Multispectroscopic Characterization of Oil on Copper Painting

A small plate of oil on copper painting from the Italian Renaissance period was characterized by means of noninvasive spectroscopic methods. The study was conducted by the use of energy-dispersive X-ray fluorescence, X-ray diffraction, and Raman and diffuse reflectance infrared Fourier transform spectroscopies to determine the technology production process in such kinds of artworks. Results allowed us to characterize the copper alloy of the support media; the preparation layer, which is composed by white lead; and the pictorial layer of variable composition (green copper sulphate compounds, red lead, carbon black, brown earth pigments, gold, vermilion, and white lead). The complementarity of the techniques used in this study has proven to be highly effective.     

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.     

Identification of pigments from the Shrine of Kaiping Diaolou by micro‐Raman spectroscopy

Shrines (or altars) are constructed in China for worshiping ancestors, Bodhisattva, and God of Wealth. In this work, pigments from the shrine of Kaiping Diaolou tower were analyzed by micro‐Raman spectroscopy, in conjunction with other analytical methods including scanning electron microscopy (SEM) with energy dispersive X‐ray spectroscopy (EDX) and X‐ray fluorescence (XRF). Paintings of the shrine were composed of 2–3 pigment layers and the total thickness was determined as about 200–300 µm by optical microscopy and SEM, indicating the fine painting skills applied in the construction of the shrine. The green pigments on the surface layer of the green fragment were identified as a mixture of lead phthalocyanine (PbPc) and cornwallite (Cu₅(AsO₄)₂(OH)₄) by XRF and micro‐Raman spectroscopy with two different excitation wavelengths (488 and 785 nm). Underneath the green layer, red and yellow ochre were found. The pigments on the surface layer of red and blue fragments were identified as hematite (Fe₂O₃) and lazurite or synthetic ultramarine [(Na₈(Al₆Si₆O₂₄)S₃)], respectively. Finally, the pigments under the two surface layers were identified by EDX and micro‐Raman spectroscopy as chromium oxide (Cr₂O₃), gypsum (CaSO₄·2H₂O) and calcite (CaCO₃). Copyright © 2011 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.     

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。     

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.     

北京故宫养心殿燕喜堂及西围房建筑彩画的分析研究——一种检测颜料和胶结物的集成检测方法

北京故宫是现存规模最大、保存最完整的木结构古建筑群。2015年底,故宫养心殿启动研究性保护修缮工程,燕喜堂是养心殿的后殿西耳房,是此次维修的重点对象之一。彩画是古建筑的重要组成部分,不仅具有美化装饰的作用,更有对木材的防腐保护功能。为了能更好地辅助燕喜堂及西围房建筑彩画的保护与修复,需要对彩画原始材料以及工艺进行检测研究。使用一套集成检测方法：包括样品横截面分析、扫描电子显微镜背散射及能谱技术、拉曼光谱技术、荧光染色法、酶联免疫法、免疫荧光法以及热裂解气相色谱法,分析了故宫养心殿燕喜堂及西围房建筑彩画样品的颜料、沥粉、胶结材料的成分,以及结构关系。结果表明燕喜堂西围房使用的颜料有朱砂、铁红、群青、石青、石绿以及副氯铜矿型铜绿;沥粉的无机组成为石英、滑石、白垩或白云石。胶结材料检测结果发现彩画地仗层中普遍掺加了桐油,颜料层中掺加了动物胶。梁上彩画除了表面图案,地仗层底部还有一层朱砂颜料,同时地仗层内部也不规则地发现朱砂颜料。此外,表层红色颜料通常由两层颜料组成,内层的显色成分是铁红和朱砂,颜料颗粒直径1 μm左右,外层颜料由朱砂组成,颜料颗粒大小不一,直径1～30 μm范围内。上述检测结果不仅可以部分看出燕喜堂及西围房建筑彩画的工艺特征,也表明该集成检测方法可行、所需样品量少,是一种经济实用的彩画文物检测方法。     

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.     

