Stress corrosion cracking behavior of X70 pipe steel in an acidic soil environment

Stress corrosion cracking (SCC) behavior of X70 pipe steel was investigated in an extracted acidic soil solution by slow strain rate test (SSRT), potentiodynamic polarization curve measurements and surface analysis technique. The SCC process and mechanism of X70 steel in the acidic soil solution is mixed-controlled by both anodic dissolution and the hydrogen involvement. With the different applied potentials, the dominance of SCC process changes. At a relatively less negative potential, the steel SCC is based primarily on the anodic dissolution mechanism. When the applied potential is shifted negatively, hydrogen is involved in the cracking process, resulting in a transgranular cracking mode. With the further negative shift of applied potential, the SCC of the steel follows completely a hydrogen-based mechanism, with a river-bed shaped brittle feature of the fracture surface. Heat treatment alters the microstructure of the steel, resulting in a change of SCC susceptibility. In particular, the quenched steel with a bainite microstructure has a high susceptibility to SCC in the acidic soil, while the as-received steel with a ferrite matrix have a low SCC susceptibility.     

Strain-rate dependence of low cycle fatigue behavior in a simulated BWR environment

The strain-rate dependence of low cycle fatigue behavior of ASTM A533B low-alloy steel was investigated in a simulated BWR environment. Fatigue resistance of the steel was found to be closely dependent on cyclic strain rate in high-temperature water. A tortuous cracking morphology was dominant at high strain rate and typical fan-like or quasi-cleavage cracking patterns were frequently observed on the corresponding fracture surface. An entirely straight cracking morphology, however, became dominant at low strain rate. Evidence of crack arrest was found on the fracture surface rather than fan-like or quasi-cleavage cracking patterns. The above cracking behavior in simulated BWR water may be attributed to a strain-rate-induced change in the dominant environmentally assisted cracking (EAC) mechanism from hydrogen-induced cracking to film-rupture/slip-dissolution-controlled cracking.     

Stress corrosion cracking study of microalloyed pipeline steels in dilute NaHCO3 solutions

Studies were carried out to evaluate the stress corrosion cracking (SCC) behavior of a X-70 microalloyed pipeline steel, with different microstructures by using the slow strain rate testing (SSRT) technique at 50 °C, in NaHCO₃ solutions. Both anodic and cathodic potentials were applied. Additionally, experiments using the SSRT technique but with pre-charged hydrogen samples and potentiodynamic polarization curves at different sweep rates were also carried out to elucidate hydrogen effects. The results showed that the different microstructures in conjunction with the anodic applied potentials shift the cracking susceptibility of the steel. In diluted NaHCO₃ solutions cathodic potentials close to their rest potential values decreased the SCC susceptibility regardless the microstructure, whereas higher cathodic potentials promote SCC in all steel conditions. Certain microstructures are more susceptible to present anodic dissolution corrosion mechanism. Meanwhile concentrated solution did not promotes brittle fracture.     

Quantitative characterization by micro-electrochemical measurements of the synergism of hydrogen, stress and dissolution on near-neutral pH stress corrosion cracking of pipelines

Occurrence of stress corrosion cracking of pipelines under a near-neutral pH condition depends on the synergism of stress, hydrogen and anodic dissolution at the crack tip of the steel. In this work, micro-electrochemical techniques, including localized electrochemical impedance spectroscopy and scanning vibrating electrode technique, were used to characterize quantitatively the synergistic effects of hydrogen and stress on local dissolution at crack-tip of a X70 pipeline steel in a near-neutral pH solution. Results demonstrate that, upon hydrogen-charging, the anodic dissolution of the steel is enhanced. The resistance of the deposited corrosion product layer depends on the charging current density. There is a non-uniform dissolution rate on the cracked steel specimen, with a highest dissolution current density measured at crack-tip. For a smooth steel specimen, the synergistic effect factor of hydrogen and stress is equal to 5.4, and the total effect of hydrogen and stress on anodic dissolution of the steel is 7.7. In the presence of a crack, the hydrogen effect factor, stress effect factor and the synergistic effect factor are approximately 4.3, 1.3 and 4.0, respectively. The total effect factor is up to 22.4, which is very close to the 20 times of difference of crack growth rate in pipelines in the presence and absence of the hydrogen involvement recorded in the field.     

