\

Pergamon

Corrosion Science\ Vol[ 39\ No[ 5\ pp[ 898829\ 0887 0887 Elsevier Science Ltd[ All rights reserved[ Printed in Great Britain[ 9909827X:87 ,*see front matter

PII] S9909827X"87#999114

STRESS CORROSION CRACKING OF DUPLEX AND SUPER DUPLEX STAINLESS STEELS IN SOUR ENVIRONMENTS
A[ A[ EL!YAZGI and D[ HARDIE
Dept[ of Mechanical\ Materials and Manufacturing Engineering\ University of Newcastle upon Tyne\ Newcastle upon Tyne NE0 6RU\ U[K[ Abstract*The resistance of two commercial duplex stainless steels to sulphide stress corrosion cracking in sour environments has been assessed by means of slow straining in a variety of solutions saturated with hydrogen sulphide over the temperature range from 1 to 84>C[ The results suggest that\ although one is not susceptible to any loss in ductility\ the other su}ers a signi_cant loss in ductility and a ductility minimum occurs at some temperature between 14 and 79>C that depends upon the environment[ The embrittlement at lower temperatures is attributed to absorption of the hydrogen generated at the steel surface\ but this is mitigated by the barrier to permeation presented by the passive _lm also generated[ Associated polarisation measurements and appropriate pitting experiments clearly indicate a reduction of the range of potential in which passivation occurs with increasing temperature and severe pitting above a temperature that depends upon the alloy content of the steel[ The prevalence of severe pitting corrosion provides an explanation of the attenuation of the hydrogen embrittlement e}ects at the higher temperatures\ and the resultant occurrence of a minimum ductility[ 0887 Elsevier Science Ltd[ All rights reserved Keywords] A[ stainless steel\ C[ stress corrosion cracking

INTRODUCTION Sulphide stress corrosion cracking "sscc# has long been recognised as a serious problem for the petroleum and petrochemical industries\ particularly in high strength and stainless steels[07 In recent years\ the rising energy demand\ increasing oil and gas prices\ and dwindling reserves have led to the development of deeper oil and gas wells "often 5999 m#[ The environments often encountered in such deep wells contain substantial amounts of salt water\ hydrogen sulphide\ and carbon dioxide "sour wells#[ This hostile environment\ depending upon its composition and temperature\ may cause general corrosion\ localised corrosion\ and stress corrosion cracking of the materials used[ One means of combating such problems is to inject inhibiting agents\ but it was soon realised that these were neither wholly e}ective nor economically viable[ Another solution relied on the use of highly alloyed materials that can withstand the corrosiveness of the well ~uids[ Among the various special materials that can be utilised in such hostile environments\ duplex stainless steels represent an optimum technical!economic choice[

Dr A[ A[ El!Yazgi has now returned to the Department of Materials Science\ Tajura Nuclear Research Centre\ Tripoli\ Libya[ Manuscript received 04 July 0886^ in amended form 09 September 0886[ 898

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When\ as in a sour environment\ H1S comes into contact with water\ it dissociates to form a weak acid according to the reactions] H1S:HSH H1S:1H S
1

"0# "1#

and hence\ a corrosion reaction takes place between these ions and steel resulting in the formation of ferrous ion at the anoxic sites and the reduction of hydrogen ion at the cathodic sites on the steel surface] Fe:Fe1e "at the anoxic site# 1H1e:1H and 1H:H1 "at the cathodic site# Thus the overall reaction can be represented as] FeH1S"aq#:FeS1H "4# "2# "3#

