不锈钢过钝化－二次钝化的研究

通过对３０４不锈钢在较高电位下过钝化和二次钝化的稳态过程和电化学交流阻抗（ＥＩＳ）的分析，认为不锈钢过钝化和二次钝化现象与膜／溶液（ｆ／ｓ）界面上的电化学反应有密切关系，并通过理论模型分析，解释了过钝化和二次过钝化膜在高电位下溶解速度高，而在开路自腐蚀电位下反而有较好的稳定性这一现象．     

添加剂对电镀锌层烷氧基硅烷钝化膜电化学行为的影响

为提高镀锌层钝化膜的耐蚀性,利用极化曲线和交流阻抗谱,研究了不同添加剂对镀锌层烷氧基硅烷钝化膜腐蚀性能的影响.并与加速腐蚀试验结果进行了对比.试验结果表明,添加剂的加入明显改变了钝化膜层的腐蚀电位,提高钝化膜的交流阻抗值,烷氧基硅烷钝化膜的耐蚀性明显提高.     

SUS36不锈钢阳极钝化膜的研究

用恒电位极化、电位衰退、充电曲线和交流阻抗等电化学方法,结合表面分析技术,研究了SUS36不锈钢在H_2SO_4介质中在不同电位下形成的钝化膜的组成及其与耐蚀性的关系。在过钝化区形成的钝化膜,其耐蚀性比较好。     

阳极钝化电位对黄铜表面钝化膜半导体性能的影响

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。     

氢对310不锈钢钝化膜半导体性质的影响

采用交流阻抗和光电化学方法研究了氢对310不锈钢钝化膜半导体质的影响,结果表明,氢对310不锈钢钝化膜的半导体类型没有影响,均是n型,对未充氢的试样,随钝化电位的升高,钝化膜的施主浓度降低而平带电位则升高,氢能升高310不锈钢钝化膜的电容。施主浓度和平带电位,氢使310不锈钢钝化膜的光电流峰值升高、峰位后移,即氢降氏钝化膜的光学禁带宽度,这和氢使化膜中Cr的化合物含量下降有关。     

奥氏体不锈钢在高温磷酸浓溶液中的阳极极化行为

测量了奥氏体不锈钢９０４Ｌ在１４０℃、８５％磷酸溶液中的阳极极化曲线，讨论了不同电位区域内的阳极极化行为，并用交流阻抗法研究了不同电位区域内钝化膜的阻抗行为．在活化－钝化过渡区，阻抗谱的高频部分为容抗弧，在低频出现扩散控制现象．在稳定钝化区；阻抗谱由容抗半圆组成，受表面钝化膜的生长和溶解过程所控制．在该区域内，钝化膜的阻抗值达到最大，弥散系数和膜电容值达到最小，表明所生成的钝化膜的耐蚀性好，致密度高，膜较厚且表面均匀．在过钝化区，高频容抗弧的直径大为减小，说明由于过钝化溶解，膜的耐蚀性大大下降；低频出现两个感抗弧，说明出现了阴离子的吸附．阳极充电曲线和电位衰减曲线的结果表明在稳定钝化区内，膜的组织和成分应该是均匀的；钝化膜的生长电位越高，膜越稳定．综上结果表明奥氏体不锈钢在高温磷酸浓溶液中实施阳极保护具有保护电位范围宽（０．３～０．８Ｖ，ＳＣＥ），钝化膜稳定等优点．磷酸的温度越低，保护效果越明显．     

恒电位阳极氧化对锆合金表面钝化膜的影响

采用动电位扫描极化曲线、电化学阻抗谱、Mott-Schottky曲线等电化学测试方法,研究了在室温0.1 M Na_2SO_4溶液条件下,不同极化电位对锆合金钝化膜性能的影响。结果表明,锆合金表面钝化膜表现出n型半导体性质,随着极化电位的增加,锆合金钝化膜缺陷密度下降,半导体性质减弱,阻抗值增大。阻抗谱可以用RQ并联后与溶液电阻Rs串联的等效电路来拟合。在相同的极化电位下,含Nb的N18合金表面钝化膜的缺陷密度要小于出厂退火态Zr-4合金。     

H2S水溶液中的腐蚀与缓蚀作用机理的研究Ⅳ．碱性硫化物溶液中Cl-对碳钢钝化行为的影响

利用交流阻抗和动电位极化技术,在碱性硫化物溶液中,分别研究了阳极极化电位下 对 低碳钢钝化过程阻抗行为的影响,钝化膜临界孔蚀电位 与 浓度的关系以及临界 浓度随 温度的变化．结果表明,在除氧的碱性硫化物溶液中,阳极极化的初期阻抗具有两个时间常数,随极化电位的升高,钝化膜逐步趋于完整;在点蚀的形成过程中,容抗弧半径逐渐变小,当极化电位为-600mV时容抗弧半径大幅度下降,并出现低频实部电感性收缩现象;在点蚀形成后的发展阶段,容抗弧半径继续减小,阻抗谱出现两个时间常数的双容抗弧．极化研究结果表明,不同温度下,随介质Cl-浓度增加,电极表面的钝化倾向降低,临界孔蚀电位随Cl-浓度增加而线性正移．     

