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。     

新石器晚期祭祀彩石的多种谱学方法研究

作为"中国古代文明探源工程"在淮河流域确定的唯一一处重要的龙山文化时期遗址,安徽省蚌埠市禹会遗址出土了大量彩石,引起考古学界广泛关注。本文利用同步辐射X射线荧光(SR-XRF)、X射线衍射(XRD)、激光拉曼光谱(LRS)、热释光光谱(TL)等多种光谱分析手段,并结合电子探针(EPMA)分析结果,对禹会遗址出土"红-黄"彩石不同颜色区域的元素、物相组成及经热历史进行了测定。结果表明,该矿石主体为褐铁矿,有大量石英夹杂,表层黄色物质主要为针铁矿(α-FeOOH),红色物质主要为赭石(α-Fe2O3+粘土+硅土);内部主要是隐晶质针铁矿,并含有一定数量铬铁矿、二氧化锰,及少量重晶石和金属铋。该类彩石并无人工热历史,应属于一种性质独特、地质起源复杂的多金属天然矿石,大量出现在新石器时代晚期遗址之中,可能与某种原始信仰和特殊祭祀活动有关。     

北红玛瑙的颜色成因及光谱学特征研究

在我国东北大、小兴安岭南段,广泛产出一种外观以红色为主,常带有黄色调的半透明玛瑙,被称为"北红玛瑙"。通过偏光显微镜观察、 X射线粉晶衍射分析、拉曼光谱、紫外-可见光吸收光谱、岩石化学全分析对北红玛瑙及黄色、白色对比样品的物相组成、化学组成和光谱学特征进行了测试分析。结果显示,北红玛瑙的主要矿物组成为α-石英,次要矿物组成为斜硅石和针铁矿,另外还含有极少量的赤铁矿。北红玛瑙的红色、黄色与针铁矿和极少量的赤铁矿有关,与南红玛瑙主要为赤铁矿致色明显不同。显微观察时,针铁矿、赤铁矿以橙红色点状和浸染状两种形式存在,其中点状分布的针铁矿、赤铁矿大小约10μm,但不具备明显的单晶晶体形状,推测是由亚微米级大小的针铁矿及极少量的赤铁矿聚集形成的集合体;浸染状分布的橙红色针铁矿、赤铁矿不可见矿物颗粒大小,推测其颗粒大小和点状分布的致色矿物类似,均为亚微米级大小,但与点状分布的致色矿物不同的是,并未聚集形成显微镜下可见的点状集合体。整体上外观呈红色的北红玛瑙中针铁矿、赤铁矿的含量多于黄色对比样品中的致色矿物含量,致色矿物的含量会直接影响北红玛瑙的颜色色调。紫外-可见光吸收光谱中,针铁矿中Fe~(3+)的~6A_1→~4E,~6A_1→~4E~4A_1, 2(~6A_1)→2(~4T_1)(4G),~6A_1→~4T_2(4G)和极少量赤铁矿中Fe~(3+)的~6A_1→~4E~4A_1,~6A_1→~4T_2吸收带与针铁矿、赤铁矿中O~(2-)和Fe~(3+)之间的电荷转移共同作用,形成了北红玛瑙带黄色调的红色外观。紫外-可见光吸收光谱的一阶导数谱中,可见光范围内北红玛瑙的一阶导数谱极小值的位置为555和556 nm,黄色对比样品为530 nm,淡黄色对比样品为502 nm,随着玛瑙红色调的逐渐减少,可见光范围内一阶导数谱的极小值位置也逐渐减小,可以据此衡量红色～黄色玛瑙的色调深浅,这也对石英质玉石的品种鉴定及颜色分级具有重要参考意义。     

唐代苏同家族墓天王俑彩绘的光谱分析

天王俑是中原地区的达官贵人墓葬的镇墓俑,是唐墓葬冥器中重要的一种神煞俑。为探究天王俑彩绘颜料的组成元素以及彩绘工艺,使用X射线荧光光谱分析了陕西省咸阳市渭城区苏同家族墓KTJ-2019-019M2、 KTJ-2019-019M3坑出土的天王俑彩绘区域的元素组成。分析结果表明陶俑表面金色贴片主要为金箔(Au);红色颜料的组成元素则是Hg、 S以及少量的Pb、 P;蓝色颜料和绿色颜料的组成元素均为Cu,白色颜料的组成元素为P、 S、 Pb。使用拉曼光谱对彩绘颜料层的鉴定物相,使用拉曼光谱分析技术对彩绘层分析结果确定了红色颜料的主要组成物相为朱砂(HgS)和铅丹(Pb₃O₄)的混合颜料;蓝色颜料的主要组成物相为石青;绿色颜料的主要组成物相为石绿;白色颜料的组成物相可能为铅白。进一步使用XRF面扫描技术分析了天王俑的彩绘工艺,解析金、红、蓝、绿色区域的组成元素位置,发现陶块样品中的M₂-1金色陶块、 M₃-1白色陶块、 M₃-2红色陶块、 M₃-3蓝色陶块、 M<...     

