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双语推荐：钝化电位

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目的研究黄铜在不同阳极钝化电位下形成的钝化膜的半导体性能。方法通过动电位极化曲线获取黄铜在硼酸盐缓冲溶液中的维钝电位区间,并选取3个钝化电位值对黄铜进行钝化处理,采用电化学阻抗谱和Mott-Schottky半导体理论研究阳极钝化电位对钝化膜半导体性能的影响,并进一步利用PDM模型进行点缺陷扩散系数的计算。结果黄铜在硼酸盐缓冲溶液中有明显的钝化区间,不同钝化电位对应的Mott-Schottky直线斜率均为负值,且点缺陷扩散系数均为10-14数量级。随着阳极钝化电位的正移,钝化膜的阻抗值不断增加,受主密度降低,平带电位变小,空间电荷层厚度增加。结论黄铜在不同钝化电位下形成的钝化膜均表现出p型半导体的特性,膜中载流子以空穴为主,随着阳极钝化电位的正移,钝化膜的导电性能变差,耐蚀性能增强,对基体的保护作用更好。
Objective To investigate the semi-conducting property of passive films formed on brass under different passivation potential. Methods The passivation range of brass in borate buffer solution was obtained by potentiodynamic polarization curves, and three passivation potentials were chosen. The electrochemical impedance spectroscopy and Mott-Schottky theory were used,and the diffusion coefficient of passive film was calculated using PDM. Results The brass showed obvious passivation state in borate buffer solution. The Mott-Schottky plots were linear with a negative slop. With the passivation potential moving towards positive, the film impedance increased, the acceptor density and the flat potential decreased, the space charge layer thickness increased, and the order of magnitude of point defect diffusion coefficient was 10-14 . Conclusion Under different passivation potential, the passive films on the brass surface showed the property of p-type semiconductor, the majority of the carriers

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采用循状阳极极化,交流阻抗和动电位扫描技术研究了模拟循环冷却水中氯离子对304L不锈钢耐蚀性的影响。结果表明:随着氯离子浓度增大,不锈钢的点蚀电位Eb降低;循环阳极极化曲线上的保护电位与击穿电位的差值的大小反应了不锈钢钝化膜自我修复的能力的强弱,差值越小不锈钢表面钝化膜的修复功能越强即钝化膜的性能;从交流阻抗图谱得到的不锈钢电荷转移电阻值随氯离子浓度增大而降低。
The anticorrosion property of 304 L stainless steel in simulated cooling water with chlorine ion by methods of cyclic anodic polarization , AC impedance and dynamic potential scan was studied.The experimental results indicated with the increase of the concentration of chlorine ion , the pitting corrosion potential Eb of stainless steel would lower.The difference between the breakdown potential and the protection potential reflected the self -repair ability of the passivated film of stainless steel.The difference was smaller , and the self-repair ability of the passivated film of stainless steel was stronger.The resistance of charge transfer obtained from AC impedance spectrum decreased when the concentration of chlorine ion increased.

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采用动电位极化曲线测量、开路电位测量等技术，研究了304奥氏体不锈钢在不同浓度硝酸溶液中的电化学腐蚀行为，并对304奥氏体不锈钢在硝酸溶液中的电化学反应历程进行了探讨。结果表明：304奥氏体不锈钢在硝酸溶液中具备不锈钢典型的极化曲线特征，有多个钝化区和过钝化区；硝酸浓度升高促进不锈钢表面钝化膜的生成，使开路电位向正电位方向移动，降低了硝酸溶液对不锈钢的腐蚀倾向，同时，随着硝酸浓度的升高，不锈钢的点蚀电位升高，提高了不锈钢耐点蚀能力；在硝酸溶液中，不锈钢的腐蚀速率同时受到酸度和硝酸根浓度的影响，二者相互矛盾，导致硝酸浓度对腐蚀速率的影响呈不规律性。结果表明，在0.5 mol/L硝酸中，不锈钢的腐蚀速率最高。
The effect of varying concentrations of nitric acid on the electrochemical corrosion of 304 austenitic stainless steel has been investigated.The study was carried out using poten-tiodynamic cyclic polarization,open-circuit potential measurements.The reaction process of 304 austenitic stainless steel in nitric acid was under discussion.304 austenitic stainless steel shows the same electrochemical characteristics with other stainless steel,and its polarization curve contains several passive regions and active regions.Electrochemical measurements indicate that nitric acid improves the pitting corrosion resistance capacity of 304 austenitic stainless steel by promoting the formation of passive film on the surface,and shifts the open-circuit potential to more positive values.Furthermore,nitric acid effects the corrosion rates of stainless steel in two contradictory ways.The result shows that 0.5 mol/L nitric acid has the highest corrosion rate.

