The impact of urban rain on the changes of bare and artificially patinated bronze during 9-year exposure

Atmospheric pollutants in the air form acid rain which interacts with bronze surfaces exposed in urban outdoor environment. In this study, different types of patinas on bronze were investigated during and after 9 years of exposure to urban environment in moderately polluted continental city. Natural bronze patina and artificial brown sulphide, green chloride, and green–blue nitrate patinas were investigated. Visual assessment was carried out at defined periods. After 9 years of exposure, an electrochemical study was performed to investigate the electrochemical activity of the patinas in artificial urban rain. Additionally, the patinas were characterised using a variety of techniques, including metallographic examination, scanning electron microscopy/energy dispersive X-ray spectroscopy, Raman spectroscopy, X-ray diffraction analysis, X-ray-photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry to analyse the surface morphology, chemical composition, and stratigraphic features of the patinas. Evolution of the patinas was shown to be a result of both, the composition of the acid rain and the hydrophobicity of the patinated surfaces.