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[利用红外光谱法对纤维状文化材料进行的研究]

[Investigation of fibrous cultural materials by infrared spectroscopy].

作者信息

Luo Xi-yun, Du Yi-ping, Shen Mei-hua, Zhang Wen-qing, Zhou Xin-guang, Fang Shu-ying, Zhang Xuan

出版信息

Guang Pu Xue Yu Guang Pu Fen Xi. 2015 Jan;35(1):60-4.

Abstract

Cultural fibrous material includes both important categories, i. e. textile and paper, consisting of precious cultural materials in museum, such as costume, painting, and manuscript. In recent years more and more connoisseur and conservator's concerns are, through nondestructive method, the authenticity and the ageing identification of these cultural relics especially made from fragile materials. In this research, we used attenuated total reflection infrared spectroscopy to identify five traditional textile fibers, alongside cotton, linen, wool, mulberry silk and tussah silk, and another five paper fibers alongside straw, wheat straw, long qisong, Chinese alpine rush and mulberry bar, which are commonly used for making Chinese traditional xuan paper. The research result showed that the animal fiber (wool, mulberry silk and tussah silk) and plant fiber (cotton and linen) were easier to be distinguished by comparing the peaks at 3 280 cm-1 belonging to NH stretching vibration and a serious peaks related to amide I to amide III. In the spectrum of wool, the peak at 1 076 cm-1 was assigned to the S-O stretching vibration absorption of cystine in wool structure and can be used to tell wool from silk. The spectrum of mulberry silk and tussah silk seems somewhat difficult to be identified, as well as the spectrum of cotton and linen. Five rural paper fibers all have obvious characteristic peaks at 3 330, 2 900 cm-1 which are related to OH and CH stretching vibration. In the fingerprint wavenumber range of 1 600 - 800 cm, the similar peaks also appeared at 1 370, 1 320 cm-1 and 1 162, 1 050 cm-1, both group peaks respectively are related to CH and CO vibration in the structure of cellulose and hemicellulose in paper fibers. Although there is more similarity of the infrared spectroscopy of these 5 paper fibers, some tiny difference in absorbance also can be found at 3 300 cm-1 and in the fingerprint range at 1 332, 1 203, and 1 050 cm-1 which are related to C-O-C vibration in cellulose. Moreover, in order to explore direct and simple method to identify different materials with similar spectrum,. the principal component analysis (PCA) was applied to separate cotton and linen, mulberry silk and tussah silk, as well as five paper fibers. To eliminate and reduce the spectral scattering caused by sample uneven surface roughness, the multiplicative scatter correction (MSC) has been applied based on total spectral data. The result showed that the score plot using the first two principal components can effectively categorize both group textiles of cotton and linen, as well as mulberry silk and tussah silk, and they have similar chemical structure. For five paper fibers, the PCA was applied in different spectral range (918-550, 1 280-918, 1 700-1 280 and 3 800-2 800 cm-1), and the best result appeared in the range from 3 800 to 2 800 cm-1, in which the five paper fibers can be well categorized. This research showed that infrared spectroscopy combined with principal component analysis has great potential advantage on identifying fibrous materials with similar structure.

摘要

文化纤维材料包括两个重要类别,即纺织品和纸张,它们由博物馆中的珍贵文化材料组成,如服装、绘画和手稿。近年来,越来越多的鉴赏家和文物保护者关注通过无损方法对这些特别是由易碎材料制成的文物的真伪和年代鉴定。在本研究中,我们使用衰减全反射红外光谱法来鉴定五种传统纺织纤维,除了棉、麻、羊毛、桑蚕丝和柞蚕丝之外,还有另外五种造纸纤维,即稻草、麦秸、龙须草、蓑草和桑枝,它们常用于制作中国传统宣纸。研究结果表明,通过比较属于NH伸缩振动的3280 cm-1处的峰以及与酰胺I至酰胺III相关的一组峰,动物纤维(羊毛、桑蚕丝和柞蚕丝)和植物纤维(棉和麻)更容易区分。在羊毛的光谱中,1076 cm-1处的峰归因于羊毛结构中胱氨酸的S-O伸缩振动吸收,可用于区分羊毛和丝绸。桑蚕丝和柞蚕丝的光谱似乎有些难以区分,棉和麻的光谱也是如此。五种造纸纤维在3330、2900 cm-1处都有明显的特征峰,它们与OH和CH伸缩振动有关。在1600 - 800 cm的指纹波数范围内,在1370、1320 cm-1以及1162、1050 cm-1处也出现了类似的峰,这两组峰分别与造纸纤维中纤维素和半纤维素结构中的CH和CO振动有关。尽管这5种造纸纤维的红外光谱有更多相似性,但在3300 cm-1处以及指纹范围内1332、1203和1050 cm-1处与纤维素中C-O-C振动相关的吸光度也存在一些微小差异。此外,为了探索直接且简单的方法来识别光谱相似的不同材料,主成分分析(PCA)被用于区分棉和麻、桑蚕丝和柞蚕丝以及五种造纸纤维。为了消除和减少由样品表面粗糙度不均匀引起的光谱散射,基于全光谱数据应用了多元散射校正(MSC)。结果表明,使用前两个主成分的得分图可以有效地对棉和麻以及桑蚕丝和柞蚕丝这两组纺织品进行分类,并且它们具有相似的化学结构。对于五种造纸纤维,PCA应用于不同的光谱范围(918 - 550、1280 - 918、1700 - 1280和3800 - 2800 cm-1),最佳结果出现在3800至2800 cm-1范围内,其中五种造纸纤维可以很好地分类。本研究表明,红外光谱结合主成分分析在识别结构相似的纤维材料方面具有很大的潜在优势。

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