中国古代朱砂的应用之调查

朱砂,化学成分为天然硫化汞（ＨｇＳ）。古代有丹砂等多种名称,它是我国古代各族人民最喜爱 的红色颜料和涂料,距今６０００多年,浙江余姚县河姆渡遗址中就有外涂朱砂的漆碗,此后,在江浙 一带的良渚文化、西北马家窑文化、四川广汉三星堆、河南殷虚等遗址都曾发现用朱砂涂染的装饰 品和尸骨。西周以来用途较广,秦汉时不仅大量用作颜料还用来炼制水银,北朝至清代全国各地的 壁画及其它彩绘艺术中都用朱砂做颜料。历代对朱砂做颜料的选择、加工制作也积累了不少经验。     

Scientific study of the pigments and binders used in mural painting from the 16th-century ce St Mary's Church of Cheriapally,Kottyam, Kerala,and its relevance to conservation

The aim of this investigation was to analyze the materials and techniques of the paintings in the 16th-century ce St Mary's Church, to evaluate deterioration of the paintings, and to propose a suitable conservation treatment for their preservation. The material analysis of ground, pigments, binders, and plasters was undertaken using binocular microscopy, field emission scanning electron microscopy (SEM)–energy dispersive X-ray spectroscopy, X-ray fluorescence, Fourier transform infrared spectroscopy in reflectance (KBr) and transmittance mode (attenuated total reflection), thin-film X-ray diffraction, and micro-Raman spectroscopy. Gas chromatography–mass spectrometry (GC-MS) was used for identifying proteinaceous and lipidic materials extracted from the micro-samples. The study generated data on two different red and green pigments used as decorative materials. The red pigments were identified as cinnabar along with traces of hematite and clay minerals, and green as malachite and the minor presence of other minerals. SEM analysis identified cotton fiber embedded in the coarse plaster layer that provided better strength to the plaster. Plant oils and proteins found as the binder in the pigment samples suggested that the painting technique was executed as tempera. Lead white and gypsum materials were used in previous restoration works.     

新疆阿斯塔那唐墓出土彩塑的制作工艺和颜料分析

新疆阿斯塔那古墓群出土了大量的彩塑,为了解其制作工艺与彩绘颜料成分,采用显微激光拉曼光谱,结合剖面观察和能量色散X射线荧光光谱等科技手段,对出土于唐墓的6个样品进行了分析鉴定.结果表明,泥胎表面先用硬石膏做打底层,再施以彩绘,且彩绘颜料厚薄有异.所使用的红、黄、黑、白和绿色颜料有铅丹、密陀僧、朱砂和土红、雌黄、炭黑、硬石膏及氯铜矿等无机颜料,而粉色彩绘是由铅丹(或铅丹和密陀僧的混合物)与硬石膏调和而成,且密陀僧作为彩绘颜料在新疆是较早的发现.其最为重要的发现是蓝色彩绘为植物性染料——靛蓝.这一研究结果,为进一步的彩塑修复与保护方案的制订提供了有价值参考.     

湖北省鄂州五里墩出土孙吴时期“红色粉状物”的测试分析

利用X射线荧光（XRF）,红外光谱（FTIR）和X射线衍射（XRD）等方法对湖北省鄂州市五里墩M2墓葬出土孙吴时期的红色物质进行了分析,结果表面这种红色物质主要是超细的朱砂粉料与油脂等的混合物,结合考古资料推测可能是调制的古代化妆品;其制作工艺是：从矿石中选出朱砂,研磨成很细的粉状,加入油脂（或许还加入了白色的高岭土）调和成膏状。本研究结果不但为该墓葬分析提供重要考古信息,对古代朱砂质化妆品的相关研究也有借鉴和参考作用。     

Allochthonous red pigments used in burial practices at the Copper Age site of Valencina de la Concepción (Sevilla,Spain): characterisation and social dimension

The use of red pigments linked to burial practices is widely documented in the Iberian prehistoric record and very often it has been traditionally interpreted as a ritual practice entailing the utilisation of local raw materials (iron oxides). Some research works, nevertheless, have also detected the use of red pigments which can only be interpreted as allochthonous. The red pigments spread over a single inhumation in a monumental Megalithic tomb surrounding Valencina de la Concepción Copper Age settlement was studied by means of X-ray diffraction, field emission scanning electron microscopy with energy dispersive X-ray spectroscopy, X-ray microfluorescence, micro-Raman and Fourier transform infrared spectroscopies. This approach allowed characterising the red pigments as cinnabar, mixed with tiny amounts of iron oxides. The presence of cinnabar, a product that was necessarily imported, in a context of an exceptional set of grave goods, suggests that the use of cinnabar was linked not only to ritual but also to practices related to the display of social status.     

