山东聊城山陕会馆彩画红色颜料分析

山东聊城山陕会馆始建于乾隆八年，历经多次扩建与重修，布局紧凑，装饰华美，是我国古代会馆里保存较好的精品。会馆兼具神庙与商业会馆功能，是古运河商业繁荣的见证，具有较高的艺术和文化价值。目前对于聊城山陕会馆的科学研究聚焦于其建筑形制、装饰艺术美学等，尚未开展对其建筑彩画的制作工艺及材料的科学分析。本研究利用显微观察、扫描电子显微镜-能谱分析、激光拉曼光谱分析和红外光谱分析，对取自聊城山陕会馆的27个建筑彩画的红色颜料进行分析鉴定。结果表明，使用的彩画红色颜料有铁红、朱砂、铅丹和茜草染料。制作工艺方面，发现普遍性的重层彩画，既有重做地仗以后涂刷新颜料的技法，也有“章丹打底朱砂盖面”这种直接绘制两层颜料的古代建筑彩画中的常用工艺，这与聊城山陕会馆历经多次修缮的史实相符。此外，还发现在红色颜料中加入钙、钡的硫酸盐作为红色颜料改性剂的工艺。研究中首次发现将茜草染料用作建筑彩画颜料，是对清代使用有机染料制作建筑彩画文献记载的有力佐证。此前对于古代文物中茜草染料的分析鉴定研究，主要集中于考古纺织品文物上，多使用质谱技术，对设备和样品前处理要求高。研究中利用显微激光拉曼光谱仪对古建筑彩画上的茜草染料进行...     

故宫奉先殿清初彩画颜料成分分析

故宫奉先殿是明清两代皇帝祭祀祖先的家庙,地位仅次于太庙。奉先殿始建于明成祖时期,现存建筑主要建于康熙时期,其上保留了为数不多的清初彩画,是研究清初彩画的珍贵实物。利用显微观察、扫描电子显微镜能谱和激光拉曼光谱分析,对取自奉先殿的彩画颜料进行分析鉴定。结果表明,奉先殿彩画中部分红色和蓝色颜料层存在分层现象,表层颜色鲜艳明亮,中层和下层颜色偏浅,每层所用颜料配方不同。红色颜料有朱砂、铅丹和铁红,绿色颜料均为氯铜矿,蓝色颜料均为石青,用铅白打底。浅色颜料由主显色矿物颜料加入以铅白为主的白色颜料混合调制而成。其中浅红色由铅丹与铅白调和而成,浅绿色由氯铜矿与铅白调和而成。浅蓝色颜料中未发现铅白,但含有大量Al元素和Si元素,推测含有高岭土。浅蓝色颜料有可能是由石青与高岭土调制而成。奉先殿彩画中未发现清晚彩画常用的合成群青、巴黎绿等颜料,反映出奉先殿彩画的绘制年代很有可能就是档案记载的康熙年间,之后未有大修。高岭土作为白色颜料调配浅色颜料在彩画制作中比较少见,奉先殿彩画中高岭土的发现丰富了清代早期彩画颜料制作的资料,具有一定的学术意义。     

北京先农坛建筑彩画颜料的光谱学研究

北京先农坛是明清时期皇家祭祀建筑的重要历史遗迹,是中华民族传统重农思想的传播载体,见证着中华文化源远流长。在自然和人为因素的长期影响下,先农坛建筑彩画出现了烟熏、剥落等多种病害,亟待保护。为了获取先农坛建筑彩画中的物质成分信息以支撑彩画的保护修复工作,应用便携式拉曼光谱仪、便携式X射线荧光(XRF)对先农坛具服殿中三幅具有代表性的建筑彩画进行无损分析,结合显微拉曼光谱、扫描电镜-能谱(SEM-EDS)、 X射线衍射(XRD)等方法对残片的分析,成功获得了绘制彩画所用颜料的主要成分。结果表明,三幅彩画的打底材料均含有碳酸钙,金龙图案表面有金箔留存。此外,在原始彩画中使用了朱砂、铅丹、铅白、氯铜矿和靛蓝等颜料;修复彩画中除上述朱砂、铅丹、铅白外,在金龙图案区域检测到了铅丹和雌黄的混用,且所用蓝色和绿色颜料分别为群青和巴黎绿,这与原始彩画中所使用的颜料不同;在重绘彩画中鉴别出多种近代合成颜料,如钛白、铬黄、苏丹红Ⅰ、酞菁绿、群青、亮红色β-萘酚等。根据颜料的使用情况结合史料记载,确定了三幅彩画的绘制时期分别为1754年、 1860年以及1997年左右。由于缺乏对原始彩画中所用颜料的了解,导致...     

