The speciation of Si and other alloying elements in the oxide surface film of galvanically corroded weld fusion zone of laser welded AA6061 aluminium alloy

It has recently been proposed that on galvanic corrosion of laser weldments of AA6061 aluminium alloy the temporal increase in galvanic corrosion resulted from either the build up of intermetallic phases in the surface oxide layer and/or a significant increase in the surface area of the cathodic weld fusion zone due to the porous nature of the surface layer. This proposition has motivated a comprehensive surface analytical study of the incorporation of alloying elements into the oxide surface film, which is composed predominately of alumina. Si is found to be present as silicate and silicides. The Gibbs free energy of formation, per cation, of silicate is more negative than that for alumina and hence silicate formation is thermodynamically, relatively, favourable. In contrast the Gibbs free energy for oxide formation, per cation, for the other alloying elements is less negative and hence relatively unfavourable compared to the formation of alumina. We propose therefore that Fe, Cu and Cr are present in the metallic form, possibly as silicides, within the oxide surface layer. Magnesium is found to be depleted relative to the weld fusion zone presumably due to dissolution within the electrolyte.