0.805 V.
The agent (oxidizer) that is reduced on the cathode is defined in the existing corrosion terminology as the depolarizer of the cathodic process. Accordingly, a corrosion process at which a cathodic reaction (1.4) takes place is termed as corrosion with oxygen depolarization.
Dissolved chlorine, ions of metals of the highest valence, for example, Fe³+ and Cu²+ and so forth can act as oxidizers in corrosion processes.
The condition of the metal, which can be characterized as stable or unstable in a given aggressive medium, depends on the nature of the metal and on the properties of the aggressive medium. Metals of the first group – lithium, potassium and sodium – are the most unstable, being at the left end of the electrochemical series of metals. The electrode potentials values of these metals (−3.045, −2.925 and −2.714 V, respectively) belong to the most negative. On contact with water, their dissolution is accompanied by strong evolution of hydrogen.
Iron is positioned in the middle of the electrochemical series. The standard potential of the reaction Fe = Fe²+ + 2e− is equal to −0.44 V. The standard potential of the reduction of hydrogen ions in water at pH 7 is equal to −0.414 V, which is a slightly more positive than the standard electrode potential of iron. At such a potential value, dissolution of iron in water with hydrogen evolution is theoretically possible. However, owing to the impedance of the discharge of hydrogen ions on iron, hydrogen evolution in the corrosion process of iron in neutral solutions practically does not occur. Corrosion of iron in water and in neutral solutions that do not contain oxidizers occurs with oxygen depolarization, according to reaction (1.4). In conditions of an easy access of air to the surface, the solubility of oxygen in water is low, of the order of 8 mg/l at ambient temperature. Therefore, the corrosion rate of iron is limited by reaction (1.4), which usually depends on the rate of oxygen delivery to the metal surface.
Metals of the platinum group and gold possess the highest standard electrode potentials values: the potentials of palladium, iridium and platinum are equal, respectively, to 0.99, 1 and 1.2 V; and the potential of gold is equal to 1.5 V. These metals exhibit corrosion stability in most types of aggressive media, including neutral media containing oxygen and other oxidizers.
The estimation of the corrosion stability of metals by the magnitude of the standard potential can be considered only as preliminary since it does not consider the properties of the aggressive media and the ability of the majority of metals to form passive layers on their surface which interfere with the development of the corrosion process.
To execute a more complete analysis of the thermodynamic metal state, potential/pH diagrams for metal/water systems (Pourbaix diagrams) are used [1]. These diagrams take into account the thermodynamic balance between the metal, its ions in solution, insoluble products of reactions between the metal and the solutions at various values of metal potential and the pH of the solutions. Thus, alongside the nature of the metal, the properties of the aggressive medium and its interaction with the metal are considered in Pourbaix diagrams.
Areas of the thermodynamic states of the metal, solution and products of their interaction are separated on Pourbaix diagrams by equilibrium curves. As examples, we shall consider simplified diagrams for the equilibrium conditions at which the activity of metal ions or its soluble corrosion products in a solution is equal to 10−6 N. Such an activity value can be considered a border: below this value the metal possesses corrosion stability.
A Pourbaix diagram of iron in aerated water solutions at temperature 25°C is shown in Figure 1.1. The horizontal line a corresponds to the equilibrium of the reaction Fe = Fe²+ + 2e−. Above this line, in the area limited by lines a and b, Fe²+ ions are stable. The area above lines b and c, where solid corrosion products of iron are stable, was determined by Pourbaix as the area of passivity.
Figure 1.1. Simplified Pourbaix diagram of iron. Temperature, 25°C.
Lines a, b and c divide the diagram into three main areas. The area of thermodynamic stability of iron, which was named by Pourbaix as the immunity area, is disposed below lines a and c. Between lines a and b, there is an area of iron corrosion.
The dashed lines 1 and 2 mark the area of thermodynamic stability of water. The top line 1 is pertinent to the equilibrium of the water oxidation reaction, and the bottom line 2, to the equilibrium of the water reduction reaction, with hydrogen evolution. The electrode potentials of iron in neutral water, in the area of its corrosion, are disposed in the area corresponding to the thermodynamic stability of water. Equilibrium potentials of the iron ionization reaction are, in this area, more negative than the equilibrium potential of the reaction (1.4) of oxygen reduction. This makes the development of a spontaneous process of iron corrosion with oxygen depolarization possible according to reaction (1.4).
The primary products of the reaction of iron with water, ferrous oxide and ferrous hydroxide Fe(OH)², are oxidized in an aqueous solution to form ferric hydroxide Fe(OH)³, which is known as rust. The layer of this secondary corrosion product practically does not possesses protective properties. At the high concentration of alkali, which has not been indicated in the diagram, soluble products of corrosion – hypoferrites (HFeO²−) – are formed.
The simplified diagram given does not consider the influence of widespread aggressive components of the environment, such as chlor-ions. These ions take part in intermediate reactions of the ionization of iron and other metals. In many cases, they stimulate and accelerate the corrosion process. The lines that characterize the ratio of bivalent and trivalent iron ions at various potentials are also not considered