High-temperature Reference Electrodes Used in Molten Fluorides

The thermodynamic and dynamic behaviour of Ni^(2+)|Ni couple in FLINAK melt is investigated by us- ing EMF measurement and micropolarization method.The couple shows the Nernstian reversibility and a large exchange current density(6 mA·cm^(-2)).A single crystal LaF_3 which is a fluoride ion conductor used as a membrane of the Ni^(2+)|Ni couple reference electrode is reliable in FLINAK melts at 973 K.The poten- tial of LaF_3 membrane reference electrode is constant within±2 mV.The boron nitride used as a salt bridge was not good in FLINAK melts.The platinum electrode is studied by using micropolarization.The equilibrium potential of Pt electrode is dependent on the absorption and the electrochemical reaction.The potential is stable for a constant composition at constant temperature.

Electrolytic Codeposition of Y(Ⅲ) and Al(Ⅲ) and Surface Metalliding in Molten Fluorides—Oxides Systems

The mechanism of the electrolytic codeposition of Y Al alloy in molten LiF AlF 3 Al 2O 3 YF 3, LiF YF 3 Y 2O 3 AlF 3 and LiF YF 3 Y 2O 3 Al 2O 3 systems was investigated by means of cyclic voltammetry. The electrodeposited products were analysed by X ray diffraction. The results show that the electrolytic codeposition of Y Al alloy in the LiF YF 3 Y 2O 3 Al 2O 3 system without AlF 3 can be achieved at the same potential for Y(Ⅲ) and Al(Ⅲ) which have great difference in deposition potential. It is beneficial to codeposition of Y(Ⅲ) and Al(Ⅲ) when temperature rises. The potential of beginning codeposition is about -0.85 V ( vs Pt reference electrode), but only at the potential of -0.95 V or more negative can Y based Al alloy containing a great amount of yttrium be obtained.

Electrochemical behaviors of Mg^(2+) and B^(3+) deposition in fluoride molten salts

By using cyclic and linear sweep voltammetry,the electrochemical deposition behaviors of Mg^2＋ and B^3＋ in fluorides molten salts of KF-MgF2 and KF-KBF4 at 880℃ were investigated,respectively.The results show that the electrochemical reduction of Mg^2＋ is a one-step reaction as Mg^2＋＋2e-→Mg in KF-1%MgF2 molten salt,and the electrochemical reduction of B^3＋ is also a one-step reaction as B^3＋＋3e-→B in KF-KBF4 （1%,2% KBF4） molten salts.Both the cathodic reduction reactions of Mg^2＋ and B^3＋ are controlled by diffusion process.The diffusion coefficients of Mg^2＋ in KF-MgF2 molten salts and B^3＋ in KF-KBF4 molten salts are 6.8×10^-7 cm^2/s and 7.85×10^-7 cm^2/s,respectively.Moreover,the electrochemical synthesis of MgB2 by co-deposition of Mg and B was carried out in the KF-MgF2-KBF4 （molar ratio of 6：1：2） molten salt at 750℃.The X-ray diffraction analysis indicates that MgB2 can be deposited on graphite cathode in the KF-MgF2-KBF4 molten salt at 750℃.

Study on Mechanism of Electrodeposition of Y(Ⅲ) in Molten LiF-YF_3-Y_2O_3 by Cyclic Voltammetry

The mechanism of the cathodic process of Y(Ⅲ) on platinum and molybdenum electrode in molten LiF YF 3 Y 2O 3 was investigated by means of cyclic voltammetry. The number of electron transferred was calculated. The results show that the electrochemical reduction of Y(Ⅲ) is a reversible one step three electrons reaction and the cathodic process is diffusion controlled. The reductive product easily forms the intermetallic compounds with the platinum electrode, but it is pure yttrium on the molybdenum electrode.

Cathodic Process of Ti(Ⅳ) in Molten LiF-NaF

The mechanism of the cathode reduction of Ti(Ⅳ) at platinum electrode in molten LiF-NaF containingvarious concentrations of K_2TiF_6 has been investigated by means of cyclic voltamrnetry and convolutiontechnique. The transfered electron number of each reduction step has been determined. It is found that thereduction of Ti(Ⅳ) proceeds in three steps: Ti(Ⅳ)→Ti(Ⅲ)→Ti(Ⅱ)→Ti(0). The first step is accompanied bythe chemical disproportionation reaction: ZTi(Ⅲ)→Ti(Ⅳ)+Ti(Ⅱ). The cathodic product is soluble and prob-ably forrns alloy with the platinurn electrode.

Electrochemical Reduction of Niobium lons in Molten NaF-CaF_2

The mechanism of the electrochemical reduction of niobium ions in molten NaF-CaF_2 (2 : 1 mol) wasinvestigated by means of cyclic voltammetry and chronoamperometry. It is found that the reduction ofNb ( V ) proceedsintwosteps : Nb ( V)→ Nb (Ⅳ)→Nb ( 0 ) . Theelectrochmical reaction Nb ( Ⅳ) + 4e →Nb( 0 ) is a reversible and diffusion-controlled process.

