Electrodeposition of tungsten from ZnCl2–NaCl–KCl–KF–WO3 melt and investigation on tungsten species in the melt

The electrodeposition of tungsten in ZnCl2–NaCl–KCl–KF–WO3 melt at 250 °C was further studied to obtain a thicker deposit. In the ordinary electrolysis at 0.08 V vs. Zn(II)/Zn, the current density decreased from 1.2 mA cm−2 to 0.3 mA cm−2 in 6 h. A thickness of the obtained tungsten layer was 2.1 μm and the estimated current efficiency was 93%. A supernatant salt and a bottom salt were sampled after 6 h from the melting and were analyzed by ICP-AES and XRD. It was found that the soluble tungsten species slowly changes to insoluble ones in the melt. The soluble species was suggested to be WO3F− anion. One of the insoluble species was confirmed to be ZnWO4 and the other one was suggested to be K2WO2F4. Electrodeposition was carried out under the same condition as above except for the intermittent addition of WO3 every 2 h. The current density was kept at the initial value and the thickness was 4.2 μm. The intermittent addition of WO3 was confirmed to be effective to obtain a thicker tungsten film.