Mechanical and electrochemical behavior of nanocrystalline surface of 304 stainless steel

This paper reports our recent studies on nanocrystalline surface layer of 304 stainless steel (304SS) produced using a sandblasting and annealing process. The grain size of the sandblasted surface layer was less than 20 nm. Mechanical and electrochemical properties of the nanocrystalline surface and its passive film were investigated using nano/micro/-indentation, micro-scratch, scanning Kelvin probe (SKP), potentiodynamic scanning and electrochemical scratch techniques. It was demonstrated that the nanocrystalline surface was markedly superior to that of original 304SS with enhanced passive film. The polarization, electrochemical scratch and SKP measurements indicated that the nanocrystalline surface had higher resistance to corrosion, greater capability of repassivation and higher chemistry stability. All results demonstrated that the nanocrystallization surface did not only enhance the mechanical properties of the surface layer and its passive film, but also benefited the passivation capability of the steel with improved corrosion resistance.     

Stainless steel electrode characterizations by electrochemical impedance spectroscopy for dye-sensitized solar cells

Electrochemical impedance spectroscopy (EIS) was used to understand the electrochemical mechanisms which appear in dye-sensitized solar cells (DSSCs). This qualitative and quantitative technique permits identification of the phenomena proceeding within the different elements composing the cell and at their interfaces.In this study, the classical conducting glass substrate was replaced by a protected stainless steel (304 type) substrate as the counter-electrode (cathode) in dye-sensitized solar cells. Platinum was deposited at the substrate surface to optimize the charge transfer resistance of the electrode.After a few days of immersion in the electrolytic solution, stainless steel substrates coated with low thickness of Pt show pitting corrosion due to iodine. Defects in the Pt layer such as discontinuity of the film and micro-cracks may explain the corrosion of the stainless steel substrate. However the Pt layer degradation is retarded for thicker films. On the other hand, polished substrates show a better behaviour probably due to the elimination of the defects on the stainless steel surface.Electrolytic solution was optimized. For this, components such as 1-butyl-3-methylimidazolium iodide (BMII), guanidine thiocyanate (GT) and 4-tert-butylpyridine (TBP) were added. No corrosion phenomena on stainless steel 304 appeared within 3 days when TBP was added. This means that TBP acts as a corrosion inhibitor.A schematic equivalent circuit is also proposed.     

Comparative electrochemical study of 08H18N10T, AISI 304 and AISI 316L stainless steels

The aim of this work was to determine the main characteristics of the passivation and surface oxidation of 08H18N10T, AISI304 and AISI316L stainless steels, which serve as structural materials of VVER and PWR nuclear reactors. With the help of electrochemical experiments these materials were ranked according to their resistance against uniform corrosion. The measurements were done as a function of temperature in the range between room temperature and 80 °C. A sample of 08H18N10T steel was irradiated in the Budapest research reactor.With cyclic voltammetry we found that AISI 304 exhibits a very large passivation peak as a classical example for passivation. The peak is much smaller for AISI 316L and it is very small for 08H18N10T. This implies that the native oxide layer on AISI 316L and 08H18N10T is more protective than on AISI 304. The 08H18N10T steel has the best protective passive oxide layer which forms already in air and it is very difficult to remove it even at negative potentials. By comparing impedance spectra of the various stainless steels results lead to the same conclusions we obtained from cyclic voltammetry. Our experimental results of the irradiated steel are in accord with the fact that neutron irradiation increases the number of defect sites within the oxide layer. We found that irradiation has no considerable effect on the active-to-passive transition process. The small variations in the alloy composition do not alter the transition process significantly, as well.     

PTA加氢反应器在碱洗条件下的安全分析

通过用SUS304L不锈钢制作的楔形张开加载预裂纹试样,在280℃、质量分数为3．0%的NaOH溶液的条件下进行应力腐蚀试验,以模拟对苯二甲酸(PTA)装置的加氢反应器PD-201不停车碱洗工作过程中SUS304L不锈钢在该介质环境下的抗应力腐蚀性能。结果表明：SUS304L不锈钢在此条件下经720h的浸泡,未发生应力腐蚀开裂现象,设备泵用SUS304L不锈钢作为内衬复合层是安全的。     

Microelectrodes for corrosion studies in microsystems

Electrochemical techniques using microcapillaries as electrochemical cells allow to study local processes on metal surfaces. Since the usual large-scale electrochemical techniques provide only average data integrating over a large surface area (mm²–cm²), they are inadequate to investigate local corrosion processes. Due to the enhanced current resolution of the microelectrochemical methods down to pA and fA, processes in the micro- and nanometer range can easily be studied. This method allows to perform local electrochemical investigations of single areas of special interest, such as grain boundaries, second-phase precipitates or inclusions. Therefore, the microcapillary technique is well suited to study the corrosion behavior of microsystems. Results obtained from studies of localized corrosion processes of stainless steels are presented and discussed.     

