Optical and impedance characteristics of passive films on pure aluminium

Optical and Impedance behavior of pure bulk aluminum and pure sputtered aluminum film were studied in order to gain a better understanding of their fundamental passivation and pitting characteristics. Constant potential experiments at the passivation and pitting potentials, and potentiostatic anodic polarization were conducted while simultaneously monitoring the current, impedance and optical behavior, in-situ. Noise characteristics in the current data during the pit incubation period indicate that Cl- ions migrate with little impediment to the metal surface through defects in the passive film. Impedance experiments indicate that the polarization resistance fluctuates continuously with time during the pit incubation period, suggesting that impedance spectroscopy is sensitive to localized processes. The interfacial capacitance increases continuously during this time. The smallest pits observed on the sample surface (less than 10μ) are clearly crystallographic, indicating activation controlled dissolution at pits. The film capacitance increases with exposure time at the passivation potential, while the polarization resistance decreases continuously. The decrease in the film resistance is thought to be due to chloride incorporation at defects in the passive film. The increase in film capacitance at the passivation and pitting potential is due to an increase in the film dielectric constant caused by either a compositional change or anion incorporation. Ellipsometry results indicate growth of a dual layered film on the pure aluminum surface, with the outer layer probably containing varying amounts of incorporated chloride depending on the applied potential. Preliminary experiments indicate that in the case of sputtered aluminum film, the passive film resistance is at least an order of magnitude higher than that of bulk aluminum. This is due to the fine grain structure of sputtered Al and hence a more defect free passive film than that formed on bulk aluminum. There is also a small decrease in the passive film capacitance (7 %) with anodic polarization within the passive range of the aluminum film