Research & Development Center, Saline Water Conversion Corporation P.O.Box # 8328, Al-Jubail 31951, Kingdom of Saudi Arabia
SUMMARY
Corrosion problems in desalination plants can increase substantially the operation and maintenance cost. The shutdowns resulting from the failures of components due to corrosion are extremely expensive. Stress corrosion cracking (SCC) is one such corrosion failure commonly encountered due to combined action of stress and corrosion medium.
This report describes a study on the Stress Corrosion Cracking (SCC) behavior of alloys resulting from the synergistic action of corrodents such as chlorides, oxidants, H 2 S, etc. In this study, the threshold stresses for SCC have been determined for few generic alloys namely; carbon steel, 316L, 317L, 904L, 430 and Monel 400 used in the desalination plants. The standard Proof Rings and U-Bend samples in NACE and SHELL solutions containing H 2 S are used for the purpose. Electrochemical polarization measurements were performed on these alloys in the specified environments to study the effect of electrochemical potential on the intergranular SCC. Fractographic analyses were conducted by Scanning Electron Microscopy supplemented by Energy Dispersive Spectroscopy. The test results showed that the intergranular and transgranular SCC fracture of carbon steel and alloy 430 in H 2 S environment occurs only in the limited potential environment, where as, the alloys viz., 316L and 317L are immune to SCC under the condition of test performed. The alloy Monel 400 was also found susceptible to SCC in presence of H 2 S.
1 Issued as Technical Report TR 3804/APP 90001 in October 1999. A paper entitled Studies on the Stress Corrosion Cracking Behavior of Few Alloys used in the Desalination Plants was presented at the WSTA 4 th Gulf Conference, Bahrain, 13-18 Feb. 1999. 2 2 8 2 Fractography of alloy 430 indicated that the failure is attributed mainly to the sulfide stress cracking due to synergistic action of sulfide and chloride that had greatly enhanced the sensitivity of phases present in the alloy. A tentative ranking of the alloys has been established on the basis of the threshold stress values obtained from the tests conducted.
1 INTRODUCTION
One of the major factors that control the use of structural alloys in desalination industry is its resistance to corrosion in marine environments and other distillation conditions. The high chlorinity of seawater associated with its complex salt composition render it inherently corrosive to many structural alloys. Its deleterious effects on ocean interfacing structures have been documented and the wealth of information is compiled. In spite, we continue to experience corrosion related problems on structures that must interface with the marine environment. Stress Corrosion Cracking (SCC) is one such problem which essentially controls and determines the suitability of materials from a wide range of materials as they are very expensive modes of failures, of particular relevance to desalination and power plants.
SCC is a stress assisted anodic process as a result of synergistic action of ions, such as Cl- , H 2 S and oxidants like elemental sulfur present in the solution. The susceptibility to SCC is influenced by factors like environmental condition, temperature, hardness of the material, level of applied stress and microstructure of the material. The SCC of materials in acidic solutions containing dissolved hydrogen sulfide (H 2 S) has been termed as sulfide stress cracking (SSC). The failure characteristics in SSC are most consistent with a hydrogen embrittlement mechanism where the fracture modes are mostly intergranular. The literature available on SCC is quite vast, hence the present literature survey is restricted to the following sections keeping in view of the objectives of this project.
2 2 8 3 In the past it was thought by several investigators that SCC of a given alloy occurs only in limited range of specific environments [1]. Subsequently, the above notion was diluted when it was found that SCC occurs in wide range of environments including pure water [2,3]. A brief account of literature information on few important categories of structure alloys where SCC/SSC occurs by environment interaction is given below.
The carbon steels are prone to SCC in carbonate, bicarbonate, acetates and phosphate environments and is identified as the main reason of cracking in natural gas transmission lines. In low alloy steels, oxygenated water at high temperature, NaNO 2 - Na 2 SO 4
solutions, alkaline chloride solutions such as NaCl - Ca (OH) 2 under pitting conditions [4,5], and anhydrous ammonia - methanol solution [6] in the presence of chloride caused SCC. Studies on J-55 and N-80 steels have shown that H 2 S containing chloride solutions promote SSC [7]. Similar observation was also made in AISI 1075 steels and hardness of steel is also found to influence the SCC [8]. Strong tendency of SCC in carbon steels have been noticed in diethanolamine and manoethanolamine solutions [9], 0.5M NaHCO 3 and 0.5M Na 2 CO 3 solutions at 70 o C at high stress levels [10] and CO 2
environment [11]. Synergistic effect of low concentration chloride in bicarbonate solutions [12] and low concentration of sulfate [13] causing SCC in low alloy steels have also been reported. The effect of sulfide in NACE standard solution (5% NaCl + 0.5% Acetic acid) was found different from SHELL standard solution (solution containing 0.5% Acetic acid) in the promotion of SCC for high strength low alloy steels [14].
