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.     

Understanding the effects of electrode inhomogeneity and electrochemical heterogeneity on pitting corrosion initiation on bare electrode surfaces

The effects of electrode inhomogeneity (EI) and electrochemical heterogeneity (EH) on pitting corrosion initiation have been analysed by revisiting research findings reported in the literature and experimental evidences obtained in our laboratories using the wire beam electrode (WBE) method. Two mechanisms of pitting corrosion initiation have been identified on bare metal surfaces exposed directly to electrolytes. For WBE surface under free corrosion or low anodic polarisation conditions the initiation of pitting corrosion was found to be due to the disappearance of minor anodes, leading to accelerated dissolution of a few remaining major anodes. The nucleation stage of pitting corrosion appeared to be controlled by EI, while the propagation stage appeared to be determined by EH. For WBE surface under large anodic polarisation the initiation of pitting corrosion was found to be due to the formation of active new anodic sites, which is in agreement with the conventional mechanism of pitting nucleation.     

Evaluation of corrosion inhibition at sand-deposited carbon steel in CO2-saturated brine

The adsorption of four CO₂ corrosion inhibitors on silica sand and their subsequent inhibition activity at sand-deposited steel has been investigated. The presence of a sand deposit affects the performance of inhibitors at carbon steel due to their competitive adsorption on sand. Sulfur-containing organic compounds show minimal adsorption on sand compared to pyridinium surfactants and provide the highest inhibition efficiency at the sand-deposited steel. The extent of inhibitor adsorption onto sand is discussed in relation to their chemical structures. The significance of determining the adsorption affinity to sand in the selection of inhibitors to mitigate under-deposit corrosion is demonstrated.     

Study of localized corrosion of 304 stainless steel under chloride solution droplets using the wire beam electrode

Localized corrosion of 304 stainless steel under droplets of 1 M sodium chloride solution was investigated by the wire beam electrode (WBE) method. It was found that the current distributions were heterogeneous with isolated anodic current peaks mostly located near the edge of the droplet. During the corrosion process, the stainless steel WBE exhibited the stochastic characteristics with the disappearance of some anodic sites. In addition, stainless steel suffered more serious localized corrosion with the increase of the droplet size. The increase of the cathodic area and the three-phase boundary (TPB) length was believed to be the reason.     

Heterogeneous corrosion of mild steel under SRB-biofilm characterised by electrochemical mapping technique

Heterogeneous corrosion of mild steel under sulphate reducing bacteria (SRB)-biofilm was characterised by wire beam electrode (WBE) technique and electrochemical impedance spectrum. The potential/current distributions of the WBE under SRB-biofilm showed that the potential maps could not indicate the localised corrosion of steels beneath biofilm due to the fact that all wire electrodes were short-circuited by the highly conductive sulphide precipitates embedded in SRB-biofilm. Instead, the galvanic current maps may give a good indication. The characteristic of super-capacitance (0.21 F/cm²) of SRB-biofilm was attributed to the huge specific surface area of conductive pore walls inside biofilm.     

Detection and characterization of stress-corrosion cracking on 304 stainless steel by electrochemical noise and acoustic emission techniques

This paper focuses on the corrosion process of 304 stainless steel in acidic NaCl solution during slow strain rate testing experiment by using electrochemical noise (EN) and acoustic emission (AE) techniques. Meanwhile, the EN and AE characteristics of corrosion process were studied. The results show that stress corrosion occurs easily in the experimental system, and corrosion forms develops gradually from localized corrosion including stress corrosion and pitting corrosion to general corrosion. The AE signal characteristics of pitting corrosion, crack and bubble break-up are significantly different during the corrosion process.     

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.     

Galvanic corrosion of titanium coupled to welded titanium in LiBr solutions at different temperatures

The galvanic corrosion generated between the titanium-welded titanium pair has been studied in heavy brine LiBr solutions at 25, 50 and 100 °C under open circuit conditions using a zero-resistance ammeter (ZRA). The results showed that welded titanium was the anode of the pair, so that its corrosion resistance decreases due to the galvanic effect. However, the extremely low galvanic current densities registered by the pair reveal the poor severity of the coupling under the studied conditions. Furthermore, it was observed that the electrodes were in the passive state, increasing the probability of localized corrosion with temperature.     

