The capacitance and resistance of an electrochemical cell have been measured to determine the effect of the pH (3.6–8.2) of aqueous potassium nitrate and perchlorate electrolytes upon 360Aå thick anodic oxide films formed on polycrystalline 99.99% aluminum. While the film has been found to be quite stable upon exposure to electrolytes having pH values in the range 5.1–8.2, frequency dependent capacitance increases and resistance decreases have been observed during a 3000 min test period for cells having electrolytes of pH 3.6. The data for electrochemical cells having
1.0MKNO3
electrolytes of pH 3.6 have been corrected for the presence of the electrolyte by two electrical analogs. This corrected aluminum cell data represent average anodic oxide film properties. The authors have interpreted the large capacitance increases and resistance decreases of electrochemical cells having an electrolyte of pH 3.6 in terms of the growth of pores in the anodic oxide film. The data for cells having
1.0MKNO3
electrolytes of pH 3.6 have been quantitatively analyzed as a function of exposure time and frequency by modeling the electrochemical cell as a parallel combination of two parallel RC circuits in series with a third parallel RC circuit. Transmission electron microscopy of films before and after testing supports the interpretation of the data in terms of a porous film structure. Some comments are forwarded on the defect structure of the film before and after environmental exposure.
Nonporous anodic aluminum oxide films were potentiostatically formed at 30V and subsequently exposed to neutral aqueous ammonium tartrate for 3000 min at 30V, 10V, and at rest potential. Porous film growth was observed at the formation potential in accordance with Part I . Some factors responsible for the observed stability of the film capacitance and resistance at 30V have been determined by modeling the porous film as a parallel combination of two parallel RC circuits. Films tested at 10V thinned slowly by the development of a large number of fine pores at the oxide/electrolyte interface; in addition, pore colonies were observed in the metallic substrate below the thinning film. At rest potential the film developed a nonporous cellular topography, presumably an artifact of a selective dissolution process. The film capacitance at 10V and rest potential has been expressed as film thickness vs. time profiles under the assumption of uniform thinning.
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