钝化与过钝化状态下304不锈钢的点蚀行为研究

为了进一步了解不锈钢钝化膜与过钝化膜的性质,本文对比研究了在不同电位下极化处理后304不锈钢样品的点蚀及表面膜性质,发现空白对照组样品的点蚀电位和1.1 V过钝化处理后样品的点蚀电位相近,而0.5 V钝化处理后样品的点蚀电位较高. 扫描Kelvin探针（SKP）实验结果也验证了这一现象. 扫描电子显微镜（SEM）结果显示,空白对照组样品表面只呈现一般样品抛光后形貌;0.5 V钝化处理后的样品表面被颗粒状钝化膜所覆盖,该膜层决定了样品具有较好的耐蚀性;而1.1 V过钝化处理后的样品表面出现裂缝,导致不锈钢基体继续发生严重的局部腐蚀,可能成为过钝化膜保护性变差的主要原因.     

模拟混凝土孔溶液中钢筋钝化膜的光电化学方法研究

利用光电化学方法研究了钢筋在模拟混凝土孔溶液中钝化膜的电子性质，结果表明，钢筋在该溶液中形成的钝化膜是一种无定形的ｎ－型半导体成相膜，膜由多种铁氧化物组成，其组成受溶液中的离子、ＰＨ值、成膜电位影响，腐蚀抑制ＮａＮＯ２影响钝化膜的组成和生长过程，从而提高钢筋的抗氯离子点蚀能力。     

Cu-Ni合金在NaCl溶液中的孔蚀特性

采用慢速电位扫描法和电位台阶计时电流法分别研究铸态铜镍合金以及由机械合金化方法制备的纳米晶铜镍合金于不同浓度NaCl溶液中的孔蚀特性.讨论含Ni量,Cl-浓度等因素对合金孔蚀敏感性的影响,探讨了不同结构合金的孔蚀发展.     

抗菌处理含铜铁素体不锈钢的耐微生物腐蚀性能

采用电化学测试技术及微生物学方法, 研究了抗菌处理含铜铁素体不锈钢在含有培养基的异养菌溶液中的耐蚀性能. 结果表明, 不锈钢的腐蚀电位随异养菌的新陈代谢呈现规律性变化, 抗菌处理使不锈钢在菌液中钝化膜的稳定性得到改善, 点蚀敏感性降低; 抗菌不锈钢表面弥散分布的ε-Cu析出相的杀菌作用, 降低了异养菌的活性, 减缓了异养菌对抗菌不锈钢的腐蚀, 提高了抗菌不锈钢耐微生物腐蚀性能.     

人工体液中TiNiCu形状记忆合金的电化学行为

在Hank’s人工模拟体液中对TiNiCu形状记忆合金的电化学行为进行了研究 .结果表明 ,TiNiCu合金阳极极化时 ,于酸性条件下合金的钝化区较窄、在 10 0～ 150mV电位区间出现了阳极活性溶解 ,钝化膜受到破坏 .pH的降低和Cl- 浓度的升高 ,使孔蚀电位负移 .在Hank’s人工模拟体液中TiNiCu合金的电化学性能比TiNi形状记忆合金劣 ,其原因是TiNiCu合金的晶体结构不单一 ,造成电化学性质不均一 ,构成腐蚀原电池 ,加之晶界析出富Ti的Ti2 Ni析出物成为孔蚀诱发的敏感位置     

锡含量对铅锡合金在硫酸溶液中钝化膜性能的影响

利用线性电位扫描法(LSV)、循环伏安法(CV)和交流伏安法(ACV), 结合Mott-Schottky分析, 研究了锡含量对铅锡合金在硫酸溶液中形成的钝化膜性能的影响. 结果表明: 铅合金中加入Sn可以显著提高其耐腐蚀性能、减小其阳极膜电阻, 同时这些性能的改善随Sn含量的增加更为显著, 另外氧在铅合金上的析出过电位随合金中锡含量的增加而增加. Mott-Schottky分析表明, 钝化膜呈n型半导体特征, 钝化膜中缺陷浓度随锡含量的增加而增加, 说明其施主密度N_D和膜的导电性能随锡含量的增加而增加.     

