Numerical simulations study of the localized corrosion resistance of AISI 316L stainless steel and pure titanium in a simulated body fluid environment

The resistance of both AISI 316L stainless steel (AISI 316L SS) and commercially pure titanium (cpTi) to localized corrosion in a simulated body fluid solution was investigated using numerical simulations. The resulting model, based on transport equations in dilute solutions, is designed to predict the susceptibility of these two biomaterials to crevice corrosion initiation. The results show that cpTi and AISI 316L SS alloy are very resistant to the initiation of crevice corrosion in 0.9% NaCl solution and AISI 316L SS alloy is more susceptible to corrosion initiation over the long term than cpTi.     

Corrosion behaviour of carbon S-phase created on Ni-free biomedical stainless steel

Following the success of forming a carbon S-phase (expanded austenite) surface layer on medical grade Ni-free austenitic stainless steel by DC plasma carburising, the established commercial carburising process Kolsterising® was performed on both Ni-containing (AISI 304) and Ni-free austenitic stainless steels. While the Ni-containing stainless steel responded very well to Kolsterising®, the Ni-free alloy did not. The carbon absorption and the hardness of the Kolsterised® Ni-free alloy are inferior to Kolsterised® AISI 304 Ni-containing stainless steel, however, the hardness of the untreated Ni-free alloy was doubled by Kolsterising®. The response of both Kolsterised® Ni-free and Ni-containing alloys to pitting, crevice corrosion and intergranular corrosion resistance was similar. From this work it can be concluded that the Kolsterised® austenitic stainless steels do not suffer from intergranular corrosion but are susceptible to intragranular pitting when tested in boiling sulphuric acid and copper sulphate solution. It was also observed that Kolsterising® improves significantly the pitting and crevice corrosion resistance of the alloys used in this study.     

三效连续蒸发结晶装置中TA10换热器的失效分析

目的 针对国内某化工厂氯化铝生产线上三效连续蒸发装置中换热器发生的换热管束泄漏事故,进行相应的失效分析,找出其原因,以避免相似的腐蚀失效事故再次发生.方法 采用宏观检测方法确定发生腐蚀的位置及腐蚀的宏观形貌,由全浸试验确定TA10合金在管、壳程工况下的耐蚀性,通过电镜扫描观察表面腐蚀的微观形貌,最后借助能谱分析和X射线衍射的方法确定腐蚀产物的成分.结果 换热器中挡流板被腐蚀,其表面金属发生大面积不规则剥落,换热管束外侧发生严重腐蚀,金属大面积剥落,管程出口处只有焊缝处发生明显腐蚀.TA10合金在管程工况下不会发生腐蚀,而在壳程工况下,会发生较为严重的腐蚀,腐蚀表面呈现出多层状结构,且表面形状无规则,生成的腐蚀产物为TiH2.结论 TA10合金在壳程工况下,并不能达到良好的耐蚀效果,现有工艺条件下,露点的产生使换热管外侧有高浓度盐酸产生,其会和TA10合金发生严重的吸氢反应,从而导致氢致开裂以及吸氢脆化,伴随气体的冲刷,便出现了金属大面积剥落现象,换热管与管板在连接处发生缝隙腐蚀,缝隙内钛作为阳极发生溶解.最后针对性地提出了防腐蚀建议.     

Loch- und Spaltkorrosion von Chrom- und Chromnickelstählen in chloridhaltigen Lösungen

Pitting and crevice corrosion of stainless steels in chloride solutions In practice stainless steels in chloride containing waters are found to be susceptible to crevice corrosion and pitting. Corrosion tests were carried out on AISI 304 L stainless using a simulated crevice and the compositions of the electrolyte in the crevice determined. Long term potentiostatic tests were used to determine the critical potentials for crevice corrosion (U_S), for various steels in sodium chloride solutions at different concentrations and temperatures. The steels studied were 22 CrMo V 121, X 22 CrNi 17 and AISI 304 L. Like the critical pitting potential (U_L), U_S was found to have a strong dependence on the chloride content of the external solution. At higher concentrations the two potentials were similar. At lower concentrations the U_S was lower than U_L. The knowledge of these critical potentials together with well known rest potentials for a steel in an electrolyte of known concentration, allows conclusions to be drawn about its susceptibility to pitting and crevice corrosion. The method is suitable also for other passive metals.     

