Tin amalgam mirrors: investigation by XRF, SEM-EDS, XRD and EPMA-WDS mapping

Ancient mirrors were constituted by a tin-mercury amalgam layer superimposed to a glass sheet. This was the only one method used until the nineteenth century, when the wet silvering process was invented. The tin amalgam is a binary alloy of tin and mercury constituted by two different phases: a mercury-rich liquid phase and a tin-rich solid phase. The amalgam alteration produces mercury loss and a general growth of the solid crystalline phase. In addition, tin dioxide and monoxide are formed with a consequent decrease of the amalgam adhesion to the glass. These degradation phenomena led to reduction or disappearance of the mirror reflective power.The aim of this study was the characterization of the amalgam layers of eight mirror samples dating during the seventeenth and nineteenth centuries. The samples were analyzed by X-ray diffraction and by a Scanning Electron Microscope with an Energy Dispersive Spectrometer (SEM-EDS), and for the first time on this type of alloy by X-ray Fluorescence and EPMA-WDS (Electron Probe Micro Analysis with Wavelength Dispersive Spectrometry) elemental mapping.The contents of tin, mercury, and some trace elements in the amalgam layers have been determined. The investigation of the superficial patterns of the amalgam by SEM, EPMA-WDS mapping, and SEM-EDS allowed a first understanding of some morphologies and processes of the degradation of the amalgam layer.