Kwon Heehong, Kim Leeyun
Department of Conservation and Art Bank, National Museum of Modern and Contemporary Art, Korea, Cheongju-si 28501, Republic of Korea.
Materials (Basel). 2025 Feb 20;18(5):924. doi: 10.3390/ma18050924.
Copper alloys form various corrosion products such as sulfides and chlorides. Chlorides can cause severe structural damage in 'bronze disease', making the early identification of corrosion products and conservation treatment important tasks. In this study, standard spectra were established for nine minerals of corrosion products using a portable Raman spectrometer, and their identification was verified by comparing them with benchtop micro-Raman spectra. The main characteristic bands were detected for most corrosion products, and the in situ applicability of the portable Raman spectrometer was demonstrated. However, for some samples, the signal-to-noise ratio was low, while the main characteristic peaks were still identifiable. In particular, dicopper chloride trihydroxides (such as atacamite and clinoatacamite) were clearly distinguished as corrosion products whose early identification is crucial. After the on-site analysis of copper alloy artworks exposed to outdoor environments for over 30 years, corrosion products such as malachite, brochantite, and moolooite were detected, indicating that portable Raman spectrometers are an effective tool for diagnosing conservation conditions. This study demonstrates that portable Raman spectrometers can be effectively used to identify corrosion products and assess the conservation state of copper alloy artworks and are expected to make significant contributions to future conservation and restoration efforts.
铜合金会形成各种腐蚀产物，如硫化物和氯化物。氯化物会在“青铜病”中造成严重的结构损坏，因此早期识别腐蚀产物和进行保护处理是重要任务。在本研究中，使用便携式拉曼光谱仪为九种腐蚀产物矿物建立了标准光谱，并通过与台式显微拉曼光谱进行比较来验证其识别结果。检测到了大多数腐蚀产物的主要特征谱带，并证明了便携式拉曼光谱仪的现场适用性。然而，对于一些样品，信噪比很低，而主要特征峰仍然可以识别。特别是，三水氯铜矿（如氯铜矿和斜氯铜矿）被明确鉴定为腐蚀产物，其早期识别至关重要。在对暴露于户外环境超过30年的铜合金艺术品进行现场分析后，检测到了孔雀石、羟铜矾和水氯铜矿等腐蚀产物，表明便携式拉曼光谱仪是诊断保护状况的有效工具。本研究表明，便携式拉曼光谱仪可有效地用于识别腐蚀产物和评估铜合金艺术品的保护状态，并有望为未来的保护和修复工作做出重大贡献。
