J. Mater, Sel Teehaol, Vol No.1, 2002 3 e Review Article Stress Corrosion Cracking of Pipeline Steels Bingyan FANG, Enhou HAN', Ziyong ZHU, Jiangiu WANG and Wei KE State Key Lab for Corrosion and Protection of Metals, institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China [Manuscript received January 12, 2001, in revised form April 27, 2001] ‘This paper provides a review of the differences between high pH and neat-neutral pH stress corrosion cracking of pipeline steels, influencing factors, and mechanisms. The characteristics and historical information on both forms of SCC are discussed. The prospect for research in the future is also presented. KEY WORDS: Pipeline steels, Stress corrosion, High pH SCC, Near-neutral pH SCC 1. Introduction, ‘The failure of pipeline steel is usually catastrophic and causes economic, environment and conservation losses. About 20% failure of pipeline was caused by outer corrosion, and 5% by inner corrosion. ‘The first incident of stress corrosion cracking (SCC) on natural gas pipelines occurred in the mide 1960's"), ‘Since that time, there have been hundreds of fail- ures reported in Australia, Canadal?, Iran, Iraq, aly, Pak istan, Saudi Arabia, the former Soviet Union and the United States), In the last 30 years, the pipeline SCC problem has been investigated by different laboratories”. Most of the early failures were intergranular in nature, whereas, many of the recent failures, such as what have occurred in Canada are transgrananular®*. [tis now recognized that there are at Teast two forms of external SCC on underground pipelines. ‘The intergranular form is referred to as high-pH, classical SCO, while the transgranular form is referred to as low-pH, non-classical, or near-neutral-plH SCC. Now China plans to build a natural gas pipeline from the Xinjiang Uygur Autonomous Region in Northwest China to Shanghai in East China. It is a 4,200-kilometre pipeline, which is expected to wind its way through six provinces and ‘one autonomous region. The total cost of the gigantic project, is expected to be more than 140 billion yuan (USS 16.86 billion) and it will be China's second largest infrastructure project next to the Three Gorges Dam Project. So itis es- sential and urgent to design the pipeline soundly and con- tinue research into SCC to provide against possible troubles or predict the consequences. Moreover, with the constructions of the Sino-Russia and the Sino-Kazakstan transnational gas and oil pipeline imminent, itis very important to continue to research failure causes of pipeline 2. Near-neutral pH and High pH SCC in Pipelines ‘There are a lot of differences between near-neutral pHT 1C and high pH SCC, and further details are given below 2.1 High pH SCC Although pipelines are coated for protection against cor- rosion when they are put into the ground, there is always the risk that the steel pipe could become exposed to the sur- rounding environment. The pipe would then be vulnerable to corrosion. Since the corrosion is an electrochemical reaction, an electric current is passed through the soil to the pipe to effectively prevent corrosion. This process of applying a volt- ‘age to the pipe through the soil gives the pipeline a cathodic, potential and is referred to as cathodic protection Hiigh pH SCC oceurs only in a relatively narrow cathodic potential range in the presence of a earbonate/bicarbonate environment and at a pHT greater than 9. In the eathodic potential range and environment required for high pH SCC, |77To whom correspondence should be addressed, Ph.D, Prof E-mails chhanGicpm.syb.ac.en 4 protective film forms on the steel surface), ‘This film is a thin oxide layer that forms from the electrochemical reaction that takes place. If the protective film on the pipe surface is not broken, SCC cannot start because the film acts as a barrier between the pipe surface and the environment. But ifthe steel is sub= jected to a strain that stretches the metal until it is perma- nently deformed, the film, being brittle, will erack and bare ‘metal will be exposed to the environment, This process of rupturing the film to expose the metal is what creates the ‘opportunity for SCC to initiate 2.2 Near-neutral pl S¢ For near-neutral pli SCC, it can develop in pipelines under normal operating conditions when a coating is broken dow (debonded is formed) and it lacks cathodic protection of the pipeline surface and ground water contacts with the outside surface. Because the characteristics of the coating are differ- ‘ent and one may be more prone than another to debonding. ‘or forming holiday, they have different effect. In the presence of a cathodic current, the solution exhibits higher pH, then high pH SCC will occur ‘In comparison with high pH SCC, there are only about ten years of research on near-neutral pit SCC. Because of the differences between the two types of cracking, the research is generally not transferable. Consequently, additional knowl edge must be developed about near-neutral pH SCC. ‘The characteristics of near-neutral pH and high pH SCC are come pared in Table 1 Parkins cautioned that the way in which near-neutral pH SCC initiates and then develops is not yet completely undet- stood, and so what we discuss here should be taken in that light!