Effect of microstructure on the sulphide stress cracking susceptibility of a high strength pipeline steel

The sulphide stress cracking (SSC) susceptibility of a newly developed high strength microalloyed steel with three different microstructures has been evaluated using the slow strain rate testing (SSRT) technique. Studies were complemented with potentiodynamic polarization curves and hydrogen permeation measurements. Material included a C–Mn steel having Ni, Cu, and Mo as main microalloying elements with three microstructures: martensitic, ferritic and ferritic + bainitic. Testing temperatures included 25, 50, 70 and 90 °C. Detailed SEM observations of the microstructure and fracture surfaces were done to identify possible degradation mechanisms. The results showed that in all cases, the corrosion rate, number of hydrogen atoms at the surface and the percentage reduction in area increased with temperature. The steel with a martensitic microstructure had the highest SSC susceptibility at all temperatures, whereas the ferritic steels were susceptible only at 25 °C, and the most likely mechanism is hydrogen embrittlement assisted by anodic dissolution.     

Failure mechanisms of high strength steels in bicarbonate solutions under anodic polarization

High strength steels used in prestressing concrete structures are not exempt from the effects induced by corrosion on the normal concrete reinforcement. Carbonation of surrounding concrete or mortar is not unlikely for prestressing tendons and strands. Moreover, these steels undergo to brittle fracture as a consequence of stress corrosion cracking phenomena. To evaluate if concrete carbonation can promote this kind of failure, constant load tests in bicarbonate aqueous solutions under anodic polarization were carried out on high strength steel wires. Microscopic examination pointed out that the wires exhibited a brittle fracture mode, while its natural feature is ductile, as indicated by air testing. Failure mechanism was evaluated by a fracture mechanic approach. Cracks initiation was attributed to an anodic dissolution mechanism, while its propagation, interpreted by means of the surface mobility theory, was related to interaction between hydrogen atoms and magnetite at a crack tip.     

The effect of potential on the high-temperature fatigue crack growth response of low alloy steels,part 2: sulfide–potential interaction

Environmentally assisted cracking (EAC) of low-alloy steels exposed to high temperature dehydrogenated water was found to be dependent on externally applied potential. EAC became active when the specimen was polarized anodically above a critical potential, which was not a function of steels sulfur. However, the plateau crack propagation rate was determined to be dependent on both overpotential and steels sulfur concentration. Hydrogen additions inhibited the ability of applied potential to activate EAC. The behavior was related to the formation of hydrogen ions on the specimen surface through hydrogen oxidation during anodic polarization. A mechanism based on the formation of hydrogen sulfide at the crack tip and hydrogen ions at the crack mouth is presented to describe the process by which sulfides and hydrogen ions affect the critical sulfide concentration at the crack tip needed to establish EAC.     

Effects of corrosion product deposit on the subsequent cathodic and anodic reactions of X-70 steel in near-neutral pH solution

The effects of corrosion product deposit on the subsequent anodic and cathodic reactions of X-70 steel in a near-neutral pH solution were investigated by localized electrochemical impedance spectroscopy (LEIS), scanning vibrating micro-electrode (SVME) and macroscopic EIS measurements as well as surface analysis technique. It is found that the deposit layer formed on the steel surface is porous, non-compact in nature. The presence of a corrosion product layer would enhance adsorption, but significantly inhibit absorption and permeation of hydrogen atoms into steel. It is due to the porous structure of the deposit that generates a spatial separation of cathodic and anodic reaction sites, resulting in an increased effective surface area for hydrogen adsorption and, simultaneously, a “blocking” effect on hydrogen absorption and permeation. The deposit enhances greatly anodic dissolution of the steel, which is attributed to the adsorption of the intermediate species and the resultant “self-catalytic” mechanism for corrosion of the steel in near-neutral pH solution. In the presence of corrosion product deposit on the pipeline steel surface, pipeline corrosion, especially pitting corrosion, is expected to be enhanced. Stress corrosion cracks could initiate from the corrosion pits that form under deposit. However, deposit does not contribute to hydrogen permeation, although the hydrogen evolution is enhanced.     