溶液环境对模拟剥离涂层下X70钢腐蚀行为的影响

采用矩形缝隙装置,研究了阴极极化条件下本体Na₂SO₄溶液浓度、pH 值以及本体溶液的含氧状况对模拟剥离涂层下溶液的化学和电化学环境的影响,分析了剥离区域内X70钢表面发生的电化学反应。结果表明,增加本体Na₂SO₄溶液的浓度虽然有利于阴极电流在剥离涂层内传输,但会导致钢板表面钝化膜的破坏而发生腐蚀。本体溶液pH值为酸性时缝内的化学环境变化迅速,缝口处发生腐蚀反应;而碱性条件下剥离区的pH值基本不变。本体溶液供氧量的减少降低了剥离区域内阴极保护的有效距离。外加电位的中断使缝内溶液酸化,X70钢处于自腐蚀状态。     

Study on constitutive relation of AISI 4140 steel subject to large strain at elevated temperatures

We conducted hot torsion and compression tests of AISI 4140 steel (medium carbon and low alloy steel) to investigate the effect of deformation mode on constitutive relation. It was noted that shapes of the curves formed by the experimental data were different, although the overall stress levels were similar. To formulate constitutive relation of AISI 4140 steel, various constitutive equations were considered. Among them, Voce’s constitutive equation was selected as the model to possibly modify. Results showed that the modified constitutive equation could predict the flow stress of AISI 4140 steel accurately, in comparison with the results of the other constitutive models such as Misaka’s and Shida’s equations. It has been found out that the approach to obtain a constitutive equation applicable to large strain ranges was fruitful and this modified equation might have a potential to be used for hot strip rolling process where more precise calculation of stress decrement due to dynamic recrystallization is important.     

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。     

Investigation of compound layer formed during ion nitriding of AISI 4140 steel

Low alloy AISI 4140 steel was ion nitrided at temperatures of 500, 550 and 600 °C for various times in a 50%N₂---50%H₂ gas mixture. The nature of the compound layer formed was studied by X-ray diffraction and optical metallography. The X-ray analysis shows the existence of a γ-Fe₄N compound zone on the surface at all three temperatures. The thickness of the compound layer increases with increasing time at 500 and 550 °C; however, it begins to decrease with increasing time at 600 °C.     

Corrosion behaviour of a dissimilar joint TIG weld between austenitic AISI 316L and ferritic AISI 444 stainless steels

The AISI 444 stainless steel (SS) has become an option to substitute the AISI 316L SS because of its low cost and satisfactory corrosion resistance. However, the use of AISI 444 alloy tubes in heat exchangers causes the welding of a dissimilar joint. The aim of this study was evaluate the corrosion resistance of the tube-to-tubesheet welded by a TIG process composed of AISI 316L and AISI 444. Preparation of samples was executed through replication of tube-to-tubesheet joints. In order to test the corrosion resistance of the welded joint, the following tests were applied: sensitisation, mass loss from room temperature up to 90 °C and electrochemical corrosion tests in 0.5 mol/L HCl and 0.5 mol/L H₂SO₄ electrolytes. The results have shown that the dissimilar joint suffers galvanic corrosion with increased degradation of the heat-affected zone of the AISI 444 tube. Nevertheless, the mechanisms of localised corrosion (pit and intergranular) were more active in the AISI 316L alloy. It is concluded that the dissimilar joint showed better corrosion resistance than the welded joint composed solely of AISI 316L at temperatures up to 70 °C, as the conditions observed in this work.     

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.     

Rainbow fringes around crevice corrosion formed on stainless steel AISI 316 after ennoblement in seawater

The crevice corrosion occurrence probability of stainless steel (SS) AISI 316 was increased under ennoblement condition due to chemically added H₂O₂ into seawater. The H₂O₂ was used to simulate the important factor causing ennoblement in natural marine biofilm. Morphology of the crevice corrosion was observed using an incident‐light source microscopy. Some interesting “rainbow” fringes were observed around micro‐crevices. The mechanism was discussed from the ions diffusion and potential distribution during the crevice formation. This result shows that under ennoblement condition the colored fringe is a distinct characteristic of the morphology of localized corrosion for stainless steel.     

Hot-corrosion resistance of dissimilar AISI 4340 and AISI 304L weldments in the molten salt environment at 600°C

High temperature corrosion resistance of welded components in power plant industry, hot sections of gas turbines, boilers, industrial waste incinerators, metallurgical furnaces and petrochemical installations is one of the serious necessity. The failure of hot sections of welded component is due to the deposition of molten salt which accelerates the hot corrosion reactions in the weld joint. In this research work, the oxy-chlorination of dissimilar weldments between AISI 304L austenitic stainless steel and AISI 4340 alloy steel at 600°C in eutectic mixture of K₂SO₄?+?60% NaCl under molten salt conditions was investigated. Corrosion kinetics for this dissimilar joints calculated from the thermogravimetric charts were represented. Corrosion on the dissimilar joint employing E309L filler in pulsed current gas tungsten arc welding process is found to be very aggressive, due to the fragmented delta ferrites at numerous locations resulting in the formation of the micro electrochemical cells, which act as sites for corrosion initiation and thus leading to higher corrosion rate. However, in the case of continuous current, the joint is able to protect itself better in this environment due to lower amounts of delta ferrites in weld zone, which is attributed to the higher temperature available in continuous mode leading to austenisation of delta ferrites in the multipass welding.     

