CORROSION BEHAVIOR OF NI-RESIST CAST IRONS IN SEAWATER1

A.U. Malik, S. Basu, Ismail Andijani and Shahreer Ahmad SUMMARY

The corrosion behavior of Ni-Resist cast irons in seawater has been studied under varying temperature and dissolved oxygen conditions. The studies involve investigations on the failure of a Ni-Resist cast discharge column of a brine recycle pump from a desalination plant and laboratory tests on two types of Ni-Resist irons. Weight loss measurements, electrochemical polarization techniques and metallographic methods of analysis have been used to determine the corrosion rates and to investigate the nature of corrosion in Ni-Resist irons.

It has been established that discharge column of the brine recycle pump has failed by stress corrosion cracking (SCC). The cracks are initiated from the pores and the cracking pattern is characterized by the emanation of fine cracks from big cracks. The region near the weld/base metal interface has been found to be a preferential site for the initiation and propagation of SCC due to presence of higher concentration of chromium carbide. The corrosion rates of Ni-Resist T2 iron having graphite flake structure are higher than the corresponding 02 alloy having graphite nodule structure. The corosion rates of Ni-Resist irons are strongly dependent on the dissolved oxygen. The corrosion rates are minimum in deaerated conditions although no passive region is observed in the potentiodynamic polarization and open circuit corrosion potential plots. Under fully aerated conditions, only a region of limited passivity is invariably observed because of the poor adherence of the oxide scales. 1 . INTRODUCTION Ni-Resist cast irons are high nickel chromium containing austenitic cast irons used primarily for their corrosion resistance especially in sea water environments. These alloys tend to maintain their corrosion resistance under high velocity conditions and show good wear resistance. Ni-Resist cast irons are the most frequently used materials for components handling sea water and brine such as large intake, recycling and blow down pumps for desalination and power plants. Pitting of Ni-Resist type 2 in deaerated sea water is minimal and therefore these materials provide excellent cover to stainless steel components against pitting and crevice corrosion during shut downs.

1 Issued as Tech Report No. SWCC (RDC)-12 in October, 1991

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The graphite in Type 1 through 5 in Ni-Resist iron is in the form of flakes as is common in the structure of gray cast irons. It has been reported that austenitic flake graphite cast irons are more resistant to graphitization because the potential difference between matrix and graphite is less than between the ferrite in cast iron and graphite. The corrosion rate of Ni-Resist types 1,2 and 3, showed an average corrosion rate of 1.6 mils per year (mpy) in quiet seawater, and 2 and 3 mpy at flow rates of 5 and 27 fps, respectively. In deaerated sea water, the corrosion rate of Ni-Resist Type 2 was independent of velocity but in aerated sea water, the corrosion and pitting rates are strong functions of velocity2. The pitting rate of Ni-Resist Type 2 is related to velocity by : mpy (pitting) = 210 (v)0.37 In spite of their good service performance in desalination plants, there are some reported cases of Ni-Resist component failures by stress corrosion cracking (SCC) in warm sea water. The failure has been attributed generally to castings that have not been stressrelief heat treated or in rare cases the cracking was associated with a high carbide content in the iron. Miyasaka and Ogure3 have carried out a detailed investigation of the stress-corrosion cracking of austenitic irons studying the effect of applied stress, alloying elements, temperature, NaCl concentrations, dissolved oxygen concentration and electrode potentials. It has been shown that, at high stress levels, ductile type D2 Ni-Resist would be susceptible to SCC in warm seawater. Failures have occurred in castings which were stress-relief heat treated. In such cases, local internal stresses close to proof strength might occur (200 N/nm2) particularly if any weld repairs have been carried out. Dawson and Todd4 studied the influence of Carbide content on the stress corrosion cracking (SCC) of Ni-Resist cast irons in warm seawater (45%). It has been shown that the exposure of highly stressed, Type D2 Ni-Resist castings to warm aeraeted seawater can promote the occurrence of SCC in fairly short time which could be minimized by a stress-relief heat treatment. They concluded that the form and amount of SCC likely to occur appears to be related to the carbide content of the iron, which is determined by the silicon and chromium contents and the efficiency of the inoculating process used during production. Irons with high Si and relatively low Cr within the specifications, which have been effectively inoculated to give the minimum amount of carbide in the structure, are least susceptible to SCC. The studies on the behavior of Ni-Resist cast irons in seawater are motivated by a series of failures of Ni-Resist cast discharge columns of recirculation pumps of a seawater desalination plant in the Kingdom of Saudi Arabia. The studies are comprised of failure investigation on the discharge columns of brine recirculation pumps along with laboratory testings of Ni-Resist irons in seawater environments under different dissolved

