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Introduction

This book is not about corrosion; rather it is about paints that prevent corrosion. It was written for those who must protect structural steel from rusting by using anticorrosion paints. The philosophy of this book is this: if one knows enough about paint, one need not be an expert on rust. In keeping with that spirit, the book endeavors to cover the field of heavy-duty anticorrosion coatings without a single anode or cathode equation explaining the corrosion process. It is enough for us to know that steel will rust if allowed to; we will concentrate on preventing it.

1.1 SCOPE OF THE BOOK
The scope of this book is heavy-duty protective coatings used to protect structural steel, infrastructure components made of steel, and heavy steel process equipment. The areas covered by this book have been chosen to reflect the daily concerns and choices faced by maintenance engineers who use heavy-duty coating, including: • • • • • • • Composition of anticorrosion coatings Waterborne coatings Blast-cleaning and other heavy surface pretreatments Abrasive blasting and heavy-metal contamination Weathering and aging of paint Corrosion testing — background and theoretical considerations Corrosion testing — practice

1.1.1 TARGET GROUP DESCRIPTION
The target group for this book consists of those who specify, formulate, test, or do research in heavy-duty coatings for such applications as: • • • • • • • • Boxes and girders used under bridges or metal gratings used in the decks of bridges Poles for traffic lights and street lighting Tanks for chemical storage, potable water, or waste treatment Handrails for concrete steps in the fronts of buildings Masts for telecommunications antennas Power line pylons Beams in the roof and walls of food-processing plants Grating and framework around processing equipment in paper mills

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© 2006 by Taylor & Francis Group, LLC

When the steel begins rusting. • • 1. This eliminates organic paints. Given a chance. These exist and are already well covered in the technical literature. In addition. it cannot be pulled out of service and sent back to a factory for treatment. and coatings for cathodic protection. so maintenance painting in the field is not possible. and chromating. This imposes certain limitations on the choices the maintenance engineer can make. (Automotive and powder coatings) Aluminium — not steel —is used as the substrate. hot-dip galvanizing. but they are almost always a one-time-only treatment.2 PROTECTION MECHANISMS OF ORGANIC COATINGS This section presents a brief overview of the various mechanisms by which organic coatings provide corrosion protection to the metal substrate. During the service life of one of these structures. Coatings that must be applied in a factory cannot be reapplied once the steel is in service.1. such as phosphating. more good paints are available now than ever before. (Airplane coatings) The circumstances under which marine coatings and coatings with cathodic protection must operate are so different from those experienced by the infrastructure in the target group that different coating and testing technologies are needed. the iron in them will turn to iron oxide. New construction can commonly be protected with these coatings. 2. maintenance painting will have to be done on-site. the number of practical techniques is narrowed. such as powder coatings or electrodeposition coatings. including those dealing with automotive. and several inorganic pretreatments. and the coatings experience temperature extremes and ultraviolent loads that earth-bound structures and their coatings never encounter. and the number of feasible pretreatments for cleaning steel in-situ is growing. Corrosion of a painted metal requires all of the following elements [1]: • • Water Oxygen or another reducible species © 2006 by Taylor & Francis Group. 1. coatings users now face such pressures as environmental responsibility in choosing new coatings and disposing of spent abrasives as well as increased awareness of health hazards associated with certain pretreatment methods. When the steel has been in service for a number of years and maintenance coating is being considered. and marine coatings.2 Corrosion Control Through Organic Coatings All of these forms of structural steel have at least two things in common: 1. These methods are all economically important and scientifically interesting but lie outside of our target group for one or more reasons: • The way in which the paint is applied can be done only in a factory. airplane.2 SPECIALTIES OUTSIDE THE SCOPE Certain anticorrosion coating subspecialties fall outside the scope of this work. LLC . powder coatings. This is not to say that the maintenance engineer must face corrosion empty-handed.