壁画制作工艺和材料光谱分析——以北京延庆花盆关帝庙壁画为例

光谱学是利用光与物质的相互作用,展示物质微观结构,提供不同化学分析方式,从而实现对物质的定量和定性分析。壁画制作工艺分析中运用了大量的光谱分析技术,该研究以北京延庆花盆关帝庙为例,通过光谱及其他技术分析壁画的制作材料和工艺。花盆关帝庙位于北京延庆区花盆村,始建于清雍正四年(1726年),是当时祭祀的重要场所,也是延庆地区关帝庙的典型代表之一。运用X射线衍射、拉曼光谱和激光粒度分析仪等一系列光谱技术发现关帝庙壁画的地仗层成分为石英、方解石和钠长石,白粉层成分为石膏,颜料层中红色颜料为铁红、铅丹和朱砂,蓝色颜色为蓝铜矿,黄色颜色为铬黄,黑色颜色为炭黑,白色颜料为石膏,绿色颜色为巴黎绿、绿土和铬绿。沥粉贴金工艺的胶结物为熟桐油和松香树脂,金箔采用含金量86.1%的赤金。拉曼光谱不仅可以辨析壁画颜料,还能通过颜料历史研究佐证和丰富壁画修复历史信息。结合文物光谱分析数据与文献资料,充分挖掘文物背后的信息,对研究和保护古代壁画有着重要意义。通过花盆关帝庙壁画同面墙不同位置的壁画地仗层制作工艺的差异,说明壁画制作材料和工艺受位置影响。期待日后研究者通过研究壁画制作材料和工艺差异,发现符合规制的典型壁...     

青海热贡地区传统建筑彩画颜料光谱特征分析研究

青海省热贡地区是安多藏区藏式建筑彩画艺术的重要产地,作为热贡艺术的重要组成部分影响甚广。热贡地方建筑彩画不仅是附着建筑栋梁之上的艺术瑰宝,更是一项延续至今的传统技艺,至今仍有大批传统匠人画师从事相关行业。热贡地方建筑彩画有独立的用色方法和颜料制作工艺,对其所用传统颜料进行科学检测是系统研究该地区建筑彩画的基础性工作,在进一步研究热贡地区建筑彩画的制作工艺和艺术特色,传承地方建筑彩画技艺和完善保护政策等方面具有积极意义。通过对同仁市隆务寺夏日仓行宫火供殿所用当地传统建筑彩画颜料的采样,运用X射线荧光光谱、X射线衍射分析、激光显微拉曼光谱分析等多种实验分析方法,对颜料样品进行分析,测定其主要显色物质和成分占比。结果表明,热贡地方建筑彩画所用颜料多为无机颜料;蓝色颜料主要是人造群青;绿色颜料的主要矿物组成为绿土,显色物质为蒙脱石,存在将植物色染料加入当地所产的富镁蒙脱石中混合使用的可能性;红色颜料的主要矿物组成为铁红（赭石类红土）,通过焙烧富铁矿土来人工合成,材料来自于当地吾屯村所产红色赭石类粘土;黄色颜料主要矿物组成为密陀僧、硫磺及其他植物色染料制备而成;黑色颜料为碳黑,符合木炭黑的性状特征;白色颜料主要为生石灰及氧化镁粉,并在其他颜料中广泛使用石灰及氧化镁粉作为调色颜料;推测部分样品中含有包金土及植物色素染料、其他人工合成颜料的可能性。整体来看,热贡地区建筑彩画所用颜料成本价格较低,制取难度不大,来源大多是当地常见的矿土料和动植物染料,传统的制料工艺较简单,颜料多呈现为组分复杂的混合物状态;密陀僧、包金土和群青等颜料多来自于内地及国外,颜料人工合成的历史较早,反映出热贡地区建筑彩画在颜料使用上不仅使用本土材料制备,也广泛使用外来颜料的历史传统,为进一步研究热贡地区建筑彩画领域内汉、藏等多民族文化交往、交流、交融历史提供了良好实证材料。     

