Zur Lochkorrosionsneigung von austenitischen CrNiMo-Stählen in konzentrierten Ammoniumrhodanidlösungen

Pitting corrosion of austenitic CrNiMo-steels in concentrated ammoniumrhodanide solutions Quasipotentiostatic and potentiokinetic polarisation measurements at various 18 Cr-10 Ni steels with molybdenum contents up to 4,3% were performed in 25 and 45% ammoniumrhodanide solutions. It was found that pitting corrosion is caused by incomplete passivation in the potential range of –300 to +250 m V _H. At these potentials the formation of stable passive layers is hindered by the formation and local oxidative dissolution of sulfidic layers. Above +250 m V _H rhodanide ions act in these weak acidic ammoniumrhodanide solutions as agents which destroy passive layers, comparable with chloride ions. The limiting potentials for stable pitting corrosion, obtained from potentiostatic experiments, are shifted from –300 to –150 m V _H with increasing molybdenum content of the steel. The least tendency of pitting corrosion was found for that steel with the highest molybdenum content.     

Lochkorrosion an Nichtrostenden Stählen

Pitting corrosion of stainless steels Stainless steels can get pitting corrosion in halide containing solution, which make them a big risk in industrial production. Many investigations were made in the past in order to understand processes involved in pitting corrosion, pit initiation and pit growth. Results about the influence of alloying elements, their contents, the state of the structure, the condition of the surface, the content of chloride, the temperatures, the pH-value, the velocity of flow and of the oxidizer on the chloride induced pitting corrosion of passive stainless steels are presented. Electrochemical measurements and the application of surface analytical methods (SEM, SAM, XPS) with high lateral resolution are carried out. A part of the samples received a diffusion annealing in order to obtain reproducible results. Pitting Resistance Equivalents (PRE) – Pitting Index – with different multipliers are given and discussed critical. An electrochemical method for selecting materials without susceptibility to pitting corrosion are also presented.     

Untersuchungen über die Lochfraßkorrosion des passiven Eisens in chlorionenhaltiger Schwefelsäure

Investigation into pitting corrosion of passive iron in sulphuric acid containing chloride ions Pitting corrosion of metallic materials is generally connected with presence of a surface layer giving rise to a local differentiation of the electrochemical behaviour of the metal surface. The pitting corrosion by halogen ions on passive metals is investigated using passive iron in chloride ion-containing sulphuric acid as the model system. Quantitative data are presented concerning the mechanism and kinetics of the individual processes giving rise to pitting corrosion in a chloride ion concentration range covering three powers of ten, and in the whole potential range of iron passivity, from the Flade potential to the transpassive breakthrough potential. Pit formation normally follows a linear kinetic law, the rate depending in particular from the chloride ion concentration and from the thickness of the passive layer. The growth of pit diameters follows a linear kinetic law, too; the dissolution current density in the pits depends from the chloride ion concentration. Comparative investigations carried out on active iron, and potential distribution as measured in the pits show that the metal is active in the pits, too. The heterogeneous mixed electrode condition — active pit/passive metal surface — is stabilised by resistance polarisation. The investigations so far do not permit any statement concerning the specific effect of the chloride ions.     

Influence of the molybdenum content of high-alloy stainless steels and of the precipitation of intermetallic phases on pitting resistance in chloride-containing media

The influence of molybdenum on the resistance of stainless steels and nickel alloys (NiCrMoFe) to pitting corrosion is determined by means of electrochemical measurements (0.5 M NaCl/N2, 0…90°C) in both homogeneous and heterogeneous materials. As far as homogeneous materials are concerned, this influence is due to the inhibiting effect of molybdate formed at the interface passive layer/electrolyte and to a change in structure of the passive layer. The molybdate becomes effective as inhibitor of pitting corrosion only after the transpassive dissolution potential of molybdenum has been exceeded. Due to the precipitation of intermetallic phases, the pitting potential is shifted in cathodic direction. From a certain amount of precipitated intermetallic phases onward, the pitting potential remains constant. Consequently, the pitting potential is not dependent on the concentration of the alloying elements in the depleted matrix. Pitting corrosion preferably occurs at the phase boundaries intermetallic phase/depleted matrix and is due to lattice irregularities. Pit nucleation is observed at potentials at which the molybdate required for the inhibition of pitting corrosion has not yet been formed. Additions of molybdate to the electrolyte inhibit nucleation at the phase boundaries. Molybdenum segregates heavily in the weld microstructure of the afore-mentioned materials when compared with chromium. Pitting corrosion occurs at the dendrites that are poorer in molybdenum. A comparison of solution-annealed materials with different molybdenum contents shows that the molybdenum concentration of the dendrites imparts the same pitting resistance as is observed with solution-annealed materials with the same constant molybdenum content, respectively.     

