Thermodynamic analysis on the direct preparation of metallic vanadium from NaVO3 by molten salt electrolysis☆

A novel and environmentally friendly route to directly prepare metallic vanadium from Na VO_3 by molten salt electrolysis is proposed.The feasibility about the direct electro-reduction of NaVO_3 to metallic vanadium is analyzed based on the thermodynamic calculations and experimental veri fications.The theoretical decomposition voltage of NaVO_3 to metallic vanadium is only 0.47 Vat 800°C and much lower than that of the alkali and alkali earth metal chloride salts.The value is slightly higher than that of low-valence vanadium oxides such as V_2O_3,V_3O_5 and VO.However,the low-valence vanadium oxides can be further electro-reduced to metallic vanadium thermodynamically.The thermodynamic analysis is veri fied by the experimental results.The direct preparation of metallic vanadium from NaVO_3 by molten salt electrolysis is feasible.     

Seamless joining of silicon carbide ceramics through an sacrificial interlayer of Dy3Si2C2

A ternary carbide Dy₃Si₂C₂ coating was fabricated on the surface of SiC through a molten salt technique. Using the Dy₃Si₂C₂ coating as the joining interlayer, seamless joining of SiC ceramic was achieved at temperature as low as 1500 °C. Phase diagram calculation indicates that seamless joining was achieved by the formation of liquid phase at the interface between Dy₃Si₂C₂ and SiC, which was squeezed out under pressure and continuously consumed by the joining interlayer. This work implies the great potential of the family of ternary rare-earth metal carbide Re₃Si₂C₂ (Re = Y, La-Nd) as the sacrificial interlayer for high-quality SiC joining.     

Bi(Ⅲ)在NaCl-KC1熔盐体系中的电化学行为

为开发环境友好型铋提取技术,在700℃下采用循环伏安、方波伏安和计时电位等方法研究了NaCl?KCl熔盐体系中Bi(III)在玻碳电极上的电化学行为。在–0.3 V (vs. Ag/AgCl)电位下以玻碳电极为工作电极对NaCl?KCl?BiCl3进行恒电位电解。结果表明,Bi(III)在NaCl?KCl熔盐体系中的还原反应是一步得到3个电子的准可逆反应Bi3++3e?=Bi,起始还原电位为0.05 V (vs. Ag/AgCl),该反应受扩散控制。Berzins-Delahay方程和Sand方程计算的700℃下Bi(III)在熔盐中的扩散系数分别为0.83×10–5和1.0×10–5 cm2/s。阴极产物为致密纯金属Bi,不含杂质。     

Calciothermic reduction of NiO by molten salt electrolysis of CaO in CaCl2 melt

Metallic nickel powders with low and uniform residual oxygen content were produced from NiO using the molten salt electrolysis of CaO in CaCl₂ melt. Suitable amount of CaO for the reduction was in the range of 0.5–3.0 mol% CaO.The electrical isolation of NiO from both electrodes could produce metallic Ni in CaCl₂ melt. Separating the metal oxides from the cathode confirmed the mechanism of calciothermic reduction that the electrolysis of dissolved CaO in CaCl₂ melt produces Ca, and that the dissolved Ca in molten CaCl₂ successfully reduces NiO to metallic Ni. An average of about 600 ppm oxygen in Ni sample was achieved directly from oxide, when NiO was detached from the cathode.     

难熔金属含氧酸盐电化学解离-合金化短流程绿色工艺

针对难熔金属传统冶金流程长、能耗高和污染重的问题,介绍了以难熔金属含氧酸盐(如CaTiO3, NaVO3, Na2CrO4等)中间体直接熔盐电解(液态阴极)制取合金的短流程新过程。以熔点低、可溶、可电离的难熔金属含氧酸盐为电解反应物直接实现难熔金属的合金化,构建冶金?材料一体化的熔盐电解新体系,是缩短流程和实现冶金资源“快速成材”的创新路径。新过程弃用污染性工艺,环境友好,符合高效绿色冶金原则,有潜力成为一种普适性新方法。     

熔盐电解法制备硼粉的研究

对熔盐电解法制备硼粉的方法进行了论述,比较了各熔盐体系的优点和缺点,得出了氯化钾或氯化钾和氟化钾混合物的熔盐体系最适宜。用冷却曲线法对KF-KCl-KBF4体系熔盐体系的初晶温度进行了研究,研究表明:KF-KCl-KBF4体系的初晶温度为1 023—1 033 K,即750—760℃之间,当电解温度高于初晶温度20—30℃时,电解效率最高。这就为熔盐电解法制备元素硼提供了依据。     

Synthesis of vanadium carbide nanopowders by thermal processing and their characterization

Vanadium carbide (V₈C₇) nanopowders were successfully prepared by thermal processing the precursor which originated from the mixture of ammonium vanadate (NH₄VO₃) and nanometer carbon black. The products were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmett-Teller (BET) methods. The single phase V₈C₇ powders can be prepared at ∼ 1100 °C for 1 h with the average crystallite size of 32.6 nm and the powders show good dispersion and are mainly composed of uniformly-sized spherical particles with a mean diameter of ∼ 100 nm.     