The recombination of atomic to produce molecular hydrogen is inhibited by the presence of the dissociated hydrogen sulphide\ and this results in a greater hydrogen fugacity\ which facilitates penetration of hydrogen into the steel\ hence intensifying any embrittlement e}ects[ Many variables are known to in~uence sscc of iron base alloys and these may be classi_ed into two broad categories] i# Environmental e}ects that include hydrogen sulphide concentration "pressure#\ chlor! ide concentration\ temperature and applied potential and ii# Mechanical and metallurgical variables such as alloy composition\ microstructure\ heat treatment\ cold work\ hardness or strength level\ and surface condition[ The aim of this work was to assess the contribution of some of these factors to embrittlement induced in commercial duplex stainless steels[ EXPERIMENTAL The investigation was facilitated by the availability of two commercial duplex stainless steels] types 1294 and 1496 "Table 0#[ A three!dimensional assessment of the microstructures of these materials after polishing and etching in an aqueous solution containing 19) hydrochloric acid and 2g potassium metabisulphite "K1S1O4# reveals "Fig[ 0# that both consist of elongated islands of austenite "light!etching phase# in a matrix of ferrite "dark! etching phase#[ The proportions of the two phases were assessed by optical image and X! ray di}raction analysis as well as by means of a ferrometer\ as previously described[8 All

Table 0[ Chemical Analysis "wt)# of the Duplex Stainless Steel Pipes Used Cr Steel A Steel B Ni Mo 1[88 2[72 Mn 9[87 9[18 Si 9[37 9[13 N 9[03 9[18 Cu 9[92 9[09 Co 9[91 9[04 V 9[94 9[93 C P S Ti

12[99 4[99 14[29 5[69

9[904 9[905 9[990 9[90 9[913 9[904 9[991 9[992

Cracking of stainless steels in sour environments

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gave consistent results with an average value of 24[4 and 49[1) austenite for steels A and B respectively[ Smooth tensile specimens having an 00[24 mm gauge length of 2[19 mm diameter and an overall length of 069 mm were machined with their axis parallel to the longitudinal direction of the pipes and the gauge lengths were polished to 599 mm before straining in solution[ The straining was achieved in a hard tensile machine at a cross head speed that produced a strain rate "as referred to the original gauge length# of 1[9095:s[ The straining was conducted in three di}erent solutions\ all saturated with H1S at 0 bar] "i# 2[4) sodium chloride solution with initial pH"pHi 5[4#\ "ii# NACE standard solution\ 49 g sodium chloride 4 g glacial acetic acid in 834 ml deionized water "pHi 1[6#\ and "iii# Deionized water with varying amounts of sodium chloride\ from 9 to 599 wppm Cl"pHi 5[4#[ The test cell was a specially designed cylindrical PTFE cell closed by a screw!in top lid that could be sealed to the main body of the cell by an O!ring seal "Fig[ 1#[ It incorporates a thermometer\ a control thermocouple\ a reference electrode "saturated calomel electrode for solution "i# and "ii# but sulphate reference electrode for solution "iii##\ a platinum counter electrode for testing under controlled potentials\ and glass inlet and outlet tubes to allow continuous bubbling of the hydrogen sulphide gas into the solution during the whole of the test[ The outlet from the cell is connected to a 1[9 litre container of 0 M NaOH solution\ through a 0[9 litre plastic container to prevent back ~ow of the caustic solution into the test cell\ in order to absorb hydrogen sulphide waste before venting to atmosphere[ The

Fig[ 0[ Three!dimensional representation of the microstructure of the as!received materials[

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Fig[ 1[ Arrangement of the test cell for straining in solutions saturated with hydrogen sulphide[

H1S saturation was initially achieved by continuous bubbling through the test solutions at a rate of 299 ml:min for 2 hours\ at which time the open circuit potential\ which was monitored continuously\ stabilised at about 499 mV "sce#\ which was taken as the criterion for hydrogen sulphide saturation[ The bubbling rate is then lowered to 099 ml:min\ which proved to be su.cient to maintain saturation throughout the entire test period[ The test solution is heated or cooled to the desired test temperature "from 1 to 84>C# before tensile straining is applied[ Sub!ambient temperatures were achieved by using an immersion cooler[ A copper block\ into which the cooling coil was inserted\ was fastened next to the testing cell and the whole arrangement was wrapped with glass wool for insulation[ The arrangement was then left for 5 hours to cool and stabilise at the desired

