Effects of nitric acid passivation on the corrosion behavior of ZG06Cr13Ni4Mo stainless steel in simulated marine atmosphere

ZG06Cr13Ni4Mo martensitic stainless steel was nitric acid-passivated to improve its corrosion performance. The effects of nitric acid passivation on the surface morphology, chemical composition, electrochemical properties, semiconductor behavior, and long-term corrosion performance of the stainless steel were investigated using various analytical techniques. An in-depth analysis of X-ray photoelectron spectroscopy (XPS) showed that the passive film formed after the acid passivation process showed high thickness and a duplex character as it consisted of a hydroxide layer and an oxide layer. The oxide layer affected the corrosion resistance and thickness of the passive film. The thickness of the passive film was calculated theoretically as well as experimentally by fitting the electrochemical impedance spectroscopy and XPS results. The electrochemical tests revealed that the dramatic increase in the corrosion resistance of the stainless steel after the passivation was due to the formation of a thick, low-disorder passive film rather than Cr enrichment. The removal of inclusions resulted in higher pitting resistance, whereas the increased roughness showed a negative effect on the corrosion behavior of the stainless steel. During the wet–dry cyclic tests, the modification of the passive film was examined. The passivated stainless steel exhibited good corrosion resistance for up to 50 days of exposure in the simulated environment.     

温度对Cr26Mol超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响

通过循环极化曲线、Mott-Schottky曲线以及电化学阻抗谱等方法研究了温度对Cr26Mo1超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响.结果表明:随着温度升高,Cr26Mo1超纯高铬铁素体不锈钢的自腐蚀电位降低,腐蚀电流密度增大,点蚀电位下降,钝化膜阻抗降低.Cr26Mo1不锈钢钝化膜的半导体类型和性质在不同温度下发生改变.Cr26Mo1不锈钢发生点蚀的孕育期随着温度的升高而缩短,点蚀敏感性增加,已发生点蚀的试样不能够自修复.     

温度对Cr26Mo1超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响

通过循环极化曲线、Mott-Schottky曲线以及电化学阻抗谱等方法研究了温度对Cr26Mol超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响.结果表明:随着温度升高,Cr26Mol超纯高铬铁素体不锈钢的自腐蚀电位降低,腐蚀电流密度增大,点蚀电位下降,钝化膜阻抗降低.Cr26Mol不锈钢钝化膜的半导体类型和性质在不同温度下发生改变.Cr26Mol不锈钢发生点蚀的孕育期随着温度的升高而缩短,点蚀敏感性增加,已发生点蚀的试样不能够自修复.     

Electrochemical Behavior of 2205 Duplex Stainless Steel in NaCl Solution with Different Chromate Contents

The electrochemical behavior of 2205 duplex stainless steel in NaCl solution with different chromate contents were investigated by potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), Mott-Schottky analysis, and scanning electron microscope (SEM). The effect of chromate on passivity and pitting behavior of stainless steel was also studied. The results showed that pitting susceptibility as well as semiconducting properties of passive film is heavily dependent on the chromate concentration. There exists a critical chromate value (about 0.03?M in 1?M NaCl solutions) below which the pitting corrosion on the stainless steel would be inhibited and above which it would be accelerated.     

马氏体相变对304不锈钢点蚀发展过程的影响

采用模拟闭塞电池法和交流阻抗法研究了奥氏体304不锈钢形变诱发马氏体相变对点蚀发展过程中化学和电化学行为的影响。结果表明，随着马氏体含量的增加，闭塞区溶液pH值下降得更快，Cl^-迁入闭塞区的量更多。马氏体相的存在增强了材料的电化学活性，既减小了点蚀发展过程中钝化膜孔隙内的欧姆电阻，又减小了孔隙内的反应极化电阻，从而促进了点蚀发展。     

Enhancements of Passive Film and Pitting Resistance in Chloride Solution for 316LX Austenitic Stainless Steel After Sn Alloying