Effect of LiF dosage on morphology of ZrO2 prepared by the molten salt method

Zirconia nanorods and polyhedral particles were prepared using the molten-salt method. The effects of the LiF dosage on the ZrO₂ crystal morphology were studied using XRD combined with Rietveld refinement, FE-SEM combined with EDS, FTIR, Raman spectroscopy, and high-temperature microscopy. The results show that the ZrO₂ obtained with LiF is in the monoclinic phase. ZrO₂ nanorods were synthesized at low LiF dosages. Polyhedral ZrO₂ particles were synthesized, and the ZrO₂ crystal planes (100) and (200) were exposed to a high LiF dosage. LiF promoted the dissolution of ZrO₂ and was adsorbed onto the ZrO₂ crystal surface. This work provides a new strategy for controlling morphology and crystal surface exposure.     

熔盐电解NiO制备Ni的机理探讨

通过固态NiO在CaCl_2-NaCl熔盐中直接电化学还原制备Ni的电解产物随时间变化分析,石墨阳极破损研究以及对NiO低于理论分解电压的槽电压分解现象的解释,探讨了熔盐电解NiO制备Ni的电解反应机理。认为电解反应基本服从氧离子化机理,且NiO阴极片在低于理论分解电压的槽电压下,电化学还原反应和热还原反应同时发生。     

Synthesis of Ti3SiC2 coatings onto SiC monoliths from molten salts

Coatings with composition close to Ti₃SiC₂ were obtained on SiC substrates from Ti and Si powders with the molten NaCl method. In this work, the growth of coatings by reaction in the salt between monolithic SiC substrates and titanium powder is obtained between 1000 and 1200 °C. At 1000 °C, a coating of 8 µm thickness is formed in 10 h whereas a thin coating of 0.5 µm has been grown in 2 h. A lack in silicon was first found in the coatings prepared at 1100 and 1200 °C. For these temperatures, the addition of silicon powder in the melt had a favorable effect on the final composition, which is found very close to the composition of Ti₃SiC₂. The reaction mechanism implies the formation of TiC_x layers in direct contact with the SiC substrate and the presence of more or less important quantities of Ti₃SiC₂ and Ti₅Si₃C_x in the upper layers.     

High-quality SiC-HfC coating with interpenetrating structure based on a two-step low temperature molten salt method

To improve the ablation resistance of carbon fibre (Cf), alleviate the interdiffusion between Cf and the matrix, and improve the complex preparation process of double-layer carbide coating, a high-quality SiC-HfC double interpenetrating coating was prepared on the surface of Cf using a molten salt synthesis (MSS) method. The microstructure, formation mechanism, and ablation behaviour of the coating were studied. The results show that the coating is composed of interpenetrating HfC and SiC phases. The interpenetrating structure was formed due to the transport of Hf ions into the interior of porous SiC nanowires facilitated by the molten salt medium, followed by diffusion through carbon. The SiC-HfC double-layer interpenetrating coating can serve as an oxygen barrier to protect Cf from oxidative damage under extreme temperature (2000 °C) and aerobic environment (oxyacetylene flame).     

Low-temperature molten salt synthesis of high-entropy carbide nanopowders

Synthesis of the powders is critical for achieving the extensive applications of high-entropy carbides (HECs). Previously reported studies focus mainly on the high-temperature (>2000 K) synthesis of HEC micro/submicropowder, while the low-temperature synthesis of HEC nanopowders is rarely studied. Herein we reported the low-temperature synthesis of HEC nanopowders, namely (Ta_0.25Nb_0.25Ti_0.25V_0.25)C (HEC-1), via molten salt synthesis for the first time. The synthesis possibility of HEC-1 nanopowders was first theoretically demonstrated by analyzing lattice size difference and chemical reaction thermodynamics based on the first-principle calculations, and then the angular HEC-1 nanopowders were successfully synthesized via molten salt synthesis at 1573 K. The as-synthesized nanopowders possessed the single-crystal rock-salt structure of metal carbides and high compositional uniformity from nanoscale to microscale. In addition, their formation mechanism was well interpreted by a classical molten salt-assisted growth.     

Novel synthesis and characterization of silicon carbide nanowires on graphite flakes

Silicon carbide nanowires were synthesized on the surface of graphite by partially reacting with silicon powders in NaF–NaCl based salt at 1150–1400 °C in argon. The effects of temperature and time of heat treatment as well as Si/graphite ratio on synthesis of SiC nanowires were studied. The results showed that the formation of SiC nanowires started at about 1200 °C, and the amounts of SiC nanowires increased in the resultant powders with increasing temperature. Their morphologies were characterized by scanning electron microscopy and high-resolution transmission electron microscopy. It was found that β-SiC nanowires with diameter of 10–50 nm and various lengths grew along their preferred direction perpendicular to (111). The zeta potential of graphite was also increased after coating with silicon carbide nanowires. SiC nanowires that formed on the graphite surface acted as an anti-oxidant to a certain extent, and they protected the inner graphite from oxidation.     

