Effect of cathodic protection on corrosion of pipeline steel under disbonded coating

In this work, a test rig was developed to study the effect of cathodic protection (CP) on corrosion of X70 pipeline steel in the crevice area under disbonded coating through the measurements of local potential, solution pH and dissolved oxygen concentration. Results demonstrated that, in the early stage of corrosion of steel, CP cannot reach the crevice bottom to protect steel from corrosion due to the geometrical limitation. Corrosion of steel occurs preferentially inside crevice due to a separation of anodic and cathodic reaction with the depletion of dissolved oxygen in the crevice solution. The main role of CP in mitigation of sequential corrosion of steel in crevice under disbonded coating is to enhance the local solution alkalinity. With the increase of distance from the open holiday, a high cathodic polarization is required to achieve appropriate CP level at crevice bottom. A potential difference always exists between the open holiday area and inside crevice, reducing the CP effectiveness.     

Effect of CO2 and R-ratio on near-neutral pH stress corrosion cracking initiation under a disbonded coating of pipeline steel

This study investigates the role of CO₂ and cyclic stress R-ratio (R = minimum stress/maximum stress) on near-neutral pH SCC initiation mechanism(s) under a disbonded coating of pipeline steel protected by cathodic protection (CP). It was found that depending on CO₂ concentration and level of CP, different localized environments with various pH could be formed under the disbonded coating. When cyclic loading was applied, different SCC initiation mechanisms were involved depending on the pH of the localized environments. Reducing the R-ratio had different effects on the initiation mechanisms.     

剥离涂层下管线钢腐蚀研究进展

综述了在有阴极保护的条件时剥离涂层下缝隙内电位电流的分布和化学环境的变化、阴极保护防止缝隙腐蚀的机理、微生物腐蚀的机理以及前人提出的关于剥离涂层下微生物腐蚀与阴极保护相互作用的规律，并展望了对于解决剥离涂层下微生物腐蚀难题需进一步的实验研究.     

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。     

Local environment under simulated disbonded coating on steel pipelines in soil solution

Taking advantage of microelectrode technique, the local potential and pH in a crevice simulating disbonded coating on X70 pipeline steel were investigated as a function of cathodic protection (CP) in a near neutral pH soil bulk solution bubbled with 5% CO₂/N₂ gas. The experimental potential–pH (E–pH) diagrams were established for the steel in the crevice. Stress corrosion cracking (SCC) susceptibility of the steel in the local environment in the crevice was analyzed based on the experimental E–pH diagrams. The results showed that the local steel potential in the deep of the crevice was independent on CP potential applied at the opening. Due to the effect of the atmospheric CO₂, a near-neutral pH local environment promoting near-neutral pH SCC (also known as transgranular SCC, TGSCC) might be harbored in the crevice even with normal CP at the opening. During CP interruption, the steel potential decay and CO₂ absorption (pH decrease) might shift E–pH points into a susceptibility region of near-neutral pH SCC.     

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.     

Electrochemical polarization behavior of X70 steel in thin carbonate/bicarbonate solution layers trapped under a disbonded coating and its implication on pipeline SCC

Potentiodynamic polarization measurements were performed on X70 pipeline steel in thin carbonate/bicarbonate solution layers trapped under a disbonded coating. A conceptual model was developed to illustrate the effects of the thickness and concentration of the trapped solution layer, cathodic protection (CP) potential and stress on stress corrosion crack initiation and propagation in pipelines. It was found that the passivity of the steel depended on the solution layer thickness, and the passive current density decreased with the thinning of the solution layer. With an increasing solution concentration, the role of the solution layer thickness in the steel passivity became unapparent, which was attributed to a strong passivating ability of bicarbonate and carbonate ions. Furthermore, with the decrease of the solution layer thickness, the pitting potential was shifted negatively. However, an increase of the solution concentration enhanced the resistance of the steel to pitting. A pre-application of CP would degrade the passivity of the steel due to the hydrogen-enhanced activity of the steel. Moreover, an applied stress shifted the pitting potential negatively, and decreased the passive potential range.     

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.     

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.     

