Structure and thermoelectric properties of higher manganese silicides synthesized by pack cementation

Higher manganese silicides (HMS) are promising alternative materials for middle to high temperature thermoelectric applications as a low-cost, non-toxic and highly stable p-type leg. Many of the preparation methods that have been reported previously require long-time and energy consuming processes, as well as expensive equipment, and often do not result in a material of sufficient quality. In this study, the simple, cost-effective and eco-friendly technique of pack cementation is applied. HMS powders synthesized at different experimental conditions are studied and compared considering their structure, composition, short-term thermal stability in air and thermoelectric properties. X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, thermogravimetry and thermoelectric measurements (in terms of Seebeck coefficient, electrical and thermal conductivity) were employed for the characterization of the material and evaluation of its performance. All samples were identified as HMS and only some negligible traces of MnSi were detected. They moderately oxidize when heated non-isothermally under air atmosphere up to 1473 K, while the presence of HMS remains dominant even at such high temperatures. Their thermoelectric properties were remarkable for an undoped material, with a maximum figure of merit (ZT) of 0.47 at 777 K. Pack cementation appeared to have a great potential as the synthesis route of high-efficiency HMS.     

Rapid synthesis of garnet-type Li7La3Zr2O12 solid electrolyte with superior electrochemical performance

Li₇La₃Zr₂O₁₂-based garnet-type solid electrolytes are promising candidates for use in all-solid-state lithium batteries (ASSLBs). However, their potential in large-scale commercial applications is largely hindered by the time/energy-consuming and lithium-wasting synthetic method which typically needs a long-duration high temperature solid state reaction process. Herein we invent a fast preparation route that involves a short-period thermal reaction (1100 °C for 10 min) in laboratory muffle furnaces following by conventional hot pressing technique to get almost fully dense (Al, Ga, Ta, Nb)-doped garnet-type electrolytes with high phase purity (>99.9 %). The large and compact grains, low porosity and high phase purities of garnet ceramic electrolytes synthesized in this study ensure superior electrochemical performance. Particularly, Ga-doped cubic Li₇La₃Zr₂O₁₂ shows extremely low E_a values (0.17?0.18 eV) and record-high lithium ionic conductivities (>2 × 10^?3 S cm^-1 at 25 °C).     

Numerical modelling of a low power non-transferred arc plasma reactor for methane conversion

Thermal flow characteristics and the methane conversion reaction in a low power arc plasma reactor for efficient storage and transport of methane, which is the main component of shale gas, were simulated. The temperature and velocity distributions were calculated according to the type of discharge gases and arc current level by a self-developed magnetohydrodynamics (MHD) code and a commercial ANSYS-FLUENT code; the transport of chemical species was analyzed as including the chemical reactions of methane conversion. The simulated results were verified by the comparison of calculated and measured arc voltages with permissible low error as under 4%. Three C₂ hydrocarbon gases with ethane (C₂H₆), ethylene (C₂H₄), and acetylene (C₂H₂) were selected as the converted species of methane from experimental data. The mass fraction of C₂ hydrocarbons and hydrogen as the product of the conversion reaction at the reactor was also calculated. Those values show good agreement with the actual experimental results in that the major conversion reaction occurred in C₂H₂ and hydrogen, and the conversions to C₂H₆, C₂H₄, and hydrogen were minor reactions of methane pyrolysis conversion.     

Maximization of quadruple phase boundary for alkaline membrane fuel cell using non-stoichiometric α-MnO2 as cathode catalyst

Oxygen can only be reduced at the quadruple phase boundary (catalyst, carbon support, ionomer and oxygen) of the cathode catalyst layer with non-conducting electrocatalyst. To maximize the quadruple phase boundary sites is crucial to increase the peak power density of each membrane electrode assembly. The quadruple phase boundary is depending on the ratio of catalyst, carbon support and ionomer. The loading of catalyst layer is also crucial to the fuel cell performance. In this study, non-stoichiometric α-MnO₂ manganese dioxide nanorod material has been synthesized and the ratios of carbon, ionomer and catalyst loadings were optimized in alkaline membrane fuel cell. In total, ten membrane electrode assemblies have been manufactured and tested. Taguchi design method has been applied in order to understand the effect of each parameter. The conclusion finds out the ionomer has more influence on the alkaline membrane fuel cell peak power performance than carbon and loading.     

