Double pyrovanadates CaMgV2O7: Formation mechanism,phase structure,and thermodynamic properties

A double pyrovanadate CaMgV₂O₇ sample was synthesized via a facile solid-state route under an air atmosphere. The nonequilibrium formation pathways of the CaMgV₂O₇ were investigated via powder X-ray diffraction. A multistep reactions path (metavanadates–pyrovanadates–double pyrovanadate CaMgV₂O₇) was proposed to describe the formation of the CaMgV₂O₇ considering the thermodynamic and kinetic factors. The cell unit parameters of the CaMgV₂O₇ sample indicated the crystallization according to a monoclinic system with space group P12/c1(14), and the lattice parameters of a = 6.756 Å, b = 14.495 Å, c = 11.253 Å, β = 99.12, and V = 108.806 Å³. X-ray photoelectron spectroscopy also confirmed the +5 oxidation state vanadium in CaMgV₂O₇. The endothermic effects at 1033 and 1143 K were related to the incongruent melting and liquidus temperatures of CaMgV₂O₇, respectively. The comprehensive thermodynamic properties of CaMgV₂O₇ were established in both low- and high-temperature regions, utilizing a physical property measurement system and multi-high-temperature calorimetry (96 lines). The heat capacity (200 J mol K⁻¹) and entropy (198 J mol K⁻¹) at 298.15 K were computed based on the low-temperature heat capacity values, and the enthalpy of formation at 298.15 K was also estimated. The fitted high-temperature capacity can be used to obtain the changes in the enthalpy, entropy, and Gibbs free energy. This study is part of building a reliable thermodynamic database of the CaO–MgO–V₂O₅ system.     

Isostructural phase transition (IPT) in CaMoO4 with Scheelite structure

The ceramic compound CaMoO₄ is synthesized via a solid-state reaction technique. Rietveld refinement studies were done on the powder X-ray diffraction data of CaMoO₄ and revealed that the compound is crystallized in the tetragonal Scheelite structure with I4₁/a space group. The differential scanning calorimetry (DSC) studies on CaMoO₄ divulged an anomaly around 440 °C. This anomaly is further probed using the temperature-dependent Raman and dielectric spectroscopic measurements and are corroborating with the results obtained from DSC. A detailed investigation on the temperature-dependent Raman spectroscopic data revealed that the A_1g mode of CaMoO₄ showed a soft phonon behavior up to the phase transition temperature. It is observed that the A_1g mode displayed phonon hardening behavior with further increasing the temperature. The anomaly is attributed to an isostructural phase transition (IPT), a rarely observed phenomenon in the compounds with Scheelite structure. The IPT in CaMoO₄ is elucidated with a phonon softening mechanism.     

Flash Lamps as Ignition and Initiation Sources of the VS-2 Pyrotechnic Composition

In the present work it is found that the pyrotechnic composition VS-2 can be initiated with flash lamps IFC-500 and EVIS. VS-2 pyrotechnic composition contains 90% of mercury（Ⅱ） 5-hydrazinotetrazolate perchlorate and 10% of optically transparent copolymer of 2-methyl-5-vinyltetrazole and methacrylic acid （PVMT）. We have found that the flash lamps make it possible to initiate combustion of VS-2 composition with its transition to detonation both in cylindrical charges placed in brass caps of 5 mm diameter and 2 mm high， and film charges with 10 mm×80 mm in size and surface weights of 60 mg·cm^-2 and 90 mg·cm^-2， showing ignition delay times 10 μs and 3 μs， respectively. We also measured detonation velocities for VS-2 composition film charges， which were 4375-4505 m·s^-1 （of the charge being surface mass 60 mg·cm^-2） and 4221-4281 m·s^-1 （of the charge being surface mass 90 mg·cm^-2） and their blasting action on the aluminum plate. The depths of the normal shock wave imprints at the charge-barrier interface were 0.6-0.7 mm （for surface mass of the film charges 60 mg·cm^-2） and 1.2-1.3 mm （for surface mass of the film charges 90 mg·cm^-2）.     

基于卷积神经网络的5G蜂窝网络无线定位方法

5G蜂窝网络发展迅猛，其覆盖面积将逐渐增大，因此使用5G蜂窝网络进行定位是有研究潜力的研究方向。本文提出一种新的深度学习技术来实现高效、高精度和低占用的定位，以代替传统指纹定位过程中繁重的指纹库生成以及距离计算。该方法建立了一个特殊的卷积神经网络，并根据5G天线信号的接收信号强度指示、相位和到达角等特征量，选择合适的输入数据格式构造样本组建训练集，对该卷积神经网络进行训练。训练得到的卷积神经网络可以替代指纹定位中的庞大指纹库，非常有利于直接在5G移动设备端实现定位。虽然卷积神经网络在训练过程中需要大量时间，但在训练完毕后直接进行分类定位的速度非常快，可以保障定位实现的实时性。本文所实现的卷积神经网络权重与偏置所占内存不到0.5 MB，且能够在实际应用环境中以95%的定位准确率以及0.1 m的平均定位精度实现高精度定位。     

Thermal properties of hierarchical YSZ and LZO ceramic microspheres with multi-scaled voids investigated by using theoretical,experimental and simulation methods

Heat transfer within ceramic feedstock powders is still unclear, which impedes optimization of the thermal and mechanical properties of the thermal sprayed coatings. The microspheres (yttria-stabilized zirconia YSZ and lanthanum zirconate LZO) were prepared via the electro-spraying assisted phase inversion method (ESP). The thermal properties of the two ESP microspheres and a commercial hollow spherical powder (HOSP) were investigated by using theoretical, experimental, and simulation methods. Thermal conductivity of the single microsphere was estimated via a novel nest model that was derived from the Maxwell-Eucken 1 and the EMT model. Thermal conductivity of a single YSZ/LZO-ESP microsphere prepared at 1100–1200 °C was within 0.36–0.75 W/m K, which was ～ 20 % lower than that of a single YSZ-HOSP microsphere with a similar porosity. Heat flux simulation showed that high tortuosity around the multi-scaled voids of the ESP microsphere led to a more efficient decrease in thermal conductivity compared with total porosity.     

