CORROSION STUDIES ON SS 316 L IN LOW pH HIGH CHLORIDE PRODUCT WATER MEDIUM1

A.U. Malik, M. Kutty, Nadeem Ahmad Siddiqi, Ismaeel N. Andijani, and Shahreer Ahmad ABSTRACT A detailed laboratory study has been carried out to determine the pitting behavior of 316L in chloride - containing aqueous solutions. The effects of Clconcentration, pH, dissolved oxygen and temperature on the pitting have been investigated under dynamic and static conditions. Weight loss, metallography and electrochemical techniques have been employed during the investigation. The weight loss measurement indicate extremely low losses during 4 months immersion tests, however, weight losses recorded were highest at pH = 4 under static conditions, and were lowest at pH = 7 under dynamic conditions. Metallographic studies indicate that the number and depth of pits increased with increasing Cl- concentration and immersion time and maximum number of pits were found on specimens immersed in solutions of pH 4. A parabolic relationship exists between pit depth and Cl- concentration. Polarization resistance, potentiodynamic polarization and cyclic polarization were the electrochemical techniques used during pitting investigations. Corrosion rate values were computed from polarization resistance plots and it was found that in general, corrosion rate increased linearly with increased Cl- concentration in the range of 100 to 5000 ppm. With increasing pH, the corrosion rate decreases being highest at pH=4 and lowest at pH=9. Potentiodynamic polarization studies indicate shifting of E corr to more negative values with increasing Cl- concentration and temperature. From the results of cyclic polarization studies it is inferred that pitting potential, E pit is shifted to more negative (or active) value with increasing Cl- concentration and temperature. The electrochemically measured pit potential, E pit and repassivating potential, Er are found to be linear junctions of the logarithm of Cl- concentration. At a particular temperature and Cl- concentration, the value of E pit shifts to more noble potential with increase in pH.

1 Issued in September, 1990.

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The results of this study exemplify the otent roles of various parameters in influencing the pitting mode of 316L in CI- containing medium. It has been established that low pH, high Cl- content and stagnancy are the conditions most suitable for initiation and propagation of pitting in 316L. 1. BACKGROUND INFORMATION Corrosion in the distillate header pipe line (WJ 11) at SWCC Azizya desalination plant was reported in early August 1989 and SWCC Research and Development Center (RDC) was asked to inspect the line and was subsequently assigned to investigate the problem. The RDC carried out extensive field and laboratory investigations for determining the cause of failure and subsequently, submitted a brief report ( 1) containing the main results of investigations, possible causes of failure and remedial actions to be taken. Considering the seriousness of the problem on corrosion and materials point of view in general and SWCC water transmission systems in particular, a project proposal on Corrosion Studies of SS316L in low pH, High Chloride Product Water Medium was submitted to SWCC, Riyadh on August 19, 1989 and was accepted on August 29, 1989. In the original proposals a time period of 2 months was suggested for completion of the work. However,. when the project was initiated in September 1989, it was the considered opinion of all the investigators that long term tests some up to one year durations are necessary under simulating conditions existing in the pipe lines. Moreover, electrochemical measurements which are an important part of the corrosion study could only be started when the EG and G corrosion system model 342-2 was installed in the middle of June 1990. In August 1989, RDC inspected 50 diam SS 316L pipe line (WJ11) which served to carry product distillates from a train of MSF units to the CO2 and line dosing facilities. On inspection of the pipe line it was found that the inner surface of the pipe line was not uniformly or severely corroded albeit it has randomly scattered corrosion products at the walls and at the bottom. The bottom surface (5 to 7 Clock position) was found to be pitted with pits vary from pin hole to large worm hole sizes, Each pit was either enveloped or encircled with brownish red corrosion products. The section of the pipe between the two injection points of CO2 and lime was found to be particularly more corroded than the section up stream of the CO2 dosing point. During later visits in October - November, the condition of the pipe line (WJ 11) was deteriorated, many new pits were formed and the old pits became deeper and some to the extent of the whole thickness (1.6 mm) of the pipe line. Recently, the pipe line (WJ 11) was repaired and put in operation and the alternative/parallel pipe line (WJ12) was drained off for inspection. WJ12 pipe line was examined in July 1990 and it was also found pitted but the condition of the pipes was much better. On some locations on the wall of the pipes (about 8 Clock position), green or brownish green deposits were found. On scratching the corrosion products with a thin sharp edge, the pits could be seen clearly. Figures 1 to 6 show some photographs of the pitted sections of the pipe lines.