西藏扎什伦布寺壁画的科学研究

壁画是寺院建筑的重要装饰元素,也是藏传佛教艺术的重要组成部分。扎什伦布寺始建于明正统12年（公元1447年）,作为后藏最大的寺院,寺内保存了大量精美壁画,这些壁画对研究藏传佛教及佛教艺术具有重要意义。扎什伦布寺自建寺起一直为传播佛教文化服务,经历了频繁的大规模修建。为了解扎什伦布寺壁画的制作材料与工艺,为今后壁画的保护及修复提供重要的参考及科学支撑,选取寺内强巴佛殿四层北壁、吉康扎仓南殿西侧的典型壁画,共采集8个样品。采用超景深三维视频显微镜观察壁画的制作结构,显微激光拉曼光谱仪对有机与无机颜料的成分信息进行表征,偏光显微镜根据晶体的光学信息鉴别拉曼光谱相似的颜料颗粒,X射线衍射仪用于测定地仗成分,扫描电镜/能谱仪则对微观数据进行确认和补充。通过分析研究,壁画由地仗层、准备层、颜料层构成。颜料包括矿物及人工合成颜料,其中红色颜料为朱砂与颜料红14,绿色颜料为块铜矾、酞菁绿,黑色颜料为碳黑,黄色颜料为雌黄,蓝色颜料为合成群青。颜料红14与酞菁绿为有机合成颜料,合成群青则为无机合成颜料。块铜矾作为矿物颜料,在欧洲曾用于架上画、壁画、手稿等艺术作品中,但在国内还未曾发现其使用历史,这一发现扩展了对绿色颜料的认识。壁画的地仗层依据藏式壁画制作传统使用了阿嘎土,准备层则由黄土制备。研究结果表明,壁画制作时以阿嘎土打底,刷一层黄土找平壁面,以胶调和颜料绘制于黄土层之上。壁画除了使用一些常见的传统藏式壁画材料,还发现了一些近代人工合成材料,说明扎什伦布寺强巴佛殿四层北壁及吉康扎仓南殿西侧壁画曾经历过重绘或补绘。该研究结果不仅弥补了扎什伦布寺壁画的研究空缺,也为扎什伦布寺修缮历史的补充及完善提供了重要证据。     

陶寺遗址陶器彩绘颜料的光谱分析

利用拉曼光谱结合X衍射和红外光谱物相检测方法,对山西襄汾县陶寺遗址出土陶器的表面含量极少的彩绘颜料及其胶结物质的物相结构进行了分析鉴定。结果表明,红色矿物颜料,白色矿物颜料保存都较为完好,未发生显著的变化,分别为朱砂(HgS)和碳酸钙(CaCO₃)无机矿物,此外红外光谱的分析结果表明红色颜料是通过熟石灰(Ca(OH)₂)胶结材料胶结到陶器表面的,碳酸钙的形成应当是熟石灰长期吸收空气中的二氧化碳的结果。这一研究表明显微拉曼光谱和红外光谱分析技术非常适合考古发掘中含量较少的彩绘颜料的科学鉴定,较X衍射的物相鉴定更为简洁明了; 另外朱砂中并未发现石英矿的伴生,这一结果或可表明早在4000年前的陶寺先民已掌握朱砂颜料的合成技术。     

