起甲、脱落、酥粉陶质文物胶料彩绘的回位修复研究
摘要
我国有着悠久的文明史,早在新石器时代就出现了彩绘,这些文物彩绘蕴含着人类发展各个时期的科技、文化、风俗、宗教信仰等丰富信息,因而成为古代文明的重要组成部分,对研究古代历史、文化、艺术具有重要价值。但是数千年来,随着环境的变迁,这些文物彩绘发生了多种病害,如风化褪色、起甲脱落、酥粉、滋生霉菌、粘结土锈等,给其艺术、考古价值带来不可估量的损失,文物彩绘及金箔起甲、脱落、酥粉是其中最为严重的病害之一,急待科学保护。目前,国内针对该方面的研究比较零散,主要集中在起甲壁画的修复,生漆彩绘的保护,而对已经起甲、脱落的陶质文物胶料彩绘及金箔的修复还没有系统的研究,且对修复材料没有统一的系统评价体系。本文以起甲、脱落、酥粉的陶质文物胶料彩绘及石刻文物上的金箔作为主要研究对象,建立修复材料性能评价体系,进行修复研究,主要包括以下内容：
第一章介绍了我国古代文物彩绘发生的主要病害,包括风化褪色、粘结土锈、滋生霉菌、起甲脱落等,其中发生起甲、脱落、酥粉文物彩绘类型,包括壁画起甲、生漆彩绘起甲脱落、胶料彩绘起甲脱落、彩绘酥粉、金箔起甲脱落。综述了文物彩绘的相关物质组成及分析方法。分析了温度、湿度、光照、有害气体及可溶性盐等对文物彩绘的危害。综述了国内对起甲、脱落、酥粉病害的研究进展。
第二章针对起甲、脱落、酥粉文物彩绘病害的本质是彩绘层与基体之间失去了附着力,提出了本文的研究思路：即增加彩绘层与基体之间的附着力,同时增加彩绘层的柔韧性,不改变文物的原有颜色,并能耐久保持。在此基础上提出了本文的研究方法,包括修复材料的筛选和应用两部分。
第三章针对发生起甲、脱落、酥粉彩绘的特点,建立了修复材料性能系统评价体系,该体系包括附着力测试、柔韧性测试、色差测试及加速老化测试。针对文物胶结材料分析常用的色谱及色谱与其他技术联用方法对鉴定文物胶料种类存在的不足,提出了用元素分析和X光电子能谱对胶结材料种类进行简便、快速的分析。
第四章对西汉彩绘兵马俑起甲、脱落、酥粉彩绘进行了回位修复研究。通过扫描电镜能谱、激光拉曼光谱、X射线衍射相结合,分析了咸阳博物馆西汉彩绘兵马俑的红色、白色、绿色及黑色颜料的主要成分,结果表明其成分分别为为朱砂、粘土、石绿和碳黑。同时采用光电子能谱、元素分析方法分析了其所用胶料,结果表明其中含有氮元素,推测其为动物胶。
通过对ZB-F600水性氟、水溶性环氧树脂B-63、聚乙烯醇、聚醋酸乙烯、Paraloid B72与颜料混合后制成样品的附着力与柔韧性进行测试,筛选了ZB-F600水性氟与水溶性环氧树脂B-63作为起甲、脱落陶质文物胶料彩绘的回贴修复剂。对ZB-F600水性氟与水溶性环氧树脂B-63以不同配比浓度组成的回贴修复剂与颜料混合后制成的样品,进行柔韧性与色差测试,结果表明,ZB-F600水性氟与水溶性环氧树脂B-63、水最佳的质量百分比为25：3：72。对该修复剂与颜料制成的样品进行紫外老化、湿热老化、臭氧老化,测试样品老化前后柔韧性、附着力、色差,结果表明其上述各项性能均保持较好,耐久性稳定,可以作为起甲、脱落陶质文物胶料彩绘的同贴修复剂。
对水性氟、聚醋酸乙烯、骨胶三种材料与颜料混合制成的样品,进行紫外、湿热、干热老化,结果表明以水性氟制备的颜料样品的附着力老化前后都保持较好,耐久性能优异,可作为酥粉彩绘的修复剂。同时,通过对不同浓度水性氟制备的朱砂、石绿颜料的附着力、柔韧性及色差进行测试,表明,质量浓度为0.4%-1%的修复剂既能使颜料保持较好的附着力和柔韧性,又对文物的颜色改变较小。
采用上述筛选的修复剂分别对起甲、脱落、酥粉的西汉彩绘兵马进行了小面积修复,效果显著。
第五章针对西安某公司收藏的北魏时期贴金石质文物上金箔大面积起甲、脱落的现状,分析了其上金箔的成分,金的含量在56.6%。将金箔分别用5%质量浓度的聚醋酸乙烯水溶液、聚乙烯醇水溶液、ZB-F600水性氟水溶液、Paraloid B72丙酮溶液贴在平整的汉白玉与柔韧性试板上,分别在紫外、湿热、臭氧条件下老化30天,测试样品老化前后的柔韧性、附着力,结果表明,ZB-F600水性氟回贴的金箔样品在这几种材料中柔韧性、附着力最好,耐久性也最强,选择其做为起甲、脱落金箔的回贴修复剂。通过对以不同浓度水性氟回贴金箔样品的附着力、柔韧性、色差进行了测试,表明3%-8%的水性氟柔韧性、附着力居中,色差变化较小,可应用于起甲、脱落金箔的回贴修复剂。在石质贴金佛像上应用,完整再现了其原有的风貌。
综上所述,本文建立了起甲、脱落、酥粉文物彩绘修复材料性能评价体系,利用该体系筛选了以水性氟为主的修复材料,能增加颜料与基体之间的附着力、增加颜料层的柔韧性,并能耐久保持,利用筛选的修复材料分别对起甲、脱落、酥粉的西汉彩绘兵马俑及西安某公司收藏的贴金彩绘上起甲金箔进行了回花修复,效果显著。
China has a long history of civilization. At the early period of Neolithic age, colored drawing has appeared which contains culture, customs, religion belief and other rich information of all periods of human development in science and technology. Thus, it has become an important part of the ancient civilization, and is importance for studing ancient history, culture and art. However, due to the complexity