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.     

Effects of alternating current on corrosion of a coated pipeline steel in a chloride-containing carbonate/bicarbonate solution

In this work, the alternating current (AC)-induced corrosion of a coated pipeline steel was studied in a chloride-containing, concentrated carbonate/bicarbonate solution, which simulated the trapped high pH electrolyte under coating, by potentiodynamic polarization measurements, immersion tests and surface characterization technique. It was found that an application of AC resulted in a negative shift of corrosion potential of the steel, caused an oscillation of anodic current density, and degraded the steel passivity developed in the solution. With the increase of AC current density, the corrosion rate of the steel increased. At a low AC current density, a uniform corrosion occurred, while at a high AC current density, pitting corrosion occurred extensively on the steel electrode surface. At individual applied AC, there was a higher electrochemical dissolution activity of the coated steel electrode containing a 1 mm defect than that of the electrode containing a 10 mm defect.     

Electrochemical corrosion of X65 pipe steel in oil/water emulsion

The electrochemical corrosion behavior of X65 pipeline steel in the simulated oil/water emulsion was investigated under controlled hydrodynamic and electrochemical conditions by rotating disk electrode technique. Results demonstrated that mass-transfer of oxygen plays a significant role in the cathodic process of steel in both oil-free and oil-containing solutions. Electrode rotation accelerates the oxygen diffusion and thus the cathodic reduction. The higher limiting diffusive current density measured in oil-containing solution is due to the elevated solubility of oxygen in oil/water emulsion. The anodic current density decreases with the increase of electrode rotating speed, which is attributed to the accelerated oxygen diffusion and reduction, enhancing the steel oxidation. Addition of oil decreases the anodic dissolution of steel due to the formation of a layer of oily phase on steel surface, increasing the reaction activation energy. The steel electrode becomes more active at the elevated temperature, indicating that the enhanced formation of oxide scale is not sufficiently enough to offset the effect resulting from the enhanced anodic dissolution reaction kinetics. The corrosion reaction mechanism is changed upon oil addition, and the interfacial reaction is activation-controlled, rather than mass-transfer controlled. When sand particles are added in oil/water emulsion, there is a significant increase of corrosion of the steel. The presence of sands in the flowing slurry would impact and damage the oxide film and oily film formed on the steel surface, exposing the bare steel to the corrosive solution.     

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.     

Micro-electrochemical characterization of corrosion of welded X70 pipeline steel in near-neutral pH solution

The local corrosion behavior of welded X70 pipeline steel in near-neutral pH solution was studied by micro-electrochemical measurements, including scanning vibrating electrode and local electrochemical impedance spectroscopy. The microstructure of the welded steel was observed by optical microscopy and scanning electron microscopy. It is demonstrated that the microstructure of weld metal consists of acicular ferrite and grain boundary ferrite, while that of heat-affected zone is a mixture of acicular ferrite, bainitic ferrite and a few martensite/austenite microconstituents. The microstructure of base steel is typically ferrite and pearlite. Electrochemical corrosion mechanism of welded X70 steel does not experience change upon hydrogen-charging, or stressing, or both. Hydrogen-charging is capable of enhancing the local anodic dissolution of the steel. The resistance of corrosion product layer decreases with hydrogen-charging, and heat-affected zone has the largest dissolution current upon hydrogen-charging. The increase of applied stress enhanced the anodic dissolution of welded X70 steel, especially the heat-affected zone, in near-neutral pH solution. Maximum current is observed in heat-affected zone, and increases with the increase of applied stresses. The total synergistic effect of hydrogen-charging (10 mA/cm²) and applied stress (550 MPa) on anodic dissolution of welded X70 steel in near-neutral pH solution is determined to be within the range of 5.7 and 6.5, with a maximum value encountering in heat-affected zone.     

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.     

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.     

Fe-Ni基合金在热浓碱溶液中的阳极溶解与钝化行为

采用快速与慢速动电位扫描法研究了Fe-Ni基合金在含与不含杂质的沸腾50%NaOH溶液中的阳极溶解与钝化行为.Cr、Ni对Fe-Ni基合金低电位钝化起主要作用,高电位钝化主要是Fe与Ni的作用.Na2S2O3对碱性溶液中元素Fe与Ni的阳极溶解有明显的促进作用,并加速Fe-Ni基合金的溶解导致多处新的阳极电流峰出现.Fe-Ni基合金在相同介质条件下快速扫描的电流密度值比慢扫的大,并对快、慢扫描极化曲线计算出SCC的指数值与SCC行为进行了相关分析.     

