Anodic Protection

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Chapter 12 Anodic Protection 121 Inroduetion 122 Passity of Metals 123 Equipment Required for Anodle Protection 1231 Cathode 12.22 Reference electrode 12.2. Potential control and power supply 124 Design Concerns 125 Applications 126 Practical Example: Anode Protection Inthe Pulp and Paper industry References 88 geese ges 12.1. Introduction In contrast to cathodic protection, anodic protection is relatively new. Edeleanu first demonstrated the feasibility of anodic protection in 1954 and tested it on small-scale stainless steel boilers used for sulfuric acid solutions. This was probably the first industrial application, although other experimental work had been carried out elsewhere.’ This tech- nique was developed using electrode kinetics principles and is some- what difficult to describe without introducing advanced concepts of electrochemical theory. Simply, anodic protection is based on the for- mation of a protective film on metals by externally applied anodic cur- rents. Anodic protection possesses unique advantages. For example, the applied current is usually equal to the corrosion rate of the pro- tected system. Thus, anodic protection not only protects but also offers a direct means for monitoring the corrosion rate of a system. As an 922 Chapter Twelve enthusiast and famous corrosion engineer claimed, “anodic protection can be classed as one of the most significant advances in the entire his- tory of corrosion science.”* Anodic protection can decrease corrosion rate substantially. Table 12.1 lists the corrosion rates of austenitic stainless steel in sulfuric acid solu- tions containing chloride ions with and without anodic protection. Examination of the table shows that anodie protection causes a 100,000- fold decrease in corrosive attack in some systems. The primary advan- tages of anodic protection are its applicability in extremely corrosive environments and its low current requirements. Table 12.2 lists several systems where anodic protection has been applied successfully. Anodie protection has been most extensively applied to protect equip- ment used to store and handle sulfuric acid. Sales of anodically pro- tected heat exchangers used to cool H,SO, manufacturing plants have represented one of the more successful ventures for this technology. ‘TABLE12.1_Anodie Protection of $30400 Stainless Steel Exposed to ‘an Aerated Sulfuric Acid Environment at 30°C with and without Protection at 0.500 V ve. SCE osion Fate NaClM Unprotected Protected 10 "360 068 10-4 4 11 10" 81 51 10" 49,000 oan 10 29,000, 10 10 2,000 53 TABLE 122 Current Requirements for Anodic Protection Topasiate, Tomaintan, 180 ‘Temperature, °C mam 1M 2 23 15% 24 oa 06 24 ost 45% 6 180 6% 24 5a. 8% 24 ost 8% 24 Nos020 0.43, 93% 24 Mild steel 0.28 9.9% (oleum) 24 Mild steel 4.7 HPO, Ta 24 Mild steel 41 115% 82 NaOH 2066 24 Anodic Protection 923, ‘These heat exchangers are sold complete with the anodic protection systems installed and have a commercial advantage in that less costly materials can be used. Protection of steel in H,SO, (~> 78% concentra- tion) storage vessels is perhaps the most common application of anodic protection. There is little activity directed toward developing applica- tions to protect metals from corrosion by other chemicals.’ Anodic protection is used to a lesser degree than the other corrosion control techniques, particularly cathodic protection. This is mainly because of the limitations on metal-chemical systems for which anodic protection will reduce corrosion. In addition, it is possible to accelerate corrosion of the equipment if proper controls are not implemented. However, anodic protection has its place in the corrosion control area, provided some important basics are respected. 