of environmental changes through thousands of years, these colored drawing suffered a variety of diseases such as fading, flaking, chalking and contaminated, which lead to the immeasurable losses to archaeological research. So it needs scientific conservation urgently. At present, the research on these aspects is comparative few, and mainly concentrated on the restoration of murals cracking and abscission. System research on the restoration of colored drawing having be cracking and chalking has not been carried out. This paper focused on the restoration of flaking and chalking colored drawing on pottery and gold foil on stone relics.
In Chapter1, the main disease of Chinese ancient colored drawing were introduced firstly, which includes fading, flaking, chalking and contaminated. The composition of colored drawing and the analytical technique were reviewed. The main factors, such as temperature, humidity, hamful gas and soluble salts which caused the colored drawing deteriorated were parsed. The types of flaked colored drawing, including mural, lacquer-painting, glue-painting and goil, waere introduced. At last, current research on restoring flaking and chalking colored drawing was reviewed.
In Chapter2, the research idea of this paper was put forward according to the nature of flaking and chalking colored drawing:losing adhesion. The methods to research the restoration material of this paper were introuduced, including material chosing and applying.
In chapter3, the system to estimate the properties of restoration material was established, including adhension test, flexbility test, chromatic aberration test and durability test. The method to identify the kind of binding material in colored drawing easily and fastly was put forward.
In chapter4, the restoration of flacking colored drawing of Western Han Dynasty terra-cotta warriors was researched. First, scanning electron microscopy-energy spectroscopy, X-ray diffraction and Raman spectroscopy were applied to analysis the pigments of red, white, green and black color. The results show that the compositions of them are respectively cinnabar, white clay, mineral green and carbon black. At the same time, photoelectron spectroscopy (XPS) and elemental analysis were applied to analysis the binding material of the Western Han Dynasty terra-cotta warriors. The results show that it contains nitrogen element. So the binding material is animal glue.
