Journal of the Electrochemical Society, Vol.141, No.6, 1446-1452, 1994
Evolution of Microscopic Surface-Topography During Passivation of Aluminum
The time evolution of microscopic topography on corroding aluminum surfaces during oxide film passivation was characterized. Passivation was studied after galvanostatic etching in 1N HCl at 65-degrees-C, in both aluminum etch tunnels (by scanning electron microscopy) and micron-size cubic etch pits (by atomic force microscopy). Step reductions of applied current initiated passivation. At times of 1 to 300 ms after current steps, the corroding surface was microscopically heterogeneous, consisting of a number of small corroding patches 0.1 to 1 mum in width, which were surrounded by passive surface. As some patches grew by dissolution, others were passivated, until eventually only one patch remained on the pit or tunnel surf ace. The topography of the corroding surf ace was controlled by the potential : the surf ace dissolved uniformly at the repassivation potential E(R), while partial passivation to produce patches occurred at potentials more cathodic than E(R). Patches were unstable at potentials below E(R) and would ultimately passivate. Topographic evolution during passivation was very similar f or pits as f or tunnels, except that the time scale of the process is much longer for tunnels than for pits (200-300 ms vs. 11-20 ms). The difference of time scales was due to the different corroding surface areas of pits and tunnels. Patches are probably defined by a surface layer which inhibits passivation.