*1. In this submission, Parkins discussed how diss tion and hydrogen are believed to be factors in the growth of near-neutral pH SCC. He conceived that the mechanism of| ‘rack growth involves dissolution and the ingress of hydrogen into the steel, the hydrogen facilitating crack growth by pro- moting reduced ductility. While itis clear from evidenee of corrosion on the sides of cracks, developed in service or labo- ratory tests, that dissolution occurs within erack enclaves itis doubtful that growth can be accounted for entirely in terms of ‘a dissolution process. That is because at high stress or strain ‘observed growth rates are markedly greater than that can be accounted for by rates of dissolution in near-neutral pH en- Vironments. “However, the evidence in support of hydrogen playing a rote in the overall growth process is circumstantial, rather than direct), Parkins indicated that the factors contributing to the development of near-neutral pH cracking would appear to include the following: (1) Cracks are probably initiated at pits on the steel sur- face wherein a localized environment is generated that has pH low enough to produce atomic hydrogen in the pit (2). The presence of carbon dioxide in the groundwater assists in creating near-neutral pH levels, (3) Some of the discharged atomic hydrogen enters. the4 5. Mater. Sei. Technol, Voli Nowt, 2002 ‘Table 1 Comparisons betwoon high pH and near-neutral pH SCC of pipeline!*"~2°1 Pipeline High pit SCC ‘Nearneutral pH SCC Location Corrosive environment concentrated 1 N carbonate/bicarbonate, of pH near 9.5 Crack morphology Intergranular Crack orientation Longitudinal [Numerous surface cracks Yes Linking of erack Yes Patches of eracks Yes Corrosion of crack faces No Corrosion of pipe Usually not Width of potential range Narrow (<100 mV) P/S potential, CS 722 mV ‘Temperature dependence Arrhenius behavior Crack appearance secondary steel, degrading the mechanical properties locally 20 that tracks are initiated or grown by a combination of dissolution ct hydrogen embrittlement. (4) Continuing anodic dissolution in the crack is neces: sary for crack growth, assisted by hydrogen entry into the see (6) ‘The plastic stots level necessary to produce cracking aay not be related solely to fracturing the embritiled see, Tt nay also contribute by upturing the protective film, allowing liydrogen to reach and then penetrate the steel ‘Thus, Parkins sof the view that near-neutral pH SCC cack growth involves dseolution and hydrogen, and he is sup- ported in that view by Leis”, Wilmott and Jack'*"!, Lambert and Plumtree®"! and Beavers! 2.3 High pHl vs near-neuteal pH SCC crack characteristics ‘The majority of instances of SCC in high pressure gas pipelines at high pH has been associated with the propagation of intergranular cracks (IGSCC), but several instances of nar- ave been found in the form of transgranular ). High pH SCC generally produces inter- ranulas cracking, where the eracks grow around of between the grains in the steel. In IGSCC, the very small amount of iron carbonate that sometimes is present is incorporated in the thin magnetite films that invariably form. ‘These films are strongly adherent to the crack sides and effectively pre- vent any lateral dissolution on the sides. As a result, IG eracks are very tight, narrow of fine. Conversely, TGSCC, where the cracks follow a path across of through, is often associated with the formation of relatively large amount of white iron eaeby ate between the coating and pipe surface. ‘TG crack sides suf- fer significant lateral dissolution, with appreciable amounts of loosely adherent corrosion products forming in the crack enclaves, The side walls of the cracks corrode and the eracks appear much wider than high pH SCC cracks. However, the crack generally becomes narrower as the erack deepens. ‘The different nature of the erack propagation is the result of the different effects of the environments and the suscepti- bility of the steel. In the high pH SCC, the grain boundaries are more susceptible to dissolution than the grains and so that is where the cracks form, Parkins viewed that transgranular cracking can also occur in high pH SCC when the eracks be- come relatively deep or are subjected to relatively high stress levels or high fluctuating stress!