Investigating the mechanism of stress corrosion cracking in near-neutral and high pH environments for API 5L X52 steel

Stress corrosion cracking behaviour of API-5L-X52 steel under cathodic protection in near-neutral and high pH conditions was studied using slow strain rate test method and electrochemical measurements. The slow strain rate test showed ductile and brittle fracture feature at low and high applied potentials, respectively. In order to identify the mechanism contributes in stress corrosion cracking; the electrochemical potentiodynamic polarisation test was done at fast and slow sweep rate. The results revealed that at near-neutral pH condition the anodic dissolution at crack tip was the dominant mechanism. While at high pH medium, the hydrogen based mechanism was dominant.     

Effect of inclusions on initiation of stress corrosion cracks in X70 pipeline steel in an acidic soil environment

The effect of inclusions on the initiation of stress corrosion cracking (SCC) X70 pipeline steel was investigated in an acidic soil solution using slow strain rate test, scanning electron microscopy and energy-dispersive X-ray techniques. The results demonstrated that stress corrosion cracks are not initiated in X70 steel when it is under anodic polarization. At cathodic polarization, hydrogen evolution is enhanced, and hydrogen is actively involved in SCC processes. Two types of inclusions exist in the steel and play different role in crack initiation. The inclusions enriching in Al are brittle and incoherent to the metal matrix. Microcracks and interstices are quite easily to be resulted in at the boundary between inclusions and metal. There is no crack initiating at inclusions containing mainly Si.     

Effect of AC on stress corrosion cracking behavior and mechanism of X80 pipeline steel in carbonate/bicarbonate solution

The influence of various AC current densities on stress corrosion cracking behavior and mechanism of X80 pipeline steel was investigated in carbonate/bicarbonate solution by polarization curves and slow strain rate tensile tests. With the increasing AC current density, the SCC susceptibility of the steel increases, especially at high AC current density. A significant difference in the SCC behavior and mechanism is found for the steels with or without AC application. In the absence of AC, the fracture mode is intergranular and the mechanism is attributed to anodic dissolution. Under AC application, the cracks propagation is transgranular, and the mechanism is mixed controlled by both anodic dissolution and hydrogen embrittlement.     

Environmentally Assisted Cracking of Drill Pipes in Deep Drilling Oil and Natural Gas Wells

Corrosion fatigue (CF), hydrogen induced cracking (HIC) and sulfide stress cracking (SSC), or environmentally assisted cracking (EAC) have been identified as the most challenging causes of catastrophic brittle fracture of drill pipes during drilling operations of deep oil and natural gas wells. Although corrosion rates can be low and tensile stresses during service can be below the material yield stress, a simultaneous action between the stress and corrosive environment can cause a sudden brittle failure of a drill component. Overall, EAC failure consists of two stages: incubation and propagation. Defects, such as pits, second-phase inclusions, etc., serve as preferential sites for the EAC failure during the incubation stage. Deep oil and gas well environments are rich in chlorides and dissolved hydrogen sulfide, which are extremely detrimental to steels used in drilling operations. This article discusses catastrophic brittle fracture mechanisms due to EAC of drill pipe materials, and the corrosion challenges that need to be overcome for drilling ultra-deep oil and natural gas wells.     

