The corrosion behavior of carbon steel in CO2‐saturated NaCl crevice solution containing acetic acid

The corrosion behavior of X52 carbon steel electrodes in CO₂‐saturated NaCl crevice solution containing HAc was investigated by electrochemical measurements. Chemical environment measurements by Cl^? and pH microprobes show an enrichment of Cl^? ions and an increase of pH values inside the crevice. Moreover, both increments could accelerate with the decreasing dimension of the crevice mouth due to the high diffusive resistance. When the electrode in the crevice solution is coupled with the electrode in bulk solution, the alkalization and the enrichment of Cl^? ions in the crevice solution can result in a negative shift of potential of the electrode in crevice solution, while the potential of the electrode in bulk solution shifts positively during the corrosion process. Thus, a galvanic corrosion is established with the electrode in the crevice solution acting as anode while another in the bulk solution as cathode, i.e., the corrosion in the crevice solution was enhanced while the corrosion in the bulk solution was retarded. The anodic dissolution and the cathodic reduction processes dominate in the crevice solution and in the bulk solution, respectively.     

Slow strain rate stress corrosion testing at elevated temperatures and high pressures

Slow strain rate stress corrosion cracking experiments have been performed on single phase and duplex phase 304 stainless steels at 290°C. Environmental variables included chloride concentrations (0–1000 ppm), oxygen concentration (0–2 ppm) and potential (?_corr to + 500 mV vs Ag/AgCl). These experiments have shown that s.c.c. resistance is relatively unaffected by Cl^? if O₂ concentrations approach zero. However, at 2 ppm O₂ concentration, there is a large decrease in resistance with increasing Cl^? concentrations. Anodic polarization of the steels during straining in solutions containing 100 ppm Cl^? and 0 ppm O₂ showed a threshold potential for s.c.c. at ～ 500 mV more noble than the corrosion potential (? 650 ± 60 mV vs Ag/AgCl at temperature).     

Effect of Chloride and Fluoride on the Rate of Corrosion of dental amalgam alloys

The anodic behaviour of massive and dental amalgam alloys in artificial saliva containing different concentrations of Cl^? or F^? ions has been studied. Quantitative relations could be established between concentrations of these ions and the height of the peaks corresponding to anodic oxidation of Sn or Ag. Contrary to f^?, Cl^? ions from Ag complexes via AgCl which excess cl^?ions. The massive alloy is stable below 0.15 V. Calcium fluoride can be safely admixed with dental amalgam alloy without enhancing its corrosion.     

The enrichment of hydrogen and chloride ions in the crevice corrosion of steels

The changes in concentration of hydrogen and chloride ions during corrosion in an artificial crevice on steel were observed from potential changes of Pd-H and Ag/AgCl micro-electrodes inserted in the crevice. Increasing the bulk chloride ion concentration accelerated the rate of pH change and resulted in more acidic conditions in the crevice. Such pH changes were delayed by the addition of inhibitor such as dialkylamines. Though the free chloride ion concentration did not change appreciably, the total concentration of free and complex ions in the crevice increased with continuous dissolution of the steel. Increasing the hydrogen and total chloride ion concentration in the crevice accelerated the anodic dissolution of steels within the crevice.     

Initiation and repassivation of crevice corrosion of type 444 stainless steel in chloride solution

Effects of chloride ion concentrations, solution temperature, and crevice-forming materials on the crevice corrosion of type 444 stainless steel were investigated using a potentiostatic method. Critical crevice potential (E_crev) and repassivation potential (E_r) of the creviced alloy decreased with an increase in chloride concentration [Cl⁻], satisfying the logarithmic relationship between E and [Cl⁻]. In addition, E_crev and E_r of the alloy with silicone crevice former were measured to be higher than those of the alloy with an EPDM (Ethylene Propylene Diene Monomer) crevice former, suggesting that silicone was more effective in preventing water from penetrating crevices between a stainless steel sheet and the crevice former. In electrochemical current transient measurements with an applied potential, the intensity of current transients corresponding to the initiation of metastable pits increased abruptly near the E_r of the alloy, indicating that the stability of crevice corrosion is associated with the initiation of metastable pits.     

