Localised corrosion of cathodically protected pipeline steel under the effects of cyclic potential transients

Cathodic protection (CP) may lose its effectiveness for protecting buried steel pipeline from soil corrosion due to the effects of potential excursions caused by stray currents. In this work, dynamic localised corrosion processes of buried steel due to the effects of cyclic potential transients have been visualised using an electrochemically integrated multi-electrode array, often referred to as the wire beam electrode (WBE). The focus has been on the understanding of the effect of cathodic transients. The WBE maps suggest that the amplitude of cathodic transient, as well as the ratio of anodic cyclic to cathodic cyclic, can significantly affect the corrosion rates and patterns. In particular, if the cathodic transient leads to a very negative potential, e.g. ?1350?mV_vs.CSE, rapid corrosion would occur on buried steel surface. These results have implications for CP parameter selection for preventing stray current-affected buried steel pipelines.     

Novel corrosion experiments using the wire beam electrode. (IV) Studying localised anodic dissolution of aluminium

An electrochemically integrated multi-electrode array namely the wire beam electrode (WBE) has been applied in novel experiments to study the anodic dissolution behaviour of aluminium (AA1100), which was exposed to corrosive media with and without the presence of corrosion inhibitor potassium dichromate. The objective of this work is to demonstrate the applicability of the WBE for investigating corrosion processes under anodic polarisation. Anodic current measurements and mapping have been made, for the first time, with the WBE surface being anodically polarised. Pitting potential as well as anodic dissolution profile has been successfully determined by mapping anodic dissolution currents over the anodically polarised WBE surface. The pitting potential determined using the WBE method was found to correlate well with that determined using the conventional pitting scan method; and the anodic dissolution profile determined using the WBE method was found to correlate with maps obtained using the scanning reference electrode technique (SRET). Potassium dichromate was found to significantly affect the pitting potential, anodic dissolution profile and pitting initiation characteristics of aluminium. Two mechanisms of localised corrosion initiation have been identified. For WBE surface under free corrosion or low anodic polarisation conditions, the initiation of localised corrosion was found to be due to the disappearance of minor anodes, which lead to accelerated dissolution of a few major anodes. For WBE surface under large anodic polarisation, the initiation of localised corrosion was found to be due to the formation of active new anodic sites. This work suggests that the WBE method is useful for understanding the electrochemical behaviour of localised anodic processes, and their dependence on externally controllable variables.     

Novel corrosion experiments using the wire beam electrode: (III) Measuring electrochemical corrosion parameters from both the metallic and electrolytic phases

The wire beam electrode (WBE) and the scanning reference electrode technique (SRET) have been applied in a novel combination to measure, for the first time, electrochemical parameters simultaneously from both the metallic and electrolytic phases of a corroding metal surface. The objective of this work is to demonstrate the application of this combined WBE-SRET method in obtaining unique information on localised corrosion mechanism, by investigating typical corrosion processes occurring over a mild steel WBE surface exposed to the classic Evans solution. The WBE method was used to map current and potential distributions in the metallic phase, and the SRET was used to map current or potential distribution in the electrolytic phase. It has been found that the combined WBE-SRET method is able to gain useful information on macro-cell electrochemical corrosion processes that involve macro-scale separation of anodes and cathodes. In such macro-cell corrosion systems, maps measured using WBE and SRET were found to correlate with each other and both methods were able to detect the locations of anodic sites. However the movement of the scanning probe during SRET measurements was found to affect the SRET detection of cathodic sites. In micro-cell corrosion systems where the separation of anodic and cathodic sites were less distinct, SRET measurement was found to be insensitive in detecting anodic and cathodic sites, while the WBE method was still able to produce results that correlated well with observed corrosion behaviour. Results obtained from this work suggest that the WBE-SRET method is applicable for understanding the initiation, propagation and electrochemical behaviour of localised corrosion anodes and cathodes, and also their dependence on externally controllable variables, such as solution pH changes and the existence of surface coatings.     

