Abstract
Stresses generated during the anodic oxidation of metals in aqueous solution were measured as a function of applied current density, potential step and chloride ion concentration by using a beam deflection technique. In the absence of chloride ion, the stresses which amounted to a few GPa were developed in the oxide film and were mainly composed of the volume-generated stress and electrostrictive stress components. The transition from compressive to tensile deflection occurred at applied current densities of 0.05 and 0.10 mA cm −2. The compressive stresses developed in films grown in chloride ion-containing solutions amounted to about 10 times larger than those in films grown in chloride ion-free solutions. In the presence of chloride ion, before the oxide film breakdown, specimens moved increasingly in a compressive direction with increasing chloride ion concentration. In contrast, after the oxide film breakdown, the reverse movement in a tensile direction was encountered and the deflection rates increased with increasing chloride ion concentration. The changes in the sign and magnitude of deflection in the absence/presence of chloride ion are well accounted for in terms of the relevant reactions occurring both at the metal/oxide and at the oxide/electrolyte interfaces during the oxide growth.
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