The study of the mural painting in the 12th century monastery of Santa Maria delle Cerrate (Puglia‐Italy): characterization of materials and techniques used

A multidisciplinary research was conducted by the University of Salento in collaboration with the Lecce Provincial Museum, in order to study different forms of art widespread in the Salento peninsula (Southern Italy) very valuable from an artistic point of view and important as driving force for the tourism of the area. In this research, the archaeometrical analysis was used to study the first cycle of paintings of the church of Santa Maria delle Cerrate, an italo‐greek monastery located in the country about 15 km north‐east of Lecce, probably built in the 12th century. Microscopic, chromatographic and spectrometric techniques were used: optical microscopy was used to study samples and the relevant stratigraphy, micro‐Raman Spectroscopy to identify pigments and Gas Chromatography with Mass Spectrometric Detection to investigate the techniques masters used to decorate the monastery church. Further information on organic and inorganic materials present in the samples were obtained from Fourier transform infrared analysis in attenuated total reflectance. Materials and techniques were clearly ascertained, and, interestingly, pigments were applied both by fresco and egg‐based tempera. Among the various pigments detected, the identification of both lapis lazuli and lead white opened new perspectives both from the historical and conservative points of view. Copyright © 2013 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.     

Shades of green in 15th century paintings: combined microanalysis of the materials using synchrotron radiation XRD, FTIR and XRF

A representative selection of green paintings from fifteenth century Catalonia and the Crown of Aragon are analyzed by a combination of synchrotron radiation microanalytical techniques including FTIR, XRD, and XRF. The green pigments themselves are found to be a mixture of copper acetates/basic copper acetates and basic copper chlorides. Nevertheless, a broader range of green shades were obtained by mixing the green pigment with yellow, white, and blue pigments and applied forming a sequence of micrometric layers. Besides the nature of the pigments themselves, degradation and reaction products, such as carboxylates, formates and oxalates were also identified. Some of the copper based compounds, such as the basic copper chloride, may be either part of the original pigment or a weathering product. The high resolution, high brilliance, and small footprint of synchrotron radiation proved to be essential for the analysis of those submillimetric paint layers made of a large variety of compounds heterogeneous in nature and distribution and present in extremely low concentrations.     

μ-XRF/μ-RS vs. SR μ-XRD for pigment identification in illuminated manuscripts

For the non-destructive identification of pigments and colorants in works of art, in archaeological and in forensic materials, a wide range of analytical techniques can be used. Bearing in mind that every method holds particular limitations, two complementary spectroscopic techniques, namely confocal μ-Raman spectroscopy (μ-RS) and μ-X-ray fluorescence spectroscopy (μ-XRF), were joined in one instrument. The combined μ-XRF and μ-RS device, called PRAXIS unites both complementary techniques in one mobile setup, which allows μ- and in situ analysis. μ-XRF allows one to collect elemental and spatially-resolved information in a non-destructive way on major and minor constituents of a variety of materials. However, the main disadvantages of μ-XRF are the penetration depth of the X-rays and the fact that only elements and not specific molecular combinations of elements can be detected. As a result μ-XRF is often not specific enough to identify the pigments within complex mixtures. Confocal Raman microscopy (μ-RS) can offer a surplus as molecular information can be obtained from single pigment grains. However, in some cases the presence of a strong fluorescence background limits the applicability. In this paper, the concrete analytical possibilities of the combined PRAXIS device are evaluated by comparing the results on an illuminated sheet of parchment with the analytical information supplied by synchrotron radiation μ-X-ray diffraction (SR μ-XRD), a highly specific technique. PACS  33.20.Fb; 61.05.cp; 33.20.Rm; 07.85.Qe; 91.65.An     

A study of smalt and red lead discolouration in Antiphonitis wall paintings in Cyprus