In the present work, the electrochemical behavior and properties of the passive film of a new Sn-alloyed 316 LX austenitic stainless steel were investigated. With the increase in Sn content in 316 LX austenitic stainless steel from 0 to 0.21%, the critical pitting temperature value increased from 32.6 to 38.8 °C, and the pitting potential increased from 0.252 V_(SCE) to 0.317 V_(SCE). Electrochemical impedance spectroscopy results showed that the corrosion resistance of passive film rose with the increase in Sn content, indicating a more stable passive film. The Mott–Schottky measurement revealed an n-type passive film with a decreased carrier concentration on the 316 LX austenitic stainless steel surface. The Cr, Sn~(2+) and Sn~(4+)(SnO, SnOHCl or SnO_2) enrichments were observed in the passive layer by X-ray photoelectron spectroscopy. The enrichment of Sn and Cr in the passive film can account for the enhanced pitting resistance of 316 LX austenitic stainless steel in chloride solution.     

Electrochemical polishing as a 316L stainless steel surface treatment method: Towards the improvement of biocompatibility

A 316L stainless steel (316L-SS) surface was electrochemically polished (EP) in an electrolyte of a new chemical composition at different cell voltages, with the aim of improving its corrosion resistance and biocompatibility. X-ray photoelectron spectroscopy results revealed that the EP-formed oxide films were characterized by a significantly higher atomic Cr/Fe ratio and film thickness, in comparison to the naturally-grown passive oxide film formed on the untreated (control) 316L-SS surface. As a result of the increase in the oxide film thickness and relative Cr enrichment, the EP-treated 316L-SS surfaces offered a notable improvement in general corrosion resistance and pitting potential. In addition, the attachment of endothelial cells (ECs) and smooth muscle cells (SMCs) to the 316L-SS surfaces revealed a positive effect of electropolishing on the preferential attachment of ECs, thus indicating that the EP surfaces could be endothelialized faster than the control (unmodified) 316L-SS surface. Furthermore, the EP surfaces showed a much lower degree of thrombogenicity in experiments with the platelet-rich plasma. Therefore, the use of the electrochemical polishing technique in treating a 316L-SS surface, under the conditions presented in this paper, indicates a significant improvement in the surface’s performance as an implant material.     

不锈钢盐酸露点腐蚀行为的原位研究

利用一种新型的露点腐蚀模拟装置结合原位的电化学阻抗谱,电化学噪声等测试手段评价了304和316L两种不锈钢的盐酸露点腐蚀行为.结果表明,316L不锈钢表现出更优异的耐盐酸露点腐蚀性能,主要原因可归结为两点:一是316L不锈钢钝化膜中含有较高的Cr/(Cr+Fe) 比以及较低含量的Fe;二是316L不锈钢钝化膜中含有能改善抗点蚀性能的Mo.     

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。     

Improvement on the pitting corrosion resistance of 304 stainless steel via duplex passivation treatment

A remarkable improvement in the pitting corrosion resistance of 304 stainless steel was attempted using a novel duplex passivation treatment method. First, chemical passivation in nitric acid followed electrochemical passivation via potential polarization of step cycling in sodium nitrate electrolyte. Compared with traditional chemical passivation, breakdown potential was increased from 0.31 V_SCE to positive than 0.9 V_SCE at 70°C in a solution bearing 0.6 M [Cl^?] concentration. The critical pitting temperature was enhanced from 21.5°C to above 70°C in a solution with 6 M [Cl^?] concentration. Impedance analysis and X‐ray photoelectron spectroscopy results show that a more compact passive film with a higher ratio of chromium oxide on iron oxide was achieved by electrochemical passivation compared with chemical passivation. Morphology observation suggested that the potential polarization of step cycling slightly increased the dissolution of inclusions after being subjected to chemical passivation. The probable reason for the improvement on pitting resistance is discussed in detail based on inclusion dissolution and the protectiveness in passive film.     