By testing adhesion and flexibility of samples prepared with ZB-F600water soluble fluoride, water-soluble epoxy resin B-63, polyvinyl alcohol, polyvinyl acetate, Paraloid B72respectively, the results show that the adhesion and flexibility of samples prepared with ZB-F600water soluble fluoride and water-soluble epoxy resin B-63were better in above materials, so the two materials was chosed as sticking material to restore flaking colored drawing. The adhesion and flexibility of samples prepared with different composition ratio of the two materials were tested. It was found that, when the mass ration of ZB-F600water soluble fluoride, water-soluble epoxy resin B-63, and water is25:3:72, the samples' adhesion and flexibility were best. After UV aging, heat aging and ozone aging, the samples' flexibility, adhesion and chromatic aberration prepared with the best ratio of above were tested, the results show that the performance of sticking material is durability and stability, it fits to stick the flaked colored drawing. The two materials mixed with the best ratio were applied to restore flaked Western Han Dynasty terra-cotta warriors collected in Xianyang Museum.
The samples were made by ZB-F600water soluble fluorides, polyvinyl acetate, glue mixed with cinnabar, mineral green respectively. UV light, high heat, high humidity were applied to age the samples. Afer aging, the samples' adhension was tested. The results show that the samples prepared with ZB-F600water soluble fluoride have better adhesion than those prepared with polyvinyl acetate and bone glue, In order to reinforce chalking painting, without changing the original color, the concentration of the strengthening agent was selected. The results show that0.4%-3%of water soluble fluoride can be used to restore chalking pigment.
Chapter5is the research on the restoration of flaking gold foil on stone relics collected in a company of Xi'an. Through analysis of components in the gold foil of Buddha statue in the Northern Wei Dynasty, the mass concentration of gold is56.6%, and the thickness is about0.015-0.02mm.5%ZB-F600water soluble fluoride solution, polyvinyl acetate aqueous solution, polyvinyl alcohol aqueous solution, and Paraloid B72acetone solution were used to stick gold foil to the white marble and test plates. After UV, heat and ozone aging for30days repectively, the samples' flexibility and adhesion before and after the aging were tested, the results show that the samples prepared with water soluble fluoride had better adhesion stress and flexibility, and its durability was also the best. Thus, water soluble fluoride was chosen to restore flaked gold foil. The best mass concentration is3%-8%.5%ZB-F600water soluble fluoride was applied to restore the flaked gold foil of stony colored Buddha statue.