The present analytical study focuses on the degradation phenomena observed in fifteenth century wall paintings of the Christ Antiphonitis monastery in Cyprus. Examination of ten fragments by means of optical microscopy (OM), scanning electron microscopy (SEM/EDS), μRaman and FTIR spectroscopy revealed smalt discolouration and loss, and transformation of red lead from orange Pb₃O₄ to black PbO₂. The chromatic changes have affected the aesthetic effect of the paintings insofar as these pigments were extensively used. The mechanisms of smalt weathering, i.e. leaching of alkali and formation of micro-cracks, are interpreted in relation to its chemical composition and to the aggressive environmental conditions. In addition, it is assumed that red lead degradation may have been induced not only by the effect of temperature, light and humidity but also by the presence of chlorine salts. These phenomena of pigment alteration and loss underline the unsuitability of smalt and minium on wall paintings, regardless of the painting technique (fresco, fresco-secco, secco).     

Crocoite PbCrO4 and mimetite Pb5(AsO4)3Cl: rare minerals in highly degraded mediaeval murals in Northern Bohemia

Mural paintings of exceptional quality, which can be discerned in spite of their extensive mechanical damage and colour fading, have been uncovered in the church of St. Gallus in Kuřívody, Northern Bohemia, dated to the second half of the 13th century. Materials research with particular use of portable X‐ray fluorescence, Raman micro‐spectroscopy and powder X‐ray micro‐diffraction revealed the presence of rare pigments. In Kuřívody, it is only a second identification of intentionally used yellow mineral crocoite (PbCrO₄) in European art. Its identification is facilitated by providing a very good Raman scattering, even when present in small amounts in fragmentarily preserved colour layers. Light yellow mimetite (Pb₅(AsO₄)₃Cl) was never before mentioned as intentionally used pigment in Europe. Its finding in Kuřívody, however, corresponds more likely with undesirable physical–chemical conditions causing its formation by alteration of orpiment (As₂S₃) and minium (Pb₃O₄). Obtained results highlight the importance of Raman spectroscopy for direct identification of mineral pigments in low concentrations, which may be crucial for interpreting cultural heritage objects in historical context. By materials, the almost forgotten paintings in Kuřívody can be seen as outstanding and rare example of ancient artistic tradition that has spread to Europe from Mediterranean in early Middle Ages. After all, mineral crocoite was already used by ancient Egyptians to paint sarcophagi and degraded orpiment decorates the walls of the Nefertari's tomb in Thebes. Copyright © 2014 John Wiley & Sons, Ltd.     

Laboratory two-dimensional X-ray microdiffraction technique: a support for authentication of an unknown Ghirlandaio painting

Europe has a very rich and diversified cultural heritage of art works, including buildings, monuments and objects of all sizes, involving a great variety of materials. The continuous discovery of new art works opens the problem of their authentication. Advanced analytical techniques can be fundamental to understand the way of life, the culture and the technical and intellectual know-how of the artists. Indeed, the authentication of an art work involves the identification of the used materials, their production techniques and procedures used for the work realization. It is possible to know the origin and provenance of materials, including the location of the natural sources. Advanced analytical techniques also help one to understand degradation processes, corrosion, weathering, and preservation-conservation protocols. In this paper we present a painting attributed to Domenico Ghirlandaio. Ghirlandaio is a well-known artist of fifteenth century who contributes to the apprenticeship of Michelangelo Buonarroti. The study of the pigments used in this painting, which belongs to a private collection, has been supported mainly by means of laboratory two-dimensional X-ray microdiffraction (μXRD²). The possibility to obtain information about not only the phase, but also microstructure allows one to extract interesting consideration and to obtain evidence of the painter’s style and intention. PACS  61.10.Nz; 61.10.Eq; 78.70.En     