Stress corrosion cracking of gas pipelines - Effect of surface roughness, orientations and flattening

The primary corrosion mitigation of the external surface of high pressure steel gas pipelines is protective coatings with secondary protection usually by cathodic protection. Adhesion and resistance to cathodic disbondment of the coating is critical for its integrity and grit blasting is an important process in achieving this adhesion. The effect of surface roughness, from grit blasting, on the intergranular stress corrosion cracking resistance of X70 gas pipelines was investigated using slow strain rate testing in carbonate/bicarbonate solution at 75 °C. The effect of orientation of test pieces with respect to the axial direction of pipes was also investigated.Time to failure ratios decreased with increasing surface roughness indicating reduced stress corrosion cracking resistance. The reduced resistance to cracking with increasing roughness would be predominantly associated with stress concentration effects related to the surface roughness resulting from the grit blasting. Crack concentration decreased with increasing roughness, which is likely to be associated with the concentration of surface damage from the grit blasting using varying sized grit. As formed pipe surfaces, with no grit blasting, resulted in some of the lowest time to failure ratios and hence some of the lowest resistances to stress corrosion cracking. These also showed some of the deepest cracks. The influence of roughness and residual stresses on threshold stress is currently being investigated.Time to failure ratios indicated a greater resistance to stress corrosion cracks for circumferentially orientated test pieces compared to those longitudinally orientated. Whilst further testing would be required for confirmation, the current results suggest that flattening the test pieces had only a minor, if any, effect on stress corrosion cracking susceptibility as measured by slow strain rate testing to fracture.     

X80管线钢在近中性pH溶液中腐蚀行为研究

目的研究X80管线钢在近中性p H溶液中的腐蚀与应力腐蚀裂纹萌生行为。方法采用电化学实验和浸泡实验研究X80管线钢在近中性p H溶液中的腐蚀行为,采用慢应变速率拉伸实验研究X80管线钢在近中性p H溶液中,在自腐蚀电位和外加电位下的应力腐蚀裂纹萌生行为。结果 X80管线钢在近中性p H溶液中的极化曲线只有活化区,没有钝化区,其自腐蚀电位约为-750 m V,浸泡195天后,试样表面没有氧化膜出现,但是观察到点蚀坑。在自腐蚀电位下,X80管线钢试验表面有大量的应力腐蚀裂纹;在-500 m V阳极外加电位下,X80管线钢试验表面几乎没有观察到应力腐蚀裂纹;在-850 m V阴极外加电位下,X80管线钢试验表面的应力腐蚀裂纹很少,但是随着外加阴极电位负移到-1300 m V时,X80管线钢试验表面的应力腐蚀裂纹增多。结论 X80管线钢在近中性p H溶液中发生均匀腐蚀,但是夹杂物剥落能在X80管线钢表面形成点蚀坑。在近中性p H溶液中,在自腐蚀电位下,X80管线钢应力腐蚀裂纹萌生敏感性最强;外加阴极电位抑制应力腐蚀裂纹萌生,但是随着外加阴极电位的负移,应力腐蚀裂纹萌生敏感性增强;外加阳极电位下,由于均匀腐蚀的作用,应力腐蚀裂纹萌生敏感性较弱。     

X100管线钢在酸性土壤模拟溶液中的应力腐蚀行为

采用慢拉伸(SSRT)、动电位极化和SEM观察等方法,研究了在不同的阴极保护电位条件下X100钢在酸性土壤模拟溶液中的应力腐蚀行为.结果表明,X100钢发生穿晶裂纹的应力腐蚀,裂纹的萌生和发展与阴极保护电位有关.完全阳极过程控制时,X100钢无裂纹出现,但出现晶间腐蚀;在混合过程控制时,应力腐蚀敏感性较低,裂纹发展缓慢;在完全阴极过程控制时,氢脆机制起主要作用,裂纹扩展迅速.     

