Studies on influence of hydrogen and carbon monoxide concentration on reduction progression behavior of molybdenum oxide catalyst

Temperature programmed reduction (TPR) analysis was applied to investigate the chemical reduction progression behavior of molybdenum oxide (MoO₃) catalyst. The composition and morphology of the reduced phases were characterized by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM). The reduction progression of MoO₃ catalyst was attained with different reductant types and concentration (10% H₂/N₂, 10% and 20% CO/N₂ (%, v/v)). Two different modes of reduction process were applied. The first approach of reduction involved non-isothermal mode reduction up to 700 °C, while the second approach of reduction involved the isothermal mode reduction for 60 min at 700 °C. Hydrogen temperature programmed reduction (H₂-TPR) results showed the reduction progression of three-stage reduction of MoO₃ (Mo⁶⁺ → Mo⁵⁺ → Mo⁴⁺ → Mo⁰) with Mo⁵⁺ and Mo⁴⁺. XRD analysis confirmed the formation of Mo₄O₁₁ phase as an intermediate phase followed by MoO₂ phase. After 60 min of isothermal reduction, peaks of metallic molybdenum (Mo) appeared. Whereas, FESEM analysis showed porous crater-like structure on the surface cracks of MoO₂ layer which led to the growth of Mo phase. Meanwhile, the reduction of MoO₃ catalyst in 10% carbon monoxide (CO) showed the formation of unstable intermediate phase of Mo₉O₂₆ at the early stage of reduction. Furthermore, by increasing 20% CO led to the carburization of MoO₂ phase, resulted in the formation of Mo₂C rather than the formation of metallic Mo, as confirmed by XPS analysis. Therefore, the presented study shows that hydrogen gave better reducibility due to smaller molecular size, which contributed to high diffusion rate and achieved deeper penetration into the MoO₃ catalyst compared to carbon monoxide reductant. Hence, the reduction of MoO₃ in carbon monoxide atmosphere promoted the formation of Mo₂C which was in agreement with the thermodynamic assessment.     

Size-controlled synthesis of Mo powders via hydrogen reduction of MoO2 powders with the assistance of Mo nuclei

The size-controlled preparation of Mo powders is always a challenge and important task in the molybdenum metallurgy. In the current study, Mo powders with controllable sizes are synthesized by hydrogen reduction of MoO₂ powders with the assistance of Mo nuclei in the range of 900–1100 °C. The influences of the particle sizes of Mo nuclei, the additive amount as well as reaction temperature on the morphology and particle sizes of the final products are studied. For the hydrogen reduction of MoO₂ without any additive, the obtained Mo powders always have large particle sizes. However, the addition of small amounts of nuclei in MoO₂ can help Mo nucleate dispersedly, and the growth of Mo could be also controlled by adjusting the sizes of added nuclei, amount of addition and the reaction temperature. With the addition of Mo nuclei, the different sizes of Mo powders with the good dispersity can be prepared. As adding commercial Mo powders with the particle size of about 2.03 μm, the micron-sized Mo powders ranged from 2.11 μm to 3.25 μm could be prepared. While for the case of adding ultrafine Mo nuclei of about 170 nm, Mo powders from 0.28 μm to 0.88 μm can be obtained. Moreover, the more the amounts of nuclei added and the lower the reaction temperature (in the range of 900–1100 °C) is, the smaller the particle size of the prepared Mo powder will be. The current method is a facile and feasible method, and is potential to be used for industrial production of Mo powder with controllable particle sizes.     

A first-principles investigation on mechanical and metallic properties of titanium carbides under pressure

The titanium carbides are potential candidates to achieve both high hardness and refractory property. We carried out a structural search for titanium carbides at three pressures of 0 GPa, 30 GPa and 50 GPa. A phase diagram of the Ti-C system at 0 K was obtained by elucidating formation enthalpies as a function of compositions, and their mechanical and metallic properties of titanium carbides were investigated systematically. We also discussed the relation of titanium concentration to the both mechanical and metallic properties of titanium carbides. It has been found that the average valence electron density and tractility improved at higher concentrations of titanium, while the degree of covalent bonding directionality decreased. To this effect, the hardness of titanium carbide decreases as the content of titanium increases. Our results indicated that the titanium content significantly affected the metallic properties of the Ti-C system.     