西藏扎什伦布寺壁画的科学研究

壁画是寺院建筑的重要装饰元素,也是藏传佛教艺术的重要组成部分。扎什伦布寺始建于明正统12年（公元1447年）,作为后藏最大的寺院,寺内保存了大量精美壁画,这些壁画对研究藏传佛教及佛教艺术具有重要意义。扎什伦布寺自建寺起一直为传播佛教文化服务,经历了频繁的大规模修建。为了解扎什伦布寺壁画的制作材料与工艺,为今后壁画的保护及修复提供重要的参考及科学支撑,选取寺内强巴佛殿四层北壁、吉康扎仓南殿西侧的典型壁画,共采集8个样品。采用超景深三维视频显微镜观察壁画的制作结构,显微激光拉曼光谱仪对有机与无机颜料的成分信息进行表征,偏光显微镜根据晶体的光学信息鉴别拉曼光谱相似的颜料颗粒,X射线衍射仪用于测定地仗成分,扫描电镜/能谱仪则对微观数据进行确认和补充。通过分析研究,壁画由地仗层、准备层、颜料层构成。颜料包括矿物及人工合成颜料,其中红色颜料为朱砂与颜料红14,绿色颜料为块铜矾、酞菁绿,黑色颜料为碳黑,黄色颜料为雌黄,蓝色颜料为合成群青。颜料红14与酞菁绿为有机合成颜料,合成群青则为无机合成颜料。块铜矾作为矿物颜料,在欧洲曾用于架上画、壁画、手稿等艺术作品中,但在国内还未曾发现其使用历史,这一发现扩展了对绿色颜料的认识。壁画的地仗层依据藏式壁画制作传统使用了阿嘎土,准备层则由黄土制备。研究结果表明,壁画制作时以阿嘎土打底,刷一层黄土找平壁面,以胶调和颜料绘制于黄土层之上。壁画除了使用一些常见的传统藏式壁画材料,还发现了一些近代人工合成材料,说明扎什伦布寺强巴佛殿四层北壁及吉康扎仓南殿西侧壁画曾经历过重绘或补绘。该研究结果不仅弥补了扎什伦布寺壁画的研究空缺,也为扎什伦布寺修缮历史的补充及完善提供了重要证据。     

Portable XRF as a valuable device for preliminary in situ pigment investigation of wooden inventory in the Trski Vrh Church in Croatia

The aim of this work was the investigation of pigments from the painted wooden inventory of the pilgrimage church of Saint Mary of Jerusalem in Trski Vrh – one of the most beautiful late-baroque sacral ensembles in Croatia. Being an object of high relevance for the national cultural heritage, an extensive research on the wooden polychromy was undertaken in order to work out a proposal for a conservation treatment. It consists mainly of two painted and gilded layers (the original one from the 18th century and a later one from 1903), partly overpainted during periodic conservation treatments in the past. The approach was to carry out extensive preliminary in situ pigment investigations using a portable XRF (X-ray fluorescence) device, and only the problems not resolved by this method on site were further analyzed using sophisticated laboratory equipment. Therefore, the XRF results acted as a valuable guideline for subsequent targeted sampling actions, thus minimizing the sampling damage. Important questions not answered by XRF (identification of organic pigments, ultramarine, etc.) were subsequently resolved using additional ex situ laboratory methods, primarily μ-PIXE (particle-induced X-ray emission) at the nuclear microprobe of the Rudjer Boskovic accelerator facility as well as μ-Raman spectroscopy at the Institute of the Academy of Fine Arts in Vienna. It is shown that by the combination of these often complementary methods a thorough characterization of each pigment can be obtained, allowing for a proper strategy of the conservation treatment. PACS  89.20.-a; 82.80.Ej; 82.80.Gk     

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.     

Optimum spectral window for imaging of art with optical coherence tomography

Optical coherence tomography (OCT) has been shown to have potential for important applications in the field of art conservation and archaeology due to its ability to image subsurface microstructures non-invasively. However, its depth of penetration in painted objects is limited due to the strong scattering properties of artists’ paints. VIS–NIR (400–2,400 nm) reflectance spectra of a wide variety of paints made with historic artists’ pigments have been measured. The best spectral window with which to use OCT for the imaging of subsurface structure of paintings was found to be around 2.2 μm. The same spectral window would also be most suitable for direct infrared imaging of preparatory sketches under the paint layers. The reflectance spectra from a large sample of chemically verified pigments provide information on the spectral transparency of historic artists’ pigments/paints as well as a reference set of spectra for pigment identification. The results of the paper suggest that broadband sources at ~2 μm are highly desirable for OCT applications in art and potentially material science in general.     