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水力压裂是目前改善低渗透油藏的主要开发手段，由于压裂液成分复杂，对套管产生严重的局部腐蚀破坏，极大地限制了压裂施工的安全运行。以油田常用套管钢为研究对象，借助电化学工作站，研究套管钢在压裂液中的电化学腐蚀行为，分析不同套管钢材质、压裂液交联比、浓度、KCl含量以及温度等参数对其腐蚀行为的影响规律。结果表明：与N80和J55钢相比，P110钢在压裂液中具有最稳定的钝化特征，点蚀电位最高且钝化电流密度最低，成分中高含量的Cr和Mo及膜层中低的缺陷浓度提高了其钝化稳定性。随压裂液中KCl浓度增加，P110钢钝化稳定性下降；压裂液交联比对其腐蚀行为无影响；点蚀电位敏感于压裂液浓度变化，浓度增加钝化稳定性增加。温度升高，压裂液黏度降低，Cl-迁移作用增加，P110钢点蚀电位降低。
The hydraulic fracturing technology is the main measure to explore the low permeability reservoir. The complex composition of fracturing fluid can lead to the localized corrosion of casing steel and limit the application of hydraulic fracturing technology. The corrosion behavior of P110 casing steel in the hydraulic fracturing fluid was investigated by electrochemical method. The effects of casing steel materials,crosslinking ratio,the concentration,the KCl content and temperature of the fracturing fluid on corrosion behavior of P110 casing steel were studied in detail. The results show that P110 steel exhibits the stable passivation behavior including the highest pitting potential and lowest passivation current density. The high content of Cr and Mo existing in the passive film,and the lowest defect concentration of the film attribute to the stable passivation of P110. The stable passivation of P110 decreases with the increase of KCl concentration. The corsslinking ratio sho

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随着能源需求的日益紧张，海洋能的利用受到了各国的广泛关注，对海洋能发电设备的需求也日益迫切。现有的水力发电设备常用金属材料能否满足海洋腐蚀性介质中的应用值得探讨。本文利用电化学工作站对人工海水介质中水轮机常用金属ZG00Crl3Ni4Mo，0Crl8Ni9，1Crl8Ni9Ti，Q235，Q345B等的腐蚀极化曲线、交流阻抗谱进行了测量，并且利用扫描电子显微镜对腐蚀极化曲线测试后样品的表面形貌进行了观察。结果表明，碳钢Q235和Q345B自腐蚀电位较低，耐腐蚀性较差。而奥氏体不锈钢0Crl8Ni9和1Crl8Ni9Ti自腐蚀电位和钝化膜击破电位较高，钝化区较宽，耐腐蚀性较好。水轮机过流部件常用材料ZG00crl3Nj锄伯自腐蚀电位和钝化膜击破电位较低，存在较为严重的点腐蚀现象，在海洋能发电设备应用中应配合有效的防腐措施。
With the increase of energy assumption, development of ocean energy technology and ocean energy conversion equipment with high efficient are highly demanded all over the world. Therefore, it is necessary to research the application of metal materials commonly used in hydroturbine. In this paper, electrochemical workstation was utilized to measure the polarization curves and electrochemical impedance spectroscopy (EIS) of metals including ZG00Cr13Ni4Mo, 0Cr18Ni9, 1Cr18Ni9Ti, Q235, Q345B in artificial seawater. Furthermore, scanning electron microscope (SEM) was applied to observe the pitting behaviors of specimens made of ZG00Cr13Ni4Mo and 0Cr18Ni9, respectively. The results show that the corrosion potential of carbon steel (Q235 and Q345B) is low. While the austenite stainless steels (0Cr19Ni9 and 1Cr18N9Ti) show higher corrosion potential and passivating film breakdown potential comparing to martensite stainless steel ZG00Cr13Ni4Mo. It is recommended that the effective anti-corrosion