The main protection mechanisms used by organic coatings are: • • • • Creating an effective barrier against the corrosion reactants water and oxygen Creating a path of extremely high electrical resistance. There seems to be general agreement that the amount of water that can diffuse through organic coatings of reasonable thickness is greater than that needed for the corrosion process [2–8]. oxygen permeation was the rate-controlling factor for the same coatings [2].93 g/m2/day [9.1 DIFFUSION OF WATER AND OXYGEN Most coatings. Similar results have been obtained by other studies [2.Introduction 3 • • • A dissolution process at the anode A cathode site An electrolytic path between the anode and cathode Any of these items could potentially be rate controlling. the usefulness of each mechanism depends on the service environment. where water penetration is kept as low as possible.11]. However. 1. Other coatings must provide protection through other mechanisms. the role of water permeation through the coating cannot be completely ignored. In addition. Table 1. Guruviah studied corrosion of coated panels under various accelerated test methods with and without sodium chloride (salt). pigments whose dissolved ions passivate the metal surface require the presence of water.10]. LLC . electrolytic resistance of the coatings was the dominant factor in predicting performance.10]. Thus. © 2006 by Taylor & Francis Group.07 g Fe/cm2/year is estimated to be 0. Haagan and Funke have pointed out that. The amount of water necessary for corrosion to occur at a rate of 0. Where salt was present. This rules out their use in a true barrier coating. However. The attractive force for water within most coatings is simply too strong. It must be noted that it is impossible to use all these mechanisms in one coating. thus inhibiting anode-cathode reactions Passivating the metal surface with soluble pigments Providing an alternative anode for the dissolution process The last two protection mechanisms listed above are discussed extensively in Chapter 2. A coating that can suppress one or more of the items listed above can therefore limit the amount of corrosion. it may be the rate-determining factor in adhesion loss [11]. This section will therefore concentrate on the first two protection mechanisms in the list above. coatings with the lowest permeability rates might possibly be applied in sufficient thickness such that water does not reach the metal in the amounts needed for corrosion. except specialized barrier coatings such as chlorinated rubber. do not protect metal substrates by preventing the diffusion of water.1 shows the permeation rates of water vapor through several coatings as measured by Thomas [9. For example. although water permeability is not normally the rate-controlling step in corrosion.2. in a generally similar method with no sodium chloride.

Soc. nearly five times the amount of oxygen available in air. Advances in Corrosion Protection by Organic Coatings. 19. N.. Symp. Soc. N. In Earth’s atmosphere. 1989. Proc. 1991. because water carries dissolved oxygen with it when permeating the coating. The amount of oxygen required for a corrosion rate of 0. N.L. 101. 1989. 19. It should perhaps be noted that these were measurements of oxygen gas permeating through the coating.. Thomas studied oxygen permeation rates for several types of coatings and found that they have rates far below what is needed to maintain the corrosion reaction. TABLE 1. 451. Prog.2 Oxygen Permeability Coating Type Chlorinated rubber Coat tar epoxy Aluminium epoxy mastic Red-lead oil-based White alkyd Oxygen Permeability. Electrochem. Proc.. g/m2/25µm/day 20 30 42 214 258 ± ± ± ± ± 3 1 6 3 6 Sources: Thomas. Thomas. however. Prog.. Advances in Corrosion Protection by Organic Coatings.2 [9. © 2006 by Taylor & Francis Group. Org. cc/m2/100µm/day 30 213 110 734 595 ± ± ± ± ± 7 38 37 42 49 Sources: Thomas. their permeation through the coating is not a rate-determining step [13–15]. as shown in Table 1. These measurements were taken using 1 atmosphere of pure oxygen — that is. LLC .07 g Fe/cm2/year is estimated to be 575 cc/m2/day. 451. Electrochem. N. Coatings. Coatings. Thomas.. water and oxygen are necessary for the corrosion process.L. Symp. oxygen transport rates may be expected to be lower than this [12]. In general. 1991.1 Water Vapor Permeability Coating Type Chlorinated rubber Coat tar epoxy Aluminium epoxy mastic Red-lead oil-based White alkyd Water Vapor Permeability. The amount of oxygen reaching the metal surface will be higher. 101. Org.10].L.4 Corrosion Control Through Organic Coatings TABLE 1..L.

