Mechanism of anodic oxidation of tungsten in neutral sulphate-fluoride solutions |
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Authors: | Vassil Karastoyanov Martin Bojinov |
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Affiliation: | (1) Department of Physical Chemistry, University of Chemical Technology and Metallurgy, Kl. Ohridski Blvd. 8, 1756 Sofia, Bulgaria |
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Abstract: | The anodic oxidation of tungsten has been studied in 1 M Na2SO4 solutions containing 0–0.25 M NaF. Steady-state currents measured in the passivation and passivity ranges increase significantly with increasing fluoride concentration, indicating enhanced dissolution of the oxide film. The electrochemical impedance response is dominated by the processes in the barrier layer and at its interface with the electrolyte. The presence of a pseudo-inductive loop in the impedance spectra at intermediate frequencies indicates point defect interaction during film growth and dissolution processes. A kinetic model including the recombination reaction between oppositely charged point defects at the film/solution interface as well as a kinetic scheme for tungsten dissolution through the film mediated by cation vacancies is proposed. It is found to reproduce satisfactorily the steady-state currents and the impedance spectra in the potential range 0.2–2 V. Such a model for the conduction mechanism in the barrier layer is believed to be an essential part of a modelling approach to the formation of a nanoporous overlayer on tungsten in fluoride-containing solutions. |
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Keywords: | Tungsten Anodic oxide film Point defect Impedance spectroscopy Kinetic model |
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