Zirconium(IV) electrochemical behavior in molten LiF-NaF

Abstract

Zirconium has a large number of properties that make it very attractive for different applications in several activity fields (nuclear, pyrotechnics, armament …). This article is devoted to the study of zir conium electrochemical behavior and crystallization phenomena on silver electrode in the LiF NaF eutectic mixture in the 690 900 C temperature range, using cyclic voltammetry, square wave vol tammetry and chronoamperometry. The result showed that Zr(IV) is reduced into Zr in a simple step exchanging four electrons and that zirconium nucleation is progressive whatever the temperature and the overvoltage. Nuclei growth takes place in all three dimensions and is limited by diffusion of Zr(IV) ions. The influence of overvoltage on the zirconium nucleation rate was also studied.

Electrochemistry of uranium in molten LiCl-LiF

“…In comparison to chloride salts, fluoride solvents limit the number of species oxidation states as reported for instance by Lambertin et al [23] for the americium case. The results obtained by Quaranta et al [24] and Sakamura et al [25] on Zr(IV) electrochemical reduction in LiF-NaF and LiCl-KCl also illustrate the difference between chloride and fluoride solvent in terms of complexation: in LiF-NaF, a single transition from Zr(IV) to Zr is obtained, whereas Zr(IV), Zr(II) and Zr(I) are observed in LiCl-KCl. Limiting the number of stable oxidation states helps the quantitative recovery of metals by molten salt electrolysis as showed for neodymium and dysprosium by Diaz et al [26] .…”

Effects of F– on the Electrochemical Behavior of Zr(IV) and the Nucleation Mechanism of Zr in the LiCl–KCl–K2ZrF6 System

“…Zr is a strategic metal, and it has been extensively employed in a wide variety of fields for its advantages of low thermal neutron capture cross-section, strong corrosion resistance, prominent mechanical properties, and high spontaneous combustion. , To be specific, 90% of the Zr metal products are applied in the nuclear field, , which comprise cladding materials for nuclear fuels (Zircaloy-2, Zircaloy-4, etc. ) and the additives to stabilize the U–Pu alloy, leading to an increased melting point and reduced interactions of the cladding material and fuel. , …”

In situelectrochemical investigation of the reaction progress between Zr and a CuCl–SnCl2mixture in a LiCl–KCl molten salt

“…Commonly, the electrorening of Zr occurs in alkali chloride, uoride, or chloride-uoride mixed fused melts. [5][6][7][8] Sohn et al 9 studied the electrolytic recovery of highpurity Zr from radioactively contaminated zircaloy-4 alloys in LiCl-KCl-ZrCl 4 salts. Han and Zhang 3,10,11 have also studied the recovery of Zr from LiCl-KCl-K 2 ZrF 6 molten salts using Fe, Cu, and Sn electrodes.…”