These are soluble and can diffuse away from the site of corrosion. This electrical resistance reduces the flow of current available for anode-cathode corrosion reactions. because the ferrous ions and hydroxyl ions form ferrous hydroxide (Fe(OH)2).2. This mechanism of blocking ions has several names. Therefore. and ionic resistance. Overall. 28]. After diffusing away. they react with steel to form ferrous chloride and sulphate complexes. hydrolyzed. precipitates at the site of corrosion. LLC . Bacon and colleagues have performed extensive work establishing the correlation between electrolytic (ionic) resistance of the coating and its ability to protect the steel substrate from corrosion. This theory has received some support from the work of Khullar and Ulfvarson. which takes weeks or months [26] The fast change is related to the amount of water in the film. and then inhibits the diffusion necessary to continue corrosion. which takes place within minutes of immersion A slow change. An exchange of cations in the electrolyte for hydrogen ions in the coating may lie behind this steady fall.2 ELECTROLYTIC RESISTANCE Perhaps the single most important corrosion-protection mechanism of organic coatings is to create a path of extremely high electrical resistance between anodes and cathodes. Mayne deduced the importance of electrolytic resistance as a protection mechanism from the high rates of water and oxygen transport through coatings. Specifically. In a study involving more than 300 coating systems. In other words. they observed good corrosion protection in coatings that could maintain a resistance of 108 Ω/cm2 over an exposure period of several months. On the other hand.Introduction 5 1. The stimulating Cl– or SO42– anion is liberated and can re-enter the corrosion cycle until it becomes physically locked up in insoluble corrosion products [16-21]. the water that reaches a metal substrate is relatively ionfree [12]. From their studies. © 2006 by Taylor & Francis Group. Mayne and coworkers [7. they can be oxidized. The structural changes brought about by this ion exchange might slowly destroy the protective properties of the film [29]. Steel corrodes very slowly in pure water. The slow change is controlled by the concentration of electrolytes in the immersion solution. in the coating resistance. the electrolytic resistance of an immersed coating can be said to depend on at least two factors: the activity of the water in which the coating is immersed and the nature of the counter ion inside the polymer [1]. resistance inhibition. if chloride or sulphate ions are present. they did not observe the same results in coatings whose resistance fell below this [23]. over months. Its controlling factor is osmotic pressure. because Kittleberger and Elm showed a linear relationship between the diffusion of ions and the reciprocal of the film resistance [22]. who found an inverse relationship between the ion exchange capacity and the corrosion protection efficiency of paint films [13. The terms electrolytic resistance and ionic resistance are used more-or-less interchangeably. including electrolytic resistance. 24-27] found that the resistance of immersed coatings could change over time. they concluded that at least two processes control the ionic resistance of immersed coatings: • • A fast change.0067 g/L at 20° C). water — but not ions — may readily permeate most coatings. Fe(OH)2 has low solubility in water (0. and precipitated as rust some distance away from the corrosion site.