中国古代艺术品常用矿物颜料的拉曼光谱(二)

在本刊前一篇文章中,我们讨论了拉曼光谱在艺术品分析和考古学应用方面的实验技术并报道了一些中国古代艺术品中经常使用的红色、黄色和白色矿物颜料的拉曼光谱。本文延续前文工作,测量了一些中国古代艺术品中常用的蓝色、绿色和黑色矿物颜料的拉曼光谱,介绍了相关的背景知识,并对这些光谱进行了解析,我们相信,一套比较全面的颜料拉曼光谱数据,对于拉曼光谱技术在考古学和艺术品分析方面的应用将会起到重要的参考价值。     

和田玉糖玉的致色机理研究

采用X射线粉晶衍射(XRD)、激光剥蚀等离子体质谱(ICP-MS)、拉曼光谱(RAMAN)和高分辨率透射电子显微镜(HRTEM)对和田玉糖玉的致色机理进行研究。结果显示,糖玉的主要矿物成分为透闪石,化学成分中的Fe含量和糖玉黄褐色色调有正相关关系,颜色越深Fe的含量越高,Fe在糖玉中以独立铁质矿物的赋存形式分布于透闪石的颗粒间、微裂隙中。铁质矿物由于其含量低、粒度细小,本文设计实验对其进行富集后进行测试。将铁质矿物富集后的样品进行透射电镜测试,铁质矿物呈云状集合体,电子花样衍射图显示其矿物为针铁矿。因此,针铁矿分布于透闪石颗粒间、微裂隙中致使糖玉呈现黄褐色。拉曼光谱显示糖玉表面少见红褐色矿物颗粒为金红石,由于金红石含量少,仅对颜色成因有部分贡献。     

成都武侯祠彩绘泥塑颜料的拉曼光谱分析

利用显微镜、激光拉曼光谱和扫描电子显微镜对成都武侯祠彩绘泥塑颜料进行了分析。结果表明:颜料有红色朱砂、赭石、铅丹,蓝色颜料为酞菁蓝和群青,绿色颜料是酞菁绿,黄色颜料为密陀僧,白色颜料钛白,黑色颜料是炭黑。研究发现合成有机颜料酞菁蓝和酞菁绿作为彩绘颜料使用,颜料分析结果为文物的保护修复和修复材料选择提供了科学数据。     

湖北竹山黄绿色-绿色绿松石伴生矿的谱学研究

近年来绿松石市场上出现了俗称"绿松石伴生矿"的天然矿物,颜色丰富,有紫色、白色、褐黄色、黄绿色、绿色等,其中黄绿色-绿色系绿松石伴生矿相对其他颜色绿松石伴生矿与绿松石外观较为相似,鉴别难度较大。为探究其鉴别特征,选取两块来自湖北省竹山县市场的黄绿色-绿色系伴生矿原石(样品E和F),对其进行基础宝石学、电子探针、 X射线粉晶衍射、显微激光拉曼光谱及紫外-可见分光光谱测试。测试结果显示该色系绿松石伴生矿的主要矿物成分为氟磷灰石(Ca_5(PO_4)_3F)、白云母(KAl_2(AlSi_3O_(10))(OH)_2)等。电子探针背散射照片显示样品为结晶颗粒细小的多物相混杂的混合物,化学成分定量测试结果表明深色物相为含铝的硅酸盐,而浅色物相为含钙的磷酸盐,此外两样品含有2.27～6.22 Wt%的CuO和2.43～4.99 Wt%的FeO;有损测试X射线粉晶衍射可准确测试样品主要矿物为氟磷灰石和白云母及少量绿松石;样品的氟磷灰石和白云母典型拉曼谱峰可作为有效鉴别依据,其中964 cm~(-1)附近氟磷灰石的典型拉曼谱峰以及203, 432, 709和3 626 cm~(-1)附近白云母的典型拉曼谱峰可将其与绿松石有效鉴别。紫外-可见吸收光谱测试结果表明样品的颜色成因与绿松石相似,主要是由Cu~(2+)和Fe~(3+)的电子跃迁所致。通过对该色系样品相对较系统的谱学测试,笔者认为拉曼光谱是鉴别绿松石伴生矿中不同矿物相的无损、快速、有效的方法,氟磷灰石和白云母典型拉曼谱峰可将其与绿松石有效区分。     