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The average analysis results of chloride in distillate before and after treatment for the months : September 1988 to July 1989 are given in table 1. Table 2 provides chemical analysis of the distillate (before treatment) collected from distillate header (OWJ-12) on August 9, 1989. It represents typical data for a daily analysis. The distillate is normally slightly acidic (pH - 6.2) and having Cl- contents varying from 15 to 150 ppm. The pipe line was under stagnant conditions for some months during the service period of approximately 6 years. This report presents the results of a detailed study on the effects of temperature, dissolved oxygen, pH, Cl- concentration and total dissolved solids (TDS) in water on the pitting behaviour of SS 316L under simulated dynamic and stagnant conditions. The main objective of this study is to assess the performanance of SS 316L as structural material under various conditions operative in desalination plants. The major investigative procedures employed are : weight loss, electrochemical measurements, metallography and microstructural determinations. 2. INTRODUCTION Pitting is a localized corrosion attack on metals and alloys in aqueous environments. It is a major cause of failure of chemical process and desalination plants, water storage tanks and pipe lines, pumps and valves, petroleum refineries etc. Due to localized nature of pitting corrosion, formation of pits is confined to much smaller areas compared to overall exposed surface. Broadly speaking, the initiation of pitting is the result of the breakdown of the passive film on the metal due to the presence of some anions such as Cl- and subsequent establishment of an electrochemical cell in which damaged site acts as an anode and the passive site acts as a cathode. The building up of corrosion products on the mouths of the pits may result in the formation of crevices thus producing more aggressive corrosion attack. Iron - base alloys including carbon steels and stainless steels are most prone to pitting in dissolved CO2 - and Cl- containing environments as observed in brine recycle and blow down pumps, flash chambers and demisters of desalination plant, and steam boiler, feed water heater tubes and steam turbine blades of power plants, (2-6). Austenitic stainless steels are the most commonly used materials due to their high strength and superior corrosion resistance in moderately severe environment. AISI 304L (Cr : 18, Ni : 9, C : .02) provide acceptable corrosion resistance in most of the technological applications, however, in Cl- containing aqueous environments 304L SS invariably undergoes pitting and Mo- containing austenitic steels of similar compostion have been found more resistant to pitting.(7-10). Austenitic AISI 316L (Cr : 16.5, Ni : 10, Mo : 2, C :.02) is considered to be one of the most resistant of common stainless steels under marine environments and therefore, is an important structural material for desalination plants. Even this alloy may fail under conditions of high chloride content and stagnations (11-13). Figure 7 to 10 show some photomicrographs of cross- sections from a 316 pipe which failed while stored in a marine environment. A range of high alloy austenitic steels such as 254 SMO, AL-6XN, 20 Cb3, Hastelloy C, cronifer 1925 LC etc. have been recommended for applications under more severe