Effects of coolant chemistry on corrosion of 3003 aluminum alloy in automotive cooling system

In this work, effects of coolant chemistry, including concentrations of chloride ions and ethylene glycol and addition of various ions, on corrosion of 3003 Al alloy were investigated by electrochemical impedance spectroscopy measurements and scanning electron microscopy characterization. In chloride‐free, ethylene glycol–water solution, a layer of Al‐alcohol film is proposed to form on the electrode surface. With the increase of ethylene glycol concentration, more Al‐alcohol film is formed, resulting in the increase in film resistance and charge‐transfer resistance. In the presence of Cl^? ions, they would be involved in the film formation, decreasing the stability of the film. In 50% ethylene glycol–water solution, the threshold value of Cl^? concentration for pitting initiation is within the range of 100 ppm to 0.01 M. When the ethylene glycol concentration increases to 70%, the threshold Cl^? concentration for pitting is from 0.01 to 0.1 M. In 100% ethylene glycol, there is no pitting of 3003 Al alloy even at 0.1 M of Cl^?. Even a trace amount of impurity cation could affect significantly the corrosion behavior of 3003 Al alloy in ethylene glycol–water solution. Addition of Zn²⁺ is capable of increasing the corrosion resistance of Al alloy electrode, while Cu²⁺ ions containing in the solution would enhance corrosion, especially pitting corrosion, of Al alloy. The effect of Mg²⁺ on Al alloy corrosion is only slight.     

The effect of molybdenum ion implantation on the general and pitting corrosion behaviour of pure aluminium and a high strength aluminium alloy

The effect of Ar and Mo ion implantation on the corrosion behaviour of pure Al and a high strength aluminium alloy (7075-T6) has been investigated in Cl^?-free and Cl^?-containing sulphate solutions. In Cl^?-free environments, Mo implantation markedly affects the general corrosion behaviour of both the pure metal and the alloy. Ar implantation, on the other hand, has no permanent effect on the potentiodynamic polarization behaviour of pure Al but does alter somewhat the polarization characteristics of 7075-T6. In Cl^?-containing environments, Mo implantation significantly improves the resistance of pure Al to pitting corrosion, and increases the breakdown potential by about 200 mV. A similar, though less marked effect is observed with the alloy. Ar implantation has no major effect on the behaviour of either the pure metal or 7075-T6 in Cl^?-containing environments. On the basis of Rutherford backscattering and potential-time measurements it is suggested that the beneficial effect of Mo may be due to either the incorporation of Mo in the passive film or to dissolution and reprecipitation of some Mo-containing species on the passive film.     

局部腐蚀微区电化学测试技木的研究

本文研究了KCl-Ag/AgCl微参比电极、微Cl~-选择电极和钨微电极的制备与性能,初步的结果表明:微参比电极具有稳定的电位及较小的温度系数;在没有其它卤离子存在的情况下,微Cl~-电极的电位与logαci~-有良好的线性关系,溶液酸度的改变和其它离子的存在对这一线性关系影响不大;在酸性条件下,在NaCl或MgCl_2溶液中,钨微电极具有稳定的电位,这一电位与溶液pH值有良好的线性关系,而且与溶液浓度无关,当溶液中存在的其他离子浓度不高时,对上述线性关系也没有影响。将上述微电极应用于缝隙腐蚀和应力腐蚀研究,得到一些现场跟踪测量的结果,这些结果可与其他作者用其它方法所获得的结果相印证。     

Corrosion resistance of the high‐strength filler metal NiCr20Fe14Mo11WN (alloy 50 PLUS)

The Nb‐free NiCr20Fe14Mo11WN alloy has been developed as a new filler metal which combines high strength and excellent corrosion resistance in wet environments at ambient temperatures. The alloy is characterized by exceptional resistance to pitting and crevice corrosion, no sensitiveness to chloride induced stress corrosion cracking and shows high mechanical properties, e.g. 0.2 %‐yield strength. Because the alloy is practically free of stable nitride formers like niobium, titanium etc., no nitride formation during welding of super austenitic, duplex and super duplex steels is possible, which proves the alloy to be superior to alloy 625.     

The effect of fluoride on the electrochemical behavior of Ti and some of its alloys for dental applications

Titanium is the best metal for making dental implants and restorations. In the last decade, new titanium alloys have been developed in different areas of dentistry. Concurrently, treatments using fluoride supplementation, such as odontology fluoride containing gels, have also been widely used in odontology. The aim of this study is to investigate the electrochemical behaviour of a new titanium alloy containing Cu and Ag, in fluoride‐containing media, and compare it with the behavior of Ti and Ti6Al4V, which are used frequently as biomaterials. Open circuit potential, polarization resistance and electrochemical impedance spectroscopy measurements revealed that the corrosion resistance of titanium and its alloys is controlled by the fluoride ion concentration and the pH of the solution. The presence of F^? ions in neutral solution does not hinder the formation of a protective layer of Ti and its alloys. Thus, the corrosion resistance of Ti is maintained in this medium. However, the corrosion of Ti and its alloys are enhanced in an acidic environment, because F^? ions in the solution combines with H⁺ ion to form HF, even in low fluoride concentration.     

