红外光谱定量分析古代漆膜的可行性研究  

Feasibility Study on Quantitative Analysis of Ancient Lacquer Films by Infrared Spectroscopy

作　　者：肖庆 魏书亚 付迎春 XIAO Qing;WEI Shu-ya;FU Ying-chun(Institute of Cultural Heritage and History of Science&Technology,University of Science&Technology Beijing,Beijing 100083,China)

机构地区：[1]北京科技大学科技史与文化遗产研究院,北京100083

出　　处：《光谱学与光谱分析》2020年第9期2962-2967,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(51704023)资助。

摘　　要：漆器是中国文化遗产的一个重要组成部分,贯穿中国古代历史发展的整个过程。为了改善生漆的性能,古人将干性油与生漆混合使用,所添加干性油的比例直接影响生成漆膜的性能。由于相关历史文献的匮乏和考古出土古代漆器的老化降解,当前的科技分析主要是定性分析漆膜材料成分,而对于油/漆比例方面的研究却非常少。为了了解古代漆器在制作时所添加的干性油与生漆比例,建立一种定量分析古代漆器漆膜油/漆比例的方法是十分必要的。通过制作标准样品,分别采用FTIR-ATR和NIR对古代漆膜进行了定量分析,结果表明FTIR-ATR在漆膜老化严重的情况下,将不能达到定量分析的目的。而采用近红外光谱技术结合化学计量学方法建立的PLS模型,能对古代漆膜制作时的油/漆比例进行快速、无损的定量分析。结果表明PLS定量模型具有良好的稳定性和预测性,校正均方差(RMSEC)、预测均方差(RMSEP)和交叉验证均方差(RMSECV)均较低,相关系数Rc,Rp和Rv均在0.99以上。将该方法应用到考古发掘出土漆器漆膜材料的分析中,通过PLS定量模型计算出古代漆膜制作时的干性油添加量,确定了不同时代和不同地区漆器制作所用油/漆比例的不同,为解读古代中国的"油漆"技术提供科学依据,为漆器文物的保护修复提供一些数据支撑。Lacquerware is an important part of Chinese tangible cultural heritage, which runs through the whole Chinese history. In order to improve the performance of raw lacquer, ancient people mixed drying oil with raw lacquer.The proportion ofdrying oil directly affected the propertiesof the lacquer film. Unfortunately, due to the lack of relevant historical literature and the aging degradation of ancient lacquerwares from archaeological excavations, it is difficult to determine the materials used in the lacquer film quantitatively. Therefore, in order to understand the ratio of drying oil to raw lacquer usedin the ancient lacquer making process, it is necessary to establish a method for quantitative analysis of the ancient lacquer film oil/lacquer ratio. In this study, the ancient lacquer film was quantitatively analyzed by FTIR-ATR and NIR through standard samples. The results showed that FTIR-ATR could not achieve the purpose of quantitative analysis when the lacquer film seriously aged. The PLS model established by near-infrared spectroscopy combined with chemometrics could quickly and non-destructively analyze the oil/raw lacquer ratio of ancient lacquer film. The results show that the PLS model has good stability and predictability, with lower the root mean square error of calibration(RMSEC), root means square error of prediction(RMSEP), root mean square error of cross-validation(RMSECV), and correlation coefficients of Rc, Rp, Rv above 0.99. The method was applied to analyze ancient lacquerwares. The relative content of the drying oil contained in the ancient lacquer film was calculated by the PLS quantitative model, and the different proportions of oil/rawlacquer used in lacquer making in different times and regions were determined. It provides a scientific basis for interpreting the "oil and lacquer" technology of ancient China and provides scientific support for the conservation and restoration of lacquer artifacts.

关 键 词：近红外光谱 傅里叶变换显微红外光谱 干性油 生漆 主成分回归 定量分析 

分 类 号：O657.3[理学—分析化学]