酸性土壤环境中剥离涂层下X80钢应力腐蚀行为及机理

目的研究酸性土壤环境中剥离涂层下X80管线钢应力腐蚀行为及机理。方法采用电化学极化曲线测试、慢应变速率拉伸试验和腐蚀形貌扫描电子显微镜观察,对服役于鹰潭土壤环境的X80管线钢在剥离涂层下滞留液中的应力腐蚀行为及机理进行了分析研究。结果 X80管线钢在剥离涂层下的滞留液中具有一定的SCC敏感性,应力腐蚀开裂类型属于TGSCC,敏感性较大位置为近漏点处、剥离区中下部及剥离区底部,且近漏点处滞留液体系中X80钢的SCC机理受阳极溶解(AD)机制控制,剥离区底部滞留液中SCC机理受阳极溶解+氢脆(AD+HE)的混合机制控制。结论服役于酸性土壤中的X80管线钢在外防腐涂层破损后,除开放破损处将发生腐蚀外,剥离涂层下的管线钢还会存在一定的应力腐蚀敏感性。     

Micro-electrochemical characterization of corrosion of pre-cracked X70 pipeline steel in a concentrated carbonate/bicarbonate solution

The electrochemical corrosion behavior of a stressed, pre-cracked X70 pipeline steel was studied in a bicarbonate/carbonate solution by electrochemical and micro-electrochemical measurements, numerical calculation and surface analysis technique. The effects of stress and potential on passivity, corrosion and electrochemical behavior of the steel at crack-tip were mechanistically determined. It was found that the passive film formed at crack-tip was less stable than that formed in the region ahead of the crack. Moreover, the crack-tip is more susceptible to pitting corrosion than other region of the specimen. The applied stress enhances the anodic dissolution of the steel. In particular, the stress concentration at crack-tip further increases the local anodic dissolution rate. The enhancement of the anodic dissolution of the steel at crack-tip is also resulted from the formation of a galvanic couple, i.e., the crack-tip as an anode and the surrounding region as a cathode.     

Corrosion behaviour of steel in concrete in the presence of stray current

Effects of stray current on the corrosion behaviour of steel in concrete have been studied, with regards to both corrosion initiation and propagation. Results showed that DC current can induce corrosion initiation on the reinforcement in the anodic zone only after it has circulated for a certain time, which depends on the anodic current density, the presence of chloride in the concrete and interruptions in the current. AC current proved to be much less dangerous than DC, although it can influence the corrosion rate of steel in chloride-contaminated concrete and stimulate macrocouples.     

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.     

SCC initiation for X65 pipeline steel in the “high” pH carbonate/bicarbonate solution

The initiation of stress corrosion cracking (SCC) was studied using scanning electron microscope observations of linearly increasing stress test specimens. SCC initiation from the following surfaces was studied: (i) initiation from the commercial pipe surface covered by the Zn coating, (ii) initiation from a mechanically polished surface with a deformed layer, and (iii) initiation from an electro-polished surface. SCC initiation involved different features for these surfaces as follows. (i) For the Zn coated commercial pipe surface, a crack in the Zn coating led to the dissolution of the deformed layer and when the deformed layer was penetrated, intergranular SCC initiation became possible. (ii) For a mechanically polished surface with a deformed layer, cracks in the surface oxide concentrated the anodic dissolution to such an extent that there was transgranular SCC in the deformed layer. SCC was intergranular when the deformed layer had been penetrated. Transgranular stress corrosion cracks were stopped at ferrite grain boundaries (GBs) oriented perpendicular to the SCC propagation direction. (iii) For an electro-polished surface, the surface oxide film was cracked at many locations, but intergranular SCC only propagated into the steel when the oxide crack corresponded to a GB. An oxide crack away from a GB is expected to be healed. The observed SCC initiation mechanism was not associated with simple preferential chemical attack of the ferrite GBs.     

Environmentally assisted cracking mechanism of pipeline steel in near-neutral pH groundwater

A modified Devanathan dual cell was used in environmentally assisted cracking (EAC) tests to independently control the concentration of dissolved hydrogen and anodic current density. The experimental evidence indicates that the corrosion may reduce the micro-hardness of steel, suggesting a dissolution-induced degradation of the mechanical properties in the surface layer. An EAC model is described in which surface micro-plastic deformation can be enhanced by the dissolved hydrogen and anodic dissolution, and plays a crucial role in cracking processes. The model can provide a reasonable prediction for the dependence of the cracking resistance of pipeline steel on the applied potential.     

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。     

A New Understanding of Stress Corrosion Cracking Mechanism of X80 Pipeline Steel at Passive Potential in High-pH Solutions

Susceptibilities to stress corrosion cracking(SCC) of X80 pipeline steel in relatively concentrated carbonate/bicarbonate solutions with different chloride ion concentrations or p H value at a passive potential of-200 m V vs SCE were investigated by slow strain rate tensile test.In order to explore the SCC mechanism and the evaluation criterion for the SCC susceptibility of the steel in passive state,electrochemical measurements were taken.Potentiodynamic polarization curves were obtained at different potential sweep rates,and electrochemical impedance spectroscopy measurements were taken after fast polarization to the passive potential.The effects of chloride ion and p H on SCC behaviors of X80 steel at the passive potential were also discussed.The results showed that the SCC mechanism of X80 pipeline steel was greatly influenced by the passive film formed in these solutions.The SCC behaviors followed the film suppressed anodic dissolution mechanism in these circumstances,because the filming process accounted for a considerable proportion of the overall electrode process.The criteria for evaluating the SCC susceptibility of the steel at passive potential were proposed and validated.Decreasing in the concentration of chloride ion or increasing in p H value resulted in the reduction in SCC susceptibility.The existence of chloride ion greatly lowered the passivation tendency and the film stability,while its concentration determined the dissolution rate of the steel matrix.Higher p H value was responsible for the stable and tenacious passive films and the high repassivation capability.It was also inclined to lower the anodic dissolution rate at crack tips by retarding the cathodic oxygen reduction.     