690合金在300 ℃含硫模拟碱性水化学中的腐蚀行为

690 合金作为压水堆核电站蒸汽发生器传热管的一种关键材料, 其在碱性环境下还原态硫导致的钝化膜的腐蚀退化是引发应力腐蚀开裂的关键原因之一. 本文采用动电位极化曲线, 结合扫描电镜(SEM)、俄歇能谱(AES)、二次离子飞行时间质谱(ToF-SIMS)研究了690合金在300 ℃模拟碱性水化学中的腐蚀行为, 并分析了硫代硫酸根与硫酸根对钝化膜特性的影响. 实验结果表明: 300 ℃碱性溶液中690合金表面钝化膜为外层的多孔层与内层的紧密层组成的双层结构, 所加入的硫酸盐种类对690合金的耐蚀性有较大影响; 硫代硫酸根使690合金钝化电流密度增加, 过钝化电位降低, 即钝化膜的耐蚀性降低; 此外, 硫代硫酸根使钝化膜中的Cr含量降低而Ni 含量提高, 硫代硫酸根会在合金表面电化学还原成为更低价态的硫进入钝化膜, 使钝化膜中的硫化物增多也是导致钝化膜防护性能变差的原因; 而硫酸根与钝化膜的作用较弱, 对钝化膜的影响较小.     

不同浓度比的硫酸根和氯离子溶液中钝化膜的半导体特性转变机制研究

800合金作为核电站蒸汽发生器的一种关键材料,服役环境下其表面钝化膜的特性一直是人们研究的热点. 本文用Mott-Schottky方法研究了800合金在不同硫酸根离子和氯离子浓度比的溶液中钝化膜的半导体特性,并结合电化学阻抗谱（EIS）、扫描电镜（SEM）、扫描电化学显微镜（SECM）研究了钝化膜的耐蚀性和表面活性. Mott-Schottky结果表明,800合金表面钝化膜的半导体特性与溶液中硫酸根、氯离子的浓度比有关,随硫酸根与氯离子浓度比的降低,半导体特性发生转变. 当硫酸根与氯离子的浓度比较高时,钝化膜为p型半导体;而当硫酸根与氯离子的浓度比较低时,钝化膜为n型半导体. EIS、SECM、SEM结果表明,随浓度比的降低钝化膜由过钝化溶解转为明显的点蚀特征,钝化膜表面活性增加. 钝化膜特性的改变与其半导体类型的转变密切相关,而半导体特性的转变由氯离子、硫酸根离子在800合金钝化膜表面的竞争吸附所致,其在表面的竞争吸附直接影响钝化膜表面发生的化学反应,改变电极/溶液界面电势差,使钝化膜中的空位类型改变,最终决定半导体类型.     

不同浓度比的硫酸根和氯离子溶液中钝化膜的半导体特性转变机制研究

800合金作为核电站蒸汽发生器的一种关键材料,服役环境下其表面钝化膜的特性一直是人们研究的热点.本文用Mott-Schottky方法研究了800合金在不同硫酸根离子和氯离子浓度比的溶液中钝化膜的半导体特性,并结合电化学阻抗谱(EIS)、扫描电镜(SEM)、扫描电化学显微镜(SECM)研究了钝化膜的耐蚀性和表面活性.Mott-Schottky结果表明,800合金表面钝化膜的半导体特性与溶液中硫酸根、氯离子的浓度比有关,随硫酸根与氯离子浓度比的降低,半导体特性发生转变.当硫酸根与氯离子的浓度比较高时,钝化膜为p型半导体;而当硫酸根与氯离子的浓度比较低时,钝化膜为n型半导体.EIS、SECM、SEM结果表明,随浓度比的降低钝化膜由过钝化溶解转为明显的点蚀特征,钝化膜表面活性增加.钝化膜特性的改变与其半导体类型的转变密切相关,而半导体特性的转变由氯离子、硫酸根离子在800合金钝化膜表面的竞争吸附所致,其在表面的竞争吸附直接影响钝化膜表面发生的化学反应,改变电极/溶液界面电势差,使钝化膜中的空位类型改变,最终决定半导体类型.     

烯胺阻锈剂对钢筋在模拟碳化混凝土孔隙液中的点蚀抑制

通过电化学噪声(ECN)、电化学阻抗(EIS)及极化曲线研究了四乙烯五胺(TEPA)在碳化模拟混凝土孔隙液中对Q345B碳钢点蚀的抑制机理. 结果表明: 通过吸附成膜和隔离Cl^-离子对钝化膜的侵蚀, TEPA浓度升高导致碳钢点蚀电位正移. 低浓度的TEPA会造成亚稳态蚀点形核速率略微增加, 但会降低其寿命. 随着TEPA浓度增加, 噪声电阻上升, 而亚稳态蚀点寿命和平均点蚀电量则迅速下降, 表明其明显加速了亚稳态蚀点修复, 当TEPA浓度达0.10 mol·L^-1时, 噪声峰消失, 基底电流趋于零, 蚀点全面钝化. TEPA不仅能抑制Cl^-离子引起的亚稳态和稳态蚀点生长, 还可吸附于钝化膜表面, 抑制膜的均匀溶解. 形貌观察表明, 亚稳态蚀点主要在稳态蚀点周围形核和生长, 并不断为稳态蚀点所吞并, 造成碳钢表面蚀坑一般沿平面而不是垂直方式扩展.     