Cracking of stainless steels in sour environments

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lower temperature before the solution was saturated with hydrogen sulphide[ The lowest temperature used was 1>C\ to avoid partial solidi_cation of the solution[ Long term pitting tests were conducted on 09 mm09 mm specimens cut from both materials A and B[ Specimens were polished to 0 mm _nish\ after which they were slightly etched in order to identify the sites of pit initiation[ They were then carefully washed with acetone\ to prevent crevice e}ects that might be caused by dirt or oil spots\ before being immersed in test solution "ii#[ Tests were conducted at two di}erent temperatures *29 and 89>C* in glass ~asks[ After the solution in the ~ask had been saturated with hydrogen sulphide\ the ~ask was sealed and left at the desired temperature for the duration of the test "619 hours#[ Specimens were removed and washed successively with distilled water and alcohol before examination by optical and scanning electron microscopy[ After soaking at the higher temperature\ where corrosion product is expected to form\ the fracture surfaces were subjected to cathodic polarisation in alkaline sodium cyanide solution\ for a few minutes\ with simultaneous ultrasonic cleaning\ and this produced very clean fracture surfaces[ Polished sections perpendicular to the fracture surface were also examined after etching in 119 ml HCl79 ml H1O2 g K1S1O4\ which attacks the ferrite "dark# and leaves the austenite unattacked "bright#[ Potentiodynamic polarisation measurements were conducted\ on 1[9 cm1 standard cyl! indrical specimens of both materials\ using a potentiogalvanic scan coupled with a log! arithmic output current sink[ The specimens were _rst dry polished to 599 grit paper followed by a wet polish[ The test cell was _lled with the test solution and heated or cooled to the desired temperature\ before purging the solution with hydrogen sulphide for 09 minutes[ The bubbling rate is lowered to 099 ml:min until the open circuit potential of the specimen stabilised "1 hours#\ which was the criteria adapted for hydrogen sulphide saturation\ before commencing with the potential scan which was conducted from 0999 to 0999 mV at a rate of 09 mV:s[ Some polarisation tests were conducted in a solution purged with nitrogen for one hour before saturation with hydrogen sulphide\ in order to investigate the e}ect of excluding oxygen from the environment\ but the curves subsequently obtained were identical to those done without such purging\ which indicates that adequate saturation with hydrogen sulphide is as e}ective in the expulsion of oxygen from the test solution[ DISCUSSION OF RESULTS The variation in percent reduction in area with straining temperature reveals that embrittlement of steel A _rst increases with temperature up to a certain intermediate temperature and then decreases at higher temperatures "Fig[ 2#[ Maximum embrittlement occurs at 5969>C in NACE!90!66 solution but at 2939>C in non!acidi_ed sodium chloride solution[ Many investigators have observed similar trends in results for both high strength and duplex steels17\0902 using di}erent loading methods[ The signi_cance of this relation! ship\ however\ is not so much the particular temperature at which maximum loss in ductility occurs\ but rather the fact that the increasing amount of embrittlement as temperature increases is curtailed by recovery of ductility at a higher temperature\ which suggests that two competing processes are involved[ One possibility would involve hydrogen embrit! tlement at lower temperatures and increasing corrosion at higher temperatures[ The decrease in the susceptibility at lower temperatures could be attributed to a decrease in the rate of hydrogen arrival at the critical site within the bulk of the specimen due to a decrease in the

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Fig[ 2[ E}ect of test temperature upon the ductility of duplex stainless steel A strained at 1095:s in either NACE "solid symbols# or 2[4) sodium chloride "open symbols# solution\ saturated with hydrogen sulphide[

thermally!activated hydrogen di}usion process and the prevention of hydrogen entry by the formation of some form of protective _lm[ On the other hand\ it is feasible to assume that the recovery of ductility at the higher temperatures is due to increased dissolution\

