Portable XRF study of pigments applied in Juan Hispalense’s 15th century panel painting

Several medieval paintings and polychrome sculptures have been analysed in the frame of a collaboration between the Fine Arts Museum of Seville and the National Centre of Accelerators, dedicated to a non‐destructive study of artworks that belong to the wide museum’s collection. Among the oldest artworks in the collection is the panel painting Archangel St. Michael attributed to Juan Hispalense, one of the first painters in the 15th‐century Seville known by name. The panel was analysed by a portable X‐ray fluorescence (XRF) to get more information about the pigments applied and to identify possible later interventions. The results showed that the pigments were those commonly used in that period. Lead white was found in the preparation of the painting and in colour layers. For yellow colour, yellow ochre was used, while for the red one, the painter usually mixed red earth and vermillion. Blue pigment is azurite, while the copper‐based green one could not be determined more specifically by XRF. Brown colour is made with yellow ochre and organic black or, in some cases, umbra. Black pigment is probably bone or ivory black. Many decorative parts of the panel are gilded, which were confirmed by Au peaks. Later interventions were carried out on the base of Ti–Zn white mixed with earth pigments, while for green areas such as Archangel's wings also chrome green was applied. The research is part of a larger study which is still going on, whose aim is to gain more knowledge about the 15th‐ and 16th‐century Spanish painting and polychromy. Copyright © 2011 John Wiley & Sons, Ltd.     

Microanalysis of clay‐based pigments in painted artworks by the means of Raman spectroscopy

FT Raman spectroscopy and micro‐Raman spectroscopy with lasers of three different wavelengths (1064 nm, 785 nm and 532 nm) were used for analysis of reference samples of natural clay pigments including white clay minerals (kaolinite, illite, montmorillonite), green earths (glauconite and celadonite) and red earths (natural mixtures of white clay minerals with hematite). In addition, eight micro‐samples obtained from historical paintings containing clay pigments in ground and colour layers have been examined. Powder X‐ray diffraction and micro‐diffraction were used as supplementary methods. It was found that laser operating at 1064 nm provided the best quality Raman spectra for distinguishing different white clay minerals, but the spectra of green and red earths were affected by strong fluorescence caused by the presence of iron. Green earth minerals could be easily distinguished by 532 or 785 nm excitation lasers, even in small concentrations in the paint layers. On the other hand, when anatase (TiO₂) or iron oxides (such as hematite) were present as admixtures (both are quite common, particularly in red earths), the collection of characteristic spectra of clay minerals which form the main component of the layer was hindered or even prevented. Another complicating factor was the fluorescence produced by organic binders when analysing the micro‐samples of artworks. In those cases, it is always necessary to use powder X‐ray micro‐diffraction to avoid misleading interpretations of the pigment's composition. Copyright © 2013 John Wiley & Sons, Ltd.     

故宫奉先殿清初彩画颜料成分分析

故宫奉先殿是明清两代皇帝祭祀祖先的家庙,地位仅次于太庙。奉先殿始建于明成祖时期,现存建筑主要建于康熙时期,其上保留了为数不多的清初彩画,是研究清初彩画的珍贵实物。利用显微观察、扫描电子显微镜能谱和激光拉曼光谱分析,对取自奉先殿的彩画颜料进行分析鉴定。结果表明,奉先殿彩画中部分红色和蓝色颜料层存在分层现象,表层颜色鲜艳明亮,中层和下层颜色偏浅,每层所用颜料配方不同。红色颜料有朱砂、铅丹和铁红,绿色颜料均为氯铜矿,蓝色颜料均为石青,用铅白打底。浅色颜料由主显色矿物颜料加入以铅白为主的白色颜料混合调制而成。其中浅红色由铅丹与铅白调和而成,浅绿色由氯铜矿与铅白调和而成。浅蓝色颜料中未发现铅白,但含有大量Al元素和Si元素,推测含有高岭土。浅蓝色颜料有可能是由石青与高岭土调制而成。奉先殿彩画中未发现清晚彩画常用的合成群青、巴黎绿等颜料,反映出奉先殿彩画的绘制年代很有可能就是档案记载的康熙年间,之后未有大修。高岭土作为白色颜料调配浅色颜料在彩画制作中比较少见,奉先殿彩画中高岭土的发现丰富了清代早期彩画颜料制作的资料,具有一定的学术意义。     