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environmental conditions. In these alloys, the stability of passive film with respect to pitting initiation is controlled primarily by Cr, Mo and N. The relative effect of these elements on pitting/crevice corrosion can be assessed from widely used PREN, pitting resistance equivalent. PREN = Cr% + 3.3 Mo% + 16 N% Table 3 provides composition and PR EN of some important high corrosion resistance structural steels. Numerous papers have appeared in recent years regarding the pitting behaviour of stainless steels in aqueous solutions containing single or combination of anions (7- 10,14,15). Particular interest has been shown for the Cl- due to its presence in the seawater as the major constituent and its role as an active pitting agent. Besides the influence of temperature, flow/velocity, pH and Clconcentration on pitting, the synergic effect of anion such as SO4--, S2 O3--, Cl O4- etc. have also been studied. The main objective of these studies is to determine the exact role of Cl- in initiation of the pits and to determine the mechanism. Electrochemical techniques have been the main tool of these investigations. It will be revealed from the survey of the recent literature on pitting, as given in the following section, that the exact role of different parameters in pitting of stainless steels is yet to be fully understood and more work is needed particularly with reference to pitting and crevice of stainless steels in industrial environments. The effect of Cl- on the pitting susceptibility of various metals and alloys and particularly stainless steels has been extensively investigated by numerous researchers and is reviewed in a number of books, reviews and articles (16-22). Smialowska (23) found that a majority of construction materials suffer pitting only in solutions containing Cl- or other halogen ions. Three main reasons are given for the specific effects of chloride and its ability to produce pitting. Firstly forming complex with cation and hydroxide, secondly, increasing the activity of hydrogen ions in the pit electrolyte and thirdly, forming a salt layer at the bottom of pits. The third factor appears to explain the specific role of halides in pitting attack. It is suggested that transmission from passivity to pitting condition can be explained by competitive adsorption mechanism (24,25) in which chloride ions move into the double layer (oxide/liquid interface) of the electrode surface, eventually reaching at a critical potential (E pit), corresponding to the Cl- concentration required to displace adsorbed oxygen species. The presence of adsorbed Cl- increases the potential difference across the passive film thereby enhancing the rate of Fett diffusion from the metal/film interface to film/solution interface. This leads to the formation of cation vacancies at the metal/film interface which normally disappear into the bulk of the metal. When the Cl- concentration is such that the rate of cation diffusion and thus the formation of cation vacancies is greater than the rate of disappearance of cation vacancies, voids develop at the metal/film interface. Continued growth of a void results in the localized collapse of the passive film, which will subsequently dissolve faster than other regions of the passive film leading to pit growth and ultimately substrate alloy dissolution. Anions other than Cl- such as BO3--, SO4-- and ClO4-- also adsorb on the surface, displacing Cl-. Thus in presence of these anions if the competitive adsorption mechanism is applicable;

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it will take longer for the Cl- to achieve critical concentration required for pit formation (26,27). This would result in a shift of E pit to move noble potentials. Perchlorate ions have been reported to adsorb least of all the common ions (26). The would explain the inferior inhibiting ability of C1O4- compared to that of SO4--. In neutral aqueous solutions containing chromate and nitrate as inhibitors, with Cl-, Br- and SO4-- as pitting corrosion agent, the order of decrease of corrosivity of the aggressive ions is SO4-- > Cl- > Br- and aggressiveness of halides towards passivated steels was found to decrease in the order : Cl- > Br> I- (28). Nitrogen has been found to encourage the retention of Cr in the passive films and near surface layers during corrosion of stainless steels, which improve pitting resistance (29). In newspaper machines, pitting is observed despite low chloride concentration in the process water. This is now known to be caused by thiosulfate ions, which can induce pitting on 304 SS without assistance from chloride if sulfate thiosulfate ratio is within a certain range. For 316L, this sulfate pitting did not occur unless the Cl- concentration is fairly high (l0-2 M or 350 ppm) and unless the molar concentration of chloride exceeded that of sulfate (30). This explains the previously unexpected pitting of 316L equipments in splash zones, where a concentrated chloride/sulfate solution can develop by evaporation. While studying pitting corrosion of 304 and 316 austenitic steels covered with anodic oxide film it was found that pitting current, ip constits of 3 periods : pit incubation ( O < t < ti) in which ip scarcely flows, pit nucleation (ti < t < T) and pit growth (T < t ) (31). The incubation time, ti is the time at which the outermost layer of a film is dented by Cl- ions, depends up on the nature of the bound water and the stability of the film, but not the film thickness. The induction time, T is the time at which the film is completely perforated, it increases with increasing film thickness and increasing potentials. Nishimura etal (32,33) found that pit initiation is trongly related to 2 different types of bound water in a film. It was found that the pitting behaviour of alloys covered with the passive film is largely dependent on the film thickness and ion selectivity. From investigations on pitting susceptibility of 304 SS it was concluded that pitting is related to semiconductive property of the oxide film (34). During pitting of 304 SS in Cl- containing aqueous solutions, it was found that a linear relationship exists between pit nucleation time and log chloride concentration, and between pitting potential and log induction time (35). The impedance measurements showed that the charge transfer resistance decreased with increasing temperature. Higher the Cl- concentration, lower the charge transfer resistance, hence less the protective oxide film. Kineties of pit generation of stainless steel in presence of Cl- was studied by measuring pit initiation under potentiostatic and pitting potential under potentiokinetic conditions (36, 37). Pitting generation rate, g is expressed by g = K. Cn exp (naqE/KBT). For short holding times and for high scanning rates, g does not depend upon scanning rate. For longer tests, the passive film properties vary during the test and g decreases with time, and therefore, the measured pitting potential must be considered vary cautiously.