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.     

Investigation on Pitting Corrosion of Nickel-Free and Manganese-Alloyed High-Nitrogen Stainless Steels

Pitting corrosion behavior of three kinds of nickel-free and manganese-alloyed high-nitrogen (N) stainless steels (HNSSs) was investigated using electrochemical and immersion testing methods. Type 316L stainless steel (316L SS) was also included for comparison purpose. Both solution-annealed and sensitization-treated steels were examined. The solution-annealed HNSSs showed much better resistance to pitting corrosion than the 316L SS in both neutral and acidic sodium chloride solutions. The addition of molybdenum (Mo) had no further improvement on the pitting corrosion resistance of the solution-annealed HNSSs. The sensitization treatment resulted in significant degradation of the pitting corrosion resistance of the HNSSs, but not for the 316L SS. Typical large size of corrosion pits was observed on the surface of solution-annealed 316L SS, while small and dispersed corrosion pits on the surfaces of solution-annealed HNSSs. The sensitization-treated HNSSs suffered very severe pitting corrosion, accompanying the intergranular attack. The addition of Mo significantly improved the resistance of the sensitization-treated HNSSs to pitting corrosion, particularly in acidic solution. The good resistance of the solution-annealed HNSSs to pitting corrosion could be attributed to the passive film contributed by N, Cr, and Mo. The sensitization treatment degraded the passive film by decreasing anti-corrosion elements and Cr-bearing oxides in the passive film.     

Inhibition der Lochkorrosion von Eisenwerkstoffen in neutralen Lösungen durch organische Phosphonsäurederivate

Inhibition of pitting corrosion of Iron and steel in neutral solutions by organic phosphonic acid derivatives Pitting corrosion and inhibition by organic phosphonic acid derivatives were investigated for pure iron, mild steel, 99,5% nickel and annealed austenitic steel (AISI 304) electrodes in aerated, not stirred and chloride ions containing borate buffer solution of pH = 8.0. Inhibition efficiency is different for the electrode materials investigated. Best results were obtained for nickel, were the inhibition efficiency decreases following the row: benzole-1.4-diphosphonic acid, hexane-l.6-diphosphonic acid-monohydrate, propane- 1.3-diphosphonic acid-monohydrate, amino-tris(methylene-phosphonic acid) and 1-hydroxyethane-1.1-diphosphonic acidmonohydrate. For iron and mild steel the last two substances do not show any inhibition efficiency. For stainless steel none of the compounds investigated can be used as inhibitor for pitting corrosion. For all materials inhibition depends significantly on the ratio of the inhibitor to the chloride concentration. Potentiodynamic measurements as well as cathodic discharging experiments of passive electrodes show that the inhibiting molecules are not incorporated into the passive layers but work by the adsorption mechanism. Results of Photopotential- and AES-investigations are in agreement with this statement.     

Oberflächenanalytische Deckschichtenuntersuchung der Lochkorrosion (Typ I) an Kupfer

Surface analysis of protective layers of pitting corrosion (type I) at copper Pitting type I at copper tubes is characterized by a typical protective layer formation of the corrosion product. Electronoptical and electronspectroscopical methods of surface analysis as ESCA, SAM and AES, respectively enable a qualitative and quantitative investigation of the protective layer. Moreover, this surface analysis permits conclusions of the pitting I-formation mechanism.     