Modeling pipeline crevice corrosion under a disbonded coating with or without cathodic protection under transient and steady state conditions

Underground steel pipelines are protected by coatings and cathodic protection (CP). The pipeline corrosion occurs when the coating is disbonded away from a defect or holiday to form a crevice and the corrosion rate varies temporally and spatially in the crevice. In the presence of dissolved oxygen (O₂) in soil ground water, a differential O₂ concentration cell may develop in the crevice because O₂ diffuses more readily into the crevice through the holiday than through the disbonded coating. CP can decrease or eliminate the O₂ concentration cell depending on the potential applied at the holiday. Since the coatings are usually non-conductive, CP is unable to protect the steel surface deep inside the crevice. The transport of dissolved O₂, and that of dissolved carbon dioxide (CO₂) if present, into the crevice through holiday can be key to determining the crevice corrosion rate. In this work, the transient and steady state behavior of the corrosion process is investigated. The effect of the cathodic portion of iron vs. ferrous ion redox reaction on the crevice corrosion rate, which is often neglected traditionally, is further studied. At steady state, the effect of dissolved O₂ on the crevice corrosion rate and the added effect of dissolved CO₂ are mathematically modeled.     

弹塑性应力作用下X80管线钢的菌致开裂行为

目的 揭示硫酸盐还原菌（SRB）在管线钢表面裂纹萌生中的作用。方法 采用恒载荷实验装置施加弹性和塑性应力,通过XPS和EDS分析产物成分,利用SEM观察微生物膜形态、管线钢腐蚀形貌,研究弹性和塑性应力作用下管线钢的微生物致裂裂纹萌生和扩展行为。结果 弹性和塑性应力对SRB生长无明显影响。不管是在弹性应力还是塑性应力作用下,SRB生理活动均改变了腐蚀产物的结构,增加了腐蚀产物的硫含量,提高了管线钢局部腐蚀敏感性。与弹性应力作用相比,塑性应力和SRB协同作用对管线钢微裂纹萌生和扩展的影响更大。塑性应力作用下,灭菌和接菌环境中管线钢表面均产生了微裂纹分叉。结论 弹性应力和塑性应力均促进了管线钢的微生物腐蚀过程。塑性应力作用下管线钢菌致开裂更加剧烈,裂纹扩展过程与SRB生理活动有关。     

Study on H2S stress corrosion test of welded joint for X65pipeline steel and numerical analysis

The susceptibility of welded joint for the X65 pipeline steel to H2S stress corrosion cracking (SCC) is investigated.SCC tests on the steel are carded out in the environment based on NACE TM-O1-77 solution with saturated gaseous H2S. The threshold stress intensity factor and crack propagation velocity are calculated according to wedge-opening loading (WOL)specimens. The three-dimensional elastic-plastic finite element analysis of WOL specimens is pesformed by using the FEM programming package ANSYS. Stress field and concentration of hydrogen distribution property ahead of the crack tip are obtained. This paper surveyed the microstructure of welded joint and studied on the mechanical properties of X65 pipeline steel.It provides experimental basis for studying stress corrosion. The results of numerical analysis are consistent with conclusions of stress corrosion test.     

油气管线钢土壤环境硫酸盐还原菌腐蚀研究进展

结合国内外埋地管线钢微生物腐蚀的研究,综述了腐蚀性土壤微生物种类和特点、环境因素对硫酸盐还原菌腐蚀的影响、生物腐蚀研究方法和进展,以及微生物腐蚀防护与监检测技术.最后,对埋地管线钢微生物腐蚀研究进行了展望.埋地管线钢服役环境复杂,受到土壤类型、杂散电流、阴极保护、应力、剥离涂层和微生物等多种因素的影响,而各种因素之间又存在着相互的耦合作用.多因素耦合作用下埋地管线钢微生物腐蚀将成为土壤微生物腐蚀今后的主要研究方向.土壤微生物腐蚀研究涉及土壤学、材料学、腐蚀科学和微生物学等多学科,是一个多学科交叉的研究课题,而化学和电化学分析技术、微生物分析技术以及材料表征技术等的联用也将为土壤微生物腐蚀行为和机制的研究提供更多的研究方法,这也有助于更好地理解微生物/材料之间的相互作用机制.随着对微生物腐蚀研究的深入,人们对硫酸盐还原菌腐蚀机理的认识也更加全面,"生物阴极催化还原"理论从生物能量学和生物电化学角度解释了微生物腐蚀的过程和机理.抗菌涂层开发和耐微生物腐蚀管线钢研发为MIC防治提供了一个新的研究路径.     