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Electrochemical techniques have been frequently used for determining the corrosion behaviour of materials in general, and pitting performance in particular. A large number of publications appeared in recent years on practical applications of electrochemical polarization methods in pitting corrosion (38-45). Potentio-dynamic polarization techniques were used to determine the characteristic pitting potential for alloy 800 in Cl- and Cl- + SO4-- media (46). Decreasing the Cl- concentration resulted in noble shifts of the critical nucleation potential whereas increasing sulfate concentration resulted in improved chloride pitting resistance. Immunity to pitting corrosion was evident at Cl- below 300 ppm. The critical nucleation potential varies linearity with the logarithm of Clactivity. The occurance of pit initiation at transpassive potentials can be rationalized in terms of localized breakdown of a surface film that is somewhat less protective than that prevalent in the passive region. Measurements of pit initiation and pit propagation for Fe-Cr-Ni alloys in Cl- environments by electrochemical techniques were reported (47). Correlations based on the values of the pitting potential, E Pit, Crossover or protective potential Ex, corrosion potential, E corr and Slope E/i were used to predict pit initiation and pit propagation. For example, if Ecorr > Ep + 0.1 V, then good resistance to pitting, if E/i < 0.18 V/decade then there is good resistance of pitting. Systems exhibiting poor resistance to pit propagation should have E Corr values between Ep and Ep + 0.lV. 3. EXPERIMENTAL Commercial grade SS 316L (17.1 Wt% Cr, 11.3 wt%, Ni 2.1 wt% Mo, 0.02 wt%C and balance - iron) in sheet and rod forms was used for the studies. For immersion tests, coupons of about 5 cm2 area were cut from the sheet and abraded sequentially with 180,320,400 and 600 grit SiC papers. The abraded coupons were cleaned in an ultrasonic cleaner followed by drying. The dried specimens were weighted. For electrochemical measurements, circular flat test specimens as well as cylindrical test specimens were used. The circular flat test specimens of 1.5 1.6 cm diameter were punched or cut. The exposed area of the test specimens which was screwed in the sample holder was 1 cm2. Figure 11 shows a drawing of a flat specimen holder. Potentiodynamic polarization tests were carried out on an EG & G model 342-2 soft corr measurement system. The system was consisted of Model 273 polentiostat/galvanostat, Model 342 soft Corr Soft ware and Model 301 BM PS/2. All the experiments were carried out using a corrosion cell with saturated calomel as reference and graphite as counter electrodes (EG&G Model K 0047). Several series of experiments were carried out in order to study the effect of Cl concentration, pH, TDS and stagnancy on the behaviour of 316L steel using test solutions with varying compositions and conditions as shown below: PH 4, 7, 9 - concentration (ppm) 0, 10, 100, 150, 300, 500, 1000 Cl

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TDS (ppm) 100, 200, 300 (see Table 4A for details) Artificial sea water Condition Temperature
Dissolved oxygen (ppm)

See Table 4B Static and Dynamic 25 + 2oC

6
+ 0.5

Immersion time (weeks) 4, 8, 12, 16

Previously weighed coupons were immersed in test solutions for various time intervals of 1,2 and 4 months. At the end of the test periods the coupons were taken out, washed in distilled water, dried and their weights were determined. Following the immersion test, the microstructural examination of all the test specimens was carried out to assess the extent of the localized attack and morphology of the corrosion products. The shape, size and density (distribution) of the pits were determined metallographicaly using an optical microscope (ASTM G46-76). 4. ELECTROCHEMICAL MEASUREMENTS 4.1 Open Circuit Corrosion Potential (OCP) OCP of 316L immersed in chloride solutions were recorded under static and dynamic conditions. For these measurements, a separate cell with 316L coupon as W.E. and S.C.E as a reference electrode was used. It took 24 - 48 hrs. to achieve a constants potential corresponding to open circuit potential (OCP). Figures 12 to 15 show time vs OCP plots for 316L steel immersed in solutions of 300 and 1000 ppm Cl- at pH 4,7 and 9 at different temperatures deaerated conditions. 4.2 Potentiodynamic Polarization Potentiodynamic Polarization measurements were carried out using a scan rate of 0.1 mv/s commencing at a potential about 250 mv more active than the stable OCP and terminating at a potential about 500 mv more positive than OCP. Before starting the polarization scan, the specimen in the sample holder (W.E) was left in the cell for about 1 hr for attaining a steady state which is shown by a constant potential and current at the commencement of the experiment. All potentials were measured vs SCE. 4.3 Cyclic Polarization During a potentiodynamic run, upon attaining a current density of 25 uA/cm2, the scan direction was reversed, potentials were scanned back to the starting potential.