时效处理对CrCoMo不锈钢耐蚀性能的影响

采用循环极化和电化学阻抗谱研究了退火状态和时效状态的CrCoMo不锈钢在3．5％NaCl溶液中的腐蚀行为。结果表明,退火态CrCoMo不锈钢经时效处理后点蚀电位负移,钝化膜保护性下降,材料的耐蚀性能降低。其原因是时效处理使得第二相沿晶界析出,材料的组织均匀性变差。     

镀铌不锈钢双极板的电化学性能

采用对水和空气稳定的氯化胆碱:乙二醇=1:2（摩尔比）的离子液体为电解质,在316不锈钢基体上进行电镀铌,考察模拟质子交换膜燃料电池（PEMFC）环境中镀铌不锈钢双极板的电化学性能。结果表明,以氯化胆碱类离子液体为电解质在316不锈钢表面可获得平整均匀的颗粒状铌镀层。在模拟质子交换膜燃料电池环境中,镀铌316不锈钢的腐蚀电位得到提高,维钝电流密度减小,阳极极化性能得到改善;孔蚀电位正移,反应电阻增大,耐蚀性能提高。能谱和X射线衍射分析结果表明,镀铌后316不锈钢表面生成化学惰性良好的NbO和Nb₂O₅,形成耐蚀“屏障”,改善了不锈钢表面膜的钝化能力,提高了不锈钢的电化学稳定性能。     

Passivation Behavior of 2507 Super Duplex Stainless Steel in Hot Concentrated Seawater: Influence of Temperature and Seawater Concentration

The electrochemical behavior and passivation properties of 2507 super duplex stainless steel (SDSS) in the hot concentrated seawater with different concentrations at different temperatures are characterized by electrochemical methods and X-ray photoelectron spectroscopy. The passive film formed on 2507 SDSS belongs to n-type semiconductor and mainly composed of hydroxides and oxides of Fe and Cr under all circumstances. The protectiveness of the passive film decreases with the increase in temperature mainly because of the increase in defect density in the passive film. The corrosion resistance of 2507 decreases with the increase in seawater concentration, and the critical pitting temperature also decreases.     

Effect of p H on the Electrochemical Behaviour and Passive FilmComposition of 316L Stainless Steel

The effect of pH on the electrochemical behaviour and passive film composition of 316 L stainless steel in alkaline solutions was studied using electrochemical measurements and a surface analysis method. The critical pH of 12.5 was found for the conversion from pitting corrosion to the oxygen evolution reaction(OER). OER was kinetically faster than pitting corrosion when both reactions could occur, and OER could postpone pitting corrosion. This resulted in pitting being initiated during the reversing scan in the cyclic polarization at the critical pH. According to the X-ray photoelectron spectroscopy analysis, the content of Cr and Mo decreased with pH, while Fe content increased. This induced the degradation of the passive film, which resulted in the higher passive current densities under more alkaline conditions. The selective dissolution of Mo at high p H was found, which demonstrated that the addition of Mo in austenitic stainless steels might not be beneficial to the corrosion resistance of 316L in strong alkaline solutions.     

温度对316L不锈钢耐海水腐蚀性能的影响

运用临界点蚀温度(CPT)、环状阳极极化曲线和电化学阻抗谱等方法研究了不同温度下316L不锈钢的海水腐蚀行为. 结果表明, 晶粒尺寸不同的两种316L不锈钢的CPT基本相同; 随着海水温度升高, 点蚀电位和再钝化电位均呈线性降低, 但是细晶钢的点蚀性能下降更大, 85℃时粗晶钢比细晶钢的点蚀电位约高60 mV. 与粗晶钢相比, 细晶钢在65℃下形成的钝化膜微缺陷更多, 且点蚀诱导时间较短.     

HCO3–对超级13Cr马氏体不锈钢钝化行为及点蚀行为的影响

目的研究在0.1 mol/L NaCl硼酸缓冲溶液中,研究HCO_3~–对超级13Cr马氏体不锈钢的钝化及点蚀行为的影响。方法采用动电位极化、恒电位极化、Mott-Schottky曲线、电化学阻抗谱等电化学测试手段,并结合3D超景深显微镜进行点蚀形貌观察,研究超级13Cr马氏体不锈钢的电化学腐蚀行为。结果随着HCO_3~–浓度的增加,超级13Cr的钝化区间变宽,点蚀电位向正向移动,稳态点蚀发生的敏感性降低。HCO_3~–减少了超级13Cr亚稳态点蚀数量,降低了亚稳态点蚀电流密度峰值的平均值。随着HCO_3~–浓度的增大,超级13Cr钝化膜电阻Rf升高,电荷转移电阻Rct升高,钝化膜电容Cf逐渐减小。HCO_3~–使得超级13Cr钝化膜半导体特性由n型转变为n+p型双极性,且随着溶液中HCO_3~–浓度的增大,钝化膜中的施主密度ND和受主密度NA减小。结论 HCO_3~–的加入使得超级13Cr不锈钢钝化膜厚度增大,钝化膜内点缺陷密度降低,对基体的保护作用增强,抑制了超级13Cr的亚稳态和稳态点蚀发生。     

