Visualization of pigment distributions in paintings using synchrotron K-edge imaging

X-ray radiography plays an important role in the study of artworks and archaeological artifacts. The internal structure of objects provides information on genesis, authenticity, painting technique, material condition and conservation history. Transmission radiography, however, does not provide information on the exact elemental composition of objects and heavy metal layers can shadow or obscure the ones including lighter elements. This paper presents the first application of synchrotron-based K-edge absorption imaging applied to paintings. Using highly monochromatic radiation, K-edge imaging is used to obtain elemental distribution images over large areas. Such elemental maps visualize the distribution of an individual pigment throughout the paint stratigraphy. This provides color information on hidden paint layers, which is of great relevance to art historians and painting conservators. The main advantage is the quick data acquisition time and the sensitivity to elements throughout the entire paint stratigraphy. The examination of a test painting is shown and further instrumental developments are discussed. PACS 07.85.Qe; 07.05.Pj     

Nanoindentation and the micromechanics of Van Gogh oil paints

Understanding the mechanical properties of ancient paintings is a major issue for conservation and restoration. One strategy is to measure the mechanical properties of reconstructed paints: however, the aging process is poorly known, so it is also desirable to measure mechanical properties directly on ancient paint samples. Using nanoindentation, we have characterized submillimetric samples recovered from restoration of two Van Gogh paintings and compared the results with reconstructed paint samples. We demonstrate that the reduced modulus and hardness of historical paints can be measured at a very local scale, even differentiating between each paint layer. Our reconstructed paint samples exhibit elastic moduli comparable to values of the literature, but the values measured on the two 19th century paint samples are found to be significantly larger. Similarly, the compositional dependence of the elastic modulus is consistent with literature results for our reconstructed samples while our preliminary results for ancient samples do not readily fall into the same pattern. These results all point out to a significant impact of long term aging, in a manner which is difficult to predict in our present state of understanding. They demonstrate that nanoindentation is a very adequate tool to improve our knowledge of art paint mechanics and aging.     

A non invasive method to detect stratigraphy, thicknesses and pigment concentration of pictorial multilayers based on EDXRF and vis-RS: in situ applications

Energy dispersive XRF analysis (EDXRF) in association with visible reflectance spectroscopy (vis-RS), both achieved by portable instruments, can be successfully applied, in a wide range of cases, to investigate wood or canvas paintings in order to obtain some stratigraphic information with non-invasive techniques. The specific aim of this work is to use them as quantitative tools: EDXRF to reconstruct the thicknesses of the detected layers, vis-RS to report pigment concentration in the uppermost layer. The method has been tested in the laboratory on paint layers with different composition of about 50 multilayers and more than 100 single layers [12]. We present here some in situ analyses of famous paintings by Andrea Mantegna and Giovanni Bellini, compared with stratigraphic optical microscopy observations on cross sections. Advantages and limits are pointed out. PACS  78.40.-q; 78.30.-j; 78.70.En     

The first in situ Raman spectroscopic study of San rock art in South Africa: procedures and preliminary results

Southern Africa has a rich heritage of hunter‐gatherer, herder and farmer rock art traditions made by using both painted and engraved techniques. Until now, there have been only a handful of studies on the chemical analysis of the paint, as all previous types of analysis required the removal of pigment samples from the sites a practice which has been avoided. Raman spectroscopy is an ideal techniques to analyse the paint non‐destructively and also offers the possibility of in situ work with portable instruments. This article describes the procedures and reports the preliminary results of the first in situ Raman spectroscopic study of rock art in South Africa (also a first worldwide), where we, first, evaluate the capability of a Raman portable instrument in very difficult conditions, second, analyse the paints in order to contribute to a better knowledge of the technology used and, third, evaluate the possible contribution of in situ analyses in conservation studies. The paintings from two different rock art sites were studied. The instrument proved to be highly suitable for in situ analyses in physically very challenging conditions. Most of the pigments and alteration products previously detected under laboratory conditions were identified, thereby giving information on both the pigments and conservation state of the paintings. A layered structure of alteration products and pigment was identified in situ for the first time by controlling the laser power, thereby obtaining the same results as in mapping experiments of cross sections of paint. Copyright © 2010 John Wiley & Sons, Ltd.     

Evolution of Entropy in Art Painting Based on the Wavelet Transform

Quantitative studies of art and aesthetics are representative of interdisciplinary research. In this work, we conducted a large-scale quantitative study of 36,000 paintings covering both Eastern and Western paintings. The information entropy and wavelet entropy of the images were calculated based on their complexity and energy. Wavelet energy entropy is a feature that can characterize rich information in images, and this is the first study to introduce this feature into aesthetic analysis of art paintings. This study shows that the process of entropy change coincides with the development process of art painting. Further, the experimental results demonstrate an important change in the evolution of art painting, and since the rise of modern art in the twentieth century, the entropy values in painting have started to become diverse. In comparison with Western paintings, Eastern paintings have distinct low entropy characteristics in which the wavelet entropy feature of the images has better results in the machine learning classification task of Eastern and Western paintings (i.e., the F1 score can reach 97%). Our study can be the basis for future quantitative analysis and comparative research in the context of Western and Eastern art aesthetics.     

