B4C–TiB2 composites fabricated by hot pressing TiC–B mixtures: The effect of B excess

Previous research have reported that B₄C–TiB₂ composites could be prepared by the reactive sintering of TiC–B powder mixtures. However, due to spontaneous oxidation of raw powders, using TiC–B powder mixtures with a B/TiC molar ratio of 6: 1 introduced an intermediate phase of C during the sintering process, which deteriorated the hardness of the composites. In this report, the effects of B excess on the phase composition, microstructure, and mechanical properties of B₄C–TiB₂ composites fabricated by reactive hot pressing TiC–B powder mixtures were investigated. XRD and Raman spectra confirmed that lattice expansion occurred in B-rich boron carbide and B_xC–TiB₂ (x > 4) composites were obtained. The increasing B content improved the hardness and fracture toughness but decreased the flexural strength of B_xC–TiB₂ (x > 4) composites. When the molar ratio of B/TiC increased from 6.6:1 to 7.8:1, the Vickers hardness and the fracture toughness of the composites were enhanced from 26.7 GPa and 4.53 MPa m^1/2 to 30.4 GPa and 5.78 MPa m^1/2, respectively. The improved hardness was attributed to the microstructural improvement, while the toughening mechanism was crack deflection, crack bridging and crack branching.     

烧结烟气中含钾化合物对钒钨钛催化剂脱硝/二噁英性能的影响

采用钒钨钛催化剂可有效减排烧结烟气中NO和二噁英,而烟气中含有的钾盐会造成催化剂活性降低。在实验室采用湿式浸渍法对新鲜钒钨钛催化剂进行强制失活,研究了三种钾盐（K₂SO₄、K₂O和KCl）负载于催化剂表面对其脱硝和脱二噁英活性的影响,并采用水洗和酸洗手段考察了失活催化剂的再生性能。结果表明,不同形态钾盐会造成催化剂的脱硝和脱二噁英活性降低,催化剂对两种污染物的活性降低顺序遵循相同的规律,即KCl> K₂O> K₂SO₄。催化剂的失活机理主要包括物理失活和化学失活。物理失活主要是指钾盐在催化剂表面沉积并堵塞其孔道;化学失活主要是指钾盐与催化剂表面的活性组分产生相互作用,钝化表面活性位点,降低表面酸性,减弱氧化和还原性能,进而降低催化剂的脱硝和脱二噁英活性。再生实验结果表明,水洗可以一定程度上恢复催化剂的脱硝活性,酸洗会导致催化剂表面活性物质流失,但水洗和酸洗均无法有效恢复催化剂的脱二噁英活性。最后,提出了不同形态钾盐对钒钨钛催化剂的中毒机理。      

烟气循环烧结热风罩内气流数值模拟及优化

烟气循环技术是基于部分热废气被再次引入烧结过程的原理而开发的一种新型烧结模式,对提高烧结余热利用率、降低污染物排放和烧结能耗具有显著效果。但循环烟气在烟气罩内流动状态、烟气罩漏风状况等对烟气循环的效果及稳定性至关重要。为此,对某钢厂循环烟气罩内烟气流动状态及漏风状况进行模拟,结果表明:现有烟气罩人孔打开时虽然在一定程度上削弱了烟气进入形成漩涡的强度,但并未改善烟气旋转流动,导致料面上烟气流速不均;通过优化烟气罩内导流板结构和数量,削弱了烟气罩内烟气旋转流动,明显改善了循环烟气的流动,使烟气分布更均匀;同时烟气罩漏风状况大大改善,优化后使A侧漏风口由漏风1.2 m3?s?1变为吸风2.4 m3?s?1,有利于烧结生产的顺行。      