Crack tip chemistry and electrochemistry of environmental cracks in AA 7050

The role of the crack environment in establishing environment-assisted crack (EAC) propagation in AA 7050 alloys is elucidated. A suite of mini-electrodes provided real-time in situ measurements of the crack potential, pH, and chloride concentration during stage II cracking in a chromate-chloride electrolyte under electrochemical control. For material aged to an EAC-susceptible condition, crack growth during an incubation period is characterized by tip polarization to near the applied electrode potential (E_App) and bulk-like chemistry near the crack tip. In contrast, establishment of high-rate crack growth coincided with the development of an acidic, high chloride concentration tip environment and tip depolarization. During steady state high rate crack growth, the tip potential was ∼−0.85V_SCE; near-tip potential gradients were ∼1 V/cm. Large ohmic potential drop within fast-growing cracks is indicative of net anodic current in the near tip region and increased mass transport resistance within the crack due to solid corrosion products and/or hydrogen bubble formation. Microinjection of a corrosion-inhibiting or corrosion-promoting solution at the tip suppresses or prompts, respectively, the transition from incubation to high-rate cracking, highlighting the intimate dependence of the crack growth kinetics on the local chemistry. The exceptional EAC resistance of over-aged AA 7050 is intrinsic; injection of an acidic aluminum chloride solution at the tip of a crack of this material while polarized to a high E_App failed to induce brittle crack advance.     

A correlation between phosphorous impurity in stainless steel and a second anodic current maximum in H2SO4

Phosphorous as a minor element (0.03%) in AISI 304 austenitic stainless steel greatly affects the polarization and corrosion behavior in sulfuric acid solution. The presence of P in stainless steel created a second current maximum in the anodic polarization curve and the current increased with increasing aging in the solution. An adhesive corrosion surface layer, rich with phosphate, formed on the surface of a P-containing steel during active dissolution. The layer lowered the cathodic Tafel slope at low current densities, and is likely, due to a change in hydrogen evolution mechanism. Phosphorous increases the H-adsorbed (and/or absorbed) atoms on the surface, leading to the appearance of a second anodic current peak that is interpreted as re-oxidation of hydrogen atoms. Also, P shifted the corrosion potential to the noble side, decreased effectively the active anodic dissolution, and lowered the corrosion rate.     

CORROSION BEHAVIOR OF X70 PIPELINE STEEL IN SIMULATED KUERLE SOIL SOLUTION WITH CO2

采用动电位扫描、交流阻抗电化学方法和慢应变速率拉伸实验(SSRT)研究了CO2对X70管线钢在库尔勒土壤模拟溶液中应力腐蚀开裂(SCC)行为的影响, 并利用扫描电镜分析了不同CO2分压下的断面形貌. 结果表明: CO2能够与腐蚀膜FeCO3反应, 生成可溶性Fe的络合物 Fe(CO3)2 2-, 加速X70管线钢腐蚀; CO2与H2O形成H2CO3和HCO3-, 为阴极反应提供H+. X70管线钢在含 CO2溶液中的SCC机理为氢脆--阳极溶解协同机理, 且随CO2 分压的增加, 氢脆作用增大.     

外加电位对X70管线钢在库尔勒土壤模拟溶液中应力腐蚀开裂敏感性的影响

采用慢应变速率拉仲试验(SSRT)研究了不同外加电位下X70管线钢在库尔勒土壤模拟溶液中的应力腐蚀开裂(SCC)行为,并用扫描电镜分析了不同电位下的断面形貌.结果表明,X70管线钢在库尔勒土壤模拟溶液中具有SCC敏感性;在Ecorr附近施加弱极化时,应力腐蚀开裂敏感性增加;施加强阳极电位时,发生强烈阳极溶解,导致阳极溶解断裂;施加强阴极电位时,析氢过程加强,导致氢致应力腐蚀断裂.     

