应用衰减全反射红外光谱无损鉴别中国传统手工纸的方法研究

doi:10.3964/j.issn.1000-0593(2024)09-2450-09

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摘要：纤维种类鉴别是古代纸张保护的重要基础工作。探究中国传统手工纸的无损纤维鉴别的方法对中国古籍、档案及纸质文物的研究和保护具有重要意义。该研究应用衰减全反射傅里叶变换红外光谱（ATR-FTIR）对已知纤维成分的17类64种中国传统手工纸标准样品进行了无损分析，参考纤维素和木质素的红外峰位及部分纸样的X射线衍射（XRD）分析结果确认纸样中的所有红外谱峰归属；并采用分波段比较分析的方法对相似度极高的谱图进行比对分析，分别总结各类纸张在4 000~1 800、1 800~1 500、1 500~1 200和1 200~600 cm^-1四个波段的谱图特征；同时对4 cm^-1精度的谱图进行二阶导数处理，分别总结各类纸张在1 500~1 200和1 200~900 cm^-1两个波段的二阶导数谱图特征；最后通过红外结晶指数及其他峰高和峰面积比值计算结果实现对纸类更细致的区分。应用上述方法对16个盲测样品进行了有效性测试，红外分析结果与显微纤维鉴别结果一致，初步证明了该方法在中国传统手工纸无损纤维鉴别上的可行性和有效性。实验结果表明，应用ATR-FTIR无损分析法可对麻、桑构皮、檀皮、瑞香皮和竹几大类原料的传统手工纸纤维类型作出快速而准确的鉴别，对于混料的宣纸也同样适用；但对于显微分析也难以鉴别的亲缘关系较近的植物原料如桑、构皮之间的精细鉴别仍有一定局限性。

关键词：衰减全反射傅里叶变换红外光谱；二阶导数红外光谱；中国传统手工纸；纤维鉴别；无损分析

Abstract：Fiber identification is an important work in preserving ancient paper. Exploring a non-destructive fiber identification method of Chinese traditional handmade paper is significant to the research and preservation of ancient Chinese books, archives, and paper cultural relics. In this study, Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR) was used to analyze 64 standard Chinese traditional handmade paper samples of 17 categories whose fiber compositions were known.First, the main components in the paper and the attribution of all the infrared peaks were confirmed by referring to the infrared peaks of cellulose and lignin, as well as the X-ray diffraction (XRD) analysis results of some paper samples. Then, the comparative analysis of the spectra with very high similarity was carried out to summarize the spectral characteristics of various kinds of paper in the four bands of 4 000~1 800, 1 800~1 500, 1 500~1 200 and 1 200~600 cm^-1, respectively. At the same time, by second derivative processing, the second derivative spectrum characteristics of each kind of paper were summarized in the bands of 1 500~1 200 and 1 200~900 cm^-1, respectively. Finally, through the numerical calculation results, such as the infrared cry stallinity index and the ratios of the peak heights and the peak areas, a more detailed distinction among different kinds of paper was achieved. The above method was used for a blind test of 16 unknown samples, and the results of the infrared analysis were consistent with the results of the microscopic fiber analysis, which preliminarily proved the feasibility and effectiveness of this method. All the experimental results show that the non-destructive analysis method of ATR-FTIR can be used to make fast and accurate identification of the fiber type of hemp paper, mulberry paper, Wingceltis paper, Xuan paper, Thymelaeaceae paper and bamboo paper, but this method still has some limitations for the identification of the plant materials With closer genetic relationships,such as mulberry and paper mulberry, which are also difficult to distinguish through microscopic analysis.

Key words：Attenuated Total Reflection Fourier Transform Infrared Spectroscopy（ATR-FTIR）;Second derivative infrared spectra;Chinese traditional handmade paper;Fiber identification;Non-destructive analysis

收稿日期: 2022-06-22 修订日期: 2023-12-05

中图分类号:

O657.3

基金资助: 国家社会科学基金重大项目（19ZDA343）资助

通讯作者: 吕淑贤

作者简介: 吕淑贤，女，1986年生，北京大学图书馆古籍保护馆员 e-mail: lvsx@lib.pku.edu.cn

引用本文:

吕淑贤. 应用衰减全反射红外光谱无损鉴别中国传统手工纸的方法研究[J]. 光谱学与光谱分析, 2024, 44(09): 2450-2458.
LÜ Shu-xian. A Study on the Non-Destructive Method of Identifying Chinese Traditional Handmade Paper With Attenuated Total Reflection Fourier Transform Infrared Spectroscopy. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2024, 44(09): 2450-2458.

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https://www.gpxygpfx.com/CN/10.3964/j.issn.1000-0593(2024)09-2450-09 或 https://www.gpxygpfx.com/CN/Y2024/V44/I09/2450