In-situ synthesis of zirconium oxycarbide by electroreduction of ZrO2/C in molten salt

Homogenous ZrC_xO_y powders have been successfully synthesized by in-situ electro-reduction of solid ZrO₂–C composite precursors in molten CaCl₂. The effect of applied cell voltage and molar ratio of ZrO₂ to C on preparation of ZrC_xO_y were investigated. The reduction pathway of the composite electrode was studied based on the analysis of intermediate products using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that ZrO₂ is firstly converted to CaZrO₃. The resulting CaZrO₃ is then reduced to ZrC_xO_y. The ZrC_xO_y formation is dramatically influenced by electrolysis voltage and molar ratio of ZrO₂ to C: a higher cell voltage and lower molar ratio of the ZrO₂ to C are more preferable for the formation of ZrC_xO_y powder. Homogenous ZrC_xO_y powders with particle size of ~100 nm are synthesized by ZrO₂/C starting elemental powders in CaCl₂ molten salt at 1123 K for more than 3 h, when the cell voltage is 3.0 V and the molar ratio of the ZrO₂ to carbon starting materials is 1:1.0.     

Template formation of magnesium aluminate (MgAl2O4) spinel microplatelets in molten salt

Magnesium aluminate, MgAl₂O₄ (MA), microplatelets were synthesized using a molten salt technique. -Alumina platelets partially decomposed from aluminium sulphate were reacted with either commercial magnesium oxide or magnesium nitrate in the molar ratio 1:1 to synthesize spinel platelets. Molten salts such as chloride, MCl (M = Li, Na, and K) and potassium sulphate were used for MA synthesis and the salt to oxide ratio was kept at 3:1 for all compositions. Reactants and molten salt mixes were fired in an alumina crucible for 3 h at from 800 to 1150 °C. XRD revealed complete MA without formation of any secondary phase for powders fired for 3 h at 1100 °C. Electron microscopy revealed the MA platelet morphology and size was the same as the -alumina platelets indicating a ‘template process’ during molten salt synthesis.     

Molten salt synthesis of continuous tungsten carbide coatings on graphite flakes

Continuous tungsten carbide (WC) coatings were prepared on graphite flakes (G_f) by molten salt synthesis (MSS) technique using NaCl and KCl as reaction medium. The effect of reaction temperature, dwelling times and WO₃/G_f molar ratio on the compositions and morphologies of resultant samples was investigated, and the related formation mechanism for the coatings was also discussed. The results show that continuous WC coatings can be prepared at 1100 °C for 60 min with a WO₃/G_f molar ratio ranging from 1/15 to 1/5. These coatings exhibit homogeneous and crack free features, and their thickness increases with the increase of molar ratio. With the WO₃/G_f molar ratio below or beyond the above range, discontinuous WC coatings or W/W₂C/WC flake-like particles without graphite are obtained, respectively. The varied compositions of the samples obtained with different WO₃/G_f molar ratio can be related to the detailed chemical reaction process between WO₃ and G_f in the molten salts. A “template-growth” mechanism is proposed to explain the formation of WC coatings in the MSS process.     

A single-source molten salt synthesis of rod-shaped Na2Ti6O13 crystals

As one of the most potential negative electrode materials, Na₂Ti₆O₁₃ is expected to play an important role in the area of high-performance battery. In this work, we have developed an easy, efficient and controllable method to prepare rod-shaped Na₂Ti₆O₁₃ crystals. This approach utilized a single-source molten salt strategy and only needed to sinter a special precursor synthesized from an aqueous solution containing H₃BO₃ and (NH₄)₂TiF₆ in presence of sodium salts. The component and shape of precursor crystals can be tuned by adjusting the reagent concentration and reaction temperature. By sintering precursor crystals in air at 900 °C for 30 min, Na₂Ti₆O₁₃ with high crystallinity and purity can be obtained. X-ray diffraction and scanning electron micrographs results of different sintering times show that the sintering process can be divided into two steps. Firstly, the precursor crystals are converted to TiO₂ (anatase) nano-particles and amorphous sodium salts. Subsequently, molten salt reaction occurs between amorphous sodium salts and TiO₂ and forms rod-shaped Na₂Ti₆O₁₃ crystals.     

Simulation analysis on optimization of tungsten carbide recovery efficiency by molten salt electrolysis

Journal of Applied Electrochemistry - The molten salt electrochemical method is an efficient one-step process to extract tungsten from tungsten carbide (WC). Owing to the limitation of molten salt...     

High temperature corrosion resistance of electrically conductive nitrogen doped silicon carbide ceramics in molten fluorides

Electrically conductive nitrogen-doped SiC ceramics were exposed to molten FLiNaK at 700 °C for 100, 200, and 500 h, and at 1000 °C for 100 h in Ar atmosphere. The SEM-EDX investigations of corroded samples showed that the main corrosion attack proceeds through the intergranular phase, where the fluoride melt interacts with the oxide phases and partly dissolves also the SiC grains. It was proved that N-doped SiC has good corrosion resistance against molten FLiNaK. After corrosion at 700 °C for 100, 200, and 500 h the corroded layer thicknesses were 85, 90, and 120 µm, respectively.