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用扫描电化学显微镜（SECM）和电化学阻抗谱（EIS）原位表征了溶液pH值对核电蒸汽发生器800合金溶液中的腐蚀行为的影响．实验结果表明：在酸性氯化钠溶液中，SECM探针渐进曲线为正反馈，表明800合金为活化阳极溶解，腐蚀电位下的EIS图呈现完整的单容抗弧特征：而在中性或者碱性溶液中，SECM探针渐进曲线为负反馈，表明800合金为自钝化，不同阳极电位下的EIS图均呈现不完整的容抗弧特征，但随着阳极极化电位的增加，EIS谱容抗弧半径减小，表明钝化膜的耐蚀性下降；SECM二维扫描图像结果显示探针电流增加，表明电极表面活性增加，即钝化膜的溶解速度增加．而在中性或者碱性溶液中的SECM二维图像中均可观察到若干活性点，这可能与晶界或者金属夹杂物等有关．
The effect of pH on the corrosion resistance of Al oy 800, one of the preferred nuclear steam generator tubing materials, was investigated using in-situ scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS). The experimental results show that positive feedback is observed in the probe approach curve (PAC) in acidic chloride solutions, indicating that Al oy 800 is active in acidic solutions;the EIS at the corrosion potential in acidic solutions exhibits an intact capacitance arc. However, negative feedbacks are observed in the PAC in either neutral or basic chloride solutions, showing that Al oy 800 is self-passivated in these two solutions. The EIS plots at different anodic potentials show incomplete capacitance arcs, and the arc radius decreases with increasing potential, indicating that the corrosion resistance of the passive film decreases. The SECM images show that the surface reactivity increases (or the dissolution rate of the passive film in

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本利用电容测量方法结合Mott-Schottky分析,研究了不锈钢在硫酸溶液中所形成钝化膜的半导体性质,同时对成膜电位、成膜时间以及溶液pH值对膜半导体性能的影响也做了分析。结果表明:不锈钢钝化膜具有p型-n型-p型半导体特性,膜内的杂质浓度随成膜电位的增加而增加,随极化时间的延长而减小,这主要是由于极化电位和极化时间的变化引起了膜组成的变化所引起的。溶液PH值的改变可以显著影响0.16V~0.74V电位扫描区间内膜的平带电位EFB。溶液PH值与平带电位呈线性关系,斜率为58.58mV/pH。
The semiconductor properties of passive film formed on 304L stainless steel in sulfuric acid solution were investigated by capacitance measurement based on Mott-Schottky analysis, and the effects of film formation potential, formation time and pH value of electrolyte on the semiconductor properties of the passive film were also discussed. The results revealed an p-n-p type semiconductor characteristic of passive film on stainless steel, the impurity concentration of the passive film increased with the formation potential changing to positive, and decreased with prolonging the polarization time, this can be illustrated by the changing of the composition of the passive film formed on different formation potentials and polarization time. The pH values of the electrolyte can significantly affect the flat band potential, EFB, and a linear relationship of PH and EFB can be obtained with a 58.58mV/pH unit slope.

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根据电化学分析，5-甲基苯并三氮唑（m-BTA）的腐蚀抑制能力要高于并三唑（BTA）的-当羟基乙叉二膦酸（HEDP）电解液中同时含有m—BTA及氯离子时，其抑制解离能力比从含有m-BTA的更好，即使施加更岛的阳极氧化电位依然能保持良好的抑制能力。由电化学附抗谱法、纳米划痕实验以及能谱分析结果得知，m-BTA抑制能力的提升是因为整体钝化膜厚度的增加而引起的。由X射线光电子能谱分析得知，氯高子与m-BTA钝化层形成『Cu（1）Cl（m-BTA）]。高分子化合物，使得整体钝化层厚度增加。因此，在含有m—BTA的HEDP电解液中添加氯离了有助于m-BTA钝化层抑制能力的增强，进而更有效的电位操作区间得到扩展。
According to the electrochemical analysis, the corrosion inhibition efficiency of 5-methyl-1H-benzotriazole (m-BTA) is higher than that of benzotrizaole (BTA). The inhibition capability of the m-BTA passive film formed in hydroxyethylidenediphosphonic acid (HEDP) electrolyte containing both m-BTA and chloride ions is superior to that formed in m-BTA-alone electrolyte, even at a high anodic potential. The results of electrical impedance spectroscopy, nano-scratch experiments and energy dispersive analysis of X-ray (EDAX) indicate that the enhancement of m-BTA inhibition capability may be due to the increasing thickness of passive film. Furthermore, X-ray photoelectron spectrometry (XPS) analysis indicates that the increase in passive film thickness can be attributed to the incorporation of Cl? into the m-BTA passive film and the formation of [Cu(I)Cl(m-BTA)]n polymer film on Cu surface. Therefore, the introduction of Cl? into m-BTA-containing HEDP electrolyte is effective to enhance the