12.2. Passivity of Metals ‘The passivation behavior of a metal is typically studied with a basic electrochemical testing setup (App. D, Basic Electrochemical Instrumentation). When the potential of a metallic component is con- trolled and shifted in the more anodic (positive) direction, the current required to cause that shift will vary. If the current required for the shift has the general polarization behavior illustrated in Fig. 12.1, the metal is active-passive and can be anodically protected. Only a few systems exhibit this behavior in an appreciable and usable way. The corrosion rate of an active-passive metal can be significantly reduced by shifting the potential of the metal so that it is at a value in the pas- sive range shown in Fig. 12.1. The current required to shift the poten- tial in the anodie direction from the corrosion potential E.,,. can be several orders of magnitude greater than the current necessary to maintain the potential at a passive value. The current will peak at the passivation potential value shown as E,, (Fig. 12.1) ‘To produce passivation the critical current density (i,.) must be exceeded. The anodic potential must then be maintained in the passive region without allowing it to fall back in the active region or getting into the transpassive region, where the protective anodic film can be dam- aged and even break down completely. It follows that although a high current density may be required to cause passivation (> i,), only a small current density is required to maintain it, and that in the passive region the corrosion rate corresponds to the passive current density (i,). ‘The relative tendency for passivation is strongly dependent on the interactions between a metal and its environment. The passivation behavior can vary extensively with changes in either. Figure 12.2 illus- trates how the sensitization of a $30400 stainless steel, for example, can affect its passivation behavior when exposed to sulfuric acid.* 924 Chapter Twelve ‘passive current) | Oxygen evolution ‘tans passive passive ‘ge (ctiteal current) Potential —., (passivation Potential) cot (corrosion potentia) Log (Current density) Figure 12.1 Hypothetical polarization diagram for a passivable system with active, pas- sive, and trangpansive regions. Among the parameters that are particularly affected by sensitization are i, and i, as defined in Fig. 12.1. In this example, the ability to sus- tain passivity increases as the current density to maintain passivity ((,) decreases and as the total film resistance increases, as indicated from measurements obtained with different metals exposed to 67% sulfuric acid (Table 12.3). The lower or more reducing the potential at which a passive metal becomes active, the greater the stability of pas- sivity. The depassivation potential corresponding to the passive-active transition, called the Flade potential, can differ appreciably from Ey, measured by going through the active-passive process of the same sys- tem. This technical distinction is important for the control aspect of anodic protection where Ey, is the potential to traverse to obtain pas- sivation, and the Flade potential is the potential to avoid traversing back into active corrosion. Passivity can also be readily produced in the absence of an externally applied passivating potential by using oxidants to control the redox potential of the environment. Very few metals will passivate in nonoxi- dizing acids or environments, when the redox potential is more cathodic than the potential at which hydrogen can be produced. A good example of that behavior is titanium and some of its alloys, which can be readily passivated by most acids, whereas mild steel requires a strong oxidizing Anodic Protection 925, 5 No senstizaton \ 8 oan 8 Potertial (mY vs. SHE) 8 8 Log Current density (uA em*) Figue 12, Anodic polarization curves of $9040 tel in 1M H,SO, at 99°C aor sen agent, such as fuming HNO, for its passivation. Alloying with a more easily passivated metal normally increases the ease of passivation and lowers the passivation potential, as in the alloying of iron and chromium in 10% sulfuric acid (Table 12.4). Small additions of copper in carbon steels have been found to reduce ip in sulfuric acid. Each alloy system has to be evaluated for its own passivating behavior, as illustrated by the case Ni-Cr alloys where both the additions of nickel to chromium and chromium to nickel decrease the critical current density in a mixture of sulfuric acid and 0.25 M K,SO, (Table 12.5).! ‘The parameters defining and controlling the passivation domain of a system are thus directly related to the composition, concentration, purity, temperature, and agitation of the environment. ‘This is illus- trated with the current densities required to obtain passivity (j,.), and to maintain passivity (i,), for a 30400 steel in different electrolytes, as presented in Table 12.6. From the data in this table, it can be seen that it is approximately 100,000 times easier to passivate large areas of this steel in contact with 115% phosphoric acid than in 20% sodium hydroxide. The concentration of the electrolyte is also important, and for a 31600 steel in sulfuric acid, although there is a maximum cor- rosion rate at about 55%, the critical current density decreases pro- gressively as the concentration of acid increases (Table 12.7). 