PTA装置不锈钢材料腐蚀磨损的探讨

采用自制的实验装置,模拟PTA生产装置中回转式干燥机蒸汽列管工作条件,对奥氏体不锈钢0Cr18Ni9(304)、00Cr17Nd4Mo2(316 L)、00Cr19Ni13M03(317 L)和双相不锈钢00Cr22Ni5Mo3N(2205)在含有溴离子和对苯二甲酸颗粒的醋酸介质中,进行腐蚀磨损性能研究。结果表明,4种不锈钢的腐蚀磨损速率随着腐蚀介质温度的升高而增加;在低温时,腐蚀磨损速率差别不大;当温度超过80℃以后,腐蚀磨损性能的差异变大,其中2205的耐腐蚀磨损性能最好,其次为317 L,316 L,而304则最差。相同条件下,腐蚀磨损速率大于均匀腐蚀速率。建议用2205代替316 L制作PTA同转蒸汽管干燥机的加热列管。     

Investigations of the passive layer cracking by means of Dynamic Electrochemical Impedance Spectroscopy

The Dynamic Electrochemical Impedance Spectroscopy has been applied for stress corrosion cracking (SCC) investigations. The effect of applied potential and tensile stresses on the stress corrosion cracking behaviour of type 304L stainless steel (SS) immersed in 0.5 M NaCl solution of room temperature has been examined. This paper presents impedance spectra obtained for 304L stainless steel samples at the different potential values. The results obtained proved the possibility of providing new details about the dynamics of the initiation and propagation of the crack path compared to classical electrochemical techniques.     

304奥氏体不锈钢低温盐浴氮化处理及其耐蚀性

采用低温(430°C)盐浴对304奥氏体不锈钢进行氮化处理,研究了氮化时间对渗氮层组织、显微硬度及耐蚀性的影响。分别用X射线衍射仪(XRD)、表面显微硬度计、光学显微镜分析了渗氮层的相组成、显微硬度、截面形貌和厚度。结果表明,304不锈钢表面的渗氮层厚度和显微硬度都随处理时间的延长而增大。氮化处理1h得到的渗氮层由单一的S相组成。经盐浴渗氮处理的304不锈钢,其耐Cl-点蚀性能得到改善,430°C下氮化4h得到的渗氮层耐蚀性能最好。     

循环水中304不锈钢发生点蚀的Cl~-浓度阈值研究

采用电化学法研究了循环水中304不锈钢点蚀电位(Eb)、蚀孔深度、蚀孔数量与氯离子浓度的关系。结果表明,常温下304不锈钢的Eb总是随着氯离子浓度的增大而减小,当氯离子质量浓度小于800 mg/L时,增大氯离子浓度易导致点蚀敏感,而大于该值时增大氯离子浓度不会明显增大点蚀倾向;从蚀孔深度和表面蚀孔数量得出的304不锈钢点蚀倾向由大变小的氯离子质量浓度阈值为770 mg/L。     

Surface and electrochemical characterization of pitting corrosion behaviour of 304 stainless steel in ground water media

The effectiveness of aminotrimethylidene phosphonic acid (ATMP) as a corrosion inhibitor in association with a bivalent cation like Zn²⁺ and non-ionic surfactant like polyoxyethylene sorbitan monooleate (Tween 80) were investigated by measuring corrosion losses using electrochemical techniques. The corrosion of 304 stainless steel in the ground water medium was inhibited by complexation of the inhibitor. A combined inhibition effect was achieved by adding both ATMP and Zn²⁺ along with Tween 80. The formulation functioned as a mixed type inhibitor. The synergistic effect of the inhibitor compound is calculated. Luminescence spectra, FTIR spectra, XRD, XPS and scanning electron microscopic studies were carried out to understand the mode of corrosion inhibition and also the morphological changes on the metal surface.     

