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。     

Physical study of the Cucuteni pottery technology

Most of our knowledge concerning the Cucuteni pottery is based on traditional archaeological methods (typology, style and context analysis) and only a few interdisciplinary studies have been published. As there is a strong interest in revealing the basic pottery technology used by the Cucuteni communities we have investigated a significant number of pottery samples from 22 archaeological sites located in Eastern Romania by several physical analysis techniques: X-ray diffraction (XRD) and by magnetic measurements, including a first-order reversal curve (FORC) diagram study on the samples showing a hysteretic behavior. The main results presented in this study are discussed and compared with actual knowledge on the ancient Cucuteni pottery.     

“南海Ⅰ号”出水漆器残片的成分结构分析

为了用现代化学分析手段来剖析“南海Ⅰ号”漆器的髹漆工艺,以“南海Ⅰ号”出水的3片不同髹漆工艺的漆片为例,采用显微镜(OM)、X射线衍射仪(XRD)、扫描电子显微镜-能谱仪(SEM-EDS)、傅里叶红外光谱仪(FT-IR)、共聚焦拉曼光谱仪(Raman)等科学测试仪器进行研究,从髹漆的层数、显色材料的成分、漆膜的成分、漆灰的结构和成分、胎体的结构等方面来深度剖析“南海Ⅰ号”出水漆器残片的结构及制作工艺。表面显微观察显示漆片花纹精致美观,细部处理到位;截面显微观察显示剔红样品共有9层,分别是外漆5层,内漆1层,内外漆灰各1层,胎体1层;剔犀样品共7层,分别是外漆3层,内漆1层,内外漆灰各1层,胎体1层;褐漆样品共6层,分别是外漆和内漆各1层,内外漆灰各1层,内漆灰中加杂1层编织物层,胎体1层。拉曼测试结果表明3块漆片中红色显色材料为朱砂(HgS),黄色显色材料为雌黄(As_(2)S_(3)),黑色显色材料为炭黑(C)。样品中内外漆灰成分为羟基磷酸钙[Ca_(5)(PO_(4))_(3)(OH)]、石英(SiO_(2))和水合草酸钙[CaC_(2)O_(4)(H_(2)O)_(2.375)]等常见物质。漆膜的成分是生漆中添加了少量的石英颗粒,没有添加桐油作为助剂。     

库库提尼文明——新石器时代彩陶研究资料库的建立

库库提尼的新石器时代陶器距今约5000年,它是Ariusd-- CucuteniTripolie古人类活动带的一部分,位于欧洲东南部。对这种三色彩陶器的研究是法国和罗马尼亚的合作项目,基金来源是Brancusi项目提供,研究方向是制陶的黏土成分、烧制温度、用于涂彩的颜料层（白、红、黑）,陶器式样模型材料等。库库提尼文化是19世纪末第一个被发现的,它经历了约120年的流逝,由于过去对它的研究主要为考古调查,处于对它特殊性的好奇,才带出了本课题。本文报道了用岩相学分析的结果,通过对陶质材料进行SEMEDX,XRF检测,得到了库库提尼从A期、AB期到B期的不同进化阶段的岩相学陶层资料,现已发现的Scanteia,TarguFrumos,Ruginoasa,Cucuteni,Isaia,Poienesti考古遗址也符合这种进化阶段。本项目的目的是创建一个基础数据库,使有关库库提尼的资料数据能完整统一地输入古代欧洲研究数据库。     

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。     

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.     

Chemical analyses of the earliest pigment residues from the uttermost part of the planet (Beagle Channel region,Tierra del Fuego,Southern South America)

This paper presents the results of chemical analyses of the organic and inorganic fractions of pigment residues found in three archaeological sites located in the Beagle Channel region, Tierra del Fuego, Southern South America. Twenty-one archaeological samples have been analysed through XRD, SEM–EDX, FT-IR and GC–MS in order to characterise their inorganic colouring components and to search for the presence of organic substances used as binders. Lipids found in some samples are considered as potential binders. These organic components are compared to those found in archaeological sediment samples from the same layers where the pigments have been found, in order to search for potential taphonomic contaminations of the latter by the former. Results show that such contaminations are unlikely, hence the lipid contents are deemed of anthropic origin. The pigment sample results are also compared to data from analyses of natural sediment samples collected in several localities of the Beagle Channel in order to search for potential natural pigment sources. Results show that organic and inorganic components of these sediments are not the same than those present in the archaeological pigment samples, hence the pigment raw material sources have not been yet located. All these data provide for the first time evidence of the existence of ancient activities of pigment sourcing and paint preparation with organic binders which range from 6000 BP to 1900 BP in the southernmost region of the planet.     