Electric properties and pitting susceptibility of passive films formed on iron in chromate solution

Electric properties and pitting susceptibility of passive films formed on iron in 0.01 M Na₂CrO₄ solution was investigated by using Mott–Schottky analyses, electrochemical noise analyses and anodic polarization curve measurements. It was found that the passive films were very disordered n-type semiconductors with two level donors, shallow and deep. The donor concentrations decreased as the passive film was formed at more positive potentials. The passive films were susceptible to pitting in the solution containing 0.05 M chloride ions. The pitting susceptibility of the passive film was improved as the donor concentration in the passive film decreased.     

N80油套管钢钝化膜的光电化学性能

采用电容测试法研究了N80油套管钢在浓度为0.5 mol/L NaHCO3溶液中形成钝化膜的半导体性能,结合Mott-Schottky方程分析了测试频率,成膜电位和C l-浓度对钝化膜半导体性能的影响。电容测试结果表明,钝化膜呈n型半导体特性,Mott-Schottky曲线的斜率随着测试频率的增加、成膜电位的正移和溶液中氯离子浓度的增加而增加,相应地膜内的施主密度减小。光电化学实验结果表明,光电流强度随成膜电位的正移及成膜时间的延长而增加,这主要归功于高电位和长时间下所成的钝化膜具有比较均匀的组成,光激发所成的空位或电子在膜内的迁移率的增加。     

不锈钢钝化膜耐蚀性与半导体特性的关联研究

通过极化曲线、交流阻抗谱和钝化膜半导体特性等电化学测量，研究了经电化学阳极氧化处理的不锈钢钝化膜在0.5 mol•L^-1 NaCl溶液中耐蚀性能与其半导体特性的关系，进一步探索电化学改性处理不锈钢钝化膜的耐蚀机理. 结果表明，不锈钢钝化膜在负于平带电位范围表现为p型半导体，在高于平带电位范围表现为n型半导体，这主要与组成钝化膜的Fe和Cr氧化物半导体性质有关. 与自然条件下形成的不锈钢钝化膜比较，发现经过电化学阳极氧化后不锈钢钝化膜具有较低的施主与受主浓度，平带电位负移，说明阴离子在钝化膜表面发生吸附. 低的施主与受主浓度及钝化膜表面负电荷的增强，可有效排斥侵蚀性Cl^－在钝化膜表面的特性吸附，有利于提高不锈钢的耐局部腐蚀性能.     

Relations entre la structure electronique des films de passivation formes sur les aciers inoxydables et la susceptibilite de ces derniers a la corrosion par piqures

The passive films formed on 316L stainless steel in various NaCl solutions have been investigated by capacitance measurements (Mott-Schottky study). Pitting parameters have been determined using the galvanokinetic polarisation method. The obtained results reveal the existence of a shallow and a deep donor level localised in the band gap of the semiconducting oxide film. These energy levels are due to iron ions in the tetrahedral and octahedral positions. It also appears that the participation of the deep donor level affects the electric field. The study developed allows us to compare characteristic parameters of the electronic structure of the passive film to those related to pitting susceptibility.     

双极性半导体钝化膜空间电荷电容分析

钝化膜的空间电荷电容的测量(Mott-Schottky(M-S)曲线)是研究其半导体性质的重要手段, 双极性半导体钝化膜在耗尽态电位区M-S曲线斜率往往会发生改变, 首先建立了半导体富集态、耗尽态以及反型态空间电荷电容的统一计算公式, 进而将双极性半导体钝化膜空间电荷电容等效为钝化膜/溶液界面处电容和内层钝化膜/外层钝化膜界面处的np结电容的串联, 模拟计算结果能够很好地解释M-S曲线斜率发生改变这一实验现象. 同时, 计算结果表明, 对于双极性半导体的M-S曲线, 利用其直线部分的斜率、直线与电位坐标轴的截距来确定钝化膜的载流子浓度以及平带电位会产生一定的误差.     