Application of field portable EDXRF spectrometry to analysis of pigments of Levantine rock art

The results of the analyses of elemental composition of red and black pigments of Levantine rock art from La Saltadora rock shelters (Valltorta gorge, Castellón, Spain) are presented in this paper. Nondestructive analyses were carried out using a portable energy dispersive X‐ray fluorescence (EDXRF) spectrometer developed for in situ analysis. The results revealed the strong presence of calcium in all the analyzed locations due to the contribution of the underlying calcareous bedrock and the overlying crust. Iron is the main element detected in red pigments and manganese in black pigments. Iron and calcium ratios have been found indicative of the degree of preservation of the pictorial layer. Trace elements detected in the pigment composition confirm the use of different raw materials. Therefore, this work illustrates the potential of the portable EDXRF spectrometers for in situ analysis of rock art paintings. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

The first Raman spectroscopic study of San rock art in the Ukhahlamba Drakensberg Park,South Africa

San rock art sites are found throughout southern Africa; unfortunately this unique heritage is rapidly being lost through natural weathering processes, which have been the focus of various studies conducted in the uKhahlamba Drakensberg Park since 1992. It has recently been shown that the ability of Raman spectroscopy to identify salts on rock faces on a micro, as well as nano scale, can make a contribution to these projects. In order to test the feasibility of undertaking on‐site analyses, a small rock fragment with red and white pigments still attached, which had weathered off the rock face, was analysed with Raman spectroscopy under laboratory conditions, using a Dilor XY Raman instrument and a DeltaNu Inspector Raman portable instrument. A small sample of black pigment (<1 mm²), collected from a badly deteriorated painting and a few relevant samples collected on site, were analysed as well. It was possible to identify most of the inorganic pigments and minerals detected with previous XRD and EDX measurements including whewellite and weddellite coatings, which could be a tool for carbon dating purposes. Two carotenoid pigments were detected for the first time in San rock art pigments. Animal fat was also observed for the first time on both red and white pigments, on the rock face adjacent to the paintings and in highest concentrations on the back of the rock fragment. The spectra quality makes successful on‐site measurements a good prospect. Copyright © 2008 John Wiley & Sons, Ltd.     

Pigment study by Raman microscopy of 23 paintings by the Portuguese artist Henrique Pousão (1859–1884)

Twenty‐three paintings by Henrique Pousão—a 19th century Portuguese painter—belonging to the collection of Museu Nacional Soares dos Reis, Porto, Portugal, were analysed by Raman microscopy. The fine focus of a 100× objective allowed the visualisation and individual identification of small grains. As a result, thirty‐seven compounds, namely, anatase, barium white, basic lead sulfate, brochantite, cadmium red, cadmium yellow, calcium carbonate, carbon‐based black, celadonite, chrome green, chrome orange, chrome yellow, cobalt blue, cochineal lake, copper sulfide, emerald green, iron(III) oxyhydroxide, iron(III) oxide, kaolinite, lead antimonate yellow, lead carbonate, lead white, lead sulfate, madder lake, malachite, Prussian blue, quartz, realgar/pararealgar, red lead, rutile, Scheele's green, strontium yellow, ultramarine blue, vermilion, viridian, zinc white and zinc yellow, were identified. Not all these compounds are pigments; some are extenders, others trace components and others probably products of reactions between pigments. Special attention was given to the Raman characterisation of celadonite, chrome orange, basic lead sulfate and lead antimonate yellow. Complementary techniques were used to confirm the identities of certain pigments and to characterise reference samples. Pousão, whose work has not previously been studied spectroscopically, was found to have used a remarkably wide range of pigments over his painting periods, without showing significant preference for any particular set of pigments. Copyright © 2007 John Wiley & Sons, Ltd.     

