Michal Korenko

Electrochemistry of samarium in lithium-beryllium fluoride salt mixture

The electrochemical behaviour of samarium was investigated in LiF-BeF2 system on an inert (Mo) electrode by cyclic voltammetry and chronopotentiometry at 804, 833, 847 and 872 K. Redox process Sm3++e−→Sm2+ was recognized and analysed. Cyclic voltammetry data suggested that at potential sweep rates lower than 0.25 V/s, the reduction was limited by the diffusion of Sm3+ ions. It was not possible to observe reduction process of Sm2++2e−→Sm0 due to insufficient electrochemical stability of LiF-BeF2. Diffusion coefficients of Sm3+ ions in LiF-BeF2 were calculated from voltammetric and chronopotentiometric data in the temperature range 804–872 K. Diffusion coefficient values obeyed Arrhenius law. Activation energy was calculated to be 102.5 kJ/mol.

Electrical conductivity of systems based on Na3AlF6-SiO2 melt

The electrical conductivity of molten binary and ternary mixtures based on the NaF-AlF3-SiO2 system was investigated by means of a tube-cell (composed of pyrolytic boron nitride) with stationary electrodes. An impedance/gain-phase analyser (National Instruments; a high-performance modular chassis controlled by Labview™ software) was used for the cell impedance measurement. The conductivity was found to vary linearly with temperature in all the mixtures investigated. The concentration dependence of electrical conductivity (isotherms) thus obtained was divided into two parts. The first represents the concentration region of up to 10 mole % of SiO2, the second the region with a higher concentration of SiO2 (from 10 mole % to 40 mole %). While the conductivity decreased considerably with the concentration of SiO2 in the second part, it increased surprisingly in the low concentration range. From these results, the influence of electrolyte composition and temperature on the electrical conductivity was examined.

Density, Viscosity and Electrical Conductivity of the Molten Cryolite Electrolytes (Na 3 AlF 6 –SiO 2 ) for Solar Grade Silicon (Si–SoG) Electrowinning

Density, viscosity and electrical conductivity of the molten system Na 3AlF 6–SiO 2 have been investigated in the concentration range up to 50 mole % of SiO 2. Density was measured by means of a computerized Archimedean method, viscosity of the melt by computerized torsion pendulum method and the electrical conductivity by means of the tube–cell (pyrolytic boron nitride) with stationary electrodes. It was found that the density, viscosity and conductivity vary linearly with the temperature in all investigated mixtures. On the basis of the density data, the molar volume of the melts and the partial molar volume have been calculated.

Rapid solidification processing in molten salts chemistry: X-ray analysis of deeply undercooled cryolite-alumina melts

Rapid solidification processing (cooling rate from the interval 105–106 K s−1) was used to prepare deeply undercooled cryolite-alumina melts. Such prepared samples were analyzed by the XRD method. Besides cryolite, XRD patterns belonging to ι-Al2O3 were recorded. The influence of annealing on the XRD patterns of deeply undercooled melts was also investigated.

(Oxo)(Fluoro)–Aluminates in KF–Al2O3 System: Thermal Stability and Structural Correlation

Precise investigation of part of the phase diagram of KF-Al2O3 system was performed in an experiment combining different techniques. Solidified mixtures of KF-Al2O3 were studied by X-ray powder diffraction and high-field solid-state NMR spectroscopy over a wide range of compositions. To help with the interpretation of the NMR spectra of the solidified samples found as complex admixtures, we synthesized the following pure compounds: KAlO2, K2Al22O34, α-K3AlF6, KAlF4, and K2Al2O3F2. These compounds were then characterized using various solid-state NMR techniques, including MQ-MAS and D-HMQC. NMR parameters of the pure compounds were finally determined using first-principles density functional theory calculations. The phase diagram of KF-Al2O3 with the alumina content up to 30 mol % was determined by means of thermal analysis. Thermal analysis was also used for the description of the thermal stability of one synthesized compound, K2Al2O3F2.

Phase analysis of the solidified KF–(LiF–NaF–UF4)–ZrF4 molten electrolytes for the electrowinning of uranium

The X-ray diffraction (XRD) phase analysis of different solidified uranium-based fluoride systems ((LiF–NaF)eut–UF4; (KF–LiF–NaF)eut–UF4; (LiF–NaF)eut–UF4–ZrF4 and (KF–LiF–NaF)eut–UF4–ZrF4) were examined in order to provide the basis for pyro-electrochemical extraction of uranium in molten fluorides. Several uranium-based species (Na2UF6, Na3UF7, K2UF6, K3UF7, UO2, K3UO2F5) were identified in the solidified melts. The role of oxygen in argon atmosphere was found to be critical in the formation of uranium species during the melting and solidification. In order to reduce the accumulated level of free oxygen traces in our experiments, zirconium (in the form of ZrF4) was used inside the melt as an oxygen buffer. It was found that ZrF4 can really stabilize the uranium species by complexation and protects them against the oxygenation. The results of this work highlight the importance of oxygen removal for obtaining pure deposit in the electrorefinning of uranium.

