Performance of protective oxide films on Fe–Ni alloy anodes in molten KF–AlF3–Al2O3 salts at 700 °C

Abstract

An oxide film containing NiFe2O4 was prepared by oxidizing Fe–Ni alloy in hot air, and the performance of the protective oxide film in molten KF–AlF3–Al2O3 salts at 700 °C was characterized by electrochemical methods, including electrochemical impedance spectroscopy, capacitance measurements, linear sweep voltammetry, and chronoamperometry to clarify the breakdown and growth process of the oxide film. For the pre-oxidized 57Fe–43Ni, 50Fe–50Ni, and 43Fe–57Ni alloys, the oxide films, with a thickness of 5 μm, are composed of Fe2O3 and NiFe2O4, according to X-ray diffraction and scanning electron microscopy analysis. The transfer resistance of ions in the oxide film increases with increasing nickel content, and reaches its maximum value of 91.39 Ω⋅cm2 for the pre-oxidized 43Fe–57Ni alloy based on electrochemical impedance spectroscopy measurements. Moreover, the carrier density in the oxide film determined from Mott–Schottky plots decreases as the nickel content increases. Under anodic polarization, the breakdown of oxide film follows the generation of metal cation vacancies and condensation of excess cation vacancies. Concurrently, a new oxide layer forms along the substrate owing to the annihilation of oxygen vacancies and diffusion of oxygen anion in the oxide film. After oxygen evolution, a new oxide film layer containing NiFe2O4 forms on the alloy substrate, leading to the passivation observed in the anodic polarization curves. The maximum polarization resistance in the passivation region is 4.86 Ω⋅cm−2 for the pre-oxidized 43Fe–57Ni alloy, indicating that the pre-oxidized 43Fe–57Ni alloy possesses better corrosion resistance to molten fluorides than the other two pre-oxidized Fe–Ni alloys. Chronoamperometry measurements show that the oxide film on the 43Fe–57Ni alloy is in a dynamically stable state during oxygen evolution.