Abstract
The electrodeposition of tungsten has been investigated in the molten salt systems and at 450°C. Voltammetric results showed that the reduction of tungsten species is an irreversible process. Electrodeposits were mixtures of α‐ and β‐tungstens, the former being the thermodynamically stable phase. α‐Tungsten exhibited the shape of cubic crystallites which tended to grow larger, whereas β‐tungsten always had a crystal size smaller than 1 μm. The β‐tungsten was formed during the initial stage of electrodeposition, irrespective of the substrate material, and remained predominant at high current densities or in pulsed electrolysis. It is likely that the phase transition of β‐tungsten to α‐tungsten occurs when the size of the β‐tungsten crystallites becomes larger than a critical value.
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