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.     

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.     

Molten salt synthesis of MAX phases in the Ti-Al-C system

The molten salt method was used to synthesise the MAX phase compounds Ti₂AlC and Ti₃AlC₂ from elemental powders. Between 900–1000?°C, Ti₂AlC was formed alongside ancillary phases TiC and TiAl, which decreased in abundance with increasing synthesis temperature. Changing the stoichiometry and increasing the synthesis temperature to 1300?°C resulted in formation of Ti₃AlC₂ alongside Ti₂AlC and TiC. The type of salt flux used had little effect on the product formation. The reaction pathway for Ti₂AlC was determined to be the initial formation of TiC_1-x templating on the graphite and titanium aluminides.     

Gap modulation in MCu[Q1−xQ′x]F (M=Ba, Sr; Q, Q′=S, Se, Te) and related materials

BaCuQF (Q=S, Se, Te) materials exhibit band gaps that allow transmission of much of the visible spectrum. BaCuSF is transparent in thin-film form with a band gap of 3.1 eV. Band gap estimates for powders of the solid solution series BaCuS_1−xSe_xF were obtained from wavelength-dependent diffuse-reflectance measurements using an integrating sphere. The band gap can be tuned by the substitution of Se for S to 2.9 eV for BaCuSeF. The decrease scales almost linearly with the increase in the volume of the tetragonal unit cell, which is determined primarily by the expansion of the a lattice parameter; the overall volume increase is 7.0% from x=0 to 1. Further reduction of the band gap is observed in BaCuSe_1−xTe_xF solid solutions, where a unit cell volume increase of 5.5% produces a band gap of 2.7 eV in BaCuSe_0.5Te_0.5F. Powders and films of BaCuSF exhibit strong red luminescence under ultraviolet excitation, which is suppressed by K doping. Additional tuning of band gap and electrical properties (the materials are p-type conductors) can be achieved by replacing Ba with Sr.     

炉衬产生的氧对真空钢液脱氮的动力学影响

采用 99.99%氧化镁砂捣打炉衬的 2 0kg真空感应炉 ,研究了超低碳钢熔炼时炉衬产生的氧对真空钢液脱氮的影响。试验结果表明 :钢液中氧含量在 1 2 0× 1 0 - 6 时 ,脱氮的限制性环节是界面化学反应 ;随炉衬中氧的逸出 ,当钢液中氧含量在 5 1 0×1 0 - 6 时 ,真空钢液脱氮处于界面化学反应和液相边界层扩散控制的边缘区域 ,脱氮速率降低     

Electrochemical Investigation on the Formation of Dy-Fe Alloy in Molten Chlorides

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Thermodynamic and kinetic consideration on the corrosion of Fe, Ni and Cr beneath a molten KCl-ZnCl2 mixture

Thermogravimetric (TG) experiments have been carried out to study the kinetics of hot corrosion of Fe, Cr and Ni, covered by a molten KCl-ZnCl₂ mixture of a composition close to the eutectic (50 mol% KCl-50 mol% ZnCl₂). Furthermore binary and ternary phase diagrams were calculated in order to describe the corrosion process. The tests were conducted at a temperature of 320 °C in an atmosphere consisting of argon and oxygen. For iron different stages are observed in a TG curve. They can be attributed to the different reaction steps of iron chloride formation (incubation phase), oxide precipitation (linear stage) and scale formation (parabolic or logarithmic stage). Based on these observations a model, described by Spiegel [A. Spiegel, Molten Salt Forum 7 (2003) 253], is confirmed. For Cr and Ni these stages are not observed. At 8 vol% O₂ only slight oxidation of Cr and Ni was observed accompanied by evaporation of the salt deposit. At 16 vol% O₂ the rate of oxidation increases and the experiments yield a curve that is either parabolic or logarithmic for both Ni and Cr. As a result it is shown that the solubility of iron chloride in the KCl-ZnCl₂ melt is higher than the solubility of nickel chloride and chromium (III) chloride in the KCl-ZnCl₂ melt. This enables a higher diffusibility of iron chloride to the upper region of the melt where a higher oxygen partial pressure (p(O₂)) is present leading to a higher oxidation rate of iron.     

Heterogeneous Plantinum Nucleation and Crystallization of a Heavy-Metal Fluoride Glass

The effect of controlled heterogeneous nucleation by platinum on the crystallization of a ZrF₄-BaF₂-LaF₃-AlF₃-NaF (ZBLAN) glass was studied. Various levels of platinum were incorporated into this glass by a combination of PtCl₂-doping and melting-atmosphere variation. The effect of doping levels and melting conditions on the incorporation of platinum and the subsequent nucleation of crystals was studied by optical microscopy, scanning electron microscopy, differential scanning calorimetry (DSC), and X-ray diffraction. Increased platinum in the glass resulted in an increased number of nucleation sites for the growth of β-ZrF₄-BaF₂ crystals. Analysis of isothermal and ramp-rate DSC measurements indicated that the crystallization of this glass changed from surface controlled to bulk controlled with an increased number of nuclei. This was confirmed by optical microscopy. In addition, Avrami analysis of the isothermal crystallization data gave an accurate approximation of the number of nuclei in the glass.     

Mechanistic investigation into the electrolytic formation of iron from iron(III) oxide in molten sodium hydroxide

Iron(III) oxide tablets were electrolytically reduced to iron in molten sodium hydroxide at 530 °C and recovered to produce iron with 2 wt.% oxygen suitable for re-melting. The cell was operated at 1.7 V and an inert nickel anode was used. The thermodynamics and mechanism of the process was also investigated. By controlling the activity of sodium oxide in the melt, the cell could be operated below the decomposition voltage of the electrolyte with the net sequence of events being the ionization of oxygen, its subsequent transport to the anode and discharge leaving behind iron at the cathode. A reduction time of 1 h was achieved for a 1 g oxide tablet (close to the theoretical reduction time predicted by Faraday’s laws) at a current density of 520 mA cm⁻² with iron phase yields of ∼90 wt.%. The energy consumption was 2.8 kWh kg⁻¹.     

A branch-and-price algorithm to solve the molten iron allocation problem in iron and steel industry

The molten iron allocation problem (MIAP) is to allocate molten iron from blast furnaces to steel-making furnaces. The allocation needs to observe the release times of the molten iron defined by the draining plan of the blast furnaces and the transport time between the iron-making and steel-making stages. Time window constraints for processing the molten iron must be satisfied to avoid freezing. The objective is to find a schedule with minimum total weighted completion time. This objective reflects the practical consideration of improving steel-making efficiency and reducing operation cost caused by the need for reheating. Such a problem can be viewed as a parallel machine scheduling problem with time windows which is known to be NP-hard. In this paper, we first formulate the molten iron allocation problem as an integer programming model and then reformulate it as a set partitioning model by applying the Dantzig–Wolfe decomposition. We solve the problem using a column generation-based branch-and-price algorithm. Since the subproblem of column generation is still NP-hard, we propose a state-space relaxation-based dynamic programming algorithm for the subproblem. Computational experiments demonstrate that the proposed algorithm is capable of solving problems with up to 100 jobs to optimality within a reasonable computation time.