我国古代不同时期铅釉陶表面腐蚀物的分析研究

利用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、能量色散X射线荧光(EDXRF)、拉曼光谱(RS)等方法,对3块不同时代、不同埋藏环境铅釉陶表面腐蚀物的化学组成、物相结构进行了分析测试。结果表明,汉代釉陶表面的腐蚀物主要为白铅矿;宋代绿釉陶表面的腐蚀物主要为磷酸铅钙,锈蚀物中黄色是缘自其中一定量氧化铁的存在;唐三彩表面的腐蚀物中有磷酸铅钙与白铅矿两种物相结构的存在,锈蚀物表面的棕褐色是少量氧化铁与炭黑共同致色的结果。     

彩绘瓷片的拉曼光谱分析

本文利用显微共焦拉曼光谱仪和傅里叶变换拉曼光谱仪,结合微聚焦X射线荧光光谱仪,对广州发掘出土的清代中期的彩绘瓷片进行了测试,分析了彩绘瓷上红色、蓝色、黄色、绿色、粉红色和黑色颜料以及彩绘上的腐蚀物。研究表明,红色颜料的着色剂为赤铁矿(α-Fe_2O_3),其颜色亮度的变化与其晶体晶格结构的变化有关,黄色颜料并不属于锑黄,而是铅锡黄Ⅱ型,样品5蓝色颜料是钴蓝(CoO·Al_2O_3),黑色颜料是氧化锰(MnO),彩绘的腐蚀物主要为碳酸铅、磷酸铅、炭黑等。其结果,对彩绘瓷器的保存与保护提供了一定的依据。     

Identification of Pigments in Colored Layers of a Painting by Raman Spectroscopy

Using the method of Raman spectroscopy the pigment composition is investigated of, and the brushwork technique used in, the original layer of a 19th century painting is established. It is an overdoor worked, presumably, by Antoine Jean-Etienne Faivre. It is established that the artist used the following pigments: cinnabar and dyes on the basis of goethite and hematite (for red, yellow–orange, and brown shades), ultramarine and Prussian blue (for blue shades), and Emerald green and a mixture of blue and yellow shades (to obtain a green color). It is determined that white lead was used a primer.     

1945年银行票据样品印刷颜料无损鉴定

利用超景深三维视频显微镜、激光显微共聚焦拉曼光谱仪、扫描电镜‐能谱仪等,对一张1945年银行票据样品的印刷颜料进行测试分析,结果显示该票据印刷使用了颜料红146和颜料红53∶1等有机颜料,以及朱砂、碳黑、普鲁士蓝、副雄黄和χ构型雄黄等无机颜料,并推测棕黑色手写字迹由蓝黑墨水老化褪色形成。票据中各处色块多为单一呈色,有两处印章由朱砂与不同晶型的雄黄共同呈色,并且首次发现χ构型雄黄和副雄黄作为印刷颜料使用。研究表明,上述三项技术的联用可以成功地对纸质品上的有机及无机颜料进行无损鉴定,在纸质文物研究中具有广阔的应用前景。     

西藏拉萨大昭寺转经廊壁画颜料的拉曼光谱分析

利用显微激光拉曼光谱仪对大昭寺转经廊壁画颜料进行了分析。结果表明,壁画使用的红、黄、蓝、绿和白色颜料有朱砂、铅丹、甲苯胺红、雌黄、铅铬黄、铁黄、石青、群青、石绿、水胆矾、巴黎绿、菱镁矿、立德粉和方解石。首次发现壁画中使用了合成有机颜料甲苯胺红。检测分析结果提供了准确可靠的资料,有助于清晰认识不同时期壁画绘制和修复所使用颜料成分。     

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.     