Joaquin Sorolla's pigment characterisation of the paintings ‘Vision of Spain’ by means of EDXRF portable system

In this work, portable energy dispersive X‐ray fluorescence (EDXRF) spectrometry was employed to the characterisation of the palette used by the Spanish artist Joaquín Sorolla (1863–1923) in the paintings ‘Vision of Spain’, a set of 14 oils on canvas painted by Sorolla between 1911 and 1919 by order of Mr Archer Huntington to decorate the library of the Hispanic Society of America (HSA) in New York. The analyses, sponsored by BANCAJA and provided by the HSA, were carried out in situ, prior to the cleaning and restoration process, while the paintings hanging on the walls of the library of the HSA. The results revealed that the paintings were made over different priming layers containing, respectively, lead white, zinc and barium compounds, lead white mixed with zinc white or lead white mixed with zinc and barium compounds. The EDXRF analyses of coloured zones identified up to 29 inorganic pigments and, in some cases, the probable use of organic pigments. Sorolla used traditional pigments as earth pigments, lead white, vermillion, etc., and modern pigments as cadmium yellow, zinc white, cobalt‐based blue, chromium‐based green, manganese‐based violet, etc. These results provide valuable information about the Sorolla's palette during the last stage of his life. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman identification of green and blue pigments in Etruscan polychromes on architectural terracotta panels

Micro‐Raman measurements were performed on two Etruscan polychromes on architectural terracotta panels now on display at the Villa Giulia Etruscan Museum in Rome. These painted panels, dated from 530 to 520 B .C ., are of particular interest because of the unusual presence of green and blue layers. Etruscans in the Archaic Age indeed mainly used white, red, and black colours for painted terracotta panels. Raman spectra allowed the analytical identification of green (malachite) and blue (Egyptian blue) pigments employed by Etruscans for this kind of artistic production. This finding provides evidence for a larger use of malachite and Egyptian blue, previously well documented only in Etruscan wall paintings. The use of different pigments to obtain different colour tones has been also observed. Egyptian blue is indeed mixed with malachite to obtain different green tones, and a black pigment seems to have been applied over the Egyptian blue layer to obtain a dark blue tone. Copyright © 2006 John Wiley & Sons, Ltd.     

青海热贡地区传统建筑彩画颜料光谱特征分析研究

青海省热贡地区是安多藏区藏式建筑彩画艺术的重要产地,作为热贡艺术的重要组成部分影响甚广。热贡地方建筑彩画不仅是附着建筑栋梁之上的艺术瑰宝,更是一项延续至今的传统技艺,至今仍有大批传统匠人画师从事相关行业。热贡地方建筑彩画有独立的用色方法和颜料制作工艺,对其所用传统颜料进行科学检测是系统研究该地区建筑彩画的基础性工作,在进一步研究热贡地区建筑彩画的制作工艺和艺术特色,传承地方建筑彩画技艺和完善保护政策等方面具有积极意义。通过对同仁市隆务寺夏日仓行宫火供殿所用当地传统建筑彩画颜料的采样,运用X射线荧光光谱、X射线衍射分析、激光显微拉曼光谱分析等多种实验分析方法,对颜料样品进行分析,测定其主要显色物质和成分占比。结果表明,热贡地方建筑彩画所用颜料多为无机颜料;蓝色颜料主要是人造群青;绿色颜料的主要矿物组成为绿土,显色物质为蒙脱石,存在将植物色染料加入当地所产的富镁蒙脱石中混合使用的可能性;红色颜料的主要矿物组成为铁红（赭石类红土）,通过焙烧富铁矿土来人工合成,材料来自于当地吾屯村所产红色赭石类粘土;黄色颜料主要矿物组成为密陀僧、硫磺及其他植物色染料制备而成;黑色颜料为碳黑,符合木炭黑的性状特征;白色颜料主要为生石灰及氧化镁粉,并在其他颜料中广泛使用石灰及氧化镁粉作为调色颜料;推测部分样品中含有包金土及植物色素染料、其他人工合成颜料的可能性。整体来看,热贡地区建筑彩画所用颜料成本价格较低,制取难度不大,来源大多是当地常见的矿土料和动植物染料,传统的制料工艺较简单,颜料多呈现为组分复杂的混合物状态;密陀僧、包金土和群青等颜料多来自于内地及国外,颜料人工合成的历史较早,反映出热贡地区建筑彩画在颜料使用上不仅使用本土材料制备,也广泛使用外来颜料的历史传统,为进一步研究热贡地区建筑彩画领域内汉、藏等多民族文化交往、交流、交融历史提供了良好实证材料。     

Analysis of paintings from the nineteenth century Brazilian painter Rodolfo Amoedo using EDXRF portable system