广元千佛崖石窟石刻彩妆颜料的分析

四川省广元千佛崖石窟是四川境内最大的石窟寺和摩崖造像群,承载着古代社会的历史信息,对研究当时的政治、文化和社会生活意义重大。千佛崖石窟在自然环境因素的长期作用下,目前受到多种严重病害的侵蚀,亟待保护。为了获取石刻彩妆的成分与工艺信息以支撑彩妆的保护工作,应用X射线衍射分析、剖面显微分析、扫描电镜能谱分析、激光拉曼光谱分析等方法,对广元千佛崖8处洞窟的已脱落彩妆颜料层样品进行了分析。X射线衍射分析鉴定出了铁红(Fe₂O₃)、朱砂 (HgS)、铅丹(Pb₃O₄)、炭黑等颜料成分,以及铅白 (PbSO₄)、石膏(CaSO₄·2H₂O)、长石、二氧化硅等打底层和岩体的组分,验证了样品脱落的原因是岩体的劣化。剖面显微分析和扫描电镜能谱分析表明,不同洞窟的彩妆制作工艺有区别,有的颜料直接施加在岩体表面,有的则在颜料层和岩体间有一层主要为硫酸铅的打底层;样品表面蓝绿色颜料的含量很少,仅通过激光共聚焦显微拉曼光谱成功地识别出来,其鉴定结果为蓝铜矾[Cu₄SO₄(OH)₆·2H₂O]。蓝铜矾作为颜料使用的报道很少。由于其矿物含量较少但分布广泛,古代一般不将其分离出来单独使用,而人工合成的碱式硫酸铜类颜料布勒门绿（Bremen green）出现于18世纪-19世纪,如果有纯碱式硫酸铜单独使用的情况出现,就意味着有近现代重绘的可能性,将有助于彩绘类文物保存历史的判断。该研究不仅为千佛崖石刻彩妆的保护提供了依据,丰富了文化遗产中使用蓝铜矾颜料的案例,更对彩妆的保存历史研究有潜在价值。     

Yellow pigments in painting: characterisation and UV laser‐induced modifications

Artistic yellow pigments, commonly employed from antiquity, were investigated by morphological, spectrophotometric and compositional analyses. Namely, scanning electron microscopy–energy dispersive X‐ray (SEM/EDX) characterisations and reflectance, attenuated total reflection–Fourier transform infrared spectroscopy (ATR‐FTIR) and Raman spectroscopy were carried out on egg yolk tempera models to discriminate the pigments. The models were irradiated with excimer KrF (248 nm) laser at different working conditions, and the effects induced on colour were related to chemical and physical modifications through the same analyses, as a function of laser parameters. It came out that the effects on the pictorial layers are always related to the modifications of the binding medium and, in addition, the laser radiation induces dehydration and transformation of iron oxides in natural earths. Copyright © 2009 John Wiley & Sons, Ltd.     

Electroless copper plating on 3-mercaptopropyltriethoxysilane modified PET fabric challenged by ultrasonic washing

Electroless deposition of Cu on poly(ethylene terephthalate) (PET) fabric modified with 3-mercaptopropyltriethoxysilane was investigated. Morphology, composition, structure, thermal decomposing behavior of copper coating PET fabric after ultrasonic washing in water for 1 h were characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, X-ray photoelectron spectroscopy (XPS), Raman spectrometer, X-ray diffraction (XRD), and thermogravimetric analysis (TG), respectively. Copper plating on modified fabric has good adherence stability and high electric conductivity before and after ultrasonic washing, while copper coating fabric without modification is easily destroyed during the washing process, which leads to the textile changing from conductor to dielectric. As the copper weight on the treated fabric is 28 g/m², the shielding effectiveness (SE) is more than 54 dB at frequency ranging from 0.01 MHz to 18 GHz.     

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.     

