The activation of aluminium by mercury ions in non-aggressive media

Abstract The presence of Hg at concentration less than 300 ppm in Al base alloys causes their passivation breakdown. On alloys used as sacrificial anodes, it causes a major lowering (>0.3 V) in their operational potential in chloride media. Mercury as trace constituent in the natural gas stream causes severe damage to cryogenic heat exchangers. The present paper presents evidences of the mechanism by which mercury produces its pronounced effect in aqueous non-aggressive media. The work was carried out using pure (99.99%) aluminium and mercury (II) acetate solutions of different concentrations and pH. Open circuit potential–time responses were obtained. The surface effects were followed by means of scanning microscopy and EDAX/X-Ray analysis. The results demonstrate that immediately after immersion, the initial air-formed oxide film underwent a dynamic crack–healing process at flaws in the film, possible associated to grain boundaries. The subsequent healing process, if any, depends on the media composition. Thus, in this special case, Hg 2+ ions can be directly reduced on the bare aluminium, reaching a true metallic contact, and initiating surface diffusion. This enables the formation of an amalgam. Aluminium atoms diffuse through the liquid mercury and undergo oxidation at the amalgam/electrolyte interface. This process is responsible for the oxide detachment (by undermining) and the attack morphology (i.e., wide cavities). The presence of aggressive anions is not needed to initiate activation.