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.     

Wall Paintings from the Roman Emona (Ljubljana,Slovenia): Characterization of Mortar Layers and Pigments

This study concerns the investigation of mortar layers and pigments of wall paintings from the Roman town of Emona (Ljubljana, Slovenia). Fragments of wall paintings consist of up to three preserved mortar layers. The mineralogical–petrographic compositions of the mortars were determined by means of optical microscopy and FT–IR spectroscopy. The investigated samples were divided into several groups based on similar thicknesses of the mortar layer, the binder colour and the composition of an aggregate. Furthermore, the results of mercury intrusion porosimetry showed that mortar layers consisting of carbonate grains exhibited lower porosity with respect to layers with mainly silicate grains, which is attributed to the angular shapes of carbonate aggregate. This is in accordance with the drilling resistance measurement system test (DRMS), confirming that layers with angular carbonate grains are harder than those with addition of rounded silicate ones, due to the good packing effect. The wall paintings were mainly executed using the fresco technique, while for some details secco was used. The identified pigments were red and yellow ochre, green earth, Egyptian blue, carbon black and lime white; all of them belonged to the so‐called austere pigment, which is quite common in Roman wall paintings.     

山东香山汉墓出土陶质彩绘文物材质及制作工艺的初步研究

山东青州香山汉墓陪葬坑出土了数量巨大,种类齐全陶质彩绘文物,尤其是陶马和陶俑上的彩绘保存完好,色彩鲜艳,绘画工艺精湛,非常罕见。为了研究汉代彩绘及其制陶工艺等信息,本研究使用拉曼光谱(RS)、带能谱的扫描电镜(SEM-EDX)、偏光显微镜(PLM)、体式显微镜(OM)、X射线荧光光谱(XRF)、X射线衍射(XRD)、热膨胀仪等分析方法,对出土的陶质彩绘文物进行了分析研究。结果表明这批陶质彩绘文物制作工艺是就地取土,与水混合塑型,在900~1000℃烧制陶胎。其彩绘所使用的颜料均为矿物颜料,其中白色为方解石(CaCO3)、红色为赭石(Fe2O3)和朱砂(HgS)、黑色为炭黑(C)、紫色为人造汉紫(BaCuSi2O6),采用胶料调和颜料调涂刷绘制而成。这批文物的制作工艺属于典型的秦汉时期彩绘陶器的制作方法。研究成果可为相关文物的保护提供科学数据。     

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.     

A multi-technique characterization and provenance study of the pigments used in San rock art, South Africa

During the course of a conservation project at the rock shelter known as RSA TYN2 (Eastern Cape, South Africa), a sample of 33 painted fragments that had become detached from the wall were collected. They have been studied using a multi-technique approach (optical microscopy, SEM-EDS, Raman spectroscopy and FTIR), with the aim of achieving a better understanding of their paint stratigraphy, composition, and provenance. The paintings are on a Clarens Formation sandstone and are embedded in calcium sulphates and oxalates. The red pigments show two different ‘hues’, corresponding to two different compositions. The light red is a red ochre, possibly pure, which is probably a degradation product of the Clarens Formation sandstone. The dark red contains more iron oxides and may be a mixture between the red ochre and pure haematite. Because of the presence of crystals which may be identified as augite we suggest this haematite came from the basaltic upper part of the Drakensberg, at least 4 km away from the rock shelter. The black pigments have been identified as carbon black, that is to say, incomplete combustion products of organic compounds, and are radiocarbon dated to between 2120 and 1890 cal BP, making these samples the oldest directly dated South African rock art.     

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.     

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.     

常熟彩衣堂彩画蓝色颜料研究

常熟彩衣堂建筑彩画是江南地区古建筑彩画中的杰出代表,可一直存在彩画的部分色彩与传统图案用色难以对应的问题。为明确彩衣堂彩画蓝色颜料的使用情况,在前期研究工作成果的基础上,对采集的样品采用光学显微镜、激光显微拉曼光谱仪、X射线荧光分析仪等进行了综合分析。结果表明彩衣堂彩画使用了蓝色有机颜料花青和矿物颜料石青,蓝色纹样处一般只有作为底色的花青残留,从而使得显现的颜色与传统图案用色无法匹配。     

西藏拉萨大昭寺转经廊壁画制作工艺研究

古代壁画是一定时期政治、经济、文化、艺术和科技发展水平的物质反映,因此,利用现代科技分析手段提取其信息并将之与古代文献结合,则可逆推其制作工艺和判定其制作时间,进而确定其历史价值、科学价值和艺术价值,为艺术史研究和保护修复提供信息。本工作利用拉曼光谱(Raman)、偏光显微镜(PLM)、扫描电子显微镜与能谱仪(SEM-EDS)、红外光谱(FT-IR)和X射线衍射(XRD)在西藏大昭寺转经廊壁画样品分析中获取的信息,结合文献,确定西藏拉萨大昭寺转经廊壁画绘制于清代晚期至20世纪80年代之间。此幅壁画地仗使用了阿嘎土,与文献记载一致;白粉层使用立德粉、碳酸镁和方解石等,与文献记载用白胶浆或者黄胶浆相异。同时发现壁画颜料采用藏族传统绘画配色方法。     

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.     