The pigments used in four of the most representative paintings of the Brazilian artist Rodolfo Amoedo were characterized by means of the EDXRF technique. The analyzed paintings were ‘The Last Tamoyo’ (1883), ‘Study of a Woman’ (1884), ‘Bust of Mrs. Amoedo’ (1892) and ‘Bad News’ (1895). EDXRF measurements were carried out with a portable system developed by the Nuclear Instrumentation Laboratory, consisting of an x‐ray tube Oxford TF3005 with a W anode, operating at 25 kV and 100 µA, and a Si‐PIN XR‐100CR detector from Amptek. Several spectra were obtained in each color and distinct hue of the paint layer, with an acquisition time of 300 s and a beam collimation of 2 mm. Some pigments used by the artist were zinc white, lead white, ochre, umber, vermilion, Prussian blue, cobalt blue, cadmium yellow, black iron oxide and manganese violet. In the painting ‘The Last Tamoyo’, titanium white was identified in some alteration areas, which were restored during the twentieth century. These results—together with computed radiography analyses—will be used to create a database about the nineteenth‐century collection of the National Museum of Fine Arts, in order to assist restorers, conservators, art students and researchers in the field of archeometry. Copyright © 2009 John Wiley & Sons, Ltd.     

On‐and off‐site Raman study of rock‐shelter paintings at world‐heritage site of Bhimbetka

Rock‐shelter paintings of Bhimbetka world‐heritage site near Bhopal, India have been investigated using a portable Raman spectrometer. These paintings in the rock shelters belong to periods starting from pre‐historic to the 19th century AD (Gond period). In addition, tiny fragments of pigments (100–200 µm in size) extracted from some of the artworks were also studied in laboratory using a micro‐Raman spectrometer and analyzed using energy‐dispersive X‐ray analysis for elemental composition. Based on the Raman spectra and the elemental analysis mineral‐based pigments such as calcite, gypsum, hematite, whewellite, and goethite could be identified. A comparison of the spectra recorded on‐site using a light‐weight portable spectrometer with those using laboratory equipment is also made and discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Spectroscopic investigation of modern pigments on purportedly medieval miniatures by the ‘Spanish Forger’

Five miniatures by the so‐called ‘Spanish Forger’ were acquired by the Victoria and Albert Museum in 2008. Believed to be authentic medieval miniatures until the mid‐twentieth century, they are now considered to have been painted around the end of the nineteenth and the beginning of the twentieth century. To investigate this attribution and to gather detailed knowledge about the materials used by the artist, a comprehensive pigment analysis by Raman microscopy and X‐ray fluorescence was carried out. Although traditional materials such as vermilion, carbon black, red lead, lead white and indigo were identified, many others (chrome yellow, Scheele's green, emerald green and ultramarine blue) are modern and synthetic pigments, a result which provides a firm scientific basis for stating that the miniatures are forgeries. Copyright © 2009 John Wiley & Sons, Ltd.     

Complementary use of the Raman and XRF techniques for non-destructive analysis of historical paint layers

The portable XRF spectrometer has been applied in situ for the non-destructive elemental mapping of the pigment components of the XV c. mural painting and frescos of the Little Christopher chamber in the Main Town Hall of Gdańsk, Poland. For a sufficiently large data collection the principal component analysis (PCA) was applied in order to associate the most intense lines of the elements Ca, Cu, Fe, Pb, and Hg in the XRF spectra with the palette of colors: white, brown, green, blue, red, yellow, and black observed in the painting. This allowed to limit the number of extractions of the micro-samples for the complementary Raman measurements thus assuring the practically non-destructive character of the entire analysis. The reliable identification of the pigment compositions was based on coincidence of the XRF, PCA and the Raman results which confirmed the presence of the chalk, malachite, azurite, red lead, mars red, mars yellow and candle black in the historical paints, except of the carbon-based black pigment being out of the XRF detection range. Different hues of the green paint were specified and the variety of the red and brown ones was ascribed to compositions of the Pb- and Fe-based red pigments (Fe₂O₃ and Pb₃O₄) with addition of the vermilion (HgS) and carbon black, in agreement with literature. The traces of elements: Ba and Sr, Sb and Mo, and also Cd, were ascribed to the impurities of Ca, those of some ochre pigments, and to the soluble Cd salts, respectively.     

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.     

