The determination of pH,potential and chloride concentration in corroding crevices on 304 stainless steel and 7475 aluminium alloy

The conditions in a simulated crevice have been studied for type 304 stainless steel and for 7475 T651 AlZnMg alloy in 0.6 M NaCl bulk solutions. The pH has been measured with a palladium/hydrogen diffusion electrode, and the chloride concentration with a silver/silver chloride electrode. For stainless steel the results conform with the expectations of the classical crevice corrosion model, with the crevice becoming a net anode, and the pH falling as a result of chromium ion hydrolysis. For the aluminium alloy more complex results are obtained, with parts of the crevice becoming mildly acidic (pH 3–4), while the deeper parts of the crevice become slightly alkaline (pH 8). The latter observation is not readily explained in terms of the chemistry and electrochemistry of the crevice.     

The stability of localized corrosion

Chloride pitting of iron group metals at noble potentials proceeds in the polishing state dissolution, provided that metal chloride in the pit solution is maintained above a critical concentration. It ceases to progress by pit repassivation if the pit is smaller than a critical size, or transforms into the active state pitting if the pit size is greater. The boundary potential between the polishing state and the active state pitting may be represented by the passivation-depassivation potential in the pit solution of the critical chloride concentration. Crevice corrosion is characterized by the crevice protection potential, at which the hydrogen ion concentration in the crevice solution is equivalent to pH_pd—the passivation-depassivation pH of the crevice metal. It continues to corrode at more noble potentials than the protection potential, where the crevice solution is more acidic than pH_pd, but is inhibited in the less acidic crevice solution at less noble potentials.     

Influence of ultrasound on pitting corrosion and crevice corrosion of SUS304 stainless steel in chloride sodium aqueous solution

The change of polarization curves and surface morphologies of SUS304 stainless steel was investigated in 3.5 mass% NaCl solution with or without the application of ultrasound (US). As the result, both the pitting corrosion and the crevice corrosion were largely suppressed by the application of US. The reason is attributed to the decrease in the concentration of hydrogen and chloride ions in pits or in the crevice by removing the corrosion product and stirring the liquid there.     

Sequence of steps in the pitting of aluminum by chloride ions

Corrosion pit initiation in chloride solutions is given by an electrode kinetic model which takes into account adsorption of chloride ions on the oxide surface, penetration of chloride ions through the oxide film, and localized dissolution of aluminum at the metal/oxide interface in consecutive one-electron transfer reactions. A previous model has been extended here to consider that penetration of chloride ions can occur by oxide film dissolution as well as by migration through oxygen vacancies. Pit initiation occurs by chloride-assisted localized dissolution at the oxide/metal interface. The electrode kinetic model leads to a mathematical expression which shows that the critical pitting potential is a linear function of the logarithm of the chloride concentration (at constant pH), in agreement with experiment. The model also predicts that the critical pitting potential is independent of pH (at constant chloride concentration), also in agreement with experiment. Corrosion pit propagation leads to formation of blisters beneath the oxide film due to localized reactions which produce an acidic localized environment. The blisters subsequently rupture due to the formation of hydrogen gas in the occluded corrosion cell. Calculation of the local pH within a blister from the calculated hydrogen pressure within the blister gives pH values in the range 0.85 to 2.3.     

Crevice corrosion monitoring of titanium and its alloys using microelectrodes

Crevice corrosion of titanium and its alloys in 10% sodium chloride was investigated at 100°C with the aid of microelectrodes. Potential, pH and chloride ion concentration inside the crevice were monitored using an Ag/AgCl electrode, a tungsten microelectrode and a Ag/AgCl chloride ion selective microelectrode, respectively. The pH and Cl^? concentrations within the crevice were calculated from the standard potential‐pH and potential‐log[Cl^?] calibration curves. The effect of Mo on the crevice corrosion of titanium was also studied. The passivation behavior on the titanium and Ti‐15%Mo alloy was studied using electrochemical impedance studies. There was no apparent change in pH and Cl^? ion activity inside the crevice for the alloy at 100°C, whereas a marginal decrease in pH and increase in Cl^? ion concentration were observed for pure titanium. Thus pure titanium is susceptible to crevice corrosion in hot 10% NaCl solutions at 100°C. The chloride ion activity was found to be reduced for the alloy so that the pH inside the crevice increased. The corrosion reaction resistance (R_t) was found to increase with the addition of Mo as an alloying element. It also increases with externally applied anodic potential. Hence, Mo is an effective alloying element, which enhances the crevice corrosion resistance of titanium.     