低成本钢尾渣-矿渣基矿山充填料的优化开发

 为实现多固废协同利用、降低充填成本,在矿渣基全粒级细尾砂胶结充填料基础上,以流动性和抗压强度为表征,利用热闷钢渣磁选尾渣(钢尾渣)替代部分矿渣作为胶凝材料,脱硫灰和水泥熟料替代部分专用添加剂作为外加剂,采用正交试验探寻掺量规律,优化固体填充料配比,开发钢尾渣-矿渣基软性矿山充填料,并研究了外加剂与胶材比、灰砂比等因素的影响。对比分析了矿渣基准组、钢尾渣-矿渣基准组(B1)、强度最优外加剂组分钢尾渣-矿渣组(B7)等3组充填料的微观形貌及XRD图谱以探究其水化机理。结果表明,钢尾渣替代矿渣量增加、外加剂与胶材比减小,充填料浆流动性改善,但充填体抗压强度下降。强度正交试验结果表明,钢尾渣掺量大小决定强度低高,脱硫灰掺量宜高于水泥熟料。进一步调整外加剂组分配比,在灰砂比为1∶6、钢尾渣替代矿渣为20%条件下,找出B7组外加剂组分为脱硫灰、水泥熟料分别替代30%、20%专用添加剂,B7组料浆扩展度为143 mm,充填体形貌为富铁绿泥石胶结假方体钙硅灰石,28 d抗压强度达2.13 MPa,较基准组低0.19 MPa,较B1提高0.26 MPa。该替代方案满足现场充填C2级强度的要求,改善流动性并显著降低了充填成本。优化的外加剂组分配比在灰砂比为1∶4条件下同样具有强度优化作用,但较灰砂比为1∶6条件下低。     

Effect of thermal insulation on microstructural homogeneity and onset temperature of flash sintered materials

The present work aimed to reduce the microstructure heterogeneity inherent to flash sintering by using alumina blankets as a thermal insulator around ZnO cylindrical samples during the sintering process, under different electric field conditions. Thermal insulation significantly reduced the flash onset temperature and the grain size heterogeneity. For higher electric fields, a temperature reduction as high as 480 °C was observed, which also led to lower densification. These findings were discussed in terms of changes in the heat loss dynamics coupled with the adsorbed water retention, both promoted by the applied thermal insulation. A model to estimate the temperature at stage III of flash sintering was proposed. The final temperature reached with thermal insulation did not differ significantly from the ones without it. Thus, thermal insulation could represent an alternative route to flash sinter materials with lower furnace temperatures with energy savings up to 78 % and a more homogeneous microstructure.     

Electrochemical behaviors of benzoic acid at polyaniline/CuGeO3 nanowire modified glassy carbon electrode

20 wt.% polyaniline/CuGeO₃ nanowires have been used as glassy carbon electrode (GCE) modified materials for electrochemical determination of benzoic acid (BA) in neutral solution. The intensities of the anodic cyclic voltammogram (CV) peaks increase linearly with the increase of BA concentration and scan rate. The linear range is 0.001–2 mM and detection limit is 0.96 μM and 0.47 μM for cvp1 and cvp2, respectively at a signal-to-noise ratio of 3. 20 wt.% polyaniline/CuGeO₃ nanowire modified GCE exhibits good stability and reproducibility. Polyaniline plays an important role in the electrochemical responses of BA at polyaniline/CuGeO₃ nanowire modified GCE. The detection limit decreases to 0.64 μM and 0.28 μM for cvp1 and cvp2, respectively with the polyaniline content increasing to 40 wt.%. Polyaniline/CuGeO₃ nanowire modified GCE exhibit better electrochemical performance than traditional methods.     

Microstructure and thermoelectric properties of Sb doped Hf0.25Zr0.75NiSn Half-Heusler compounds with improved carrier mobility

Half-Heusler (HH) semiconductor alloys are being widely investigated due to their promising potential for thermoelectric (TE) power generation applications. Sb is an effective doping element for n-type ZrNiSn half-Heuslers alloys. HH thermoelectric materials Hf_0.25Zr_0.75NiSn_1−xSb_x (0 ≤ x ≤ 0.03) were synthesized by induction melting combined with plasma activated sintering (PAS) technique. X-ray diffraction concluded that single-phase HH compounds without compositional segregations were obtained. Presence of bended lamellar structures was revealed by the FESEM. Sb doping significantly enhanced the electrical conductivity, power factor and carrier concentration of the alloys. An increase in the carrier mobility was also observed. Consequently, optimum values of 4.36 × 10⁻³ W/mK² and 4.7 × 10²⁰ cm⁻³ were achieved for power factor and carrier concentration, respectively. As a result, a ZT value of 0.83 at 923 K was obtained which is about 67% improvement compared to the un-doped sample.     