In austenitic stainless steels, SCC was well known since three decades. The cracking was mainly due to chloride (which were neutral at high temperature, acid at low temperature) and hydroxide solutions [15]. Thiosulphate environments of weld- sensitized stainless steels have shown SSC [16]. SCC have been reported at ambient temperature [17] and at 90 o C [18] in materials with sensitized microstructure in chloride containing aqueous environments and in 0.1M NaCl or synthetic seawater at 90 o C for SS 304 and 316 alloys [19]. Alloys SS 304 and 316 was more susceptible to SCC in HCl and H 2 SO 4 [0.82 K Mol / m 3 ] solutions [20]. Ferritic stainless steels (type AISI 405) were reported to be susceptible to SCC at 288 o C in aqueous environments [21]. It was also reported that ferritic steels of type AISI 430 shown lesser susceptibility to SCC in chloride solution when compared to sulfate solution [22]. Martensitic stainless steel 1.1 Metal - Environment I nteraction 2 2 8 4 type AISI 420 (13 Cr SS) was found prone to SCC in H 2 S environment and resistant in CO 2 environment. The CO 2 - H 2 S - Cl - system inhibited SCC by favoring the formation of protective layer [23]. In duplex stainless steels SSC is severe at 160 o C in 25% NaCl containing dissolved H 2 S and also in aerated brine solutions [24]. SCC was noticed at ambient temperature in solution of sulfide/3.5 wt % NaCl containing sulfide [25,26].
The nickel base alloys viz., C-276 and alloy 825 were susceptible to SSC in HCl oxidizing solution containing H 2 S. In chloride containing solution the SSC has been observed at temperatures above 204 o C [24]. The copper base alloys are subjected to SCC in environments like ammonia, sulfur dioxide, organic complexing solution like acetates, tartrates and sulfate solutions [27].
1.2 Threshold Stress for SCC
As the name implies the threshold stress is the stress below which no SCC occurs. The main purpose of determining the threshold stress for SCC is to establish a ranking order under given condition of metal environment combination, heat-treated microstructure, type of stressing and its magnitude. An exact threshold stress for a given condition is difficult to define. However, the relative ranking seems quite obvious.
The material which shows highest SCC resistance for a given environment may show susceptibility to SCC when it is heat-treated to different microstructure. For example, threshold stress in SCC of carbon and low alloy steels was found to be influenced by heat treatment when it is studied using 5% NaCl - 0.5% Acetic acid solution containing 3000 ppm of H 2 S [28]. The heat treatment carried out gave untempered Martensitic structure which is attacked by H 2 S and resulted in low threshold stress values for cracking. From the result of series of test in Drop Evaporation Test on highly alloyed stainless steel and duplex stainless steels as indicated by their threshold stress values, it was seen that the highly alloyed stainless steels such as 654 SMO (UNS S 32654) was most resistant to SCC than the duplex stainless steels viz., 2205 (UNS S 31803) [29] and least resistant was 304 (UNS S 32304) [30].
2 2 8 5 The fractography in SCC was used mainly for two purposes. First being failure mode determination and the other was for the studies of fracture mechanics. The conventional metallography and Scanning Electron Microscopy (SEM) were widely employed for this purpose. SEM fractography had been used in SCC tested stainless steel samples to determine the crystallography of cracking and to determine the mechanism of fracture. Normally, transgranular fracture was noticed in SCC [31]. In this study, the cleavage nature of transgranular cracking which is typical of SCC was established.
1.4 I nfluence of Metallurgy
The metallurgical aspects of the material have profound influence on SCC. The grain boundary segregation and phase transformation in steel strongly affect SCC. It was found that substitutional elements like Molybdenum in specific environment typically of type caustic medium, could affect SCC [32]. But, it is not true for all elements or in all solutions. Similarly the phase transformation occurring by aging process, heat treatment, cold working, etc. may or may not have beneficial effects. The example of beneficial effect to SCC was seen by over-aging of Aluminum-Zinc alloys, whereas, such over-aging is not found beneficial in Aluminum Lithium alloys [33].
1.5 Electrochemical Aspects
The SCC in specific environments is strongly correlated with localized (pit or crevice) corrosion. The importance of electrochemistry is in the understanding of kinetics of SCC in the context of changed local environment. The measurement of repassivation potential of localized corrosion would represent the lowest potential at which special local environment can be maintained and SCC propagation occurs in this special environments. Another factor is the critical potential for SCC. If these two potentials are determined and made to coincide by the alterations in the composition of alloys or environment (with the help of local chemistry) new SCC resistant alloys can be developed or mitigation of SCC could be achieved. Two outstanding examples of the electrochemical contribution to SCC are the development of inexpensive steel [33] without high nickel content which resist SCC upto 140 o C with 20% NaCl. The other being the usage of anodic protection from the understanding of electrochemistry, which is used worldwide.
