成都十二桥遗址新一村一期出土漆彩绘陶的分析研究

为了探究成都地区漆器制造历史和工艺,对2010年度成都十二桥遗址新一村一期地点出土的一批彩绘陶残片样品采用包括:加速器质谱碳十四年代测定(AMS-14C)、傅立叶变换红外光谱(FTIR)、显微镜形貌观察(OM)、显微激光拉曼(Micro-Raman)、能量色散X射线荧光(XRF)等分析方法进行了研究。结果表明这批陶器年代在西周中晚期至春秋。陶胎以易熔粘土为原料而成;彩绘层是用生漆(大漆)分别加炭黑、朱砂调和结膜而成;髹漆工艺为先髹饰黑色底漆层,然后再用含朱砂的红色颜料漆勾勒图案,黑红相间形成鲜明对比,起到良好装饰效果。这批漆陶的发现表明成都平原地区大漆工艺的使用年代可到西周中晚期。     

汉阳陵东阙门出土黑色颜料的科学分析

为了科学分析汉阳陵东阙门西壁黑色颜料的组成和进一步探讨汉代皇陵颜料的使用状况,采用超景深显微观察、扫描电镜能谱(SEM-EDS)以及面扫描技术、X射线衍射(XRD)等测试方法,结合文献资料进行了科学分析鉴定与深入探讨。结果表明该黑色成分是氧化铜,应是原先含铜的蓝绿色颜料经过火烧氧化后所造成,属后呈现色彩。这一结果为后续彩绘类文物颜料鉴定提供科学思维,即不仅使用现代分析测试手段分析鉴定当前状态下的颜料种类,还应结合文物所处的环境变化,科学系统地指明其色彩呈现形式。另外,实验中使用的扫描电镜能谱面扫描技术可清楚确认颜料颗粒的分布情况,在微观分析颜料颗粒方面具有不可比拟的优越性。     

延庆辽代墓葬壁画制作工艺及其颜料的物相鉴定

北京延庆发现一座辽代晚期的壁画砖室墓。为研究该墓室壁画结构和鉴定其颜料成分,运用拉曼光谱、X射线衍射和X射线荧光等多种方法进行了分析研究。结果表明该墓室壁画主要有灰泥层、白灰层和颜料层组成;红色颜料的呈色物相为α-Fe2O3,黑色颜料的呈色物相为炭黑。     

湖南桃源出土战国彩绘陶器的科学分析

为研究湖南桃源县战国楚墓出土彩绘陶器的组成结构及保存现状,采用能量色散X射线荧光光谱法(EDXRF)、扫描电镜-能谱法(SEM-EDS)、X射线衍射法(XRD)和激光拉曼光谱法(LRS)等手段对陶器胎体成分、表面彩绘、金属涂层等进行分析检测。结果表明:这批彩绘陶器胎体成分相近,为普通易熔黏土。彩绘陶器表面的红色颜料为朱砂(HgS),黑色颜料为炭黑(C)。在彩绘陶壶、陶鼎和陶敦表面发现金属涂层装饰,通过扫描电镜能谱和X射线衍射分析,确定涂层为单质锡,属于锡涂陶的范畴。同时红外光谱测试显示锡层内面棕黑色物质为生漆,可能混合其他胶结材料。以上结果为研究战国时期彩绘陶器,特别是锡涂陶的制作工艺及发展提供了新的资料。     

Chemical and mineralogical characterization of Aguada Portezuelo pottery from Catamarca,north-western Argentina: PIXE,XRD and SEM-EDS studies applied to surface pre- and post-firing paints,slips and pastes

Particle-induced X-ray emission (PIXE), X-ray diffraction (XRD), electron microprobe analysis (EDS) and scanning electron microscopy (SEM) analytical techniques were used to characterize surface paints in pre- and post-fired Aguada Portezuelo decorated pottery. Surface paintings in black, white, red, brown, burgundy and ochre were analysed. Major, minor and trace elements were detected by PIXE, whereas XRD and SEM-EDS gave information on the main mineral phases and the characteristic morphology for each analysed pigment. The results obtained indicate that the main colour groups can be easily discriminated by PIXE, and they are characterized by only one pigment for each colour: hematite (red) and manganese mineral oxides (black), respectively, whereas white pigments are characterized by calcite, ghelenite and gypsum.     

