Surface study of films formed on copper and brass at open circuit potential

Abstract

The corrosion resistance of Cu-Zn alloys strongly depends on the quality of the protective passive film. This study focuses on the influence of Zn on the composition of oxide films on copper and brass (Cu77Zn21Al2) in borax 0.1 mol L−1 (pH 9.2) solution, where the solubility of copper oxides is minimal. The effect of the presence of chloride ions at low concentration (0.01 mol L−1) in the electrolyte was also evaluated. Both conditions were studied using a set of different electrochemical, optical and surface techniques such as cyclic voltammetry, differential reflectance, X-ray photoelectron spectroscopy and Raman spectroscopy. A duplex Cu2O/CuO layer forms on copper at potentials positive to the open circuit potential (OCP), while in the case of brass, zinc compounds are also incorporated to the surface film. It also became evident that a surface film can be formed on these materials even at potentials negative to the OCP. Zn(II) species are the main constituents of the films growing on brass, while copper oxides are incorporated to the surface film when approaching the OCP. The presence of chloride ions at low concentrations contributes to the dissolution of the oxo-hydroxides formed during the early stages of the ageing process at open circuit potential. Also, copper chloro-compounds are formed, as shown by Raman spectroscopy for both copper and brass electrodes.