If the electrolyte’s concentration was above the polymer’s fixedanion concentration. the lower the number of sites remaining available for electrochemical mischief. It is only important that some degree of adhesion to the metal substrate be maintained. the degree of adhesion is in itself not important. Naturally. The more chemical bonds between the surface and coating. 29. the closer the contact and the stronger the adhesion. For all of the protection mechanisms described in the previous sections. A coating cannot passivate the metal surface. An irreverent view could be that the higher the number of sites on the metal that are taken up in bonding with the coating. the detachment occurring is the result of the corrosion processes and is not quantitatively related to adhesion [1]. and a great deal of energy has gone into developing test methods for quantifying this adhesion. the coating acts as an electrical insulator. In summary. good adhesion of the coating to the substrate could be described as a “necessary but not sufficient” condition for good corrosion protection.2. good adhesion of the coating © 2006 by Taylor & Francis Group. if some external agency causes detachment of the organic coating and there is a concurrent break in the organic coating. the concentration of fixed anions in the polymer film is critical. hydrogen evolution. 1. Further information regarding the mechanisms of ion transport through the coating film can be found in reviews by Koehler. In addition. The work of Kumins and London has shown that the chemical composition of the polymer is equally important. such as capillary structure. anions could permeate much more freely through the film [30].3. however.3 ADHESION When a metal substrate has corroded. by bonding to as many available active sites on the metal surface as possible. 1.1 What Adhesion Accomplishes Very strong adhesion can help suppress corrosion by resisting the development of corrosion products. Accordingly. Walter. or water build-up under the coating [32-35]. or prevent water or oxygen from reaching the metal surface unless it is in intimate contact — at the atomic level — with the surface. corrosion workers commonly place heavy emphasis on the importance of adhesion of the organic coating to the metal substrate.2. In particular. create a path of extremely high electrical resistance at the metal surface. the coating will no longer serve its function over the affected area. the paint no longer adheres to it. Typically. thereby suppressing the formation of anode-cathode microcells among inhomogeneities in the surface of the metal.6 Corrosion Control Through Organic Coatings Many workers in the field of water transport have concentrated on the physical properties of film. 31]. The role of adhesion is to create the necessary conditions so that corrosionprotection mechanisms can work. and Greenfield and Scantlebury [1. the passage of anions through the film was very restricted. They found that if the concentration of salt in the electrolyte was below the film’s fixed-anion concentration. Or as Koehler expressed it: The position taken here is that from a corrosion standpoint. or composition of the electrolytes. LLC .

once lost. 43]. is crucial to corrosion protection. adhesion tests in isolation cannot predict the ability of a coating to control corrosion [36]. it can still prevent sufficient amounts of electrolytes from collecting at the metal surface for the initiation of corrosion. What is the governing principle by which water collects at the organic coating-metal interface? 3. whereas chemical bonds or mechanical locking may account for residual adhesion [16]. What makes adhesion loss under wet circumstances irreversible? Is there a relationship between the coating property.2. Commonly. Permanent adhesion loss due to humid or wet circumstances also exists and is called water disbondment. LLC . Relatively little research has been done on wet adhesion phenomena. good adhesion alone is not enough. Polar bonding. Adhesion under dry conditions is probably overrated. they decrease wet adhesion [42]. could account for reduced adhesion in wet circumstances. Loss of adhesion in wet conditions.3. How well the coating clings to the substrate when it is saturated is known as wet adhesion. on the other hand. Further research on wet adhesion could answer some of the aforementioned questions and increase understanding of this complex mechanism. How can wet adhesion be quantitatively measured while the coating is wet? 2. on the other hand. wet adhesion.3 Important Aspects of Adhesion Two aspects of adhesion are important: the initial strength of the coating-substrate bond and what happens to this bond as the coating ages. and what determines this thickness? Two additional questions could be added to this list: 4. dry adhesion cannot be recovered. 1. © 2006 by Taylor & Francis Group. Funke has suggested that dry adhesion is due to a mixture of bond types. What is the thickness of the water layer at the interface. The same polar groups on the binder molecules that create good dry adhesion can wreak mischief by decreasing water resistance at the coating-metal interface — that is. although the original dry adhesion strength will probably not be obtained [16.2.Introduction 7 to the metal is a necessary condition. the failure mechanism. However. Another important difference is that.2 Wet Adhesion A coating can be saturated with water. but if it adheres tightly to the metal. 1. and water disbondment? 5. coatings with good dry adhesion have poor wet adhesion [37-41]. Perhaps it should be noted that wet adhesion is a coating property and not a failure mechanism. Why does the reduction of adhesion on exposure to water not lead to complete delamination? What causes residual adhesion in wet circumstances? As a possible answer to the last question above.3. can be reversible. Leidheiser has identified some important questions in this area [43]: 1. which is somewhat sensitive to water molecules. wet adhesion.