Characterization and origin of black and red Magdalenian pigments from Grottes de la Garenne (Vallée moyenne de la Creuse-France): a mineralogical and geochemical approach of the study of prehistorical paintings

Pigments sampled from wall paintings and from crayons taken on the floor, at the Grottes de la Garenne (Saint-Marcel – Indre, France) have been analyzed and characterized by infrared spectroscopy, Raman micro-spectroscopy, X-ray diffraction, ICP/MS and analytical TEM. The red pigment used for the wall paintings is mainly composed by hematite, clays, carbon matter and carbonates. Results on the red pigments show that the compositions of the paintings are similar to that of some crayons. Regarding these analyses, their origin is compatible with local siderolithic facieses. Analysis of black pigments shows that they are made of cryptomelane, pyrolusite, clays, carbonates and carbon matter. It shows also that paintings and some crayons compositions are compatible. On the contrary of red pigments, the origin of black pigments is probably allochtonous. Indeed, the traces of thallium detected in cryptomelane, the cerium anomaly and the absence of iron are not compatible with local facieses or other sites from the French Massif Central.     

秦始皇帝陵园出土彩绘青铜水禽表面彩绘工艺研究

为全面了解秦始皇帝陵园出土青铜水禽表面彩绘装饰工艺的技术内涵,利用显微观察、偏光显微鉴定、拉曼光谱分析等手段,对秦始皇帝陵园K0007陪葬坑出土彩绘青铜水禽表面彩绘装饰工艺进行了系统的考察和研究。研究结果显示,白色颜料为骨白,黑色颜料为炭黑;彩绘层为多层绘制而成,在结构上与秦陵出土陶俑、陶马表面彩绘具有明显区别;彩绘绘制技法包括平涂及堆绘两种,其中堆绘主要用于羽毛纹路羽轴的绘制,施彩工具可能为毛笔或毛刷。彩绘作为青铜器的装饰工艺主要出现于秦汉时期,但并没有得到广泛应用,可能与彩绘装饰自身的脆弱性以及青铜器的功能由礼容器转变为实用器有关。     

唐张臣和墓彩绘陶质文物的拉曼光谱和X衍射分析

利用拉曼光谱和X衍射方法,对张臣和墓彩绘陶质文物颜料及胎体进行分析,结果表明各种颜料保存基本完好,为以后科学保护修复这批彩绘陶质文物提供了科学依据。同时也证明,在样品量极少的情况下,利用拉曼光谱和X衍射等方法可有效鉴别古代颜料的种类及文物胎体的成分。     

四川广汉龙居寺中殿壁画制作材料与工艺研究

广汉龙居寺中殿壁画为四川地区明代建筑壁画中精品。为了解该壁画制作材料与工艺,采用显微观察、激光粒度仪分析、X射线衍射、拉曼光谱、酶联免疫等方法,对样品结构形态和材料组成进行了分析。结果表明:该壁画载体为编竹夹泥墙结构。地仗层泥土颗粒矿物成分主要为石英、钠长石,颗粒组成墙体壁画以粉粒为主、砂粒次之,垫拱板壁画粗泥层比细泥层砂粒含量偏低、粉粒含量偏高;加筋材料粗泥层为稻草秸秆、谷壳等,细泥层为棉或麻纤维。颜料层显色成分为古代壁画常见矿物颜料,红色为朱砂、铅丹,绿色为氯铜矿、副氯铜矿,白色为方解石、滑石,黑色为炭黑,蓝色为石青,黄色为针铁矿,胶料为动物胶或蛋清。该壁画在四川地区明代建筑壁画制作材料与工艺上具有典型性,主要体现在载体结构类型、地仗层材料组成、颜料层显色成分等方面。研究成果不仅可为该壁画后期保护修复提供依据,而且丰富了对四川地区明代建筑壁画的认识。     

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.     

