Assessment of Raman microscopy coupled with principal component analysis to examine egg yolk–pigment interaction based on the protein C?H stretching region (3100–2800 cm−1)

This work seeks to identify the slight changes in the characteristic C H stretching region (3100–2800 cm⁻¹) of a protein‐based binder and fatty acid esters from egg yolk, which may occur in complex paint samples due to the presence of particular pigments. To date, this protein region—where historic pigments do not show characteristic Raman bands—has not been used to identify possible interactions between painting materials, in spite of its potential due to the mentioned feature. This study is based on the investigation of pure egg yolk model samples and tempera model samples prepared by mixing this binder with some historic pigments (cinnabar, raw Sienna, lead white, gypsum, calcite, azurite, lapis lazuli and smalt) as binary samples. All samples were analyzed in this region by Raman microscopy (RM) coupled with principal component analysis (PCA) for three color groups (red, white and blue) separately. The results show relevant spectral changes in the C H stretching region of amino acids and polyunsaturated fatty acids esters of the egg yolk binder, particularly in the azurite, lead white and gypsum‐based tempera samples. Lesser interactions were discerned in the tempera samples made with smalt, as well as shift in the region of polyunsaturated fatty acid esters of the egg yolk binder in the cinnabar and raw Sienna‐based tempera paintings. No interactions were recognized between the egg yolk and the pigments calcite and lapis lazuli. The effectiveness of applying RM combined with PCA for identifying interaction processes between binders and pigments is demonstrated. Copyright © 2011 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 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.     

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.     

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。     

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.     

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.     

New insights into the colour origin of archaeological Egyptian blue and green by XAFS at the Cu K‐edge

New results on the local chemical environment of Cu²⁺ in archaeological Egyptian blue and green and also modern Egyptian green were obtained by x‐ray absorption fine structure (XAFS) analysis. The information is essential for the understanding of the colouring mechanisms in both pigments. In a previous study, a clear physico‐chemical characterisation of Egyptian blue and green was achieved using a complementary analytical approach with ancient and modern synthesized pigments. Electron microscopy (SEM–EDX and TEM), x‐ray diffraction and micro‐Raman and UV–visible spectroscopy were used to gain information about the conditions of the ancient Egyptian fabrication processes and permitted the clear distinction of both pigments. However, the exact colouring mechanisms could not be elucidated by these methods. Different Cu‐bearing amorphous and crystalline phases were found in both pigments. These phases should be at the origin of the blue and turquoise colours. Using XAFS data at the Cu K‐edge, new insights into the origin of the colouring mechanisms of both pigments could be obtained from the precision of the Cu speciation. In Egyptian blue, Cu²⁺ is mainly allocated in a square‐planar site in a crystalline cuprorivaite phase, whereas in Egyptian green, Cu²⁺ is basically situated in a distorted octahedral site in an amorphous phase. Copyright © 2006 John Wiley & Sons, Ltd.     

Pigment identification and decoration analysis of a 5th century Chinese lacquer painting screen: a micro‐Raman and FTIR study

To investigate the pigments and decoration applied to a wood‐based lacquer painting screen from the tomb of Si‐ma Jin‐long, Shanxi Province, central China, made by Chinese craftsmen in the 5th century, a combination of micro‐Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), wavelength dispersive X‐ray fluorescence (WDXRF), and microscopic examination was used. The obtained results are as follows: (1) the black, yellow, and red colors are identified as carbon black, orpiment and realgar, and cinnabar, respectively, by using micro‐Raman spectroscopy. The FTIR result shows that the white pigment filled in the leaves is not lead white, as assumed in the literature, but gypsum. Whether lead white was used at other locations remains unanswered and requires more samples for further work; (2) the thickness of each discernable pigment layer, as observed under the microscope, is approximately equal and the differences among them are small, suggesting a superfine painting skill; besides, a noticeable smooth interface between wood and the red grounding substance indicates that a polishing process might have been applied before the painting; (3) the red background was proved to contain cinnabar, but further FTIR analyses found no evidence for the presence of Chinese wood oil; and (4) the most interesting finding, rarely reported before, is that white grains of different sizes are found in both pigment layers and the grounding substance, which are perhaps an intentional addition. Further, in situ XRF and Raman analyses indicate that they are sourced from hydroxyapatite, coming probably from the intentional addition of animal bone ash to the lacquer. But how such a process could be finished and what purpose it served have not yet been answered. Copyright © 2009 John Wiley & Sons, Ltd.     

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

Six French miniature portraits on ivory and paper dating back to the 18th to 19th centuries have been studied by Raman spectroscopy. The miniatures have been investigated through their protective glass cover using different operating conditions: various laser wavelengths (1064, 785 and 532 nm), spectrometers (fixed and mobile) and objectives (10× to 200×). The results obtained for black (carbon), grey (carbon + chalk), red (lead oxide, vermillion), blue (Prussian or phthalocyanine blue), green (emerald or Paris green) and white (lead white) pigments are presented. The consistency of the period of use of the pigments with the proposed dating for each artwork is evaluated. Attention is paid to the analysis of the ivory substrates (assigned to Asian elephant ivory) and to the protective glass. Copyright © 2011 John Wiley & Sons, Ltd.     

