The influence of fluoride on the physicochemical properties of anodic oxide films formed on titanium surfaces

The influence of fluoride (and its concentration) on the electrochemical and semiconducting properties of anodic oxide films formed on titanium surfaces was investigated by performing electrochemical measurements (potentiodynamic/ pontiostatic polarization, open circuit potential (OCP), and capacitance measurements) for a titanium/oxide film/ solution interface system in fluoride-containing 1.0 M HClO4 solution. On the basis of the Mott-Schottky analysis, and with taking into account both the surface reactions (or, say, the specifically chemical adsorption) of fluoride ions at the oxide film surface and the migraion/intercalation of fluoride ions into the oxide film, the changes in the electrochemical behavior of titanium measured in this work (e.g., the blocked anodic oxygen evolution, the increased anodic steady-state current density, the positively shifted flat band potential, and the positively shifted film breakdown potential) were interpreted by the changes in the surface and the bulk physicochemical properties (e.g., the surface charges, surface state density, doping concentration, and the interfacial potential drops) of the anodic films grown on titanium. The fluoride concentrations tested in this work can be divided into three groups according to their effect on the electrochemical behavior of the oxide films: <= 0.001 M, 0.001-0.01 M, and >0.01 M. By tracing the changes of the OCP of the passivated titanium in fluoride-containing solutions, the deleterious/depassive effect of fluoride ions on the titanium oxide films was examined and evaluated with the parameter of the film breakdown time. It was also shown that the films anodically formed on titanium at higher potentials (> 2.5 V) exhibited significantly higher stability against the fluoride attack than that either formed at lower potentials (<2.5 V) or formed natively in the air.