Corrosion monitoring of type 304L stainless steel in nuclear near-high level waste by electrochemical noise

Electrochemical noise (EN) monitoring of 304L stainless steel (SS) and sensitized 304 SS in 3 N nitric acid and nuclear near-high level waste (HLW) solution was carried out using a three nominally identical electrode configuration under open circuit conditions. EN signals characteristics of passivation process was obtained for 304L SS in 3 N nitric acid throughout the measurement period, while in near-HLW solution, features of passivation and depassivation were observed. Potentiodynamic polarization of 304L SS in 3 N nitric acid and near-HLW showed spontaneous passivation. Noise resistance was evaluated from EN time record and this parameter was used in the present investigation to qualitatively assess the corrosion behavior during the immersion period. The average noise resistance was found to be lower in near-HLW solution when compared to 3 N nitric acid. The results of the investigation are presented in this article.     

Comparison of local electrochemical impedance measurements derived from bi-electrode and microcapillary techniques

In the present paper, local electrochemical impedance spectra were obtained on a 316L stainless steel from two configurations: a dual microelectrode (bi-electrode) and microcapillaries. With the bi-electrode, the local impedance measurements were made from the ratio of the applied voltage to the local current density calculated from the application of the ohm's law. With the use of microelectrochemical cells, the specimen surface area in contact with the electrolyte is limited by the use of glass microcapillaries and the local impedance was defined from the ratio of the local potential to the local current restricted to the analysed surface area. Differences and similarities observed in local impedance spectra obtained with the two configurations were described.     

酸性NaCl溶液中304控氮不锈钢腐蚀过程的声发射特征

采用声发射技术和电化学噪声技术研究了304控氮不锈钢C型环试样在0.5mol·L-1NaCl与1.5mol.L-1H2SO4的混合溶液中,恒载荷情况下的腐蚀过程。分析了腐蚀过程中所产生的声发射信号的振铃数随时间分布情况,以及不同阶段的声发射信号的频谱特征。同时对比分析了声发射检测结果与电化学噪声检测结果。结果表明,声发射检测技术对于304控氮不锈钢在酸性NaCl溶液中所产生的腐蚀声发射信号很敏感,在不同腐蚀阶段中,声发射信号特征差异明显,对于判断不同腐蚀阶段具有指导意义;声发射与电化学噪声测试结果基本一致,将声发射检测与电化学噪声检测结合使用,有助于使现场检测结果更加可靠。     

Analysis of electrochemical parameters in time domain during the passive layer cracking occurring on the 304L stainless steel in chlorides solution under tensile stresses

Dynamic electrochemical impedance spectroscopy (DEIS) has been applied for detailed analysis of the passive–active transient region during the passive layer cracking process. The effect of applied potential and tensile stresses on the passive layer rupture of type 304L stainless steel (SS) immersed in 0.5 M NaCl solution at room temperature was examined. This paper presents instantaneous impedance spectra obtained for 304L stainless steel samples at the different potential values that refer to the transition from passive into active state while crack of the passive layer took place. Besides, differential dependencies of electrochemical parameters versus relative elongation have been presented to illustrate the system's dynamics changes.     

Evaluation of microbially influenced corrosion with electrochemical noise analysis and signal processing

Corrosion behaviors of stainless steel (SS304), with attached Acidithiobacilus ferrooxidans (ATF) bacteria and exposed to three different types of artificial saliva solutions, namely: (1) Jenkin's solution, (2) Tomasi's solution, and (3) NaCl solution, have been monitored using electrochemical noise (ECN) analysis and signal processing techniques. The ECN data has been analyzed in time and frequency domains, and the time-domain analysis was used to calculate parameters such as skewness, kurtosis and noise resistance, R_n. The corrosion mechanisms were analyzed in terms of the ranges of skewness and kurtosis. The frequency analysis showed that the conventional fast Fourier transforms (FFT) method failed to differentiate among the ECN signals obtained in different solutions with and without the attachment of bacteria. Therefore, the fractional Fourier transform (FrFT) was introduced to process ECN signals and has been demonstrated as a better tool to describe the corrosion behaviors of electrodes in different solutions.     