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。     

山东临淄山王村俑坑出土陶质彩绘颜料初步分析

2008年5月山东临淄山王村俑坑出土了数量较多的彩绘陶质文物,为了了解彩绘颜料结构和成分,采用粉末偏光显微法、剖面观察结合拉曼光谱分析对彩绘文物表面颜料样品进行分析。结果表明,这批陶质文物表面彩绘是以白灰做地仗层,由碳酸钙、白土、铁黑（Fe₃O₄）、铁红（Fe₂O₃）、朱砂等颜料调和而成,且厚度不均。在个别样品中发现了少量的中国蓝颗粒(BaCuSi₄O₁₀),这是这次分析中较为重要的发现,此分析结果也可为考古研究提供科学信息。     

Non-destructive analysis of amber artefacts from the prehistoric Cioclovina hoard (Romania)

Amber beads from the Cioclovina hoard (Hunedoara County, Romania), dating from the transitional period between the Late Bronze Age and the Iron Age, were analysed by Fourier transform infrared spectroscopy – variable angle reflectance (FTIR-VAR) and Fourier transform Raman spectroscopy (FT-Raman). The aim was to determine if the raw material came from the shores of the Baltic Sea, on the Amber Route which crosses Central Europe, or if it originated from the area of the main amber occurrences in Romania, in Buz?u County, around the village of Col?i. All applied analyses strongly suggest that a large part of the amber from the Cioclovina deposit has a Romanian origin, and thus no connection with the Amber Route.     

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。     

克孜尔石窟出土蓝色颜料研究

克孜尔石窟是蜚声中外的佛教艺术宝库,其丰富的历史文化遗存,是研究丝绸之路文化交流与融合的重要实物资料。为了解克孜尔石窟第189窟前发现的蓝色颜料,采用X射线衍射(XRD)对其成分进行分析,采用拉曼、扫描电镜能谱仪(SEM-EDS)将其与第189窟壁画蓝色样品的元素组成及物相进行对比,采用酶联免疫吸附测定(ELISA)、透射傅立叶红外光谱(FTIR)对其可能含有的胶结材料进行分析。结果表明,该出土蓝色颜料样品为青金石,胶结材料为植物胶。研究表明,通过多种分析手段联合使用,可以更全面、客观地了解分析对象的各种信息,为今后克孜尔石窟壁画制作材料及制作工艺的分析提供经验和借鉴。     

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。     

应用热辅助水解甲基化裂解气相色谱质谱技术对古代漆器漆膜的分析研究

为了改良漆器漆膜的性能,古代漆工在制作过程中通常向生漆中加入干性油等添加剂。为了确定生漆及添加剂的种类,本工作采用四甲基氢氧化铵(TMAH)作为甲基化试剂,利用热辅助水解甲基化裂解气相色谱质谱(THM-Py-GC/MS)技术对所选的参考样品进行分析,然后将成熟的方法和实验条件应用到古代漆器的分析研究中。在古代样品中检测出了3-十五烷基邻苯二酚(C15)、3-十五烯基邻苯二酚(C15:1)等来源于中国、日本地区种植的Rhus vernicifera树种的生漆的特征热裂解化合物,确定了所用生漆的种类。另外,本实验在古代漆器中检测到了棕榈酸、硬脂酸、庚酸、辛酸和壬二酸等脂肪酸,推断该漆膜中添加了干性油。利用三维视频显微镜、扫描电镜、X射线衍射分析方法发现古代漆器采用了在胎体上依次髹漆灰、底漆和色漆的髹漆工艺,其中漆灰主要由漆液和钠长石、石英调制而成,黑色漆膜的呈色颜料为含铁化合物,揭示了古代漆器的髹漆工艺。该研究结果不仅增强人们对古代漆器制作材料和工艺的科学认知,而且为保护漆器这一独特的文化遗产提供科学依据。     

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.     