Organic molecules showing the characteristics of localised corrosion aggravation and inhibition

The behaviour of imidazoline and an acid functionalised resorcinarene as steel corrosion inhibitors in carbon dioxide (CO₂)-saturated brine solutions has been studied using an electrochemically integrated multi-electrode array namely the wire beam electrode (WBE). Both imidazoline and resorcinarene acid provided excellent inhibition to general CO₂ corrosion; however imidazoline was found to aggravate localised corrosion by creating a small number of major anodes that focused on a small area of the WBE surface, leading to highly concentrated anodic dissolution. The resorcinarene acid showed distinctively different behaviour by generating a large number of minor anodes randomly distributing over the WBE surface, leading to insignificant general anodic dissolution. These results indicate that resorcinarene acid provided effective localised corrosion inhibition by promoting a random distribution of insignificant anodic currents.     

Novel corrosion experiments using the wire beam electrode. (I) Studying electrochemical noise signatures from localised corrosion processes

This series of papers presents four novel experiments that were designed to study localised corrosion phenomena using an electrochemically integrated multi-electrode array namely the wire beam electrode (WBE). This present paper reports a WBE based experimental method that has been employed, for the first time, to study electrochemical noise patterns (called noise signatures) from localised corrosion processes. The objective of this work is to demonstrate the applicability of the WBE for investigating the origin of spontaneous electrode potential/current fluctuations and their effects on electrochemical processes. The key strategy of this work is to apply the WBE in a novel experimental set-up to simultaneously measure electrode potential noise and WBE current distribution maps--an approach that allows the direct comparison and correlation of electrochemical noise and corrosion events. Preliminary experiments have been carried out using a classic pitting corrosion system: stainless steel in a solution containing FeCl₃. A large number of anodic sites were found to exist on WBE surface at the very beginning of its exposure to the corrosion environment. Correlation between characteristic patterns in electrode potential noise and corrosion behaviour has been observed. More specifically, the characteristic sharp peaks in potential noise data (called noise signature I) were found to correlate with the sudden disappearance of single unstable anode in WBE current distribution maps. The characteristic noise pattern of quick potential changes followed by partial or no recovery (called noise signature II) was found to correspond with the massive disappearance of minor anodes in WBE current distribution maps. This result suggests that, in the corrosion system under study, electrode noise activities were associated with the disappearance of minor anodic sites, which lead to the eventual disappearance of most anodic sites. Localised corrosion was the result of the accelerated anodic dissolution of a small number of remaining anodic sites. The characteristics features in electrochemical noise and in WBE maps were reproducible.     

Characterising localised corrosion inhibition by means of parameters measured by an electrochemically integrated multielectrode array

Electrochemical parameters including maximum anodic current density, total anodic current density, the number of anodic sites and the localised corrosion intensity index have been extracted from galvanic current distribution maps that were acquired using an electrochemically integrated multielectrode array, namely, the wire beam electrode. Experiments have been carried out to demonstrate the application of these new electrochemical parameters for characterising localised corrosion inhibition of metals. A typical corrosion inhibitor, potassium dichromate, was found to affect localised corrosion processes in various ways, for instance in sodium chloride solutions, it was found to inhibit localised corrosion of aluminium alloy AA 2024-T3 by suppressing galvanic corrosion activities occurring over the alloy surface, whereas it was found to control localised corrosion of AA 1100 by creating a large number of minor anodes distributing randomly over the metal surface.     

A new method of studying buried steel corrosion and its inhibition using the wire beam electrode

An electrochemically integrated multi-electrode system namely the wire beam electrode (WBE) has been applied for the first time to study corrosion of mild steel buried in sand, with and without the presence of corrosion inhibitor potassium dichromate (K₂Cr₂O₇). Measurements of galvanic current distribution maps have been carried out during the exposure of the WBE to dry, damp and chlorinated sand environments. Characteristic changes in galvanic current distribution maps have been observed during the initiation and propagation of localised corrosion. Specifically, during corrosion initiation in damped sand, new anodes were found to initiate and corrosion appeared to be in general form. When the WBE was later exposed to chlorinated sand, massive disappearance of anodic sites was found to occur, resulting in accelerated anodic dissolution of a small number of remaining anodic sites. Addition of corrosion inhibitor K₂Cr₂O₇ to the sand environment was found to significantly reduce galvanic current only after an initial increase in galvanic current. This result suggests that K₂Cr₂O₇ behaved as an anodic inhibitor.     

