Study of behavior of copper in systhetic rainwater of São Paulo and Rio de Janeiro and its protection against corrosion by coating and patino exposed to climate action. / Estudo do comportamento de cobre em águas de chuva sintéticas de São Paulo e Rio de Janeiro e sua proteção contra corrosão por revestimentos e pátinas expostos à ação climática.

Rocio del Pilar Bendezú Hernández

Copper is one of the metals most widely used to produce metallic artifacts of the artistic and cultural heritage. This is partially due to its great ability to combine with other compounds, forming patinas of different colors. Many of such artifacts are permanently exposed to open air, being thus subjected to the action of atmospheric agents such as rain and pollutants. Thus, these cultural heritage monuments must be submitted to interventions of preventive nature. This work is devoted to investigate the electrochemical behavior of pure copper, with and without an artificial patina layer, in contact with São Paulo and Rio de Janeiro synthetic rainwater and in NaCl 0,1M solution. The consolidation process of these patinas and the anticorrosive action of varnishes generally used for the protection of the cultural heritage were also investigated. The electrochemical techniques used in this work were: cathodic and anodic potentiodynamic polarization curves and electrochemical impedance spectroscopy. Microstructural and chemical characterizations were performed by means of Scanning Electronic Microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results had shown that the varnishes of Paraloid type used for the protection of the historic monuments are less susceptible to the humidity than the microcrystalline wax. The experiments performed with copper in the synthetic rainwater evidenced an important role for the ammonium ions in the corrosion process. Although with a high complexation power towards copper, accelerating its dissolution rate, these ions participate in the partial regeneration of cuprite. Therefore, in the Rio de Janeiro synthetic rainwater, with low ammonium concentration, once the corrosive attack has started it proceeds in the defective regions of the cuprite layer. On the other hand, in the São Paulo synthetic rainwater, where ammonium ions are more abundant, partial regeneration of cuprite occurs and the electrochemical behavior of copper remains stable with time. The experiments performed with copper coated with an artificial patina layer showed better consolidation of these latter when exposed to the open atmosphere (Electrochemistry and Corrosion Laboratory) when compared to samples stored in a dissecator, where humidity is absent. In the intermittent tests patinated samples developed an impedance response which was typical from porous electrode with semi-infinite porous length, in accordance with the classical model proposed by de Levie (DE LEVIE, 1964). On the other hand, Paraloid B-72 coated samples presented a strong degradation when exposed to sunlight for long exposure periods, which was ascribed to the photooxidative degradation of the coating. The system copper plus patina with a Paraloid B-72 layer showed a good protection towards corrosion, as long as photooxidative degradation had not begun. On the other hand, in the continuous immersion tests, neither the patinas nor the Paraloid varnish exhibited a good performance and were detached after relatively short testing period.

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