Effect of an abrupt change in pulling rate on microstructures of directionally solidified Al2O3-Er3Al5O12 eutectic and off-eutectic composite ceramics

Directionally solidified microstructures of Al₂O₃-Er₃Al₅O₁₂ eutectic and off-eutectic in situ composite ceramics were explored under abrupt-change pulling rate conditions. Corresponding temperature distributions and interface locations were studied. In eutectic composition, fluctuation of eutectic spacing occurred when the pulling rate increased abruptly. A gradually increase or abrupt increase in eutectic spacing was observed when the pulling rate decreased abruptly. In hypoeutectic and hypereutectic compositions, formation of the primary phases were suppressed when the pulling rate increased abruptly from 10?µm/s to 100?µm/s, while primary phases precipitated when the pulling rate decreased abruptly from 100?µm/s to 10?µm/s. The interface altitude decreased after the pulling rate increased abruptly, but increased after the pulling rate decreased abruptly. The liquid composition restriction (around the eutectic composition) at the eutectic interface plays an important role in the suppression of the primary dendrite and coupled eutectic oxides can be obtained in off-eutectic compositions even under higher solidification rate conditions.     

Catalytic Hydrocracking of a Bitumen‐Derived Asphaltene over NiMo/γ‐Al2O3 at Various Temperatures

Hydrocracking of a bitumen‐derived asphaltene over NiMo/γ‐Al₂O₃ was investigated in a microbatch reactor at varying temperatures. The molar kinetics of asphaltene cracking reaction was examined by fitting the experimental data. Below a defined temperature, the molar reaction showed the first‐order kinetic feature while at higher temperatures secondary reactions such as coke formation became significant, causing deviation of the reaction behavior from the proposed first‐order kinetic model. Selectivity analysis proved that dominant products varied from gases to liquids to gases with increasing temperature, shifting the dominant reaction from C–S bonds cleavage to C–C bonds cleavage.     

Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH.     

Porous sunflower plate-like NiFe2O4/CoNi–S heterostructure as efficient electrocatalyst for overall water splitting

Constructing high-efficient and nonprecious electrocatalysts is of primary importance for improving the efficiency of water splitting. Herein, a novel sunflower plate-like NiFe₂O₄/CoNi–S nanosheet heterostructure was fabricated via facile hydrothermal and electrodeposition methods. The as-fabricated NiFe₂O₄/CoNi–S heterostructure array exhibits remarkable bifunctional catalytic activity and stability toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline media. It presents a small overpotential of 219 mV and 149 mV for OER and HER, respectively, to produce a current density of 10 mA cm^?2. More significantly, when the obtained electrodes are used as both the cathode and anode in an electrolyzer, a voltage of 1.57 V is gained at 10 mA cm^?2, with superior stability for 72 h. Such outstanding properties are ascribed to: the 3D porous network structure, which exposes more active sites and accelerates mass transfer and gas bubble emission; the high conductivity of CoNi–S, which provides faster charge transport and thus promotes the electrocatalytic reaction of the composites; and the effective interface engineering between NiFe₂O₄ (excellent performance for OER) and CoNi–S (high activity for HER), which leads to a shorter transport pathway and thus expedites electron transfer. This work provides a new strategy for designing efficient and inexpensive electrocatalysts for water splitting.     

Effects of anion and cation doping on the thermoelectric properties of n-type PbS

The PbCl_xS_1-x and Pb_1-xBi_xS (x? =?0–0.05) bulks were fabricated with a facile method of hydrothermal synthesis and microwave sintering, and the effect of anionic and cationic donors on the thermoelectric performance of PbS was investigated. Although Cl^? and Bi³⁺ both effectively improved the thermoelectric properties of n-type PbS, more excellent thermoelectric performance was obtained from Cl^? doped samples because of higher electrical property and lower thermal conductivity at higher temperature (T? >?600?K). The thermoelectric figure of merit (ZT) reaches 1.04 for PbCl_0.015S_0.985 at 800?K and increases with temperature increasing without sign of saturation, which is probably the highest value ever reported for single-phase polycrystalline n-type PbS. The results also indicate that the hydrothermal synthesis and microwave sintering can realize anion doping as well as cation doping for n-type PbS at low cost, and PbS should be a robust alternative for PbTe thermoelectric materials.     

Bearing Failure Optimization of Composite Double-Lap Bolted Joints Based on a Three-Step Strategy Marked By Feasible Region Reduction and Model Decoupling

To minimize the mass and increase the bearing failure load of composite doublelap bolted joints, a three-step optimization strategy including feasible region reduction, optimization model decoupling and optimization was presented. In feasible region reduction, the dimensions of the feasible design region were reduced by selecting dominant design variables from numerous multilevel parameters by sensitivity analyses, and the feasible regions of variables were reduced by influence mechanism analyses. In model decoupling, the optimization model with a large number of variables was divided into various sub-models with fewer variables by variance analysis. In the third step, the optimization sub-models were solved one by one using a genetic algorithm, and the modified characteristic curve method was adopted as the failure prediction method. Based on the proposed optimization method, optimization of a double-lap single-bolt joint was performed using the ANSYS^® code. The results show that the bearing failure load increased by 13.5% and that the mass decreased by 8.7% compared with those of the initial design of the joint, which validated the effectiveness of the three-step optimization strategy.