Process optimization of a closed-chamber distillation system for the recovery of FLiNaK molten salt

Low-pressure distillation has been proposed as a suitable technique for the recovery of carrier salt from molten salt reactor spent fuel.A closed-chamber distillation system,in which the pump is stopped and pressureinduced salt distillation is performed,was arranged for fluoride salt treatment.A stair-step optimization process was demonstrated to improve the recovery efficiency by up to 99%.The pressure change curve was feasible for estimating the distillation process,and a method for displaying the pressure value online in order to determine the endpoint was also developed.The decontamination factor of Nd in the condensate salt was deduced to be greater than 100 with 1 wt%NdF3–FLiNaK distillation.The optimal conditions developed in this study showed a high recovery ratio for the fluoride carrier salt and a high separation efficiency for rare earth products.

Neutronic study on the effect of first wall material thickness on tritium production and material damage in a fusion reactor

In this study,the effects of changing first wall materials and their thicknesses on a reactor were investigated to determine the displacement per atom(DPA)and gas production(helium and hydrogen)in the first wall,as well as the tritium breeding ratio(TBR)in the coolant and tritium breeding zones.Therefore,the modeling of the magnetic fusion reactor was determined based on the blanket parameters of the International Thermonuclear Experimental Reactor(ITER).Stainless steel(SS 316 LNIG),Oxide Dispersion Strengthened Steel alloy(PM2000 ODS),and China low-activation martensitic steel(CLAM)were used as the first wall(FW)materials.Fluoride family molten salt materials(FLiBe,FLiNaBe,FLiPb)and lithium oxide(LiO_(2))were considered the coolant and tritium production material in the blanket,respectively.Neutron transport calculations were performed using the wellknown 3D code MCNP5 using the continuous-energy Monte Carlo method.The built-in continuous energy nuclear and atomic data libraries along with the Evaluated Nuclear Data file(ENDF)system(ENDF/B-V and ENDF/B-VI)were used.Additionally,the activity cross-section data library CLAW-IV was used to evaluate both the DPA values and gas production of the first wall(FW)materials.An interface computer program written in the FORTRAN 90 language to evaluate the MCNP5 outputs was developed for the fusion reactor blanket.The results indicated that the best TBR value was obtained for the use of the FLiPb coolant,whereas depending on the thickness,the first wall replacement period in terms of radiation damage to all materials was between 6 and 11 years.

Molten salt synthesis of neodynium oxyfluoride in various fluoride media with different fluoride ion activities

Neodymium oxyfluoride has received much attention in the fields of anionic solid electrolytes.luminescent,catalytic and magnetic materials because of its structure combined advantages of rareearth cations with F^(-)and O_(2)^(-)anions.In this work,neodynium oxyfluoride was synthesized by the reaction between neodymium oxide and four fluoride media with different fluoride ion activities.The synthesis processes in molten LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),NaF-CaF_(2)-NdF_(3)and NaF-KF-NdF_(3)are observed in situ by a confocal scanning laser microscope.The expansion of neodymium oxide particle is observed in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts,and the growth of needle crystals on neodymium oxide particle is clearly observed in molten NaF-CaF_(2)-NdF_(3).Based on scanning electron microscopy(SEM)-energy dispersive X-ray spectroscopy(EDS)and X-ray diffraction(XRD)analyses of products,neodynium oxyfluoride was successfully synthesized in the four fluoride media.The neodynium oxyfluoride generated in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts is a tetragonal structure.However,in molten NaF-CaF_(2)-NdF_(3),neodynium oxyfluoride with a rhombohedral structure is formed.It is suggested that the substitution of Na(Ⅰ)and Ca(Ⅱ)for Nd(Ⅲ)can transform NdOF from tetragonal structure to rhombohedral structure.The growth rate of needle crystals generated in molten NaF-CaF_(2)-NdF_(3)was calculated based on the result of a confocal scanning laser microscope,and it is found that the reaction kinetics of crystal formation is zero-order reaction.The effect of fluoride media on the structure and morphology of formed NdOF were evaluated by XRD,X-ray photoelectron spectroscopy(XPS)and SEM.The neodymium oxyfluoride prepared in the fluoride media with high fluoride ion activity has low binding energy of F 1 s.The ratio of adsorbed oxygen to lattice oxygen for neodymium oxyfluoride prepared in molten LiF-NdF_(3)is larger than those in the other three fluoride media,so it can have better catalytic performance.

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.

Electrochemical formation of La-Al intermetallic compounds in fluoride melts

The electrochemical formation of La-Al alloys in LiF-CaF_(2)molten salt on a molybdenum electrode at 1123 K was investigated by electrochemical techniques,such as cyclic voltammetry,square-wave voltammetry and open-circuit chronopotentiometry.The formation signals of four types of Al-La intermetallic compounds were observed.The Al-La alloy was obtained through galvanostatic electrolysis at 2.5 A·cm^(-2)for 3 h.The phase composition and microstructure of the electrolytic products were analysed by X-ray diffraction(XRD)and scanning electron microscopy with energy-dispersive spectroscopy(EDS).XRD results show that the phase compositions of the alloys are Al_(11)La_(3)and Al,and EDS results reveal 26.7 at%La in the alloy.