预处理工艺对硬质合金与金刚石膜间粘结力的影响

在两种经不同预处理的硬质合金YG8基底上，采用微波等离子体化学气相沉积法，在微波功率2kW，压强4.0kPa和6.5kPa，CH4和H2流量分别为1.6cm/s和100.0cm/s的条件下生长金刚石薄膜。利用X射线衍射检测了金刚石薄膜是否存在，用拉曼光谱分析了薄膜的质量，用金相显微镜观察了薄膜的洛氏硬度压痕，标定并比较了不同预处理工艺膜与基底的结合力。实验结果表明，不同的预处理方法对于粘结力的影响不大，最主要的因素是钴含量的多少。     

共晶碳化物团球化对铸铁激光熔敷层抗裂性的影响

为提高铸铁表面大面积激光熔敷层抗裂性问题，通过冶金因元素控制熔敷层组织形态在熔敷材料中加入碱金属元素钾，研究了在激光快速加热条件下钾对铸铁激光熔敷层组织团球化的影响，进而分析了该球状组织对熔敷层抗裂性的影响，结果表明随熔敷金属内钾含量增多熔敷层内共晶碳化物组织呈球状及孤岛状，这种组织明显提高了熔敷层抗裂性，此外大量的渗碳体组织确保了熔敷层具有较高的耐磨性；获得了无裂纹的大面积搭接熔敷层，其对应合金系统为Fe-C-Si-Ni-K。     

Using ion implantation to adjust the transition temperature of superconducting films

We summarize a continuing investigation into using ion implantation to alter the transition temperature of superconducting thin films. The primary motivation for the work presented here was to study the feasibility of using magnetic ion doping to replace the bi-layer T_c control process currently used for certain cryogenic detector applications at National Institute for Standards and Technology. The results from work with various ion species implanted into aluminum, molybdenum, titanium and tungsten host films are presented.     

Residual stresses and transformation toughening in MoSi2 composites reinforced with partially stabilized zirconia

The results of study of the effects of yttria stabilization (0–6 mol.%) on the room-temperature fracture behavior and toughening mechanisms in zirconia-reinforced MoSi₂ are presented in this paper. Transformation toughening is shown to occur only in composites reinforced with zirconia particles stabilized with 2 mol.% yttria. However, the fracture toughness levels are comparable in the other composites with yttria levels between 0 and 6 mol.%. Toughening in the other composites is attributed to the combined effects of residual stress, microcrack shielding/anti-shielding and/or crack deflection. A rigorous micromechanics-based model is presented for the estimation of residual stress levels in brittle materials reinforced with phases that can transform during cooling or under stress. The model is applied successfully to the rationalization of the observed fracture and toughening phenomena.     

高速钢高温形变诱发析出的研究

本文探讨了高速钢在高温形变过程中碳化物析出的行为及奥氏体组织状态对析出的影响。用透射电镜和扫描电镜分析了不同热处理状态奥氏体的组织结构,分析了高温形变过程中碳化物析出的部位,颗粒尺寸及形态。试验表明, 碳化物主要在奥氏体的缺陷处呈点状和点列状析出,大小为20mμ。处于回复状态的奥氏体缺陷诱发碳化物析出,析出碳化物钉札缺陷阻止再结晶进行。当再结晶驱动力较大时,由于动态再结晶充分发展,使缺陷大量消除,碳化物析出显著地减少。     

提高检测数据准确性 促进选钼生产稳定高效

本文从6个方面对选钼2个作业段的取样方式进行了校验,通过对检测数据的比对分析,找出了选钼2个作业段数据存在矛盾的原因,并针对原因采取了有效的措施,保证了检测数据的准确性,促进了选钼生产的稳定高效。