古代纸质文物科学检测技术综述

阎春生; 黄晨; 韩松涛; 韩秀丽; 应超男; 杜远东

doi:10.37188/CO.2020-0010

古代纸质文物科学检测技术综述

doi: 10.37188/CO.2020-0010

浙江大学图书馆古籍特藏部，浙江杭州 310058

基金项目: 国家自然科学基金（No. 61875172）

详细信息

作者简介:
阎春生（1973—），男，山西文水人，博士，副教授，硕士生导师，1994年、1999年于电子科技大学分别获得学士、硕士学位，2003年于清华大学获得博士学位，主要从事光谱学、光层析成像技术及近场光学等方面的研究，2019年开始从事古代纸质文物检测与保护方面的研究。E-mail：yancs@zju.edu.cn

中图分类号: O43; O65;G262
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出版历程
- 收稿日期: 2020-01-21
- 修回日期: 2020-03-19
- 网络出版日期: 2020-09-10
- 刊出日期: 2020-10-01

Review on scientific detection technologies for ancient paper relics

Library of Zhejiang University, Zhejiang University, Hangzhou 310058, China

Funds: Supported by National Natural Science Foundtion of China (No. 61875172)

More Information

Corresponding author: yancs@zju.edu.cn

摘要

摘要: 全面论述了古代纸质文物包括纸张原料、墨、印泥和颜料等所涉及的各种现代科技检测技术与方法，主要分为成像法和波谱法两大类。成像法是包括透光、红外、紫外、X射线、中子活化等展示样品表面或内部宏观信息的摄影法，X射线、太赫兹、光相干等展示样品表面之下分层信息的层析成像方法，光学显微镜、扫描电子显微镜、透射电子显微镜、原子力显微镜等展示样品微观信息的显微成像方法。基于波与物质相互作用原理的具有指纹特征的波谱法则包括色谱、质谱、电子顺磁共振波谱、核磁共振波谱、X射线光电子能谱、X射线衍射谱、X射线荧光光谱、分子荧光光谱、拉曼光谱、紫外-可见-近红外-中红外-太赫兹吸收光谱、高光谱等。研究表明，上述技术的综合应用、各取所长和相互印证是揭示纸质文物的制造过程、艺术特征、保存历史、病害情况、真迹与否及如何修复等重要问题的有力手段。
- 纸质文物 /
- 成像法 /
- 波谱法 /
- 光谱法 /
- 文物保护
Abstract: This paper comprehensively discusses all kinds of modern scientific and technological detection methods for paper raw materials, inks, inkpads, and pigments used in ancient paper cultural relics, including imaging and spectrometric technologies. Relevant imaging methods include photography, tomography and microscopic imaging methods. Photographic methods include light transmission, infrared, ultraviolet, X-ray and neutron activation photography to display macroscopic information on a sample’s surface or inside. Tomography methods include X-ray, terahertz, and optical coherence tomographic methods to display layered information beneath the sample’s surface. Microscopic imaging methods include optical, scanning electron, transmission electron and atomic force microscopic imaging methods to display the sample’s microscopic information. Spectroscopy methods with fingerprint characteristics based on the principles of wave-matter interactions include chromatography, mass spectrometry, electron paramagnetic resonance spectroscopy, nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, X-ray fluorescence spectrum, molecular fluorescence spectrum, Raman spectrum, UV-Vis-NIR-MID-THz absorption spectrum and hyperspectral methods. It shows that the comprehensive applications, complementary advantages and mutual confirmations of the above technologies are powerful means to reveal important traits of paper cultural relics, such as one’s manufacturing process, artistic features, preservation history, disease status, authenticity, method of reparation, etc.
- paper cultural relics /
- imaging method /
- wave spectroscopy method /
- optical spectroscopy method /
- cultural relics protection

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图 1 故宫博物院藏《弘历书习字诗卷》的直射光拍摄图（a）和透射光拍摄图（b）^[16]

Figure 1. Photographs of direct light (top) and transmitted light (bottom) of the "Hongli Shu Xizi Poems" in the Palace Museum^[16]

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图 2 《倭寇图卷》局部（左）及其红外线摄影图（右）^[17]

Figure 2. Part of "Wako-zukan " (left) and its infrared photography (right)^[17]

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图 3 张大千《云山高士图》局部正光摄影图（上）和局部紫外线摄影图（下）^[18]

