Anodic dissolution and passivation of manganese monosilicide in fluoride-containing sulfuric acid solutions
Abstract
The purpose of this study was to investigate the anode resistance of manganese monosilicide MnSi in fluoride-containing sulfuric acid solutions and the concentration effect of sodium fluoride on the anodic dissolution and passivation of the silicide.
The study was carried out on a single-crystal MnSi sample in 0.5 M H2SO4 + (0.0025−0.05) M NaF solutions. The study presents micrographs and elemental composition of the electrode surface after anodic polarization from E corrosion to E = 3.2 V in 0.5 M H2SO4 and 0.5 M H2SO4 + 0.05 M NaF solutions. A stronger etching of the electrode surface was observed in the presence of fluoride ions; elemental analysis showed an increase in the oxygen content in certain areas of the silicide surface associated with the formation of manganese and silicon oxides and their partial removal at high polarization values.
The kinetic regularities of the MnSi-electrode anodic dissolution were studied by the methods of polarization, capacitance, and impedance measurements. It was established that the addition of fluoride ions leads to weaker barrier properties of the silicon dioxide surface film, which determines the high silicide resistance in a fluoride-free medium. The order of the reaction was calculated for the MnSi anodic dissolution for NaF depending on the potential. In the region of low anodic potentials (from Ecor to E ≈ –0.2 V), the reaction order ranged from 1.8 to 1.1, which was due to the high influence of silicon in the composition of the silicide and its oxidation products. With an increase in the polarization value (up to E = 0.9 V), the reaction order decreased to 0.5. An increase in the contribution of manganese ionization and oxidation reactions to the kinetics of the anodic dissolution of the silicide was observed. The silicide passivation in a fluoride-containing electrolyte
was characterized by higher values of the dissolution current density (10–4−10–3 A/cm2) as compared to a fluoride-free electrolyte (10–6 A/cm2), the reaction order in region of the passive state was ~1.0. Passivation was due to the formation of MnO2 and SiO2 oxides on the surface. In the transpassivation region (E ≥ 2.0 V), there was a weak dependence of the current density on the concentration of fluoride ions. Oxygen release was observed on the surface of the electrode, and the formation of MnO4 – ions was recorded in the near-electrode layer. The article discusses mechanisms and kinetic regularities of anodic processes on an MnSi-electrode in sulfuric acid solution in the presence of fluoride ions
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