1.3 Fractography 2 2 8 6 The prevalence of SCC in desalination plant occupies a major share when compared to other modes of material failure. In recent years many major SCC failures have been reported from Desalination plants. The details of the failure is briefly described in Appendices 1 through 4. Although there have been better understanding of the corrosion mechanism with the help of environment analysis, metallography, fractography, etc., the diversity in the failure modes and the associated mechanisms are highly complex and not completely understood, still remain to be explored.
It is clear from the above literature review that till to date no data is available to determine the susceptibility of various metals and alloys to SCC resulting from synergistic action of corrodents which are normally encountered in Desalination and Power Plants. The present investigation, although less comprehensive, is aimed to carry out a systematic study of such phenomenon and to understand the nature and mechanism so that occurrence of SCC can be minimized.
2. OBJECTIVES
The objectives of the proposed work are the following : (i) To investigate the susceptibility of materials viz., stainless steels of grade AISI 316L, AISI 317L, AISI 430 and 904, Monel 400 and Carbon steel to SCC in the standard NACE and SHELL solutions (i) containing saturated .H 2 S gas and (ii) containing 0.1M Na 2 S.
(ii) To establish a ranking order with regard to SCC resistance for the above alloys by determining the threshold stress.
(iii) To carry out fractography on the SCC failed specimen using Scanning Electron Microscope to understand the mechanism of cracking.
(iv) To assess the effect of electrochemical potential on the alloy passivity to corrodent species by performing the electrochemical polarization measurements in the specified environments. 2 2 8 7
3. EXPERIMENTAL DETAILS
The materials selected for this study are CS (Carbon Steel), AISI 316L& 317L (austenitic stainless steel), 430(ferritic stainless steel) and 904 (super austenitic stainless steel) and Monel 400 (nickel base alloy). The chemical composition and the mechanical properties of these alloys are shown in Table 1. The materials selected are typical commercial alloys normally used in desalination and power plants.
3.1 Stress Corrosion Cracking Tests
3.1.1 Round and flat tensile samples:
Round and flat tensile samples of CS, 316L, 317L, 430 and Monel 400 were machined from rod/sheet material stocks. All the materials selected were of mill finished commercial grades. The schematic drawing of round test sample is shown in Figure 1, the photograph of sheet sample is shown in Figure 2. The tests were carried out in Cortest Proof Rings [34] with corrosion testing environment chamber. An hour meter and H 2 S gas manifold were used to measure the time of failure of specimen and H 2 S gas monitoring during test respectively. The photographs of the Cortest Proof Ring and Cortest Proof Rings Battery with hour meter and manifold are shown in Figure 3.
The media employed for the tests were (i) NACE solution (having composition 5% NaCl + 0.5% CH 3 COOH) prepared from distilled water and continuously bubbled with H 2 S to maintain H 2 S saturation in solution. (ii) SHELL solution (having composition 0.5% CH 3 COOH) prepared from distilled water and continuously bubbled with H 2 S to maintain H 2 S saturation as in (i).
The samples were tested in ambient temperature with the Cortest Proof Ring at 70, 80, 85 and 90% of their respective 0.2% yield stress (YS) with the help of loading nut and calibration charts. During the test H 2 S was continuously bubbled in the solution. The time to rupture of the samples were recorded. The samples those have crossed 500 hours without rupture were withdrawn from the test. During the test, samples were periodically withdrawn for examination of any initiation of cracks or corrosion pit development. 2 2 8 8
3.1.2 U-Bend Samples
A U-bend specimen is prepared generally through a rectangular strip that is bent 180 degrees around a predetermined radius and maintained in the resulting constant strain condition during stress corrosion testing. The specimens are most easily be made from sheet or strip. The main advantage of U-Bend specimen is that it is simple and most useful for detecting large differences between SCC resistances of different alloys in the same environment or one alloy under different metallurgical conditions or one alloy in several environments.
The U-Bend specimen is stressed by bending the specimen to U-shape in a fixture either manually or through Universal Testing Machine (UTM) and maintaining it in the same shape by means of bolts and nuts. When U-Bend sample is stressed the material in the outer fibers of the bend is strained into the plastic region. The total strain on the outside of the bend is given by the following equation: T = ---------- When T << R 2 R
where, T = specimen thickness, and R = radius of bend.
The value of outer fiber stress can be obtained by the stress-strain curve of the test material by using the value of strain as determined by the above equation.
