Effects of Plastic Deformation and Carbon Dioxide on Corrosion of Pipeline Steel in Near-Neutral pH Groundwater

This paper investigates the effect of plastic deformation on the anodic dissolution behavior of pipeline steel in deaerated groundwater with near-neutral pH. The plastic deformation is introduced via two different ways: cold-rolling and in situ tension. It is observed that the cold-rolling prior to the exposure to corroding environment reduces the corrosion rate but the in situ tension increases corrosion rate slightly. In accord with thermodynamic analysis, the impacts of residual stresses and plastic deformation on active dissolution are very small except a highly non-uniform dislocation structure is formed. A preliminary analysis suggests that the reduced corrosion rate of cold-rolled steel is related to competitive adsorption of CO₂ and H⁺ on the active sites over the surface.     

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.     

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。     

Synergistic Effects of Hydrogen and Stress on Corrosion of X100 Pipeline Steel in a Near-Neutral pH Solution

In this work, scanning vibrating electrode technique and local electrochemical impedance spectroscopy measurements were used to investigate the effects of stress and hydrogen on electrochemical corrosion behavior of a X100 pipeline steel in a near-neutral pH solution. The stress distribution on the test specimen was calculated using the finite element method. Results demonstrated that the hydrogen-charging enhances the local anodic dissolution of the steel, contributing to the formation of a layer of corrosion product. However, there is little difference of the charge-transfer resistance between the regions with and without hydrogen-charging due to rapid diffusion of hydrogen atoms throughout the specimen with time. When the local stress concentration is not significant enough to approach the yielding strength of the steel, the steel is still in a relatively stable state, and there is a uniform distribution of dissolution rate over the whole surface of the steel specimen. Although the stress-enhanced activation is not sufficient to result in an apparent difference of current density of the steel, the activation of the steel would activate dislocations, which serve as effective traps to the charged hydrogen atoms. With the increase of hydrogen concentration, the hydrogen-enhanced anodic dissolution becomes dominant.     

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.     

氢对X80钢焊接接头在近中性pH值溶液中腐蚀行为的影响

采用动电位极化和电化学阻抗技术研究了电化学充氢后X80钢母材和焊缝在近中性pH值溶液中的电化学行为,并结合光学显微镜对试样充氢前后的形貌进行了观察,测量了母材和焊缝的放氢量。结果表明,电化学充氢并没有改变钢的组织结构;相同电化学充氢条件下,焊缝比母材吸收更多的氢。在近中性pH值溶液中,未充氢时母材比焊缝有更好的耐蚀性能。充氢促进母材和焊缝在近中性pH值溶液中的阳极溶解。随充氢时间增加,母材和焊缝的自腐蚀电位负移,腐蚀电流增大,腐蚀产物膜电阻和极化电阻减小,母材与焊缝电化学腐蚀行为均加剧。充氢后焊缝中位错缺陷浓度高,对氢起钉扎作用的,使焊缝的耐蚀性大于母材。     

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.     

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.     

Corrosion of Welded X100 Pipeline Steel in a Near-Neutral pH Solution

In this work, electrochemical corrosion behavior of a welded X100 pipeline steel was studied in a near-neutral pH solution by electrochemical scanning vibrating electrode technique combined with metallographic and scanning electron microscopy/energy dispersive x-ray analysis. Results demonstrated that a softening phenomenon occurs around the weld, and there is the high micro-hardness in base steel adjacent to weld. In particular, there is the highest micro-hardness in base steel containing acicular ferrite and bainite. Therefore, welding and the associated post-treatment on X100 steel alter dramatically the microstructure and mechanical property around weld, resulting in an enhanced micro-hardness in base steel. There are high and low local dissolution current densities at base steel and the welded zones, respectively. The difference between the maximum and minimum dissolution current densities decreases with time, and the distribution of dissolution current density tends to be uniform. Hydrogen-charging changes the local dissolution activity of the welded steel. Different from the hydrogen-free steel, there is the highest dissolution current density at heat-affected zone. It is reasonable to assume that the charged hydrogen would accumulate at heat-affected zone, and the synergism of hydrogen and local stress results in a high anodic dissolution rate.     

Effect of Strain Rate on Cathodic Reaction During Stress Corrosion Cracking of X70 Pipeline Steel in a Near-Neutral pH Solution

The effect of strain rate on cathodic reactions of X70 pipeline steel during stress corrosion cracking in a near-neutral pH solution was investigated by electrochemical impedance spectroscope and potentiodynamic polarization curve measurements as well as slow strain rate tests. A local additional potential model was used to understand mechanistically the role of strain rate in electrochemical cathodic reaction. It was found that an application of elastic stress would not affect the electrochemical stable state of the steel specimen at a macroscopic scale. Under a weak cathodic polarization, the interfacial charge-transfer process occurring on steel contains both cathodic and anodic reactions. Since the anodic reaction process is still significant, localized dissolution could occur even at such a cathodic potential, resulting in generation of corrosion pits. These pits could be the start sites to initiate stress corrosion cracks. Strain rate affects the corrosion reaction, which is associated with the generation of dislocation emergence points and slip steps on the specimen surface, resulting in a negative local additional potential to enhance the cathodic reaction locally.     