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回顾了我国含镉土壤的场地修复。综述了利用生物钝化技术修复镉污染土壤的研究现状,重点探讨了微生物的代谢产物与镉产生硫化物或磷酸盐沉淀的微生物沉淀作用、微生物的细胞壁和其分泌的胞外聚合物直接吸附镉的微生物吸附作用以及镉离子透过微生物的细胞膜而被固定在细胞内的微生物摄取作用等生物钝化机理,并对有机钝化过程和无机钝化过程进行了介绍和评价。分析了镉在土壤中的离子交换态、碳酸盐结合态、铁锰氧化物结合态、有机结合态和残渣态等赋存形态以及土壤中pH值、氧化还原电位、有机质、共存重金属和微生物等因素对镉的生物可利用度的影响。最后阐述了生物钝化技术的优点以及该技术不能将重金属从土壤中永久去除的问题,指出生物钝化技术与其他修复方法相结合是其未来的发展方向。
The site remediation of Cadmium contaminated soil was reviewed.The recent research in biostabilization of Cadmium in contaminated soil was summarized.The stabilization mechanisms were discussed with highlight,such as the bioprecipitation that microbial metabolites can react with Cadmium to form sulfide or phosphate precipitation,the biosorption that microbial cell walls and extracellular polymeric substances can adsorb Cadmium,and the biological uptake that Cadmium ions can pass through the cell membrane of microorganisms and be fixed in cells.Organic and inorganic stabilization were also introduced and evaluated.The state,e.g. ion-exchangeable,bound to carbonates, bound to iron and manganese oxides,bound to organic matter,and residual of Cadmium in soil,and the factors of pH,redox potential,organic matters,coexistent heavy metals and microorganisms which affect the consequential bioavailability of Cadmium were analyzed. Finally , the advantages of biostabilization technique and the fa

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研究在电位衰变期间在酸性硫酸锌电解液中，MnO4?和银的含量对5个通用铅银合金阳极电化学行为的影响。当阳极浸入不含MnO 的酸性硫酸锌电解液中时，通过开路电位测定，发现Pb?0.72%Ag进入完全钝化状态所用的时间最短，紧接着的是阳极Pb?0.67%Ag、Pb?0.60%Ag、Pb?0.58%Ag和Pb?0.29%Ag?0.1%Ca。在5 h 的浸入期间，MnO4?离子能加速钝化和增加阳极的腐蚀电流密度。通过交流阻抗法测定，发现在含有MnO4?的电解液中，阳极Pb?0.72%Ag具有最好的耐蚀性，紧接着的是阳极Pb?0.67%Ag、Pb?0.60%Ag，然后是阳极Pb?0.58%Ag和Pb?0.29%Ag?0.1%Ca。?4
The effect of MnO4?and silver content on electrochemical behaviour of five commercial Pb?Ag alloy anodes was studied in acid zinc sulphate electrolyte with and without MnO4? ions at 38 °C during potential decay periods. When the anodes were immersed into acid zinc sulphate electrolyte without MnO4?ions, the Pb?0.72%Ag anode entered complete passivation state in the shortest time among the five anodes, followed by anodes Pb?0.67%Ag, Pb?0.60%Ag, Pb?0.58%Ag and Pb?0.29%Ag?0.1%Ca by measurement of open circuit potential. During immersion of the anodes, MnO4?ions accelerated the passivation and increased the corrosion current density of the anodes. After immersion in zinc electrolyte with MnO , the anode Pb?0.72%Ag had the best?4 corrosion resistance, followed by anodes Pb?0.67%Ag, Pb?0.60%Ag, then the close anodes Pb?0.58%Ag and Pb?0.29%Ag?0.1%Ca by the electrochemical impedance spectroscopy (EIS) analysis.

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