The growth kinetics and properties of potentiodynamically formed thin oxide films on aluminium in citric acid solutions

Abstract

The growth kinetics and properties of potentiodynamically formed thin oxide films on Al were investigated in 0.05 M citric acid solutions of different pH (5, 6 and 7) by means of potentiodynamic polarization and a.c. electrochemical impedance spectroscopy (EIS) measurements. Al showed passive behaviour within the pH range that was examined. The potentiodynamic growth of the oxide film on Al takes place due to ionic conductivity under the influence of the high electric field. Characteristic kinetic oxide film growth parameters such as the high-field growth exponential law constants (A and B), ionic conductivity through the oxide film, field strength and half barrier width have been calculated. Impedance measurements were used to determine the parameters related to the characteristic sizes and properties of oxide film. The capacitive response of the impedance spectrum was related to the thickness and dielectric properties of the barrier oxide film. The oxide film resistance values were very high, indicating that the oxide films formed under potentiodynamic conditions are highly uniform in thickness and very resistant. The anodic behaviour of Al in the citric solutions under potentiodynamic conditions were characterized by the rapid growth of the oxide film which diminished the influence of relaxation processes on the growth kinetics and structural characteristics of the aluminium/anodic oxide film/electrolyte system.