The painting of the Etruscan “Tomba della Quadriga Infernale” (4th century BC), in Sarteano (Siena, Italy): technical features

This work presents the results of an investigation of the painting technique used in the Etruscan tomb “Tomba della Quadriga Infernale”. This tomb was discovered in Sarteano (Siena, Italy) in October 2003 and dated back to the second half of the 4th century BC. Red, dark red, pink, yellow, white, black, and grey colours were used in the tomb in order to create paintings, which now represent a very precious record of the Etruscan art of wall painting in a hypogeal environment. The technical features of the painting were revealed by stratigraphy using optical and electronic microscopy. The components and preparatory layers of the painted areas were characterized using Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray microanalysis (SEM-EDS), X-ray diffraction (XRD), and gas chromatography/mass spectrometry (GC/MS). XRD, SEM-EDS, and optical microscopic techniques were also used for mineralogical analysis of the rock substrate. The SEM-EDS and FTIR analyses showed that red and yellow ochre, calcite, and vegetable charcoal were used to paint the walls of the tomb: the pigments, either alone or mixed together, were utilized to produce pure colours (red, yellow, white, and black) and intermediate tonalities (pink, dark red, and grey). SEM-EDS, FTIR, and XRD highlighted that the painting was made on a preparatory layer of calcite, applied onto a levelling material made up of calcite, clay minerals, quartz, and iron oxides. GC/MS analyses revealed that egg was used as an organic binder to disperse the pigments.     

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。     

司马金龙墓出土木板漆画屏风残片的初步分析

为了解山西大同北魏司马金龙墓出土木板漆画屏风的颜料使用情况和制作工艺信息,利用Micro-Raman、FrlR、XRF、断面切片等技术,对屏风残片上的四种主要颜色(红,黑,黄,白)、红色漆底层、断面分层进行分析与鉴别,结果如下:(1)屏风所使用的颜料有朱砂、炭黑、雌黄、雄黄、石膏.(2)屏风的红色底层系由生漆与朱砂调和、结膜而成,其中可能未曾添加桐油.(3)屏风彩绘部分的颜料分层十分明确,各层的厚度相对均匀,反映出制作者较为高超的绘画技法.(4)在颜料层、木胎与红色漆底层之间的"过渡层"中,分别观察到一些白色物质.初步分析后认为,"过渡层"中白色物质为羟基磷灰石的可能性较大.颜料层中白色物质的成分和物相仍有待进一步的分析.     

Complex raw materials and the supply system: Mineralogical and geochemical study of the jade artefacts of the Longshan Culture (2400–2000 bce) from Sujiacun site in coastal Shandong,China

X‐ray fluorescence (XRF), X‐ray diffraction (XRD) and Raman spectroscopy were employed to analyse the chemical compositions and phase structures of nine pieces of jade artefacts unearthed from Sujiacun, a Longshan Culture (2400–2000 bce ) site in coastal Shandong, eastern China. The results of the analyses indicated these samples were primarily made from multiple raw mineral materials, including antigorite, actinolite, clinochlore, turquoise and muscovite. No nephrite was recovered from the Sujiacun site. This is strikingly different from other top‐ranking settlements of Longshan Culture, such as Dantu, Liangchengzhen and Xizhufeng, in which nephrite was the main material of jade artefacts. This may reflect the distinctions in the supply system of jade raw materials among different rankings of Longshan period sites. In addition, laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) was used to analyse the composition of the rare earth elements of serpentine jade. These preliminary results were compared with published data on the composition of serpentine jade and it was found that the Sujiacun serpentine jade artefacts were likely sourced from the Taishan jade deposit.     

岩鸽排泄物对壁画损害特征研究

鸟类排泄物是造成石窟寺壁画、彩塑污染的主要因素之一,科学剖析鸟类排泄物对壁画的损害特征是此类污染物有效清除的前提。本研究利用傅里叶变换红外光谱(FTIR)、气相色谱-质谱联用(GC-MS)、X射线衍射(XRD)等方法分析了炳灵寺石窟壁画表面岩鸽排泄物成分,采用扫描电镜-能谱仪(SEM-EDS)、便携式显微镜、偏光显微镜(PLM)表征了鸟类排泄物对模拟壁画的微观损害特征。结果表明,岩鸽排泄物成分主要由尿酸、纤维素、多肽类有机物,以及以石英为主的无机盐组成。排泄物造成壁画覆盖污染、颜料层和地仗层侵蚀、颜料颗粒间原始粘附结构破坏,导致颜料层起甲、脱落,可溶盐活动及其他生物侵蚀。研究结果对于古代壁画的科学保护与修复具有指导意义。