On the use of electrochemical techniques to monitor free oxide content in molten fluoride media

The electrochemical behaviour of oxide ions has been studied in fluoride melts(LiF/NaF eutectic) by cyclic voltammetry, square wave voltammetry and chronopotentiometry. The purpose is to determine whether these techniques can be used for titration of free oxide ions (O2-) in molten fluorides released by lithium oxide additions. Cyclic voltammetry is shown to be unsuitable for this purpose due to oxygen bubbling disturbing the oxidation peak, while square wave voltammetry is far more appropriate because the observed signal is a well defined oxidation peak with a height proportional to the oxide content. Thus, the present work is focused on a strategy of oxide ions titration by square wave voltammetry. In addition, this work allows assessing that the electrochemical reduction of oxide ions proceeds by diffusion of these species, and the O2- diffusion coefficient is estimated by chronopotentiometry

Preparation of tantalum carbide films by reaction of electrolytic carbon coating with the tantalum substrate

This article demonstrates that coatings of tantalum carbide can be obtained by electrodeposition of carbon in molten fluorides on a tantalum substrate as an alternative to the CVD process. The structural characteristics of the carbon deposited by the electrolytic route lead to a high reactivity of this element towards a tantalum cathode to produce tantalum carbide. Mutual reactivity was shown to be enhanced if tantalum plate is replaced by an electrodeposited layer of tantalum, where the fine microstructure provides a catalytic effec

Co-reduction of aluminium and lanthanide ions in molten fluorides : application to cerium and samarium extraction from nuclear waste

This work concerns the method of co-reduction process with aluminium ions in LiF–CaF2 medium (79–21 mol.%) on tungsten electrode for cerium and samarium extraction. Electrochemical techniques such as cyclic and square wave voltammetries, and potentiostatic electrolyses were used to study the co-reduction of CeF3 and SmF3 with AlF3. For each of these elements, specific peaks of Al–Ce and Al–Sm alloys formationwere observed by voltammetry aswell as peaks of pure cerium and aluminium, and pure samarium and aluminium respectively. The difference of potential measured between the solvent reduction and the alloy formation suggests expecting an extraction efficiency of 99.99% of each lanthanide by the process. Different intermetallic compounds were obtained for different potentiostatic electrolysis and were characterised by Scanning Electron Microscopy with EDS probe. The validity of the process was verified by carrying out cerium and samarium extractions in the form of Al–Ln alloy; the extraction efficiency was 99.5% for Ce(III) and 99.4% for Sm(III)

Electrochemical study of the Eu(III)/Eu(II) system in molten fluoride media

The electrochemical behaviour of the Eu(III)/Eu(II) system was examined in the molten eutectic LiF-CaF2 on a molybdenum electrode, using cyclic voltammetry, square-wave voltammetry and chronopotentiometry. It was observed that EuF3 is partly reduced into EuF2 at the operating temperatures (1073-1143 K). The electrochemical study allowed to calculate both the equilibrium constant and the formal standard potential of the Eu(III)/Eu(II) system. The reaction is limited by the diffusion of the species in the solution; their diffusion coefficients were calculated at different temperatures and the values obey Arrhenius' law. The second system Eu(II)/Eu takes place out of the electrochemical window on an inert molybdenum electrode, which inhibits the extraction of Eu species from the salt on such a substrate

Investigations of Zr(IV) in LiF-CaF2: stability with oxide ions and electroreduction pathway on inert and reactive electrodes

In this work, a detailed electrochemical study of the molten LiF-CaF2-ZrF4 system is provided in the 810-920°C temperature range, allowing the determination of the reduction potential, the diffusion coefficient and the reduction mechanism of dissolved Zr(IV) on an inert Ta electrode. Addition of CaO in the molten salt is shown to cause Zr(IV) precipitation into a mixture of solid compounds, most likely ZrO2 and ZrO1.3F1.4. Underpotential deposition of Zr on Cu and Ni electrodes is also evidenced