Peculiarities of the Corrosion Protection of Steel Underground Pipelines

The topics of enhancing the corrosion protection efficiency of pipelines are examined. Improuving the quality of the protective coatings enables one to preclude corrosion under the disbonded insulation, as well as the stress corrosion cracking, but causes the increase in the stray-current corrosion and other undesirable effects that are easily removed with the aid of electrochemical protection. Checking the insulation of pipelines upon completed construction by cathodic polarization ensures the reproducibility of the design parameters of the cathodic protection. The topics of the influence of insulating components, as well as protective and anodic groundings, on the effectiveness of corrosion protection are considered.     

Characterization of corrosion of X65 pipeline steel under disbonded coating by scanning Kelvin probe

Corrosion of X65 pipeline steel under a disbonded coating was studied by scanning Kelvin probe measurements. Three types of specimen were designed and prepared to investigate the effects of immersion time, oxygen concentration and wet-dry cycle on Kelvin potential profile and thus corrosion behavior of the steel. Kelvin potential measured on “intact” area is shifted negatively with time, indicating an increasing water uptake under the “intact” coating. With the increase of the amount of solution, it is expected that the electrolyte concentration and electrochemical reaction rate change, resulting in a significant decrease of interfacial potential. Moreover, there is a more negative Kelvin potential on disbonded area than that on “intact” area. The negative shift of Kelvin potential is attributed to corrosion reaction of steel occurring under the disbonded coating. Due to the narrow geometry of coating disbondment, an oxygen concentration difference exists along the depth of the disbondment. The corrosion behavior under disbonded coating strongly depends on the oxygen partial pressure and local geometry. With continuous purging of nitrogen and removing of oxygen, Kelvin potential tends to be identical throughout the disbonded area. During wet-dry cycle, the thickness of solution layer trapped under disbonded coating decreases due to evaporation of water. With the decrease of solution layer thickness, the measured Kelvin potential decreases, indicating that the effect associated with the reduction of oxygen solubility in the concentrated solution during drying of electrolyte is favored over that related to the enhanced oxygen diffusion and reduction. There exists a critical thickness of solution layer, below which the oxygen solubility is sufficiently low to support the electrochemical corrosion reaction of steel.     

X65管线钢焊接接头H2S应力腐蚀研究及其有限元数值分析

在X65管线钢H2S应力腐蚀试验的基础上，建立了三维弹塑性有限元模型．通过三维弹塑性有限元的数值分析，得到了裂纹尖端应力场分布和氢浓度的分布特征．通过对X65管线钢焊接接头的显微组织观察和基本力学性能研究，对影响其应力腐蚀影响因素提供了实验依据．并根据楔形张开加载恒位移试样得出了X65管线钢焊接接头的临界应力强度因子KISCC和裂纹扩展速率，其应力腐蚀试验结果在有限元数值分析中得到了验证。     

土壤环境中管线钢硫酸盐还原菌腐蚀

腐蚀是世界各国共同面临的问题之一,每年因腐蚀造成的经济损失占全国GDP的3%~5%,其中土壤腐蚀约占总腐蚀的20%。金属的土壤腐蚀是一种自发的冶金逆过程,它不仅会导致埋地金属构筑物腐蚀破坏,还会引发管线泄漏、燃烧和爆炸等事故,给社会带来巨大的经济损失和社会危害。微生物腐蚀是埋地管线钢腐蚀的重要腐蚀类型之一,其中以硫酸盐还原菌引起的腐蚀最为严重。从环境因素、材料因素和微生物因素三个方面,对土壤环境中管线钢硫酸盐还原菌腐蚀进行了简要概述。埋地管线钢微生物腐蚀研究最多的是环境因素的影响,包括土壤类型、土壤含水量、土壤阴离子、化肥、农药、土壤宏电池和剥离涂层。材料因素的研究多集中在阴极保护、外加应力和杂散电流等因素的影响。相比前两种影响因素,微生物因素最为复杂,也是研究最少的一个方面。微生物因素的研究是一个全新的研究领域,包括膜内生物酶的影响以及膜内电子传递等。今后一段时间,埋地管线钢微生物腐蚀仍以环境和材料因素等多因素的耦合作用为主要研究方向。