Electrochemical corrosion behavior of X80 pipeline steel in a near‐neutral pH solution

In this work, the electrochemical corrosion behavior of X80 pipeline steel was investigated in a near‐neutral pH solution using electrochemical impedance spectroscopy (EIC) and photo‐electrochemical (PEC) measurements as well as X‐ray photo‐electron spectroscopy (XPS) technique. The effects of hydrogen‐charging and stress were considered. The results show that the steel is in an active dissolution state, and a layer of corrosion product is formed and deposited on the electrode surface, which is subjected to further oxidation to form ferric oxide and hydroxide. Photo‐illumination enhances anodic dissolution of the steel when it is under anodic polarization due to destroying of the corrosion product film. When the steel is under cathodic polarization, the cathodic current density decreases upon laser illumination due to the photo‐oxidation of hydrogen atoms generated during cathodic reactions, which behaves as an anodic reaction to offset the cathodic current density. Hydrogen‐charging and stress decrease the corrosion resistance of the steel and enhance the dissolution rate of the steel.     

Mechanistic aspect of near-neutral pH stress corrosion cracking of pipelines under cathodic polarization

This paper investigates mechanistically stress corrosion cracking (SCC) of an X70 pipeline steel that is under cathodic protection (CP) in a near-neutral pH solution. It was found that there is a critical potential range, i.e., ?730 and ?920 mV_SCE, where the steel is in a non-equilibrium electrochemical state, and anodic dissolution (AD) reaction may occur when the steel is polarized cathodically. When the applied potential is more positive than this range, SCC is AD-based; while the applied potential is more negative, SCC of pipelines is under hydrogen embrittlement (HE) mechanism. When the polarization potential is within the range, SCC of the steel is under the combined effect of AD and HE. Therefore, AD may still occur on pipeline steel that is under CP with the potential within this critical range, contributing to the cracking process.     

应变速率对管线钢近中性pH值环境敏感开裂的影响

以X-70管线钢近中性pH值溶液(NS4和实际土壤溶液)为研究对象,研究了恒载荷、慢应变速率拉伸(SSRT) 和循环蓑荷等不同条件下的环境开裂行为.结果表明,在该体系中局部应变速率是联系各种不同断裂过程的纽带,决定着断裂的模式.当该局部应变速率低于发生应力腐蚀开裂(SCC)敏感局部应变速率的上限(即5×10-5 s-1)时, SCC才能够发生;在循环载荷作用下,当该局部应变速率高于此上限时,将发生力学因素起主导作用的腐蚀疲劳(CF)开裂;该局部应变速率继续升高时,将发生机械断裂.对X-70管线钢在近中性pH值的环境开裂,不论开裂过程是溶解或(和)氨的作用占主导,均受局部应变速率控制.在通常遇到的现场服役条件下, X-70管线钢在近中性pH值溶液中的开裂模式是SCC,不是CF,应称之为“近中性pH值应变促进腐蚀开裂”,实质上这是一种由局部应变速率决定的环境开裂行为.     

X70管线钢在不同温度近中性pH溶液中的应力腐蚀破裂行为

采用慢应变速率实验(SSRT)研究了不同温度和电位下X70管线钢在近中性pH溶液中的应力腐蚀破裂(SCC)行为．结果表明，不同温度下，X70管线钢在近中性pH溶液中的开裂方式都是穿晶型的，具有准解理特征，并且随着外加阴极电位的降低，SCC敏感性增加，氢致开裂占主导．随温度的下降，溶液pH值略有降低，SCC敏感性增加。     

氢在钢的硫化物应力腐蚀破裂中的作用

本文研究了12MnMoVNbTi低合金钢在饱和H_3S溶液中的极化和应力腐蚀行为,并与电解充氢条件下的应力破裂行为进行了对比。证明钢中Mo、Nb含量的变化与热处理条件的不同对其一般腐蚀行为影响很小,但能显著改变其抗应力腐蚀性能,12MnMoVNbTi钢在H_2S介质中的应力腐蚀破裂行为与它们在充氢条件下的应力破裂行为非常类似,显示其应力腐蚀破裂的实质是氢脆。充氢条件下应力弛豫和恒载荷拉伸试验结果表明,氢有引起钢的软化和硬化的双重作用。由于氢的进入所产生的软化作用使钢在屈服强度以下发生塑性变形,但随后的硬化过程又使变形速度逐步减慢。这种由氢的作用引起的在较低应力下发生的塑性变形过程并不直接导致断裂,但塑性变形行为和氢应力破裂行为之间的关系表明,这种变形过程中的位错运动能够帮助氢的移动和向塑变区及裂纹尖端集中,促进氢脆断裂。     

