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Issue 7, 2016
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Ab initio study of PbCr(1−x)SxO4 solid solution: an inside look at Van Gogh Yellow degradation

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Abstract

Van Gogh Yellow refers to a family of lead chromate pigments widely used in the 19th century and often mixed with lead sulfate to obtain different yellow hues. Unfortunately, some paintings, such as the famous Sunflowers series, suffered degradation problems due to photoactivated darkening of once bright yellow areas, especially when irradiated with UV light. Recent advanced spectroscopic analyses have proved that this process occurs mostly where the pigment presents a sulfur-rich orthorhombic phase of a PbCr(1−x)SxO4 solid solution, while chromium-rich monoclinic phases are lightfast. However, the question of whether degradation is purely a surface phenomenon or if the bulk properties of sulfur-rich pigments trigger the process is still open. Here, we use first-principles calculations to unveil the role of sulfur in determining important bulk features such as structure, stability, and optical properties. From our findings, we suggest that degradation occurs via an initial local segregation of lead sulfate that absorbs at UV light wavelengths and provides the necessary energy for subsequent reduction of chromate ions into the greenish chromic oxide detected in experiments. In perspective, our results set reliable scientific foundations for further studies on surface browning phenomena and can help to chose the best strategy for the proper conservation of art masterpieces.

Graphical abstract: Ab initio study of PbCr(1−x)SxO4 solid solution: an inside look at Van Gogh Yellow degradation

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Publication details

The article was received on 15 Nov 2015, accepted on 09 Mar 2016 and first published on 10 Mar 2016


Article type: Edge Article
DOI: 10.1039/C5SC04362J
Chem. Sci., 2016,7, 4197-4203
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Ab initio study of PbCr(1−x)SxO4 solid solution: an inside look at Van Gogh Yellow degradation

    A. B. Muñoz-García, A. Massaro and M. Pavone, Chem. Sci., 2016, 7, 4197
    DOI: 10.1039/C5SC04362J

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

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      [Original citation] - Published by The Royal Society of Chemistry.

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