926 Chapter Twelve TABLE 123 Current Density to Maintain Passivity and Film Resistance of Some Metals in 67% Sulfurie Acid Siealorally Ip phen? Filmresistance Mivem ‘Mild steel 150 0.026 S20400 steel 22 050 S21000 steel 05 21 21600 steel 0.1 175. Titanium 0.08 175 Nos020 0.03 46 ‘TABLE124 Effect on Critical Current Density ‘and Passivation Potential of Chromium Content {or ron-Chromium Alloys in 10% Sulfuric Acid Thommen > Ay, Ven SHE ° 1000 ross 28 360 0.58 a7 340 10.35 95 7 Fos uo 19 0.03 TABLE 125. Effect on Critical Current Density and Passivation Potential on Alloying Nickel with Chromium nO Mand 5 MH-S0, Containing 0.25 Ml K:SO, Nis _igymAcm™? Epp, V VS. SHE 05M osm io 100 v0.36 a 0.95 $0.06 a on 082 4007 49 0020 020 40.03 27 oo12 0041 +002 10 0.0013 oon }0.04 1 1050-032 ° 1580-030 ‘The presence in the environment of impurities that retard the for- mation of a passive film or accelerate its degradation is often detri- mental. In this context, chloride ions can be quite aggressive for many alloys and particularly for steels and stainless steels. As an example, the addition of 3% HCI hydrochloric acid to 67% sulfuric acid raises the critical current density for the passivation of a $31600 stainless steel from 0.7 to 40 mA-cm~ and the current density to maintain passivity from 0.1 to 60 pA-cm *. Therefore, the use of the calomel electrode in anodic-protection systems is not recommended because of the possible leakage of chloride ions into the electrolyte, Anodic Protection 927 ‘ABLE126 Critical Current Density and Current Density to Maintain Passivity of §30400 Stainless TamAca? ip hem 20% NaOH 465 99) 67% H,S0,24°0) 0.51 0.093 LiOH (pH ~ 9.5) 008 0.022 80% HNO; (24°C) 0.0025 0031 T15%HPO,(24°C) 0.000015 0.00015 and metal/metal oxide and other electrodes are often preferred. Because of this chloride effect the storage of hydrochloric acid requires a more passive metal than mild steel, and titanium anodi- cally protected by an external source of current or galvanic coupling has been reported to be satisfactory although even this oxide film has sometimes been found to be unstable." ‘An increase in the temperature of an electrolyte may have several effects. An increase in temperature may make passivation more diffi cult, reduce the potential range in which a metal is passive, and increase the current density or corrosion rate during passivity as indi- cated in Fig. 12.3 for mild steel in 10% H.SO,.! Note the magnitude of the critical current density that is slightly higher than 10 mA‘em Such a high current density requirement creates a problem in practical anodic protection systems where the surfaces to be protected can be quite large. 12.3 Equipment Required for Anodic Protection Figure 12.4 shows a schematic of an anodic protection system for a storage vessel. Some of the basic properties required of the compo- nents of an anodic system are described here. 2000 1600 Potential (mV vs. SHE) 8 500 1000 200 150 100 050 00 os 100 150 200 280 Log Current density (mA om*) Figure 123. Forward and backward potentiostatie anodic polarization curves for mild Steelin 106 sulfarie acid at 22 and 60°C. Hastetoy cathode vighigsoa— reference electrode Power ‘supply / Sulfuric acid N Figure 124 Schematic of an anodie protection system for a sulfuric aid storage vessel Anodic Protection 929 12.3.1 Cathode ‘The cathode should be a permanent-type electrode that is not dis- solved by the solution or the currents impressed between the vessel wall and electrode. The cathodes used in most of the first applications of anodic protection were made of platinum-clad brass. These elec- trodes were excellent electrochemically but were costly, and the active area contacting the solution was limited by this cost. Because the over- all resistance is a direct function of current density, itis advantageous to use large surface area electrodes. Many other, less costly metals have been used for cathodes instead of these costly materials. Some of these metals are listed in Table 12.8 with the chemical environments in which they were used.