Breakdown of Oxide Films on Steel Exposed to Chloride Solutions

Breakdown of the thin air-formed oxide film is the first step in the corrosion of steel exposed to aqueous chloride environments. We studied oxide-film breakdown by observing changes, with time, of appearance, weight loss, and corrosion potential while varying the three components of the system: environment, substrate, and film. Environment was varied by changes in chloride and hydrogen peroxide concentrations. Low carbon steel, stainless steel, aluminum, and titanium substrates were studied. Various types of crystalline oxide film were applied to steel substrates by RF sputtering. The results of this work demonstrated that the chemical and electronic properties of the oxide film on steel are inconsequential in determining whether film-breakdown will occur. We interpret these results in terms of a film-breakdown mechanism in which substrate dissolution begins at film defects and spreads, thus causing removal of the film by undercutting. According to this model, the ability of the substrate to spontaneously reform a stable oxide and repair the film determines resistance to film-breakdown.