Removal of brownish-black tarnish on silver–copper alloy objects with sodium glycinate

• Published in: Applied surface science 2014-10, Vol.317, p.67-72
• Main Authors: de Figueiredo, João Cura D’Ars, Asevedo, Samara Santos, Barbosa, João Henrique Ribeiro
• Format: Article
• Language: English
• Subjects: Chemical cleaning; CLEANING; Coins; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; CORROSION; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Glycinate; Immersion; Infrared absorption spectroscopy; Physics; Quantum chemistry; Scanning electron microscopy; Silver; Silver–copper alloy; Sodium; Tarnish; TARNISHING; X-ray fluorescence
• ISSN: 0169-4332; 1873-5584
• DOI: 10.1016/j.apsusc.2014.08.096

•The use of glycinate to remove brownish-black tarnish on silver–copper alloy objects is studied.•The method is easy to use and harmless. It is based in the coordination of Ag and Cu in tarnish with glycinate.•The surface of corroded silver objects and products of reaction were studied and glycinate showed to be very selective for Ag(I) and Cu(II). The selectivity for Ag(I) was studied by means of quantum chemical calculations. This article has the principal aim of presenting a new method of chemical cleaning of tarnished silver–copper alloy objects. The chemical cleaning must be harmless to the health, selective to tarnish removal, and easy to use. Sodium glycinate was selected for the study. The reactions of sodium glycinate with tarnish and the silver–copper alloy were evaluated. Products of the reaction, the lixiviated material, and the esthetics of silver–copper alloy coins (used as prototypes) were studied to evaluate if the proposed method can be applied to the cleaning of silver objects. Silver–copper alloys can be deteriorated through a uniform and superficial corrosion process that produces brownish-black tarnish. This tarnish alters the esthetic of the object. The cleaning of artistic and archeological objects requires more caution than regular cleaning, and it must take into account the procedures for the conservation and restoration of cultural heritage. There are different methods for cleaning silver–copper alloy objects, chemical cleaning is one of them. We studied two chemical cleaning methods that use sodium glycinate and sodium acetylglycinate solutions. Silver–copper alloy coins were artificially corroded in a basic thiourea solution and immersed in solutions of sodium glycinate and sodium acetylglycinate. After immersion, optical microscopy and scanning electron microscopy of the surfaces were studied. The sodium glycinate solution was shown to be very efficient in removing the brownish-black tarnish. Absorption spectroscopy measured the percentage of silver and copper lixiviated in immersion baths, and very small quantities of these metals were detected. Infrared absorption spectroscopy and X-ray fluorescence characterized the obtained products. The greater efficiency of the sodium glycinate solution compared to the sodium acetylglycinate solution was explained by chelation and Hard–Soft Acid–Base Theory with the aid of quantum chemical calculations.