Cracking of stainless steels in sour environments

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which is also thermally activated\ that causes blunting of any cracks initiated and also hinders the entry of hydrogen\ by the corrosion product[ Steel B\ however\ showed no susceptibility to either anoxic corrosion or hydrogen embrittlement over the whole tem! perature range studied[ The polarisation curves for steel A "Fig[ 3# revealed that a decrease in temperature promotes a dramatic decrease in corrosion rate\ as indicated by the measured current density[ In addition\ no passive region occurs on the polarisation curve at 74>C\ and thus small increases in the potential at this temperature will understandably result in a signi_cant increase in the corrosion rate[ However\ as temperature is lowered\ the metal tries to passivate until\ when the temperature reaches 1>C\ some form of protective _lm\ believed to be a type of iron sulphide\ occurs over a substantial range of potential between 399 and 199 mV "sce#[ The measured open circuit potential during tensile straining tests performed in both NACE!90!66 solution and non!acidi_ed sodium chloride solution satu! rated with H1S at 1>C\ was 399 mV "sce# and this appears to correlate well with the region of passivation[ This protective _lm may hinder the entry of atomic hydrogen into the metal and so prevent embrittlement\ but if the tensile specimens were polarised to slightly more noble potential this would be expected to shift the metal away from conditions that favoured formation of protecting _lms and thus facilitate hydrogen entry[ At 1>C the ductility ")RA# almost regains its value of 67) in air\ but when two specimens were strained to failure in NACE!90!66 solution at 1>C whilst polarised to a slightly more negative potential than the open circuit i[e[ 499 and 449 mV "sce#\ both failed in a brittle manner\ with )RA of 20 and 22 respectively "Fig[ 2#[ Thus\ this small cathodic shift in potential causes the steel to be embrittled by hydrogen[ This can be attributed to the expected evolution of hydrogen at such a potential and pH\ and should result in 34 to 44)RA[03 However\ the more severe

Fig[ 3[ Potentiodynamic polarisation curves for duplex stainless steel A obtained at a sweep rate of 09 mV:s in NACE!90!66 solution at various temperatures[

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loss in ductility "20 to 22) RA# may perhaps be due to the more e.cient delivery of hydrogen to the critical sites because the applied potential shifts the metal from the passive region "199 to 399 mV"sce# in Fig[ 3# to a more active potential where the _lm that presents a barrier to hydrogen becomes unstable or does not form at all and this clearly facilitates the entry of atomic hydrogen into the metal[ Furthermore\ when two specimens were strained to failure in the same solution "NACE!90!66# at 79>C\ which is near the temperature of maximum embrittlement\ whilst polarised to 249 and 399 mV "sce#\ i[e[ respectively 049 and 099 mV more noble than the measured open circuit potential at 79>C "499 mV sce#\ extensive pitting became visible "Fig[ 4# and the straining had to be terminated before _nal failure "separation#tests were stopped after about 07 h in each case[ It is obvious that the imposed potential caused the metal to be in the active state and hence extensive pitting occurred[ Thus\ a small shift in potential at a temperature where hydrogen embrittlement might be expected to play a greater part in the failure may obviously introduce excessive dissolution instead[ After establishing that specimens from steel B did not su}er any detectable damage\ under any of the test conditions used\ polarisation curves for this material were deemed necessary to shed light on possible explanations[ These revealed that\ even under the most severe embrittlement conditions\ i[e[ in NACE solution near 74>C\ a passive _lm still forms on the surface\ in marked contrast to steel A under the same conditions\ where no pas! sivation is possible[ This can be attributed to the fact that material B contains higher Cr\ Mo\ Ni\ and N\ all of which are known to stabilise the passivity of stainless steels over a wider range of temperature and pressure[04 This high alloying content gives rise to a ) Cr 2[2 Pitting Resistance Equivalent number "PREn# of 32 "calculated05 from PREn ")Mo#29 ")N## as compared with steel A where the PREn 24[ Actually\ it has been recommended that duplex stainless steels to be used in sour environments should have a minimum pitting resistance equivalent number of 39[ The corrosion potential "for steel B# appears to be 099 mV more active than that of steel A\ which is in agreement with the reported increases in corrosion potential with increasing PREn of the alloy[06 The initial pH "pHi# of both neutral solutions "i# and "iii# were 5[4 before saturating with hydrogen sulphide[ After saturation\ however\ the pH was reduced to about 3[1 for both solutions[ But for NACE!90!66 solution\ with pHi\ of 1[6\ saturation with hydrogen sulphide increased the pH to about 2[1[ Therefore the actual "e}ective# pH to which the specimens were subjected were 3[1 and 2[1 for neutral sodium chloride and NACE solutions respectively[ The degree of embrittlement was always higher in NACE!solution "pH 2[1# than in sodium chloride "pH 3[1# "Fig[ 2# and this may be attributed to the lower pH and greater hydrogen activity of the NACE solution[1 Secondary cracks were con_ned to a very small necked region in specimens tested in the range 09 to 19>C\ but as the temperature increased the number increases dramatically\