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.     

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。     

Fragmented Images: The Last Tomb Paintings of Tarquinia

Cultural decline as a result of the Roman conquest is usually invoked to explain the gradual disappearance of Tarquinian tomb paintings during the third century BC. By contrast, this paper argues that, first, the late tomb paintings of Tarquinia markedly differed from their predecessors by decorating individual burials (fragmentation), as opposed to entire chamber tombs, which should be seen as a culturally meaningful development in the iconographic approach towards representing the deceased; and that, second, the disappearance of this time‐honoured type of monument be seen as part of wider changes in the ways in which Tarquinian and other Etruscan elites chose to materialize their ideologies during the cultural and political realignments of the period of the Roman conquest.     

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。     

邯郸金代墓葬壁画保护性搬迁及后期修复

2017年7月在邯郸华耀城建筑工地发现一座金代墓葬,经清理后发现该墓葬墓室内存留有大量壁画。作为邯郸地区发现数量较少的文物类型,此壁画的发现对研究邯郸历史文化具有重大价值,因此保留壁画实物十分重要且必要。为此,文物保护修复人员按照文物保护修复规范流程,对壁画进行清理、预加固、加固、分幅、支撑、切割、搬运等操作,将全墓壁画分为17幅,全部搬运回文物库房。2020年6月开始进行后期保护修复,采取对砖体的二次打磨切割、脱盐、加固、翻转、画面层清理、补全、作色等操作,壁画保护修复工作圆满完成。     

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。     

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.     

山东危山西汉墓出土陶器彩绘颜料研究

为研究山东危山西汉墓出土彩绘陶器颜料成分,采用偏光显微镜、显微拉曼光谱仪和扫描电子显微镜-能谱仪进行了分析。研究结果显示,危山汉墓陶器彩绘颜料有朱砂、铅丹、中国紫(汉紫BaCuSi2O6)、铁红、铁黑、白土等。中国紫颜料首次在山东省的发现,扩大了该颜料的使用区域,具有重要的考古学意义。另外,还在紫色颜料中分析出了BaCu2Si2O7蓝色晶体,这是继中国蓝中国紫之后的又一重大发现。     

山西兴县红峪村元至大二年壁画墓

2008年5月,考古工作者在山西兴县康宁镇红峪村发掘了一座壁画墓。墓葬坐西朝东,由墓道、封门石、甬道、墓门及墓室组成,墓室为八角形,为夫妇合葬墓。墓顶和墓室皆绘有壁画,包括花卉、鞍马、墓主夫妇对坐图、备茶图及孝行故事等。西壁墓主夫妇之间有一牌位,题有墓主武庆及其妻景氏名字,其后座屏上题传马致远所作《天净沙.秋思》。西南壁上题记中有元代至大二年(1309年)纪年。     

X‐ray Diffraction and SEM Investigation of Wall Paintings Found in the Roman Temple Complex at Horvat Omrit,Israel

In the present study, the fragments of wall painting found in the Roman Temple Complex at Horvat Omrit were analysed for the first time using the non‐destructive techniques of X‐ray diffraction (XRD) and scanning electron microscopy (ESEM) equipped with energy‐dispersive X‐ray spectroscopy (EDS). The application of these methods enabled unambiguous identifications of the pigments and plaster components of the samples. Quantitative information on mineral composition, crystallite size and elemental composition of each studied paint layer and plaster was collected. Based on the results of the XRD and EDS analyses, the green pigment was identified as celadonite. It was revealed that the Egyptian blue pigment does not contain impurities of tin and lead, and this excludes the use of bronze scrap in its synthesis. Comparison of the mineral composition of the paint layers indicates that a wider palette of colours was obtained by mixing the available mineral pigments. The study of cross‐sections of painted specimens revealed the usage of slaked lime for plastering. The obtained results give a new insight into the wall painting technique employed by ancient artists at Horvat Omrit, in northern Israel.