Terahertz imaging for non-destructive evaluation of mural paintings

The feasibility of applying time-domain, terahertz spectroscopic imaging to the evaluation of underdrawings and paint layers embedded within wall paintings is demonstrated. Metallic and dielectric paint patterns and a graphite drawing are resolved through both paint and plaster overlayers using a pulsed-terahertz reflectometer and imaging system. We calculated the bulk refractive indices of four common pigments and used them to confirm color domains in a terahertz-beam spectral image of a painting.     

Classification of lead white pigments using synchrotron radiation micro X-ray diffraction

Lead white pigment was used and synthesised for cosmetic and artistic purposes since the antiquity. Ancient texts describe the various recipes, and preparation processes as well as locations of production. In this study, we describe the results achieved on several paint samples taken from Matthias Grünewald’s works. Grünewald, who was active between 1503 and 1524, was a major painter at the beginning of the German Renaissance. Thanks to X-ray diffraction analysis using synchrotron radiation, it is possible to associate the composition of the paint samples with the masters ancient recipes. Different approaches were used, in reflection and transmission modes, directly on minute samples or on paint cross-sections embedded in resin. Characterisation of lead white pigments reveals variations in terms of composition, graininess and proportion of mineral phases. The present work enlightens the presence of lead white as differentiable main composition groups, which could be specific of a period, a know-how or a geographical origin. In this way, we aim at understanding the choices and the trading of pigments used to realise paintings during northern European Renaissance. PACS 61.10.Nz; 07.85.Qe; 61.43.Gt     

In situ energy dispersive X‐ray fluorescence analysis of rock art pigments from the ‘Abrigo dos Gaivões’ and ‘Igreja dos Mouros’ caves (Portugal)

A portable energy dispersive X‐ray fluorescence spectrometer was used to obtain the elemental composition of Neolithic rock art paintings of the ‘Abrigo dos Gaivões’ and ‘Igreja dos Mouros’ caves. These caves, located in the Esperança parish, Arronches' county, in the San Mamede's mountains (Portugal), belong to a group of spread shelters just next to the western Spanish border. Results show the strong presence of iron in bare rock, and this element can be clearly detected as the main component of the red paintings. No evidence of manganese was detected in either the brownish or the black paintings, contrary to other Neolithic paintings in the Mediterranean area. 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.     

Optical coherence tomography in art diagnostics and restoration

An overview of the technique of optical coherence tomography (OCT) is presented, and a spectral OCT instrument especially designed for art diagnostics is described. The applicability of OCT to the stratigraphy of oil paintings is discussed with emphasis on examination of the artist’s signature. For the first time, OCT tomograms of stained glass are presented and discussed. The utilisation of Spectral OCT in real-time monitoring of varnish ablation is discussed with examples of ablation, melting and evaporation, and exfoliation of the varnish layer provided, for the first time. PACS  42.30.-Wb; 07.60.-j; 07.60.-Ly; 81.70.Fy; 79.20.Ds     

Relics in medieval altarpieces? Combining X‐ray tomographic,laminographic and phase‐contrast imaging to visualize thin organic objects in paintings

X‐ray radiography is a common tool in the study of old master paintings. Transmission imaging can visualize hidden paint layers as well as the structure of the panel or canvas. In some medieval altarpieces, relics seem to have been imbedded in the wooden carrier of paintings. These are most probably thin organic fibrous materials such as paper or textile, which in traditional radiography are shadowed by the more absorbing surrounding material. This paper studies the application potential of synchrotron‐based tomographic and laminographic imaging complemented with phase‐contrast imaging for detection of such relics. The techniques are applied to a dummy painting. The results demonstrate that by using these imaging methods it is possible to three‐dimensionally visualize hidden cavities in panels and detect thin fibrous low‐Z materials sandwiched between a high‐Z paint layer and a thick wooden panel.     

Historical evolution of oil painting media: A rheological study

Rheology is the science of flow, which is a phenomenon found in every painting operation, such as decorative paintings or protective coatings. In this article, the principles of rheology as applied to paintings and coatings are recalled in a first part and the rheological criteria required in the paint industry presented. Indeed, different flow behaviours leads to different finishes. The same procedure and techniques as in industry can be employed to explain some evolutions in oil painting aspects over the centuries. The first recipes for oil painting indicate the use of treated oil, resins and spirits. This article deals with the evolution of the composition of these systems as media for oil painting, according to rheological clues.During the Renaissance period, the media used were Newtonian or slightly shear thinning and allowed one a perfect levelling. Then techniques changed, paints became more opaque with less addition of oil/resin media, and brushstrokes appeared visible. Some preparations containing lead, oil and mastic resin, whose flow behaviour is closed to those required in industry, may have appeared during the 17th century and are still used and sold today. To cite this article: L. de Viguerie et al., C. R. Physique 10 (2009).     