™). ‘The significance of this point is that the presence of a transgranular crack by itself fs not enough to be certain that a crack is near-neutral pH SCC. a) Typically within 20 kam downstream of compressor ) Typically where discharge gas temperature exceeds 35°C. Laboratory solutions typically used to simulate cracking are Cracks show little evidence of a) Not restricted to any particular location, b) No dependence on gas discharge temperature. Solution found associated with cracking in the field are dilute, low conductivity, near neutral pH trapped waters ‘Transgranular Longitudinal Yes Yes Yes Yes Sometimes Probably> 100 mV Native potential Not established Cracks are with evidence of substantial secondary corrosion 3. Controlling Factors For SCC to occur on an engineering structure, three condi tions must be met simultaneously; a specific erack-promoting environment must be present, the metallurgy of the material must be susceptible to SCC, and tensile stress above some threshold value must be present. Bach of these factors is discussed below for high pH and near-neutral pH SCC of pipelines, 3.1 Potent environment Researchers have learned that the environment covers a range of chemical species that allow near-neutral pH SCC to develop. TGSCC has been found in environments with low ‘concentrations of carbonic acid and bicarbonate ions with the presence of other species, including chloride, sulphate, and nitrate ions. Since this range of environments all produce TGSCC, it can be expected that the envionment found at ‘TGSCC sites will vary). ‘The carbonic acid results from carbon dioxide in the soil combining with groundwater: the lower the groundwater temperature, the higher the solubil- ity of COs; the higher the COs level, the lower the pll, with the range being near-neutral, 5.5 to 7.5. ‘The carbonic-acid ‘environments measured in the field where TGSCC has been found have been relatively dilute and, therefore, not strongly "The environment for near-neutral pH SCC can only de- velop after the pipe coating is damaged or debonded and in the absence of the cathodic current which is used to control corrosion. If the cathodic current reaches the pipe surface in ‘the presence of groundwater with low level of COs, a carbon- ‘ate/biearbonate environment will be formed with a pilin the range of 9 to 13 and near- neutral pH SCC will not occur. Tn the case of high pH SCC, it was concluded that a ‘concentrated carbonate/bicarbonate solution with pH values in the region of 9.5 was responsible for the SCC observed, on pipelines! Essentially, the cathodic protection system ‘causes a pHi increase at the pipe surface. Oz, which is present in the soil, is rapidly absorbed by the high pHI so- lution to generate'the concentrated carbonate/bicarbonate ceavironment. This environment is simulated in the labora- tory using a IN NalICOs-1N NagCOs solution, which has a pH of about 9.3. However, there is significant less laboratory information on the near-neutral pH SCC form of cracking. Initial attempts to reproduce the near-neutral pH SCC in the laboratory were made with limited success. In the initial re- searches, the test techniques used were similar to those that had been successfully used or developed for the evaluationJ. Mater, Sei, Technol, Vol18 No.1, 2002 5 of high pH SCC, For example, negligible cracking has been. observed in tapered tensile tests performed in near-neutral pH environments under eyelic load conditions that simulate pipeline operating conditions. Cracking has been reported in slow strain rate tests but the cracks generally are confined to the necked region of the specimens where extreme mechanical loading conditions are aecountered While high pH SCC propagation depends very much on soil or pipe temperature (they are generally the same along, 2 pipeline), laboratory and field data have not shown a sim- ilar correlation for near-neutral pH SCC. Parkins carried out slow strain rate tests but the results showed no significant di ferences for crack propagation rates at temperatures of 5°C and 45°C"l, SCC of pipeline steels in the high pH environ- iment occurs over a very limited potential range that is about 100 mV wide and is centered around ~722 mV Cu/CuSOs at 75°C and moves in the positive (noble) direction with de- creasing temperature. This potential range is associated with the active-passive transition in a potentiodynamic po- larization curve. 