Table 1[ Mechanical Properties of the Duplex Stainless Steel Used "Strained at 1[9095s0# 9[1) Flow Stress MN:m1 Steel A Steel B 512 690 Ultimate Tensile Strength MN:m1 633 729 ) Plastic Elongation 33 30 ) Reduction in Area at Fracture 67 79

Cracking of stainless steels in sour environments

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Fig[ 4[ Tensile specimens of steel A strained in NACE!90!66 solution at 79>C whilst polarised at "a# 249 mV"sce# and "b# 399 mV"sce#!condition after about 07 h[

especially above about 59>C "Fig[ 5#[ An attempt was made to count the number of secondary cracks in the gauge length of the tensile specimens and combine the results with those from the pitting tests to provide an insight into the e}ect of temperature on both cracking and pitting "Fig[ 6#[ As temperature increases\ both the density of pit formation on polished specimens immersed in NACE solution "pH 1[6# for 37 h\ and the number of secondary cracks in the gauge length of specimens strained in NACE!90!66 solution "pH 2[1# increased only slightly up to 59>C but then showed a dramatic increase[ This agrees well with the reported pitting temperature of 59>C for steel A "PREn 24#[01 In all cases\ the pits initiate at ferrite!austenite interfaces and grow into the austenite phase[ On some of the tensile specimens strained to failure at 0419>C\ a thick black _lm formed that was analysed using an X!ray di}ractometer "CuKa radiation l 0[43940#^ the scan speed was set at 9[04 deg:min to ensure good trace resolution[ The _lm was found to consist of multiple layers of iron sulphides^ FeS1 among others "Fig[ 7#[ However\ when a

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Fig[ 5[ Tensile specimens of duplex stainless steel A strained to failure at 1095:s in NACE!90! 66 solution at various temperatures[

polished specimen of steel A was immersed in NACE!90!66 solution\ for 619 h at 29> and 89>C they showed "in both cases# that the austenite was attacked preferentially[ At 29>C the corrosion rate calculated for the dissolution of austenite "from the depth of penetration# was 9[36 mm:yr[ The austenite was uniformly attacked "Fig[ 8# and\ when this specimen was subjected to X!rays for _lm analysis\ the austenite peaks had disappeared due to the fact that the austenite was below the general level of the surface\ and hence the ferrite[ Careful scrutiny of this specimen revealed that the ferrite phase did not su}er any corrosion and\ in fact\ a thin layer of ferrite covering the austenite will provide protection[ The X!ray analysis of the _lm also revealed the presence of elemental sulphur "Fig[ 09#\ which could be removed "dissolved# by immersion in carbon disulphide for a few seconds[ When sub! sequent X!ray examination was carried out\ the sulphur lines had disappeared\ leaving behind just an indication of iron sulphide "FeS#[ At the higher temperature "89>C#\ however\

Cracking of stainless steels in sour environments

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Fig[ 6[ E}ect of temperature on the density of initiation sites for pits and cracks in steel A indicating the number of pits generated in an area of 0cm1 during immersion in NACE solution for 37h and the number of cracks found in the specimen gauge length after straining to failure in NACE!90!66 solution[

the austenite in the duplex structure was not uniformly attacked^ once initiated\ dissolution appeared to be con_ned to certain preferential sites where it accelerated[ When straining is conducted at lower temperatures "1959>C#\ the secondary cracks are very small and con_ned to the small necked region\ with no evidence of any dissolution in either of the phases "Fig[ 00a#[ The cracks initiate in the ferrite and generally propagate perpendicular to the applied stress\ although crack branching at about 34> and along the ferrite:austenite interface "Fig[ 00b# is frequently noted[ Cracks generally propagate through the ferrite phase\ the phase sensitive to hydrogen\ and avoid the austenite "i[e[ many cracks are arrested by the austenite#[ Cracking along the ferrite:austenite grain boundary can be explained by the fact that these are hydrogen traps and high concentrations of hydrogen can develop\ especially with respect to the high di}usivity of hydrogen in the ferrite as compared to that of the austenite "several orders of magnitude at room temperature#[07 That is to say that hydrogen travels much faster in ferrite and when it arrives at austenite\ in which the di}usivity of hydrogen is much reduced\ a net accumulation of hydrogen in the ferrite near the austenite boundary will develop and so provide a favourable crack propagation path[ The cracking is very similar to that occurring during the straining of tensile specimens in a hydrogen atmosphere or whilst cathodically polarised\03\08\19 which suggests that hydrogen is also the embrittling species in the H1S!bearing environment[ At temperatures above 69>C\ in both solutions\ numerous secondary cracks appear

