微区光谱分析技术在文物颜料保护中的研究进展

颜料是彩绘文物的重要物质组成和艺术表现形式，文物颜料的保护一直是文化遗产保护领域的热点和难点。文物具有不可再生的特性，文物颜料的原位、无损、微样本的准确分析是该类文物保护的重要工作。随着各种微束技术的进步，微区光谱分析技术以精准微区定位、快速光谱扫描的工作方式，在文物保护研究中具有独特的优势，因而其应用得到了快速发展。从颜料成分分析、颜料降解褪色分析、保护效果评价等方面探讨了微区X射线荧光光谱分析（μ-XRF）、微区激光诱导击穿光谱分析（μ-LIBS）、微区拉曼光谱分析（μ-Raman）、微区红外光谱分析（μ-FTIR）、微区X射线吸收近边结构光谱分析（μ-XANES）、微区时间分辨光致发光光谱分析（μ-TRPL）、微区褪色测试（μ-FT）等技术在彩绘文物颜料保护中的应用、特点及技术难点，并从消除测量干扰、改进测量装置、研发联合装置等方面展望了微区光谱技术的发展趋势。其中，μ-XRF，μ-LIBS，μ-Raman和μ-FTIR是目前颜料成分分析常用的微区光谱分析技术，而且μ-Raman和μ-FTIR在保护效果评价中应用广泛，μ-FTIR和μ-XRF还可用于颜料降解分析。常用微区光谱技术联用并结合PCA分析和相关分析技术不仅可以鉴别文物颜料，还能为文物产地、文物断代及其真伪鉴别提供科学依据。特别是μ-XANES，μ-TRPL和μ-FT等方法属于国际领先的文物颜料分析技术，对文物颜料降解产物鉴别和分布可视化分析、颜料的起源和历史、颜料粒子迁移相关的降解现象、颜料的耐光性等研究起着关键作用。然而，目前这些方法在国内文物保护领域应用很少。因此，该研究对于推动我国文物分析及文物保护的发展具有重要意义，为文物颜料的鉴定、保护和修复提供科学指导。

Research Progress of Microspectral Analysis Technologies in Protecting Pigments of Cultural Relics

Pigments are important material composition and artistic expression of polychrome cultural relics. The protection of cultural relics pigments has always been a hot and difficult issue in the field of cultural heritage protection. Cultural relics have non-regenerative characteristics, so the in-situ, non-invasive and accurate analysis of micro samples of cultural relics pigments plays an important role in protection of cultural relics. With the progress of various micro-beam technologies, micro spectral analysis technologies have unique advantages in the study of cultural relic the protection with the working mode of precise micro-area positioning and rapid spectral scanning, so the application has been developed rapidly. This paper presented the application, characteristics, and technical difficulties of the micro spectral analysis technologies, such as micro X-ray fluorescence(μ-XRF), micro-laser induced breakdown spectroscopy(μ-LIBS), micro-Raman spectroscopy(μ-Raman), micro-Fourier transform infrared spectroscopy(μ-FTIR), micro X-ray absorption near-edge spectroscopy(μ-XANES), micro time-resolved photoluminescence microscopy(μ-TRPL) and micro-fade tester(μ-FT) in order to get the information about composition analysis, depigmentation and degradation analysis, and protective effect evaluation. Also, the development tendency of microspectral technologies was prospected from eliminating measurement interference, improving measurement devices, and developing hybrid setup. Among these micro spectral technologies, μ-XRF, μ-LIBS, μ-Raman and μ-FTIR are conventional technologies for pigment composition analysis. Moreover, μ-Raman and μ-FTIR are widely applied to assess protection effect and μ-FTIR and μ-XRF can also be used to analyze degradation products. Combined with PCA and other relevant analyses, conventional micro spectral technologies can be used to identify the pigments of cultural relics and to provide valuable information for the origin, dating and authenticity identification of cultural relics. Especially, μ-XANES, μ-TRPL and μ-FT belong to the advanced international technologies which play a key role in the analysis of cultural relics pigments, the identification and visualization of distributions of the degradation products, the origin of the pigment and its history, degradation phenomena associating with the migration of ions from pigments and specific photochemical fading behavior. However, at present, these advanced technologies are rarely applied in the field of cultural relics protection in China. Therefore, this study has great significance for promoting the development of analysis and protection of cultural relics and brings a new insight into the identification, protection and restoration of cultural relics pigments in China.