铜质文物在<strong>CO<sub>2</sub></strong> 环境中的腐蚀行为及缓蚀剂研究

doi:10.11902/1005.4537.2022.298

中国腐蚀与防护学报

2023, Vol. 43

Issue (5): 1049-1056 CSTR: 32134.14.1005.4537.2022.298 DOI: 10.11902/1005.4537.2022.298

研究报告

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铜质文物在CO₂ 环境中的腐蚀行为及缓蚀剂研究

周浩¹, 尤世界², 王胜利²(

)

^1.上海博物馆文物保护科技中心上海 200231
^2.哈尔滨工业大学环境学院城市水资源与水环境国家重点实验室哈尔滨 150090

Corrosion Behavior and Corrosion Inhibitor for Copper Artifacts in CO₂ Environment

ZHOU Hao¹, YOU Shijie², WANG Shengli²(

)

^1.Conservation Center, Shanghai Museum, Shanghai 200231, China
^2.State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin 150090, China

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摘要:

采用石英晶体微天平 (QCM) 反应性监测技术，结合Cu表面腐蚀产物分析，揭示了铜质文物在CO₂环境中的初期腐蚀行为。进而针对性地引入苯骈三氮唑 (BTA) 和L-半胱氨酸 (CYS) 为主的复配气相缓蚀剂 (VCI) 以提高对铜质文物的抗腐蚀能力，同时结合电化学阻抗谱 (EIS) 技术和密度泛函理论 (DFT) 研究了复配VCI对铜质文物的缓蚀机制。结果表明，CO₂浓度的增大以及相对湿度的升高均会加速铜质文物的腐蚀，在CO₂环境暴露后的初期，腐蚀产物主要为Cu₂O、CuO和CuCO₃·Cu(OH)₂。BTA与CYS对铜质文物腐蚀有显著的协同缓蚀性能，当BTA与CYS复配比为4∶1时，缓蚀率最高为86.2%。由于CYS与BTA相比，其较小的尺寸而产生较少的空间位阻，可以充分填补BTA膜的空隙，使得复合缓蚀剂膜更加致密。

关键词 ：铜质文物, CO₂气氛环境, 腐蚀机理, 石英晶体微天平, 气相缓蚀剂

Abstract：

Carbon dioxide (CO₂) is a gaseous pollutant found in museums that can seriously damage the original appearance of copper artifacts through local acidification and corrosion. Aiming to simulate the CO₂induced corrosion of the real copper artifacts, a quartz-crystal microbalance (QCM) in conjunction with corrosion products analysis techniques is used to reveal the initial corrosion behavior and regularities of Cu in the CO₂ containing environment. Furthermore, vapor-phase corrosion inhibitors (VCI) compounded with benzotriazole (BTA) and L-cysteine (CYS) were specifically formulated to improve the anti-corrosion ability of Cu. In this work, we investigated the anticorrosive mechanism of VCI on Cu by means of electrochemical impedance spectroscopy (EIS) technology and density functional theory (DFT). The results demonstrated that with the increase of CO₂ concentration and relative humidity content of the environment, the Cu corrosion was accelerated, and the initial corrosion products consist mainly of Cu₂O, CuO and CuCO₃∙Cu(OH)₂after exposure to CO₂ environment. BTA and CYS have significant synergistic anti-corrosion performance for Cu. When the compound radio of BTA to CYS is 4∶1, the highest corrosion inhibition efficiency is 86.2%. Which may be ascribed to that the CYS molecular with relatively smaller size can fully fill the defects of the BTA film, thus causing a greater densification of the anti-corrosion film.

Key words： copper relics CO₂ atmosphere environment corrosion mechanism quartz crystal microbalance vapor corrosion inhibitor

收稿日期: 2022-09-26 32134.14.1005.4537.2022.298

ZTFLH:

TG174

基金资助:国家自然科学基金(51671117)

通讯作者: 王胜利，E-mail: tckitten@163.com，研究方向为应用电化学理论与技术

Corresponding author: WANG Shengli, E-mail: tckitten@163.com

作者简介: 周浩，男，1970年生，副研究馆员

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引用本文:

周浩, 尤世界, 王胜利. 铜质文物在CO₂ 环境中的腐蚀行为及缓蚀剂研究[J]. 中国腐蚀与防护学报, 2023, 43(5): 1049-1056.
ZHOU Hao, YOU Shijie, WANG Shengli. Corrosion Behavior and Corrosion Inhibitor for Copper Artifacts in CO₂ Environment. Journal of Chinese Society for Corrosion and protection, 2023, 43(5): 1049-1056.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2022.298 或 https://www.jcscp.org/CN/Y2023/V43/I5/1049

图1 镀铜石英晶振片

图2 镀铜石英晶振片的频率，质量和腐蚀速率随时间变化曲线

图3 不同条件下镀铜石英晶振片的频率、腐蚀速率随时间变化曲线

图4 不同暴露环境下的XPS谱

图5 不同BTA-CYS复配比处理后Cu的Nyquist图和相应的等效电路

表1 不同BTA-CYS复配比对Cu在CO2中电化学阻抗拟合参数

图6 BTA与CYS的优化几何结构、HOMO和LUMO轨道能量分布图

表2 基于DFT计算得到的BTA和CYS的量子化学和分子动力学参数

图7 BTA-CYS对Cu的缓蚀机制

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