3.2 Metallurgy of the material For neat-neutral pHI SCC, itis showed from pipeline fal ‘ures that near-neutral pH SCC was developed on a wide va- riety of pipe. Pipe failures occurred on pipe in which diame- ters ranged from 114 to 1067 mm, wall thicknesses ranged from 3.2 to 9.4 mm and grades varied from 241 MPa to 448 MPa, Both electric resistance welded (BRW) and dow- ble submerged arc weld (DSAW) pipe were involved in $CC- related failures, Researchers and scientists have considered ‘a number of pipe characteristics and qualities to determine if they are possibly related to the susceptibility of pipe to near-neutral pH SCC. These factors inclide the pipe mant- Tacturing process, type of steel, grade of steel, cleanliness of the steel (presence or absence of impurities or inclusions)", steel composition”), plastic deformation characteristics of the steel (cyclic-softening characteristics)", steel temper- ature and pipe surface condition. It does not appear that there is a correlation between neat-neutral pH SCC and pipe composition, grade, manufacturer or manufacturing process. With one exception, all of the stecls examined have indicated 8 comparable susceptibility to near-neutral pH SCC. The ex: ception was the ERW pipe manufactured by Youngstown, ‘The ERW seam area of Youngstown pipe has been found to exhibit a lower resistance to near-neutral pH SCC formation, ‘than the base metal!) In the case of high pH SCC, the Pipeline Research Com- mittee (PRC) of A.G.A.(American Gas Association) funded ‘many programs to investigate the relationship between high pH SCC susceptibility and metallurgical variables in an at- tompt to identify cracking resistant steels for future construc- tion. The program was conducted with little success and prac- ticable steol compositions or heat treatments that resist high pH SCC were not identified"). Tt was found that major alloy additions, >1%, of some elements could increase high pH SCC resistance, but such additions are prohibitively ex- pensive. Differences in the SCC susceptibility of diferent line pipe steels, as measured by differences in the threshold stress for crack initiation, were found in the studies, but the basic cause for these differences was not identified 33 Stress Field data and laboratory data indicate that stress has an fffect on initiation and possibly on the growth rate of near- neutral pif SCC. It is also found that pressure fluctuations and strain-rates have an effect on crack growth as identified by laboratory data, However, NEB of Canada found that the available information is limited and conflicting. While field data show significant reduction in the inci= dence of SCC below a hoop stress caused by pressure of 70 percent specified minimum yield strength, research has not found a threshold stress below which cracks will not grow to failure. Some evidence suggests that the threshold stress level and the level of pressure fuctuations are interrelated and that. the threshold may vary along the length of the pipeline. The ‘evidence indicates that the total stress on a pipeline should be ‘considered. The hoop stress caused by the internal pressure is only one component of total stress. In almost all pipeline failures associated with SCC, local stress intensifiers stich as corrosion, gouges or stress concentrations at the toe of the weld seam have been present, ‘The mechanical conditions for near-neutral pH appear to bbe more restrictive than those for high pH SCC. In slow strain rate tests, cracking is generally only observed within the necked region of the specimen where plastic deformation, and true stresses are very high. In constant displacement rate testing, cracking is only observed where dynamic loading ‘conditions are present!*l 4, Mechanism of SCC in Pipeline ‘There have been a number of mechanisms proposed for SCC of metals"). ‘Three woll accepted mechanisms, at the present time, are the anodie dissolution (AD) mechanista, the film induced cleavage (FIC) mechanism, and hydrogen related, ‘mechanisms. In the AD mechanism, the applied stress causes plastic deformation and rupture of fms on the metal surface, ‘The rupture ofthe film exposes bare metal to the environment that undergoes rapid anodic dissolution. ‘The erack actually. propagates by dissolution but the passive film prevents the corrosion of the crack walls so a erack geometry is maintained. 4.1 High pH SCC ‘When the tensile stress is applied on a specimen, the film may be damaged because of strain. The deformation type of strain is called a “plastic” strain. Once the plastic strain decreases to an “elastic” level, a strain that does not per- manently deform the pipe, the protective film is formed over the newly exposed stool, re-establishing the protective bar rier. ‘Then crack growth stops. For a crack to start growing ‘again, the film must be cracked by plastic strain deforma: tion at the crack tip. This eyclic process shows that cracks can start and stop growing depending on the level of stress for strain on the steel. Since it takes time for the film to be formed, the cracks can grow only if the rate of plastic defor- mation occurs more quickly than the rate at which the film is formed. Consequently, the strain rate, which is related to the rate at which the pressure in the pipe changes isthe con- dition that determines crack growth in high pH SCC, It is important to note that the level of stress or strain