模拟2倍浓缩海水中聚环氧琥珀酸和Na2MoO4对304不锈钢的缓蚀作用

为开发适用于循环冷却海水／不锈钢体系的绿色缓蚀剂,采用电化学阻抗谱、极化曲线及表面腐蚀形貌分析,研究了聚环氧琥珀酸（PESA）、Na2MoO4在模拟2倍浓缩海水中对304不锈钢的缓蚀作用。结果表明：在模拟2倍浓缩海水中,PESA与Na2MoO4均能在304不锈钢表面形成保护膜,产生缓蚀作用;PESA为阳极吸附型缓蚀剂,...     

Corrosion resistance of the layers formed on the surface of plasma-nitrided AISI 304L steel

Austenitic stainless steels have good corrosion resistance, but their low hardness and low wear resistance limit their use whenever surface hardness is required. Nitriding treatments have been successfully applied to stainless steels to improve their mechanical and tribological properties; however, at temperatures above 723 K, gas or salt bath nitriding processes decrease the corrosion resistance due to the formation of CrN and other phases within the modified layer. Chromium compounds draw chromium and nitrogen from the adjacent regions, degrading the corrosion resistance. The plasma nitriding technique permits the use of treatment temperatures as low as 623 K without promoting degradation in the corrosion resistance of stainless steel. In this work, the pulsed glow discharge (PGD) technique was used for nitriding steel (AISI304L) in order to investigate the effect of the temperature of this treatment in the morphology and, as a consequence, in the anodic behavior of the formed layers, in solution with and without chloride ions. Four different temperatures were employed (623, 673, 723, and 773 K). The samples were characterized by optical microscopy (OM), scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), microhardness measurements, and electrochemical tests with potentiodynamic anodic polarization curves. The nitriding temperature alters the anodic behavior due to a displacement of the polarization curve towards higher currents, in a solution free of chloride ions. In a chloride solution, the nitriding temperature increases the pitting potential up to the oxygen evolution region.     

A new strategy for corrosion protection of porous stainless steel using polypyrrole films

In this work, a method to improve the protection against corrosion of porous sintered stainless steel is presented. It is based on the electrodeposition of polypyrrole(PPy) layers doped with a large size counterion such as dodecylbenzenesulphonic acid(DBSA), a conducting polymer with high corrosion resistance and good biocompatibility. The efficacy of PPy coating depends on the adequate adhesion between the metal substrate and the coating layer. The protection against corrosion has been tested using 316 L stainless steel(SS) powder sintered at different conditions to evaluate the effect of the sintering atmosphere(nitrogen and vacuum) and cooling rates(furnace and water) on corrosion resistance, while wrought 316 L SS has been used as reference material. In addition, two electrochemical deposition techniques have been tested to select the most adequate. Open circuit potential evolution, anodic polarization measurements and electrochemical impedance spectra have been used to evaluate corrosion protection in phosphate buffer saline medium. It has been evidenced that a more homogeneous and stable coating was obtained in the case of porous stainless steel. The corrosion potential shifted to nobler values and the anodic polarization branch became more stable. Coated porous samples have a good passivation performance with a lower stable passive current density and a higher breakdown potential. The transfer electronic resistance and the impedance module increase more than one order of magnitude. Therefore,the porosity of sintered stainless steel is seen as an advantage for the improvement of the adherence of the PPy coatings. The best corrosion protection is found for samples sintered in nitrogen and water-cooled.     

聚苯胺/银复合薄膜的制备及其耐蚀性能

为了研究聚苯胺(PANI)/银复合薄膜对不锈钢的防腐蚀性能,采用循环伏安法在不锈钢表面沉积一层Ag后,再通过对苯胺的电化学聚合制备了PANI膜。利用阳极极化法和交流阻抗法研究了PANI/Ag复合膜的耐蚀性及其影响因素。结果表明:在0.1 mol/L NaC l溶液中,不锈钢覆盖复合膜后的自腐蚀电位比无膜时有所提高,其耐蚀性能得到增强;电化学聚合溶液浓度、扫描速率及扫描上限等因素对复合膜耐蚀性的影响情况为:电解液中苯胺和硫酸浓度过高或过低都会影响膜的致密度,从而影响复合膜的耐蚀性;电化学参数的变化会影响复合膜的聚合速率,使复合膜的抗腐蚀能力不同;当苯胺单体浓度为0.2 mol/L、硫酸浓度为1 mol/L、扫描电位上限为1 V、扫描次数为50次、扫描速率为50 mV/s时,采用循环伏安法聚合苯胺,可形成沉积致密度高、耐蚀性好的复合膜。     

