A transmission electron microscopy study of hard anodic oxide layers on AlSi(Cu) alloys

Transmission electron microscopy (TEM) has been employed to examine anodic oxide film formation on 99.8wt.% aluminium, Al–10wt.%Si and Al–10wt.%Si–3wt.%Cu alloys under conditions relevant to hard anodizing. In particular, anodic oxidation of silicon particles proceeded at a significantly reduced rate compared with that of the adjacent aluminium matrix. This gave rise to alumina film encroachment beneath the particles with development of tortuous porosity and, eventually, occlusion of partially anodized particle in the anodic film. Additional effects included the presence of gas-filled cavities above the silicon particles, associated with oxygen generation above the anodizing particle. The presence of such particles and the corresponding gas-filled voids across the anodic film thickness and at the alloy/film interface is considered responsible for the continuous voltage rise during anodizing of the Al–10wt.%Si alloy, effectively blocking electrolyte access to the pore base and providing local region of high resistance at the alloy/film interface. A direct consequence of the voltage rise was a thickening of the barrier layer at the base of the porous anodic film. For the ternary alloy, with the additional presence of copper and the CuAl2 particles, the latter appear to have undergone complete oxidation, with copper detected in local film regions.