青铜表面钼酸钠缓蚀转化膜XPS深度剖析研究

doi:10.3964/j.issn.1000-0593(2025)07-1979-07

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摘要：无机钼酸盐缓蚀剂因其绿色、低毒和高效的特性，在金属文物防护领域具有广阔的应用前景。采用不同浓度钼酸钠溶液通过化学沉积法在青铜表面构筑缓蚀转化膜，并通过电化学测试和XPS深度剖析研究其组成、结构及性能。实验结果表明，青铜试样经1 d浸泡处理后，采用0.2 mol·L^-1钼酸钠溶液处理的试样缓蚀效率较高，约为50%，而采用0.02和0.05 mol·L^-1钼酸钠溶液处理的试样缓蚀效率相对较低。随着浸泡时间的延长，0.2和0.5 mol·L^-1钼酸钠溶液处理的试样缓蚀效率逐渐下降，而0.02和0.05 mol·L^-1钼酸钠溶液处理的试样缓蚀效率呈现先上升后下降的趋势。XPS深度剖析揭示，缓蚀膜在1.25~5.00 μm范围内发生氧化还原反应，形成SnO₂、CuO、Cu₂O和MoO₂等金属氧化物。其中Cu元素呈现Cu₂O外层、Cu₂O+CuO过渡层和CuO内层的结构，而Mo元素由表层的MoO^2-₄向内层转变为MoO^2-₄+MoO₂，钼酸根在内层被还原为MoO₂。此外，试样经钼酸钠溶液处理后出现钼蓝现象，导致颜色变化明显，其中0.2 mol·L^-1溶液处理3 d的试样色差ΔE^*_Lab约为25，而0.5 mol·L^-1溶液处理3 d的试样色差ΔE^*_Lab约为46。本研究揭示了钼酸盐缓蚀膜的化学组成及结构特征，为其在金属文物防护中的应用提供了重要借鉴。

关键词：文物保护；金属文物；青铜器；缓蚀剂；钼酸钠

Abstract：Inorganic molybdate corrosion inhibitors have broad application prospects in conserving metal cultural relics due to their environmentally friendly, low-toxicity, and high-efficiency properties. This study used sodium molybdate solutions of varying concentrations to construct corrosion-inhibiting conversion films on bronze surfaces via chemical deposition. These films' composition, structure, and performance were systematically investigated using electrochemical testing and XPS depth profiling. Experimental results showed that after 1 day of immersion, the bronze sample treated with 0.2 mol·L^-1 sodium molybdate solution exhibited a relatively high corrosion inhibition efficiency of approximately 50%. In contrast, samples treated with lower concentrations (0.02 and 0.05 mol·L^-1) demonstrated lower efficiencies. With prolonged immersion, the inhibition efficiency of samples treated with 0.2 and 0.5 mol·L^-1 solutions gradually decreased, while those treated with 0.02 and 0.05 mol·L^-1 solutions initially increased before subsequently decreasing.XPS depth profiling analysis revealed that within the 1.25～5.00 μm depth range, redox reactions occurred, forming metal oxides such as SnO₂, CuO, Cu₂O, and MoO₂. Specifically, Cu exhibited a layered distribution, transitioning from an outer Cu₂O layer to an intermediate Cu₂O+CuO transition layer and finally to an inner CuO layer. Mo existed predominantly as MoO^2-₄ in the outer film and gradually converted into a mixed form of MoO^2-₄ and MoO₂ in the inner layers, with molybdate ions being reduced to MoO₂. Additionally, treated samples exhibited a noticeable color change due to the molybdenum blue phenomenon. After 3 days of immersion, the ΔE^*_Lab color difference of the sample treated with 0.2 mol·L^-1 sodium molybdate solution was approximately 25, whereas that of the sample treated with 0.5 mol·L^-1 solution was about 46.This study elucidates the chemical composition and structural characteristics of molybdate-based corrosion-inhibiting conversion films on bronze surfaces, providing valuable insights into their application in conserving metal cultural relics.

Key words：Cultural relic protection; Metal artifacts; Bronze ware; Corrosion inhibitor; Sodium molybdate

收稿日期: 2024-09-23 修订日期: 2025-02-27

中图分类号:

TG174.42

基金资助: 陕西省科技创新团队（2022TD-35），陕西省重点研发计划项目（2024GX-YBXM-560，2024SF-YBXM-677），国家自然科学基金项目（52303242），中国博士后科学基金项目（2023T00205，2024M751922）资助

通讯作者: 杨奔，金普军 E-mail: jinpj@snnu.edu.cn；yangben@snnu.edu.cn

作者简介: 范辰骁，1998年生，陕西师范大学材料科学与工程学院硕士研究生 e-mail: fanchenxiao2022@163.com

引用本文:

范辰骁，李昌青，罗雨佳，何贝，杨奔，金普军. 青铜表面钼酸钠缓蚀转化膜XPS深度剖析研究[J]. 光谱学与光谱分析, 2025, 45(07): 1979-1985.
FAN Chen-xiao, LI Chang-qing, LUO Yu-jia, HE Bei, YANG Ben, JIN Pu-jun. XPS Depth Profile Analysis of Sodium Molybdate-Based Conversion Film on Bronze Surface. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(07): 1979-1985.

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