腐蚀电化学阻抗谱的数据解析与物理模型研究进展

doi:10.11902/1005.4537.2024.381

中国腐蚀与防护学报

2025, Vol. 45

Issue (5): 1143-1160 CSTR: 32134.14.1005.4537.2024.381 DOI: 10.11902/1005.4537.2024.381

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腐蚀电化学阻抗谱的数据解析与物理模型研究进展

郭玉杰¹, 李艳辉², 夏大海¹(

), 胡文彬¹

1 天津大学材料科学与工程学院天津 300350
2 西安交通大学能源与动力工程学院热流科学与工程教育部重点实验室西安 710049

Data Analysis and Physical Model of Electrochemical Impedance Spectroscopy for Corrosion Systems: Progresses and Challenges

GUO Yujie¹, LI Yanhui², XIA Da-Hai¹(

), HU Wenbin¹

1 School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China
2 Key Laboratory of Thermo-Fluid Science & Engineering, Ministry of Education, School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China

引用本文:

郭玉杰, 李艳辉, 夏大海, 胡文彬. 腐蚀电化学阻抗谱的数据解析与物理模型研究进展[J]. 中国腐蚀与防护学报, 2025, 45(5): 1143-1160.
Yujie GUO, Yanhui LI, Da-Hai XIA, Wenbin HU. Data Analysis and Physical Model of Electrochemical Impedance Spectroscopy for Corrosion Systems: Progresses and Challenges[J]. Journal of Chinese Society for Corrosion and protection, 2025, 45(5): 1143-1160.

全文: PDF(6490 KB) HTML

摘要:

电化学阻抗谱(EIS)是研究金属材料及其涂覆体系腐蚀电化学行为与失效机理的最重要的方法之一。随着腐蚀电化学理论、数值计算以及相应拟合软件的发展，EIS数据解析得到了很大发展。通过数据拟合与解析可得到表征钝化膜厚度、钝化膜电阻率分布、涂层电阻率分布等关键参数。当钝化膜破裂后，通过动力学模型推导Faraday阻抗Z_F的表达式，可以解析各个电极反应的速度常数、扩散层厚度等参数。本文以钝态金属及其有机涂覆体系为案例，综述了电化学等效电路模型(ECM)、点缺陷模型(PDM)、电化学动力学模型、幂律模型(PLM)、Young模型在解析氧化膜性质、涂层性能和电极过程动力学参数中的应用，并讨论了每种方法的优缺点，最后指明了EIS数据解析与物理模型的发展趋势。

关键词 ：电化学阻抗谱, 有机涂层, 电化学等效电路, 幂律模型, Young模型

Abstract：

Electrochemical impedance spectroscopy (EIS) is one of the most important methods for studying the electrochemical corrosion behavior and failure mechanisms of metallic materials and their coating systems. With the development of corrosion electrochemistry theory, numerical calculation, and corresponding fitting software, significant progress has been made in the analysis of EIS data. Through data fitting and analysis, key parameters such as the thickness of the passive film, the resistivity distribution of the passive film, and the resistivity distribution of the coating can be obtained. When the passive film breaks down, the expression of the Faraday impedance Z_F can be derived through the kinetic model, correspondingly, the parameters such as the rate constants of each electrode reaction and the thickness of the diffusion layer can be analyzed. Taking passive metals and their organic coating systems as examples, this paper reviews the applications of the electrochemical equivalent circuit model (ECM), the point defect model (PDM), the electrochemical kinetic model, the power-law model (PLM), and the Young model in analyzing the properties of oxide films, the performance of coatings, and the kinetic parameters of electrode processes. Moreover, the advantages and disadvantages of each method are discussed. Finally, the development trends of EIS data analysis and physical models are pointed out.

Key words： EIS organic coating electrochemical equivalent circuit power-low model Young model

收稿日期: 2024-11-25 32134.14.1005.4537.2024.381

ZTFLH:

TG174

基金资助:国家自然科学基金(52031007);国家自然科学基金(52171077)

通讯作者: 夏大海，E-mail：dahaixia@tju.edu.cn，研究方向为腐蚀科学中的人工智能方法与应用

Corresponding author: XIA Da-Hai, E-mail: dahaixia@tju.edu.cn

作者简介: 郭玉杰，男，2001年生，硕士生

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图1 PDM-II及PDM-III模型中在模型金属基体与双层钝化膜界面处点缺陷生成和湮灭反应示意图[28]

图2 镍基合金在高温水相体系中电化学腐蚀的典型等效电路示意图[33]

图3 钝态金属表面覆盖完整均匀钝化膜时的电化学等效电路[39]

图4 敏化5083铝合金样品钝化膜破裂时对应的电化学等效电路[40]

图5 与钝化膜阻抗响应相对应的R//C元件的分布[7]

图6 以γ为参数计算得到的幂律模型对应的理论Bode图[44]

图7 以γ为参数计算得到的幂律模型对应的归一化电阻率与位置之间的函数[44]

图8 以δ/λ为参数计算得到的Young模型对应的理论Bode图[44]

图9 以δ/λ为参数计算得到的Young模型对应的归一化电阻率与位置之间的函数[44]

表1 5083铝合金的SCC实验条件[40]

图10 不同实验条件下敏化态5083-O样品的欧姆电阻校正Bode图[40]

图11 不同实验条件下测得的敏化态5083铝合金的EIS图谱[40]

图12 7050铝合金在3.5%NaCl溶液中空蚀条件下不同间隙宽度的EIS测试结果[58]

图13 图12进行欧姆电阻校正后的Bode图[58]

图14 7050铝合金在3.5%NaCl溶液中空蚀条件下测得EIS与非线性回归结果的对比[58]

图15 用于拟合金属/钝化膜/电解质界面阻抗响应的等效电路[59]

图16 Beaunier等提出的涂覆金属通用等效电路模型[69]

图17 Agarwal等提出的等效电路[70]

图18 金属基底/涂层/电解质系统示意图及其电化学等效电路[71]

图19 2024铝合金/混合溶胶-凝胶涂层在0.5 mol/L NaCl溶液中浸泡72 h后的阻抗图[71]

图20 在电解质中浸泡不同时间后带混合溶胶-凝胶涂层的2024铝合金的电阻率曲线[71]

图21 双层模型的示意图。假设涂层由具有均匀电阻率ρc的内层和电阻率随位置呈指数关系的外层组成[72]

图22 通过阻抗数据解析得出的在不同NaCl溶液中浸泡后的涂层电阻率随涂层厚度的变化曲线[72]

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