Pitting corrosion of Al2024-T3 in sodium chloride solution

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Lochkorrosionsverhalten von Auftragschweißungen – Schweißlagen‐ und Oberflächeneffekte –

Pitting corrosion behaviour of built‐up welds – Effects of welding layers and tarnish – The pitting corrosion resistance of nickel based deposition welds on a superduplex steel made by active‐gas metal pulsed‐arc welding was studied. Therefore the determination of the CPT (Critical Pitting Temperature) should be carried out corresponding to ASTM G 48 C. However an unexpectedly low resistance of the built‐up welds also at multilayer order was noticed. After visual assessment of the examined specimens a significant effect of the surface condition was assumed. Because the CPT determination according to ASTM does not allow any statement about the corrosion process, this method was not suitable to characterize the corrosion system. For this reason a new method was applied to clarify the causes of the low corrosion resistance. This method determines the CPT with the help of the electrochemical current noise under the same conditions demanded in ASTM G 48 C. The temperature is increased continuously and the characteristic parameters of the system are recorded and evaluated objectively within short time. So it was possible to see the influence of the surface condition on the pitting corrosion behaviour of the examined specimens. The required parameters to the post‐processing of the deposition welds were determined. The comparison of the results show that the surface tarnish formed after the shielded arc welding process influences the pitting corrosion resistance negatively. After its elimination the CPT could be determined in dependence of the welding layers.     

硫酸盐还原菌对18-8不锈钢点蚀行为的影响

利用原子力显微镜(AFM)和电化学方法研究了海水中硫酸盐还原菌(SRB)对18-8不锈钢(18-8SS)点蚀过程的影响. AFM探测显示,微观蚀孔的生长速率在含SRB介质中明显高于在灭菌介质中.阳极循环极化结果表明,SRB的代谢产物显著降低了18-8SS的点蚀电位和再钝化电位;而且在含SRB介质中,18-8SS在短时间内就能被活化,表明SRB的代谢活动极大地促进了钝化层的破坏过程.阴极极化曲线表明,含SRB介质中单质硫或多态硫的还原是促使点蚀生长的主要因素,其阴极还原电流密度可以达到很高的数值(＞10 μA/cm2).     

Pitting corrosion evaluation by computer image processing

Pitting corrosion of AISI 304L stainless steel in a solution of FeCl₃ is evaluated by computer image processing methods. Pitting probability and histograms of pit-areas are computed. Pitting probability is defined as the ratio of pitted area over the total area. The pitting probability in this work was found to be 9.73%. Computer image processing is shown to be a promising tool for statistical evaluation of pitting corrosion.     

应用扫描微参比电极研究钢筋在含氯离子碱液中的点蚀及其被抑制行为

采用扫描微参比电极技术(SRET)对钢筋在含氯离子的碱性体系中点蚀行为和缓蚀剂对钢筋再钝化性能的影响进行研究.结果表明,在实验条件下无论氯离子存在与否,微腐蚀点始终存在,且是不稳定的.氯离子只是形成宏观点蚀的必要条件.所用缓蚀剂中只有亚硝酸钠才能抑制已出现的宏观点蚀.     

Corrosion morphologies on magnesium alloy AZ 91

Initiation and early propagation of pitting and filiform corrosion on bare alloy AZ91 (9% Al, 1% Zn) are investigated by natural immersion corrosion tests, electrochemical measurements and microanalytical studies. Initiation sites are few. Corrosion spreads from these sites first in the form of filiform corrosion for a limited period of time and pitting which later develops into a cellular type of etching. The important factors affecting filiform corrosion are temperature, material structure and degree of polarization at the anodic sites. Filiform attack on AZ91, unlike the classical mechanisms of filiform corrosion on coated metals, is driven by hydrogen evolution reaction on the cathodic sites of the surface, occurs under significant anodic control, propagates at a high, constant speed independent of degree of polarization along preferential paths determined by compositional and crystallographic factors, and is a temporary phenomenon under open circuit conditions. Pitting corrosion is more predominant with decreasing anodic polarization.     

Pitting on passive metals

Certain experimental results on the composition of passive films that affect the pit formation on metals and alloys are discussed. Information on the appearance of metastable and stable pits and their stability conditions is summarized. Pitting corrosion theories are compared.     

