Theoretical investigation of intrinsic point defects and the oxygen migration behavior in rare earth hafnates

In this work, the composition-dependent point defect types and formation energies of RE₂Hf₂O₇ (RE = La, Ce, Pr, Nd, Pm, Sm, Eu and Gd) as well as the oxygen diffusion behavior are systematically investigated by first-principles calculations. The possible defect reactions and dominant defect complexes under stoichiometric and non-stoichiometric conditions are revealed. It is found that O Frenkel pairs are the predominant defect in stoichiometric pyrochlore hafnates. Hf-RE cation anti-site defects, accompanied by RE vacancies and/or oxygen interstitials, are stable in the non-stoichiometric case of HfO₂ excess. On the other hand, RE-Hf anti-site defects together with oxygen vacancies and/or RE interstitials are preferable in the case of RE₂O₃ excess. The energy barriers for the migration along the V_O48f - V_O48f pathway of pyrochlore hafnates were calculated to be between 0.81 eV and 0.89 eV. Based on these results, a defect engineering strategy is proposed and the pyrochlore hafnates investigated here are predicted to exhibit potential oxygen ionic conductivity.     

Synthesis of nanopowders with low agglomeration by elaborating Φ values for producing Gd2O3-MgO nanocomposites with extremely fine grain sizes and high mid-infrared transparency

Refining ceramic microstructures to the nanometric range to minimize light scattering provides an interesting methodology for developing novel optical ceramic materials. In this work, we reported the fabrication and properties of a new nanocomposite optical ceramic of Gd₂O₃-MgO. The citric acid sol-gel combustion method was adopted to fabricate Gd₂O₃-MgO nanocomposites with fine-grain sizes, dense microstructures and homogeneous phase domains. Nanopowders with low agglomeration and improved sinterability can be obtained by elaborating Φ values. Further refining of the microstructure of the nanocomposites was achieved by elaborating the hot-pressing conditions. The sample sintered at 65 MPa and 1300 °C showed a quite high hardness value of 14.3 ± 0.2 GPa, a high transmittance of 80.3 %–84.7 % over the 3?6 μm wavelength range, due mainly to its extremely fine-grain size of Gd₂O₃ and MgO (93 and 78 nm, respectively) and high density.     

Impact of gypsum on flotation of scheelite and fluorite using sodium oleate as collector

ABSTRACT

In this study, effect of calcium and gypsum on scheelite and fluorite was investigated using sodium oleate as collector. Micro-flotation and contact angle results showed that the adsorption of calcium could inhibit the hydrophobicity of scheelite and fluorite. Moreover, sulfate could enhance the inhibition. FT-IR results showed that calcium could be priori precipitated into calcium oleate and adsorb on mineral surface. The adsorption of calcium could increase the scheelite potential to IEP, while it showed limited effect on fluorite potential. However, the interaction of calcium on scheelite and fluorite in gypsum solution was more complex than that in calcium solution.     

Novel Bi-Doped Amorphous SnOx Nanoshells for Efficient Electrochemical CO2 Reduction into Formate at Low Overpotentials

Engineering novel Sn-based bimetallic materials could provide intriguing catalytic properties to boost the electrochemical CO₂ reduction. Herein, the first synthesis of homogeneous Sn_1−xBi_x alloy nanoparticles (x up to 0.20) with native Bi-doped amorphous SnO_x shells for efficient CO₂ reduction is reported. The Bi-SnO_x nanoshells boost the production of formate with high Faradaic efficiencies (>90%) over a wide potential window (−0.67 to −0.92 V vs RHE) with low overpotentials, outperforming current tin oxide catalysts. The state-of-the-art Bi-SnO_x nanoshells derived from Sn_0.80Bi_0.20 alloy nanoparticles exhibit a great partial current density of 74.6 mA cm⁻² and high Faradaic efficiency of 95.8%. The detailed electrocatalytic analyses and corresponding density functional theory calculations simultaneously reveal that the incorporation of Bi atoms into Sn species facilitates formate production by suppressing the formation of H₂ and CO.     

Mineralization of Para-Chlorobenzoic Acid in Water by Cobalt-Incorporated MCM-41 Catalyzed Ozonation

Cobalt-incorporated MCM-41(Co-MCM-41) was used as a heterogeneous catalyst for the ozonation of para-chlorobenzoic acid (p-CBA) in aqueous solution. Cobalt oxide supported on MCM-41(Co/MCM-41) was synthesized for comparison. Their textural properties were elucidated by various characterization techniques to understand the relationship between surface texture and catalytic activity. TOC removal at 60 min reached 91% with Co-MCM-41, 83% with Co/MCM-41 and only 52% with ozone alone, respectively. Observations from diffuse reflection spectroscopy demonstrated that different metal phases were formed in these cobalt-modified molecular sieves samples. Radical scavenger experiments indicated the formation of hydroxyl radicals that were responsible for the effective degradation of p-CBA. An integrated approach to the catalytic mechanism was proposed by considering the variation of pH in the course of ozonation as well as its subsequent influence on the dissociation of targeted compounds and surface charge of the catalyst. In the reusability experiments, the reused Co-MCM-41 was able to regain the same catalytic capability as the fresh one within 5 cycles. X-ray photoelectron spectroscopy results indicated that a part of Co²⁺ was oxidized to Co³⁺ after oxidation reaction.     