Investigation of selective corrosion resistance of aged lean duplex stainless steel 2101 by non-destructive electrochemical techniques

Lean duplex stainless steel 2101 (LDX2101) shows wide application potential due to its better corrosion performance and lower cost than traditional 304 austenite steel. This paper investigates the effects of thermal aging treatments at 700 °C for various aging times up to 100 h on the selective corrosion resistance of LDX2101 by two non-destructive electrochemical measurements: double-loop electrochemical potentiokinetic reactivation (DL-EPR) and electrochemical impedance spectroscopy (EIS). The evolution of microstructure was examined by optical microscopy, SEM microscopy and X-ray diffraction techniques (XRD). The results showed that the two applied electrochemical measurements agreed very well. Both methods were able to reveal the relationship between microstructure and selective corrosion resistance, which was related to the formation of chromium- and molybdenum-depleted zones around the precipitates, especially the σ phase, during aging. Nevertheless, more information could be obtained using EIS methods, including the interfacial charge transfer reaction and the corrosion product adsorption process. The results suggest that the susceptibility of the aged alloy to selective corrosion is presumably codetermined by the formation of chromium- and molybdenum-depleted areas, as well as by the replenishment of them, in these areas from the bulk during aging.     

Behaviour of a copper-AISI 304 stainless steel mixed anode in electrolytic copper refining with periodic current reversal

In the search for suitable materials to be used as anode supports in the periodic current reversal refining process this work covers the study of austenitic AISI 304 stainless steel. Experimental results show that the resistance of this steel to the aggressive action of the refining electrolyte is good at the working temperature of 60°C since no corrosion was detected after 24 h of electrolysis. The periodic polarization of this material results in a progressive passivation which was observed by operating under different initial surface conditions and by detecting remnant anodic currents which gradually decreased with time. For time ratios lower than twenty, a build up of metallic copper deposit on the steel part of the mixed anode occurred whatever the current density used.     

含硼水溶液上方蒸汽对奥氏体不锈钢的腐蚀行为

硼酸应用广泛,其对设备腐蚀不容忽视。针对核电站含硼水溶液循环体系中设备顶端腐蚀的实际情况,取304奥氏体不锈钢为研究对象,研究了在给定温度和一定硼浓度水溶液存在下,溶液上方含硼水蒸气对奥氏体不锈钢的腐蚀行为,并将其与相应的溶液腐蚀对比。采用扫描电子显微镜（SEM）、X射线衍射仪（XRD）和X射线光电子能谱仪（XPS）分析了试样表面氧化膜。结果表明：在180 ℃下腐蚀1 200 h后,304不锈钢在含硼水蒸气中的腐蚀程度高于相应含硼水溶液的腐蚀程度;尽管两种环境中的试样表面均形成了双层氧化膜,但在含硼水蒸气中形成的氧化膜表层富铁镍,而在含硼水溶液中形成的氧化膜表层富铬,并用氧化膜形成机理解释了此现象。     

Influence of the exposure of AISI 304L stainless steel at moderately high temperature on the susceptibility to crevice corrosion

Stainless steels passivate in air by forming a very thin (a few nanometre thick) protective film of Fe and Cr mixed oxides. The nature and the protective properties of this film change if the stainless steel surface is previously exposed to elevated temperatures. Thermal treatment, chemical processes and mechanical manufacture to which stainless steel surfaces are normally subject, result in changes to the surface conditions, and therefore to modification of the corrosion resistance. Among the various forms of corrosion of stainless steels, crevice corrosion is undoubtedly the most common in industrial environments and one of the most insidious from an engineering point of view. In this work the effects of surface conditions, in particular as a consequence of exposure at moderately high temperature ranging between 150 and 300°C, on the corrosion behaviour of type AISI 304L stainless steel have been investigated. The aim has been to verify if common treatments causing local heating, such as welding, even in remote regions, thermal stretching, grinding, exposure to superheated steam, or sterilisation processes can constitute aggravating circumstances in respect of crevice corrosion susceptibility.     

Corrosion behavior of amorphous carbon deposit in 0.89% NaCl by electrochemical impedance spectroscopy

Amorphous carbon films were deposited on SS316L substrates using a DC magnetron sputtering system, aiming at the application of the coated SS316L for biomedical implants. The biocompatibility and chemical stability of the carbon layers have been previously demonstrated. The films were deposited on top of sputtered titanium coatings introduced as a buffer layer to enhance film-substrate adhesion. The corrosion resistance of the a-C/Ti/SS316L systems was investigated by electrochemical techniques. The electrolyte used in this work was 0.89 wt.% NaCl at pH 7.4, which simulates body fluid ionic concentrations. The coated samples displayed corrosion resistance values in the saline solution much higher than the stainless steel substrates and the role of the Ti coating thickness was analysed in order to determine the optimal system for biological applications.