Figure 3. Zhang Daqian's partial orthophotograph of Yunshan Gaoshi Picture (top) and partial ultraviolet photograph (bottom)^[18]

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图 4 《汝南公主墓志铭》中印章局部原图（左）及X射线摄影图（右）^[20]

Figure 4. Partial original picture (left) and X-ray photography (right) of the seal in the epitaph of Princess Runan^[20]

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图 5 荷兰艺术家扬·斯汀的油画“老人歌唱，年轻人歌唱”原图（a）及其中子活化放射自显影图（b）^[21]

Figure 5. Original picture of Dutch artist Jan Sting's oil painting " As the old ones sing, so the young ones pipe" (top) and his neutron activated radiography (bottom)^[21]

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图 6 威尼斯国家历史档案馆折叠多次的单页手稿（a）和1351年装在信封中的遗嘱手稿（b）的X射线CT重建图像^[23]

Figure 6. X-ray CT reconstruction images of the folded single page manuscript (a) and the closed will manuscript dated 1351 (b) from the National Archives of history of Venice^[23]

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图 7 油画原图（a）及其太赫兹层析成像图，深度0−6 mm，间隔0.5 mm （b）^[26]

Figure 7. oil painting (a) and its terahertz tomography, depth 0−6 mm with an interval of 0.5 mm (b)^[26]

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图 8 （a）样品图（油漆层覆盖一个铅笔素描草图）；（b）透射太赫兹像；（c）反射太赫兹像^[27]

Figure 8. (a) Photograph of the sample (paint layers covering a pencil sketch); (b) transmission THz image; (c) reflection THz image.^[27]

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图 9 18世纪板画原图（a）及其沿A线段（b）和B线段（c）的OCT重建图像^[29]

Figure 9. 18th century panel painting (a) and its OCT reconstruction images along line A (b) and B (c)^[29]

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图 10 武英殿版《古文渊鉴》残片的染色显微图^[33]

Figure 10. Stained micrograph of the fragments of Wu Yingdian's "Gu Wenyuan Jian" ^[33]

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图 11 西夏塔龛千佛图唐卡颜料偏光显微图^[35]：（a）边框红；（b）蓝绿；（c）背景红；（d）白色；（e）蓝黑；（f）黑色

Figure 11. Polarized light micrograph for Thousands Buddha Tangka of Xixia Pagoda Niches^[35]: (a) red on border; (b) blue green; (c) red on the background; (d) white; (e) blue black; (f) black

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图 12 扫描电子显微镜图：（a）莫高窟107窟疱疹平面图显微图^[38]；（b） 1588年西班牙书封面显微图^[39]。

Figure 12. Scanning electron microscopy: (a) micrograph of herpes on the 107th hole in Mogao Grottoes^[38]; (b) micrograph of the cover of Spanish books in 1588^[39]

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图 13 手工封皮纸扫描电子显微镜图像

Figure 13. Scanning electron micrograph of manual cover paper

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图 14 法国时期的梵高画：（a） 244/4“三色紫罗兰的篮子”；（b）546/9“高更的肖像”的透射电镜图像^[40]。

Figure 14. Van Gogh's paintings in the French period: (a) 244/4 "Basket of Pansy Violet"; (b) transmission electron micrograph of 546/9 "Portrait of Gauguin"^[40].

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图 15 透射电镜照片（×10万）^[41]：（a）松烟颗粒；（b）油烟颗粒；（c）炭黑颗粒；（d）古墨颗粒

Figure 15. Transmission Electron Microscopy Photo (×100 thousand)^[41]: (a) turpentine soot; (b) oil soot; (c) carbon black; (d) ancient ink.

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图 16 含无涂层锐钛矿的亚麻籽油颜料的原子力显微图：（a）室温干燥14天，暗室储存；（b）室温干燥14天，然后紫外光照^[45]

Figure 16. Atomic force micrograph of linseed oil pigmented with uncoated anatase after (a) drying under ambient conditions for 14 days and dark storage; (b) drying under ambient conditions for 14 days followed by exposure to UV^[45].

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图 17 16和18世纪纸样清洁处理前后的高效液相色谱图^[49]

Figure 17. HPLC chromatograms of papers in the 16th and 18th centuries before and after cleaning^[49]

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图 18 18世纪意大利纸的飞行时间二次离子质谱图^[63]：质量范围（a） 20−80 m/z；（b） 80−160m/z。

Figure 18. Time-of-flight secondary ion mass spectrometry of 18th century Italian paper ^[63]: mass range (a) 20−80 m/z; (b) 80−160 m/z.

