Metastable, solid–solution Mg-0.8 at.% Cu and Mg-1.4 at.% Zn alloys have been anodized up to 250 V at 10 mA cm−2 in an alkaline phosphate electrolyte at 293 K in order to investigate the enriching of alloying elements beneath the anodic films. Rutherford backscattering spectroscopy (RBS) revealed enrichments to about 4.1×1015 Cu atoms cm−2 and 5.2×1015 Zn atoms cm−2, which correlate with the higher standard Gibbs free energies per equivalent for formation of copper and zinc oxides relative to that for formation of MgO. The enriched layers were of thickness about 1.5–4.0 nm by medium energy ion scattering (MEIS). The anodic films, composed mainly of magnesium hydroxide, contained copper and zinc species throughout their thicknesses; the Cu:Mg and Zn:Mg atomic ratios were about 18 and 25% of those of the alloys, respectively. Phosphorus species were present in most of the film regions, with a P:Mg atomic ratio of about 0.16. The magnesium ions in the film account for about 30% of the charge passed during anodizing.

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