Passivation of a CoCrMo PVD Alloy with Biomedical Composition under Simulated Physiological Conditions Studied by EQCM and XPS

Abstract

Kinetics of passive film growth on a CoCrMo biomedical alloy have been studied using the Electrochemical Quartz Crystal Microbalance technique (EQCM) in phosphate buffer solution at room temperature and 37°C. CoCrMo layers were deposited on the quartz crystals by physical vapor deposition (PVD) reaching a dense and compact deposition film with fine-grain structure. EQCM measurements were performed under potentiodynamic and potentiostatic conditions (at applied passive and transpassive potentials). Furthermore, ex-situ X-ray Photoelectron Spectroscopy (XPS) analysis of the each tested sample was performed at the end of the electrochemical test. The use of EQCM allows distinguishing between electrochemical oxidation, passive and transpassive dissolution and passive film growth. In the passive domain the passive film thickness stabilizes within 200 to 400 s after an initial fast growth. The increase in current at the onset of the transpassive domain does not affect the passive dissolution rate. Only at higher potential dissolution rate increases due to the dissolution of Cr(VI), Co(III) and Mo(VI) species. The observed constant mass loss rate at transpassive potentials indicates that the passive film at these potentials is cracked or porous. Increasing temperature accelerates the mass loss through the oxide/electrolyte interface enhancing the passive and transpassive dissolution and increasing the thickness of the oxide film.