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Thermal reconversion of oxidised lead white in mural paintings via a massicot intermediate

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Abstract

Lead white, a mixture of cerussite (PbCO3) and hydrocerussite (2PbCO3·Pb(OH)2), is the most ancient and common white pigment used in mural paintings. However, it tends to blacken with time due to its oxidation to plattnerite (β-PbO2). Chemical treatments were used but they can put the pictorial layers supports at risks. Hereby, we address the possibility of thermally reconverting black plattnerite to white lead carbonates via a massicot (β-PbO) intermediate. We first investigated the conditions (temperature, time, and environment) in which pure powders react, before studying mural painting samples. Experiments were made in ovens and thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) characterisation were achieved. Litharge (α-PbO) and massicot were obtained from plattnerite, respectively, between 564 and 567 °C and at 650 °C. Lead carbonates, namely cerussite, hydrocerussite and plumbonacrite (3PbCO3·Pb(OH)2·PbO) formed from massicot in wet CO2 below 100 °C in a few hours. Lastly, when heating plattnerite-based mural painting samples, lead species reacted with binders and mortar, yielding massicot, plumbonacrite but also lead silicate and calcium lead oxides. This demonstrates the viability of thermal reconversion of darkened lead in mural, while raising concerns about the formation of several lead species by reaction with mural painting constituents.

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Notes

  1. Reconversion is hereby used in the sense of a chemical reaction (conversion) taking place backward. Here the conversion is the oxidation to plattnerite; the reconversion is thus the formation of cerussite or hydrocerussite (white) or minium (red) from plattnerite (black) [5].

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Acknowledgements

This work benefited from a state fund, managed by the french ANR as part of the France 2030 investements (ANR-17-EURE-0021 – École Universitaire de Recherche Paris Seine Humanités, Création, Patrimoine – Fondation des sciences du patrimoine). The authors wish to acknowledge the French Ministry of Culture and Communication for financial support and the French Fondation des Sciences du Patrimoine for their financial support to the RECONVERT 2 project. The authors would also like to thank Kevin Ginestar from SCCME (CEA Saclay) for the help in the TGA and oven trials, Vasile Heresanu from CINaM (Aix-Marseille Université) for the µ-XRD experiments, Sébastien Aze (Sinopia) for helping in the preparation of mural painting samples, and Xueshi Bai for the discussion and advises throughout the RECONVERT project.

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  1. Centre Interdisciplinaire de Conservation et Restauration du Patrimoine (CICRP), 21 Rue Guibal, 13003, Marseille, France

    Théa de Seauve & Jean-Marc Vallet

  2. Service de Recherche en Corrosion et Comportement des Matériaux (S2CM), Université Paris-Saclay, CEA, 91191, Gif-sur-Yvette Cedex, France

    Sophie Bosonnet

  3. Aix-Marseille Université, CNRS – UMR 7325 CINaM, Campus de Luminy, Case 913, 13288, Marseille Cedex 9, France

    Olivier Grauby

  4. Service de Physico-Chimie, Université Paris-Saclay, CEA, 91191, Gif-sur-Yvette, France

    Alexandre Semerok

  5. C2RMF, Palais du Louvre – Porte des Lions, 14, quai François Mitterrand, 75001, Paris, France

    Vincent Detalle

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de Seauve, T., Bosonnet, S., Grauby, O. et al. Thermal reconversion of oxidised lead white in mural paintings via a massicot intermediate. Appl. Phys. B 129, 137 (2023). https://doi.org/10.1007/s00340-023-08060-5

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