Influence of dichromate ions on corrosion processes on pure magnesium

The corrosion behavior of Mg is of interest because of its growing use as an alloy in the transportation industry and also because it is a major component of some intermetallic phases in Al alloys, such as the deleterious S (Al2CuMg)-phase found in AA2024-T3. Pure Mg corrodes rapidly in a chloride-containing solution and even dissolves in water if the surface hydroxide is damaged by scratching the surface, for example. Uniform dissolution is drastically reduced in NaCl solutions (from 0.01 to 0.5 M) with the addition of very dilute concentrations of dichromate (10(-4) M). However, it is replaced by a strong localized attack in the form of fast filiform-like attack. On a large-grained sample with a defined defect structure, the attack can be seen to propagate at twin boundaries. Orientation imaging microscopy analysis found that corrosion was limited to planes near {0001} orientations with propagation being in prismatic directions. Auger electron spectroscopy analysis shows that interaction of chromate with the Mg hydroxide results in incorporation of reduced chromium ions in the hydroxide surface layer. Formation of a more resistant surface film could explain the very local nature of the corrosion in this case. The interaction between dichromate ions and Mg hydroxide can also explain the higher corrosion resistance of S-phase particles in chloride solutions containing dilute dichromate, although differences in the surface film formed compared to pure Mg are observed. Sputter-etching of the surface in order to assess the depth of the attack revealed that very hard or isolating corrosion products difficult to sputter are produced along the filiform path and that chromium compounds are not integrated in the corrosion products. Focused ion beam sectioning followed by scanning electron microscopy investigation of the sectioned area, demonstrates the presence of a continuous protective surface film. Adhesion between the Mg hydroxide and the metal is lost at the location of the corrosion filament, suggesting that the mechanism of propagation is similar to filiform corrosion under a coating. The depth of attack is a couple of micrometers with large cracks present within the corroded area that could induce severe surface damage. (C) 2003 The Electrochemical Society.