The U-Bend samples from the strips of 316L, 317L, 430 and 904 were prepared in UTM using a fixture. The preparation of a typical test sample is shown in Figure 4. The actual making of samples through fixture in an UTM is shown in Figure 5.
The testing of the samples are carried out in a plastic containers. By immersing in solutions having specified corrodents. The media employed for the tests were (i) NACE solution (same composition as that of round samples) containing 0.1M Na 2 S. (ii) SHELL solution (same composition as that used for round samples) containing 0.1M Na 2 S.
2 2 8 9 The samples were tested in ambient temperature. These samples outer fiber are stressed to approximately 70, 80, 85 and 90% of their respective 0.2% yield stress (YS) by bending them to corresponding diameter with help of rollers as detailed above. The samples outer fiber surface was critically examined with help of magnifying glass for crack freeness before they are immersed in the media selected. The samples are withdrawn periodically for the purpose of inspection (every week) till they have crossed 500 hours without any appearance of cracks at the outer most fiber surface. The samples those crossed 500 hours without crack appearance were continued up to 2000 hours.
The data obtained from U-Bend samples are quantitative and procedure allows for multiple and field-testing. The limitation of their test is that actual volume of material tested is relatively small (only small portion of the bend radius, i.e., outer most surface experiences the highest stress) [35]. Hence very accurate results are difficult to obtain in this test.
3.2 Electrochemical Tests
The electrochemical polarization techniques were performed to measure the absolute corrosion rates. Tafel plots were generated for this purpose on samples by polarizing the specimen about 300 mV anodically (positive- going potential) and cathodically (negative-going potential) from the corrosion potential, E corr . The potential is stepped in staircase waveform. The resulting current is plotted on a logarithmic scale. The corrosion current I corr is obtained from Tafel plot by extrapolating the linear portion of the curve to E corr . The corrosion rate was calculated from the I corr .
Experiments were carried out on the samples using EG&G model 273 Potentiostat with Softcorr Corrosion Software M342. A saturated calomel electrode was used as reference electrode. Photograph of the potentiostat along with cell is shown in Figure 6. Graphite electrodes were used as auxiliary electrodes. Button samples of 14 mm dia and 2 mm thick were machined from rod/ sheet stock of sample material. They were polished at one side to 600 # grade paper. The media employed in the electrochemical tests are i) NACE solution ii) Natural seawater iii) Natural seawater containing varied amounts of sulfide ion concentration obtained by dissolving known quantities of sodium 2 2 9 0 disulfide crystal iv) SHELL solution and v) SHELL solution containing known amount of sulfide ion concentration.
4. RESULTS AND DISCUSSION
The results of the SCC tests carried out on round and flat tensile samples are shown in Figure 7 & 8. The results revealed that the SCC occurred more readily in CS samples in NACE solution and SHELL solution saturated with H 2 S at stress ranges of 70, 80, 85 and 90% YS. The alloys 430 and Monel 400 are also found susceptible to SCC only when they are stressed to 90% YS in NACE solution containing H 2 S. The alloys 316L and 317L were found immune to SCC in all the condition of tests in NACE or SHELL solutions containing H 2 S.
The results of the SCC tests carried out on U-bend samples are shown in Tables 2 through 9. The results obtained were almost identical to that of round tensile samples except that the time taken was quite considerable for SCC onset due to nature of sulfide ion present in the medium. SCC occurred in the alloy 430 in NACE + 0.1M Na 2 S media stressed to 90% YS. The first appearance of crack was noticed after 1344 hrs in samples stressed to 90% YS, whereas first appearance of cracking was observed after 1920 hours of testing in sample stressed to 85% YS (Table 4). The intensity of cracking/pitting was however less in medium of SHELL + 0.1M Na 2 S (Table 9) when compared to cracking in NACE +0.1 M Na 2 S medium. The 316L, 317L and 904L samples were however free from SCC was observed upto 2000 hours of exposure. The photographs of typical alloy 316L samples after exposure are shown in Figures 9 &10 The photographs of samples of alloy 430 when exposed up to 1344 hours (70, 80, 85 & 90% YS) in NACE + 0.1M Na 2 S and close up view of cracks associated with pitting are shown in Figures 11 & 12, respectively. The photograph of alloy 430 samples exposed up to 1920 hrs (70, 80, 85 & 90% YS) in SHELL + 0.1M Na 2 S solution is shown in Figure 13. Due to some limitation of U-bend test, as explained in earlier section, the results are not discussed in detail.
The fracture of SCC tested round and flat samples of CS and alloy 430 were analyzed in Scanning Electron Microscopy (SEM). The fractures revealed intergranular as well as transgranular mode of crack propagation (Figures 14 & 15). Branching of secondary cracks from the primary cracks, which is typical of SCC failure mode were noticed. The 2 2 9 1 Energy Dispersive Spectrum obtained during SEM fractography at fracture crack tips containing corrosion products showed sulfur rich regions (Figures 14b & 15b). This also confirms the onset of SCC due to sulfide activity.