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.     

X65管线钢在模拟土壤中的腐蚀行为

以华南某地酸性土壤为参考土壤体系,采用硅藻土模拟土壤实验室加速腐蚀法,应用X射线衍射仪、扫描电镜、电化学工作站等系统研究了X65管线钢在模拟土壤腐蚀环境介质中埋地腐蚀不同周期的腐蚀行为。结果表明:在该模拟土壤环境中X65管线钢表面腐蚀形貌由不均匀的点蚀发展为较为均匀的全面腐蚀,电化学极化曲线表现为阳极活化控制,自腐蚀电位出现正移,腐蚀产物主要由α-FeOOH、Fe_3O_4、Fe_2O_3等组成。     

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.     

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.     

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。     

对相钢在流动中性含砂氯化物中的磨损腐蚀

研究了双相钢在流动含砂的3．5％NaCl溶液中的磨损腐蚀规律,测定、分析了流动体系中的电化学阻抗谱,揭示了双相钢磨损腐蚀过程中电化学的作用及其机制。结果表明,腐蚀曜 磨损腐蚀过程中起主要作用,流体力学因素只是加速了腐蚀电化学过程,阻抗谱在低频区出现一直线段和低频收缩现象。分别是双相钢在磨损腐蚀过程中电极处于自钝化状态,并受离子在钝化膜中的扩散、迁移过程控制和电极表面局部遭受破坏的特征,对于流动体系中电化学阻抗谱的分析,曹氏阻抗理论同样适用。     

A novel experimental arrangement for corrosion study of X60 pipeline steel weldments at turbulent flow conditions

Electrochemical noise (EN) measurements were carried out to study the effect of turbulent flow conditions on corrosion kinetic of API X60 pipeline steel weld immersed in synthetic seawater. In order to control the hydrodynamic conditions, two rotating cylinder electrodes were used. The EN data were analysed by three different statistical methods: currents transients, noise resistance and localisation index (LI). On the other hand, the spectral method was used in order to get the noise impedance. The superficial analysis using a scanning electron microscopy was carried out. According to EN analyses, the current transients indicate that the aggressiveness of the corrosion increased as the rotation speed also increased. The highest corrosion rate values were obtained at turbulent flow conditions. In the superficial analysis, a localised corrosion form was found in all corrosion processes; these results are agreed with the results obtained by LI.     

辽河油田土壤中溶解氧对X70管线钢腐蚀的影响

目的 降低腐蚀对油气管线运行的危害。方法 通过控制溶液中不同通氮时间,获得不同溶解氧浓度的辽河油田土壤模拟溶液,利用交流阻抗技术和动电位极化技术研究不同的溶解氧浓度对X70管线钢在模拟溶液中电化学腐蚀行为的影响,并结合金相显微镜对管线钢表面的腐蚀形貌进行表征,以阐明该条件下不同浓度溶解氧对管线钢腐蚀行为的作用机制。结果 在该环境下,X70钢的腐蚀机理为阳极溶解机制。随着溶解氧含量的不断降低,电极极化电阻变大,腐蚀电流密度明显减小,此时,电极表面点蚀坑数量也变少,点蚀坑的直径变小,金属腐蚀速率显著下降。当溶解氧质量浓度为10.0 mg/L时,试件的腐蚀速率最大,腐蚀现象最明显。当溶解氧质量浓度从10.0 mg/L降低至0.3 mg/L时,金属电极表面生成了一层以FeCO3为主的腐蚀产物膜,产物膜明显抑制了腐蚀反应的进行,对X70钢起到保护作用,此时试样腐蚀现象最不明显。结论 溶解氧浓度的不同导致了X70管线钢电极表面产物膜形态的不同,从而影响了该环境下金属的电化学腐蚀行为。     