汉江上游干支流沉积物细菌群落多样性和影响因素

为了解汉江上游干支流沉积物细菌多样性以及确定性过程和随机性过程在沉积物细菌群落构建过程中的相对重要性,基于Illumina高通量测序技术,分析了环境因子对细菌群落组成的影响,采用非度量多维尺度(NMDS)排序探究了季节之间沉积物细菌群落的差异,并结合中性群落模型和标准化随机率量化了确定性过程和随机过程对群落构建的影响。结果表明:汉江上游及其支流细菌群落主要由变形菌门(Proteobacteria)、拟杆菌门(Bacteroidetes)、蓝藻门(Cyanophyta)、浮霉菌门(Planctomycetes)和酸杆菌门(Acidobacteria)等组成；细菌群落在不同季节有显著差异；地理距离和环境因子对细菌群落结构影响较小,确定性过程并未在细菌群落组成中起到主导作用；随机过程很大程度上影响了群落在秋季和春季的组成,是沉积物细菌群落构建的主导因素。     

Influence of thermal runaway in styrene–acrylonitrile bulk copolymerization revealed by computational fluid dynamics modeling

The computational fluid dynamics (CFD) and kinetic-based moment methods coupled approach is adopted to simulate the bulk copolymerization of styrene–acrylonitrile (SAN) in a stirred tank reactor. Numerical simulations are carried out to investigate the impacts of impeller speed, monomer ratio, initiator ratio, and initial reaction temperature on the copolymerization process and product properties. Particularly, the Chaos theory is selected as a criterion for evaluating the occurrence of the thermal runaway. The Flory's and Stockmayer's distributions are employed to calculate chain length distribution and copolymer composition distribution of copolymer. The simulation results highlight that the appearance of thermal runaway can be postponed by properly increasing the rotation speed, decreasing the initiator loadings, initial acrylonitrile contents and initial reactor temperature. Furthermore, significant differences exist in the product properties that predicted by the ideal and non-ideal models, which demonstrates that the temperature heterogeneity plays a crucial role in SAN copolymerization. This study could offer references for the safe operation and design of polymerization processes.     

Revealing active species of CePO4 catalyst for selective catalytic reduction of NOx with NH3

Revealing the active species of the catalyst is conducive to the design of more efficient catalyst. Herein, we tried to demonstrate the roles of amorphous and crystalline structures on CePO₄ catalyst during selective catalytic reduction (SCR) of NO_x by NH₃. Higher calcination temperature promotes the transfer of amorphous structure to crystalline structure on the surface of CePO₄. Both amorphous and crystalline CePO₄ species on CePO-X samples can provide acid sites for NH₃ adsorption, but the former can provide more acid sites. The superior redox property of surface amorphous CePO₄ species contributes to its high NH₃-SCR activity at low temperature, but it also leads to the decrease of high temperature (>350 °C) NH₃-SCR activity due to the oxidation of NH₃. In contrast, crystalline CePO₄ species shows high activity only at high temperature because of its poor redox property. Therefore, it can be inferred that amorphous and crystalline structures on CePO₄ catalyst can be the efficient active species of NH₃-SCR at low and high temperature, respectively.     

In-situ measurement of mineral phase transition and kinetics in roasting process of Bayan Obo mixed rare earth concentrate by sodium carbonate

In this study, the Bayan Obo rare earth concentrates mixed with Na₂CO₃ were used for roasting research. The phase change process of each firing stage was analyzed. The kinetic mechanism model of the continuous heating process was calculated. This study aims to recover valuable elements and optimize the production process to provide a certain theoretical basis. Using X-ray diffraction (XRD), Fourier infrared spectroscopy, scanning electron microscopy with energy dispersive spectrometry, the reaction process and the existence of mineral phases were analyzed. The variable temperature XRD and thermogravimetric method were used to calculate the roasting kinetics. The phase transition results show that carbonate-like substances first decompose into fine mineral particles, and CaO, MgO, and SiO₂ react to form silicates, causing hardening. Further, REPO₄ and NaF can directly generate CeF₃ and CeF₄ at high temperatures, and a part of CeF₄ and NaF forms a solid solution substance Na₃CeF₇. Rare earth oxides calcined at a high temperature of 750 °C were separated to produce Ce_0.6Nd_0.4O_1.8, Ce₄O₇, and LaPrO_3+x. Then, BaSO₄, Na₂CO₃, and Fe₂O₃ react to form barium ferrite BaFe₁₂O₁₉; the kinetic calculation results show that during the continuous heating process, the apparent activation energy E reaches the minimum in the entire reaction stage in the temperature range of 440–524 °C, and the reaction order n reaches the maximum, which indicates that the decomposition product REFO significantly impacts the reaction system and reduces the activation energy. The mechanism function is F(α) = [?ln (1?α)]^1/3. The reaction order n reaches the minimum in the temperature range of 680–757 °C, and the apparent activation energy E is large. The difficulty of the reaction increases during the final stage. The reaction mechanism function is F(α) = [1?(1?α)^1/3]². Observing the entire reaction stage, the step of controlling the reaction rate changes from random nucleation to three-dimensional diffusion (spherical symmetry).