彩绘文物颜料无损分析鉴定和保护材料研究

发布时间：2018-06-26 11:34

本文选题：光导纤维反射光谱法 + 彩绘文物　；参考：《西北工业大学》2006年博士论文

【摘要】： 彩绘类文物研究与保护的重要工作是颜料成分鉴定和表面加固保护。由于文物具有不可再生的特性，决定了理想的文物分析技术应当是无损的。目前常用的XRD、XRF等分析方法通常需要从文物上刮取粉末或制成合适规格的样品进行测试，会对文物产生破坏。国外有人采用价格昂贵的光导纤维反射光谱仪对颜料成分作鉴定，，但在我国大多博物馆和文博单位这种昂贵的仪器是很难推广使用。彩绘文物保护的另一个亟待解决的难题是彩绘颜料表面的封护、加固保护问题。虽然，越来越多的有机高分子材料被“移殖”于文物保护领域，但对材料的稳定性缺乏系统、科学、全面的研究，选择材料具有很大的盲目性和片面性。根据文物保护的特殊要求，针对我国文物保护的具体现状和急需解决的难题，我们首次对国产仪器改装，研制出了一种价格低廉、性能优良的光导纤维反射光谱仪，并成功地分析鉴定了重庆大足石刻区、汉阳陵博物馆等处彩绘文物上的颜料成分。对常用彩绘类文物保护材料的稳定性进行了系统研究，通过加入紫外线吸收剂、由物理共混的方式提高了有机高分子文物保护材料的耐光老化性能。本论文的主要研究内容如下：研制出了一种简易光导纤维反射光谱仪。该仪器是在对国产72G型分光光度计改装基础上研制而成的，仪器由钨灯、单色器、双臂光纤、暗盒、光电倍增管检测器、读数装置、高压电源等部分组成。改装仪器的核心是采用玻璃双臂光纤传输光线，利用检测反射光谱信号实现对样品的无损测量。以高灵敏度的光电倍增管替代光电管作为检测器，这样对微弱的反射光信号能够实施有效的检测。设计防光性好的金属暗室来消除外界的干扰，提高了测量的准确性。同时，采用Perkin-Elmer Lambda 17紫外-可见分光光度计进行了对比分析，表明所研制的光导纤维反射光谱仪性能稳定，完全能够用于文物颜料的鉴定。通过对大量中国古代彩绘颜料的分析，归纳出颜料反射光谱曲线的三种类型：“钟”形、“S”形、和“斜线”形，总结出每种颜料反射光谱曲线的特征。研究了影响颜料反射光谱的因素，包括颜料饱和度、颜料粒度、颜料中的粘接剂、颜料底层材料、颜料表面保护材料等。建立了光导纤维反射光谱分析彩绘颜料的基本方法，即通过比较文物颜料样品和标准颜料的反射光谱曲线的形状、特征反射峰或一阶导数峰，实现对彩绘文物颜料的鉴定。采用自行研制的仪器对重庆大足千手观音、西汉彩俑、西安市长安县墓葬壁画等文物颜料进行了无损鉴定。通过用XRF、XRD方法进行验证，表明光导纤维反射光谱仪用于颜料分析鉴定结果是准确、可靠的。通过表征光老化过程中实验材料的反射光谱、红外光谱、显微分析、接触角、硬度等各项性能，系统地探讨了4类8种常用文物保护材料在老化降解中所产生的颜色、分子结构、表面形态、亲水性能、物理强度的变化，对这些材料的耐光老化性能进行了全面评估，并推导出降解机理。这4类8种材料分别是：①聚氨酯类：包括TDI型聚氨酯、MDI型聚氨酯、HDI型聚氨酯；②丙烯酸树脂：包括丙烯酸清漆、Primal AC 33、B72；③有机硅；④环氧树脂。实验所选择的人工加速老化光源是UVB紫外灯。实验结果表明，在所考察4类材料中，丙烯酸树脂较其它3类材料具有更优异的耐光老化性能，特别是Primal AC 33和B72，作为最佳的文物保护和修复材料值得大力推广、普遍使用。首次将UV-326、UV-327、UV-328、UV-531和UV-P紫外线吸收剂用于B72、MDI型聚氨酯和环氧树脂的改性研究，通过物理共混将紫外线吸收剂引入树脂体系，以提高现有文物保护材料的耐光老化性能。实验表明，这些紫外线吸收剂性能稳定，70h紫外光辐照后的损失不超过1.0％。通过对常用文保材料添加紫外线吸收剂改性，光老化后其颜色、红外光谱、硬度、失重、可逆性都有所改善，紫外线吸收剂的最佳浓度为0.5％～3％。综合多项考察指标，选择出3体系的最佳改性方案分别是3％UV327改性B72体系、0.25％UV327+0.25％UV531改性MDI型聚氨酯体系或0.25％UV328+0.25％UV531改性MDI型聚氨酯体系、3％UV328改性环氧树脂体系。
[Abstract]:The important work of research and protection of coloured cultural relics is pigment composition identification and surface strengthening protection.
Because of the non renewable characteristics of the cultural relics, the ideal analysis technology of cultural relics should be nondestructive. The commonly used methods such as XRD, XRF and other analytical methods usually need to scrape powder from cultural relics or make samples of suitable specifications for testing and destroy the cultural relics. Pigment composition is identified, but expensive instruments are widely used in most museums and cultural institutions in China.
Another difficult problem to be solved for the protection of painted relics is the sealing and protection of painted paint surface. Although more and more organic polymer materials are "migrate" to the field of cultural relic protection, the stability of the materials is lack of systematic, scientific and comprehensive research, and the selection of materials has great blindness and one-sided nature.
According to the special requirements of cultural relic protection, in view of the specific status of cultural relic protection in China and the difficult problems to be solved urgently, we have reformed domestic instruments for the first time, and developed a kind of light guided fiber reflection spectrometer with low price and excellent performance, and successfully analyzed and identified the painted relics in Chongqing Dazu stone carving area and Hanyang Tombs Museum. Pigment composition. The stability of the commonly used color painting relics protection materials is systematically studied. By adding ultraviolet absorbents, the light aging resistance of organic polymer protection materials is improved by physical blending. The main contents of this paper are as follows:
A simple light guided fiber reflection spectrometer is developed. The instrument is made up of a domestic 72G spectrophotometer. The instrument consists of a tungsten lamp, a monochromator, a double arm fiber, a dark box, a photomultiplier detector, a reading device and a high voltage power source. The core of the reloaded instrument is the use of glass double arm fiber transmission light. Line, using the detection of the reflection spectrum signal to realize the nondestructive measurement of the sample. The high sensitivity photomultiplier tube instead of the photoelectric tube is used as the detector, so the weak reflective light signal can be effectively detected. The design of a good anti light metal dark room to eliminate the external interference and improve the accuracy of the measurement. At the same time, the Perkin-Elm is used. The ER Lambda 17 UV VIS spectrophotometer has been compared and analyzed. It shows that the developed optical fiber reflective spectrometer has a stable performance and can be used for the identification of cultural relics.
Through the analysis of a large number of Chinese ancient painted pigments, three types of pigment reflection spectral curves were summed up: "clock", "S", and "oblique line", and summed up the characteristics of the reflectance spectra of each pigment. The factors affecting the pigment reflectance spectrum were studied, including pigment saturation, pigment granularity, pigment in the pigment, pigment. Basic materials, pigment surface protection materials, etc., a basic method for the analysis of painted pigments by optical fiber reflectance spectroscopy is established, that is, by comparing the shape of the reflectance spectra of the samples of cultural relics and standard pigments, the characteristics of the reflection peaks or the first derivative peaks, which can be used to identify the pigment of the painted relics.
Chongqing Dazu thousand hand Guanyin, the Western Han Dynasty figurines and the murals of the tombs in Changan County, Xi'an, were identified by self developed instruments. The results were verified by XRF and XRD. The results showed that the optical fiber reflection spectrometer was accurate and reliable for the analysis and identification of pigment.
By characterizing the properties of the reflective spectra, infrared spectra, microanalysis, contact angle and hardness of the experimental materials during the photoaging process, the color, molecular structure, surface morphology, hydrophilic energy, physical strength and light aging resistance of the 4 kinds of 8 kinds of common cultural relics protection materials were systematically investigated. The 4 kinds of 8 kinds of materials are: (1) polyurethane: TDI polyurethane, MDI type polyurethane, HDI type polyurethane; (2) acrylic resin, including acrylic varnish, Primal AC 33, B72; (3) organosilicon; (4) epoxy resin. The artificial accelerated aging light selected by the experiment is UVB violet The experimental results show that in the 4 kinds of materials, the acrylic resin has better light aging resistance than the other 3 kinds of materials, especially Primal AC 33 and B72. As the best material for cultural relic protection and repair, it is worth popularizing and widely used.
The UV Absorbents of UV-326, UV-327, UV-328, UV-531 and UV-P were used for the first time in the modification of B72, MDI polyurethane and epoxy resin. The UV Absorbents were introduced into the resin system by physical blending to improve the light aging properties of the existing cultural relics protection materials. The experiments showed that the UV Absorbents were stable and UV irradiated by 70h. The subsequent loss does not exceed 1.0%. by adding UV Absorbents to commonly used cultural materials. After light aging, the color, infrared spectrum, hardness, weight loss and reversibility have improved. The optimum concentration of ultraviolet absorbents is 0.5% to 3%., and the best modification scheme of the 3 system is 3%UV327 modified B72, respectively. System, 0.25%UV327+0.25%UV531 modified MDI polyurethane system or 0.25%UV328+0.25%UV531 modified MDI polyurethane system, 3%UV328 modified epoxy resin system.
【学位授予单位】：西北工业大学
【学位级别】：博士
【学位授予年份】：2006
【分类号】：G264

【引证文献】