Influence of Sulphur Impurities on the Interfacial Tension between Aluminium and Cryolite Alumina Melts

The interfacial tension (IFT) between aluminium and cryolite melts containing different salt additions (AlF3, NaF,Na2SO4) has been measured during electrolysis by the capillary depression method. The technique is based on the measurement of the capillary depression occurring when a capillary, which is moved vertically down through the molten salt layer, passes through the metal/salt interface. The depression is measured by simultaneous video recording of the immersion height of the alumina capillary. The interfacial tension is strongly dependent on the n(NaF)/n(AlF3) ratio. The addition of Na2SO4 decreases the IFT of the aluminium/electrolyte interface. We also found the different influence of the conditions of electrolysis on the IFT in systems with and without Na2SO4. In systems without Na2SO4 the IFT decreases with increasing current density, and in systems with Na2SO4 it increases.

Oxo- and Oxofluoroaluminates in the RbF–Al 2 O 3 System: Synthesis and Structural Characterization

Precise research on the RbF-Al2O3 system was carried out by means of combining X-ray powder diffraction, high-field solid-state NMR spectroscopy, and thermal analysis methods. α-Rb3AlF6, RbAlO2, Rb2Al22O34, and new phase, Rb2Al2O3F2, were identified in the system. The structure of this new rubidium oxofluoroaluminate was determined. It is built up from single layers of oxygen-connected AlO3F tetrahedra, those layers beeing separated by fluorine atoms. This type of structure exhibits a decent ionic conductivity at ambient temperature, 1.74 × 10-6 S cm-1. The similar structural arrangement of O3Al-O-AlO3 and FO2Al-O-AlO2F tetrahedra of the conduction planes in Rb2Al22O34 and Rb2Al2O3F2 were confirmed by 27Al NMR measurements. A thermal analysis of the RbF-Al2O3 system revealed that it can be defined as a pseudobinary subsystem of the more general quaternary RbF-AlF3-Al2O3-Rb2O phase diagram. From a phase analysis of individual phase fields, the mutual metastable behavior of all founded phases can be considered. It was observed that fluoro- and oxoaluminates exist together. Rb2Al2O3F2 is more stable under high temperature. Rubidium fluoro- and oxoaluminates are metastable precursors of the thermodynamically more stable structure of rubidium oxofluoroaluminate.

Preparation of Solar Grade Silicon Precursor by Silicon Dioxide Electrolysis in Molten Salts

Al-Si alloy, a precursor of solar grade silicon, was prepared by direct electrolysis in cryolite molten salt at 950 °C using high purity silica as material, liquid aluminum as the cathode and high purity graphite as the anode. The electrochemical behavior of Si(IV) ion was investigated using cyclic voltammetry method. The electrolysis products were characterized by XRD, SEM/EDS and ICP. The results indicate that the reduction process of Si(IV) on tungsten electrode is a two-step process and there is about 0.6 V gap between the two steps. The contents of boron and phosphorus in the aluminum-silicon alloy are 3 ppmw and 8 ppmw, which will make the directional solidification purification effectively and reduce the cost of preparation solar grade silicon from metallurgical grade silicon.

Electrical conductivity and viscosity of cryolite electrolytes for solar grade silicon (Si-SoG) electrowinning

Abstract Electrical conductivity of molten binary and ternary mixtures based on the system NaF–AlF 3 –SiO 2 was investigated by means of a tube–cell (made of pyrolytic boron nitride) with stationary electrodes. Viscosity of the binary system Na 3 AlF 6 –SiO 2 was measured by computerized torsion pendulum method. It was found that conductivity and viscosity varied linearly with temperature in all investigated mixtures. Obtained content dependence of electrical conductivity (isotherms) was divided into two parts. First, one represented the content region up to 10% (mole fraction) of SiO 2 ; second, the region was with a higher content of SiO 2 (from 10% up to 40%). While the conductivity considerably decreased with content of SiO 2 in the second part; it surprisingly rose in the low content range. A small addition of SiO 2 to the molten cryolite (up to 10%) could slightly increase viscosity, but had no influence on the slope of this dependence since it is responsible for a glassy-networks formation in the melt. Further addition of SiO 2 to the molten cryolite had a huge effect on the viscosity.