The threshold stress for CS in NACE and SHELL solution is 75% YS, whereas it is 85% for 430 and Monel 400 alloys in NACE solution. Such threshold stress was not found to exist for the 430 and Monel 400 alloys in SHELL solution at all the stress levels. The alloys 316L and 317L, however, did not show any threshold limits up to 90% YS either in NACE or SHELL solutions containing H 2 S. It is possible that threshold stress might be greater than the YS of these materials. CS has shown greater susceptibility to SCC in the tested medium when compared to other alloys (Figures 7 & 8)
Sulfides play a dominant role in the structural steels particularly in their resistance to sulfide stress cracking. The water present would obviously assist the corrosion mechanism. The reaction will be of the type
H 2 S + Fe FeS + 2 H
The nascent hydrogen is then expected to embrittle the alloy. The presence of chloride all the more aggravate corrosion leading to early failure of steel. The instances of Sulfide Stress Cracking of stainless steels have been reported [36] wherein failure of specimens have been promoted in high chloride environment (>25% NaCl) at elevated temperature and pressure saturated with H 2 S. The chloride content used in some of the test being 5% , it is conceivable that the stainless steel of type 316L and 317L are less likely to be affected by H 2 S as evidenced in the experiment. The effect of H 2 S in SHELL solution suggest that except CS, other alloys were immune to SCC. CS was found prone to SCC > 75% YS. The synergistic effect of chloride in presence of oxidant (CH 3 COOH) and H 2 S to promote SCC in alloys 430 and Monel 400 at stresses > 85% YS was clearly demonstrated as seen from the results of NACE solution experiment (Figure 7).
The presence of H 2 S seems to have exerted a strong influence on the repassivation which is manifested by cracking in alloy 430. The hydrogen embrittlement is well known in alloy 430 particularly when cathodically protected. It is possible that 2 2 9 2 embrittlement is brought about by ferrite phase of the alloy much more than austenite [37]. It is also known that cracking of ferrite taken place by mechanical twinning [38], in this respect, hydrogen embrittlement could greatly enhance the sensitivity of ferrite to cracking. This point is very important at low temperature and indeed evidenced in the fractography performed on the failed samples of alloy 430 (Figures 15a & b). Cracked regions had contained products rich in sulfides as determined in EDAX. Reports have been published elsewhere that high ferrite duplex stainless steels (70% ferrite) is inferior to that of low ferrite duplex stainless steels (50% ferrite) for hydrogen embrittlement [39].
The Tafel plots generated from potentiostatic polarization experiments are shown in Figures 16 through 23. The data obtained from the electrochemical experiments are shown in Tables 10 & 11. The results obtained from NACE solution and natural seawater containing 0.1M of sulfide indicated that alloys 316L and 317L showed higher current densities relative to the Monel 400. The current density in natural seawater solution for alloy 430 with 0.1M sulfides was lowest can be attributed to the development of a stable passive film over the surface of the alloy.
The electrochemical data from the SHELL solution revealed that lowest current densities for 317L alloy in 0.1M sulfide solution, while the highest was observed for alloy Monel 400 except CS. In general, for all the alloys studied, high sulfide content moved the corrosion potential to active direction thus enhancing localized corrosion. Lowest current densities exhibited by alloys 316L and 317L indicated that they are least susceptible to corrosion in presence of sulfide.
From the results of electrochemical tests it is seen that the synergistic effect of chloride and sulfide on the corrosion behavior were prominent particularly for alloys 316L and 317L. For alloys 430 and Monel 400 such effect were not noticed. However, under the influence of stress as noticed from the SCC test results, the trend was reverse. It is plausible that the passive films formed over the alloy 430 and Monel 400 was less stable and get disrupted easily, leading to SCC.
The data generated in this investigation suggests a tentative ranking of alloys could be made with respect to their susceptibility to SCC. On the whole, at ambient temperature, austenitic steels (alloys 316L, 317L and 904L) were better resistant than the Monel 400 2 2 9 3 and alloy 430 in solutions containing chloride and sulfide ions when stressed beyond 80% YS. The tentative ranking can be expressed as (in order of most resistant to SCC):
316L, 317L & 904L > Monel 400 > 430 > CS
5. CONCLUSIONS
The following conclusions are drawn on the basis of investigations carried out.