*® The electrode size is chosen to conform to the geometry of the vessel and to provide as large a surface area as possible. The location of the cathode is not a critical factor in simple geometry, such as storage vessels, but in heat exchangers, it is neces- sary to extend the electrode around the surface to be protected. Multiple cathodes can be used in parallel to distribute the current and to decrease circuit resistance. 12.32 Reference electrode Reference electrodes must be used in anodic protection systems because the potential of the vessel to be protected has to be carefully controlled. The reference electrode must have an electrochemical potential that is constant with respect to time and that is minimally affected by changes in temperature and solution composition. Several reference electrodes have been used for anodic protection, including those listed in Table 12.9." The reference electrode has been a source of many problems in anodic protection installations because of its fragile nature. Platinum-clad brass Sulfuric acd of various concentrations Steel Kraft pulping liquor Chromium nickel steel Hy8O, 78-105%) Silicon east iron 80, (89-105) Copper Hydroxplamine sulfate 20100, Liquid fertilizers (nitrate solutions) Sulfurie acid Nickel-plated steel Chemical nickel plating solutions Hastelloy © Liquid fertilizers (nitrate solutions) Sulfur acid of various concentrations Kraft digester liquid 990 Chapter Twelve ‘TABLE129_ Reference Electrodes Used for Anodic Protectir [actos Calomel __Sulfurie aid of various concentrations Kraft digester Ag/AgCl Sulfur acd, fresh or spent Kraft solutions Fertilizer solutions Sulfonation plant HygHgSO, HsS0, Hydroxylamine sulfate PuPLo H,S0, ‘AvlAud Alcohol solution Mo‘Mo0; Sodium earbonate solutions Kraft digester Green of black liquors Platinum = H,SO, Bismuth NH,OH. 531600 steel Fertilizer solutions H,S0, Nickel Fertilizer solutions Nickel plating solutions Silicon Fertilizer solutions 12.3.3 Potential control and power supply ‘The de power supplies used in anodic protection systems have similar design and requirements as the rectifiers for cathodic protection, with one exception. Because of the nature of the active-passive behavior of the vessel, the currents required to maintain the potential of the ves- sel wall in the passive range can become very small. Some designs of de power supplies must be specially modified to reduce the minimum amount of current put out of the power supply.* ‘The potential control in anodic protection installations has two func- tions. First, the potential must be measured and compared to a desired preset value. Second, a control signal must then be sent to the power sup- ply to force the de current between the cathode and vessel wall. In early systems, this control function was done in an ON-oFF method because of the high costs of electronic circuitry. The recent progress in power elec- tronics has resulted in all systems having a continuous proportional-type control.’ Packaging these electronic components occasionally involves special requirements because most of the installations are made in chemical plants. Explosion-proof enclosures are sometimes required, and chemically resistant enclosures are necessary in other installations. 12.4. Design Concerns Designing an anodic protection system requires knowledge of the basic electrochemical behavior of the system and of the geometry of the ‘Anodic Protection 931 equipment to be protected, considering any special operational condi- tions. As described earlier, the electrochemical parameters of concern are the potential at which the vessel must be maintained for corrosion protection, the current required to establish passivity, and the current required to maintain passivity. The electrode potential can be deter- mined directly from polarization curves, and the required currents can be estimated from the polarization data. However, because the current is so strongly time dependent, its variations with respect to time must be carefully estimated. Empirical data available from field installations are the best source for this type of information. Special care and attention should also be focused on estimating the solution resistivity of a system because it is important in determining the overall circuit resistance. The power requirements for the de power supply should be as low as possible to reduce operating costs. The solution resistivity should usually be sufficiently