oxygen concentrations using electrochemical methods of analysis and metallographic analysis.

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2.

STUDIES ON THE FAILED PUMP DISCHARGE COLUMN

2.1 General Observations The failed brine recirculation pump discharge columns on inspection and physical examination showed that the columns were severely corroded and revealed deep macro and micro cracks mostly in the upper column of pump (Fig.1). Microscopic observations showed that the Ni-Resist casting used in the discharge columns was highly porous with patch welded areas. Thecasting was deleteriously corroded and several macro cracks, some of them more than 1 mm wide and penetrating the entire thickness of the discharge column, appeared mostly in the upper column of the pump. Most of the cracks initiated from the inside surface of the discharge column traversing longitudinally upwards culminating either within the wall section or at the upper surface. Interestingly, from these main cracks, many micro or semi micro cracks emanated. This was revealed by the microscopic examination of the cross-sections, and inner and outer surfaces of the failed discharge column specimenss. A considerable number of the cracks emanated from the patch welded zones although no crack was found on the welded area. 2.2 Results 2.2.1 Chemical Analvsis Chemical analysis of a sample of the pump discharge material showed that the composition of the material was similar to that of Ni-Resist type D2 (Table 1). 2.2.2. Microstructural Studies Photomicrograph of a standard specimen of Ni-Resist D2 showed graphite nodules and lamellar carbides in an austenite matrix. The microstructure of a specimen in the vicinity of weld/base metal interface showed progression of cracks deep inside the section5. The cracks showed a tendency to pass through the graphite nodules. Two types of structures were revealed. The base metal structure, which was porous showed the presence of one or two fine cracks originated from the weld/base metal interface and traversing some of the graphite nodules. The structure of the weld zone revealed a dendrite type structure in which Cr 7C3 grains are entangled in between lamellar intermetallic phase5. The microstructures of the specimen prepared by cutting through the cracked areas revealed the penetration of the crack into the section. These are transgranular cracks from which several fine cracks emanated.
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The passage of cracks in the failed material was also studied through scanning electron micrography - the cracks have progressed mainly through the austenitic phase and show extensive branchings. The energy dispersive X-ray (EDAX) profiles of the specimen prepared by cutting through cracked area in the vicinity of weld zone show much higher concentration of Ni and Cr in the weld metal than in the base metals. SEM pictures have also been taken for cracks originated from the pores found on the surface of the casting near the weld zones. The cracks propagate through the austenitic matrix and culminate only at the deep cavities or pit holes found on the surface of the discharge column. 2.3 Discussion Observation of the pattern of cracking provide indisputable evidence that the failure occurred predominantly by stress corrosion cracking (SCC). From metallographic studies it is evident that there are 2 possible sites from which the cracks have initiated. The pores in the pump discharge column casting have stress concentrations and cracks could initiate from these pores progressing longitudinally from the inner surface of the discharge column to the outer surface or culminating in the midway of the wall section. In either case, fine cracks emanated from the big cracks. The other region where cracks originated are in the vicinity of weld zone. These regions have greater concentration of stresses and the pattern of cracking is similar to that observed where cracks initiate from pores albeit there are fewer number of cracks. In both cases, the cracks progress by passing through the graphite nodules and austenitic phase or through austenitic phase only. It has been reported that SCC is most likely to occur more rapidly in areas that have been ground to smooth surface for welding, the grinding process removes original casting skin. The discharge column material castings have higher silicon and low chromium contents and therefore, the microstructure has predominant concentration of graphite and smaller carbide concentration which is apparently more resistant to corrosion. However, in the region near the weld/base metal interface there is very high chromium content resulting in an abnormal rise in carbide concentration. The region near the weld/base metal interface is the preferential site for the initiation and propagation of SCC cracking. The cracks initiated from this area are fewer but are larger and penetrate more deeply into the section as is evident from metallographic studies.