便携式X射线荧光现场分析壁画颜料适用性研究——以西藏拉萨大昭寺壁画为例

便携式X射线荧光光谱仪作为快捷的无损分析技术,广泛应用于壁画文物的现场分析中.本文利用便携式X射线荧光光谱仪分析了西藏拉萨大昭寺转经廊壁画,选取部分样品,利用实验室X射线荧光分析,发现所分析颜料的主要显色元素具有一致性,并利用拉曼光谱确定了壁画颜料的成分.通过比较研究,发现便携式X射线荧光光谱仪可确定大部分色彩较为纯正的颜料的成分,同时,由于西藏拉萨大昭寺壁画颜料的杂多性,对于含砷的橙色颜料、含砷或含铅与含铁的黄色颜料、含铜砷的绿色颜料、含钙硫的白色颜料、群青与孔雀石的混合颜料则需结合拉曼光谱确定之.本研究工作显示,利用便携式X射线荧光光谱仪开展现场检测,可极大地减少实验室分析样品的取样数量,有利于壁画颜料的无损分析与微损分析.     

唐墓彩绘文物的保护研究

针对唐代墓葬的几件彩陶文物和壁画的特殊要求,选择性能优良的保护材料对彩绘文物进行加固保护。通过X-射线荧光光谱仪和分光光度仪进行彩绘文物颜料成分分析,选用浓度为2%的B72和2%的改性B72加固保护彩绘文物,测试保护后文物的表面颜料粘结性、耐水性、耐酸碱等性能,同时选用分光光度仪和粘接强度仪测试光照老化后文物的颜料颜色和粘接强度的变化。试验结果表明,文物颜料主要成分包括铅丹、铅丹和朱砂混合物、土红以及石绿;加固保护后文物的粘结性、耐水性和耐酸碱度都有所提高,且改性B72的提高程度比B72大;光照老化后改性B72保护的彩绘文物颜料主波长、色纯度和亮度变化均小于B72的变化,改性B72的粘接强度提高指数是B72的3倍之多,粘接性能优于B72。综合对比可以看出,加入紫外线吸收剂的改性B72保护材料很好地起到加固和保护彩绘文物的作用,在彩绘文物加固保护材料的选择上具有借鉴和指导意义。     

Analytical study of Roman and Arabic wall paintings in the Patio De Banderas of Reales Alcazares’ Palace using non-destructive XRD/XRF and complementary techniques

A portable XRD/XRF system and complementary laboratory techniques were employed to improve the knowledge of the procedures used to create Roman and Arabic wall paintings. Integrated physico-chemical investigations were conducted on fragments of artworks collected from the archaeological excavation of the Patio de Banderas in the Reales Alcazares’ Palace of Seville (Spain), and a comparative study on the pigments from both historical periods was performed. As a result, pigments such as vermilion, red ochre, yellow ochre, green earth, Egyptian blue, carbon and phosphor-based black pigments were detected in Roman samples; however, in the Arabic fragments, only haematite was observed. In addition, the size and shape of the particles of the wall paintings were studied with an XRD 2-dimensional detector and SEM-EDX.     

A TECHNOLOGICAL EXAMINATION OF NINTH–TENTH CENTURY AD ABBASID BLUE‐AND‐WHITE WARE FROM IRAQ,AND ITS COMPARISON WITH EIGHTH CENTURY AD CHINESE BLUE‐AND‐WHITE SANCAI WARE*