Drugs: A review of promising novel corrosion inhibitors

Due to the toxicity of widely used corrosion inhibitors and the ever tightening environmental regulations surrounding their use and disposal, there is great interest in replacing harmful inhibitors with effective non-hazardous alternatives. Over the past two decades, extensive research and development have led to the discovery of new classes of corrosion inhibitors, and the importance on the use of several drugs as corrosion inhibitors has grown. This review presents most of the contributions made to the literature on the use of drugs as corrosion inhibitors of various metals in recent years.     

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.     

注水海底管道穿孔原因分析

采用宏、微观形貌观察,化学成分、腐蚀产物分析等方法对某油田平台注水穿孔海底管道的穿孔原因进行了分析。结果表明:穿孔弯管段碳含量超标,管道内壁疏松的腐蚀产物为Fe_2O_3和Fe_3O_4,是氧腐蚀产物;弯管段穿孔由冲蚀和垢下腐蚀共同作用引起,垢层下的穿孔则是由于垢下腐蚀导致的。     

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.     

Novel corrosion experiments using the wire beam electrode: (II) Monitoring the effects of ions transportation on electrochemical corrosion processes

An electrochemically integrated multi-electrode system namely the wire beam electrode (WBE) has been applied for the first time to study the effects of the transportation of electrochemically active species on the process, rate and pattern of electrochemical corrosion. The objective of this work is to demonstrate the applicability of the WBE method for investigating ion transportation related corrosion processes. A series of experiments have been carried out using WBEs made from mild steel and stainless steel wires. The WBE working surfaces were exposed to simulated diffusion-controlled corrosion environments where there were diffusion induced ions concentration gradients (termed diffusion-corrosion environment). Corrosion potential and current distribution maps (CPCD maps) were measured from WBE surfaces in continuous bases. Typical patterns have been identified from CPCD maps and the characteristics of these patterns have been found to depend heavily upon the type of electrode material and the type of corrosive ion. For mild steel WBE surface exposed to a diffusion-corrosion environment containing NiSO₄ or FeCl₃, the characteristic pattern in CPCD maps was found to emulate NiSO₄ or FeCl₃ concentration gradients, suggesting an ion-concentration controlled corrosion behaviour. However, when the mild steel WBE surface was exposed to a diffusion-corrosion environment containing NaCl, the characteristic pattern was found to show higher cathodic currents along the WBE edges with the magnitude decreasing in a contour-like manner towards the centre of the WBE surface, suggesting an oxygen concentration-controlled corrosion behaviour. When a stainless steel (SS316L) WBE surface was exposed to a diffusion-corrosion environment containing NiSO₄ or NaCl, the corrosion pattern appeared to be mainly determined by the random distribution of weak sites in passive film. When the SS316L WBE was exposed to a diffusion-corrosion environment containing FeCl₃, the CPCD map revealed a characteristic pattern that shows localised damage to passive film. This work demonstrates that the recognition and analysis of characteristic maps from WBE measurements can be used as a means of studying diffusion, migration and other forms of mass transportation related electrochemical corrosion processes.     

Corrosion inhibition of aluminium in acidic and alkaline media by Sansevieria trifasciata extract

The inhibitive action of leaf extracts of Sansevieria trifasciata on aluminium corrosion in 2 M HCl and 2 M KOH solutions was studied using the gasometric technique. The results indicate that the extract functioned as a good inhibitor in both environments and inhibition efficiency increased with concentration. Synergistic effects increased the inhibition efficiency in the presence of halide additives. Temperature studies revealed a decrease in efficiency with rise in temperature and corrosion activation energies increased in the presence of the extract. A mechanism of physical adsorption is proposed for the inhibition behaviour. The adsorption characteristics of the inhibitor were approximated by Freundlich isotherm.     

Study on corrosion resistance of palladium films on 316L stainless steel by electroplating and electroless plating

Palladium films with good adhesive strength were deposited on 316L stainless steel by electroless plating and electroplating. Scanning electronic microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, weight loss tests and electrochemical methods were used to study the properties of the films. The electroless plated palladium film mainly consisted of palladium, phosphorus and nitrogen, and the electroplated palladium film was almost pure palladium. XPS analysis indicated that palladium was present in the films as metal state. The palladium plated stainless steel samples prepared by both methods showed excellent corrosion resistance in strong reductive corrosion mediums. In boiling 20% dilute sulfuric acid solution, the corrosion rates of the palladium plated 316L stainless steel samples were four orders of magnitude lower than that of the original 316L stainless steel samples. In the solution with 0.01 M NaCl, the palladium plated samples also showed better corrosion resistance. In comparison, the electroplated samples showed slightly better corrosion resistance than electroless plated samples, which may be attributed to less impurities and thereby higher corrosion potential for the former.     