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.     

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.     

Raman spectroscopy of synthetic organic pigments used in 20th century works of art

Raman microscopy allows a non‐destructive characterisation of inorganic and organic painting materials such as pigments and organic dyestuffs. The objectives of this study are the more recent organic pigments typically present in paintings and other art works from the 20th century. More than 20 organic synthetic pigments from different chemical classes could be identified by Raman spectroscopy using different excitation wavelengths (457.9, 476.5, 487.9, 514.5, 632.8, and 1064 nm). To evaluate the performance for real paint samples, varying paint mixtures of the Hansa Yellow pigment PY 3 and the binding medium Mowilith, a polyvinyl acetate (PVAC) compound, were characterised; PY 3 was determined at a 1 wt% level in the binder. In addition, commercial tube paints containing the quinacridone violet PV 19 were studied. The pigment was clearly identified in all of these more complex oil and acrylic paints. Finally, alizarin (PR 83) and a green copper phthalocyanine pigment (PG 7) could unambiguously be identified by Raman microscopy in the painting ‘Woman with mandolin in yellow and red’ of Max Beckmann dating 1950. The discovery of a red naphthol AS pigment by Raman spectroscopy in a sample from the ‘Three field workers’ by Georg Baselitz (1964/1965) demonstrated that in some cases complementary chromatographic methods are needed for a comprehensive identification of the organic pigments. Copyright © 2008 John Wiley & Sons, Ltd.     

X‐ray techniques applied to surface paintings of ceramic pottery pieces from Aguada Culture (Catamarca,Argentina)

X‐ray diffraction (XRD), energy dispersive spectrometry (EDS), x‐ray imaging (XRI) and scanning electron microscopy (SEM) techniques were applied to characterize and differentiate surface paintings of archeological pottery from the Aguada Ambato and Portezuelo styles (Catamarca, Argentina). Standard procedures are not always appropriate for such samples (paint layers are porous, nonplanar and discontinue). Image processing is necessary when chemical contrast is not discriminated. Soft x‐ray lines (e.g. Fe L) are more revealing because those detected come from shallower depths, clearly depicting the composition of the paint layer. These styles differ in mineralogy and chemistry suggesting that they are two distinctive entities not only on their designs but also on the materials chosen and the technology used. Aguada Portezuelo paints contain Ca (white), Fe? Mn (black), Fe? Mn? Ca (dark reddish) and Fe? Ca (reddish). The white ones correspond to gehlenite, a firing product (possible firing temperature ≥900–1000 °C); calcite and CaO occur in cases of firing temperatures <900 °C. Aguada Ambato presents difficulties for paint discrimination; only EDS spectra show slight differences. White paint from Tricolor Ambato contains mainly Pb‐phases (hatchite, anglesite, plumalsite), reddish paint resembles the paste (～Fe, hematite); reddish surfaces may have not been painted but polished. Black paint has scarce Mn–minerals. On Black Incised sherds no particular phase was identified suggesting possible organic pigments or resulting from the firing technique. The chemistry and mineralogy of the paste almost always overlap that of the paints; painted layer is irregular and partially worn by years of burial. Copyright © 2009 John Wiley & Sons, Ltd.     

Nondestructive evaluation of incipient corrosion in a metal beneath paint by second-harmonic tomography

A second-harmonic optical scanning imaging method for nondestructive evaluation of corrosion of painted metals is demonstrated. Two-dimensional images of the sectional structure from a sample of painted metal with corrosion were obtained by detection of second-harmonic generation (SHG). The second-harmonic signals generated from paint, corrosion, and metal can be spatially imaged in ~10-mum sliced subsurface layers. Corroded metal layers covered with paint are found to have more intensity variation than normal polished metal. The spatial mapping of the second-harmonic signals shows depth differentiation of paint, corrosion, and metal surfaces. The depth of corrosion beneath the paint can be measured from the SHG images.     

Development of confocal X-ray fluorescence (XRF) microscopy at the Cornell high energy synchrotron source

A confocal X-ray fluorescence microscope was built at the Cornell High Energy Synchrotron Source (CHESS) to obtain compositional depth profiles of historic paintings. The microscope consists of a single-bounce, borosilicate monocapillary optic to focus the incident beam onto the painting and a commercial borosilicate polycapillary lens to collect the fluorescent X-rays. The resolution of the microscope was measured by scanning a variety of thin metal films through this confocal volume while monitoring the fluorescence signal. The capabilities of the technique were then probed using test paint microstructures with up to four distinct layers, each having a thickness in the range of 10–80 microns. Results from confocal XRF were compared with those from stand-alone XRF and visible light microscopy of the paint cross-sections. A large area, high-resolution scanner is currently being built to perform 3D scans on moderately sized paintings. PACS 29.30.Kv; 68.37.Yz; 41.50.+h     

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。