Investigation on the reaction of sulphur with Ag–Cu–Zn-Ge alloy: Experimental and computational study

Silver and its alloys undergo tarnishing with time, which is a black stain on the surface due to the formation of Ag 2 S. Developing a tarnish resistant Ag alloy was attempted by alloying Ag with elements that form a passive oxide layer on the surface. Germanium is proven to provide better tarnish resistance to sterling Silver alloy (92.5 wt% pure) which is available under the trade name of Argentium©. The present work investigates the tarnish resistance behavior of sterling silver alloy (92.5 wt% pure) containing various additions of Copper, Zinc, and Germanium. The alloys were prepared by melting and casting route, followed by Passivation Heat Treatment (PHT) to create a stable and continuous oxide layer. The temperature for PHT was optimized using thermogravimetry analysis (TGA) of the alloys prepared. Accelerated tarnish test was carried out to investigate the tarnishing behavior of alloy samples obtained before and after PHT. The samples were characterized using XRD, SEM-EDX, and micro-Raman Spectroscopy. The change in reflectance of the samples after tarnish test is determined using UV–Visible reflectance spectroscopy. The mechanism behind the tarnish resistance was derived using Density Functional Theory (DFT) by comparing sulphur (S 2 ) and Oxygen (O 2 ) adsorption energies (BE) of the alloying elements. The lower value of S 2 (BE)/O 2 (BE) indicates better oxidation and tarnish resistance. The ratio ranges between 222 % (Pure Ag) and 132 % (for Ag-4.2Cu-2.8Zn-1.4Ge) and the p-p between Ge and O has contributed to the reduction in the ratio.