it is possible to pay too much attention to measuring the difference between very good initial adhesion and excellent initial adhesion. and Wray. It is certainly true that good adhesion between the metal and the coating is necessary for preventing corrosion under the coating. Off.M and Gent. Maitland. In other words.2.L.O.A. NACE. What matters is what happens to the adhesion over time. see Chapter 2. Houston. and ions may be present. A. 28. 481. E. 991. For more information on zinc-rich coatings. J.. Phys. because studying changes in the failure loci in adhesion tests before and after weathering can yield a great deal of information about coating deterioration. 972. JOCCA.L. REFERENCES 1. they provide another metal that will corrode instead of the substrate. and Mayne. 4. This area deserves greater attention.. S. W. Evans International Conference on Localized Corrosion... 324.O.I. 3. These coatings do not protect by suppressing the corrosion process. and Wright. McSweeney. 2.E. E. J.R.. 32. 57. or soluble pigments have not passivated the metal surface.... C. Koehler.. Unfortunately. 1945. Their dissociated ions migrate to the coating-metal interface and passivate it by supporting the formation of thin layers of insoluble corrosion products. 1. Engng. Anderson. 549. Mayne. then it does not matter whether that adhesion is simply very good or great. whose zinc pigment acts as a sacrificial anode. 33. © 2006 by Taylor & Francis Group.. 37.D. Chem. the most important example of cathodic protection is zinc-rich paints. 53. Dig. Soc. 34. This aspect is much more crucial to coating success or failure than is the exact value of the initial adhesion.E. Thomas. U.4 PASSIVATING WITH PIGMENTS Anticorrosion pigments in a coating dissolve in the presence of water. R. the coating does not offer much electrical resistance. K. water. completely missing the question of whether or not that adhesion is maintained. 1936 7. corroding preferentially to the steel substrate. 1962. rather. as long as the coating has good initial adhesion.. LLC . A..8 Corrosion Control Through Organic Coatings A great deal of work has been done to develop better methods for measuring the initial strength of the coating-substrate bond.2.P. 1941. Adhesion tests on aged coatings are useful not only to ascertain if the coatings still adhere to the metal but also to yield information about the mechanisms of coating failure. 5. However. 1965.5 ALTERNATIVE ANODES (CATHODIC PROTECTION) Some very effective anticorrosion coatings allow the conditions necessary for corrosion to occur — for example.. see Chapter 2. oxygen.. 117. 1970. 669. 626.C. Corrosion under organic coatings. the emphasis on measuring initial adhesion may miss the point completely. 8. Proc. Chem.E. J. 1971. Engng. JOCCA. 1. Dig. Off. Guruviah.. This mechanism is referred to as cathodic protection. For more information about anticorrosion pigments. which inhibit further corrosion [44-46]. Industr. Edwards. Proc. Industr. In protective coatings. 1949. 6.

