Revealing the Origin and History of Lead-White Pigments by Their Photoluminescence Properties

The lead white pigment, composed of two main mineral phases cerussite PbCO₃ and hydrocerussite 2PbCO₃·Pb­(OH)₂, has been used in paintings since the Antiquity. The study of historical sources revealed that a large variety of lead white qualities were proposed, depending on the degree of sophistication of the pigment synthesis. Investigation of photoluminescence of the two constitutive mineral phases gave insight into the origin of the visible emission of these materials and emphasized the influence of structural defects on their photoluminescence properties. These effects were observed by combining emission and excitation spectra in two-dimensional representations. For each excitation wavelength, between 250 and 400 nm (4.9–3.1 eV), luminescence spectra were collected between 400 and 800 nm (3.1–1.5 eV). Two types of emission-excitation bands were identified: an emission excited in the optical bandgap of the compounds (about 5 eV), which depends on the constitutive phase (2.8 eV in cerussite and 2.1 eV in hydrocerussite), and broad emission bands in the same energy range excited below the optical gap, which are sensitive to the synthesis method and the nature of postsynthesis treatments. It is proposed that this sensitivity of photoluminescence properties of lead-white pigments could be used as fingerprints of their origin and history

Degradation Process of Lead Chromate in Paintings by Vincent van Gogh Studied by Means of Spectromicroscopic Methods. Part 5. Effects of Nonoriginal Surface Coatings into the Nature and Distribution of Chromium and Sulfur Species in Chrome Yellow Paints

The darkening of lead chromate yellow pigments, caused by a reduction of the chromate ions to Cr­(III) compounds, is known to affect the appearance of several paintings by Vincent van Gogh. In previous papers of this series, we demonstrated that the darkening is activated by light and depends on the chemical composition and crystalline structure of the pigments. In this work, the results of Part 2 are extended and complemented with a new study aimed at deepening the knowledge of the nature and distribution of Cr and S species at the interface between the chrome yellow paint and the nonoriginal coating layer. For this purpose, three microsamples from two varnished paintings by Van Gogh and a waxed low relief by Gauguin (all originally uncoated) have been examined. Because nonoriginal coatings are often present in artwork by Van Gogh and contemporaries, the understanding of whether or not their application has influenced the morphological and/or physicochemical properties of the chrome yellow paint underneath is relevant in view of the conservation of these masterpieces. In all the samples studied, microscopic X-ray fluorescence (μ-XRF) and X-ray absorption near edge structure (μ-XANES) investigations showed that Cr­(III)-based alteration products are present in the form of grains inside the coating (generally enriched of S species) and also homogeneously widespread at the paint surface. The distribution of Cr­(III) species may be explained by the mechanical friction caused by the coating application by brush that picked up and redistributed the superficial Cr compounds, likely already present in the reduced state as result of the photodegradation process. The analysis of the XANES profiles allowed us to obtain new insights into the nature of the Cr­(III) alteration products, that were identified as sulfate-, oxide-, organo-metal-, and chloride-based compounds. Building upon the knowledge acquired through the examination of original paint samples and from the investigation of aged model paints in the last Part 4 paper, in this study we aim to characterize a possible relation between the chemical composition of the coating and the chrome yellow degradation pathways by studying photochemically aged model samples covered with a dammar varnish contaminated with sulfide and sulfate salts. Cr speciation results did not show any evidence of the active role of the varnish and added S species on the reduction process of chrome yellows

Degradation Process of Lead Chromate in Paintings by Vincent van Gogh Studied by Means of Spectromicroscopic Methods. 3. Synthesis, Characterization, and Detection of Different Crystal Forms of the Chrome Yellow Pigment

The painter, Vincent van Gogh, and some of his contemporaries frequently made use of the pigment chrome yellow that is known to show a tendency toward darkening. This pigment may correspond to various chemical compounds such as PbCrO₄ and PbCr_1‑<i>x</i>S_<i>x</i>O₄, that may each be present in various crystallographic forms with different tendencies toward degradation. Investigations by X-ray diffraction (XRD), mid-Fourier Transform infrared (FTIR), and Raman instruments (benchtop and portable) and synchrotron radiation-based micro-XRD and X-ray absorption near edge structure spectroscopy performed on oil-paint models, prepared with in-house synthesized PbCrO₄ and PbCr_1‑<i>x</i>S_<i>x</i>O₄, permitted us to characterize the spectroscopic features of the various forms. On the basis of these results, an extended study has been carried out on historic paint tubes and on embedded paint microsamples taken from yellow-orange/pale yellow areas of 12 Van Gogh paintings, demonstrating that Van Gogh effectively made use of different chrome yellow types. This conclusion was also confirmed by in situ mid-FTIR investigations on Van Gogh’s <i>Portrait of Gauguin</i> (Van Gogh Museum, Amsterdam)