A study of the effects of inhibitive and aggressive ions on oxide-coated aluminium using secondary ion mass spectrometry

A Cameca Ion Analyser has been used to examine aluminium surfaces, supporting barrier-type anodic films ca. 720Å thick, after natural immersion for 1–25 h in 1M chloride and chromate/dichromate solutions of varying pH, and neutral 1M phosphate solution. In chloride solutions, chloride is present on the film surface, but not within the film material per se, within the limits of measurement. The degree of film thinning is governed by pH, being more pronounced in alkaline than acid solutions. In chromate/dichromate solutions, chromium uptake occurs by two distinct mechanisms. The first is associated with relatively rapid chromate/dichromate reduction to Cr₂O₃, probably hydrated, within flaws in the anodic film. The second is associated with a more gradual direct chromate/dichromate anion entry into the bulk material probably through the intercrystalline regions in the film, ultimately resulting in film thinning, even in neutral solutions. In phosphate solutions, phosphate anions penetrate and thin bulk anodic alumina in a similar manner to chromate/dichromate anions. The results are interpreted on the basis of the differing surface chemical properties of the various anions in relation to bulk alumina.