An impedance study of two types of stainless steel in Ringer physiological solution containing complexing agents

The effect of complexing agents EDTA and citric acid on the electrochemical behaviour of AISI 304 and orthopaedic stainless steels in Ringer physiological solution was investigated by potentiodynamic polarization method and electrochemical impedance spectroscopy (EIS). The content of Mo has a pronounced effect on the corrosion resistance, as evident by the broader passive range of the orthopaedic stainless steel containing Mo. The addition of complexing agents induces significant changes in polarization and impedance characteristics, i.e., the shift of corrosion and breakdown potentials in a more negative direction, an increase in current density, and a significant decrease in charge transfer resistance. The results were interpreted by the formation of soluble complexes of metal ions with chelating agents, especially EDTA, which suppressed the formation of the outer Fe(III) layer of the passive film. The impact of complexing agent on the electrochemical parameters was found to be related to its concentration in electrolyte and the stability constant of the complex formed with the related metal ion.     

高氮奥氏体不锈钢耐点蚀性能研究

目前产于高氮不锈钢的研究多集中于理论基础、制造工艺和力学性能等方面,有关耐蚀性方面的研究有限。通过循环极化、Mott-Schottky曲线以及电化学阻抗(EIS)等方法,研究了Cr23Mo1N奥氏体不锈钢(高氮钢,HNSS)和316L不锈钢在Cl-溶液中的耐点蚀性能。结果表明:与316L不锈钢相比,高氮钢具有更正的自腐蚀电位,更小的维钝电流密度。阻抗谱表明高氮钢的钝化膜比316L更加稳定,且电荷转移电阻更大。Mott-Schottky曲线表明高氮钢的点缺陷施主浓度比316L不锈钢低一个数量级,钝化膜的绝缘性更好。循环极化曲线表明高氮钢的点蚀敏感性更小,钝化膜的自修复能力更强,耐蚀性能更加优越。     

Effects of phosphate on the chloride-induced corrosion behavior of reinforcing steel in mortars

The influence of phosphate as a corrosion inhibitor on the corrosion behavior of as-received and pre-rusted reinforcing steels in mortar specimens was investigated after 360 days exposure in 3.5% NaCl solution. This involved the use of electrochemical techniques for studying the steel surface reactions and microscopic observations of the steel–mortar interface. The electrochemical methods, including electrochemical impedance spectroscopy (EIS) and measurements of corrosion potential (E_corr) and linear polarization resistance (LPR), were employed to evaluate the corrosion tendency and general corrosion rate of steel. In addition, the pitting corrosion resistance of steel was also determined by cyclic polarization (CP) measurements. The results indicate that different from nitrite, which is generally accepted as an anodic inhibitor, phosphate may be a cathodic inhibitor according to its reduced corrosion rate and more negative E_corr at the same dosage as nitrite in mortar specimens. The study also reveals that the inhibiting efficiency of phosphate against general corrosion of both as-received and pre-rusted specimens is lower than 10%, which is inferior to nitrite in some respects. However, as indicated by cyclic polarization measurements, the presence of phosphate provides slightly higher pitting corrosion resistance in comparison to nitrite. Furthermore, it suggests that the corrosion inhibition mechanism of phosphate in mortars mainly depends on a dual effect occurring at the steel–mortar interface. Furthermore, it is confirmed that phosphate has little effect on the long-term mechanical properties of mortars.     