(i) In solutions containing sulfide, the chlorides demonstrated the synergistic effect promote SCC in alloys 430 and Monel 400 at stress levels > 85% YS. (ii) Alloys 316L and 317L were found SCC resistant under all conditions of the tests performed. (iii) Alloys 316L and 317L had shown higher current densities relative to the other alloys in presence of specified oxidant, chloride and sulfide ionic species. Under the influence of stress, they were least susceptible to corrosion. (iv) CS was found prone to SCC at stress levels > 75% YS in solutions containing specified amounts of sulfide, chloride and oxidants. (v) A tentative ranking of the alloys have been established on the basis of threshold stress value in solutions containing chloride and sulfide ions (in the order of increasing resistance to SCC) 316L, 317L, 904L > Monel 400 > 430 > CS. (vi) The failure of alloy 430 is mainly attributed to sulfide stress cracking as sulfides greatly enhanced the sensitivity of phases present in the alloy to cracking as evidenced from fractography. (vii) Sulfide ion displaces the corrosion potential in active direction thereby increasing the risk for localized corrosion for all the alloys studied.
6. RECOMMENDATIONS
(1) From the investigation carried out it is apparent that austenitic stainless steels of type AISI 316L, 317L and high alloy 904L are the alloys of choice in desalination plant environments containing high chloride. In these steels if any stresses arising from fabrication, fit-up, welding and differential heating could 2 2 9 4 increase the susceptibility of these alloys to SCC and hence these stresses should be avoided in practice.
(2) Chlorides and sulfides do cause SCC in carbon steel and alloy 430. Although it is not possible to eliminate chlorides in desalination plants, meticulous care should be exercised to minimize their introduction as an effective and essential alloy. Satisfactory use of these alloys could be permitted by minimizing the fabrication stress and cold work avoiding thermal insulation and gasket material high in chloride, avoiding elastomers, lubricants, sealants and other material containing halogens.
(3) Alloy Monel 400 is deemed to have moderate susceptibility to SCC in desalination plant environment containing chlorides. However, its successful use could be made by decisively controlling the stress levels, water chemistry, design parameters, thermo-hydraulic characteristics, presence and absence of crevices and biological activity as evidenced from the reported Bio-Corrosion of Monel 400 bolts by sulfur reducing bacteria [40] in Al-Jubail intake system.
7. FURTHER SCOPE OF SCIENTIFIC WORK
(1) The susceptibility of alloys to SCC is significantly affected by the synergistic action of chloride in presence of sulfide. Hence further testing is therefore required to determine sources and levels of sulfide and possible prevention approach in desalination process.
(2) Temperature plays dominant role in the repassivation and hydrogen embrittlement of alloy 430. Hence the response of ferrite phase to temperature changes should obviously be further investigated. It is likely that at high temperature hydrogen embrittlement (cathodic cracking) decreases while repassivation (anodic cracking) is very much accelerated which are not only important from metallurgical and scientific view point, it is also of practical interest since alloy 430 is one of the major material of construction in many pumps used in Line 3 (water transmission system of SWCC).
2 2 9 5 (3) Due to lack of standardized test method for particular application, more test results should be obtained on enlarged list of commercial alloys from various laboratories and industries which can be realistically compared and used by design engineers to select materials which will ensure reliable operation in environments where stress corrosion cracking or sulfide stress cracking could be a problem.
2 2 9 6
Table 1. Chemical Composition and Mechanical Properties of Alloys
A. Chemical Composition:
S. Alloy UNS Composition (%) Others No. No. Fe Cr Mo Ni C Cu Mn Si 1 Mild Steel J2503 Bal 0.5 Max 0.2 Max 0.5 Max 0.25 Max 0.3 Max 1.2 Max 0.6 0.04P,0.04S 2 316L S31603 Bal 16.0 3.0 11.0 0.02 0.2 1.0 1.0 0.04P,0.02S 3 317L S31703 Bal. 18.5 3.2 13.5 0.02 - 1.0 - 0.08 N 4 904L N08904 Bal. 20 4.74 24.5 0.017 1.4 1.5 - 1.4Cu,1.0Si 5 430 S43000 Bal. 18.0 - - 0.12 - 1.0 1.0 0.04P,0.03S 6 Monel 400 N4000 2.5 - - 66.5 0.3 Bal. - 0.5 0.024S