In summary, the system to estimate the properties of materials to restore flaking and chalking colored drawing was established. According to the system, water soluble fluoride was chosed as the main restoration material. Through application in flaking and chalking colored drawing, the results are highly visible.
第一章介绍了我国古代文物彩绘发生的主要病害,包括风化褪色、粘结土锈、滋生霉菌、起甲脱落等,其中发生起甲、脱落、酥粉文物彩绘类型,包括壁画起甲、生漆彩绘起甲脱落、胶料彩绘起甲脱落、彩绘酥粉、金箔起甲脱落。综述了文物彩绘的相关物质组成及分析方法。分析了温度、湿度、光照、有害气体及可溶性盐等对文物彩绘的危害。综述了国内对起甲、脱落、酥粉病害的研究进展。
第二章针对起甲、脱落、酥粉文物彩绘病害的本质是彩绘层与基体之间失去了附着力,提出了本文的研究思路：即增加彩绘层与基体之间的附着力,同时增加彩绘层的柔韧性,不改变文物的原有颜色,并能耐久保持。在此基础上提出了本文的研究方法,包括修复材料的筛选和应用两部分。
第三章针对发生起甲、脱落、酥粉彩绘的特点,建立了修复材料性能系统评价体系,该体系包括附着力测试、柔韧性测试、色差测试及加速老化测试。针对文物胶结材料分析常用的色谱及色谱与其他技术联用方法对鉴定文物胶料种类存在的不足,提出了用元素分析和X光电子能谱对胶结材料种类进行简便、快速的分析。
第四章对西汉彩绘兵马俑起甲、脱落、酥粉彩绘进行了回位修复研究。通过扫描电镜能谱、激光拉曼光谱、X射线衍射相结合,分析了咸阳博物馆西汉彩绘兵马俑的红色、白色、绿色及黑色颜料的主要成分,结果表明其成分分别为为朱砂、粘土、石绿和碳黑。同时采用光电子能谱、元素分析方法分析了其所用胶料,结果表明其中含有氮元素,推测其为动物胶。
通过对ZB-F600水性氟、水溶性环氧树脂B-63、聚乙烯醇、聚醋酸乙烯、Paraloid B72与颜料混合后制成样品的附着力与柔韧性进行测试,筛选了ZB-F600水性氟与水溶性环氧树脂B-63作为起甲、脱落陶质文物胶料彩绘的回贴修复剂。对ZB-F600水性氟与水溶性环氧树脂B-63以不同配比浓度组成的回贴修复剂与颜料混合后制成的样品,进行柔韧性与色差测试,结果表明,ZB-F600水性氟与水溶性环氧树脂B-63、水最佳的质量百分比为25：3：72。对该修复剂与颜料制成的样品进行紫外老化、湿热老化、臭氧老化,测试样品老化前后柔韧性、附着力、色差,结果表明其上述各项性能均保持较好,耐久性稳定,可以作为起甲、脱落陶质文物胶料彩绘的同贴修复剂。
对水性氟、聚醋酸乙烯、骨胶三种材料与颜料混合制成的样品,进行紫外、湿热、干热老化,结果表明以水性氟制备的颜料样品的附着力老化前后都保持较好,耐久性能优异,可作为酥粉彩绘的修复剂。同时,通过对不同浓度水性氟制备的朱砂、石绿颜料的附着力、柔韧性及色差进行测试,表明,质量浓度为0.4%-1%的修复剂既能使颜料保持较好的附着力和柔韧性,又对文物的颜色改变较小。
采用上述筛选的修复剂分别对起甲、脱落、酥粉的西汉彩绘兵马进行了小面积修复,效果显著。
第五章针对西安某公司收藏的北魏时期贴金石质文物上金箔大面积起甲、脱落的现状,分析了其上金箔的成分,金的含量在56.6%。将金箔分别用5%质量浓度的聚醋酸乙烯水溶液、聚乙烯醇水溶液、ZB-F600水性氟水溶液、Paraloid B72丙酮溶液贴在平整的汉白玉与柔韧性试板上,分别在紫外、湿热、臭氧条件下老化30天,测试样品老化前后的柔韧性、附着力,结果表明,ZB-F600水性氟回贴的金箔样品在这几种材料中柔韧性、附着力最好,耐久性也最强,选择其做为起甲、脱落金箔的回贴修复剂。通过对以不同浓度水性氟回贴金箔样品的附着力、柔韧性、色差进行了测试,表明3%-8%的水性氟柔韧性、附着力居中,色差变化较小,可应用于起甲、脱落金箔的回贴修复剂。在石质贴金佛像上应用,完整再现了其原有的风貌。
综上所述,本文建立了起甲、脱落、酥粉文物彩绘修复材料性能评价体系,利用该体系筛选了以水性氟为主的修复材料,能增加颜料与基体之间的附着力、增加颜料层的柔韧性,并能耐久保持,利用筛选的修复材料分别对起甲、脱落、酥粉的西汉彩绘兵马俑及西安某公司收藏的贴金彩绘上起甲金箔进行了回花修复,效果显著。
China has a long history of civilization. At the early period of Neolithic age, colored drawing has appeared which contains culture, customs, religion belief and other rich information of all periods of human development in science and technology. Thus, it has become an important part of the ancient civilization, and is importance for studing ancient history, culture and art. However, due to the complexity of environmental changes through thousands of years, these colored drawing suffered a variety of diseases such as fading, flaking, chalking and contaminated, which lead to the immeasurable losses to archaeological research. So it needs scientific conservation urgently. At present, the research on these aspects is comparative few, and mainly concentrated on the restoration of murals cracking and abscission. System research on the restoration of colored drawing having be cracking and chalking has not been carried out. This paper focused on the restoration of flaking and chalking colored drawing on pottery and gold foil on stone relics.