New material for orthopedic implants: Electrochemical study of nickel free P558 stainless steel in minimum essential medium

Nickel, a component of stainless steels (SS) applied in orthopedic implants may cause allergic processes in human tissues. P558 nickel free SS was studied to verify its viability as a substitute for stainless steel containing nickel. Its performance is compared to ISO 5832-9 and F138 most used nowadays grades in implants fabrications, in minimum essential medium, MEM, at 37 °C. Potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and “in vitro” cytotoxicity were used as techniques. From the electrochemical point of view P558 SS is comparable to ISO 5832-9 SS in MEM. It remains passivated until the transpassivation potential, above which generalized corrosion occurs. F138 presents pitting corrosion at 370 mV/SCE. The cytotoxicity results showed that P558, ISO 5832-9 and F138 do not present cytotoxic character. Therefore, these results suggest that P558 SS can be applied in orthopedic implants.     

含H2S的NaCl溶液中溶解氧对PH13-8Mo钢腐蚀性能的影响

为研究新型马氏体沉淀硬化不锈钢PH13-8Mo在含饱和H_2S的NaCl溶液中的腐蚀行为,利用极化曲线、电化学阻抗谱等电化学测试和浸泡实验相结合的方法,通过扫描电子显微镜(SEM)和X射线光电子能谱分析技术(XPS),观察了该高强钢在含H_2S的除氧和不除氧的NaCl溶液中的腐蚀形貌,并对其腐蚀产物的成分进行了分析.结果表明:在除氧的NaCl溶液中,阳极极化曲线的形状发生了明显的变化,电化学阻抗谱的容抗弧的幅值也较未除氧的溶液中变小;在除氧的NaCl溶液中浸泡7 d后,由于H_2S水解后的S~(2-)或HS~-离子侵入到钝化膜的内部,并与钝化膜或金属基体发生反应,使得试样表面发生全面腐蚀,腐蚀产物主要为Fe、Cr、Ni、Mo的氧化物和硫化物;而在未除氧的NaCl溶液中浸泡后,试样表面仅发生局部腐蚀.     

钛阳极氧化膜的半导体特性及腐蚀行为

目前,国内外还鲜见有关金属钛阳极氧化膜半导体特性与腐蚀行为的报道。采用极化曲线、交流阻抗和Mott-Schottky曲线研究了TA2硫酸和磷酸阳极氧化膜的腐蚀性能和半导体特性。结果表明：在1％NaCl溶液中,钛阳极氧化膜的自腐蚀电位升高,自腐蚀电流密度降低,耐蚀性能提高;氧化电压对氧化膜的厚度有较大影响;磷酸阳极氧化膜...     

Effects of sulfidation of passive film in the presence of SRB on the pitting corrosion behaviors of stainless steels

Pitting corrosion of stainless steels is a very complex process in the media with sulfate-reducing bacteria (SRB). Bacterial activities not only instantaneously affect the pit-initiation and the pit-growth, but also induce the changes of passive film in structure/properties and in turn affect the pitting corrosion behaviors of stainless steels as well. In this work, sulfidation of passive film in the cultures of SRB and its effects on the pitting corrosion behaviors of stainless steels were investigated by electrochemical techniques and X-ray photoelectron spectroscopy (XPS). As results showed, anodic cyclic polarization curves demonstrated that sulfidation caused a loss of passivity of stainless steels, but sulfidation happening in the short term is more detrimental than that in the long term; from standing point of cathodic depolarization of corrosion, sulfidation polarized the cathodic reactions to a greater extent, which means that sulfidation helps impede the pit-growth; XPS revealed that almost only iron oxides in the passive film were converted into sulfides in forms of FeS and FeS₂, while elements of Cr and Ni still remained essentially as oxides/hydroxides. So, in understanding the mechanisms of pitting corrosion of stainless steels in the media with SRB, effects of sulfidation of passive film must be taken into consideration.     

