In recent years, with the excavation of an increasing amount of gold and silver artifacts, there has been an urgent need to optimize the formulations and methods of metallographic etching. Herein, a kinetic control study is performed to investigate the mechanisms leading to poor results when etching ancient gold materials with aqua regia, i.e., when secondary AgCl impurities form during the etching of the sample surface. To this end, a concentrated ammonia and sodium thiosulfate solution is used to dissolve AgCl impurities and obtain high-quality metallographic images of ancient gold materials using a coordination reaction to generate stable free-state coordination ions from Ag+. On this basis, a ferric chloride + sodium thiosulfate method is proposed to optimize the formulation of the etchant for ancient silver materials. The formulation is efficient, safe and easy to handle, and solves the problems of the easy failure of the commonly used etchant of ammonia + hydrogen peroxide and the complicated preparation process of acidified potassium dichromate while maintaining the long-term stability of the etched Ag–Cu alloy samples.