构成白光LED的单色光对中国淡彩绘画色彩的影响

为得到构成白光LED光谱的主要单色光对中国传统淡彩绘画色彩的影响规律,确定不同波长单色光对绘画色彩的量化损伤程度,进而根据研究结果得到最低损伤白光LED的光谱功率分布,以构成白光LED光谱的4种主要单色光作为实验光源,分组照射中国传统淡彩绘画模型试件。在每个照射周期后,对试件的色彩参数进行检测,根据检测数据绘制主波长、兴奋纯度、亮度3个参数随总曝光量积累的衰变曲线,基于曲线分析得到各种淡彩绘画颜料在光照下的色彩衰变规律,并根据实验数据计算得到4种单色光对绘画色彩主波长的影响关系为482 nm∶510 nm∶583 nm∶650 nm=8 147∶9 067∶9 772∶9 121;对兴奋纯度的影响关系为482 nm∶510 nm∶583 nm∶650 nm=89 446∶85 250∶76 895∶69 229;对亮度的影响关系为482 nm∶510 nm∶583 nm∶650 nm=137∶238∶190∶177。     

Limewashing paintings in Alentejo urban heritage: pigment characterization and differentiation by WDXRF and XRD

Pigments used in traditional limewashing paintings in Alentejo urban Heritage are inorganic materials and can be grouped into four categories: a) reds – red ochre (from terras rossas, red schists and iron ore deposits weathering), almagres, terra roxa (natural processed red ochres) and synthetic red iron oxides; b) yellows – yellow ochre (from schists and iron ore deposits), processed natural ochres, yellow iron synthetic oxides, c) blacks – black earths and black iron synthetic oxides and d) blues – artificial ultramarine. The present work proposes to characterize natural, natural processed and synthetic pigments by comparing phase and elemental compositions. The results reveal differences in Fe, Si, K and Al total content according to their origin and fabrication process and reveal intentional addition of white charges like carbonates. Elements like Zr, Ti, Cr, Mn, Ca and Zn are present in all categories. Under optical microscopy, some samples of processed natural pigments do not exhibit optical activity, thus revealing mixtures with synthetic pigments, while natural pigments present a strong birefringence colorless due to optically active minerals. PACS 78.70.En; 07.60.Pb; 61.10.Nz; 81.70.-q; 91.60.-x     

Study of two large-dimension Murillo's paintings by means of macro X-ray fluorescence imaging,point X-ray fluorescence analysis,and stratigraphic studies

During the recent restoration of two large-dimension paintings by Murillo, entitled “Miracle of the loaves and fishes” and “Moses and the water from the rock of Horeb,” several studies about the materials employed for their execution were carried out. Macro X-ray fluorescence scanning technique was performed on both works complemented by point X-ray fluorescence and stratigraphic analyses, in order to characterize the different components of the paintings (i.e., ground layer, pigments, and binders). The results allowed us to better elucidate Murillo painting technique and his creative process. Ground layer was prepared in the usual fashion of the artist, using earths, calcium carbonate, iron oxide pigments, and white lead. The polichromy is composed of lead white mixed with various pigments, depending on the colour tone to be obtained in the pictorial composition: Red and yellow ochres, vermilion, azurite, smalt, and lead-tin yellow were the main pigments identified during our study. Finally, the presence of previous conservation treatments was evidenced by detecting pigments (zinc white, Prussian blue, etc.) not coeval with the artist palette.     

光导纤维反射光谱技术在彩绘文物颜料无损分析鉴定中的应用

文物颜料成分分析鉴定是文物材质分析和文物保护工作的重要内容。利用自行研制的光导纤维反射光谱仪对唐代彩绘陶器和壁画上的颜料成分进行了无损分析鉴定,通过比较彩绘文物颜料和标准颜料的反射光谱曲线的形状以及特征峰或一阶导数峰来完成颜料的鉴定工作。光导纤维反射光谱法鉴定出西安市唐代彩绘文物1#样品墓葬壁画上的深红色颜料是纯度较高的土红;2#样品陶器残片上的绿色颜料为石绿;3#样品陶缸残片上的橙红色和朱红色颜料分别是由大量铅丹和微量土红及大量朱砂和微量土红的混合物所组成。采用X射线荧光分析法进行验证,实验结果表明光导纤维反射光谱技术鉴定彩绘文物颜料成分的结果是准确、可靠的,提供了一种文物颜料无损分析的简捷方法。