The laser doppler vibrometer as an instrument for nonintrusive diagnostic of works of art: Application to fresco paintings

The purpose of this paper is to present the application of the Laser Doppler Vibrometer as a nonintrusive measurement instrument to detect shape and location of damage in fresco paintings. The paper discusses performance of the measurement instrument and outlines a measurement procedure capable of nonintrusive diagnostic of the state of conservation of works of art, based on frequency response analysis of wall surface vibration induced by acoustic excitation.The procedure for the measurement of wall surface vibration is described. A 2D map of surface vibration amplitude is produced by scanning the measurement point across the surface. This pseudo-image is then processed by image analysis techniques to determine the position and the shape of damaged areas. Experiments are performed on an artificial fresco with induced damage and on a real painting inside a church.     

中国古代艺术品常用矿物颜料的拉曼光谱

拉曼光谱技术在艺术品文物和考古学领域的应用正变得日益重要, 其中对艺术品文物中所使用的颜料的分析是这方面应用的一个重要研究课题, 本文讨论了有关的实验技术, 测量了一些在中国古代艺术品中经常使用的红色、黄色和白色颜料的拉曼光谱, 介绍了相关的背景知识, 并对这些光谱进行了解析, 这些基础数据对于进一步开展对古代壁画、彩塑、雕刻、陶瓷等的拉曼光谱分析有着重要的基础参考价值。     

Revealing the invisible: using surface‐enhanced Raman spectroscopy to identify minute remnants of color in Winslow Homer's colorless skies

The fading of pigments in items of importance to cultural heritage, such as paintings, works of art on paper, and textiles, is a ubiquitous problem. Tools currently available that can detect and identify organic colorants in severely degraded works of art are rare, given the heavy deterioration and restricted availability of the sample. Recently, however, surface‐enhanced Raman scattering (SERS) spectroscopy has shown great promise in detecting and identifying mass‐limited samples. The art conservation field has seized upon the opportunity opened up by this powerful analytical technique to enable the identification of microscopic amounts of organic molecules used as artists' colorants in complex matrices, such as biomaterials (i.e. dyed natural textiles, linseed oil biofilms present in oil paintings, etc.), a possibility that was previously precluded due to interfering fluorescence and small sample size. Here, we report SERS spectra recorded directly on single particles of red lake pigments from an important historical watercolor by the American master Winslow Homer (1836–1910) that suffered some degree of fading. The accurate colorant identification provided by SERS, enhanced by comparison with reference samples of historical watercolors, has thus enabled important discoveries regarding the materials and intended meanings behind artworks from one of the most influential American watercolor painters. Copyright © 2011 John Wiley & Sons, Ltd.     

Terahertz spectroscopy applied to the analysis of artists’ materials

Terahertz (THz) spectroscopy and imaging have been actively studied in these decades. THz waves (0.1–10 THz) are non-invasive, can penetrate opaque materials, and can be used to obtain fingerprint spectra whose characteristics depend upon molecular and intermolecular behavior. Unlike the mid-infrared region, no commercial spectral library is available for the THz region. Consequently, a spectral database of artists’ materials was developed in order to include THz spectroscopy among conservation science techniques. Most pigments and some synthetic polymers have characteristic fingerprint spectra in the THz region. With this technique most of these materials used in paintings can be identified alone or as paint, a combination of pigments and binders. Although the meaning of the spectral features has so far not been fully explained, previous studies on optical materials suggest that phonon absorption and the behavior of hydrogen bonds contribute to their spectral features. Examples of THz spectra of various art materials are discussed on the basis of measurements obtained using a conventional Fourier transform system.     

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.