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Fig[ 7[ X!ray di}raction Analysis of black deposit on the surface of tensile specimen of duplex stainless steel strained to failure at 1095:s in NACE!90!66 solution at 04>C[

along the gauge length and microscopical examination of the gauge length indicates that these initiate at pits "Fig[ 01a# in marked contrast to the initiation of cracks at lower temperatures "Fig[ 01b#[ After pitting occurs\ small cracks tend to initiate and propagate by cracking of the ferrite and simultaneous dissolution of the austenite "Fig[ 02a#[ As temperature increases\ the cracks tend to become blunted by the accelerated corrosion reaction and this produces a recovery in the measured ductility[ When the temperature reaches 84>C the dissolution of the austenite is very extensive "Fig[ 02b# and leads to the greatly enhanced ductility[ SEM examination of fractured surfaces has indicated that the ferrite always fractures in the cleavage mode and river markings are revealed[ The cleavage surfaces are invariably clean and free from any corrosion product[ On the other hand\ although the austenite phase showed some ductility at temperatures up to 29>C "Fig[ 03#\ the austenite islands near the crack initiation site were severely corroded above this temperature "i[e[ 39>C# and there were deposits of corrosion product[ When the corrosion product was analysed using EDX\ it was found to be rich in sulphur "Fig[ 04#\ indicating that some form of iron sulphide is present[ Removal of these corrosion products by means of ultrasonic cleaning during cathodic polarisation in a sodium cyanide bath produced remarkable results[ The new cleaned surface "Fig[ 05# showed distinct crevicing of various orientations\ within the austenite islands[ The fractured surface was subsequently polished slightly to produce a smooth mirror!like _nish\ and viewed under a microscope to con_rm that all crevices marks had disappeared[ When this surface was etched with 19) HCl 79)H1O9[4 g K1S1O4 the structure revealed transformation of the austenite near the fracture surface to martensite "Fig[ 06#[ The crevicing that was present before polishing was the result of corrosive attack of martensite plates by the environment[ The martensite was distinguished by its brown! blue appearance\ the same colour as the ferrite\ depending on the etching time[0

Cracking of stainless steels in sour environments

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Fig[ 8[ Dissolution of austenite from a specimen of A immersed in NACE!90!66 solution for 619 h at 29>C] "a#exposed surface and "b# a section perpendicular to "a#[

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Fig[ 09[ X!ray di}raction Analysis of the _lm formed on the polished surface of duplex stainless steel immersed in NACE!90!66 solution for 619 h at 29>C[ Note the absence of austenite lines[

