The electrochemical behaviour of three ZrTi alloys (Zr5Ti, Zr25Ti and Zr45Ti) in Ringer's solution has been investigated. Their resistance against localized corrosion has been determined from cyclic potentiodynamic polarization (CCP) and electrochemical impedance spectroscopy (EIS) measurements, whereas scanning electrochemical microscopy (SECM) was applied to investigate the local reactivity of the passive films developed on the materials, and scanning electron microscopy (SEM) was employed to characterize the surface morphology of the alloys subjected to anodic polarization. An increased reactivity could be detected with SECM when the metal samples were polarized at +0.50 VSHE, though the extent of this feature greatly depended on the nature of the metallic material. At 37 0 C, the Zr5Ti alloy was susceptible to localized corrosion. Though Zr25Ti alloy presented rather low pitting potential, the spontaneous corrosion potential of the material was sufficiently negative to require overpotentials around 600 mV for breakdown to occur. Finally, the Zr45Ti alloy exhibited a larger passive range in the polarization curve, and it was resistant to localized corrosion.

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This paper addresses on the electrochemical behaviour of three TiMo alloys exposed to simulated physiological environments. Their stability and corrosion resistance was characterized in order to explore the potential application for the manufacturing of implant materials. Ringer's solution together with an acidic modification of the Ringer's solution (pH = 3.1) at room temperature were considered. Both electrochemical methods (namely, potentiodynamic polarization curves and electrochemical impedance spectroscopy, EIS), and spatially-resolved scanning electrochemical microscopy (SECM), were used. Additionally, surface characterization was made employing optical microscopy and scanning electron microscopy (SEM). The oxide films formed on the TiMo alloys in neutral and acidic Ringer's solutions effectively protect the metal from dissolution in this environment, and no breakdown of the passive layer occurs in the potential range up to +1.00 V vs. SCE. SEM micrographs of retrieved samples do not show corrosion pits, cracks, or any other defects despite the rather high positive potential values reached during the potential excursion. EIS data reveal that two-layer oxide films are formed, consisting of a porous outer layer and a compact inner layer (approximately 5-6 nm thick), the latter accounting almost completely for the corrosion resistance of the materials. The corrosion resistance of the inner compact film towards metal dissolution is smaller in the acidic environment, whereas it increases with higher Mo contents in the alloy. The passive oxide films exhibit dielectric characteristics towards charge transfer, and they are imaged as insulators by scanning electrochemical microscopy.

Oxidation in air of ZrTi alloys at 500 ºC for 2 h produces oxide-covered materials with a very high corrosion resistance in Ringer's solution at 37 ºC. The oxide layers present a double-layer structure, comprised by a thin and very compact inner layer of ca. 5 nm thickness, and a less compact, more porous and thicker outer layer. The thickness of the outer layer greatly varies with the composition of the base ZrTi alloy, but has very little influence in the overall electrochemical behaviour of the material. The nature of the oxide layer is a mixture of ZrO2 and TiO2, and no evidence of higher oxidation states of the metal could be found using XRD data. Anodic dissolution through the passive layers formed on the oxidized alloys is greatly diminished compared to those measured from the untreated materials, allowing all the alloying ratios between Zr and Ti to be potentially considered for implant application. The combination of alloying with titanium and oxidation in air at 500 ºC resulted in the materials that do not exhibit the characteristic susceptibility of zirconium towards the initiation of localized corrosion processes in aqueous chloride-containing electrolytes even for anodic polarizations up to +1.00 VSCE, a value well above the highest polarization experienced in the human body. Though all the oxidized alloys exhibited remarkable corrosion resistances, the best behaviour was found for oxidized Zr45Ti.