不锈钢表面电化学合成导电聚苯胺膜的研究

在酸性电解液中分别用电化学恒电位法和恒电流法在不锈钢基材上成功制备了导电聚苯胺膜，该膜在空气中呈绿色，稳定、完整致密，为结晶态结构，与基体的结合情况较好。在氯化钠溶液中测定试样的阳极极化曲线后发现，表面覆盖聚苯胺膜后的不锈钢，其点蚀电位比无膜时升高1000mV左右，表明导电聚苯胺膜可显著提高不锈钢的抗点蚀性能，具有良好的点腐蚀防护效果。     

Stress corrosion cracking and hydrogen embrittlement cracking of welded weathering steel and carbon steel in a simulated acid rain environment

Abstract

The stress corrosion cracking (SCC) and hydrogen embrittlement cracking (HEC) characteristics of welded weathering steel and carbon steel were investigated in aerated acid chloride solution. The electrochemical properties of welded steels were investigated by polarisation and galvanic corrosion tests. Neither weathering steel nor carbon steel showed passive behaviour in this acid chloride solution. The results indicated that weathering steel had better corrosion resistance than carbon steel. Galvanic corrosion between the weldment and the base metal was not observed in the case of weathering steel because the base metal was anodic to the weldment. However, the carbon steel was susceptible to galvanic corrosion because the weldment acts as an anode. Slow strain rate tests (SSRT) were conducted at a constant strain rate of 7.87 × 10⁷ s^-1 at corrosion potential, and at potentiostatically controlled anodic and cathodic potentials, to investigate the SCC and HEC properties in acid chloride solution. The welded weathering steel and carbon steel were susceptible to both anodic dissolution SCC and hydrogen evolution HEC. However, weathering steel showed less susceptibility of SCC and HEC than carbon steel at anodic potential because of Cr and Cu compounds in the rust layer, which retarded anodic dissolution, and at cathodic potential due to the presence of Cr, Cu, and Ni in alloy elements, which inhibit the reduction of hydrogen ions. SEM fractographs of both steels revealed a quasicleavage fracture in the embrittled region at applied anodic and cathodic potentials.     

Austenitizing treatment influence on the electrochemical corrosion behavior of 0.3C-14Cr-3Mo martensitic stainless steel

Effects of austenitizing treatment temperatures on aqueous corrosion properties of martensitic stainless steels were investigated by electrochemical tests (potentiodynamic test, potentiostatic test and electrochemical impedance spectroscopy), and surface analyses (optical microscopy and XRD). The results of potentiodynamic test revealed that the breakdown potential increased with the increased austenitizing temperature, indicating increased relative resistance to initiation of localized corrosion. EIS measurements showed that MSS3 (1030 °C) exhibits larger polarization resistance value than MSS1 (970 °C) and MSS2 (1000 °C) at passive and breakdown states. This was caused by decreasing the amount of Cr-rich M₂₃C₆ carbide which acts as preferential sites for pitting corrosion.     

Steady-state and impedance study of n-GaAs in H2SO4 solution: Mechanism analysis

In this paper, a study on the electrochemical impedance of anodic decomposition of n-GaAs in 0.5 M sulfuric acid, combined with steady-state polarization techniques, is presented. Both dark and daylight conditions have been investigated for comparison of their influence on polarization curves and impedance by hole injection in a potential range from open circuit to breakdown. An inductive loop appears if a high enough positive potential is applied for both conditions, while recombination resistance is only observed for the daylight case. Quantitative simulation of the impedance spectra suggests that the rate-determining step for corrosion/photocorrosion is the generation of mobile intermediates, e.g., AsGa⁺, which are then replaced by competition between a Faradaic process involving immobile intermediate formation and a parallel chemical step to form AsGa-OH.     

Some aspects of corrosion and film formation of austenitic stainless steel type 316LN using electrochemical impedance spectroscopy (EIS)

Corrosion and passive film characteristics of 316LN stainless steel with different degrees of cold work (0–25%) were studied using electrochemical impedance spectroscopy (EIS) and potentiodynamic anodic polarization techniques in deaerated acidic and alkaline (pH = 8) media. EIS measurements were conducted at open circuit potential (OCP) as well as after passivation in these media. Using the capacitance data from EIS measurements, film thickness was calculated. A definite correlation was observed between film thickness and corrosion rate after passivation. Analysis of the series capacitance and series resistance data from the EIS spectra showed that the films formed at OCP and after passivation were of semiconducting type. The nature of the semiconducting type of films was determined to be n-type using the ratios of anodic and cathodic transfer coefficients (α_a/α_c).     