工业纯钛TA2在含硫化物深海水环境中的应力腐蚀行为

深海水环境具有静水压力大、溶氧量低、侵蚀性离子复杂等特点,使得深海水环境具有较强的腐蚀性。目前,钛及钛合金在深海环境下的腐蚀及应力腐蚀行为机理尚不清楚,这对钛合金在深海环境中的应用造成较大的威胁。文中采用电化学方法及U型弯试验研究了工业纯钛TA2在模拟深海环境下的电化学行为及应力腐蚀行为。结果表明,静水压力对TA2均匀腐蚀及阴极析氢反应均有所促进,随着静水压力增大,TA2腐蚀电流密度及析氢电流密度均增加。硫化物的加入一定程度上降低了TA2钝化膜稳定性,并对阴极析氢反应有较为明显的促进。应力腐蚀试验表明深海硫化物作用下TA2具有一定的应力腐蚀敏感性。TA2在深海条件下,虽然SCC以氢致开裂为主,但是由于氧含量与浅海等环境的不同,阳极溶解机制也是TA2在深海条件下SCC开裂的原因。     

The synergy between deformation and anodic dissolution of an austenitic stainless steel in acidic chloride solution

In corrosion medium, metals can deform under tensile stress and form a new active surface with the anodic dissolution of the metals being accelerated. At the same time, the anodic dissolution may accelerate the deformation of the metals. The synergy can lead to crack nucleation and development and shorten the service life of the component. Austenitic stainless steel in acidic chloride solution was in active dissolution condition when stress corrosion cracking (SCC) occurred. It is reasonable to assume that the anodic dissolution play an important role, so it's necessary to study the synergy between anodic dissolution and deformation of austenitic stainless steels. The synergy between deformation and anodic dissolution of AISI 321 austenitic stainless steel in an acidic chloride solution was studied in this paper. The corrosion rate of the steel increased remarkably due to the deformation‐accelerated anodic and cathodic processes. The creep rate was increased while the yield strength was reduced by anodic dissolution. The analysis by thermal activation theory of deformation showed a linear relationship between the logarithm of creep rate and the logarithm of anodic current. Besides, the reciprocal of yield strength was also linearly dependent on the logarithm of anodic current. The theoretical deductions were in good agreement with experimental results.     

304 不锈钢在模拟深海和浅海环境中的应力腐蚀行为

目的研究304不锈钢在模拟深海和浅海中的应力腐蚀开裂(SCC)行为。方法通过控制不同环境因素模拟南海某海域环境,利用动电位扫描、交流阻抗谱、慢应变速率拉伸(SSRT)及SEM表面分析等手段进行研究。结果 304不锈钢在模拟海水溶液中呈现钝化状态,出现应力腐蚀敏感性,且裂纹扩展方式为穿晶开裂。在深海中的SCC机制为氢致开裂,浅海中的SCC机制主要为阳极溶解。结论 304不锈钢在深海与浅海中的SCC机制不同,但两者的SCC敏感性相近且相对较低,在模拟海水环境中的应用不受海水深度限制。     

Corrosion of 304 stainless steel exposed to nitric acid-chloride environments

In an effort to examine the combined effect of HNO₃, NaCl, and temperature on the general corrosion behavior of 304 stainless steel (SS), electrochemical studies were performed. The corrosion response of 304 SS was bifurcated: materials were either continuously passive following immersion or spontaneously passivated following a period of active dissolution. Active dissolution was autocatalytic, with the corrosion rate increasing exponentially with time and potential. The period of active corrosion terminated following spontaneous passivation, resulting in a corrosion rate decrease of up to five orders of magnitude. The length of the active corrosion period was strongly dependent on the solution volume-to-surface area ratio. This finding, coupled with other results, suggested that spontaneous passivation arises solely from solution chemistry as opposed to changes in surface oxide composition. Increasing NaCl concentrations promoted pitting, active dissolution upon initial immersion, a smaller potential range for passivity, longer active corrosion periods, larger active anodic charge densities preceding spontaneous passivation, and larger corrosion current and peak current densities. In contrast, intermediate HNO₃ concentrations promoted active dissolution, with continuous passivity noted at HNO₃ concentration extremes. During active corrosion, increased HNO₃ concentrations increased the anodic charge density, corrosion current density, and peak current density. The time required for spontaneous passivation was greatest at intermediate HNO₃ concentrations. Susceptibility to pitting was also greatest at intermediate HNO₃ concentrations: the pit initiation and repassivation potentials decreased with increasing HNO₃ concentration until the HNO₃ concentration exceeded a critical concentration beyond which susceptibility to pitting was entirely eliminated. Increasing solution temperature increased the susceptibility to both pitting and active dissolution.