Effect of Alloying Tin on the Corrosion Characteristics of Austenitic Stainless Steel in Sulfuric Acid and Sodium Chloride Solutions

The effect of tin on general and pitting corrosion behaviors of the austenitic stainless steel in sulfuric acid and sodium chloride solutions was investigated by potentiostatic critical pitting temperature, cyclic potentiodynamic polarization, electrochemical impedance spectroscopy, and scanning electron microscopy. The results showed that there is an optimal tin addition which is around(0.062–0.1) wt%, and the general corrosion resistance of B316 LX with 0.08 wt% tin addition in boiling H2SO4 increased remarkably with a corrosion rate of an order of magnitude lower than that of 316 L.Hydrolyzation of tin ions induces more metastable pit occurrence on the material surface. However, the pitting resistance of B316 LX increases because tin oxides improve the density and uniformity of the passive film, and hydroxide and oxide of tin inhabit the process of pit growing. The effect of tin on pitting corrosion process is illustrated schematically.     

循环冷却水中 2507 双相不锈钢微生物腐蚀研究

目的研究2507双相不锈钢在循环冷却水模拟溶液(添加微生物SRB+IOB)中的腐蚀特征,确定其腐蚀机理。方法模拟某炼油厂循环冷却水溶液,采用SEM,EDS和电化学测试等手段分析2507双相不锈钢在SRB+IOB循环冷却水中浸泡不同时间后的腐蚀产物形貌及其电化学腐蚀情况。结果2507双相不锈钢的腐蚀速率很低,属于轻度腐蚀;在循环冷却水模拟溶液中的阳极极化曲线具有明显的钝化区,且钝化膜具有良好的自修复能力;腐蚀倾向随时间增加先增大后减小,腐蚀速率随时间增加先减小后增大。结论 SRB和IOB及其代谢活动与Cl-协同作用是点蚀的主要原因;2507双相不锈钢具有良好的钝化性和耐微生物腐蚀性能。     

不锈钢点腐蚀发生的早期过程Ⅱ.电化学扫描隧道显微研究

应用电化学扫描隧道显微技术,考察外加电位、介质条件及时间等因素对不锈钢发生微点腐蚀早期阶段表面形貌的影响,从纳米级空间分辨度进一步探索不锈钢表面钝化膜破坏及微点腐蚀发生早期过程机理.结果表明,不锈钢在点蚀早期阶段,首先发生不稳定微点腐蚀,其表面形貌随着不稳定微点腐蚀的发生、消长而变化.不稳定微点腐蚀的几何尺寸约为10nm,极化电位愈正,不锈钢钝化膜局部溶解破坏和微点腐蚀发生的倾向性愈大,不稳定的微点腐蚀在一定的条件下可发展为稳定点腐蚀.即使在开路电位下,Cl-也可能在不锈钢表面呈不均匀分布,进而导致钝化膜     

炼油厂冷却水系统硫酸盐还原菌对316L不锈钢点腐蚀的研究

用开路电位、动电位扫描、电化学阻抗技术和扫描电镜等方法,研究了316L不锈钢在硫酸盐还原菌(SRB)溶液中的腐蚀电化学行为,分析了炼油厂冷却水系统微生物腐蚀的特征及机制.结果表明,在含有SRB溶液中的自腐蚀电位(Ecorr)和点蚀电位(Epit)随浸泡时间的增加而负移,极化电阻(Rp)随浸泡时间的增加而减小;在含有SRB溶液中的腐蚀速率均大于在无菌溶液中;SRB的生长代谢活动影响了316L SS表面的腐蚀过程,使不锈钢表面的钝化膜层腐蚀破坏程度增加,加速了316L SS的腐蚀.