and Scantlebury.W. H. A. 10. 58. 25. 1957.W. Cherry. 16. 28. 40. and Mayne.L. 38. 1967. Werkstoffe u. 1971. 10. 165. Science. H. 31. 379. J. W. Mayne. 29. H.O. New York. 1960. 15.. Off. Fédération d’Associations de Techniciens des Industries des Peintures. London. J.H. Cherry. 1964. Ind.. Leidheiser. 21.L. Corros.. Patton. and London.E. 107.E. J. 441. 420. Australag. 101.. and Mayne. P. J. Paper 5. Washington DC. London. 19. Korrosion. Leidheiser. F. 26. 124.O. Werkstoffe u.E. Knotkowa-Cermakova. Eng. A.R. M. J. 27. 25. Ed. Eur.W. Chem. Chem.. 40.. JOCCA... Dig.E.. Appl. 1974. Soc. 161. 41. First International Congress on Metallic Corrosion.. 19..C. Washington DC.. Walter.W. Paint Technol. M. 26.L. C. Washington DC. A. 1988. in Pigment Handbook. 18.. D. Proc. Eds. 1968. J. 2000. © 2006 by Taylor & Francis Group.L. J. 38. Eng. 46. Mayne. 299.A. U. 21. W.. N.. Ind. N. J.D.. Dickie. Paris. B. Technol. Polymer Science. 457. B.A. 457.. 18. Coat.. 1964. 1952. and Ramshaw. 55. JOCCA. 44. J. and Rugg. Watson. Proc. and Elm. in Surface Coatings – 2. W. W. in ACS Symposium Series 322: Polymeric Materials for Corrosion Control. F. A. Proc. JOCCA. 37. Eds.. 1962..W. Bullett... and Ulfvarson. G. 31. Cherry. Org. 46. E.W. Smith. and Floyd. Symp. 326. Werkstoffe u. 1969. R. Funke. Kittleberger. C. 13. Thomas.A.. U. IXth FATIPEC Congress. 46. Chem. J. 222. 31. 23.. in Handbook of Adhesives. Vernis. 1986. 42. 15. Skeist.. Gowers. Science and Eng. Dunkan. 1961. American Chemical Society. Funke. LLC . Barton. 32. American Chemical Society. 1946. 29.J. 1991.J. 604.M. 1981. 10. 1965.. J. 1974. 53... Ed. 40. Technol. 24. Kumins. and Funke. J. Martin’s Press... Vol. Butterworths.L. W. G. 39. H. and Beranek..J. Electrochem.L. 161. 395. 40. B... 36. P. Walker. R. Dickie. Advances in Corrosion Protection by Organic Coatings. Korrosion.. and Millar. 16. 1959. Prot. D.. 41. 1965. Coat.. Troyk. 1986. 15. and Elm.. 114. T. Bacon. Eng. 35. 1998. Chem.E. A. 359.D... M. 602. 43. Paint Technol. Trans. Haagen.. Finish. 1970. 121. Ulfvarson.. Inst.R. 183. Chem. J. Ind.J. P. Coat.. J.R. E.. in ACS Symposium Series 322: Polymeric Materials for Corrosion Control. 3. Korrosion.. 37. Eng. 22. Korrosion.. 377. Mayne. 33. 1986. Met. 30. Wheat. Corros.. Mayne. and Khullar.R. Thomas. F. New York. Corrosion and Oxidation of Metals. Off. 20. JOCCA. 1973.O. JOCCA. Coat. 1989. Reinhold Publishing Corp. T. Patrick. 1561. Khullar. Werkstoffe u. et al.. 22.. 1988. I. Dig. 24.W.L. Wilson.C. and Prosser. Elsevier Applied Science.. 1960. Eds. U.. 3. 13. R.. Walker.A. K. N.L. 695. St. Eds. Bacon. 1975. Schikorr. III.O. 1948.C...R. Kittleberger. Dickie. Prog. 1967. Korrosion. Nicholson.. Werkstoffe u..O. 37. 34. Funke. J.Introduction 9 9.O. R. American Chemical Society. in ACS Symposium Series 322: Polymeric Materials for Corrosion Control. 1986. 44. 54. Evans. and Poyezdala.. W. 4. K. 45. 31. 1964. 451. 15.. J. C. 1948. 553. and Scantlebury. 27. and Floyd. Corr.. 13. 11. and Eng.R. 1963. Wiley Interscience Publ. Walker... H. 1983.. and Floyd. and Vlekova. 12. J. Emaux et Encres d’Imprimerie de l’Europe Continentale (FATIPEC). R. Ind. P. 14...E. F. Greenfield. 17 Kaesche.

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