不锈钢载波钝化参数对钝化膜层耐蚀性的影响

运用电化学交流阻抗谱、原子力显微镜研究了在不同的载波钝化参数下形成的不锈钢钝化膜的耐蚀性,测定了极化电阻值Rp和相应的钝化膜的表面形貌。结果表明：载波钝化条件参数对膜层的耐蚀性有较大的影响,各参数(频率、占空比、高电位、低电位)的变化使得电极表面钝化膜的形貌发生很大的变化,从而影响到膜层的耐蚀性。     

H2S水溶液中的腐蚀与缓蚀作用机理的研究——Ⅳ.碱性 ？…

利用交流阻抗和动电位极化技术，在碱性硫化物溶液中，分别研究了阳极极化电位下Ｃｌ＾－对低碳钢钝化过程阻抗行为的影响，钝化膜临界孔蚀电位Ｅｂ与Ｃｌ＾－浓度的关系以及临界Ｃｌ＾－浓度随温度的变化。结果表明，在除氧的碱性硫化物溶液中，阳极极化的初期阻抗具有两个时间常数，随极化电位的升高，钝化膜逐步趋于完整；在点蚀的形成过程中，容抗弧半径逐渐变小，当极化电位为－６００ｍＶ时容抗弧半径大幅度下降，并出现低频实     

Electrochemical impedance spectroscopy of anodic processes on cobalt disilicide in sulfuric acid solutions

The frequency dependences of the impedance of a CoSi₂ electrode in solutions of 0.5 M H₂SO₄ and 0.05 M H₂SO₄ + 0.45 M Na₂SO₄ are measured in the range of potentials of the active-passive transition, passive state, and transpassive state. Impedance spectra are described using an equivalent circuit with regard to the presence of an oxide layer on the electrode surface. The dependence of equivalent circuit parameters and time constants on the electrode potential is analyzed. It is found that the high anodic stability of cobalt disilicide in sulfuric acid solutions is due to the barrier properties of the oxide film. The variations in the thickness of the oxide layer with increasing electrode potential in the range of passive dissolution are estimated. It is revealed that the time constant related to the oxide layer increases before the transpassive transition.     

The transpassive dissolution mechanism of highly alloyed stainless steels: I. Experimental results and modelling procedure

The transpassive dissolution of austenitic stainless steels (AISI 316L, AISI 904L, 254SMO and 654SMO) in a 0.5 M sulphate solution with pH 2 was studied by conventional and rotating ring-disc voltammetry, as well as electrochemical impedance spectroscopy. The main process in the transpassive potential region was found to be the release of soluble Cr(VI), while small amounts of lower-valency Cr or Mo species are released as well. Secondary passivation readily occurs for AISI 316L, whereas the remaining highly alloyed steels dissolve at high current densities in the whole potential range studied. The dissolution rate was found to increase in the order AISI 904L<254SMO<654SMO. Thus it can be correlated to the increase in the Cr and especially Mo content of the steel substrate. The impedance spectra contain contributions from the transpassive dissolution of Cr and secondary passivation, probably due to enrichment of Fe in the outermost layer of the surface film. A kinetic model of the process is proposed, including a two-step transpassive dissolution of Cr via a Cr(VI) intermediate and the dissolution of Fe(III) through the anodic film. The model was found to be in quantitative agreement with steady state current vs. potential curves and electrochemical impedance spectra. The kinetic parameters of transpassive dissolution were determined and the relevance of their values is discussed.     

The transpassive dissolution mechanism of highly alloyed stainless steels: II. Effect of pH and solution anion on the kinetics

The transpassive dissolution of austenitic stainless steels (AISI 316L, AISI 904L, 254SMO and 654SMO) in a 0.5 M sulphate solution with pH 2 was studied by conventional and rotating ring–disc voltammetry, as well as electrochemical impedance spectroscopy. The main process in the transpassive potential region was found to be the release of soluble Cr(VI), while small amounts of lower-valency Cr or Mo species are released as well. Secondary passivation readily occurs for AISI 316L, whereas the remaining highly alloyed steels dissolve at high current densities in the whole potential range studied. The dissolution rate was found to increase in the order AISI 904L<254SMO<654SMO. Thus it can be correlated to the increase in the Cr and especially Mo content of the steel substrate. The impedance spectra contain contributions from the transpassive dissolution of Cr and secondary passivation, probably due to enrichment of Fe in the outermost layer of the surface film. A kinetic model of the process is proposed, including a two-step transpassive dissolution of Cr via a Cr(VI) intermediate and the dissolution of Fe(III) through the anodic film. The model was found to be in quantitative agreement with steady state current vs. potential curves and electrochemical impedance spectra. The kinetic parameters of transpassive dissolution were determined and the relevance of their values is discussed.     