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3. 3.1

STUDIES ON THE CORROSION BEHAVIOR OF NI-RESIST IN SEAWATER ENVIRONMENT Experimental The corrosion behavior of Ni-Resist alloys in seawater environment was studied by the following techniques : 1. Electrochemical studies involving measurement of polarization resistance and determination of Tafel plots.

2 . Measurement of free corrosion potentials with time. 3 . Weight loss measurements.

3.1.1. Techniques and General Procedure The Electrochemical measurements were carried out under two variables : temperature and deaeration/aeration conditions. Four temperatures were used : ambient (~25oC), 40oC, 60oC and 80oC. Three different aeration conditions were used : (1) Full deaeration by purging the seawater solution with purified nitrogen; the nitrogen from cylinders was bubbled through an alkaline solution of pyrogallol to remove the traces of oxygen. (2) Partial deaeration by purging the solution with nitrogen from cylinders directly. This nitrogen contains a few ppm of O 2. (3) Full aeration by bubbling air through the solution. The weight loss measurements were conducted under conditions similar to those used in electrochemical studies. The corrosion rates were determined by following standard test procedure (ASTM,G31-72) by exposing coupons and measuring the weight loss due to corrosion. Electrochemical polarization experiments were carried out on an EG&G model 342-2 soft Corr measurement system. The system is consisted of model 273 potentiostat/galvanostat, model 342 corrosion software and model 30 IBM PS-2. All the experiments were carried out using a corrosion cell with saturated calomel as reference electrode (SCE) and graphite as counter electrode (EG&G model K 0047). Open circuit corrosion potential (OCP) were recorded under fully deaerated, partially deaerated and fully aerated conditions. For these measurements, a separate cell with Ni-Resist coupon as WE and SCE as reference electrode was used. It took 24-43 hrs to achieve a constant potential corresponding to OCP.
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Tafel plot measurements were carried out using a scan rate of 0.1 mV/S commencing at a potential about 2.50 mV more active than the stable OCP and terminating at a potential 250 mV more positive than OCP. Before starting the polarization scan, the specimen in the sample holder (WE) was left in the cell for about 2 hr for attaining a steady state which is shown by a near constant potential and current at the commencement of the experiment. All potentials were measured vs SCE. Polarization resistance measurements were conducted at a scan rate of 0.1 mV/S with starting and final potentials corresponding to -20 mV and + 20 mV Vs OCP, respectively. The max. current range was 10 uA. 3.1.2 Materials Two types of Ni-Resist alloys, namely Ni-Resist D2 and Ni Resist T2 were used for corrosion studies. The samples used for Ni-Resist D2 were obtained from sound portion of the failed brine recirculation pump discharge column. After preparing the samples, they were examined carefully under microscope to confirm that they were free from any defect, like cracks, porosities etc. Ni-Resist T2 coupons were obtained from Metal Samples, Munford, U.S.A. The chemical composition of the two Ni-Resist alloys used in the studies is given in Table 1. Chemical composition of the artificial sea water used in the tests is given in Table 2. This water has a composition which is very similar to that of seawater from Arbian Gulf. 3.2 Results 3.2.1 Metallographic Studies Figure 1 shows microstructure of Ni-Resist D2 while Fig.2 shows the structure of Ni-Resist T2. The main difference between the two structures is in the forms of graphite-D2 has the graphite in the nodular form while in T2 it is in the form of flakes. 3.2.2. Electrochemical Studies Polarization resistance (PR) curves obtained for Ni-Resist D2 at different temperatures under complete deaeration with purified nitrogen are shown in Fig.3. Figures 4 and 5 show the PR curves under partial deaeration and full aeration conditions, respectively for Ni-Resist D2. Similar curves for Ni-Resist T2 are shown in Figures 6 to 8. Figures 9 to 14 present Tafel plots
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for Ni-Resist samples under varying experimental conditions. Table 3 presents the results of all electrochemical tests (PR and Tafel experiments) conducted on Ni Resist D2 at different temperatures under the three deaeration conditions. Similarly, Table 4 presents the results of all electrochemical tests conducted on Ni Resist T2. 3.2.3. Free Corrosion Potential Measurements Plots of free corrosion potential vs time for Ni Resist D2 at different temperatures under fully deaerated conditions are shown in Fig.15 The plots of free corrosion potential vs time for Ni Resist D2 under partially deaerated condition are given in Fig.16 while Fig.17 shows the free corrosion potential vs time plots for Ni Resist D2 under fully aerated condition. The potential time plots for Ni Resist T2 under fully deaerated, partially deaerated and fully aerated conditions, respectively, are shown in Fig.18 to 20. 3.2.4 Weight Loss Experiments Corrosion rates as determined from weight loss measurements for Ni Resist D2 alloy under conditions of full deaeration, partial deaeration and full aeration at 40oC and 60C are presented in Table 5. 3.3 Discussion Some interesting features relating to the corrosion behavior of Ni-Resist alloys in sea water are revealed by electrochemical studies. As expected the corrosion rates of Ni-resist alloys in artificial seawater under fully aerated condition are much higher (at least by one order of magnitude) than under fully deaerated or partially deaerated conditions. However, the corrosion rates of Ni-resist alloys under fully deaerated or partially deaerated condition are only marginally different. This is presumably due to very small difference in oxygen activities under the two conditions. Considering the effect of temperature on corrosion rates, it is noted that in most cases, the highest corrosion rate is found in the temperature range of 40 to 60oC. While explaining this behavior, two factors are to be considered: negative effect of temperature on dissolution of oxygen in water and positive effect of temperature on the kinetics of metal dissolution or oxidation. The temperature range of 40oC-60C provides an optimum combination of two factors so as to exhibit maximum corrosion rates.