Electrochemical extraction of europium from molten fluoride media

This work concerns the extraction of europium from molten fluoride media. Two electrochemical ways have been examined: (i) the use of a reactive cathode made of copper and (ii) the co-deposition with aluminium on inert electrode, leading to the formation of europium-copper and europium-aluminium alloys respectively, as identified by SEM-EDS analysis. Cyclic voltammetry and square wave voltammetry were used to identify the reduction pathway and to characterise the step of Cu-Eu and Al-Eu alloys formation. Then, electrochemical extractions using the two methodologies have been performed with extraction efficiency around 92 % for copper electrode and 99.7 % for co-reduction with aluminium ions

Silver as Anode in Cryolite—Alumina-Based Melts

The anodic behaviour of silver was investigated in cryolite—alumina-based melt. Silver has a lower melting point (ca. 960◦C) than the other metals considered as possible inert materials for aluminium electrolysis. The working temperature used in aluminium industry is approximately 960◦C, depending on the melt composition. Therefore, the stability of silver during the anodic process was tested at 870◦C in an acidic electrolyte consisting of 65.5 mass % Na3AlF6 + 22.9 mass % AlF3 + 5.7 mass % CaF2 + 3.9 mass % LiF + 2 mass % Al2O3 with the melting point ca. 850◦C. The electrolyte without alumina was prepared as well, with the melting point ca. 860◦C. The resulting cryolite ratio (CR = n(NaF)/n(AlF3)) for both electrolytes was equal to 1.6. The behaviour of the silver anode was studied by voltammetry measurements. The electrochemical study showed that an oxidation reaction occurred at a potential below the oxygen evolution potential. Silver was not found to be stable under oxygen evolution. The degradation of the silver anode was apparent after electrolysis

Method for recovering elemental silicon from cutting remains.

This invention relates to a method for recovering elemental silicon cutting remains containing silicon particles, wherein the method comprises manufacturing solid anodes from the cutting remains, arranging one or more manufactured anode (s) in an electrolytic cell with a molten salt electrolyte and one or more cathode (s), and applying a potential difference between the one or more anode (s) and cathode (s) to obtain an oxidation of metallic silicon in the one or more anode (s), transportation of dissolved silicon in the electrolyte, and reduction of the dissolved silicon to a metallic phase at the one or more cathode (s)

Silicon recovery from silicon-iron alloys by electrorefining in molten fluorides

Electrorefining of a silicon-iron material (Si-4.7at%Fe) in molten NaF-KF at 850°C has been investigated in view of recovering pure Si, using electrochemical techniques, SEM-EDS and ICP-AES analyses. The selective electrochemical dissolution of Si was evidenced. Electrorefining runs led to a maximum Si recovery of 80% of the initial Si contained in the material, in the form of a dense deposit at the cathode, with very high current efficiencies. The Si purity has been examined and no Fe was detected by ICP-AES analysis: the recovered Si purity is thus assumed to be higher than 99.99%

Electrochemical behaviour of thorium(IV) in molten LiF–CaF2 medium on inert and reactive electrodes

The electrochemicalbehaviour of the Th(IV)/Th system was examined in moltenLiF–CaF2medium on inert (molybdenum), reactive (nickel) and liquid (bismuth) electrodes in the 810–920 °C temperature range by several electrochemical techniques. Experimental results showed that (i) thorium fluoride was reduced in a single step exchanging 4 electrons and limited by thorium ions diffusion in the solution, (ii) the oxide ions induce the precipitation of Th(IV) in the form of thorium oxide (ThO2), in a process involving as intermediate compound a soluble oxifluoride (ThOF2), (iii) the reduction of thorium ions on reactive (Ni and liquid Bi) electrodes yields compounds Ni–Th and Bi–Th with a potential shift of around 0.7 V (for Ni and Bi) more anodic than the reduction of Th(IV) on inert substrate