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图 19 四种蓝色颜料硫酸蓝、群青蓝、汉蓝和埃及蓝的低频电子顺磁共振波谱^[65]

Figure 19. LFEPR spectra of the four blue pigments blue vitriol, ultramarine blue, Han blue, and Egyptian blue in paint.^[65]

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图 20 1430年意大利米兰古纸的¹H高分辨率魔角旋转NMR波谱^[68]

Figure 20. ¹H high-resolution magic angle rotating NMR spectrum of Milan ancient paper in 1430^[68]

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图 21 18世纪意大利纸X射线光电子能谱图^[63]：（a）古纸A和现代纸F的光电子能谱图；（b）$ \mathrm{C}1\mathrm{s} $的曲线拟合图。

Figure 21. X-ray photoelectron spectroscopy of Italian paper in the 18th century ^[63]: (a) photoelectron spectroscopy of ancient paper A and modern paper F; (b) curve fitting of C1s.

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图 22 潘玉良油画颜料样品的XRD图^[73]

Figure 22. XRD pattern of Pan Yuliang's oil paint samples^[73]

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图 23 法国印象派画家古斯塔夫·卡勒波特的油画局部及其主要化学元素的分布图^[77]

Figure 23. French Impressionist painter Gustave Caillebotte's oil painting parts and its main chemical element maps^[77]

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图 24 （a）不同年龄纸的荧光光谱；（b） 443 nm荧光峰一次导数值与纸样品年龄的关系；（c） 47种纸的主成分分析^[79]

Figure 24. (a) Fluorescence spectra of the paper samples with different ages; (b) the relationship between the first-derivative spectral peak at 443 nm and the years of paper samples; (c) principal component analysis based on the fluorescence spectra of all 47 paper samples.^[79]

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图 25 （a）手工纸显微拉曼光谱；（b）意大利中世纪纸和现代纸的拉曼光谱^[89]；（c）纤维素老化降解动力学模型：C-O-C单键含量随1100 cm⁻¹、1376 cm⁻¹拉曼强度之比和老化时间的变化曲线^[90]

Figure 25. (a) Micro Raman spectroscopy of Chinese handmade paper; (b) comparison between Medieval Paper (Carta de Logu) and Modern paper^[89]; (c) the kinetic model of ageing and degradationprocess of cellulose: COC residual percentage of inter‐monomers bonds as a function of ageing time and I1, 100/I1, 376 intensities ratio^[90]

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图 26 梵高油画“蓝色花瓶里的花”局部的X射线吸收近边结构谱图^[97]。

Figure 26. X-ray absorption near-edge structure spectrum of Van Gogh's oil painting "Flower in blue vase"^[97]

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图 27 印度几种现代纸的紫外-可见光谱图^[99]

Figure 27. UV-Vis spectra of several modern papers in India^[99]

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图 28 毕加索的油画《牡丹》（a）及其假彩色图（b），（c）颜料的可见-近红外光谱图：(1)镉黄和朱红；(2)翡翠绿；(3)钴蓝；(4)“棕色颜料”；(5) 锌白；(6)普鲁士蓝；(7)朱红；(8)黄色（锌）；(9)红色染料^[102]

Figure 28. Picasso's "Peony" oil painting (a) and its false color drawing (b), (c) Visible-near infrared spectrum of pigment: (1) cadmium yellow and vermilion, (2) emerald green, (3) cobalt blue, (4) “brown paint,” (5) zinc white, (6) Prussian blue, (7)vermilion, (8) yellow (zinc), (9) red dye^[102]

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图 29 印泥中几种颜料（a）和粘合剂（b）的太赫兹吸收光谱^[116]

Figure 29. THz absorption spectroscopy of several pigments (a) and binders (b) in inkpad^[116]

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图 30 《崇庆皇太后八旬万寿图》的局部不同波长高光谱成像图^[119]：（a） 453 nm；（b） 980 nm；（c） 1302 nm；（d）前三波长的假彩色合成图；（e）第二主成分图；（f）第三主成分图

Figure 30. The local hyperspectral images of different wavelengths in the picture of “Empress Dowager Chongqing’s 80th Birthday Celebration”^[119]: (a) 453 nm; (b) 980 nm; (c) 1302 nm; (d) false color composite of the first three wavelengths; (e) second principal component diagram; (f) third principal component diagram

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