In Chapter1, the main disease of Chinese ancient colored drawing were introduced firstly, which includes fading, flaking, chalking and contaminated. The composition of colored drawing and the analytical technique were reviewed. The main factors, such as temperature, humidity, hamful gas and soluble salts which caused the colored drawing deteriorated were parsed. The types of flaked colored drawing, including mural, lacquer-painting, glue-painting and goil, waere introduced. At last, current research on restoring flaking and chalking colored drawing was reviewed.
In Chapter2, the research idea of this paper was put forward according to the nature of flaking and chalking colored drawing:losing adhesion. The methods to research the restoration material of this paper were introuduced, including material chosing and applying.
In chapter3, the system to estimate the properties of restoration material was established, including adhension test, flexbility test, chromatic aberration test and durability test. The method to identify the kind of binding material in colored drawing easily and fastly was put forward.
In chapter4, the restoration of flacking colored drawing of Western Han Dynasty terra-cotta warriors was researched. First, scanning electron microscopy-energy spectroscopy, X-ray diffraction and Raman spectroscopy were applied to analysis the pigments of red, white, green and black color. The results show that the compositions of them are respectively cinnabar, white clay, mineral green and carbon black. At the same time, photoelectron spectroscopy (XPS) and elemental analysis were applied to analysis the binding material of the Western Han Dynasty terra-cotta warriors. The results show that it contains nitrogen element. So the binding material is animal glue.
By testing adhesion and flexibility of samples prepared with ZB-F600water soluble fluoride, water-soluble epoxy resin B-63, polyvinyl alcohol, polyvinyl acetate, Paraloid B72respectively, the results show that the adhesion and flexibility of samples prepared with ZB-F600water soluble fluoride and water-soluble epoxy resin B-63were better in above materials, so the two materials was chosed as sticking material to restore flaking colored drawing. The adhesion and flexibility of samples prepared with different composition ratio of the two materials were tested. It was found that, when the mass ration of ZB-F600water soluble fluoride, water-soluble epoxy resin B-63, and water is25:3:72, the samples' adhesion and flexibility were best. After UV aging, heat aging and ozone aging, the samples' flexibility, adhesion and chromatic aberration prepared with the best ratio of above were tested, the results show that the performance of sticking material is durability and stability, it fits to stick the flaked colored drawing. The two materials mixed with the best ratio were applied to restore flaked Western Han Dynasty terra-cotta warriors collected in Xianyang Museum.
The samples were made by ZB-F600water soluble fluorides, polyvinyl acetate, glue mixed with cinnabar, mineral green respectively. UV light, high heat, high humidity were applied to age the samples. Afer aging, the samples' adhension was tested. The results show that the samples prepared with ZB-F600water soluble fluoride have better adhesion than those prepared with polyvinyl acetate and bone glue, In order to reinforce chalking painting, without changing the original color, the concentration of the strengthening agent was selected. The results show that0.4%-3%of water soluble fluoride can be used to restore chalking pigment.
Chapter5is the research on the restoration of flaking gold foil on stone relics collected in a company of Xi'an. Through analysis of components in the gold foil of Buddha statue in the Northern Wei Dynasty, the mass concentration of gold is56.6%, and the thickness is about0.015-0.02mm.5%ZB-F600water soluble fluoride solution, polyvinyl acetate aqueous solution, polyvinyl alcohol aqueous solution, and Paraloid B72acetone solution were used to stick gold foil to the white marble and test plates. After UV, heat and ozone aging for30days repectively, the samples' flexibility and adhesion before and after the aging were tested, the results show that the samples prepared with water soluble fluoride had better adhesion stress and flexibility, and its durability was also the best. Thus, water soluble fluoride was chosen to restore flaked gold foil. The best mass concentration is3%-8%.5%ZB-F600water soluble fluoride was applied to restore the flaked gold foil of stony colored Buddha statue.
In summary, the system to estimate the properties of materials to restore flaking and chalking colored drawing was established. According to the system, water soluble fluoride was chosed as the main restoration material. Through application in flaking and chalking colored drawing, the results are highly visible.
引文
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