Study by grazing incident diffraction and surface spectroscopy of amalgams from ancient mirrors

Characterization of four amalgam surfaces, with different alteration degrees from Andalusia historical mirrors, has been carried out by grazing-incidence X-ray diffraction (GIXRD), and other spectroscopic techniques (SEM/EDX, XPS, and REELS). The combination of all these techniques allows determining the corrosion state of the amalgams. The results show that the amalgams are composed in all cases of a binary alloy of tin and mercury. As mercury has high vapour pressure at RT, it slowly segregates and eventually evaporates, it leaves finely divided particles of tin that easily can be oxidize, forming tin monoxide (SnO) and tin dioxide (SnO₂). In one of the samples, most of the amalgam remains unoxidized, since Hg_0.1Sn_0.9 and metallic Sn phases are the major components; in two other samples, Hg_0.1Sn_0.9 and Sn phases are not detected while SnO₂ and SnO phases appear. Finally, in the last studied sample, only SnO₂ phase is detected. The surface analyses of these samples by XPS show that, for most of them an unique chemical species (Sn⁴⁺) is found.