甘肃庄浪县云崖寺石窟明代彩塑制作工艺与材料分析研究——以6号窟、7号窟为例

甘肃省是我国石窟寺分布最为广泛的区域之一,且多文明于世界。云崖寺位于庄浪县,初兴于北魏,发展于北周,繁荣于明代,是陇东地区极为重要的石窟。此处明代彩塑在石窟中独树一帜,因文物价值高、造型精美、保存完整而备受关注,对研究佛教艺术具有极为重要的价值。以云崖寺石窟6号窟和7号窟彩塑为研究对象,综合运用可见光摄影、红外摄影、超景深显微镜(OM)、扫描电子显微镜及能谱(SEM-EDS)、 X射线衍射(XRD)、便携X射线荧光(XRF)、激光拉曼(Raman)等技术进行制作材料与工艺分析。结果显示,此处彩塑制作工艺与甘肃地区传统彩塑制作工艺相一致,结构为骨架层、泥塑层和彩绘层。其中,骨架层分两种,即木骨架、石胎结合木骨架。石胎为崖体,主要成分为石英、钠长石、钾长石、微斜长石、针铁矿等,是典型的砂岩;泥塑层分为粗泥层和细泥层,制作时向内加入麦秆和麻作为添加材料,主要成分有石英、钠长石、斜长石。彩绘层由颜料层和金层组成,其中,红色颜料为朱砂和铅丹、棕色颜料为铁红、绿色颜料为氯铜矿、白色颜料为白垩、黑色颜料为炭黑,7号窟部分彩塑使用雌黄作为橙色颜料。彩塑在领口、袖口、纹样等多处使用沥粉贴金,与贴金、泥金...     

中国北方古建油饰彩画中绿色颜料的光谱分析

古建油饰彩画中颜料成分的分析鉴定是古建维修、保护的重要基础工作。文章利用X射线荧光分析、X射线衍射分析、扫描电镜-能谱分析技术,首次系统地分析检测了来自北京、山西、甘肃等中国北方地区的27个古建油饰彩画中的绿色颜料。结果表明,其中15个样品使用了巴黎绿这种含铜、砷的人工合成颜料,其余样品未检测出矿物颜料,显色成分应为人工合成的有机物。在所有分析样品中未检测到古代常用的绿色颜料石绿和氯铜矿的存在。该研究工作开辟了光谱分析技术应用于古建油饰彩画颜料鉴定的新领域,为该类文物分析鉴定、修复材料的选择提供了科学数据。     

西夏千佛龛唐卡的显微偏光及拉曼光谱分析

利用偏光显微镜和激光拉曼光谱仪对1963年出土的西夏时期唐卡表面彩绘颜料进行分析,结果表明,唐卡使用的红色、背景红、蓝色、白色、黑色颜料是由朱砂、铅丹、靛蓝、铅白、炭黑制成。检测分析结果为西夏千佛龛唐卡实施保护修复提供了准确可靠的科学依据,也为保护修复时提供准确的颜料使用依据。     

Analysis of mural paintings using in situ non‐invasive XRF,FTIR spectroscopy and optical microscopy

An analytical protocol consisting of X‐ray fluorescence spectroscopy, optical microscopy and Fourier transform infrared spectroscopy was used to study the origin and the nature of the materials (pigments, binders and coating preparation) of the Fundenii Doamnei church mural paint from Bucharest. The main interest of the present study consisted in the original votive paint from narthex, painted in 1757 in a secco technique. During analysis, an unexpected pigment in the votive paint could be detected by the combined analytical techniques: ultramarine blue. Along with this pigment, the presence of gypsum binder based on egg and flax seed oil could also be evidenced. These results demonstrated a secco execution technique of the votive paint and also the presence of a restoration treatment. Moreover, during the present study, the components of the preparation layer and the constitutive pigments from both 1699 and 1757 years mural paints have been analyzed. Hence, the following pigments could be identified: vermilion, azurite, cinnabar, lead white, ochre, natural umber and gold, by using the combination of the analytical techniques. The novelty of our results consists in detecting the composition of the materials used in this church painting (fresco and a secco) during these 254 years since its first restoration. The results of these investigations pointed to the suitability of the non‐destructive and semi‐destructive analytical techniques in the complex characterization of the paints realized in different techniques, at different periods. Copyright © 2013 John Wiley & Sons, Ltd.     