at a partie ‘ular location on a pipe may differ from the level of stress or strain on the pipeline as a whole, Intergranular SCC failures, are frequently attributed to this mechanism since imputities, at the grain boundaries have pronounced effects on repassiva- tion and creep, 42 Near-neutral pH SCC Zhang et al. shows that the cracking in the near-neutral pH SCC appears to be unlikely the dissolution mechanisin, because the maximum anodic current densities ate also low for the observed cracking velocities". “And in recent. re- search, it was observed that crack velocities were at least two orders of magnitude higher than those in constant displace- ‘ment rate testing of precracked specimens of pipeline steels, in near-neutral pH environment!“ ‘The lack of specificity of the conditions for crack propagation in the near-neutral pll environment is also not consistent with an anodic dissolution, ‘mechanism for crack propagation!) ‘The characteristics of near-neutral pH SCC do not appear to be consistent with a FIC mechanism either, ‘This mecha- nism requires the presence of a brittle coherent oxide film, dealloyed layer, or some other britle film or layer ‘The most plausible mechanism for crack propagation in ‘the near-neutral pH environment is a hydrogen related mech- anism. A number of effects of hydrogen at the crack tip have been postulated. Hydrogen makes the lattice dilatant, low- ers the maximum cohesive force against the separation of the6 J. Mater, Sci Technol, Vol18 No.1, 2002 metal atoms, and decreases the interactive atomic cohesion, resulting in increased corrosion susceptibility. For some met~ al, such as Ti, Zr, V and Ta, there are stable hydrides that are inherently brittle” The exposure of such materials to a souree of hydrogen can result in the formation of hydride phases in the crack tip stress fied. And it is in this location that the compatibility of the strain field and the volume change associated with hydride formation assists the latter. In the tase of enhanced local plasticity due to the presence of hydro- gen model, hydrogen concentration is locally increased in the stress field associated with a crack tip and the presence of hy- rogen that includes adsorption and absorption decreases the resistance to dislocation motion, with shear localization as consequence. Hydrogen can also interact with dislocation and pin the latter. Sometimes, when the strained sample exposes to the hydrogen included environment, martensite phase can form. What Parkins discussed before is one of these cases. Gu et al.) conducted slow strain rate tests and frac- tographic examination of X80 and X52 pipeline steels The re- sults showed that TGSCC could accur in a dilute aqueous so- lution with near-neutral pH. Moreover, the effect of hydrogen ‘on SCC of pipeline steels was studied by using slow strain rate tests, polarization techniques, scanning electron microscopy, and secondary ion mass spectrometry. Results showed that the mechanism of SCC for pipeline steels in near-neutral pH solutions might be that, as the anodie potential comes close to Bvver local dissolution or pitting occurs frst, generating H™, which result in local acidification within individual pits In turn, that acidification could facilitate some reactions— hhydrogen ions resulting from acidification would form atomic hydrogen that could diffuse into the steel, enhancing local ‘anodic dissolution, which were involved in’ the crack initia tion and propagation process. So, in the present case, SCC was dominated by the mechanism of hydroges-facilitated AD. At cathodie potentials, when hydrogen concentration reached ‘critical value, HIC controlled the cracking process. How- fever, the synergistic effects of hydrogen and dissolution on the cracking process of pipeline steels in the non-classical SCC enviroment need further studies 5. Looking Forward 1k is essential to continue research into SCC, because many of the basic questions about SCC have not yet been answered. ‘The SCC mechanism, which accounts for why IGSCC is inter” granular and why TGSCC is transgranular, should be under- stood. There is aso a need to continue to develop mitigative measttes to deal with SCC. Most notably, the development of a fully reliable SCC in-line inspection tool will significantly improve the industey ability to detect SCC, Overall, further focused research will enhance knowledge ‘of SCC aud will contribute to the development of measures to protect the public and the environment from the consequences ‘of pipeline failures due to SCC. Acknowledgement ‘This wor is supported by ‘The Hundred Talents Program and The Special Funds For The Major State Basic Research Projects Go0i0650, The authons acknowledge the nesistance REFERENCES [1] H.B-Townsend, Jes MP, 1972, 10, 38. [2] P.Kentish: Brit. 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