Crevice corrosion initiation and propagation on Alloy-22 under galvanically-coupled and galvanostatic conditions

The initiation and propagation of crevice corrosion on the Ni–Cr–Mo Alloy-22 has been studied in concentrated chloride solutions under galvanically-coupled and galvanostatic conditions. Under galvanically-coupled natural corrosion conditions crevice corrosion initiated but propagation was limited by repassivation. This was attributed to the slow kinetics of oxygen reduction on passive surfaces external to the crevice. Under galvanostatic conditions a potential more positive than 200 mV_Ag/AgCl and an applied current greater than 5 μA were required to stabilize propagation. A minimum critical current density to establish active sites within the crevice was estimated to be around 250 μA cm⁻².     

Study on initiation of localised corrosion on copper thin film electrode by combinational use of an EQCM with a liquid-phase ion gun

A new method allowing simultaneous measurements of anodic currents and small mass changes during initiation and early growth of a single localised corrosion site was discussed. An electrochemical quartz crystal microbalance (EQCM) was combined with a liquid-phase ion gun consisting of an Ag/AgCl microelectrode which produces chloride ions, causing local breakdown of passive film and pit growth. The method was applied to copper thin films polarised anodically at 0.6 or 0.8 V (SHE) in pH 8.4 borate buffer solution. It was found from comparison between coulometry and gravimetry that copper dissolves as Cu²⁺ during the pit growth. The shape of the pit was almost circular and the average pit current density, i_p=25 A cm⁻² was evaluated from the kinetics of 2D pit growth.     

合金元素铁对钛缝隙腐蚀性能的影响

用浸泡腐蚀试验及电化学测试技术研究了合金元素铁对钛抗缝隙腐蚀性能的影响。试验结果表明,加入铁使缝隙腐蚀再钝化电位ＥＲ变负,缝隙腐蚀诱导期缩短,腐蚀率增大。通过电子探针分析和ＳＥＭ观察发现,铁以ＴｉＦｅ形式在晶界析出,腐蚀优先在ＴｉＦｅ析出物上发生,并且沿晶界向内部发展。由此得知,缝隙腐蚀起源于ＴｉＦｅ析出物,继而成长并促进了缝内活性溶解。     

油气开采用钛合金石油管材料耐腐蚀性能研究

选取5种油气开发常用钛合金材料(Ti-6Al-4V、Ti-6Al-4V-0.1Ru、Ti-6Al-2Sn-4Zr-6Mo、Ti-3Al-8V-6Cr-4Zr-4Mo和Ti-5.5Al-4.5V-2Zr-1Mo)为研究对象,使用高温高压釜模拟国内典型严酷服役工况环境,研究了不同钛合金材料耐均匀腐蚀、局部腐蚀、点蚀、应力腐蚀开裂(SCC)及缝隙腐蚀的性能,通过使用扫描电镜和能谱分析等手段对腐蚀形貌和腐蚀产物进行了分析,并使用电化学方法对不同合金的耐腐蚀机理进行了研究。结果显示,在所测试工况条件下,所有钛合金材料腐蚀反应均为阳极控制过程,均匀腐蚀速率均低于0.001mm/a,并且对应力腐蚀开裂均有良好的抗力。Ti-6Al-4V和Ti-5.5Al-4.5V-2Zr-1Mo合金出现明显的点蚀和缝隙腐蚀问题。对腐蚀机理研究表明,在工况条件温度下,随着pH值的降低,所有钛合金均发生自腐蚀电位降低,极化电阻减小,腐蚀电流增大,耐腐蚀性能下降,其中Ti-6Al-4V耐腐蚀性能下降的最为明显,研究结果为油气开发工况下钛合金石油管的选材和缝隙腐蚀问题防治提供理论基础。     

Crevice Corrosion of Titanium in High Temperature-Concentrated Chloride Environments

Crevice corrosion of titanium is activated in concentrated chloride media at 100 °C. This was possible only with the tightest gap (0.005 cm) between Ti-Ti surfaces. No crevice corrosion was observed with greater gap dimensions. The design of the crevice led to the occurrence of two concentric circular rings of corroded areas, with many pits on them. After potentiostating in the passive region for 5 h in 25% NaCl (pH = 4.7)—where hydrogen evolution is thermodynamically prohibited—hydrogen gas bubbles were observed to egress out of the crevice mouth during ongoing crevice corrosion. This indicates that hydrogen evolution occurs within the crevice. The results are compatible with the occurrence of gradually increasing ohmic potential shift and localized acidification in the crevice electrolyte as judged by the measured gradual increase of the crevice corrosion current. The high acidity of the bulk electrolyte does not seem to be sufficient or even a necessary condition for crevice corrosion to occur.     