Predicting the chemistry,corrosion potential and corrosion rate in a crevice formed between substrate steel and a disbonded permeable coating with a mouth

A model developed in an earlier work was used in this work to investigate the effect of coating permeability on the evolution of solution chemistry, corrosion potential, and rate in a crevice formed between a steel surface and a coating disbonded from it. The crevice gap varies along distance from the mouth, and the coating is permeable to ions and/or oxygen (O₂). The earlier work focused specifically on modeling the effect of variable gap (on crevice corrosion) with the coating impermeable to either ions or O₂. In both works, the crevice chemistry was an aerated, diluted sodium chloride solution, which at the mouth was set to be different from that initially in the crevice. The results of this work show that a permeable coating behaves like a membrane, which, under a cathodic polarization at the crevice mouth, tends to raise the in-crevice sodium ion concentration and pH more rapidly relative to an impermeable coating. Later, as the sodium ion concentration and pH in the crevice become greater than at the mouth, the permeable coating tends to reverse the transport direction for ions. At a mouth potential of ?0.900 V vs. saturated Cu/CuSO₄, the cathodic current is sufficient to suppress all O₂ penetrating the crevice both from the mouth and through the coating. The practical implication is that in the presence of sufficient cathodic polarization, a permeable coating, when disbonded, can still be capable of protecting the substrate steel from corrosion attack.     

Implications of internal cathodic reactions for crevice attack of stainless steels in chloride environments

Abstract

Modelling of the crevice chemistry in stainless steels in chloride environments at ambient temperatures has been conducted in order to evaluate the impact of internal cathodic reactions on the potential and pH within the crevice. Consideration of the internal cathodic reactions is of particular importance in predicting the behaviour of crevices formed between dissimilar metals. The model is based on mass conservation of species and incorporates a range of chemical and electrochemical reaction processes. Hydrogen ion reduction within the crevice has a marked effect on the time evolution of the pH in the crevice and consequently on predictions of the time to passivity breakdown based on the critical pH concept. The impact on the steady state pH depends on the corrosion potential and on crevice dimensions. In the latter context, decreasing the gap or increasing the length does not invariably create more severe conditions for passivity breakdown. There is an optimum magnitude of the dimensions for inducing crevice attack. Coupling the stainless steel to a more noble material within the crevice, when the main cathodic reaction is reduction of hydrogen ions, may be more likely to retard crevice attack by virtue of the higher crevice pH, provided that effective coupling of the materials in the external environment is constrained. A specific bulk conductivity exists below which the critical crevice chemistry does not develop, but this is associated with potential drop in the bulk solution rather than in the crevice.     

Corrosion of galvanised steel cord reinforcement in HDPE composite pipes in petroleum production

In this work, corrosion of galvanised steel cord reinforcement in high density polyethylene (HDPE) composite pipes was studied in electrolytes that developed on the cord surface due to permeation of corrosive species through HDPE liner or damage of the liner in petroleum production. Parametric effects, including solution pH, temperature and concentration of chloride ions, were investigated by electrochemical corrosion measurements. A model was developed to illustrate the mechanism of corrosion of the cord. Corrosion of the galvanised steel cord includes anodic dissolution of Zn coating and the steel substrate. A deposit layer of zinc carbonate and iron carbonate forms on the cord surface to provide protection to further corrosion in the environment. Corrosive ions can diffuse into holes or crevices of the cord assembly to cause corrosion of galvanised steel wires in inner layers. The unique geometry of the cord assembly results in an accelerating localised corrosion at the crevices and holes. Generally, corrosion of the cord is accelerated by increased chloride concentration, reduced solution pH, and elevated temperature.     

Influence of Cl- and polarization potential on crevice corrosion behavior of X70 pipeline steel北大核心CSCD

The crevice corrosion behavior of X70 pipeline steel in NaHCO3 solution with varying Cl- concentration was investigated by potentiostatic polarization method in terms of the initiation and development of crevice corrosion. Results show that inside the crevice the X70 steel could suffer from localized corrosion in NaHCO3 solution by polarization potential-0.4 V. The acidification initiated firstly at the crevice mouth and then extended gradually to the bottom. The hydrogen evolution could be observed with the development of corrosion and acidification. The cathodic reaction changed from the reduction of the dissolved oxygen to the reduction of hydrogen ions. The presence of Cl- did not change the crevice corrosion mechanism. With the increase of Cl- concentration, however, the crevice corrosion rate increased. The corrosion region moved towards the crevice bottom gradually and then pitting corrosion occurred with the increasing polarization potential. The initiation of crevice corrosion was determined by the polarization potential. © 2016, Corrosion Science and Protection Technology. All rights reserved.     

