Thermal Reconversion of Oxidised Lead White in Mural Paintings via a Massicot Intermediate

Lead white 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 (\b{eta}-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 (\b{eta}-PbO) intermediate, with a view to developing a restoration procedure using continuous wave laser heating. 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 TGA and XRD and SEM characterization were achieved. Litharge (α-PbO) and massicot were obtained from plattnerite respectively between 564 and 567 °C and at 650 °C. Lead carbonates (cerussite, hydrocerussite and plumbonacrite) 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.