Leonardo da Vinci’s drapery studies: characterization of lead white pigments by µ-XRD and 2D scanning XRF (original) (raw)
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Scientific Reports
Leonardo da Vinci (1452–1519) is a key artistic and scientific figure of the Renaissance. He is renowned for his science of art, taking advantage of his acute observations of nature to achieve striking pictorial results. This study describes the analysis of an exceptional sample from one of Leonardo’s final masterpieces: The Virgin and Child with St. Anne (Musée du Louvre, Paris, France). The sample was analyzed at the microscale by synchrotron-based hyperspectral photoluminescence imaging and high-angular X-ray diffraction. The results demonstrate Leonardo’s use of two subtypes of lead white pigment, thus revealing how he must have possessed a precise knowledge of his materials; carefully selecting them according to the aesthetical results he aimed at achieving in each painting. This work provides insights on how Leonardo obtained these grades of pigment and proposes new clues regarding the optical and/or working properties he may have tried to achieve.
Analytical chemistry, 2017
Micro-samples collected on 28 major paintings by Old European Masters dating from the Middle Ages to the late 19th c. were analyzed using Synchrotron-based X-ray diffraction. Two complementary analytical configurations were used at beamlines ID22 (high-angle resolution) and ID21 (high lateral resolution), in order to highlight markers of the different grades of the lead white pigments (mixture of cerussite PbCO3 and hydrocerussite Pb3(CO3)2(OH)2). Rietveld analysis and crystalline phases mapping at the micro-scale revealed the composition and microstructure of the pigments, shedding light on the preparation recipes and pigment choices of the artists through History.
Fifteen lead white-containing painting samples, about 1-3 μg in weight, from a selection of easel painting masterpieces of the Louvre and other French museums, dating from the Renaissance to the late 19 th century, were investigated using synchrotron diffraction on the ESRF high resolution XRD beamline ID22. The Rietveld analysis revealed the nature of the pigments through the cerussite:hydrocerussite (PbCO 3 :Pb 3 (CO 3 ) 2 (OH) 2 ) ratios, the approximate dimensions of the crystallites and the presence of crystalline extenders. This first insight into a still widely unknown domain gives some hints, but also raises questions about the artists' preferences for selecting, preparing and post-treating white pigments. A significant increase of the crystallites size over five centuries also suggests an evolution of these processes.
Journal of Raman Spectroscopy, 2020
This work reports the results of an extensive study carried out on the wall paintings preserved inside the Saint Stephen's chapel in Montani (Val Venosta, Bozen, Italy), by means of μ‐Raman spectroscopy, portable X‐ray fluorescence (XRF) spectrometry, and powder X‐ray diffraction, in order to characterize materials and their alteration products that cause the blackening of paintings. In situ XRF analysis allowed identifying the areas of interest where the blackening appeared. The complementary analytical techniques allowed reconstructing a chromatic palette used by the artists that includes expensive pigments, such as lapis lazuli and cinnabar, indicating a wealthy client. Raman spectra at very low power recorded on blackened degraded samples showed the presence of a mixture of the two polymorphs of lead (IV) dioxide, plattnerite (β‐PbO2), and scrutinyte (α‐PbO2), as degradation products of lead‐based pigments. On these samples, no evidence of white lead was found, although a wh...
Classification of lead white pigments using synchrotron radiation micro X-ray diffraction
Applied Physics A, 2007
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.
Heritage
The palette used on a small painting on copper support, with the inscription “Boceto di Pablo Veronese” on the back, was characterized. Non-invasive techniques such as X-ray diffraction (XRD) and hand-held X-ray fluorescence (XRF) were proven to be highly effective for this. The objectives of the proposed work were twofold. On the one hand, the objective was the study, in situ, of the pigments of a painting on a copper support. On the other hand, it was to enrich the literature related to the study of paintings on metal supports, since few related studies are available despite the relatively large number of such 16th and 17th century paintings from Italy and Northern Europe. The results of the analysis showed a copper support with a base layer of gypsum mixed with ochre earths. Atop this layer is a sketch with lead white in the lighter areas and bone black in the darker shadow areas, suggesting that the artist performed a preliminary study of the luminosity of the scene. Finally, th...
Analytical Chemistry, 2017
Microsamples collected on 27 major paintings by Old European Masters dating from the 14th to the late 19th centuries were analyzed using synchrotron-based X-ray diffraction. Two complementary analytical configurations were used at beamlines ID22 (high angle resolution) and ID21 (high lateral resolution), in order to highlight markers of the different grades of the lead white pigments (mixture of cerussite PbCO 3 and hydrocerussite Pb 3 (CO 3) 2 (OH) 2). Rietveld analysis and crystalline phases mapping at the microscale revealed the composition and microstructure of the pigments, shedding light on the preparation recipes and pigment choices of the artists through History.
Spectrochimica Acta Part A-molecular and Biomolecular Spectroscopy, 2009
The palette used in two paintings by Paul Cézanne, L’étang des sœurs dated c. 1875 and La route tournante, made in the last year of his life (1902), were analyzed using non-invasive spectroscopic methods. X-ray fluorescence combined with principal components analysis (PCA) and supported by reflectance near- and mid-FTIR was shown to be a powerful analytical tool to draw conclusions about the chemical identification of inorganic materials in paintings. Pigments and fillers such us Thénard's blue, Prussian blue, red ochre, kaolin, vermilion, lead white, zinc white and barium sulphate, were identified. Evidence for three different pigments, namely a copper arsenite pigment, chrome green (a mixture of chrome yellow and Prussian blue) and viridian has been obtained by the PCA analysis of elemental compositions of green hues.
The combined use of lead–tin yellow type I and II on a canvas painting by Pietro Perugino
Journal of Cultural Heritage, 2007
non-destructive x-ray fluorescence (XRF) technique. Three anomalous characteristics were frequently identified, concerning a brown earth pigment containing zinc, the presence of manganese in some red lakes and the association of the presence of copper and tin with grey-blue regions. In an effort to understand these anomalies better, five micro-samples, taken from selected easel paintings by Perugino at the Galleria Nazionale dell'Umbria and a fresco at the Monastero di Sant'Agnese in Perugia, were studied by micro-Raman spectroscopy and scanning electron microscopy (SEM). Micro-Raman spectroscopy was a useful tool to investigate the molecular nature of such uncommon pigments and SEM provided useful information on the stratigraphy of the paint layers. The brown earth pigments, used by the master in the last period of his production, were definitely confirmed to be characterized by zinc impurities. The manganese contained in red lakes was shown to be due to ground alkaline glass, with a small quantity of manganese and iron, probably added to the oil binder in an attempt to speed up drying. Finally, in the sampled paintings, the grey-blue colour characterized by copper and tin was not present.
Red lead, a semiconductor pigment used by artists since antiquity, is known to undergo several discoloration phenomena. These transformations are either described as darkening of the pigment caused by the formation of either plattnerite (b-PbO2) or galena (PbS) or as whitening by which red lead is converted into anglesite (PbSO4) or (hydro)cerussite (2PbCO3·Pb(OH)2 ; PbCO3). X-ray powder diffraction tomography, a powerful analytical method that allows visualization of the internal distribution of different crystalline compounds in complex samples, was used to investigate a microscopic paint sample from a Van Gogh painting. A very rare lead mineral, plumbonacrite (3PbCO3· Pb(OH)2·PbO), was revealed to be present. This is the first reported occurrence of this compound in a painting dating from before the mid 20th century. It constitutes the missing link between on the one hand the photoinduced reduction of red lead and on the other hand (hydro)cerussite, and thus sheds new light on the whitening of red lead.