Effect of corrosion medium composition on rate of crack growth in X70 pipeline steel

The growth rates of corrosion cracks in X70 pipeline steel are determined in weakly acidic (pH 5.5) buffer solution with additives of a number of compounds that are a part of the soil electrolyte or are steel corrosion inhibitors. It is shown that the effect of components of electrolyte on the rate of crack growth agrees fairly well with their stimulating or inhibiting effect on the anodic dissolution of iron. The rates of hydrogen permeation into steel are measured and the effect of hydrogen absorbed by the metal on the anodic process in the studied corrosion media is considered.     

不同外加电位下 X80 管线钢在近中性 pH 溶液环境中的裂纹扩展行为研究

目的研究不同外加电位下,X80管线钢在近中性p H溶液环境中的裂纹扩展行为。方法对X80管线钢紧凑拉伸试样进行近中性p H溶液环境中的循环加载试验,利用拍摄装置记录不同循环次数下的裂纹长度,并利用扫描电镜(SEM)观察裂纹扩展面上的微观形貌。研究不同外加电位下,X80钢在近中性p H溶液环境中的裂纹扩展速率,分析其裂纹扩展规律。结果在开路条件下,循环加载755次时,裂纹扩展4.6 mm后失稳断裂;在外加电位为-775 m V(vs.SCE)的条件下,循环加载671次时,裂纹扩展3.677 mm后失稳断裂;在外加电位为-1125 m V(vs.SCE)的条件下,循环加载625次时,裂纹扩展3.882 mm后失稳断裂。结论在开路电位和弱阴极电位下,裂纹扩展受到阳极溶解机制和氢脆机制的混合控制,以阳极溶解机制为主,裂纹扩展速率均较低;随着外加电位降低,裂纹扩展机制逐渐过渡为主要受氢致开裂作用控制,裂纹扩展速率显著增加。     

The role of residual stress in neutral pH stress corrosion cracking of pipeline steels – Part II: Crack dormancy

This investigation provides a quantitative analysis of the effect of Type I residual stresses on the occurrence of pitting and stress corrosion cracking (SCC) formation in pipeline steel exposed to neutral pH aqueous environments. It has been shown that SCC generated in neutral pH environments can be readily blunted due to plastic deformation (room temperature creep) and/or extensive anodic dissolution. As a result, a high positive tensile residual stress gradient is necessary for continued growth of SCC in pipeline steels exposed to this neutral pH environment. The tensile residual stress represents a large mechanical driving force for crack nucleation and short crack growth. Active cracks may become dormant as the near-surface residual stress gradient changes, due to self-equilibration, from highly tensile to a lower tensile state or to a compressive state. The change in residual stress level can occur within 1 mm of the surface, resulting in a large proportion of dormant SCC.     

电化学充氢条件下TWIP钢应力腐蚀敏感性的研究

通过慢应变速率拉伸和观察断口形貌等方法,研究了TWIP钢在电化学充氢条件下的应力腐蚀敏感性.结果表明,在电化学充氢条件下,TWIP钢具有应力腐蚀敏感性.恒定应变速率6.67×10-6 s-1时,具有单向奥氏体结构的TWIP钢有较小的应力腐蚀敏感性,具有形变孪晶的TWIP钢有较高的应力腐蚀敏感性.这是因为孪晶的形成导致氢在局部浓度更高,因而促进了局部塑性变形,降低了内氢压,导致TWIP钢的应力腐蚀敏感性上升.     

Simulation of crack growth during hydrostatic testing of pipeline steel in near-neutral pH environment

The objective of this investigation was to understand the role of crack dimension, hydrogen, room-temperature creep and loading procedure on crack growth during hydrostatic testing of pipeline steels in near-neutral pH aqueous soil environments. Crack growth was found during hydrotesting, but was not linearly related to the stress intensity factor at the crack tip. Crack growth is mainly driven through the internal-hydrogen-assisted-cracking mechanism, instead of the hydrogen-environmental-assisted-cracking mechanism. Excessive plastic deformation induced by room-temperature creep prior to hydrotesting reduces crack advance during hydrotesting. Lower loading rate generally induces larger crack growth by hydrostatic loading. More crack growth occurs during loading in high stress regime.