光谱学与光谱分析, 2021, 41 (3): 796, 网络出版: 2021-04-07  

红外光谱结合PCA-LDA对嘉峪关戏台文物建筑彩画胶料种类的判别

PCA-LDA Analysis of Binders Used in the Theater Color Painting of Jayuguan Pass Based on FTIR Spectra
作者单位
1 西北大学文化遗产学院, 陕西 西安 710069
2 西北大学化学与材料科学学院, 陕西 西安 710127
3 文化遗产研究与保护技术教育部重点实验室, 陕西 西安 710069
4 秦始皇帝陵博物院, 陕西 西安 710600
5 陶质彩绘文物保护国家文物局重点科研基地, 陕西 西安 710600
摘要
为了判别嘉峪关戏台文物建筑彩画的胶料种类, 采用皮胶、 鱼鳔胶、 蛋清、 蛋黄、 牛奶为参考样品, 使用傅里叶红外光谱仪采集了参考样品及三件文物样品胶料的红外吸收光谱, 利用主成分分析结合线性判别分析(PCA-LDA)构建胶料种类判别的数学模型, 并应用于文物样品。 发现参考样品红外光谱在1 800~1 000 cm-1区间包含了丰富的分子结构特征信息。 该区间中蛋白类胶料的共同特征为1 650 cm-1附近的仲酰胺CO键伸缩振动峰, 1 542 cm-1附近的酰胺C—N键伸缩振动和N—H键弯曲振动峰, 1 240 cm-1附近的酰胺C—N键伸缩振动峰。 此外, 蛋黄、 皮胶和牛奶因其中含有较多脂类物质, 在1 745 cm-1附近还存在饱和脂肪酸酯羰基CO键伸缩振动峰。 在此基础上, 通过对参考样品红外吸收光谱主成分得分散点图的分析, 发现不同胶料参考样品的红外光谱类间差异显著。 据此, 使用参考样品红外光谱的主成分得分为训练集, 添加类别变量拟合判别函数, 绘制函数组质心图并进行交叉验证, 得出方程的判别正确率为93.3%。 发现因老化降解导致三件文物样品的红外吸收光谱与参考样品光谱有所不同, 但仍具有蛋白类胶料的特征。 利用PCA-LDA分析模型对文物胶料种类进行判别, 结果均为皮胶。 该胶料种类判别模型稳定、 有效, 用该模型判定嘉峪关建筑彩画胶料为动物胶中皮胶。
Abstract
To identify the types of binder used in the theater color painting of Jiayuguan pass, the Fourier infrared spectra were collected, which of the reference samples consist of leather glue, fish glue, egg white, egg yolk, and casein prepared by traditional technology and three cultural relics samples. The factor analysis combined with the linear discriminant analysis (PCA-LDA) was used to construct the mathematics model and determine the kind of the binder of relics samples. It was found that there was abundant information about the molecular structure in the range of 1 800~1 000 cm-1 of the reference samples infrared spectra. The common infrared spectrum characteristics of protein compounds in this range are the peak of CO bond stretching vibration around 1 650 cm-1, the peak of C—N bond stretching vibration and N—H bond bending vibration around 1 542 cm-1, and the peak of C—N bond stretching vibration around 1 240 cm-1. Besides, due to the fatty substances contained in yolk, skin glue and milk reference samples, there is also a stretching vibration peak of saturated fatty acid ester carbonyl CO bond near 1 745 cm-1. Through the analysis of factor score scatter diagram, it could be seen that there are differences among different reference samples. According to this, factor scores of the reference sample infrared spectrum were used as the training database to calculate the discriminant function by LDA. The group center figures, and cross-validation of the functions were performed and the accuracy of the discriminant equation is 93.3%. Base on the spectrum of three relics samples, which still have the characteristics of protein binder, the spectrum difference between them and reference can be seen due to degradation. PCA-LDA analysis model was used to identify the kinds of the binder for cultural relics, and the results were all leather glue. According to the analysis above, it could be concluded: A stable and effective infrared spectrum discrimination PCA-LDA model can be established for the discrimination of binder. The theater color painting binder used in the Jiayuguan pass was identified as leather glue by this model.
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杨璐, 黄建华, 陈欣楠, 王丽琴, 卫引茂. 红外光谱结合PCA-LDA对嘉峪关戏台文物建筑彩画胶料种类的判别[J]. 光谱学与光谱分析, 2021, 41(3): 796. YANG Lu, HUANG Jian-hua, CHEN Xin-nan, WANG Li-qin, WEI Yin-mao. PCA-LDA Analysis of Binders Used in the Theater Color Painting of Jayuguan Pass Based on FTIR Spectra[J]. Spectroscopy and Spectral Analysis, 2021, 41(3): 796.

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