Green preparation of vanadium carbide through one-step molten salt electrolysis

Vanadium carbide (VC) as excellent ceramic and functional material is usually prepared by carbothermal reduction of V₂O₅ which must be extracted from a typical V slag by complex processes. Pollutants, such as ammonia-nitrogen wastewater, NH₃ and CO₂ are inevitably discharged. A novel and green method for VC preparation was proposed by one-step co-electrolysis of soluble NaVO₃ and CO₂ in molten salt. It was found that VC with high purity was easily obtained by reducing electrolysis temperature and CO₂ flow rate to 600 °C and 10 mL min⁻¹ at 3.0 V. Besides VC with particles and layered stacking structure in products, a small amount of carbon and oxygen elements existed. The atomic percentage contents of C, V, and O elements in VC were about 50.0%, 44.5% and 3.8%, respectively. During electrolysis, CO₃²⁻ and VO₃⁻ was reduced at about −0.55 V (vs. Ag/AgCl) and −1.38 V (vs. Ag/AgCl), respectively. CO₃²⁻ ions were more easily reduced than VO₃⁻, and was firstly reduced to CO₂²⁻ and then converted to C. Then, VC was prepared by two routes from CO₂ and NaVO₃. One route is that VO₃⁻ ions are firstly electroreduced to VO₂⁻ ions and then are further electroreduced to VC with C. Another route is that VO₃⁻ ions are electroreduced to V which in-situ reacted with C to VC. Both VO₃⁻ and CO₃²⁻ ions are electroreduced by two-step process. In final, VC is in-situ deposited on cathode. It provides a novel and green way to prepare VC and also achieves the high value-added utilization of vanadium slag and CO₂.     

Potassium titanate whiskers on the walls of cordierite honeycomb ceramics for soot catalytic combustion

In this paper, potassium titanate whiskers was prepared via the Molten salt synthesis on the surface of cordierite ceramics for the regeneration of diesel particulate filters (DPFs). SEM, EDS, XRD, FT-IR, TG-DSC and TPO were carried out to characterize the morphology, microstructure, growth mechanism and catalytic performance of the samples. Potassium titanate whiskers with diameter (100–500 nm) and length (about 3 μm) is tightly combined with the cordierite ceramic substrate. The catalyst performance investigation demonstrates that potassium titanate whiskers decrease the soot combustion temperature apparently. The soot combustion process was studied by thermal analysis tests, and the activation energy of the combustion reaction can be calculated using Freeman-Carroll method. The carbon oxidation activation energy is 14.009 kcal/mol, and the activation energy for the catalytic reaction with potassium titanate whiskers is 6.287 kcal/mol, it can be illustrated that potassium titanate whiskers/cordierite catalyst possess excellence performance for carbon catalytic combustion. The coarseness of the interface increased because potassium titanate whiskers grew on the cordierite substrate, and the trapping ability could improve. This unique microstructure has potential application in the DPF field.     

The phosphorescence emission in undoped lead-halide Cs4PbBr6 single crystals at low temperature

Recently, all-inorganic cesium lead-halide perovskites have shown their promise for light emission applications, due to the excellent optical performance. Herein, we report that the initially nonphosphorescent undoped lead-halide Cs₄PbBr₆ single crystals (SCs) exhibit an ultralong phosphorescence emission under X-ray excitation at low temperatures. It is shown that the dramatic change has been taken place in radioluminescence spectra and the broad-band emission gradually appeared with the decrease of temperature. Below 210 K, the radioluminescence spectra can be deconvoluted into one narrow peak located at 530 nm and two broad peaks centered at 595 nm and 672 nm respectively. Subsequently, the time-dependent radioluminescence spectra in undoped lead-halide Cs₄PbBr₆ SCs were investigated. The ultralong phosphorescence emission can persist over 120 min at 70 K. We consider that ultralong phosphorescence originates from defect-related emission. To the best of our knowledge, our finding is the first time that undoped Cs₄PbBr₆ SCs exhibit the phosphorescence emission, which will offer a paradigm to motivate revolutionary applications on perovskite.     

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.     

Generation-IV reactors and nuclear hydrogen production

There are dozens of hydrogen production methods and techniques from many sources such as fossil fuels, renewable energy sources and nuclear energy in the literature. Thermo-chemical methods are more efficient at higher temperatures to produce large quantities of hydrogen. In this study, a comparative overview of Generation VI nuclear reactor types for major hydrogen production methods have been researched in the literature and suggestions have been carried out.This research work is addressing that both electric power cycle and hydrogen production based on nuclear technologies need to be developed. Generation IV nuclear reactors can provide hydrogen for a worldwide hydrogen economy. Both thermo-chemical and electrolysis (hybrid) processes in hydrogen production have a promising future, especially when integrated with Generation IV nuclear power plants. Efficient heat transfer is required for both high temperature thermodynamic cycles and the high temperature steam electrolysis. Hence, highly efficient heat exchanger designs are one of the key technologies for that purpose.     