Corrosion inhibition of AA6063 alloy by vanadates in alkaline media

Vanadium aqueous compounds are considered as promising environmentally friendly inhibitors for heterogeneous aluminium alloys. In this study, mechanism of corrosion inhibition of AA6063 in alkaline media by vanadate inhibitors is presented. A combination of weight loss and open circuit potential measurements, potentiodynamic polarization and electrochemical impedance spectroscopy was used to compare corrosion behavior of AA6063 alloy in aerated pH 10 0.05 M sodium chloride solutions in the absence and presence of 0.003 mol/l sodium orthovanadate. Tetrahedrally coordinated mono‐ and polyvanadates, that are main forms in such solutions, cause a decrease in corrosion current density and significantly increase amplitude of impedance spectra and impedance modulus |Z| values due to mixed cathodic‐anodic inhibition effect mainly associated with the formation of adherent surface film on cathodic and anodic intermetallic particles of alloy.     

Electrochemical characterization of AISI 316L stainless steel in contact with simulated body fluid under infection conditions

Titanium and cobalt alloys, as well as some stainless steels, are among the most frequently used materials in orthopaedic surgery. In industrialized countries, stainless steel devices are used only for temporary implants due to their lower corrosion resistance in physiologic media when compared to other alloys. However, due to economical reasons, the use of stainless steel alloys for permanent implants is very common in developing countries. The implantation of foreign bodies is sometimes necessary in the modern medical practice. However, the complex interactions between the host and the can implant weaken the local immune system, increasing the risk of infections. Therefore, it is necessary to further study these materials as well as the characteristics of the superficial film formed in physiologic media in infection conditions in order to control their potential toxicity due to the release of metallic ions in the human body. This work presents a study of the superficial composition and the corrosion resistance of AISI 316L stainless steel and the influence of its main alloying elements when they are exposed to an acidic solution that simulates the change of pH that occurs when an infection develops. Aerated simulated body fluid (SBF) was employed as working solution at 37 °C. The pH was adjusted to 7.25 and 4 in order to reproduce normal body and disease state respectively. Corrosion resistance was measured by means of electrochemical impedance spectroscopy (EIS) and anodic polarization curves.     

Electrochemical properties of 316L stainless steel with culturing L929 fibroblasts.

Potentiodynamic polarization and impedance tests were carried out on 316L stainless steel with culturing murine fibroblast L929 cells to elucidate the corrosion behaviour of 316L steel with L929 cells and to understand the electrochemical interface between 316L steel and cells, respectively. Potential step test was carried out on 316L steel with type I collagen coating and culturing L929 cells to compare the effects of collagen and L929 cells. The open-circuit potential of 316L steel slightly shifted in a negative manner and passive current density increased with cells, indicating a decrease in the protective ability of passive oxide film. The pitting potential decreased with cells, indicating a decrease in the pitting corrosion resistance. In addition, a decrease in diffusivity at the interface was indicated from the decrease in the cathodic current density and the increase in the diffusion resistance parameter in the impedance test. The anodic peak current in the potential step test decreased with cells and collagen. Consequently, the corrosion resistance of 316L steel decreases with L929 cells. In addition, collagen coating would provide an environment for anodic reaction similar to that with culturing cells.     

Corrosion behavior of plasma sprayed ceramic and metallic coatings on carbon steel in simulated seawater

Al₂O₃, ZrO₂ and Ni60 coatings were produced on carbon steels by plasma spray. Ni60 was used as the bond coat in all the cases. The microstructure of these coatings was analyzed by scanning electron microscopy (SEM). The corrosion behavior of the plasma spray coated samples as well as uncoated samples was evaluated by open circuit potential (OCP) measurements, potentiodynamic polarization tests, and electrochemical impedance spectroscopy (EIS) in simulated seawater. The results showed that Ni60 coating protected carbon steels against the corrosion and plasma spraying ceramic powders on metallic coating improved the corrosion resistance of the coatings further. The corrosion resistance of the Al₂O₃ coating was superior to that of the ZrO₂ coating due to the relatively few defects in Al₂O₃ coating.