Some forensic applications of a combined micro‐Raman and scanning electron microscopy system

The structural chemical analyser (SCA) is a novel accessory that allows the analytical advantages of Raman spectroscopy and scanning electron microscopy with energy dispersive x‐ray detection (SEM/EDX) to be realised in a single hybridised instrument. The combined Raman–SEM/EDX system permits in situ characterisation of a sample based on both its molecular and elemental makeup. This article demonstrates the potential of using the SCA for interrogating trace evidence for criminalistic purposes. Illustrative evidentiary examples (taken from our laboratory's archives) include the examination of a white paint fragment consisting of several layers of the same colour and a sample of explosive mixture recovered from a place of interest. The sensitive SEM imaging contrast mechanisms enabled the optically identical multiple layers of the white paint to be distinguished easily. The individual layers were then unambiguously analysed to establish their elemental profile (from energy dispersive x‐ray (EDX)) and this was cross‐referenced with the chemical information derived from in situ Raman measurements. X‐ray mapping was used as a fast and convenient way of characterising simultaneously multiple solids constituting the explosive mixture. Typical particles were targeted and analysed both by EDX and Raman spectroscopy revealing an unusual chlorate‐based energetic mixture that also contained 2, 4, 6‐trinitrotoluene (TNT) and 2, 4, 6‐trinitrophenylmethylnitramine (Tetryl). Copyright © 2009 John Wiley & Sons, Ltd.     

Pigment analysis of Portuguese portrait miniatures of 17th and 18th centuries by Raman Microscopy and SEM‐EDS

Seventeen Portuguese miniature portraits on copper support from the Évora Museum collection (Portugal) were analyzed in situ and nondestructively by Raman microscopy (RM), SEM‐EDS, and stereomicroscopy. This work constitutes a great breakthrough in the study of miniature paintings from the 17^th and 18^th centuries, since the chemical information known about this unique kind of paintings are still scarce, and in particular, this exclusive collection was never been subjected to any physicochemical study. In this work, each portrait was examined in detail in order to characterize the pigments palette used by the miniaturists. The μ‐Raman analysis, in particular, guaranteed an exceptional visualization and good individual identification of small grains of pigments and other constituents of the pictorial layer. Using this technique, 19 compounds were identified, including bluish black covellite, a pigment rarely found in oil paintings. SEM‐EDS was used as an important complementary technique to confirm the chemical nature of some pigments and to identify shell gold (gold dust) in some portraits. Overall, the pigments identified in this large set of old paintings are broadly consistent with those mentioned in the painting treatises of that time or reported in other more modern bibliographic sources. Copyright © 2014 John Wiley & Sons, Ltd.     

Analysis of mural paintings using in situ non‐invasive XRF,FTIR spectroscopy and optical microscopy

An analytical protocol consisting of X‐ray fluorescence spectroscopy, optical microscopy and Fourier transform infrared spectroscopy was used to study the origin and the nature of the materials (pigments, binders and coating preparation) of the Fundenii Doamnei church mural paint from Bucharest. The main interest of the present study consisted in the original votive paint from narthex, painted in 1757 in a secco technique. During analysis, an unexpected pigment in the votive paint could be detected by the combined analytical techniques: ultramarine blue. Along with this pigment, the presence of gypsum binder based on egg and flax seed oil could also be evidenced. These results demonstrated a secco execution technique of the votive paint and also the presence of a restoration treatment. Moreover, during the present study, the components of the preparation layer and the constitutive pigments from both 1699 and 1757 years mural paints have been analyzed. Hence, the following pigments could be identified: vermilion, azurite, cinnabar, lead white, ochre, natural umber and gold, by using the combination of the analytical techniques. The novelty of our results consists in detecting the composition of the materials used in this church painting (fresco and a secco) during these 254 years since its first restoration. The results of these investigations pointed to the suitability of the non‐destructive and semi‐destructive analytical techniques in the complex characterization of the paints realized in different techniques, at different periods. Copyright © 2013 John Wiley & Sons, Ltd.     

A pigment (CuS) identified by micro‐Raman spectroscopy on a Chinese funerary lacquer ware of West Han Dynasty

A blue pigment was identified by micro‐Raman spectroscopy, X‐ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM)/energy dispersive X‐ray (EDX) and X‐ray diffraction (XRD). The test sample, a funerary lacquer tray, belongs to West Han Dynasty (206 BC–AD 8) of China and was decorated with faint blue patterns. The result from Raman spectroscopy showed that the faint blue is covellite (CuS) due to the presence of a characteristic peak at 474.5 cm⁻¹, which further was confirmed by XRF, SEM–EDX and XRD. This research indicated that CuS had been used as a blue pigment to decorate lacquer wares from the West Han Dynasty in China. Copyright © 2009 John Wiley & Sons, Ltd.     