Identification of materials in post-Byzantine textiles from Mount Athos

Numerous textiles of inestimable historical significance have been preserved in the monasteries of Mount Athos for several centuries. However, our knowledge regarding the materials used in these objects is very limited. In the present study, microsamples extracted from ecclesiastical textiles (16th – 19th c.) of the monastery of Xeropotamou (Mount Athos) are investigated using Optical Microscopy (OM), Fourier Transform Infrared Spectroscopy (FTIR), High Performance Liquid Chromatography coupled to a Photodiode Array Detector (HPLC-PDA) and Scanning Electron Microscopy equipped with an Energy Dispersive X-ray spectrometer (SEM-EDX). The first goal of the study is to identify the colouring materials of the historical samples, which were of silk nature (OM). The presence of Prussian blue is revealed using FTIR and organic colourants such as cochineal, dyer’s broom (Genista tinctoria L.), fuchsin, indigo carmine, old fustic (Chlorophora tinctoria L.), soluble redwood (Caesalpinia trees), weld (Reseda luteola L.), young fustic (Cotinus coggygria Scop.) and indigoid dyestuff source(s) are identified using HPLC-PDA. Dyestuff extraction from silk substrates is achieved using the TFA method, which preserves the contained glycosides. Thus, the report provides further evidence to support the efficacy of the TFA method to extract various organic colourants from historical silk samples (second goal). Finally, metal threads included in some historical samples are studied using OM and SEM-EDX. The latter is employed to analyse the composition of the metal surfaces. Silver (Ag) and gold (Au) are detected on the surfaces of the majority of the samples. Two samples were manufactured only with Ag.     

长沙风篷岭M1出土漆器检测研究

长沙市风篷岭M1出土漆器百余件,为研究该批漆器的制造工艺及保护修复方法。选取多个样品采用扫描电子显微镜、X荧光光谱仪、红外光谱仪、X射线衍射仪等进行含水率、木胎种质、漆膜和漆灰成分多项检测。结果显示:木胎漆器含水率远大于夹纻胎;木胎漆器材质有楠木、梓木等;底漆层厚度大于面漆层;漆膜中的红色颜料为HgS,黑色颜料为C,白色颜料中含Ag较高;漆灰中含有大量SiO_2和CaO。本研究成果为研究夹苎胎漆器制作工艺提供了可靠依据。     

STUDY ON THE PIGMENTS IN THE CRUCIFORM GALLERY OF ANGKOR WAT,CAMBODIA

In the cruciform gallery of Angkor Wat in Cambodia, red, orange, white and black pigments were widely painted on the surfaces of pillars, walls and friezes. The application sequence of the pigments is different from area to area. The following substances were confirmed from the pigments: hematite (laterite), minium, calcium oxalate hydrates (whewellite and weddellite), Pb–Cl compounds (cotunnite, laurionite and blixite), calcium phosphates (whitlockite), gypsum, hydrocerussite, calcite, anglesite, lead dioxide, azurite and carbon black. The orange pigment (minium) underlies the red pigment (hematite). The former may have been applied at the time of the foundation (the Angkor Wat style period), and the latter in the Bayon style period or later, but mainly before the early 17th century of the current era.     

新疆和田达玛沟佛寺遗址出土壁画颜料分析

达玛沟佛寺是新疆和田地区重要的佛教遗址,具有极高的佛教及艺术价值,对我国乃至东亚的佛教艺术都有着重要的影响。为研究新疆达玛沟佛寺遗址出土壁画颜料成分及工艺,以壁画文物残块为研究对象,利用体视显微镜、X荧光光谱仪、X射线衍射仪、拉曼光谱仪、偏光显微镜等多种仪器对其进行了分析鉴定。结果表明,达玛沟佛寺所使用的颜料全部为矿物颜料,其中蓝色颜料为青金石,绿色颜料为氯铜矿,白色颜料为石膏,红色颜料为朱砂,褐色颜料为铁红,赭黄色颜料为铁黄。该研究为探索中国西域佛教史、美术工艺史及后期修复保护材料、工艺选择提供科学依据。     

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.     

甘肃武威磨咀子出土汉代彩绘木马颜料 分析与修复保护

武威磨咀子考古出土的汉代彩绘木马,不仅数量多,而且形体较大,具有河西汉马的典型特征;根据彩绘木马的材质状况,其类型属于潮湿而糟朽木器,急需进行修复保护。为此,针对目前彩绘木马的保存现状,本修复工作运用现代X-射线衍射分析技术,对木马彩绘颜料进行了分析,物相结果表明:黑色为墨,白色为石膏,红色为朱砂、铅丹。同时遵循原始制作工艺,选用汉代棺板木作为复原材料对残缺部件进行了复原修复,采用无色、透明的有机玻璃(MMA)材料为其制作了辅助支撑底座,使用Paraloid B-72试剂对表面严重糟朽木质、彩绘层实施加固,使用聚醋酸乙烯酯对脱落部件实施粘接,利用原始铆眼套合与加楔技术对木马部件进行了组装;最后,通过安装辅助支撑底座使受损彩绘木马得到了妥善保护,修复取得良好效果。     