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4.4 Polarization Resistance Polarization resistance measurements were conducted at a scan rate of 0.1 m v/s with starting and final potentials corresponding to -20m V and + 20 mV vs OCP, respectively. The maximum current range was 0.1 uA. 5. RESULTS 5.1 Weight Loss Studies Figures 16 and 17 show weight loss vs Cl- concentration plots at a fixed immersion time (4 months) and at different pHs. As seen from the plots, no regular trend was observed under static or dynamic conditions. However, the following generalizations can be made regarding the behaviour of 3 16L under varying parameters e.g., pH, time interval and Cl- concentrations. (i) (ii) No perceptible weight loss was observed during immersion periods of upto 6 weeks irrespective of Cl- concentration, pH and dynamic or static con-ditions. Extremely low weight losses (10 - 50 ug/cm2) were observed during immersion time exceeding 6 to 8 weeks.

(iii) Weight losses recorded were highest at pH = 4 under static conditions, and were lowest at pH = 7 and under dynamic conditions. 5.2 Metallographic Examinations Figures 18 to 23 show some surface microstructures of SS 316L steel specimens immersed in Cl- containing solutions at pH 4,7 and 9 under static and dynamic conditions. Pitting of 316L occurs under varying Cl- concentration and pH. Under similar conditions, maximum number of pits were found on specimens immersed in solutions of pH 4 and minimum on specimens immersed in solutions of pH 7. Under dynamic conditions (when the solutions were agitated continuously during the entire periods of immersion test) the number of pits observed on the surface of the specimen was much smaller than under static or stagnant condition. In general, the number and depth of the pits increased with increasing Cl- concentration and immersion time. For example, when the immersion time was increased to 4 months, there was an over all increase in pit numbers as well as their sizes. At pH 4 in static conditions, several big and small pits could be identified. At pH 7 and 9 pitting was comparatively less severe but a few deep pits could be seen under static as well as dynamic conditions. The studies also indicate that in presence of TDS, pitting occurs but the effect is much less aggressive. 5.3 Pit Depth Measurements The depth of the pits on 316L specimens was measured microscopically. Minimum and maximum pit depths were measured for a particular specimens and also average depths were determined by considering the depth of all the pits present. Figure 24 shows plots of maximum pit depths vs Cl- concentration,

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for 316L immersed in solutions of 300 ppm Cl- concentration and differing pH for an immersion period of 4 months. The plots provide following interesting informations. (i) The pit depth increases with increasing Cl- concentration. A parabolic relationship appears to exist between pit depth and Cl- concentration as indicated by the linear nature of pit depth vs concentration of chloride plots (fig. 25). (ii) Pit depths of the specimens immersed in solutions of pH4 was much greater than those immersed in solutions of higher pH e.g., 7 and 9.

Figures 26 to 31 show the optical micrographs of pits produced by potentiodynamic anodic polarization or cyclic polarization of 316L in different chloride concentrations. Most of the pits were generally of small diameter (i.e less than 50 um). Table 5 describes the morphology of pits generated in chloride media under different conditions. 5.4 Electrochemical Measurements. 5.4.1. Polarization Resistance: Polarization resistance measurements using 316L coupons immersed in Cl- containing solutions were carried at 25, 50 and 80 C under varying pH, Cl- and aerated and deaerated conditions. Typical polarization resistance plots are shown in Fig. 32 to 38. Table 6 lists the corrosion rate values computed from the plots. The polarization data provide following information regarding the behaviour of 316L in Clcontaining solutions. i) At pH = 4 the corrosion rate increases linearly with increasing Clconcentration in range of 100 ppm to 5000 ppm although higher corrosion rates are observed at 500 ppm. ii) With increasing pH, the corrosion rate decreases being highest at pH = 4 and lowest at pH = 9. iii) Corrosion rate increases with increasing temperature being highest at 80 C and lowest at 30 C. iv) Corrosion rates under deaeration are much lower than aerated conditions. v) Corrosion rates of 316L in seawater is 0.064 MPY which is about the same as that in a solution containing 1000 ppm Cl-.

