光谱学与光谱分析, 2020, 40 (2): 356, 网络出版: 2020-05-12  

太平天国侍王府壁画表面修复材料的原位无损FTIR分析

In-Situ Non-Invasive FTIR Analysis of Conservation Materials on the Surface of Mural Paintings in Prince Shi’s Palace of the Taiping Heavenly Kingdom
作者单位
1 国家古代壁画与土遗址保护工程技术研究中心, 甘肃 敦煌 736200
2 甘肃省古代壁画与土遗址保护重点实验室, 甘肃 敦煌 736200
3 太平天国侍王府纪念馆, 浙江 金华 321000
摘要
太平天国侍王府壁画是中国南方壁画的典型代表, 具有重要的历史、 文化和艺术价值。 历史上曾对多幅壁画进行过化学保护, 部分壁画表面形成了一定厚度的有机物涂层, 分析研究壁画保护修复材料成分对于文物保护具有重要的理论和现实意义。 由于文物的珍贵性与不可再生性, 原位无损分析技术的研究和应用是未来文物分析的发展趋势, 基于便携红外光谱仪的反射红外光谱技术是对文物表面材质较为理想的无损分析手段。 利用反射傅里叶变换红外(FTIR)光谱对侍王府壁画的地仗层和表面修复材料涂层进行了现场原位无损分析, 这在我国古代壁画及其保护修复材料分析中属首次。 首先测试了无涂层壁画白色背景位置反射FTIR光谱, 并与标准无机矿物光谱比对确定了壁画地仗层成分主要为方解石和生石膏。 在此基础上, 分析了无涂层和有涂层壁画表面的红外反射特性及地仗层化学成分对表面涂层反射FTIR光谱测试的影响, 探讨了应用Kramers-Kronig(K-K)变换处理数据的可行性, 确定了K-K变换的应用范围, 分析了壁画涂层K-K变换后反射光谱与衰减全反射(ATR)光谱的差异, 并通过显微ATR FTIR光谱和热裂解气相色谱质谱联用(Py-GC/MS)技术分析验证了原位反射FTIR光谱测试结果的可靠性, 扫描电子显微镜(SEM)测量了涂层厚度, 证明不同厚度涂层均能得到可解析的高质量反射FTIR光谱。 最终确定侍王府壁画曾使用过聚醋酸乙烯酯、 聚二甲基硅氧烷和三甲树脂三种高分子材料进行过表面加固, 并得出壁画保存现状和修复材料及涂层厚度有较大关系。 证明了基于反射模式的FTIR光谱技术能准确有效地获取文物表面有机物和部分无机物成分信息。 该方法对表面有机涂层尤为敏感, 是壁画类文物较为理想的无损分析方法, 在壁画保护研究领域具有十分广阔的应用前景。 同时, 该研究弥补了我国壁画类文物表面有机物原位无损分析的不足, 为该领域研究提供了一条新思路。
Abstract
The murals in Prince Shi’s Palace of the Taiping Heavenly Kingdom are the typical examples of the murals in southern China, which have important historical, cultural and artistic values. In history, chemical conservation was carried out on many murals, and part of the murals formed a certain thickness of organic coating on the surface. It is of great theoretical and practical significance to analyze and study the compositions of mural conservation materials for the protection of cultural relics. Due to the rarity and non-renewability of cultural relics, the research and application of in-situ non-invasive analytical technique will be the trend in the future. Reflection infrared spectroscopy based on portable infrared spectrometer is an ideal method for non-invasive analysis of surface materials of cultural relics. In this paper, reflection Fourier transform infrared (FTIR) spectroscopy was used to analyze ground layer and conservation materials of murals in Prince Shi’s Palace, and it is the first time that this method was applied to the analysis of ancient Chinese murals and their conservation materials. In this study, the reflection FTIR spectrum of uncoated mural’s white background was measured at first, and the compositions of ground layer were identified as calcite and gypsum by comparison with standard inorganic minerals by reflection FTIR spectra. On this basis, the infrared reflection features of uncoated and coated mural surfaces and the influence of ground layer on surface coatings were analyzed. The feasibility and applied range of using Kramers-Kronig (K-K) transform as a data processing method were discussed. The differences between K-K-transformed reflection spectra and attenuated total reflection (ATR) spectra of mural coatings were analyzed. The reliability of in-situ reflection FTIR spectroscopy was verified by microscopic ATR FTIR spectroscopy and pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS). The thicknesses of coatings were measured by scanning electron microscopy(SEM), demonstrating that high-quality reflection FTIR spectra can be obtained for different thicknesses. Finally, it was confirmed that the murals in Prince Shi’s Palace were strengthened with three kinds of polymers: polyvinyl acetate, polydimethylsiloxane and acrylic resin, and it was concluded that the current preservation situations of murals are closely related to conservation materials and coating thicknesses. The above research proves that the information of organic compounds and some inorganic substances on the surface of cultural relics can be effectively obtained by reflection FTIR spectroscopy. This method is particularly sensitive to organic coatings on the surface, making it an ideal non-invasive analytical method for cultural relics of mural paintings, and it has a very broad application prospect in the field of mural conservation research. Meanwhile, this study makes up for the deficiency of in-situ non-invasive analysis of organic compounds on the surface of Chinese murals, and provides a new idea for the research in this field.

王卓, 苏伯民, 于宗仁, 水碧纹, 赵金丽, 崔强, 善忠伟, 李倩. 太平天国侍王府壁画表面修复材料的原位无损FTIR分析[J]. 光谱学与光谱分析, 2020, 40(2): 356. WANG Zhuo, SU Bo-min, YU Zong-ren, SHUI Bi-wen, ZHAO Jin-li, CUI Qiang, SHAN Zhong-wei, LI Qian. In-Situ Non-Invasive FTIR Analysis of Conservation Materials on the Surface of Mural Paintings in Prince Shi’s Palace of the Taiping Heavenly Kingdom[J]. Spectroscopy and Spectral Analysis, 2020, 40(2): 356.

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