In situ monitoring of corrosion processes within the bulk of AlMgSi alloys using X-ray microtomography

Susceptibility to localized corrosion of AlMgSi (AA6016 and AA6111) alloys in certain aggressive environments is high. In this study, synchrotron X-ray microtomography was used to monitor non-destructively corrosion processes within bulk materials. In the selected aggressive solutions, surface–deformed layers showed high localized corrosion susceptibility, but are more stable than the bulk of the alloy during corrosion propagation. In addition, exfoliation-like attack was observed as a transition from intergranular attack. This directed corrosion is not related to grain or crystallographic structure. Finally, intermetallic particles dissolution inside the materials after contact with aggressive solution of the intergranular corrosion path was evidenced.     

Role of the reversible electrochemical deprotonation of phosphate species in anaerobic biocorrosion of steels

Sulphate reducing bacteria are known to play a major role in anaerobic microbiological influenced corrosion of steels, but mechanisms behind their influence are still source of debates as certain phenomena remain unexplained. Some experiments have shown that hydrogen consumption by SRB or hydrogenase increased the corrosion rate of mild steel. This was observed only in the presence of phosphate species. Here the cathodic behaviour of phosphate species on steel was studied to elucidate the role of phosphate in anaerobic corrosion of steel. Results showed: a linear correlation between reduction waves in linear voltammetry and phosphate concentration at a constant pH value; that phosphate ions induced considerable anaerobic corrosion of mild steel, which was sensitive to hydrogen concentration in the solution; and that the corrosion potential of stainless steel in presence of phosphate was shifted to more negative values as molecular hydrogen was added to the atmosphere in the reaction vessel. Phosphate species, and possibly other weak acids present in biofilms, are suggested to play an important role in the anaerobic corrosion of steels via a reversible mechanism of electrochemical deprotonation that may be accelerated by hydrogen removal.     

The heterogeneous electrochemical characteristics of mild steel in the presence of local glucose oxidase—A study by the wire beam electrode method

The influence of glucose oxidase (GOD) activity on the heterogeneous electrochemistry at artificial biofilm/mild steel interface was first characterized by the wire beam electrode (WBE) method. Potential/current distribution maps show that a cathodic zone can be formed at the GOD capsule site. The cathodic zone is gradually weakened due to the gluconic acid production in seawater. When GOD capsule is confined on rusted WBE surfaces, the formerly formed anodic zone is gradually changed into cathodic zone, in the presence of glucose. The novel device developed in our laboratory demonstrates powerful applications in heterogeneous electrochemistry measurements at the biofilm/mild steel interfaces.     

A novel device for the wire beam electrode method and its application in the ennoblement study

A novel device used in the wire beam electrode (WBE) method was developed in our lab. The system consists of standard modules, and is controlled by a LabVIEW software (National Instruments Co., NI). Since all the components in this WBE test device are commercially available, and the detailed information of the modules can be readily accessed by researchers, the system is easy to be built and modified, depending on experimental designs. The device can perform desired measurements, which is controlled by programs written in LabVIEW, for which the researchers can easily design and modify to create user-defined tests and control applications. This device has a faster measurement rate than that in published literature. In our study, we have used this device for the first time to investigate the relationship between local potential/current patterns and H₂O₂ distribution in an artificial biofilm/stainless steel interface. The results showed that the electrochemical distribution of the biofilm-related system is closely correlated with the biofilm heterogeneity. The device improves the WBE measurement techniques and is expected to be widely used in academic and industrial fields.     

苯并三唑对碳钢/铜合金电偶腐蚀行为的影响

目的 研究NaCl溶液中苯并三唑(BTA)对碳钢/铜合金电偶腐蚀行为的影响.方法 使用丝束电极(WBE)技术和电化学阻抗谱(EIS)技术研究在未添加和添加BTA的NaCl溶液中,丝束电极表面的电位分布、电流密度分布和电化学阻抗谱演化,同时对比分析碳钢区域与铜合金区域的阻抗谱特征.结果 在未添加BTA的条件下浸泡72 h...