重庆钓鱼城遗址悬空卧佛彩绘颜料初步分析

钓鱼城悬空卧佛造像系创作于晚唐时期的一尊巨型石刻,具有极高的历史、艺术、科学、宗教价值,但造像保存现状较差,存在颜料脱落、酥碱粉化、起甲等病害,亟待保护修复。为了解悬空卧佛彩绘颜料层的成分与结构,采用金相显微镜、拉曼光谱、X射线荧光(XRF)、X射线衍射(XRD)、扫描电镜-能谱仪(SEM-EDS)等多种现代方法与技术对彩绘样品进行了分析。结果表明:所用红色颜料为铁红、铅丹;蓝色颜料为群青;绿色颜料为碱式氯化铜;青色颜料为墨绿砷铜矿;白色颜料为硫酸铅;局部有贴金。结果还表明,该造像历史上曾多次重绘。本研究成果以期填补钓鱼城悬空卧佛研究的空白,同时为修复工作的开展提供科学依据。     

Minateda rock shelters (Albacete) and post-palaeolithic art of the Mediterranean Basin in Spain: pigments,surfaces and patinas

The inorganic and organic fractions of two microsamples of prehistoric paint from the same site, the Minateda rock shelters, are analysed here for the first time. The two samples correspond to two rock shelters of different styles (Levantine and schematic) – Abrigo Grande de Minateda (The Great Rock Shelter of Minateda) and Abrigo del Barranco de la Mortaja (Del Barranco de la Mortaja Rock Shelter). Since its discovery, historiographical tradition has emphasised the Abrigo Grande de Minateda, with its magnificence and complexity, as emblematic of the origin and evolution of rock art in the Mediterranean Basin of the Iberian Peninsula (a UNESCO World Heritage Site). Four complementary techniques –Microphotography, Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy (SEM-EDX), Raman Spectroscopy and Gas Chromatography–Mass Spectroscopy (GC–MS)– were combined to identify and characterise the physicochemical properties of the paint and of the surface. We present an interpretation of the results that leads us to define complex taphonomic alterations beyond the usual distinction of layers that include the surface, pigments and patinas.     

BLOOD AS A BINDING MEDIUM IN A CHUMASH INDIAN PIGMENT CAKE

As part of a study of Chumash Indian pigments, some black pigment cakes have been examined. One pigment cake was characterized as soot by polarized light microscopy, and Fourier transform infrared microscopy showed that the binder was proteinaceous. Protein determination was followed by examination using gas chromatography-mass spectrometry analysis which showed a characteristic suite of amino acids to be present, proportionally similar to blood. The blood identification was confirmed by immunological analysis. The binder was shown to be a mixture of human and animal blood, the animal being pronghorn antelope. This is the first successful identification of a binding medium from a Chumash Indian pigment cake.     

Early Islamic pigments at Nishapur,north-eastern Iran: studies on the painted fragments preserved at The Metropolitan Museum of Art

Pigments appearing on ninth–twelfth-century AD-carved stucco, wall painting, and terracotta friezes excavated at Nishapur in north-eastern Iran were investigated by optical reflectance spectroscopy, micro X-ray fluorescence spectrometry (μ-XRF), X-ray diffractometry (XRD), micro-Raman spectroscopy (μ-Raman), and scanning electron microscopy (SEM). Many of the pigments identified including vermilion, red lead, hematite, limonite, carbon black, atacamite, calcite, and gypsum have been identified in previous studies of pigments used in later Islamic periods. However, a series of unusual pigments such as wulfenite, pyromorphite, phoenicochroite, and jarosite were also found in the present study. The association of kaolinite and alunite with limonite and other Fe-bearing yellow pigments points to a local provenance for these pigments. In addition, the presence of orpiment in the vermilion may be indicative that the vermilion was artificially manufactured. These findings suggest that pigment use and manufacturing during the ninth to eleventh centuries in Nishapur was still in a trial-and-error stage and the palette known from the twelfth century onwards had not yet been systematized.