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In any condition, the corrosion rates of Ni Resist T2 alloys are higher than Ni Resist D2 alloys. A graphite flake structure (exhibited by T2 alloys) is perhaps more accessible to corrosion than a graphite nodular type structure exhibited by Ni Resist D2. The corrosion rates obtained from the Tafel plots are invariably much lower(in some cases lower by a factor of 2 to 5) than those obtained from the respective polarization resistance measurements. The simplest and most plausible explanation appears to be that in polarization resistance measurements, the range of potential traverse is very small : within+20 mV from the corrosion potential. Because of such a small potential range applied on the surface, its surface characteristic would not have changed appreciably during the period of P.R. experiment. On the other hand, in Tafel measurements, the potential traverse is much greater : +200 to 250 mV from the corrosion potential, so that during scan period the surface characteristic of the specimen changed in such a way so as to resulting in lowering of corrosion rates. The values of corrosion rates of Ni-resist irons as determined from weight loss measurements were far less than the values obtained from electrochemical methods under similar conditions of temperature and aeration or deaeration. Under either conditions of aeration, the corrosion rates obtained by the electrochemical techniques are several times higher than the rates determined from weight losses incurred during 30 to 40 days immersion tests. The long term immersion of Ni-resist coupons in artificial seawater results in the formation of thick and adherent scales of iron oxides which act as a barrier against further corrosion. As the corrosion rate has been calculated in terms of weight loss it is expected that the corrosion rates could be reduced further on increasing the immersion time. Useful information is inferred from the study of free corrosion potential vs time plots for Ni-resist D2 and T2 alloys under different experimental conditions. Both the alloys behave almost similarly as far as the corrosion behavior is concerned. Under condition of complete deaeration, near passivity is achieved in a few hours at room temperature. At other temperatures, the behavioral pattern of potential vs time plots is rather irregular. Plateaus of constant potentials ranging from 6 to 12 hrs are observed which are disturbed by a small drop or rise in potential. In general, regimes of steady potential are shown after about 50 hours. Initially, a protective film is formed which is broken as indicated by a change in potential followed by curing of the film which is indicated by a plateau and this process of breaking and curing of film goes on intermittently till a stable film is formed. The variations in potential are quite significant at 80oC where relatively less oxygen is available for oxide film formation.