Discussion on “Failure mechanisms of high strength steels in bicarbonate solutions under anodic polarization” by E. Proverbio and P. Longo: [Corrosion Science 45 (9) (2003) 2017]

Proverbio and Longo have reported some results on the stress corrosion cracking behaviour of cold drawn pearlitic steels in a sodium bicarbonate aqueous solution. On the basis of fractographic observations, mechanical analysis and the application of the surface mobility mechanism (SMM) they conclude that cracks are generated by anodic dissolution at localized ruptures of the passive film, with hydrogen playing an essential role in their propagation. A close examination of the paper shows a misinterpretation of the fractographical evidence, and an inappropriate mechanical reasoning as well as an incorrect application of the SMM. As a consequence, the conclusions are not supported by the results.     

Electrochemical conditions for environment-assisted cracking of 6061 Al alloy

We have investigated the influence of electrochemical conditions on environment-assisted cracking (EAC) of 6061 aluminum alloy in acidic chloride solutions. An EAC test was conducted by means of potential-controlled slow strain rate technique. In addition, thermal desorption spectroscopy (TDS) was employed to determine amount of hydrogen absorbed in the specimens under the same electrochemical conditions as those in the EAC tests. As a result, almost no EAC and very small amount of hydrogen absorption were found in a potential range lower than the film breakdown potential, while the higher potential induced severer EAC and much larger hydrogen absorption. The specimen pre-immersed in the chloride solution of pH 1, which derived voluntary breakdown of the oxide film, suffered preferential grain boundary attack. When the tensile test was conducted in air for the specimen with pre-immersion, the fracture strain became slightly smaller than that without pre-immersion. Moreover, the fracture strain drastically decreased and deep cracks was observed, namely the EAC occurred, when the pre-immersed specimen was examined by the EAC test under the cathodic condition which induced no EAC and very small hydrogen absorption for the specimen without pre-immersion.     

带镀层GC-4超高强度钢的腐蚀断裂

应用慢拉伸及断裂力学方法研齐了带镀层的GC-4钢(40CrMnSiMoVA)在3.5％NaCl中的应力腐蚀特性,并与裸钢作了对比。结合扫描电镜及宏观断口分析,探讨了失效机理。研究表明,阴、阳极镀层均使钢的KIscc降低,da/dt(Ⅱ)显著增加,其影响依无氰Cd、Cd-Ti、Cr的次序增加。慢拉伸试验结果说明,阴、阳极极化均使GC-4裸钢延性降低。根据BL-WOL试样裂纹扩展在表面处较内部为快以及阴、阳极镀层、平面应变状态对断口形貌的影响,可以认为带镀层与不带镀层GC-4钢的腐蚀断裂机理为裂尖阳极溶解与氢脆共同作用,并且裂尖溶解将直接参与导致裂纹扩展.从而对高强度钢腐蚀断裂的纯氢脆机理作出修正。     

Monte Carlo simulation of stress corrosion cracking on a smooth surface of sensitized stainless steel type 304

Stress corrosion cracking (SCC) on a smooth surface of structural metal materials occurs by initiation and coalescence of micro cracks, subcritical crack propagation and multiple large crack formation or final failure under combination of material, stress and corrosive environment. In this paper, a Monte Carlo simulation of the SCC process is proposed based on stochastic properties for micro crack initiation and concepts in fracture mechanics for crack coalescence and propagation. The procedure is as follows: The possible number of grain-sized micro cracks which can be initiated is set for a given space and initiation times for all cracks are assigned by random numbers based on exponential distribution. Sites and sizes of cracks are assigned by uniform random numbers and normal random numbers, respectively. Coalescence and propagation of cracks are determined based on fracture mechanics. The emphasis in the model is put on the influence of semi-elliptical surface cracks. Numerical simulations are carried out based on the results of creviced-bent-beam tests for sensitized stainless steel type 304 under high-temperature and high-purity water containing dissolved oxygen and the influence of micro crack initiation rate and coalescence condition on the simulation results is discussed.