钛的缝隙腐蚀行为研究

采用电化学测试技术，研究了工业纯钛和Ｔｉ－０．３％Ｍｏ－０．８％Ｎｉ合金在２５％ＮａＣｌ和ＨＣｌ沸腾溶液中的缝隙腐蚀行为。结果表明，由于合金元素Ｎｉ具有低的氢超电势，促进了阴极极化过程，从而提高了钝化能力，且缝内表面Ｎｉ的富集增强了膜的钝化稳定性，因此，Ｔｉ－０．３％Ｍｏ－０．８％Ｎｉ合金抗缝隙腐蚀性能优于工业纯钛。     

Kühlwasserseitige Korrosionsbeständigkeit von metallischen Werkstoffen zur Handhabung von Schwefelsäure

Cooling water side corrosion resistance of high alloyed materials for handling of process side sulfuric acid The approved materials for use in sulfuric acid alloy 825 (German material No. 2.4858) and alloy 20 (German mater. No. 2.4660) have only a low resistance against localized corrosion in chloride containing water and are unsuitable for handling of sulfuric acid. The newly developed austenitic Cr-base alloy, alloy 33, (X1CrNiMoCuN 33-32-1, German mater. No. 1.4591) with 33 % Cr, 31 % Ni, 0,6 % Mo and 0.4 % N should have an excellent resistance against pitting and crevice corrosion additional to its high sulfuric acid resistance, too, because its Pitting Resistance Equivalent No. calculated according to PREN = %Cr + 3,3 · %Mo + 30%N runs to 50. Pitting and crevice corrosion properties of the alloy 33 are tested in comparison to those of reference materials in high chloride containing solutions (1M NaCl, artificial and modified sea water, 10% FeCl₃ · 6H₂O; 500 g/l CaCl₂ ). Pitting potentials and potentials of repassivation of pitting, critical temperatures of localized corrosion (FeCl₃-test, CaCl₂-test, artificial sea water), potentials of repassivation of crevice corrosion as well as depassivation pH values of crevice corrosion following Crolet have been determined. The results confirm that the localized corrosion behaviour of the alloy 33 corresponds to its PREN. With regard to pitting corrosion alloy 33 is comparable with the special stainless steel alloy 31 (mater. No. 1.4562), with regard to crevice corrosion it is comparable with alloy 926 (German mater. No. 1.4529).     

Characterisation and corrosion resistance of Zn–Mn coatings electrodeposited from acidic chloride bath

Zn–Mn alloy coatings were galvanostatically electrodeposited from an acidic chloride bath. Effects of deposition current density, pH and temperature on surface morphology, microstructure and corrosion resistance of Zn–Mn coatings were studied. The coatings deposited at 10, 50 and 100 mA cm^?2 had a single η-Zn phase structure. However, a dual phase structure of η-Zn and ?-Zn–Mn with higher Mn content was found for the coatings deposited at 200 mA cm^?2. The dual structure degraded the corrosion resistance of the coatings. The highest corrosion resistance was achieved for the Zn–Mn coating deposited at 100 mA cm^?2, pH 4·9 and 25°C. This coating contained 4·1 wt-%Mn and showed a unique surface morphology consisting of randomly arranged packs of very thin platelets, laid perpendicular to the surface and provided a high compactness deficient free structure.     

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。     

Untersuchungen zum Korrosionsverhalten nichtrostender Stähle in Phosphorsäure in Abhängigkeit von dem Chlorid- und Fluoridgehalt und einer Wärmebehandlung beim Schweißen

Investigations into the corrosion behaviour of stainless steels in phosphoric acid in dependence on the chloride and fluoride contents and a heat-treatment during welding In the present investigation the corrosion behaviour of recently developed high-alloyed austenitic (X 2 NiCrMoCU 25 20) and austenitic-ferritic (X 2 CrNiMoCuN 25 5) steel has been tested towards phosphoric acid, the composition and concentration of which was adjusted to correspond to crude phosphoric acid with varying contents of Cl^?, F^?, Fe³⁺, and SO₃. Current density-voltage curves were recorded on steel test-specimens at room temperature, 45°C, and 80°C. In addition, test-pieces of both steels, after annealing treatment between 800°C and 500°C, as well as welded specimens of similar type were examined for the effect of heat input and consequent structural alterations on the corrosion behaviour. Both steels exhibit good corrosion resistance towards pure phosphoric acid. Cl^? and F^? ion impurities render the acid more aggressive. Austenitie-ferritic steel reacts more sensitively than austenitic steel towards heat input, resulting in deterioration in corrosion resistance. This may be attributed to the precipitation of inter-metallic phases in the ferritic structure.