The mechanisms of passive dissolution of titanium in a model physiological environment.

The surface chemistry, oxidation, and disolution kinetics of titanium were measured to establish the mechanisms of passive dissolution in physiological environments. Titanium thin films were immersed in 8.0 mM ethylenediamine-tetraacetic acid in simulated interstitial electrolyte (EDTA/SIE) and maintained at 37 degrees C, 10% O2, 5% CO2 and 7.2 pH for periods of time up to 3200 h (133 days). Two immersion schemes were employed: the integral sequentially determined the titanium released into a solution of accumulated dissolution products; and the differential continuously replenished the test solution. The solutions were analyzed for titanium by electrothermal atomic absorption spectrometry (EAAS), and the sample surfaces were analyzed by Auger electron spectroscopy (AES) and x-ray photoelectron spectroscopy (XPS) to determine oxide composition, stoichiometry, and thickness. Prior to immersion two types of hydroxyl (OH) groups were distinguished on the TiO2 surface. Upon immersion, the chemistry of the surface changed as a function of immersion: the presence of OH groups increased and P (nonelemental) was detected at the surface. The dissolution kinetics obeyed a two-phase logarithmic model, where the transition between phases occurred simultaneously with the adsorption of the P-containing species. The dissolution kinetics depended on surface reactions, electric field strength, and molecular diffusion. These mechanisms explain the observed dependence of dissolution kinetics on the properties of the surface oxide and solution ligands.