Klimt artwork (Part II): material investigation by backscattering Fe-57 Mössbauer- and Raman- spectroscopy,SEM and p-XRF

In a rediscovered Klimt-artwork “Trompetender Putto” material tests have been conducted. We report studies on different points of the painting. The spots are of different colors, mainly taken in spots of the painting not restaurated. MIMOS II Fe-57 Mössbauer spectroscopy revealed mainly haematite and nano particle oxides in red and red/brown colors. Brown colors also contain crystallized goethite. In brown/ochre colors the same pigments as in brown colors are observed, but there is less quantity of goethite and more quantity of haematite. The green colors show Fe-rich clays, like celadonite or glauconite and or lepidocrocite as main component. Raman spectroscopy revealed cinnabar in red colors of the Scarf; and massicot in brown/ochre points, i.e. in the Left Wing of the “Putto”. With scanning electron microscopy, various layers of the original and of overpainting could be recognized. The investigations of sample 1 show three layers of colored materials, which were identified as zinc-white, cinnabar and galena as well as carbon compounds. In sample 2 four layers could be detected. These are identified (bottom to top) as gypsum and lead-white (layer 1), zinc-white (layer 2), lead-white and cinnabar (layer 3) and titanium-white (layer 4). The elementary composition was examined with the portable X-ray-fluorescence analysis for qualitative manner at different points.     

Study of two large-dimension Murillo's paintings by means of macro X-ray fluorescence imaging,point X-ray fluorescence analysis,and stratigraphic studies

During the recent restoration of two large-dimension paintings by Murillo, entitled “Miracle of the loaves and fishes” and “Moses and the water from the rock of Horeb,” several studies about the materials employed for their execution were carried out. Macro X-ray fluorescence scanning technique was performed on both works complemented by point X-ray fluorescence and stratigraphic analyses, in order to characterize the different components of the paintings (i.e., ground layer, pigments, and binders). The results allowed us to better elucidate Murillo painting technique and his creative process. Ground layer was prepared in the usual fashion of the artist, using earths, calcium carbonate, iron oxide pigments, and white lead. The polichromy is composed of lead white mixed with various pigments, depending on the colour tone to be obtained in the pictorial composition: Red and yellow ochres, vermilion, azurite, smalt, and lead-tin yellow were the main pigments identified during our study. Finally, the presence of previous conservation treatments was evidenced by detecting pigments (zinc white, Prussian blue, etc.) not coeval with the artist palette.     

A multi-analytical approach for the study of the pigments used in the wall paintings from a building complex on the Caelian Hill (Rome)

In the present study, shards from Roman wall paintings (from the end of the first century to the fourth century A.D.) decorating the domus below the Basilica of SS. John and Paul on the Caelian Hill (Rome), were analyzed in order to identify the pigments used. The analytical techniques employed for the characterization of the pigments were the scanning electron microscope coupled with an energy dispersive spectrometer (SEM-EDS) and infrared spectroscopy (ATR and micro ATR). While SEM-EDS allowed to perform a qualitative analysis of the material, by FT-IR chemical species have been identified. The pigments identified were those mentioned in the literature for the Imperial Roman fresco painting: different types of ochre (yellow and red), mixtures containing lead, green earths and precious pigments such as cinnabar and Egyptian blue. They were often used as mixtures and the use of the most valuable pigments (cinnabar and Egyptian blue) were found in the most ancient rooms.     