Synthetic organic pigments in contemporary Balinese painting: a Raman microscopy study

The colour palette from two 20th century and one 21st century Indonesian paintings from the island of Bali was determined by Raman microscopy. There is very little information concerning the artistic techniques from this region of the world and the influences in materials introduced by western artists. The most interesting finding of our study was the increasing substitution of natural pigments by modern synthetic organic pigments. The findings were also compared with samples of representative pigments commonly used by Bali artists, donated by a renowned Balinese painter. Raman microscopy, combined with Fourier transform infrared spectroscopy, high‐performance liquid chromatography and μ‐EDXRF, was able to separate the different components on several colours, and to identify both synthetic organic pigments and inorganic components. Three azo pigments from the diarylide subclass, PY 83, PY 55 and PO 16, were identified on the yellow, brown, red and orange colours. A copper phthalocyanine blue PB 15:x and a basic dye BB 26 were responsible for the blue colours, the former admixed with ultramarine blue. Goethite was sometimes introduced to create the green colour. Two other basic dyes, BY2 and PG 4, were the main chromophores of the yellow and green samples of local pigments. The inorganic pigments comprised bone white, bone black, carbon‐based black pigment, haematite, goethite, vermilion, ultramarine blue and anatase. Finally, the ground layer of all the paintings was identified as rice starch, with a double function of a white pigment. Copyright © 2012 John Wiley & Sons, Ltd.     

A combined analytical approach applied to Medieval wall paintings from Puglia (Italy): The study of painting techniques and its conservation state

A combined analytical approach has been applied to the wall paintings, dated from 10th to 14th centuries, of the Santi Stefani crypt at Vaste (Lecce, Southern Italy). These paintings are a precious testimony of Medieval art in Southern Italy. However, the church shows problems of damp as well as clear evidences of flora, fungi and mold presence, and there is little knowledge of the pictorial methodologies used. Raman spectroscopy allowed to determine the palette and to reconstruct the worksite and the chronological sequence of the various paint layers. Kaolinite, calcite, carbon black, hematite, massicot, goethite, indigo and azurite were identified as pigments along with synthetic pigments, like phthalocyanine blue and chrome yellow. Attenuated total reflectance‐Fourier transform infrared spectroscopy suggested the presence of egg as a binder in some pictorial layers. The conservation state of the crypt is poor, and detachments of pigmented layers are frequent because of the presence of subflorescence and efflorescence: nitrate, sulfate and chloride salts have been identified spectroscopically and quantified by ion chromatography. The extensive use of kaolinite in Santi Stefani, actually not uncommon in Medieval art, is observed for the first time in a crypt of Puglia: its use to stabilize some pigments and to improve their adhesion on substrate is proposed. Copyright © 2015 John Wiley & Sons, Ltd.     

Testing of Raman spectroscopy as a non‐invasive tool for the investigation of glass‐protected pastels

Five French pastels and a sanguine drawing dating from the 17th to the 20th century were studied by Raman spectroscopy. Different operative conditions were used: the pastels were investigated through their protective glass, and the results obtained were compared with those obtained after removing the glass and after sampling a micrometric particle of pigment. Different parameters (wavelengths, powers of excitation and objectives) were tested in order to assess the optimal procedure of analysis for this fragile work of art. The results obtained for black (carbons), yellow (chrome/cobalt yellow), red (lead oxide, vermillion, orpiment), brown (red lead and chrome yellow), blue (Prussian blue, lapis lazuli/ultramarine), green (mixture of above blue and yellow pigments) and white (calcite, lead white, anatase) pigments are presented and the consistency of the pigments' period of use with the dating proposed for each pastel is evaluated. In one of the pastels, the blackening of the carnation colour made of an unstable mixture of lead white, red lead and vermilion was studied. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

Raman analysis assessed by Fourier‐Transformed infrared and X‐ray fluorescence spectroscopies: a multi‐analytical approach of ancient chromolithographs from the 19th century

A set of chromolithographs from the 19th century were analysed to identify the fillers and pigments used for their elaboration. Because of the delicacy of the chromolithographs, the research involved the use of Raman, Fourier‐transform infrared and energy dispersive X‐ray fluorescence spectroscopies for a complete characterization of the works on paper without removing any microsamples. Despite the high fluorescence of the samples when analyzed by Raman spectroscopy, in this paper, we demonstrated that ink spectra can be successfully enhanced by subtracting the spectra of the supporting background paper. The results of the study showed that, apparently, the lithographer used a limited range of common inorganic pigments from the 19th century (carbon black, chrome yellow, Prussian blue, red ochre, red lead and vermilion) together with organic pigments (indigo blue, gamboge and a red organic pigment). The study also found that despite the fact that during the 19th and early 20th century the use of mixtures of several pigments was a common practice, unusual admixtures were used for the preparation of some colours of the studied chromolithographs. Copyright © 2011 John Wiley & Sons, Ltd.