Effect of oxygen vacancies in anodic titanium oxide films on the kinetics of the oxygen electrode reaction

The effect of oxygen vacancies in the anodic oxide film on passive titanium on the kinetics of the oxygen electrode reaction has been studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Oxide films of different donor density were prepared galvanostatically at various current densities until a potential of 20.0 V_SHE was achieved. The semiconductive properties of the oxide films were characterized using EIS and Mott-Schottky analysis, and the thickness was measured using ellipsometry. The film thickness was found to be almost constant at ∼44.7 ± 2.0 nm, but Mott-Schottky analysis of the measured high frequency interracial capacitance showed that the donor (oxygen vacancy) density in the n-type passive film decreased sharply with increasing oxide film formation rate (current density). Passive titanium surfaces covering a wide range of donor density were used as substrates for ascertaining relationships between the rates of oxygen reduction/evolution and the donor density. These studies show that the rates of both reactions are higher for passive films having higher donor densities. Possible explanations include enhancement of the conductivity of the film due to the vacancies facilitating charge transfer and the surface oxygen vacancies acting as catalytic sites for the reactions. The possible involvement of surface oxygen vacancies in the oxygen electrode reaction was explored by determining the kinetic order of the OER with respect to the donor concentration. The kinetic orders were found to be greater than zero, indicating that oxygen vacancies are involved as electrocatalytic reaction centers in both the oxygen evolution and reduction reactions. This paper was submitted in honor of the many contributions to electrochemistry that have been made by Professor Boris Grafov. The article is published in the original.     

铬对碳钢在NaHCO3/NaCO3缓冲溶液中所成钝化膜半导体性能的影响

应用电化学阻抗谱技术研究铬对碳钢钝化膜半导体性能的影响.实验表明,在碳酸氢钠/碳酸钠缓冲溶液中碳钢形成的钝化膜具n型半导体特性,而含有3%铬的碳钢钝化膜则呈n-p型半导体特性,随着成膜电位的增加,以上两种钝化膜之Mott-Schottky直线部分的斜率均呈增大的趋势,表明成膜电位升高,膜内的杂质密度减小,但铬的加入使得碳钢钝化膜的施主密度增加约一个数量级,从而增加了碳钢点蚀发生的趋势.EIS分析表明:铬的加入降低了钝化膜的传递电阻R1和膜电阻R2,特别是膜电阻R2下降达3个数量级,这就有可能增加碳钢在高pH值环境中的腐蚀.     

电容测量研究铬表面氧化膜的半导体性能

利用电容测量技术,基于Mott-Sckottky分析,研究了在0.5 mol•L－1 H2SO4溶液中铬表面氧化膜的半导体性质,以及膜形成条件的影响.结果表明,铬在钝化电位区内所形成的表面氧化膜具有p-型半导体特性,膜的厚度约(1.2±0.3) nm.膜的阻抗响应表现出低频弥散行为,可以用介电弛豫普适定律来描述.膜的掺杂浓度NA随成膜电位及极化时间的延长而增大,溶液pH值则通过改变膜的表面电荷而影响膜的平带电位EFB.     

The adsorption and condensed film formation of cetyltrimethylammonium bromide at the mercury/electrolyte interface

The adsorption of cetyltrimethyammonium bromide (CTAB) on a hanging mercury electrode is studied in various electrolyte systems and temperatures. A condensed film is formed at negative potentials and at room temperature only in the presence of KBr. The decrease of the temperature favors the formation of the condensed film. Hysterisis phenomena are observed during the potential scans at both directions. Capacity time curves at the potentials where the film is formed show a nucleation and growth mechanism, with induction time depending on potential, which has been investigated using Avrami formulation and has been explained as a progressive one-dimensional nucleation with constant growth rate. The nucleation rate increases while moving toward more negative potentials. A linear decrease of the capacitance with time was observed in some cases independent of the measuring potential in a relative large potential range. The different types of micelles can affect the adsorption of CTAB on mercury. An unusual capacitance transient observed at a very narrow negative potential range is attributed to the formation of hemicylinders. The condensed film in the presence of the other electrolytes is observed only at high concentrations (1 M) and very low temperatures (5 degrees C).     

Electrochemical behavior of passive films on Al–17Si–14Mg (wt.%) alloy in near-neutral solutions

The anodic polarization behavior of alloy Al–17Si–14Mg in borate solutions with and without 0.01 M NaCl was compared to that for pure Al. Results showed that, for the alloy, the passive current density increased but the pitting susceptibility decreased. The first effect was ascribed to a significant electrochemical activity of the Mg₂Si intermetallics and the second to improved stability of the oxide film. X-ray photoelectron spectroscopy analysis of potentiostatically formed passive film on the alloy showed that it consisted of aluminum oxyhydroxide with incorporation of silicon in its elemental and two oxidized states (+3 and +4). Mott–Schottky analysis showed that trivalent silicon ion acted as an n-type dopant in the film. The interrelationship between passive film composition, electronic properties, and pitting behavior has been discussed.