铁在不同pH值的NaCl溶液中的腐蚀行为

    采用线性扫描伏安法(LSV)和Tafel方法测定铁的极化曲线,研究了铁电极在不同pH值NaCl溶液中,以及在不同浓度NaCl溶液中腐蚀规律.结果表明,酸的浓度越增加,铁的腐蚀越容易;Cl^-对铁有腐蚀促进作用.通过极化曲线得到腐蚀参数和动力学参数,探讨了不同溶液中铁的腐蚀机理：氯离子的存在能够改变钝化膜的组织结构,提高膜的溶解速率.     

金属缝隙腐蚀的成因及实验验证

在制品和工程结构中,缝隙腐蚀是一种很普遍且隐蔽的局部腐蚀,其结果会导致构件强度降低,既降低服役寿命,也存在安全隐患。指出缝隙腐蚀发生的三个必要条件——制品或工程结构中有金属或合金、有缝隙的存在、缝隙内有腐蚀介质滞留,概述了缝隙腐蚀的特征及三个阶段。分析了缝隙腐蚀的影响因素,包括金属性质、环境因素(溶液中氧、氯离子浓度,温度,p H值以及溶液的流速)和缝隙的几何形状。介绍了在实验室用三氯化铁溶液验证不锈钢及其合金的缝隙腐蚀敏感性的基本步骤,提出了在工程实际中如何预防缝隙腐蚀的基本思路。     

Influence of pH and chloride ion concentration on the corrosion of Mg alloy ZE41

The influence of pH and chloride ion concentration on the corrosion behaviour of ZE41 was studied using immersion tests and electrochemical measurements. A shorter incubation period to the onset of corrosion; a more negative corrosion potential; and a higher corrosion rate correlated with a higher chloride ion concentration at each pH value and correlated with a lower pH value for each chloride ion concentration. This corrosion behaviour is consistent with the current understanding that the corrosion behaviour of magnesium alloys is governed by a partially protective surface film, with the corrosion reactions occurring predominantly at the breaks or imperfections of the partially protective film. The implication is that the fraction of film free surface increases with decreasing bulk pH and with increasing chloride ion concentration. This is consistent with the known tendency of chloride ions to cause film breakdown and the known instability of Mg(OH)₂ in solutions with pH less than 10.5. The electrochemical measurements of the corrosion rate, based on the corrosion current at the free corrosion potential, did not agree with direct measurements evaluated from the evolved hydrogen, in agreement with other observations for Mg.     

Effect of nickel alloying on crevice corrosion resistance of stainless steels

The crevice corrosion behaviour of stainless steels containing 25 mass% Cr, 3 mass% Mo and various amounts of Ni was investigated in natural seawater. The results showed that ferritic steels containing nickel were more resistant to corrosion than both ferritic steels without nickel and austenitic steels. The superiority of the Ni bearing ferritic steel over the other steels was in close agreement with the depassivation pH of those steels in acidic chloride solutions. The results showed that the addition of Ni to ferritic steel was effective in decreasing the depassivation pH and the dissolution rate in acidic chloride solutions at crevices.     

碱性条件下碳钢的缝隙腐蚀行为

采用动电位扫描法研究了碱性条件下氯离子浓度、pH值、PO43-和NO2-两种缓蚀性离子对Q235钢缝隙腐蚀行为的影响.研究表明,碱性条件下氯离子对缝隙腐蚀有极强的促进作用,溶液pH值变化对缝隙腐蚀影响较小,PO43-对缝隙腐蚀可以起到抑制作用,并且PO43-的缓蚀作用明显大于NO2-.     

Corrosion Behavior of 35CrMn and Q235 Steel in Simulated Acid Rain Conditions

Effects of pH value, chloride ion concentration and alternation of wetting and drying time in acid rain on the corrosion of 35CrMn and Q235 steel were investigated through the measurement of polarization curves, electrochemical impedance spectroscopy, x-ray diffraction, and quantum mechanical calculations. The corrosion rate of 35CrMn and Q235 steel increased with decreasing pH values of the simulated acid rain, whereas the corrosion potential of 35CrMn and Q235 steel became more negative. The impedance became higher and the corrosion rate decreased with increasing test time. The dissolution rate of samples increased with chloride ion concentration. Results suggested that the corrosion rate of 35CrMn steel was obviously lower than that of Q235 steel for a more compact rust, α-FeOOH. Quantum chemical calculations further revealed that the increase in corrosion rate of the steel resulted from pitting corrosion caused by the corrosive chloride ion.     