Moiré based method for real‐time crevice corrosion monitoring

A novel real‐time technique was developed to monitor localized corrosion occurring over a metal surface. It is an optical method based on the Moiré technique that has undergone further improvements and fine tuning for more accurate measurements. Upon testing, good agreements were obtained with the microscopically determined penetration depth. Application for this technique was demonstrated through real‐time monitoring of crevice corrosion activity occurring on the surface of AISI 316 (UNS S31600) stainless steel immersed in 3% NaCl at 60 °C. The crevice was an artificial clear glass/metal crevice with a gap thickness of 5 μm. Based on the findings of these results it was shown that this method can effectively and accurately be used to monitor crevice corrosion.     

The effect of annealing on the corrosion behaviour of 444 stainless steel for drinking water applications

In this study, the corrosion behaviour of annealed and not annealed AISI 444 ferritic stainless steel in tap water with and without addition of selected concentrations of chloride ions was investigated. Cyclic potentiodynamic macro (large area) and micro (small area) polarization measurements (CPP), salt spray test, SEM and EDS analysis were employed to evaluate the pitting and crevice corrosion susceptibility of annealed and not annealed AISI 444. The results obtained indicate that annealing does not improve the resistance to pitting and crevice corrosion. Moreover, micro CPP indicates local susceptibility to pitting on both annealed and not annealed materials; such susceptibility was not evident from macropolarization tests.     

Corrosion of stainless steels under heat transfer conditions in nitric acid

Abstract

Novel test rigs are described for the study of the corrosion of metal specimens under controlled heat fluxes. In the corrosion of stainless steels in nitric acid, tests at various heat fluxes with steel surface temperature kept constant have shown that the cooler acid present at the surface under higher heat fluxes leads to slightly smaller corrosion rates than under isothermal conditions. Crevice corrosion can develop under the gasket sealing the stainless steel specimen to the test cell. This crevice corrosion can produce enhanced corrosion rates (by factors up to 100), not only on surfaces within the crevice, but also on those external to the crevice. The factors influencing the development of crevice corrosion are discussed.     

Microbially influenced corrosion on stainless steels in waste water treatment plants: Part 1

Abstract

Field tests on stainless steels have been carried out at five waste water treatment plants for one year. Three grades of stainless steel, i.e. AISI 304 (UNS S30400), AISI 316 (UNS S31600), and duplex 2205 (UNS S31803) were tested in the final settling tank in the plants. The time dependence of the open circuit potential (OCP) was measured for all coupons. Ennoblement of the OCP, similar to that reported from investigations in sea water, was found in one of the plants. Waters from three of the exposure sites, containing dispersed deposits from exposed coupons, were chemically analysed. Pitting corrosion was observed after the field test on steel grade AISI 304 in three of the five plants, and on AISI 316 in one plant. No corrosion was found on 2205 in any of the plants. Laboratory measurements of the OCP were carried out for the AISI 304, AISI 316, and duplex 2205 steels in water collected from one of the plants. Cathodic polarisation curves were recorded in waste water from the same plant. T he cathodic reaction rate increased at the highest OCP. Simulation of the ennoblement was carried out by potentiostatic polarisation in a 600 ppm chloride solution. The current response indicated corrosion of welded AISI 304 material and of AISI 304 and AISI 316 steels in crevice assemblies after a long induction time. Part 2 of this study presents the results of further testing and a risk assessment design.     

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.     

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.     

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.     

Corrosion resistance properties of glow-discharge nitrided AISI 316L austenitic stainless steel in NaCl solutions

Glow-discharge nitriding treatments can modify the hardness and the corrosion resistance properties of austenitic stainless steels. The modified layer characteristics mainly depend on the treatment temperature. In the present paper the results relative to glow-discharge nitriding treatments carried out on AISI 316L austenitic stainless steel samples at temperatures ranging from 673 to 773 K are reported. Treated and untreated samples were characterized by means of microstructural and morphological analysis, surface microhardness measurements and corrosion tests in NaCl solutions. The electrochemical characterization was carried out by means of linear polarizations, free corrosion potential-time curves and prolonged crevice corrosion tests. Nitriding treatments performed at higher temperatures (>723 K) can largely increase the surface hardness of AISI 316L stainless steel samples, but decrease the corrosion resistance properties due to the CrN precipitation. Nevertheless nitriding treatments performed at lower temperatures (?723 K) avoid a large CrN precipitation and allow to produce modified layers essentially composed by a nitrogen super-saturated austenitic metastable phase (S-phase) that shows high hardness and very high pitting and crevice corrosion resistance; at the same polarization potentials the anodic current density values are reduced up to three orders of magnitude in comparison with untreated samples and no crevice corrosion event can be detected after 60 days of immersion in 10% NaCl solution at 328 K.