微型步进马达线架组自动卷线设备设计

微型步进马达线圈组卷线上下料基本靠手动作业,效率低下,同时因工人技术水平的不同造成产品品质不稳定的问题多发.为此专门设计了微型步进马达线圈组自动卷线及上下料设备.通过结合现阶段的先进工业技术,采用振动盘分离区分进料,多机构并联三菱PLC及威纶人机界面触摸屏研发了此微型步进马达线圈组自动上下料及卷线设备.通过该设备实现了微型步进马达因工人不足导致产能减少和品质多发问题,减少企业成本,提升产品品质.     

Oxygen transport,thermal and electrochemical properties of NdBa0.5Sr0.5Co2O5+δ cathode for SOFCs

In this study, the crystal structure, thermal, oxygen transport, electrical conductivity and electrochemical properties of the perovskite NdBa_0.5Sr_0.5Co₂O_5+δ (NBSC55) are investigated. In the temperature range of 250 °C–350 °C, the weight loss upon heating was due to a partial loss of lattice oxygen and along with a reduction of Co⁴⁺ to Co³⁺. The tend of weight-loss slows down as temperature increased above 350 °C indicating a reduction of Co³⁺ to Co²⁺ during this stage. The oxygen migration is dominated by surface exchange process at high temperature range (650-800 °C); however, the bulk diffusion process prevails at low temperature range (500–600 °C). For long-term testing, the polarization resistance of NBSC55 increases gradually form 3.13 Ω cm² for 2 h to 3.34 Ω cm² for 96 h at 600 °C and an increasing-rate for polarization resistance is around 0.22% h^?1. The power density of the single cell with NBSC55 cathode reached 341 mW cm^?2 at 800 °C.     

Cyclic thermal shock resistance of h-BN composite ceramics with La2O3–Al2O3–SiO2 addition

The effects of La₂O₃–Al₂O₃–SiO₂ addition on the thermal conductivity, coefficient of thermal expansion (CTE), Young's modulus and cyclic thermal shock resistance of hot-pressed h-BN composite ceramics were investigated. The samples were heated to 1000 °C and then quenched to room temperature with 1–50 cycles, and the residual flexural strength was used to evaluate cyclic thermal shock resistance. h-BN composite ceramics containing 10 vol% La₂O₃–Al₂O₃ and 20 vol% SiO₂ addition exhibited the highest flexural strength, thermal conductivity and relatively low CTE, which were beneficial to the excellent thermal shock resistance. In addition, the viscous amorphous phase of ternary La₂O₃–Al₂O₃–SiO₂ system could accommodate and relax thermal stress contributing to the high thermal shock resistance. Therefore, the residual flexural strength still maintained the value of 234.3 MPa (86.9% of initial strength) after 50 cycles of thermal shock.     

Synergistic flame retardant effects of activated carbon and molybdenum oxide in poly(vinyl chloride)

The synergistic effects of activated carbon (AC) and molybdenum oxide (MoO₃) in improving the flame retardancy of poly(vinyl chloride) (PVC) were investigated. The effects of AC, MoO₃ and their mixture with a mass ratio of 1:1 on the flame retardancy and smoke suppression properties of PVC were studied using the limiting oxygen index and cone calorimeter tests. It was found that the flame retardancy of the relatively cheaper AC was slightly weaker than that of MoO₃. In addition, the incorporation of AC and MoO₃ greatly reduced the total heat release and improved smoke suppressant property of PVC composites. When the total content of AC and MoO₃ was 10 phr, PVC/AC/MoO₃ had the lowest peak heat release rate and peak smoke production rate values of 173.80 kW m^?2 and 0.1472 m² s^?1, which represented reductions of 47.3 and 59.9%, respectively, compared with those of PVC. Furthermore, thermogravimetric analysis and gel content tests were used to analyze the flame retardant mechanism of AC and MoO₃, with results showing that AC could promote early crosslinking in PVC. Char residue left after heating at 500 °C was analyzed using scanning electron microscopy and Raman spectroscopy, and the results showed that MoO₃ produced the most compact char, with the smallest and most organized carbonaceous microstructures. © 2017 Society of Chemical Industry