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Copper alloys interact with air pollutants to form corrosion products and, consequently, a patina on outdoor bronze sculptures. In this study, corrosion experiments were conducted to clarify the corrosion behaviors of artificial sulfide patina in an urban–industrial environment on a quaternary bronze alloy (Cu–Zn–Sn–Pb) with a composition and metallurgical properties similar to those of outdoor bronze sculptures. The correlation between the chromaticity and reflectance of the patina revealed increasing brochantite with the corrosion of the patina and an association between the chromaticity a* and patina growth. Cuprite and brochantite were distinguished, and the point at which brochantite covered the patina surface was determined. The quantitative changes in brochantite were mainly influenced by physical causes such as the crystal size and patina layer thickness as well as by Cu2+ ions working as color formation ions moving to the outermost layer. Atmospheric corrosion of the alloy resulted in reduced Cu and Zn contents and increased Sn and Pb contents. The patina consisted of brochantite in the outermost layer and cuprite and cassiterite in the inner layers. These findings should clarify corrosion characteristics such as the surface color, composition, and changes in corrosion products of outdoor bronze sculptures and contribute toward their preservation.

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Silver objects tarnish with black from reaction with sulfurous acid or hydrogen sulfide of atmospheric. Blackening of silver objects results from formation of silver sulfide(Ag2O) on the surface. Silver sulfide usually is usually removed by conservation treatment. There are several cleaning methods such as chemical, electrochemical and micro-abrasion cleaning, but all of them consume silver. This study investigated the safe and effective parameter of laser cleaning by test on silver coupons. Laser cleaning is a selective process for the removal of specific substances. At first, laser cleaning applied to plain silver coupons, which were not corroded, to find out the safe range of laser energy density. From results, plain silver coupons were not changed at 1064nm below 4.00J/cm 2 and at 532nm below 2.39J/cm 2. The corrosion layer(silver sulfide) of artifical corroded silver coupons was removed at 1064nm with 2.39J/cm 2 by 5~10 pulses and at 532nm with 1.19J/cm 2 by 5~10 pulses. The removal thickness of corrosion layer was about 13-25nm per a laser pulse using AES analysis. In addition, laser cleaning tested the tarnish silver rings based on the results of silver coupons. As a result of test, the black surface were clean successfully and gave luster of silver, which showed the application possibility of laser cleaning for silver objects.