low so that the cir- cuit resistance is controlled by the cathode surface area. It is essen- tial for a system to have good throwing power or good ability for the applied current to reach the required value over complex geometry and variable distances. In general, a uniform distribution of potential over a regular-shaped passivated surface can be readily obtained by anodic protection. It is much more difficult to protect surface irregu- larities, such as the recessions around sharp slots, grooves, or crevices because the required current density will not be obtained in these areas. This incomplete passivation can have catastrophic conse- quences. This difficulty can be overcome by designing the surface to avoid these irregularities or by using a metal or alloy that is easily passivated with as low a critical current density as possible. In the rayon industry, crevice corrosion in titanium has been overcome by alloying it with 0.1% palladium. ‘The actual passivation of a surface is very rapid if the applied cur- rent density is greater than the critical value. However, because of the high current requirements, it has been found to be neither technically nor economically practical to passivate the whole surface of a large vessel in the same initial period. For a storage vessel with an area of 1000 m®, for example, a current of 5000 A could be necessary. It is therefore essential to avoid these very high currents by using one of a few techniques. It may be possible and practical, for example, to lower the temperature of the electrolyte, thereby reducing the critical cur- rent density before passivating the metal. Ifa vessel has a very small floor area, it may be treated in a stepwise manner by passivating the base, then the lower areas of the walls, and finally the upper areas of the walls, but this technique is not practical for very large storage tanks with a considerable floor area.t Another method that has been successful is to passivate the metal by using a solution with a low critical current density (such as phosphoric 992 Chapter Twelve acid), which is then replaced with the more aggressive acid (such as sul- furic acid) that has to be contained in the vessel (cf. Table 12.6). The crit- ical current density can also be minimized by pretreating the metal surface with a passivating inhibitor. 12.5 Applications Anodie protection has been used for storage vessels, process reactors, heat exchangers, and transportation vessels that contain various cor- rosive solutions. The majority of the applications of anodic protection involve the manufacture, storage, and transport of sulfuric acid, more of which is produced worldwide than any other chemicals. Storage of 93% H,SO, and above in low-carbon steel vessels has met with some success in terms of vessel life. Anodie protection has been successful in reducing the amount of iron picked up during storage. Field studies have shown that the iron content of H,SO, in concentrations of 93% and above increases at rates of 5 to 20 ppm per day of storage, depend- ing on acid concentrations vessel size, acid residence time, and storage temperature. Several anodic protection systems have been successful in reducing the rates of iron pickup to 1 ppm per day or less. The level of purity of the acid has been sufficient to meet market demands for low iron content acid. Sulfuric acid will continue to pick up iron dur- ing transportation in trucks, railroad cars, and barges. Portable anodic protection has been used for such vessels to maintain the purity of the acid and to extend storage time.* lange market has developed for anodically protected heat exchang- ers as replacements for cast iron coolers. Shell and tube, spiral, and plate-type exchangers have been sold complete with anodie protection as an integral part of the equipment. Sulfuric acid of 96 to 98% con- centration at temperatures up to 110°C has been handled in S31600 stainless steel heat exchangers by the use of anodic protection. Corrosion rates have been reduced from unprotected rates of more than 5 mm-y-* to less than 0.025 mm-y-, and cost savings have been substantial because of extended equipment life and the higher-purity acid that was produced by using these protected heat exchangers. Several other corrosive systems have also been handled in anodically protected heat exchangers.’ ‘One consequence of reducing the rate of corrosion of steel in an acid is also to reduce the production of hydrogen, which has been reported as the cause of explosions in phosphoric acid systems. ‘The presence of hydrogen may also induce the formation of blisters at inclusions in the metal and can also produce grooving on vertical surfaces. Anodic pro- tection has been found to significantly stifle the formation of hydrogen, therefore minimizing such problems. Anodic Protection 933, 12.6. Practical Example: Anodic Protection in the Pulp and Paper Industry Anodic protection is a powerful technique used to mitigate corrosion of liquor tankage. However, the electrochemistry of Kraft liquors is com- plex due to the multiple oxidation states of sulfur compounds, the number of possible Fe-S-H.O reactions, and the existence of active- passive behavior. The electrochemical behavior may be further com- plicated because some Fe-S compounds are semiconductors.* ‘The major sulfur species in Kraft liquors are listed in Table 12.10. Anodic protection of a Kraft liquor tank was first successfully real- ized at the end of 1984, and the success of this system resulted in many commercial installations. Unfortunately, unexpectedly high cor- rosion rates were reported at localized areas in several of the tanks even though the remainder of the surfaces corroded at rates less than 0.13 mm-y-! Most of the problems experienced have been attributed to incomplete understanding of the electrochemistry of carbon steel! in these liquors and the coexistence of active and passive areas, which had not been addressed properly in earlier control strategies. ‘Tromans deduced an elegant yet simple model of passivation in caustic sulfide that explains the role of sulfide in the process.” According to Tromans, after the initial nucleation of Fe;O,, sulfide is incorporated as substitutional ions into the Fe,0, spinel lattice, form- ing a nonprotective compound Fe,O-x8x. At the peak of the active-pas- sive transition, Tromans predicted x to be approximately 0.19. Because passivation cannot occur until the sulfide in the film is completely removed by oxidation, high current densities are required to force this reaction. However, once devoid of sulfide, the film can remain stable if the potential is kept more positive than the Flade potential corre- sponding to the reduction reaction of oxidized sulfur species such as S,0,"" and $= Figure 12.5 depicts one anodic and four cathodic idealized polariza- tion curves, including the possible intersection points. The number and location of the intersection points creates four types of behavior, namely, monostable (active), bistable, astable, and monostable (pas- ‘TABLE12.10 Major Sulfur Species in Kraft Liquors Species Symbol Sulfur valence Sulfate (SOF) (80;) ‘Thinsulate (8,0,?-) Sulfur S. ide $2 s 994 Chapter Twelve 200 200 Monastabi ate 200 200 a as 2 is 4 vs OBC Log current density (mA em") Figure 125 Possible combinations of anodiclcathodie intersections in the mixed poten- fial representation of earbon steel exposed to Kraft liquors, sive). A potentiodynamic curve of each of these types of behavior is shown, respectively, in Figs. 12.6 through 12.9. Astable behavior occurs infrequently because it requires a single anodic-cathodic intersection on the negative resistance portion of the anodic curve. This is an unsta- ble operating condition that results in continuous oscillations between active and passive potentials. Various alloys in elevated temperature sulfuric acid are known to exhibit such behavior:® ‘The four types of mixed potential models presented in Figs. 12.6 to 129 are simplistic and do not necessarily reflect the complete behav- ior of carbon steel in Kraft liquors because the models all assume some sort of steady states. Figure 12.10 depicts typical curves from an in situ test in a white liquor clarifier at different scan rates. The passive state does not exist until after the active-passive transition is tra- versed. Therefore, unless sufficient anodic current density is dis- charged from carbon steel by a naturally occurring cathodic reaction or an applied anodic protection current, the carbon steel liquor interface remains monostable (active) because the passive film and its low cur- rent density properties do not exist. Under normal operating chemistries in white and green Kraft liquors, carbon steel exhibits a monostable (active) behavior, and the bistable behavior occurs only after the passivation process has reached some degree of completion, as predicted by romans and verified by Anodic Protection 995, 300 200 Potential (V vs. SSE) 200 00 a 1 Log current density (mA em") Figure 12.6 ‘Theoretical polarization curve illustrating the monostable (active) behavior of mild steel exposed to Kraft liquors 300. 