2 2 9 7 Table 2. U-Bend Specimen Testing of AISI 316L Exposed to NACE Solution Containing 0.1M Na 2 S
S.No. Applied Stress ( % of YS) Time of first appearance of crack (Hours) Appearance of surface/cross section Remarks 1 70 NFC NC - 2 70 NFC NC - 3 75 NFC NC - 4 75 NFC NC - 5 85 NFC Brown coloration over the bent portion No cracking 6 85 NFC --DO-- --DO-- 7 90 NFC --DO-- --DO-- 8 90 NFC --DO-- --DO--
NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change
Table 3. U-Bend Specimen Testing of AISI 317L Exposed to NACE Solution Containing 0.1M Na 2 S
S.No. Applied Stress ( % of YS) Time of first appearance of crack (Hours) Appearance of surface/cross section Remarks 1 70 NFC - - 2 70 NFC - - 3 75 NFC - - 4 75 NFC - - 5 85 NFC - - 6 85 NFC - - 7 90 NFC Brown coloration over the bent portion - 8 90 NFC --DO -
NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change
2 2 9 8 Table 4. U-Bend Specimen Testing of AISI 430 Exposed to NACE Solution Containing 0.1M Na 2 S
S.No. Applied Stress ( % of YS) Time of first appearance of crack (Hours) Appearance of surface/cross section Remarks 1 70 NFC NC - 2 70 NFC NC - 3 75 NFC NC - 4 75 NFC NC - 5 85 1920 Few pits at outer radius - 6 85 1920 --DO--- - 7 90 1344 Pitting at few places over the bent radius Cracking is prominently associated with pitting over the bent radius when test contd. Beyond 1920 hrs. 8 90 1344 Moderate pitting at few places over the bent radius --DO---
NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change
Table 5. U-Bend Specimen Testing of AISI 904L Exposed to NACE Solution Containing 0.1M Na 2 S
S.No. Applied Stress ( % of YS) Time of first appearance of crack (Hours) Appearance of surface/cross section Remarks 1 70 NFC NC - 2 70 NFC NC - 3 75 NFC NC - 4 75 NFC NC - 5 85 NFC NC - 6 85 NFC NC - 7 90 NFC Faint brown coloration over the bent radius No cracking 8 90 NFC --DO-- --DO--
NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change 2 2 9 9 Table 6. U-Bend Specimen Testing of AISI 316L Exposed to SHELL Solution Containing 0.1M Na 2 S
S.No. Applied Stress ( % of YS) Time of first appearance of crack (Hours) Appearance of surface/cross section Remarks 1 70 NFC NC - 2 70 NFC NC - 3 75 NFC NC - 4 75 NFC NC - 5 85 NFC Faint brown coloration over the bent radius No cracking 6 85 NFC --DO-- --DO-- 7 90 NFC --DO-- --DO-- 8 90 NFC --DO-- --DO-- NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change
Table 7. U-Bend Specimen Testing of AISI 317L Exposed to NACE Solution Containing 0.1M Na 2 S
S.No. Applied Stress ( % of YS) Time of first appearance of crack (Hours) Appearance of surface/cross section Remarks 1 70 NFC NC - 2 70 NFC NC - 3 75 NFC NC - 4 75 NFC NC - 5 85 NFC NC - 6 85 NFC NC - 7 90 NFC Brown coloration over the bent radius No cracking 8 90 NFC --DO-- --DO--
NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change
2 3 0 0 Table 8. U-Bend Specimen Testing of AISI 904L Exposed to NACE Solution Containing 0.1M Na 2 S
S.No. Applied Stress ( % of YS) Time of first appearance of crack (Hours) Appearance of surface/cross section Remarks 1 70 NFC NC - 2 70 NFC NC - 3 75 NFC NC - 4 75 NFC NC - 5 85 NFC NC - 6 85 NFC NC - 7 90 NFC NC - 8 90 NFC NC -
NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change
Table 9. U-Bend Specimen Testing of AISI 430L Exposed to SHELL Solution Containing 0.1M Na 2 S
S.No. Applied Stress ( % of YS) Time of first appearance of crack (Hours) Appearance of surface/cross section Remarks 1 70 NFC NC - 2 70 NFC NC - 3 75 NFC NC - 4 75 NFC NC - 5 85 NFC NC - 6 85 NFC NC - 7 90 1920 Small pits and cracks are seen at outer radius. Hair line cracking distributed all along the bent radius 8 90 1920 --DO-- --DO--
NFC-indicates no first crack beyond 2000 hours. NC - indicates No Change 2 3 0 1
Table 10. Potentiostatic Polarization data from NACE Solution and Natural Seawater (NSW).
F i g u r e 7 . S C C o f a l l o y s i n N AC E S o l n . C o n t a i n i n g Hy d r o g e n S u l f i d e 7 5 8 0 8 5 9 0 3 0 0 4 0 0 5 0 0 6 0 0 T i m e t o F a i l u r e ( H r s . ) 0 .2 O f f s e t Y i e l d S t r e n gt h %
316, 317, 430, 400, MS 316, 317, 430, 400 316, 317, 430, 400 316, 317 Indicates no failure 400 MS 430 2 3 0 8
Figure 8. SCC of Alloys in SHELL Solution Containing Hydrogen Sulfide 75 80 85 90 300 400 500 600 0.2 Offset Yield Strength % Time to Failure (Hrs.)