Assessment of Raman microscopy coupled with principal component analysis to examine egg yolk–pigment interaction based on the protein C?H stretching region (3100–2800 cm−1)

This work seeks to identify the slight changes in the characteristic C H stretching region (3100–2800 cm⁻¹) of a protein‐based binder and fatty acid esters from egg yolk, which may occur in complex paint samples due to the presence of particular pigments. To date, this protein region—where historic pigments do not show characteristic Raman bands—has not been used to identify possible interactions between painting materials, in spite of its potential due to the mentioned feature. This study is based on the investigation of pure egg yolk model samples and tempera model samples prepared by mixing this binder with some historic pigments (cinnabar, raw Sienna, lead white, gypsum, calcite, azurite, lapis lazuli and smalt) as binary samples. All samples were analyzed in this region by Raman microscopy (RM) coupled with principal component analysis (PCA) for three color groups (red, white and blue) separately. The results show relevant spectral changes in the C H stretching region of amino acids and polyunsaturated fatty acids esters of the egg yolk binder, particularly in the azurite, lead white and gypsum‐based tempera samples. Lesser interactions were discerned in the tempera samples made with smalt, as well as shift in the region of polyunsaturated fatty acid esters of the egg yolk binder in the cinnabar and raw Sienna‐based tempera paintings. No interactions were recognized between the egg yolk and the pigments calcite and lapis lazuli. The effectiveness of applying RM combined with PCA for identifying interaction processes between binders and pigments is demonstrated. Copyright © 2011 John Wiley & Sons, Ltd.     

A multi-analytical study of the fifteenth century mural paintings of the Batalha Monastery (Portugal) in view of their conservation

The systematic characterization of the painting’s palette and technique applied on the execution of the mural paintings of the Batalha Monastery (Batalha, Leiria, Portugal) is presented. These are the oldest mural paintings known in Portugal (apart from Roman frescoes) and represent the beginning of an artistic Portuguese tradition that continues until the nineteenth century. The aim of the study was to identify for the first time by adopting a multi-analytical physico-chemical approach of the pigments, binder, and alteration products (white veils, crusts, and pigment alteration) of these unique works of arts in order not only to better understand the painting technique, but also to support a conservation-restoration intervention that took place from April to August 2010. Micro-sampling of paint layers was performed on representative areas of the paintings. The characterization of the pigments and binders was carried out by microscopy and microanalysis of cross sections using optical microscopy, scanning electron microscopy coupled with energy dispersive X-ray spectrometry (SEM-EDS), micro-FTIR, and micro X-ray diffraction. The combined analysis of the paintings allowed the identification of the painting’s palette: Vermillion (HgS) and red ochre for the reds, yellow ochres for the yellows, green earths and malachite for the greens, azurite for the blues, and carbon for the blacks. The use of the pigment is dependent of the motive painted while the most expensive materials were used in the most important iconographic motives. Alteration of malachite was identified in darkened layers in green areas of the paintings. White veil areas on the surface of the paintings were identified as calcite from precipitation/dissolution processes due to water run-off on the sacristy dome ceiling and walls.     

Collagen-based proteinaceous binder-pigment interaction study under UV ageing conditions by MALDI-TOF-MS and principal component analysis

This study focuses on acquiring information on the degradation process of proteinaceous binders due to ultra violet (UV) radiation and possible interactions owing to the presence of historical mineral pigments. With this aim, three different paint model samples were prepared according to medieval recipes, using rabbit glue as proteinaceus binders. One of these model samples contained only the binder, and the other two were prepared by mixing each of the pigments (cinnabar or azurite) with the binder (glue tempera model samples). The model samples were studied by applying Principal Component Analysis (PCA) to their mass spectra obtained with Matrix-Assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry (MALDI-TOF-MS). The complementary use of Fourier Transform Infrared Spectroscopy to study conformational changes of secondary structure of the proteinaceous binder is also proposed. Ageing effects on the model samples after up to 3000?h of UV irradiation were periodically analyzed by the proposed approach. PCA on MS data proved capable of identifying significant changes in the model samples, and the results suggested different aging behavior based on the pigment present. This research represents the first attempt to use this approach (PCA on MALDI-TOF-MS data) in the field of Cultural Heritage and demonstrates the potential benefits in the study of proteinaceous artistic materials for purposes of conservation and restoration.