Eight sherds of ninth–tenth century ad Abbaesid blue‐and‐white glazed earthenware, excavated in 1931 at Hira in western Iraq, were analysed using, variously, quantitative wavelength‐dispersive spectrometry (WDS) and energy‐dispersive spectrometry (EDS) in association with scanning electron microscopes (SEM), and semi‐quantitative X‐ray fluorescence spectrometry (XRF). In order to compare the compositions of the cobalt pigments used, the glazes of seven complete vessels of eighth century ad Chinese Tang blue‐and‐white sancai were also analysed semi‐quantitatively using XRF. The Abbasid wares were shown to have used traditional Mesopotamian alkali–lime glazes applied to calcareous clay bodies. Half the glazes examined were opacified with tin oxide. Three types of blue decoration (i.e., raised; spreading; and flat, non‐spreading) were produced using a variety of formulations, including a mixture of cobalt pigment with lead oxide. The sources of the ores used for the cobalt pigments have not been identified. However, the analytical data showed that the cobalt ore used for the Abbasid blue‐and‐white ware could be distinguished from that used for the Tang blue‐and‐white sancai by its higher iron content and by the presence of a significant amount of zinc. The use of cobalt‐blue decoration on the ninth–tenth century ad Abbasid ware was anticipated in China by eighth century ad Tang blue‐and‐white sancai wares. However, whether its introduction by the Abbasid potters should be seen as an independent invention that followed the introduction of tin‐opacified glazes in Iraq, or whether it was influenced in some way by Chinese originals, is still unresolved.     

焦作马村汉墓和白庄汉墓出土彩绘陶仓楼的科技分析

河南省焦作马村汉墓和白庄汉墓出土彩绘陶仓楼数量众多,类型丰富。为了科学保护修复彩绘陶仓楼,通过X射线衍射仪,X射线荧光分析仪,岩相分析,热膨胀测试等技术手段对这批彩绘陶仓楼进行了深入分析。研究发现,这批陶器为当地取土烧制的加砂陶,陶片结构较密实,器物制作以模为主,部分是模制后粘贴而成,吸水率和表气孔率较高,烧成温度和岩相分析发现陶片有釉化现象。研究成果可为后续保护修复处理彩绘彩绘陶仓楼提供参考和借鉴。     

Archaeometrical characterization of pigments and paintings on Pre-Hispanic pottery from the regions of Fiambalá and Chaschuil (Catamarca,Argentina)*

The results of an analysis of pigments used in slips and designs deployed in ceramic assemblages recovered from archaeological sites located in different environments, expressing the socio-historical process developed in the regions of Fiambalá and Chaschuil (Catamarca, Argentina) during the last 1500 years are presented. The sample, formed by fragments of different ceramic styles and natural pigments, was analysed via Raman spectroscopy and X-ray diffraction. Results indicate the continuity in use of certain pigments (mainly hematite for red hues and Mn oxides in combination with magnetite for black paints) within the different socio-political organizations that inhabited the region from the first to the 14th centuries ce , in spite of the diverse shades of colour, which suggests an intentional search linked with their cultural conventions. For the Inca Period, this scenery of continuities in minerals employed for reds and blacks is complemented by the use of new compounds (Ti oxide, apatite and gypsum) in order to generate the ‘cream’ tones applied as slips, all of which have not been identified for previous moments.     

Composition of the Lustre Pigment Used in the Production Of 13th Century AD Raqqa Lustreware from Syria

The very rare find of the relic of the original lustre pigment attached to the glazed surface of a sherd of 13th century ad Raqqa type lustreware from Syria has been analysed using a combination of analytical scanning electron microscopy (SEM), micro‐X‐ray diffraction (XRD) and Rutherford backscattering spectroscopy (RBS). The composition of the pigment relic inferred from these analyses is shown to match those of recipes for lustre production given in the early treatises by Jazbir Ibn Hayyan (c. ad 721–c. ad 815) and Abū'l Qasim (ad 1301). Similarities and differences between this 13th century ad Syrian pigment and pigments used in the ninth century ad in Iraq, in the 14th century ad in Islamic and Hispano‐Moresque Spain, and in the 16th century ad in Renaissance Italy are discussed.     

重庆大足大佛湾彩绘绿色和蓝绿色颜料的分析研究

为了确定重庆大足大佛湾彩绘含铜、砷元素的绿色及蓝绿色颜料显色成分,应用便携式X射线荧光光谱仪(XRF)、便携式显微镜等无损调查方法,结合X射线衍射分析仪(XRD)、扫描电镜-能谱仪(SEM-EDX)、X射线光电子能谱分析仪(XPS)、显微拉曼光谱仪(RM)等分析方法,对取自大佛湾塑像的绿色及蓝绿色颜料进行调查和分析。结果表明绿色颜料显色成分为为巴黎绿,蓝绿色颜料显色成分为氯砷钠铜石[NaCaCu₅(AsO₄)₄Cl·5H₂O]。根据研究结论推断,氯砷钠铜石可能为巴黎绿的变色产物。该结果为探讨近代人工合成颜料变色机理提供了新的线索和方法。     

