When gold stops glittering: corrosion mechanisms of René Lalique's Art Nouveau jewellery

Abstract

Art Nouveau jewellery created by René Lalique is presently corroded. To identify the corrosion processes, Au–Ag–Cu alloys with compositions comparable to those used in René Lalique's jewellery were fabricated to be exposed to sulphide-containing environments. Using SEM-EDS, XRD, UV-Vis spectroscopy and ellipsometry, it was for the first time demonstrated that at the surface of tarnished Au alloys forms a corrosion film with a layer-by-layer structure. Considering the complex refractive indices of bulk Cu and Ag oxides and sulphides, a two-step corrosion mechanism was proposed. The formation of Cu-based compounds during the early corrosion stages is followed by the formation of Ag-based compounds. The thickness of the formed film, shown for one of the gold alloys to be 80 nm, is due to the corrosion kinetics controlled by the presence of Au and by the formation of a Au–S self-assembled monolayer. The corrosion mechanism of gold alloys raises a new conservation challenge concerning the removal of nanometric layers.