Pigments and enamelling/gilding technology of Mamluk mosque lamps and bottle

On‐site Raman spectroscopy is used to investigate four mosque lamps and a bottle dating back to the 13–14th centuries (Syria and/or Egypt, Mamluk period) from the Department of Islamic Art, Musée du Louvre, Paris. The pigments and the enamelled glass matrix have been identified in order to discuss their technology. A comparison is made with one masterpiece from the 19th century made by Brocard. The results obtained for blue (lapis lazuli or Co‐coloured glass), yellow (Naples yellows or zinc/chrome yellow), green (mixture of the aforementioned blue and yellow pigments or lead chromate for restorated foot) red (hematite), white (cassiterite or arsenate) and pink (hematite and cassiterite) pigments are presented. The consistency of the pigments period of use/technology with the datation proposed for each artefact is evaluated. For one lamp, the detection of quartz in some places of the hematite‐rich glassy layer supporting the gold is related to the search of a physical bonding with the artefact body. Carbon residues in such enamel are consistent with the use of an organic medium to place the enamel powder before the firing. Copyright © 2012 John Wiley & Sons, Ltd.     

FT‐Raman spectroscopy of pigments on a Hindu statue,Kali Walking on Siva

FT‐Raman spectroscopic analysis of eight pigmented specimens from an important Hindu statue group, Kali Walking on Siva, acquired in 1895 but of indeterminate age and now in the Horniman Museum, London, has revealed some interesting and unusual combinations of coloured pigments including cinnabar, minium, lapis lazuli and red ochre. Several specimens showed evidence of organic additives, which have been attributed to shellac resins commonly believed to have been used on this type of statuary. The Raman spectroscopic results confirm that the predominant black pigment on the Kali figure is lamp black or soot, in contrast to the SEM‐EDX data that suggests the origin of this pigment as from bone black or ivory black from the presence of phosphorus. An eclectic range of white pigments have been identified in this group including lead white, barytes, calcite and anhydrite; rutile and anatase found on one specimen on the jackal in this group have been ascribed to recent unrecorded restoration. Copyright © 2006 John Wiley & Sons, Ltd.     

“钟离君柏”墓出土彩绘陶器颜料的光谱分析

利用拉曼光谱结合X射线衍射物相检测方法,对安徽蚌埠双墩春秋中晚期“钟离君柏”墓出土彩绘陶器颜料的物相结构进行了分析测定。结果表明,陶器表面的红色、黄色和黑色颜料皆保存较好,未发生明显变化,分别是无机矿物朱砂(HgS)和针铁矿(α-FeO(OH))及炭黑。同时,拉曼光谱与X射线衍射分析的结果都显示红色颜料朱砂的组成物相单一,不含天然朱砂的伴生矿物石英,且其晶粒尺寸可能在纳米范围,应是由人工合成或经过古人的加工、纯化处理。针铁矿的发现表明春秋时期该矿物己被用作黄色颜料,这是目前己知的针铁矿作为黄颜料使用的最早的实例。     

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.     

A scientific approach to the characterization of the painting materials of Fra Mattia della Robbia polychrome terracotta altarpiece

During the last restoration (2008–2011) of the polychrome terracotta altarpiece called Coronation of Virgin between Saints Rocco, Sebastian, Peter martyr and Antonio abbot, located in the collegiate church of S. Maria Assunta in Montecassiano (Macerata, Italy), scientific investigations were carried out to acquire detailed information about the painting technique. The identification of materials allowed a correct restoration. The altarpiece is almost entirely realized by Marco della Robbia (Fra Mattia), dates back to the first half of the XVI century and represents an interesting example of painted terracotta produced by using two different techniques: glazed polychrome terracotta and the “cold painting” technique. The characterization of the samples’ material constituents was obtained by analysing the cross-sections and the fragments by different techniques (optical, SEM-EDS and ATR-FTIR microscopy as well as GC-MS), as the real nature of a component is often difficult to assess with one single technique. The optical microscope examination of paint cross-sections shows the presence of many layers, indicating the complexity of the paint stratigraphic morphologies. The original polychromy of della Robbia’s masterpiece is constituted of cinnabar, red lake, red lead, orpiment, red ochre, lead white, lead tin yellow, green earth and raw umber. Two different types of gilding technique have been distinguished. The first one presents a glue mordant, and the second one shows an oil mordant composed by a mixture of red lead, red ochre, cinnabar and orpiment. The GC-MS analysis allowed the characterisation of linseed oil and a mixture of animal glue and egg as binding media stratigraphically located by the use of ATR-FTIR mapping microscopy. The analytical results of the painted terracotta integrated investigations show that original technique adopted is characterised by the application of pigments in an oil-binding medium directly applied on the substrates, probably treated with oil and animal glue. A large number of overpaintings above the original scheme of polychromy was found, which could be ascribed to almost three different interventions; the absence of modern pigments suggests that they could be realized long ago.     

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。     

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。     

Analytical study of polychromy on exterior sculpted stone

A complete study on the remnants of the polychromy in the main entrance portal of Saint Paul's church (16th century, Úbeda, Spain) has been carried out using Raman microspectroscopy in combination with optical microscopy and scanning electron microscopy with energy dispersive X‐ray spectroscopy (SEM‐EDX). The polychromy in red areas showed the superposition of two well‐defined pictorial layers. The first one (probably original) was composed of cinnabar, red lead and hematite over a preparation coating containing calcite, gypsum and lead white. The second red pictorial layer was mainly constituted by cinnabar and was over a thicker preparation coating. Green samples showed a single pictorial layer over the weathered stone. The high fluorescence background made the examination of the latter samples extremely difficult by means of Raman microspectroscopy. SEM‐EDX detected abundance of copper and chlorine, and a detailed inspection of Raman spectra revealed the presence of a copper hydroxychloride, analogous to the naturally occurring mineral atacamite. Azurite remnants of the original polychromy were only found in the cracks of mortar joints. Alteration products like calcium and copper oxalates were also widely distributed in this layer. Copyright © 2009 John Wiley & Sons, Ltd.