Physicochemical characterization and provenance of colouring materials from Akrotiri-Thera in relation to their archaeological context and application

An assemblage of approximately 500 colouring materials and objects related to their use, found in different contexts and forms at Akrotiri, Thera, was recently investigated. The items date to the Early, Middle and Late Cycladic Bronze Age (c. 3000?C1600 bc) and include materials or pigments found in their natural state, in specifically made forms or inside vessels. Some of the contexts do not provide any indication of the pigments?? use, storage, trade or application. Among the investigated materials, which include red and yellow ochres and blue riebeckite, are those that can be associated with pigments that were widely used in the past in wall paintings or to decorate pottery. There is also evidence for the selective use of purple pigments, which were derived from shellfish, in wall paintings. However, there are other raw colouring materials, such as lead pigments that have not been previously known to have been used in wall paintings or in any other applications during the prehistoric period in the Aegean. A thorough macro- and microscopic visual examination of the quality and morphology of these items enabled the identification of physical features (colour, homogeneity, grain size and shape) that indicate their nature or degree of processing. To identify the mineral composition of the pigments and to investigate their provenance from a geological perspective, quantitative X-ray diffraction (XRD) analysis was conducted. For those samples requiring additional information on their composition and for the refining or confirming of the XRD data, scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM-EDX), micro-Raman and Fourier transform infrared (FT-IR) spectroscopies were performed. This work is part of a larger project, supported by Institute for Aegean Prehistory, that aims to clarify major archaeological queries that are not restricted to the identification of the nature, composition and provenance of the colouring materials but extend to aspects of their selection, preparation and application techniques used during the Early to the Late Bronze Age.     

Painted plaster from Bronze Age Thebes, Boeotia (Greece): a technological study

From the rather difficult excavations that have taken place in Thebes since the beginning of the last century, many fragmentary but often well-preserved paintings on plaster have been unearthed. These belong to several contexts and periods: House of Kadmos (Late Helladic IIIA), Treasury Room (Late Helladic IIIB1) and Oikopedon Spourli (Late Helladic III). Their iconography, style and technology fit well with other paintings from the Late Bronze Age sites found in the vicinity of Thebes (e.g. Gla and Orchomenos). This paper presents a technological study of the Bronze Age painted plaster from Thebes, Greece. The paintings were investigated by means of X-ray diffraction; stereo, reflected light and scanning electron microscopy; some by laser-induced breakdown spectrometry and by micro-Raman spectroscopy, in order to identify the pigments and the composition of the plaster layers, and to determine the painting technique(s) that the artisans may have employed. The plaster layer onto which the paint layer was applied was often the only layer and consisted mainly of calcite, while a clay plaster formed the backing between the lime plaster coat and the actual wall surface. The pigments identified were: yellow ochre, haematite (red), cuprorivaite (Egyptian blue), indigo and possibly riebeckite for blue, charcoal (black), calcite (white), and a combination of black and red for purple. A detailed macroscopic study of the painted surface revealed several features, which indicated that the technique of al fresco painting was employed extensively, a technique already in use since the start of the Late Minoan I phase on Crete. A generally lower level of quality in the appearance of the later paintings (Treasury Room and Oikopedon Spourli) was also noted, but this was not reflected in the materials used or in their overall manipulation.     

Polychromic structures and pigments in Guangyuan Thousand-Buddha Grotto of the Tang Dynasty (China)

This paper presents a multi-analytical study of the polychromy in the Guangyuan Thousand-Buddha Grotto. Samples taken from 15 locations in No. 512 and No. 689 caves are prepared as cross-sections for the analysis by optical microscopy (OM) and scanning electron microscopy coupled with backscattered electron imaging (SEM-BSE). The cross section analysis indicates that some paintings were repainted in the past. The chemical composition of each painting layer is obtained by scanning electron microscopy coupled with energy-dispersive X-ray analysis (SEM-EDX). The main pigments for 15 samples including green, red, blue, white and black paint layers, are identified by the combination of polarized light microscopy (PLM), Fourier Transform infrared spectrum (FT-IR), Raman spectroscopy (RS) and X-ray diffraction (XRD) analysis. The integrated analytical results reveal that the green pigments are malachite and atacamite; the red color is attributed to minium, hematite and cinnabar; the blue pigments are lazurite and organic blue materials; the white color is ascribed to anglesite and gypsum; and the black surface of polychrome is the accumulation of longtime smudging by folk burning incense in the devotional practice or the soot deposition resulting from burning bonfires in the caves. Some arsenic-containing pigment is detected in the green samples. This case study also demonstrates the advantages and the limitations of every analytical technique for the pigment identification, confirming the necessity of the integrated analytical techniques approach. The present results are not only useful to assist in the authenticity of the used pigment materials and history of the polychromic in the past, but also aimed at guiding the conservation scientists in taking into account materials and methods utilized in the past.     