The role of hydrothermal pathways in the evolution of the morphology of ZnO crystals

Understanding growth mechanisms usually leads to the successful preparation of a targeted microstructure. However, the large number of parameters that influence the shape and the size of nanostructures often make it difficult to predict the outcome. We investigated the growth of wurtzite-type ZnO by closely following such a multistage process. We associated the diverse morphology of the precipitated crystals, prepared under the same hydrothermal conditions, to the differences in the transient crystallization processes during the precipitation. By altering the pH of the suspension after the precipitation, we gain control over the resulting morphology of the ZnO and show how to grow identical crystallites with different shapes and crystal sizes. Here we report, for the first time, on how ZnO platelets grow in a certain Zn²⁺/OH⁻ ratio along the basal and one of the prismatic directions to form sphalerites with very high surface area. We also offer an explanation as to how sphere-like hierarchical structures composed of plate- or rod-like ZnO crystals form through self-assembly driven processes.     

Modeling and optimization method featuring multiple operating modes for improving carbon efficiency of iron ore sintering process

Iron ore sintering is one of the most energy-consuming processes in steelmaking. Since its main source of energy is the combustion of carbon, it is important to improve the carbon efficiency to save energy and to reduce undesired emissions. A modeling and optimization method based on the characteristics of the sintering process has been developed to do that. It features multiple operating modes and employs the comprehensive carbon ratio (CCR) as a measure of carbon efficiency. The method has two parts. The first part is the modeling of multiple operating modes of the sintering process. K-means clustering is used to identify the operating modes; and for each mode, a predictive model is built that contains two submodels, one for predicting the state parameters and one for predicting the CCR. The submodels are built using back-propagation neural networks (BPNNs). An analysis of material and energy flow, and correlation analyses of process data and the CCR, are used to determine the most appropriate inputs for the submodels. The second part of the method is optimization based on a determination of the optimal operating mode. The problem of how to reduce the CCR is formulated as a two-step optimization problem, and particle swarm optimization is used to solve it. Finally, verification of the modeling and optimization method based on actual process data shows that it improves the carbon efficiency of iron ore sintering.     

High-flux plasma exposure of ultra-fine grain tungsten

In this work, we examine the response of an ultra-fine grained (UFG) tungsten material to high-flux deuterium plasma exposure. UFG tungsten has received considerable interest as a possible plasma-facing material in magnetic confinement fusion devices, in large part because of its improved resistance to neutron damage. However, optimization of the material in this manner may lead to trade-offs in other properties. We address two aspects of the problem in this work: (a) how high-flux plasmas modify the structure of the exposed surface, and (b) how hydrogen isotopes become trapped within the material. The specific UFG tungsten considered here contains 100 nm-width Ti dispersoids (1 wt%) that limit the growth of the W grains to a median size of 960 nm. Metal impurities (Fe, Cr) as well as O were identified within the dispersoids; these species were absent from the W matrix. To simulate relevant particle bombardment conditions, we exposed specimens of the W-Ti material to low energy (100 eV), high-flux (> 10²² m^− 2 s^− 1) deuterium plasmas in the PISCES-A facility at the University of California, San Diego. To explore different temperature-dependent trapping mechanisms, we considered a range of exposure temperatures between 200 °C and 500 °C. For comparison, we also exposed reference specimens of conventional powder metallurgy warm-rolled and ITER-grade tungsten at 300 °C. Post-mortem focused ion beam profiling and atomic force microscopy of the UFG tungsten revealed no evidence of near-surface bubbles containing high pressure D₂ gas, a common surface degradation mechanism associated with plasma exposure. Thermal desorption spectrometry indicated moderately higher trapping of D in the material compared with the reference specimens, though still within the spread of values for different tungsten grades found in the literature database. For the criteria considered here, these results do not indicate any significant obstacles to the potential use of UFG tungsten as a plasma-facing material, although further experimental work is needed to assess material response to transient events and high plasma fluence.