5.4.2. Potentiodynamic Polarization: Typical potentiodynamic anodic polarization plots for 316L in Cl- containing solutions are shown in Fig.39 to 45. The values of Corrosion current (I corr), corrosion potential (E corr), Tafel constants ( Ba and Bc) and corrosion rates computed from potentiodynamic plots are given in Table 7. In general, E Corr shifts to more negative

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values with increasing Cl- concentration and temperature. The corrosion rate increases with increasing Cl- concentration and is maximum at pH = 4. 5.4.3. Cyclic Polarization: Some representative cyclic polarization curves for 316L in Cl- containing solutions are shown in Fig. 46 to 54. A hysteresis loop is traced during reverse scan indicating the the possibility of pitting. Table 8 lists the values of pitting potential (E pit) and protection potential (E Prot), which is defined as the potential where forward and reverse scans cross, repassivating pitting polential (Er) is also considered, it is defined as the most active potential at which the nucleation of unstable (i.e. repassivating) pits can occur and is characterized by a reversible increase in current density (CD). The stable nucleation potential (E Pit) is assessed as that at which a stable increase in CD occurs., indicating the initiation of non-repassivating pits. Eprot is the most active potential at which pit propagation can occur. In general,. pitting potential, E Pit is shifted to more negative (or active) value with increasing Cl- concentration and temperature. At a particular temperature and Cl- concentration, the value of E Pit shifts to more noble potential with increase in pH. The electrochemically measured pit potential, Epis found to be a linear function of the logarithm of Cl- concentration (Fig.55). 6. DISCUSSION The immersion tests carried out on 316L coupons at different Cl- concentrations, pH and time intervals and under static and dynamic conditions show extremely low weight losses (10 - 50 ug in typical 4 months runs). At a particular chloride concentration and immersion time, the weight losses were more or less independent pH and static or dynamic conditions. The number and depth of the pits generally increased with increasing immersion time. Maximum number of pits were found on specimens immersed in solutions of PH 4. At pH 7 and 9, the number of pits were smaller but some of them were deep. Under dynamic conditions, the number of pits observed on the surface of the specimen was much smaller than under stagnant condition. Austenitic steels are virtually immune to general corrosion while in contact with fresh or saline water at natural pH. However, in the presence of Cl- these steel are subjected to local attack in the form of pitting or crevice corrosion due to break-down of protective Cr2 O3 film at random sites. The pitting on the passive surface has been explained by the competitive adsorption mechanism in which chloride ion move into metal/oxide film interface at the metal surface. At a particular chloride concentration, a critical potential (E Pit) develops which is sufficient to displace adsorbed oxygen species (protective oxide layer). It appears that low pH and stagnancy provide most favourable conditions for pit growth. In a typical case, under conditions of 4-5 ppm dissolved oxygen and 25 C, the pits grow maximum to 450 and 325 microns at pH 4 under static and dynamic conditions, respectively when 316L specimens were immersed in 300 ppm chloride solutions for 4 months. At higher pHs (7 and 10) the depth rarely exceeded 70 microns. The pit depth appears to be a parabolic function of Clconcentration and therefore with increasing Cl- concentration the rate of pitting appears to slowdown.