Results of tests conducted in neutral aqueous solution\ having various chloride ion concentrations ranging from 9 to 699 wppm and saturated with hydrogen sulphide\ indicate that chloride ions play a signi_cant role in the embrittlement mechanism[ In distilled water "9) Cl# there was no signi_cant loss in ductility but\ as the concentration of chloride increased the sulphide scc susceptibility also increased until the chloride level reached 299 wppm[ Increasing the Cl! level beyond this limit seems to have little or no in~uence on the embrittlement "Fig[ 07#[ The chloride ion seems to play a signi_cant role in the repassivation of the steel[ Once the protective _lm is broken by straining\ the presence of a su.cient quantity of chloride ion will inhibit the reformation of the _lm and hence hydrogen may enter the steel and produce a loss in ductility\ which is in agreement with reported results[03\04\06 Overall\ the results indicate a complex interplay of hydrogen embrittlement\ passivation and pitting corrosion in duplex stainless steels\ where the ferrite and austenite in the microstructure have very di}erent strength and ductility\ as well as di}ering susceptibilities to hydrogen embrittlement[ The orientation of the two phases in the microstructure and the formation of e!martensite in the austenite phase as a result of deformation19 both have a profound in~uence upon crack propagation[ Hydrogen embrittlement of steel A has been well characterised in a wide variety of environments producing hydrogen at di}erent fugacities[03 Whether this embrittlement originated from straining in gaseous hydrogen\ as a consequence of thermal charging under high pressure hydrogen\ or as a result of cathodic polarisation\ it was obvious that essential preliminaries were the actual uptake of hydrogen and the necessary transport to critical sites in the steel[ The introduction of hydrogen sulphide into the system combines the provision of a high hydrogen fugacity with chemical reaction at the steel surface[ The latter reaction may\ under appropriate conditions\ result

Cracking of stainless steels in sour environments

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Fig[ 00[ Secondary cracking in the gauge length of a duplex stainless steel specimen strained to failure in NACE!90!66 solution at 19>C "a# unimpeded and "b# de~ected by austenite stringers[

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Fig[ 01[ Secondary cracking in the gauge length of a duplex stainless steel specimen strained to failure in NACE!90!66 solution at "a# 79>C and "b# 59>C[

Cracking of stainless steels in sour environments

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Fig[ 02[ Secondary cracking in the gauge length of duplex stainless steel specimens strained to failure in NACE!90!66 solution at "a# 59>C and "b# 84>C[

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Fig[ 03[ Fracture surfaces of duplex stainless steel specimens strained to failure in NACE!90!66 solution at "a# 29>C and "b# 39>C[

Cracking of stainless steels in sour environments

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Fig[ 04[ EDX analysis of corrosion product on the surface of the duplex stainless steel specimen strained to failure in NACE!90!66 at 39>C "see 03"b##[

in either formation of a passive barrier to hydrogen absorption or breakdown of this barrier to allow both ingress of hydrogen and localised pitting[ If the pitting becomes serious\ i[e[ above the critical pitting temperature for the particular steel\ then the e}ects of hydrogen become inconsequential[

CONCLUSIONS "0# Slow straining of two commercial duplex stainless steels in chloride solutions satu! rated with hydrogen sulphide between 1 and 84>C reveals that\ whilst type 1496 retains its ductility over the whole temperature range\ type 1294 su}ers a ductility loss that increases to a maximum between 14 and 79>C but depends upon the particular environment concerned[ "1# The embrittlement at the lower temperatures is attributed to absorption of hydrogen generated at the steel surface but becomes mitigated by the barrier layer to per! meation presented by the passive _lm formed concurrently[ "2# The range of embrittlement becomes attenuated because of the severe pitting that occurs at higher temperatures where the passive _lm breaks down and recovery of ductility is observed[

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Fig[ 05[ Fracture surface of duplex stainless steel specimen strained to failure in NACE!90!66 solution at 39>C "i[e[ surface shown in 03"b## after cleaning[

Fig[ 06[ Fracture surface of duplex stainless steel specimen strained to failure in NACE!90!66 solution at 39>C\ after polishing and etching[

Cracking of stainless steels in sour environments

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Fig[ 07[ E}ect of chloride ion concentration on the ductility of duplex stainless steel strained to failure in solutions saturated with hydrogen sulphide[

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A[ A[ El!Yazgi and D[ Hardie Fontana M[ G[ and Greene\ N[ D[\ Corrosion En`ineerin`\ McGraw Hill\ 0867[ Marshall\ P[ I[ and Gooch\ T[ G[ Corrosion\ 0882\ 38\ 403[ Saarinen\ K[\ Pro`ress in The Understandin` and Prevention of Corrosion\ pp[ 474478[ Perng\ T[\ Altstetter\ C[ J[ Acta metall[\ 0875\ 23\ 0660[ Zheng\ W[ and Hardie\ D[ Corrosion Science\ 0880\ 21\ 12[ Zheng\ W[ and Hardie\ D[ Corrosion\ 0880\ 36\ 681[