Corrosion resistance of stainless steel pipes in soil

To be able to give safe recommendations concerning the choice of suitable stainless steel grades for pipelines to be buried in various soil environments, a large research programme, including field exposures of test specimens buried in soil in Sweden and in France, has been performed. Resistance against external corrosion of austenitic, super austenitic, lean duplex, duplex and super duplex steel grades in soil has been investigated by laboratory tests and field exposures. The grades included have been screened according to their critical pitting‐corrosion temperature and according to their time‐to‐re‐passivation after the passive layer has been destroyed locally by scratching. The field exposures programme, being the core of the investigation, uses large specimens: 2 m pipes and plates, of different grades. The exposure has been performed to reveal effects of aeration cells, deposits or confined areas, welds and burial depth. Additionally, investigations of the tendency of stainless steel to corrode under the influence of alternating current (AC) have been performed, both in the laboratory and in the field. Recommendations for use of stainless steels under different soil conditions are given based on experimental results and on operating experiences of existing stainless steel pipelines in soil.     

Mechanistic changes in cut edge corrosion induced by variation of inhibitor pigmentation in organically coated galvanised steel

Abstract

Corrosion at the exposed cut edges of organically coated galvanised steel (OCS) used for construction is one of the primary failure mechanisms. The scanning vibrating electrode technique (SVET) has shown that corrosion is driven by differential aeration when materials are coated with organic over-layers of widely differing thickness and primer layers are pigmented with strontium chromate (SrCrO₄ ). In such materials anodic activity is localised on the zinc layer proximal to the thicker organic coating with cathodic activity focused on the steel and zinc proximal to the thinner organic coating. To overcome the localisation of anodic and cathodic activity we have prepared novel OCS panels in which cathodic inhibitor primer systems based on rare earth metal cation exchanged pigments have been employed beneath the thinner organic coating and conventional strontium chromate anodic inhibitor systems beneath the thicker organic coating. The differential inhibitor loading overrides the effects of differential aeration and leads to significant passivation within the 24 h immersion period.     

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.     

Effects of Tafel slope,exchange current density and electrode potential on the corrosion of steel in concrete

A parametric study is carried out to investigate the effect of variations in anodic and cathodic Tafel slopes, exchange current densities and electrode potentials on the rate of steel corrosion in concrete. The main goal of this investigation is to identify the parameters that have significant influence on steel corrosion rate. Since there is a degree of uncertainty associated with the selection of these parameters, particularly during modelling exercises, it is intended that the results of this study will provide valuable information to engineers and researchers who simulate steel corrosion in concrete. To achieve this goal, the effect of a parameter on the corrosion rate of steel is studied while all other parameters are kept constant at a predefined base case. For each parameter, two extreme cases of anode‐to‐cathode ratio are studied. The investigation revealed that the variations in the anodic electrode potential have the greatest impact on the corrosion rate, followed by the variations in the cathodic Tafel slope.     

M24油井采出液系统的腐蚀行为与缓蚀剂的研究

本文通过EDS法分析静态挂片表面的元素组成,将动电位扫描极化曲线和滞后环等电化学实验相结合,对实验室和现场垢样的SEM和XRD的形貌和组成进行分析,研究了Q235钢在M24油井采出液系统中的腐蚀行为,用旋转挂片法对缓蚀剂进行了筛选,参照GB/T6324.1做了水溶性测定实验,参照SYT5273-2000实验方法进行了乳化倾向测定。结果表明M24油井采出液系统中引起腐蚀穿孔的原因是垢下腐蚀而不是点蚀,腐蚀的速度受腐蚀反应的阳极过程控制;用旋转挂片仪筛选出的自制缓蚀剂用量50mg/L,缓蚀率超过90%,缓蚀剂起到缓蚀作用的根本原因是抑制了电极反应的阳极过程;缓蚀剂在水中溶解性好;有轻微乳化现象,但在水相中的有效成分没有减少。