Non-destructive in situ analysis of polychromy on ancient Cypriot sculptures

The study focuses on the characterization of polychromy on limestone sculptures from Cyprus, attributed to the Cypro-Archaic—end of the Hellenistic periods. Polychromy components were identified by integrating digital microscopy, imaging under ultraviolet (UV) light, visible-induced luminescence (VIL), X-ray fluorescence spectroscopy (XRF) and fibre optics reflectance spectroscopy (FORS). Data acquisition was performed directly in exhibition rooms at the Cyprus Museum (Nicosia) and the Paphos District Archaeological Museum (Paphos). Among the identified materials, there are iron-containing (red, yellow, green) and copper-containing (green and blue) pigments. The precision of pigment identification by non-destructive techniques is discussed, and specific pigment names are proposed: red iron oxide, yellow iron oxide-hydroxide, green earth and Egyptian blue. Interesting results were obtained by VIL, which allowed identifying traces of Egyptian blue otherwise undetectable with the naked eye. Complementary, this study discusses advantages and problems of combined and separate use of portable XRF and FORS, raising the question of their complementarity and interchangeability for the purposes of pigment identification.     

DOMUS AUREA,THE ‘SALA DELLE MASCHERE’: CHEMICAL AND SPECTROSCOPIC INVESTIGATIONS ON THE FRESCO PAINTINGS

In this paper, data collected from the wall fresco paintings of room 114, called the ‘Sala delle maschere’, of the Domus Aurea in Rome is analysed. The chemical composition of the efflorescence is investigated by infrared spectroscopy. The colour palette is determined by means of EDXRF, Raman spectroscopy and visible reflectance spectroscopy. EDXRF has allowed an extensive mapping of the elements present in the pigments and plaster; whilst in‐situ Raman spectroscopy has been determinant for attributing the molecular composition of the pigments in a number of doubtful cases. Most pigments identified are typical of Imperial Roman fresco paintings (first to fourth centuries AD) ( Ward‐Perkins 1981 ); more interestingly, we found evidence of fragments painted with Egyptian blue, which was normally used mostly in official rooms.     

Spectrochemical Characterization of Red Pigments Used in Classic Period Maya Funerary Practices

We studied the composition, colour chromaticity and form of application of red pigments in human bone samples from seven Classic period Lowland Maya sites. The samples were analysed by X‐ray diffraction, scanning electron microscopy (SEM) and X‐ray energy‐dispersive spectroscopy (EDS). Colour was measured using conventional colour identification standards (Munsell) and reflectance spectroscopy. Cinnabar and hematite were identified as the pigments used. We conclude that the reflectance method has advantages over conventional visual results, as it provides precise, objective and quantifiable optical data to distinguish the chromaticity, colour saturation and brightness of the pigments.     

铅丹、朱砂及其混合物紫外光致变色的电化学及光谱研究

铅丹(Pb₃O₄)和朱砂(HgS)是古代壁画和彩绘上常用的红色颜料,它们的变色是文物保护工作者、策展人和艺术史学家长期关注的问题。但由于其所处环境复杂,影响因素众多,这些颜料的变色机理的研究较为困难。为了探究紫外光照对这些颜料的影响,采用电化学方法和控制环境的紫外老化模拟实验研究了铅丹、朱砂及其混合物的光降解过程,并利用拉曼光谱和X射线光电子能谱(XPS)对实验样品进行分析。电化学实验中铅丹受405 nm激光照射出现还原电流,朱砂出现氧化电流。紫外老化实验确认了铅丹在光照下的还原反应,反应产物为碳酸铅(PbCO₃)和碱式碳酸铅[Pb₃(CO₃)₂(OH)₂]。因此,光照会引起铅丹发生还原反应,引起朱砂发生氧化反应,两种颜料表现出典型的半导体性质。另外,光化学反应动力学结果显示,掺杂朱砂可能会加快铅丹的光降解过程。