Corrosion Behavior of Electrochemical and Thermal Treated Titanium into Artificial Saliva: Effect of pH and Fluoride Concentration

This work investigates and compare the corrosion behavior in artificial saliva of oxide thin films grown on commercially pure titanium (cp-Ti), via electrochemical oxidation (EO) in sulphate bath at 1 V and thermal treatment (TT) at 450 °C, for durations between 20 min and 4 h. The goal is to determine which method and duration provide the optimal protection for titanium against degradation in dental environment particularly in varying fluoride concentration and acidity. Surface characterizations were performed through morphological and microstructural analysis using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). Electrochemical behavior was conducted in Fusayama-Meyer solution (pH = 6.50 and T = 37 °C) using potentiodynamic polarization curve (PPC) and electrochemical impedance spectroscopy (EIS), under varying pH and fluoride ion concentrations. The results demonstrated that a 3-h duration treatment provided the optimal corrosion resistance for both EO and TT processes. The pH of the environment influenced corrosion performance markedly: both acidic (pH 2.5) and basic (pH 9.0) conditions increased Icorr and decreased Rp, indicating degradation of the passive oxide layer outside neutral conditions. Similarly, increasing fluoride concentrations (1000; 5000; and 12,300 ppm) significantly impaired corrosion resistance. At 12,300 ppm F−, untreated Ti showed severe degradation, with EIS revealing the formation of a porous outer layer and a weakened inner barrier layer (Rf = 33 W·cm2 for the outer layer and Rct = 21 kW·cm2 for the barrier layer). In contrast, the TT-treated surface remained highly protective even under these aggressive conditions, with minimal surface damage and the highest resistances for both the outer and the inner layers (Rf = 1610 kW·cm2; Rct = 1583 kW·cm2), significantly outperforming the EO film. These findings highlight the superior performance of thermal oxidation at 450 °C for 3 h as a promising surface treatment for enhancing the corrosion resistance of titanium in fluoride-rich oral environments. Understanding these strategies helps improve the longevity and security of titanium dental implants.