In situ synthesis of Al2O3–SiC powders via molten-salt-assisted aluminum/carbothermal reduction method

Al₂O₃–SiC composite powder (ASCP) was successfully synthesized using a novel molten-salt-assisted aluminum/carbothermal reduction (MS-ACTR) method with silica fume, aluminum powder, and carbon black as raw materials; NaCl–KCl was used as the molten salt medium. The effects of the synthesis temperature and salt-reactant ratio on the phase composition and microstructure were investigated. The results showed that the Al₂O₃–SiC content increased with an increase in molten salt temperature, and the salt–reactant ratio in the range of 1.5:1–2.5:1 had an impact on the fabrication of ASCP. The optimum condition for synthesizing ASCP from NaCl–KCl molten salt consisted of maintaining the temperature at 1573 K for 4 h. The chemical reaction thermodynamics and growth mechanism indicate that the molten salt plays an important role in the formation of SiC whiskers by following the vapor-solid growth mode in the MS-ACTR treatment. This study demonstrates that the addition of molten salt as a reaction medium is a promising approach for synthesizing high-melting-point composite powders at low temperatures.     

Synthesis and characterization of Co5Cr2(P2O7)4 - New pyrophosphate as a colouring substance

A new pyrophosphate(V) of the formula Co₅Cr₂(P₂O₇)₄ was obtained in the system Co₂P₂O₇–Cr₄(P₂O₇)₃ as a result of solid-state reactions taking place between different reactants. The new compound crystallizes in the orthorhombic system and belongs to the family of pyrophosphates of the general formula M₅²⁺M₂³⁺(P₂O₇)₄ and is probably isostructural with Fe₅²⁺Fe₂³⁺(P₂O₇)₄. Powder diffraction pattern, infrared spectrum and SEM image of the new compound were presented. As a new potential inorganic pigment, Co₅Cr₂(P₂O₇)₄ was tested for its thermal stability, particle size distribution and colour properties, which were studied both for powder and after introduction into organic matrix and leadless ceramic glaze. The colour of Co₅Cr₂(P₂O₇)₄ powder was defined as deep grey with the colour coordinates L*/a*/b* = 60.63/-1.42/-3.41 and according to the hue angle (h° = 247.39°) it belongs to the blue region. Co₅Cr₂(P₂O₇)₄, with its relatively high thermal stability (t _m = 1230 ± 10 °C) and appropriate colour properties, is a good candidate to be used as inorganic pigment for colouring of acrylic paints. In the case of leadless glaze, the obtained compound acts as a dye.     

Effects of corrosion in liquid fluoride salt on the tensile strength of domestic SiC fibers

The relationship between the tensile strength of corroded domestic second-generation (2ed-gen) SiC fibers at various temperatures for 500 h in 46.5LiF-11.5NaF-42.0KF (mol. %) eutectic salt and the typical microstructure was studied. Weibull theory was used to analyze the critical defects that caused the tensile fracture, and the microstructure of fibers before and after corrosion was characterized. It is concluded that the decrease of tensile strength after corrosion at 800 °C is caused by the surface injury of fibers, which led to the shift of critical defects from the internal defects of virgin fibers to surface defects. Moreover, corrosion at higher temperature accelerates the corrosion process and dissolve the surface O-contained layer thoroughly. This shifts the critical defects back to the internal defects and will be helpful for the recovery of tensile strength of corroded fibers at the higher temperature.     

Effects of water and carbon dioxide pressure on the adhesion of Na2SiO3 and K2SiO3 binders on silica sand surface: Comparison of experimental data and molecular dynamics simulation

In this study, the effects of different water amounts, CO₂ blowing pressures, Na₂O:SiO₂ and K₂O:SiO₂ ratios were studied on the bonding strength of Na₂SiO₃ and K₂SiO₃ binders. It was concluded that the increase in water content had an adverse effect on the bonding strength of CO₂-hardened Na₂SiO₃ sand. The blowing pressure did not have a linear relationship with the bonding strength, but it was closely related to the diffusion coefficient of CO₂. Based on scanning electron microscopic results, it was inferred that the low strength was caused by the formation of lamellar crystals after the adhesive was hardened. It was found that the low strength was caused by the formation of lamellar crystals after the adhesive was hardened. Based on molecular dynamics simulations, different pressures and water contents had a great influence on the diffusion coefficient of CO₂ in the silicate binder system. This research provides an important theoretical background to improve the technology of CO₂-hardened Na₂SiO₃- and K₂SiO₃-bonded sands during the casting process.     

Corrosion mechanism of cement-bonded Al2O3–MgAl2O4 pre-cast castables in contact with molten steel and slag

In this work, a cement-bonded corundum-spinel (Al₂O₃–MgAl₂O₄) pre-cast refractory brick with two typical Al₂O₃ aggregates was designed as the refractory lining. Corroded microstructure of the used corundum-spinel bricks after industrial trials in a commercial RH refining ladle was analyzed. Degradation processes of two types of alumina aggregates in the same corroded interface also were discussed. Typical corroded microstructure revealed that needle-like calcium hexaaluminate (CA₆) was observed in the matrix of the original layer. The formation of CA₆ was attributed to the reactions with pure calcium aluminate cement and matrix components under a high-temperature gradient during refining. Furthermore, the corrosion process of the used Al₂O₃–MgAl₂O₄ bricks would be discussed based on a post-mortem microstructural characterization, and the corrosion mechanism of the two types of aggregates was also elucidated.