NiGa modified carbon-felt cathode for hydrogen production

In this study, known electrocatalytic active metal nickel and low amount of gallium were electrodeposited on carbon felt electrode for hydrogen evolution reaction in alkali medium. Morphological and structural analyses of prepared electrodes were determined by scanning electron microscopy and energy dispersive X-ray spectroscopy. The electrocatalytic activity of obtained electrodes for hydrogen evolution reaction was determined with cathodic polarization curves, electrochemical impedance spectroscopy, discharge potential measurements, hydrogen volume measurements at constant potential and durability tests. It was found that the electrodeposition of low amount of gallium over the nickel coated carbon felt electrode increases the hydrogen evolution reaction activity and decreases the overpotential for hydrogen region. The electrocatalytic activity of nickel and gallium deposited on carbon felt electrode was explained with active sites of surface and synergistic effect of nickel and gallium created by high surface area of carbon felt.     

Oxidation‐led decomposition of hexagonal boron nitride coatings on alloy substrates at 900 °C: Ti‐6Al‐4V

Hexagonal boron nitride (h‐BN) coatings on Ti‐6Al‐4V substrates undergo complete decomposition in air at 900 °C. This fate is similar to that of this ceramic material on chromia‐former alloys, and unlike that of a mass of powder treated in isolation. As the ceramic and alloy oxidize concurrently, outwardly diffusing aluminum (III) ions but not the predominant titanium (IV) ions react with the boron trioxide that forms around the h‐BN basal plane peripheries. Resultant aluminum borate is incorporated into the growing scale and the boron trioxide diffusion barrier is depleted. By this mechanism, the oxidation of h‐BN is maintained at an enhanced rate, until both this material and its oxide completely decompose. Liberated nitrogen from the oxidation of h‐BN can enter the underlying scale as a randomly distributed solute in rutile solid solution. The post‐coating oxide‐atmosphere interface comprises elongated aluminum borate crystallites protruding through at the boundaries between 3–5 at% nitrogen‐doped rutile grains. It differs significantly from that of oxidized, uncoated Ti‐6Al‐4V, which is occupied by a thin α‐alumina layer atop rutile. This interface does not change with an additional 72 h of heat‐treatment.     

The isothermal reduction kinetics of chromium-bearing vanadium–titanium magnetite sinter

The reduction of chromium-bearing vanadium–titanium magnetite sinter (CVTMS) by CO was investigated at 1123–1223?K. The reduction degree increased with increasing temperature. The isothermal reduction kinetics of CVTMS was analysed, according to Sharp analysis and ln–ln analysis, the kinetic mechanism of reduction process for all samples in different basicity can be represented as f(α)?=?1.61(1?α)[?ln(1?α)]^1–1/1.61. The reaction activation energy of all samples (R?=?1.9, 2.1, 2.3, obtained according to the components of the materials burdening used in sintering process) at different reaction degrees were calculated by the model-free method. And the pre-exponential factors of reaction also were calculated by the mathematical method. The rate controlling step for the reduction process under the present reduction condition was chemical reaction.     

Direct coagulation casting of silicon carbide suspension via polyelectrolyte dispersant crosslink reaction

A direct coagulation casting method for silicon carbide ceramic suspension using dispersant crosslink reaction is reported. Polymer electrolyte (polyethyleneimine, PEI) was used as dispersant to prepare silicon carbide suspension. Common food additives (carboxymethyl cellulose, CMC) were used to coagulate the electrosteric stabilized silicon carbide suspension. There was a well disperse silicon carbide suspension with 0.2 wt% PEI at pH = 5-6. Influence of coagulant on viscosity and zeta potential of the silicon carbide suspension was investigated. It indicates that the high solid loading silicon carbide suspension can be destabilized and coagulated at elevated temperature. It can be attribute to the gradual decrease of electrosteric force due to the crosslink reaction between PEI and CMC. Silicon carbide wet green body with compressive strength of 1.99 MPa could be demolded at 70°C which is higher than that prepared by traditional DCC and dispersant reaction method for nonoxide ceramics. Dense silicon carbide ceramics with relative density above 98.8% and 99.3% had been prepared by liquid phase pressureless and hot pressed sintering, respectively.     

Ni、Zn改性Cu/水泥催化剂及其甲醇高温裂解性能

以碱式碳酸镍、碱式碳酸锌、碱式碳酸铜和水泥为原料制备水泥负载的Cu-Ni，Cu-Zn，Cu-Ni-Zn催化剂，考察了合成催化剂的甲醇裂解反应性能。结果表明：在常压、质量空速为3.39 h-1、温度为380~420 ℃的条件下，Cu-Ni/水泥催化剂作用下的甲醇转化率均在96%以上；Cu-Zn/水泥催化剂作用下的甲醇转化率较低，但对H2和CO选择性较高；Cu-Ni-Zn/水泥催化剂经1 600 h运转，甲醇转化率和产物分布变化不大，甲醇转化率基本维持在81%以上，(H2+CO)摩尔分数大于98%，说明Cu-Ni-Zn/水泥催化剂具有良好的高温稳定性。