ZrTi alloys in artificial physiological solution simulating in vitro inflammatory conditions were investigated for biomedical application. Effect of surface treatment on the corrosion resistance of Zr5Ti, Zr25Ti, and Zr45Ti in acidified Ringer's solution (pH = 3) at 25 ºC was evaluated using electrochemical impedance spectroscopy, potentiodynamic polarization curves, and scanning electrochemical microscopy. Thermal oxidation in air at 500 ºC produces materials with high in vitro corrosion resistance to acidic environments. Higher impedance values related to passivity were observed for oxidized ZrTi alloys compared to as-cast materials. SECM reveals thermal oxidation produced more compact and electrically insulating oxide films.

Biodegradable magnesium-calcium (MgCa) alloy is a very attractive biomaterial. Two MgCa alloys below the solid solubility of Ca were considered, as to solely investigate the effect of Ca content on the behavior of magnesium and the pH changes associated to metal dissolution. X-ray diffraction analysis and optical microscopy showed that both Mg-0.63Ca and Mg-0.89Ca alloys were solely composed of α(Mg) phase. Degradation characteristics and electrochemical characterization of MgCa alloys were investigated during exposure to Ringer's solution at 37 °C by electrochemical impedance spectroscopy and scanning electrochemical microscopy. The impedance behavior showed both capacitive and inductive features that are related to the alloy charge transfer reaction and the relaxation of the absorbed corrosion compounds, and can be described in terms of an equivalent circuit. Scanning electron microscopy (SEM) was employed to view the surface morphology of the MgCa samples after 1 week immersion in Ringer's solution showing extensive precipitation of corrosion products, whereas the substrate shows evidence of a non-uniform corrosion process. Energy dispersive analysis showed that the precipitates contained oxygen, calcium, magnesium and chlorine, and the Mg:Ca ratios were smaller than in the alloys. Scanning electrochemical microscopy (SECM) was used to visualize local pH changes associated to these physicochemical processes with high spatial resolution. The occurrence of pH variations in excess of 3 units between anodic and cathodic half-cell reactions was monitored in situ.

The electrochemical behavior of Zr5Ti, Zr25Ti, and Zr45Ti, with and without surface modification were monitored in acidic artificial saliva (pH = 3) containing NaF concentrations 0.2, 0.5, and 1 wt.%, simulating the fluoride concentrations in dental rinses. A passive behaviour for thermally oxidized ZrTi alloys was found using EIS, and XPS data show that the protective oxide film contains both TiO2 and ZrO2, though titanium contents in the outer layer bigger than those in the base alloy result from thermal oxidation. High corrosion resistance to acidic fluoridated environments of ZrTi alloys treated using thermal oxidation in air at 500 ºC.

The electrochemical behaviour of two Ag-Pd alloys (Unique White and Paliag) used in dental prosthetics construction for crowns and bridges and one Co-Cr alloy (Vitallium 2000) was studied in artificial saliva using the polarization curves and electrochemical impedance spectroscopy (EIS). The corrosion resistance was evaluated by means of the corrosion currents value and by coulometric analysis. The open circuit potential of Ag-Pd are attributed to dealloying followed by surface enrichment with Ag and the possible formation of an insoluble AgCl surface film on the respective alloy surfaces. Our results have shown that these alloys have a somewhat good corrosion resistance in artificial saliva. The corrosion current densities of Unique White and Vitallium 2000 alloys were very low (~100 nA/cm 2 ). For Ag-Pd alloys, when increasing the content of Cu, corrosion resistance decreases. The passivation of all samples occurred spontaneously at the open circuit potential. The electrochemical properties of the spontaneously passivated electrodes at the open circuit potential were studied by EIS. The polarization resistance (R p ) and the electrode capacitance (C dl ) were determined. The polarization resistance of all the samples increases with the immersion time. The polarization resistances are largest for Unique White (Ag-Pd) and Vitallium 2000 (Co-Cr) alloys. Because the electrochemical behaviour of the Co-Cr alloy was compared with that of Ag-Pd alloy, this type of alloy may be a suitable alternative for use in the manufacture of fixed dental prostheses. The present study, though limited, has shown that electrochemical characteristics can be used to identify such alloys. Knowledge of the in vitro corrosion behaviour of these alloys may lead to better understanding of any biologically adverse effects in vitro.