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Under condition of partial deaeration, the corrosion behavior is similar to that observed in case of complete deaeration by purified nitrogen gas. The small variations in potential are observed intermittently. Each variation in potential is followed by a regime of constant potential represented by a plateau. Like previous case alloy at 25oC acquires passivity within hours as shown by a constant potential in the potential/time plot. Near passivity is achieved within a few hours in Ni-resist under condition of complete aeration. This behavior is observed at all the temperatures. The induction time appears to decrease linearly with increase in temperature (Fig.21). Under condition of complete aeration created by air bubbling, thick scales are formed which act as a barrier layer against further oxidation. Under partially deaerated or fully deaerated conditions, Ni-resist is not able to from protective barrier layer at temperatures above 25oC, because the oxide films formed are perhaps not sufficiently voluminous as well as adhered so as to envelope the whole alloy specimen. An examination of the Tafel plot curves for the Ni-resist irons under different aeration conditions indicates that only alloys under fully aerated conditions exhibit passivity. The sign of passivity is indicated by a no change in current (at about l03 uA/cm2) with increasing potential. Under conditions of complete or partial deaeration at no stage the Tafel plots show constancy or decrease in current with increasing potential therefore, the possibility of attaining passivity is precluded. The indications of attainment of passivity under fully aerated conditions are demonstrated by free corrosion potential vs time plots. At a particular temperature, the corrosion potential, Ecorr increases with increase in oxygen content but at a constant oxygen concentration, it decreases with increasing temperature. A state of achievement of near passivity on Ni-Resist irons in seawater under deaerated conditions is demonstrated by electrochemical measurements. However, this might not represent a true passivity since the corrosion rates are invariably higher under decreasing dearation conditions as indicated by electrochemical and immersion tests. In Ni-Resist irons a state of complete passivity will perhaps never be achieved because of the poor mechanical adherence of the oxide scales and only a short term or temporary passivity would be observed as long as voluminous oxide scales are adhered to the metal. 4 1. CONCLUSION Failure in the brine recirculation discharge column has occurred predominantly by stress corrosion cracking.

2. Cracks are initiated from the pores and progress by passing through the graphite nodules and austenitic phase or through austenitic phase only.
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3. 4.

The cracking pattern is characterized by the emanation of fine cracks from the big cracks. The failed region near the weld/base metal interface which is the preferential site for SCC is characterized by high chromium content resulting in an abnormal rise in carbide concentration. Ni-Resist irons with graphite flake structure have higher corrosion rates than the corresponding alloys with graphite nodule structure. Maximum corrosion rates for Ni-Resist irons are exhibited in the temperature range of 40 - 60oC. The corrosion rates for Ni-Resist irons decrease with decreasing dissolved oxygen concentration being lowest under deaerated conditions. However, at no stage a passive region in the electro-chemical curves is observed. Only under conditions of full deaeration, limited passivity is observed. The lack of passivity is attributed to the weak adhesion of the iron oxide scales on the alloy.

5. 6. 7.

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REFERENCES 1. 2. 3. 4. T.P.May, J.F.Mason, Jr., and W.K.Abbot, Materials Protection, 1, 40(1961). B.D.Criag and L.A. McClymonds Corrosion, 37,485 (1981). M.Miyasaka and N.Ogure, Stress corrosion cracking of austenitic cast irons in seawater and brine and its prevention. Corrosion 86, Paper No. 324, Houston, Texas. J.V. Dowson and B. Todd, Influence of carbide content on the stress corrosion cracking of Ni-Resist cast irons in warm seawater BCIRA Journal, November 1987 (Ni DI Technical Series No. 10018 pp 1-9. A.U.Malik and Shahreer Ahmed A study on the discharge columns of brine recycle pumps in Phase II desalination plant at Al-Jubail. Research Activities and Studies, Volume 1 - 1410H (1990)

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