电化学阻抗谱在有机涂层研究中的应用

doi:10.11902/1005.4537.2025.299

中国腐蚀与防护学报

2026, Vol. 46

Issue (4): 945-961 CSTR: 32134.14.1005.4537.2025.299 DOI: 10.11902/1005.4537.2025.299

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电化学阻抗谱在有机涂层研究中的应用

雍兴跃¹(

), 董晓梅¹, 高新华², 李卓玄¹, 陈燕飞³, 纪灏天¹

^1.北京化工大学有机无机复合材料全国重点实验室北京 100029
^2.中国舰船研究设计中心武汉 430064
^3.空军装备部驻北京第六军事代表室北京 100000

Application of Electrochemical Impedance Spectroscopy in Research of Organic Coatings

YONG Xingyue¹(

), DONG Xiaomei¹, GAO Xinhua², LI Zuoxian¹, CHEN Yanfei³, JI Haotian¹

^1.State Key Lab of Organic-Inorganic Composite, Beijing University of Chemical Technology, Beijing 100029, China
^2.China Ship Development and Design Center, Wuhan 430064, China
^3.The Sixth Military Representative Office of Air Force Ammarnent Department in Beijing, Beijing 100000, China

引用本文:

雍兴跃, 董晓梅, 高新华, 李卓玄, 陈燕飞, 纪灏天. 电化学阻抗谱在有机涂层研究中的应用[J]. 中国腐蚀与防护学报, 2026, 46(4): 945-961.
Xingyue YONG, Xiaomei DONG, Xinhua GAO, Zuoxian LI, Yanfei CHEN, Haotian JI. Application of Electrochemical Impedance Spectroscopy in Research of Organic Coatings[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(4): 945-961.

全文: PDF(7749 KB) HTML

摘要:

本文以有机涂层电性质为理论基础，总结了有机涂层体系在不同失效阶段的电化学阻抗谱特征及对应的等效电路模型，建立了“阻抗特征-失效阶段-等效电路”的关联体系；其次，基于等效电路模型拟合得到的涂层电阻、电容等关键参数，建立了涂层电容与介质在有机涂层中扩散系数之间的关系式，提出了涂层孔隙率计算方法和腐蚀介质扩散至涂层/金属基材界面引起的腐蚀面积计算公式，实现了涂层防护性能的量化评估。同时，介绍了采用图解法，获得阻抗谱特征参数，对不同有机涂层体系的耐蚀性能进行高效比较与排序的方法；结合阻抗谱拟合参数，深入分析了有机涂层体系失效过程中辐射作用与腐蚀之间的协同效应机制，构建了加速试验与自然大气暴晒之间的当量关系模型。最后，探讨了电化学阻抗谱在有机涂层体系研究中应用的注意事项和局限性及对应的解决之策。

关键词 ：有机涂层, 电化学阻抗谱, 等效电路模型, 涂层电化学参数

Abstract：

In this paper, the electrochemical impedance spectroscopy (EIS) characteristics of organic coating systems at different failure stages and their corresponding equivalent circuit models were summarized in terms of the theory related with the electrical properties of organic coatings, and a correlation system of “impedance characteristics-failure stages-equivalent circuits” was established. Secondly, based on key parameters such as coating resistance and capacitance obtained by fitting the equivalent circuit model, a relational expression between coating capacitance and the diffusion coefficient of the medium in the organic coating was alsoestablished. A method for calculating coating porosity and a formula for calculating the corrosion area induced by the diffusion of corrosive media to the coating/metal substrate interface were also proposed, enabling the quantitative evaluation of the protective performance of coatings. Meanwhile, a method of using the graphical approach to obtain impedance spectrum characteristic parameters for efficient comparison and ranking of the corrosion resistance of different organic coating systems was introduced. Combined with impedance spectrum fitting parameters, an in-depth analysis of the synergistic mechanism between radiation effect and corrosion during the failure process of organic coating systems was conducted, and an equivalence relationship model between accelerated tests and natural atmospheric exposure was also constructed. Finally, the paper discussed the precautions, limitations, and corresponding solutions for the application of EIS in the research of organic coating systems. The relevant results can provide a reference for applying EIS technology in conducting research related to organic coatings.

Key words： organic coating electrochemical impedance spectroscopy (EIS) equivalent circuit model electrochemical parameters of organic coatings

收稿日期: 2025-09-19 32134.14.1005.4537.2025.299

ZTFLH:

TG172

基金资助:国家自然科学基金(52171062)

通讯作者: 雍兴跃，E-mail：yongxy@mail.buct.edu.cn，研究方向为腐蚀电化学

Corresponding author: YONG Xingyue, E-mail: yongxy@mail.buct.edu.cn

作者简介: 雍兴跃，男，1966年生，博士，研究员
董晓梅，女，1997年生，博士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2025.299 或 https://www.jcscp.org/CN/Y2026/V46/I4/945

图1 绝缘材料直流电压下的电流变化与等效电路图[21,25]

图2 涂层电极典型的Bode图[26]

图3 涂层电极典型的Nyquist图及其对应的等效电路模型[26]

图4 中间频率呈现Warburg扩散阻抗的涂层电极Bode图及其对应的等效电路模型图[13]

图5 有机涂层下腐蚀的示意图及有机涂层下腐蚀时等效电容图[31]

图6 微缺陷区域百分比对涂覆钢等效电路模型阻抗模值的影响[37]

图7 环氧涂覆钢在人工海水中的Bode图[37]

图8 铝合金经过铬酸盐预处理和铬酸底漆涂层在5%NaCl溶液中暴露162 d期间的Bode图[38]

图9 暴露时间对断点频率fl或fh以及OCP和|Z|0.01值的影响[38]

图10 不同颜料环氧涂层在3.5%NaCl溶液中浸泡28 d后涂层电阻和电容与高频相位角的之间的关系[39]

图11 高、中、低耐蚀有机涂层的典型Bode图[39]

图12 涂层离子镀铝钛合金试样在模拟高原大气环境中加速试验后的EIS谱[43]

表1 涂层离子镀铝钛合金试样在模拟高原大气环境中的CIuv、CIc、CIuv,c和ΔCI值[43]

图13 涂层铝合金在中国海南的自然暴晒和模拟海洋大气环境的加速试验后的EIS谱[22]

图14 ln (Rc + Rct)随着自然暴晒年数或加速试验循环次数的变化[22]

图15 涂层电极具有两个时间常数的等效电路模型图

图16 涂层可分为两个部分，即扩散影响区和原始涂层[32]

图17 在扩散影响区电导率和相对介电常数建模的三种方式[32]

图18 当界面电阻设置为0时，模型计算的涂层电极的模值图[32]

图19 与图18对应的相位角图设定相对介电常数和电阻率的Maxwell模型预测结果，具有少量扩散微通道路径与夹杂物混合是作用[32]

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