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Advances in Molten Salts

ISSN:
1-56700-142-4 (Print)

Multistep Processes in the electrodeposition of refractory metals in molten Chlorides

O. Boiko
Institute of General and Inorganic chemistry Ukr.Acad. Sci., 252680 Kiev-142, Pr.Palladina 32/34, Ukraine

K. Serrano
Universite Paul Sabatier, Laboratoire de Genie Chimique 118, route de Narbonne 31062 Toulouse Cedex 4, France

P. Chamelot
Universite Paul Sabatier, Laboratoire de Genie Chimique 118, route de Narbonne 31062 Toulouse Cedex 4, France

P. Taxil
Universite Paul Sabatier, Laboratoire de Genie Chimique 118, route de Narbonne 31062 Toulouse Cedex 4, France

Abstract

This paper deals with examples of complications arising during the electrodeposition process in molten salts of multivalent elements such as uranium, niobium and hafnium. The electroreduction process of U(Ⅳ), Nb(Ⅴ) and Hf(Ⅳ) includes the intermediate formation of U(Ⅲ), Nb(Ⅳ) and Hf(Ⅱ) respectively, giving rise to secondary reactions such as disproportionation and adsorption. Each reaction of the overall process is characterized by using electrochemical criteria provided by chronopotentiometric and voltammetric measurements. Prereduction of U(Ⅳ) or addition of fluoride ions in the electrodeposition bath of hafnium have minimized the troubles due to these reactions.