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The corrosion rates of 316L in 1000 ppm chloride solutions at different pHs as determined from polarization resistance technique were found to be highest at pH = 4 and the lowest at pH = 9. Similar information was obtained from potentiodynamic polarization and Tafel plots. At a definite pH and a fixed chloride concentration, the corrosion rate of 316L increases with increasing temperature (Fig. 56). The corrosion rates in deaerated conditions (1.4 ppm O2) were much lower than under ordinary conditions (6.8 ppm O2). Considering the effect of pH on pitting potential, the potential was found to be shifting to move positive values with increasing pH, however, no systematic variation in protective polential values was found. The effect of chloride concentration on the stable pit nucleation potential (E Pit) is consistent with that observed with other systems whereby the potential varies with the logarithemic of Cl- activity. Lackie and Uhlig (24) reported a 88 mV shift in the critical nucleation potential on a ten fold increase in Cl- activity in the concentration range of .01 to 1M (350 to 35,000 ppm). In this study a shift of about 200 mV was observed on a similar increase in the concentration range of 100 ppm to 5000 ppm at pH = 4. The repassivative potentials (Er) were also found to shift to move moble values with decreasing Cl- content. Like pitting potential, E pit, the repassivating potential, Er also varies linearily with the logarithm of the concentration of chloride (Fig. 57). At chloride level of 100 ppm or below no repassivating potential was observed. The corrosion rate of 316L in artificial seawater (Cl- 24153 ppm and pH = 7.3) was slightly lower than the corrosion rate is solution of pH 4 but is higher than in solutions of pH 7 and 10. At chloride concentrations at which stable nucleation was evident (100 ppm to 30,000 ppm) extensive hysteresis was observed upon scan reversal with repassivation occurring in the vicinity of OCP. The pitting potential (E Pit) was invariably more positive than the protective potential (E pro). The difference between pitting and protective potential decreases with increasing Cl- concentration and is a linear function of logarithm of Cl- concentration (Fig.58). The occurrence of pit initiation at transpassive potentials can be rationalized in terms of localized breakdown of a surface film on 316L that is some what less protective (i.e. higher rate of general dissolution) than that prevalent in the passive region. The nucleation of repassivating pits at overpotentials far below that required for stable pitting indicates the enunciation of a dynamic process of pit initiation and repassivation prior to the development of propagation pits. From the foregoing studies, it is evident that at a given temperature and dissolved oxygen concentration, pH, Cl- concentration and flow conditions are important parameters affecting the corrosion behaviour of 316L in water. It has been established that low pH, high Cl- content and stagnancy are the conditions most suitable for initiation and propagation of pitting in 316L. The 316L pipe line has deep pits that were produced due to intermittent stagnancy of aerated distillate water for periods varying from a few weeks to one year. The Cl- content of the distillate varied from 30 - 150 ppm during this period as shown by laboratory analytical data sheet and having pH approached to acidic range. One important consequence of the pitting is the occurrence of crevice corrosion inside the pits. Due to the blocking of the months of some of the pits with the corrosion products, more crevice are formed resulting in spreading of corrosion throughout the length and breadth of the pipe line.

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7.

CONCLUSIONS

The pitting behavior of 316L in Cl- containing solutions is greatly influenced by the variation in Cl- concentration, pH, dissolved oxygen, temperature and flow conditions. It has been established that low pH, high Cl- and stagnancy are the conditions most favourable for initiation and propagation of pits in 316L steel. The pitting in 316L header pipe line was-primarily the-aftermath of high Cl-, low pH and intermittent stagnancy of the distillate water in the subject pipe line
.

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Industrial Problems Treatment and Control Techniques Pergamon Press Oxford (1987). H.P.Leckie, H.H.Uhlig, J.Electrochem. Soc.,ll3, 1262, 1967. J.Horvath, H.H.Uhlig, J.Electrochem.,l15, 791,(1968). H.E.H.Bird, B.R.Pearson and P.A.Brook, Corrosion Science,28, 81 (1988). H.C.Brookes and F.J.Graham, Corrosion, 45, 287 (1989). S.M.Sayed and H.A.El Shayeb, Corrosion Science, 28,153 (1988). S.J.Powell, E.E.Stansburry and C.D.Lundin, Corrosion, 45, 125 (1989). A.Garner, Corrosion, 45, 282 (1989). R.Nishimura and K.Kudo, Corrosion 44, 29 (1988). R.Nishimura, M. Araki, K.Kudo, Corrosion 40,465 (1984). R.Nishmura,Corrosion 43,486,( 1987). G.Bianchi, A.Cerguetli,F.Mazza, S.Torchio, Corrosion Science 10, 19 (1970). J.H.Wang, C.C.Su and Z.Szklarska-Smialowska, Corrosion Science, 44,732 (1988). B.Baroux, Corrosion Science, 28, 969 (1988) K.E.Heusler and L.Fisher, Werkst Und Korrosion,27, 551 (1976). B.E.Wilde, J.S.Armijo,Corrosion 23, 208 (1967). W.Schwenk, Corrosion Science, 5,245,( 1965). H.P.Leckie,J.Electrochem. Soc,l17,1152 (1970). E.A.Lizlovs, A.P.Bond, Corrosion, 31, 219 (1975). P.E.Manning, Corrosion,36, 468 (1980). H.C.Man, D.R.Gabe, Corrosion Science, 21, 323 (1981). P.E.Morris, R.C.Scarberry, Corrosion, 28,444 (1972). J.G.Stoecker, O.W.Scebert, P.E.Morris, Practical Applications of Potentiodynamic Polarization curves in Material Selection, Materials Performance, 22,13, (1983). G.Palumbo, P.J.King and K.T.Aust, Corrosion 43, 37 (1987). Measurement of Pet Initiation and Propogation for Fe-Cr-Ni alloys in acid environments by Electrochemical Techniques, P.E.Morris in Electrochemical Techniques for Corrosion Engineers, P.287, R.Baboian, Editor, NACE (1986).