The transpassive dissolution mechanism of highly alloyed stainless steels: II. Effect of pH and solution anion on the kinetics

The effect of pH and solution anion on the kinetics of transpassive dissolution of highly alloyed austenitic stainless steels (AISI 904L, 254SMO and 654SMO) was studied by a combination of electrochemical techniques. The experiments were performed in 0.5 M sulphate and 0.5 M chloride solutions, and in an equimolar mixture of the two. The transpassive dissolution was found to start at higher potentials in solutions with higher pH. The rate of transpassive dissolution was shown to decrease with increasing pH and to be the lowest in chloride solutions and the highest in sulphate electrolytes. The steady-state current vs. potential curves and the impedance spectra of the studied materials in the transpassive potential region were found to be consistent with a proposed kinetic model. The model describes the process as dissolution of Cr as Cr(VI) and Fe as Fe(III) through the anodic oxide film via parallel reaction paths. The kinetic parameters of the model in solutions with different pH values and different anions were determined. The role of pH and solution anion in the transpassive dissolution process is discussed in relation to changes induced by these parameters in the composition of the anodic passive film. The factors determining the efficiency of Fe as a secondary passivating agent are also considered.     

Untersuchungen über die Lochfraßkorrosion des passiven Eisens in chlorionenhaltiger Schwefelsäure

Investigation into pitting corrosion of passive iron in sulphuric acid containing chloride ions Pitting corrosion of metallic materials is generally connected with presence of a surface layer giving rise to a local differentiation of the electrochemical behaviour of the metal surface. The pitting corrosion by halogen ions on passive metals is investigated using passive iron in chloride ion-containing sulphuric acid as the model system. Quantitative data are presented concerning the mechanism and kinetics of the individual processes giving rise to pitting corrosion in a chloride ion concentration range covering three powers of ten, and in the whole potential range of iron passivity, from the Flade potential to the transpassive breakthrough potential. Pit formation normally follows a linear kinetic law, the rate depending in particular from the chloride ion concentration and from the thickness of the passive layer. The growth of pit diameters follows a linear kinetic law, too; the dissolution current density in the pits depends from the chloride ion concentration. Comparative investigations carried out on active iron, and potential distribution as measured in the pits show that the metal is active in the pits, too. The heterogeneous mixed electrode condition — active pit/passive metal surface — is stabilised by resistance polarisation. The investigations so far do not permit any statement concerning the specific effect of the chloride ions.     

SUS36不锈钢钝化膜的XPS研究

本文用XPS研究了SUS36不锈钢在添加Na_2MoO_4缓蚀剂的醛化液中,在不同阳极极化电位下形成的表面膜的组份及其深度分布。表明在阳极过钝化电位下形成的钝化膜在醛化液中具有较好的耐蚀性。     

Impedance of NiSi electrode in sulfuric-acid solution in the region of passive and transpassive states

The behavior of an NiSi electrode in 0.5 M H₂SO₄ in the region of passive and transpassive state (from 0.50 to 2.1 V (versus SHE)) is studied. The conclusion is made about formation of oxide film close to SiO₂ by composition on the electrode surface in the passivation process. Equivalent electric circuit modeling passive and transpassive state of nickel silicide is proposed. Thickness of oxide film and its specific resistance depending on electrode potential are calculated basing on the impedance data.     

X80管线钢钝化膜在各种高浓度NaHCO3溶液中的电化学行为

采用动电位极化曲线、恒电位极化曲线、电化学阻抗谱(EIS)、Mott-Schottky分析等电化学方法研究了X80管线钢在各种高浓度的NaHCO₃溶液中形成钝化膜的电化学行为。结果表明, X80管线钢钝化膜的稳定性和耐蚀性会受到NaHCO₃溶液浓度的影响。钝化膜电化学性质随HCO₃^-浓度升高而降低;内层Fe₃O₄的厚度不随HCO₃^-浓度变化,推测其形成与成膜电位有关;内外膜层厚度比随HCO₃^-浓度的升高而增大,钝化膜的稳定性和耐蚀性主要受外层γ-Fe₂O₃的影响。根据点缺陷(PDM)理论的分析认为,NaHCO₃溶液浓度升高时钝化膜稳定性和耐蚀性的降低与溶液电导率的升高和HCO₃^-在缺陷点处吸附作用的增强有关。     

Electrochemical impedance spectroscopy of anodic processes on Co<Subscript>2</Subscript>Si electrode in sulfuric acid solutions

Frequency dependences of the impedance of Co₂Si electrode in 0.5 M H₂SO₄ and 0.05 M H₂SO₄ + 0.45 M Na₂SO₄ solutions are measured in the ranges of the active dissolution, active-passive transition, passive state, and transpassivity. There are potential values in the active range when the impedance can be interpreted as the impedance of the selective cobalt dissolution. The impedance spectra in the passive range and in the beginning of the transpassive potential range are described with the use of an equivalent circuit taking into account the existence of an oxide layer on the electrode surface.