200. 3 Potential (Vs. SSE) Bo 200. 00. : 25 2 ie 4 os, 0 05 1 Log current density (mA em") Figure 12.7. ‘Theoretical polarization curve illustrating the bistable behavior of mild steel exposed to Kraft liquors 996 Chapter Twolve 300 200 100 (vve. se) 2 200 00 3 as 2 1s a 05 0 05 Log current density (mA em") Figure 128 ‘Theoretical polarization curve illustrating the monostable (passive) behav- Tor of mild steel exposed to Kraft iquars 300 200 10. 8 2 Potent 100 200. 200 a9 a a. 484 os oS 1 Log current density (mA.cm*) Figure 12.9.‘Theoretical polarization curve illustrating the astable behavior of mild steel exposed to Kraft liquors. Anodic Protection 997 300 2m o02mvs" N\ ume Potential (Vvs, SSE) 200 200 9 25 a 48 a 05 0 05 1 Log current density (mA om") Figure 12.10. ‘Typical in situ polarization curves of carbon steel immersed in white liquor typical curves. However, once created, the passive state is not perma- nently stable. When the direction of the curve is reversed, a second stable equilibrium potential is established. During traverse of the active-passive transition, the corrosion rate has been measured to be only 10 percent of the total Faradaic equivalent; hence 90 percent of the current is consumed in sulfide oxidation. Design of the protection and control systems now incorporates all of the features required to passivate the tank, maintain passivation, detect active areas, and repassivate if required.* Some of these features are 1. The location of cathodes. Design is based on primary current distribution with the ratio of the minimum to maximum current den- sity around the circumference of the tank greater than 0.9. 2. Fluctuating liquor level. ‘This requires higher initial current density and more frequent repassivation cycles to form a tenacious passive layer. When immersed, the wet/dry zone of a tank exhibits a more positive potential than the remainder of tank, which may account for the higher corrosion rates there. However, it has been observed that the wet/dry zone does not get covered with surface buildup or deposits. The constantly immersed zone builds a thick sur- face deposit on these protected surfaces. 8. Control scheme. Conventional control schemes rely on a simple proportional, integral algorithm (PI). ‘This technique is not optimal when active and passive areas exist simultaneously. ‘The use of this 998 Chapter Twelve type of control will, in fact, result in accelerated corrosion of active areas. When a surface is entirely passive, the measured potential is uniform to within a few millivolts around the circumference of the tank. An active area of any size significantly distorts this uniformity. ‘The impact is so acute and precise that active areas can be located by triangulation. Once this distortion is detected, the control system ini- tiates an automatic repassivation using high currents for a program- mable period of time. Implementation of this scheme has revealed when and where active areas are formed on the vessel. Several repas- sivations are common during the first month of operation. Activation seldom occurs after this stabilization period. References 1, Walker, R., Anodie Protection, in Shreir, L. L., Jarman, R. A., and Burstein, G. 7. (eds.}, Corrosion Control, Oxford, U.K. Butterworths Heinemann, 1994, pp. 10:158-10.170, Fontana, M. G., Corrosion Engineering, New York, McGraw Hi Locke, C. E., Anodie Protection, in Metals Handbook: Corn Ohio, ASM International, 1987, pp. 462-465. 4, Sedriks,A. J, Corrosion of Stainless Steels, New York, John Wiley, 1979. 5. Riggs, O. Land Locke, C. &., Anodie Protection, New York, Plenum Press, 1981 & Munro, J. i, Anodie Protection of White and Green-Liquor Tankage With and Without’ the Use of Protective Organic Linings, in Proceedings of the 7th International Symposium on Corrosion in the Pulp and Paper Industry, Atlanta, Ga. ‘TAPPI, 1992, 117-130. 7. Tromans, D., Anodic Polarization Behavior of Mild Stee! in Hot Alkaline Sulfide Solutions, Journal ofthe Electrochemical Society, 127:1253-1256 (1980), , 1986. ion, Materials Park,

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