The protective nature of passivation films on zinc: surface charge

The influence of oxide surface charge on the corrosion performance of zinc metals was investigated. Oxidised zinc species (zinc oxide, zinc hydroxychloride, zinc hydroxysulfate and zinc hydroxycarbonate) with chemical compositions similar to those produced on zinc during atmospheric corrosion were formed as particles from aqueous solution, and as passive films deposited onto zinc powder, and rolled zinc, surfaces. Synthesized oxides were characterised by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and electron probe X-ray microanalysis. The zeta potentials of various oxide particles, as determined by microelectrophoresis, are reported as a function of pH. Particulates containing a majority of zinc hydroxycarbonate and zinc hydroxysulfate crystallites were found to possess a negative surface charge below pH 6, whilst zinc oxide–hydroxide and zinc hydroxychloride crystallites possessed isoelectric points (IEP’s) higher than pH 8. The ability of chloride species to pass through a bed of 3 μm diameter zinc powder was found to increase for surfaces possessing carboxy and sulfate surface species, suggesting that negatively charged surfaces can aid in the repulsion of chloride ions. Electrochemical analysis of the open-circuit potential as a function of time at a fixed pH of 6.5 showed that the chemical composition of passive films on zinc plates influenced the ability of chloride ions to access anodic sites for periods of approximately 1 h.