Figure 9. Photograph of U-Bend samples (alloy 316L) stressed to 70%, 80%, 85% & 90% YS exposed to NACE solution containing 0.1 M Na 2 S. Exposure time 1344 hrs
Figure 10. Photograph of U-Bend samples (alloy 316L) stressed to 70%, 80%, 85% & 90% YS exposed to SHELL solution containing 0.1 M Na 2 S. Exposure time 1344 hrs
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Figure 11. Photograph of U-Bend samples (alloy 430) stressed to 70%, 80%, 85% & 90% YS exposed to NACE solution containing 0.1 M Na 2 S. Exposure time 1344 hrs
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Figure 12. Photograph of U-Bend (alloy 430) stressed to 90% YS exposed to NACE solution containing 0.1 M Na 2 S. Exposure time 1344 hrs. (a) Cross section view (b) End view showing pits and cracks. 2 3 1 2
Figure 13. Photograph of U-Bend (alloy 430) stressed to 70%, 80%, 85% & 90% YS exposed to SHELL solution containing 0.1 M Na 2 S. Exposure time 1344 hrs.
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0 5 10 Energy (keV) 0 1000 2000 3000 Counts C O Fe P S Cl Ca Cr Mn Fe Fe Cu
Figure 14. SEM Fractrograph of SCC tested CS sample. a) Fractrograph showing intergranular and intragranular fracture modes. b) EDAX spectrum taken at crack tip.
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0 5 10 Energy (keV) 0 500 1000 Counts O S Cr Cr Fe Fe Ni Cu Cu
Figure 15. SEM Fractrograph of SCC tested 430 alloy sample. (a) Fractrograph showing intergranular and intragranular fracture modes, (b) EDAX spectrum taken at a crack tip.
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Figure 16. Potential Polarization Curves (Tafel Plots) Showing the Effect of Varied Sulfide Content on 316L. 1-NACE Solution, 2-Natural Seawater, 3-Natural Seawater + 0.06M Sulfide and 4 - Natural Seawater + 0.1M sulfide. 2 3 1 6
Figure 17. Potential Polarization Curves (Tafel Plots) Showing the Effect of Varied Sulfide Content on 317L. 1-NACE Solution, 2-Natural Seawater, 3-Natural Seawater + 0.06M Sulfide and 4 - Natural Seawater + 0.1M sulfide.
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Figure 18. Potential Polarization Curves (Tafel Plots) Showing the Effect of Varied Sulfide Content on 430 alloy. 1-NACE Solution, 2-Natural Seawater, 3-Natural Seawater + 0.06M Sulfide and 4 - Natural Seawater + 0.1M sulfide.
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Figure 19. Potential Polarization Curves (Tafel Plots) Showing the Effect of Varied Sulfide Content on Monel 400 alloy. 1- NACE Solution, 2-Natural Seawater, 3-Natural Seawater + 0.06M Sulfide and 4 - Natural Seawater + 0.1M sulfide.
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Figure 20. Potential Polarization Curves (Tafel Plots) Showing the Effect of Sulfide Content on 316L. 1-SHELL Solution and 2- SHELL Solution + 0.1M sulfide.
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Figure 21. Potential Polarization Curves (Tafel Plots) Showing the Effect of Sulfide Content on 317L. 1-SHELL Solution and 2- SHELL Solution + 0.1M sulfide.
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Figure 22. Potential Polarization Curves (Tafel Plots) Showing the Effect of Sulfide Content on 430 Alloy. 1-SHELL Solution and 2- SHELL Solution + 0.1M sulfide.
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Figure 23. Potential Polarization Curves (Tafel Plots) Showing the Effect of Sulfide Content on 400 Alloy. 1-SHELL Solution and 2- SHELL Solution + 0.1M sulfide.
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APPENDIX- 1
SCC FAILURE OF INTERMEDIATE BEARING SUPPORT
LOCATION : Main Seawater Pump, Assir Plant
CAUSE : Residual stresses at rim and arm joint due to improper manufacturing practice combined with local seawater corrosion.
MATERIAL : Ni-Resist Cast Iron (ASTM - A 493 D 2 ).
Figure 24. SCC Failure Photograph of Intermediate Bearing Support
CAUSE : Cumulative buildup of residual stresses at the column inner surface due to water hammering effect during operation combined with local seawater corrosion
MATERIAL : Ni-Resist Cast Iron
Figure 25. SCC Failure Photograph of Seawater Intake Pipe
CAUSE : Presence of residual stresses due to improper heat treatment during fabrication of column pipe.
MATERIAL : Ni-Resist Cast Iron
Figure 27. SCC Failure Photograph of Brine Re-Circulating Column Pipe
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