Stress corrosion cracking of Inconel 600 in aqueous solutions at elevated temperature Part II: Effects of chloride and sulphate ions on the electrochemical behaviour of Inconel 600

The influencing effects of temperature, potential and electrolyte composition on the electrochemical behaviour of Inconel 600 in aqueous solutions are presented. Considering these effects the connection between the data have been obtained from chemo-mechanical fracture investigation on CT-samples in Part I of this paper and pitting corrosion are discussed. The results have shown that chloride ions depassivate the surfaces of cracks locally and hinder the formation of a new protective oxide layer on the fracture surfaces. Furthermore, chloride promotes the dissolution of metal and initiates the cracking, respectively. The resulting crevice corrosion promotes an increase of hydrogen absorption by the metal. The increase of the hydrogen content of the metal influences the mechanical fracture behaviour. Contrary, sulphateions inhibit the initiation of corrosion mainly due to a hinderance of chloride ions adsorption on active sites of the fracture surfaces. The initiation of localized corrosion in the crevice region may be stimulated by chromate ions formed by oxidation of chromium from the oxide layer or the base metal in oxygen containing solutions.     

Ability of acoustic emission technique for detection and monitoring of crevice corrosion on 304L austenitic stainless steel

This experimental work was aimed at investigating the ability of acoustic emission (AE) technique for detection and monitoring of crevice corrosion on 304L austenitic stainless steel. Crevice initiation, propagation and repassivation was controlled by additions of hydrogen peroxide and hydrochloric acid and by the extent of the applied torque of crevice assembly, in the presence of chloride ions. The simultaneous measurements of corrosion potential of the specimen and AE global activity during the test, as well as the characterization of acoustic parameters of AE signals, evidences a good correlation between potential and AE activity fluctuations, AE rate and amplitude of crevice damage in terms of weight loss and metallic surface affected, in each tested experimental condition. Moreover, the evolution of cumulative% of AE signals number versus selected acoustic parameters shows that rise time, counts number, duration and cumulative energy of AE signals are affected by crevice development. Finally, visualization of crevice initiation and propagation during the test allows to propose that bubbles formation from cathodic reactions within the crevice is the emissive mechanism.     

氯和氢对新型超高强度Cr12Ni4Mo2Co14钢在酸性环境中电化学腐蚀行为的影响

采用极化曲线、电化学阻抗和Mott-Schottky等电化学试验研究了酸性环境中Cl~-和氢对一种新型超高强度Cr12Ni4Mo2Co14钢电化学腐蚀行为的影响。结果表明:Cl-和氢均对Cr12Ni4Mo2Co14钢的阳极钝化区产生影响,随着Cl~-含量和氢含量的增加,点蚀电位负向移动,钝化区间缩短;Cl-通过占据氧空位促进钝化膜中形成Schottky空位对,而金属离子空位聚集会引起钝化膜的破坏;与未充氢Cr12Ni4Mo2Co14钢相比,充氢Cr12Ni4Mo2Co14钢中的施主和受主密度均有所提高,导致阳离子空位浓度提高,局部阳离子空位的聚集可诱导钝化膜的击穿。     

Electrochemical polarization studies of BS 4360 50D steel in 3.5% NaCl

Anodic and cathodic polarization studies have been carried out on the steel BS 4360 50D in de-aerated 3.5% NaCl (0.6 M) in the pH range 2–10 and 2–13 respectively. A stepwise potentiostatic method was employed and the current was allowed to attain a steady value at each potential. The free corrosion potential was observed to be independent of pH in the range 5–10.5 but to change to more positive potentials for pH values < 5 and to more negative potentials for pH values > 10.5. The rate of anodic dissolution and cathodic reduction of hydrogen ions and water also showed a complex dependence on pH. At pH 4 varying the chloride-ion concentration in the range 0.1–1.5 M had little effect on the polarization curves but in 4 M solution a decrease in the anodic current density was observed.     

碳钢在点蚀/缝隙腐蚀闭塞区模拟溶液中的腐蚀行为

研究了低碳钢在点蚀孔/缝隙腐蚀闭塞区模拟溶液中的腐蚀 行为.结果表明低碳钢在pH等于2～4的模拟闭塞区溶液中,阴极过程由氢离子的扩散步骤控 制,阴极去极化起着主要作用.当pH值小于2时,阴极过程表现为活化特征.阳极溶解过程遵 循着Bockris机理.碳钢在闭塞区的腐蚀不存在临界pH值和临界Cl-浓度,腐蚀速度(V c)的对数与pH值呈线性关系.闭塞区内溶液pH的微小变化,对腐蚀速度有明显的影响.外部 溶液中的Cl-离子迁入闭塞区后,会促使溶液pH下降.