Raman spectroscopy as a means for the identification of plattnerite (PbO2), of lead pigments and of their degradation products

The Raman spectra of plattnerite [lead(IV) oxide, PbO2] and of the lead pigments red lead (Pb3O4), lead monoxide [PbO, litharge (tetragonal) and massicot (orthorhombic)], lead white [basic lead carbonate, 2PbCO3.Pb(OH)2] and of their laser-induced degradation products were recorded using a range of different excitation lines, spectrometer systems and experimental conditions. The degradation of PbO2 is more extensive along the pathway PbO2-->Pb3O4-->PbO (litharge)-->PbO (massicot) the shorter the wavelength of the excitation line and the higher its power. The Raman spectrum of PbO2, which is black and of the rutile structure, is particularly difficult to obtain but three bands, at 653, 515 and 424 cm-1, were identified as arising from the b2g, a1g and e(g) modes respectively, by analogy with the corresponding modes of isostructural SnO2 (776, 634 and 475 cm-1). A further oxide was identified, PbO1.55, the Raman spectrum of which does not correspond to that of any of the laser-induced degradation products of PbO2 at any of the wavelengths used. The Raman results are critical to the future use of Raman microscopy for the identification of lead pigments on artworks.