碳钢在两种氯化物溶液中的极化行为

利用极化试验和交流阻抗试验研究了碳钢在0.5MNH4Cl和0.5MNaCl溶液中的点蚀行为;通过金相显微镜和电子探针对钢的腐蚀形貌进行观察。结果表明:碳钢在0.5MNaCl和0.5MNH4Cl溶液中的极化曲线都出现活化特征。随着溶液pH值的增加和NaHCO3的添加,碳钢在NH4Cl和NaCl溶液中极化曲线上均有活化、活化-钝化转变、钝化和点蚀特征。显微观察表明,钢中的夹杂物是主要的点蚀诱发源。碳钢在0.5MNaCl和0.5MNH4Cl溶液中形成的活化峰分别与形成沉积膜和络合物有关。     

利用随机方法研究纳米化对纯锌点蚀行为的影响

选择柠檬酸型镀液,用脉冲电镀法成功制备纳米锌镀层;并用电化学法和随机法等研究纳米化对纯锌点蚀行为的影响.结果表明：纳米锌和铸态锌的点蚀击破电位均服从正态分布;纳米化增加了纯锌点蚀击破电位对电位扫描速度的敏感性,使纯锌的点蚀产生类型由B1（parallel）型转为B2（series）型,并能抑制纯锌的点蚀生长.     

Microtunnelling during selective alloy dissolution and during pitting

The kinetics and the morphology of selective dissolution of alloys containing a noble component and of pitting of passive metals are discussed emphasizing common properties of both localized dissolution processes. Dealloying of CuAu(Pd)-alloys and pitting of aluminum and aluminum alloys are considered as typical cases. Dealloying requires the nucleation of terrace site vacancy clusters, since easily dissolvable kink sites of screw dislocations are blocked by noble metal atoms. Pitting requires the nucleation of pores in the passive oxide film, which inhibits active metal dissolution. In both cases, rapid local crystallographic attack, ranging from etch pitting to very narrow tunnelling, is involved in the nucleation process. The term tunnelling is appropriate for all these events. While the scale of tunnelling events is much larger in the case of pitting compared with the case of dealloying, the calculation of the breakthrough potential of dealloying and of pitting is basically equivalent. Gross pitting, ending in the formation of macroscopic holes, is the result of localized renucleation of tunnelling events due to localized accumulation and hydrolysis of metal halogenide salt solution.     

电化学阻抗谱法对304不锈钢孔蚀生长和再钝化阶段的原位研究

利用动电位电化学阻抗谱(DEIS)法研究了304不锈钢在0.1mol/L NaCl溶液中的孔蚀行为,比较了孔蚀前后钝化膜的电化学阻抗谱的变化。提出了一种改进的双层膜结构,用以评价不锈钢在孔蚀的初始阶段和再钝化阶段各个参数的不同,指出孔蚀对钝化膜外层破坏较内层严重。使用活化控制的膜破裂模式评价孔蚀的初始阶段和再钝化阶段各个参数变化。     

Einfluß von Phosphaten und/oder Silikaten auf die durch Kupferionen ausgelöste Lochkorrosion in verzinkten Warmwasserrohren

Influence of phosphates and/or silicates on copper ion induced pitting of galvanized hot water tubing In connection with studies on the copper-induced pitting of galvanized steel tubes the inhibition by phosphates and/or silicates should be investigated. The investigations were carried out in Berlin tap water, at temperatures of 65°C. Inhibitors used were o-phosphate, p-phosphate, combinations of o/p-phosphate and phosphate/silicate as well as two silicates. All these inhibitors reduced the general corrosion of galvanized steel and copper. Best results were obtained with p-phosphate. Protective layers on both metals were produced not before a time of 150–200 days. Number and depth of pits were positively influenced by nearly all the inhibitors used. But only the combination phosphate/silicate lead to a complete prevention from copper-induced pitting. O-phosphate showed the lowest efficiency. These investigations once again pointed to the importance of the phase boundaries air/water/tube or deposits/water/tube as nuclei for pitting in tubes. A second layer containing calcium and inhibitors was formed on the primary layer of zinc corrosion products. These secondary layers are responsible for corrosion protection by the inhibitors.