A study on red lead degradation in a medieval manuscript Lorvão Apocalypse (1189)

The mechanisms of red lead degradation were studied in a medieval Portuguese codex, Lorvão Apocalypse (1189), by Raman microscopy (µ‐Raman) and micro‐X‐ray diffraction (µ‐XRD). The range of pigments found for the illuminations is mainly limited to vermilion, orpiment and red lead. Micro‐Fourier transform infrared spectroscopy (µ‐FTIR) determined that the pigments were applied in a proteinaceous binding medium. In the red and orange colours, arsenic (As) was determined, by micro‐energy dispersive X‐ray fluorescence (µ‐EDXRF), to be ranging 1–4% (wt %). For those colours, lead white and calcium carbonate were found as fillers whereas orpiment was applied as a pure pigment. Raman microscopy identified, unequivocally, the degradation product of red lead as galena [lead (II) sulphide, PbS]. To determine the main factors affecting red lead degradation, a set of accelerating ageing experiments was designed to assess the influence of extenders and of the two other pigments, vermilion and orpiment. The experiments were followed by µ‐Raman, µ‐EDXRF and XRD. Raman microscopy results for the simulation of degradation of red lead, in the presence of orpiment, are in agreement to what was found in the Lorvão Apocalypse, galena being the main degradation product; also in common is a Raman band at ca. 810 cm⁻¹, which was attributed to a lead arsenate compound. It was concluded that in Lorvão Apocalypse, the degradation of red lead was a result of its reaction with orpiment. Copyright © 2009 John Wiley & Sons, Ltd.     

Direct production of carbon nanotubes decorated with Cu2O by thermal chemical vapor deposition on Ni catalyst electroplated on a copper substrate

Carbon nanotubes (CNTs) decorated with Cu₂O particles were grown on a Ni catalyst layer deposited on a Cu substrate by thermal chemical vapor deposition from liquid petroleum gas. Ni catalyst nanoparticles with different sizes were produced in an electroplating system at 45 °C using the corrosive effect of H₂SO₄ which was added to solution. These nanoparticles provide the nucleation sites for CNT growth avoiding the need for a buffer layer. The surface morphology of the Ni catalyst films and CNT growth over this catalyst was studied by scanning electron microscopy (SEM). High temperature surface segregation of the Cu substrate into the Ni catalyst layer and its exposition to O₂ at atmospheric environment, during the CNTs growth, lead to the production of CNTs decorated with about 6 nm Cu₂O nanoparticles. We used SEM to study the surface characteristics of Ni catalyst films and characteristic of grown CNTs. Raman spectroscopy, transmission electron microscopy (TEM), electron diffraction (EDX), X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) revealed the formation of CNTs. The selected area electron diffraction pattern, EDX, and XPS studies show that these CNTs were decorated with Cu₂O nanoparticles. This way of fabrication is the easiest and lowest cost method.     

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。     

Development and characterization of laser surface cladding (Ti,W)C reinforced Ni–30Cu alloy composite coating on copper

To improve the wear resistance of copper components, laser surface cladding (LSC) was applied to deposit (Ti,W)C reinforced Ni–30Cu alloy composite coating on copper using a cladding interlayer of Ni–30Cu alloy by Nd:YAG laser. The microstructure and phases of the composite coating were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray energy dispersive microanalysis (EDX). Microhardness tester and pin-on-disc wear tester were employed to evaluate the hardness and dry-sliding wear resistance. The results show that crack-free composite coating with metallurgical bonding to the copper substrate is obtained. Phases identified in the (Ti,W)C-reinforced Ni–30Cu alloy composite layer are composed of TiWC₂ reinforcements and (Ni,Cu) solid solution. TiWC₂ reinforcements are distributed uniformly in the (Ni,Cu) solid solution matrix with dendritic morphology in the upper region and with particles in the mid-lower region. The microhardness and wear properties of the composite coating are improved significantly in comparison to the as-received copper substrate due to the addition of 50 wt% (Ti,W)C multicarbides.