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Table- 1 Average Results of Chloride in Distillate Before and After Treatment CHLORIDE IN MONTH YEAR DISTILLATE AFTER TREATMENT 32.5 ppm 21.4 46.5 80.0 163.7 123.7 46.7 62.6 58.5 57.0 30.6 DISTILLATE BEFORE TREATMENT 27.5 ppm 16.0 41.5 75.0 158.7 118.0 41.0 57.0 * 53.0 53.0 26.0

September October Novermber December January February March April May June July

* Distillate after treatment with CO2, Lime & Sodium hypochlorite generated from seawater. Note: Chlorination by treatment with sodium hypochlorite contribute 5 + 1 ppm chloride to the distillate.

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Figure 1 : Photograph of the inner surface of the header pipe line showing pits at the bottom (6oClock position) covered w i t h the corrosion products (OJll)

Figure

2 : Photograph of the inner surface of the header pipe line showing pits at 4 or 8O Clock position ( OJll)

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Figure

5: Photograph of the inner surface of the header pipe line showing pit at the wall (9 O Clock) covered with the corrosion products (0512 pipe line)

Figure
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6:

Same as (0512)

Fig.6

but

after

corrosion

products

are

removed

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Figure 7: Photo micrograph, of a cross section of a 316L pipe showing a deep pit.

Figure 8: Same as Fig.7 but at a different location.

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Figure 9 : Scanning electron micrograph of a cross section of a failed 316L pipe showing a deep crack and the presence of micro pits.

Figure 10: Scanning electron micrograph of a cross section of a failed 316L pipe showing extensive cracking & pitting.
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Figure 18 : Photo micrograph of a cross section of 316L specimen showing a deep pit (Cl-: 300ppm, pH=4,immersion period: 4 months under static condition)

Figure 19: Photomicrograph of a cross section of a pitted 316L specimen ( Cl-:300 ppm,pH=7, immersion period : 4 months under static condition)

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162

Figure 20: Photo micrograph of a cross section of a pitted 316L specimen (Cl-: 300 ppm, pH=9, immersion period : 2 months under static condition.)

Figure 21: Photomicrograph of a cross section of 316L specimen showing the presence of shallow pits(Cl-: 300ppm, pI-i=4,immersion period : 4 months under dynamic condition)

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Figure 22 :

Photomicrograph of a cross section of a pitted 316L specimen (C1-:XQqm,pH=7, Immersion period: 4 months under dynamic condition)

Figure 23: Photomicrograph of a cross section of a pitted 316L specimen (TDS:200ppm, pN=7 immersion period: 3 months under condition)

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Figure

26:

Photo micrograph of a cross section of 316L specimen pitted potentiodynamically(Cl-:lOOppm pH 4)

Figure

27:

Photomicrograph of a cross section of 316L specimen pitted potentiodynamically (Cl-: 300ppm pH-4)

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Figure

28:

Photo micrograph of a cross section of 316L specimen pitted potentiodynamically (Cl-:5OOOppm pH-4)

Figure29: Photo micrograph of a cross section of 316L specimen pitted potentlodynamically (Cl-: 1000 ppm pH-7)

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232

Figure

30:

Photo micrograph of a cross section of 316L specimen pitted potentiodynamically (Cl-:1000 ppm,pH-7,under deaerated condition)

Figure

31:

Photo micrograph of a cross section of 316L specimen pitted potentiodynamically(Artificia1 sea water, pH 9.9)

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