Effect of palladium on sulfide tarnishing of noble metal alloys.

Electron spectroscopic studies of Au-Ag-Cu alloys of the type used for dental castings show that small additions (less than or equal to 3 wt%) of palladium reduce essentially the thickness of the sulfide layer formed on surfaces of samples treated in aqueous Na2S solutions. Relative to silver, palladium does not enrich in the sulfide, but statistically significant enrichment is found immediately below the sulfide layer. This enrichment probably takes place during the exposure of the substrate surface to atmosphere before the sulfiding treatment. The mechanism of the impeding effect of palladium on sulfiding is assumed to be a decrease in diffusion from the bulk alloy to the surface due to the enriched layer. The effect cannot be explained by changes in the electronic structure of the alloy due to palladium alloying.