Kevin E. Healy

Hydration and preferential molecular adsorption on titanium in vitro.

Surface sensitive spectroscopies, Auger electron and X-ray photoelectron (XPS), were used to determine changes in titanium oxide composition, oxide stoichiometry, and adsorbed surface species as a function of exposure to human serum in a balanced electrolyte (serum/SIE) and 8.0 mM ethylenediaminetetraacetic acid in a balanced electrolyte (EDTA/SIE) at 37 degrees C. Before immersion, the oxide was near ideal TiO2, covered by two types of hydroxyl groups: acidic OH(s) with oxygens doubly coordinated to titanium, and basic Ti-OH groups singly coordinated. After extended exposure to both solutions, up to 5000 h (ca. 208 d), the surface concentration of OH groups increased and non-elemental P appeared. The P LVV Auger transition and P 2p spectra indicated the peak positions were similar to reference phosphate compounds. The adsorbed phosphate species were presumed to be either Ti-H2PO4 or Ti-HPO4-. The XPS data suggested that a lipoprotein and/or glycolipid film was adsorbed to the specimens exposed to serum/SIE. Analysis of the preferential lipoprotein/glycolipid adsorption using electrostatic bonding concepts contributed to the refinement of the hierarchical model for the Ti-tissue interface. The salient features are that Ti metal is not in direct contact with the biological milieu, rather there is a gradual transition from the bulk metal, near-stoichiometric oxide, Ca and P substituted hydrated oxide, adsorbed lipoproteins and glycolipids, proteoglycans, collagen filaments and bundles to cells.

Passive dissolution kinetics of titanium in vitro

The dissolution of titanium in simulated interstitial electrolyte (SIE), human serum in SIE (serum/SIE) and 8.0 mM ethylenediaminetetraacetic acid (EDTA) in SIE (EDTA/SIE) was measured in vitro. Titanium fibre samples were immersed in these solutions and maintained at 37°C, 10% O2, 5% CO2 and 97±3% relative humidity for 0–5000 h. The concentration of titanium released was quantified using electrothermal atomic absorption spectroscopy. Changes in oxide stoichiometry were determined by Auger electron spectroscopy after processing and immersion in the test solutions. The oxide became nearly stoichiometric TiO2 after immersion, suggesting equilibration of the surface with the solutions. Solution ligands enhanced the magnitude of dissolution, with EDTA>serum/SIE>SIE. The dissolution kinetics were empirically fitted by a two-phase logarithmic relationship. The first phase of dissolution (t<300 h) was dominated by equilibration of the oxide with the solution and the second phase (t>300 h) by mass diffusion. The dissolution kinetics were similar for the EDTA/SIE and serum/SIE solutions, indicating that the mechanisms of dissolution for each solution may be the same.