WxC-MCM-48催化剂的合成、表征及加氢脱硫催化性能

以正硅酸乙酯(TEOS)为硅源，十六烷基三甲基溴化铵(CTAB)为表面活性剂，仲钨酸铵为钨源，采用水热晶化法一步合成了不同钨含量(以Si、W物质的量比n_Si/n_W表示)的WO₃-MCM-48，然后经甲烷/氢气(V/V=1/4)混和气体程序升温还原碳化(TPC)，制备出了W_xC-MCM-48(x=1、2)催化剂，采用XRD、N₂吸附-脱附和NH₃-TPD对样品的结构进行了表征，用噻吩作为模型化合物，对W_xC-MCM-48催化剂的加氢脱硫催化活性进行了评价。结果表明，在一定钨含量的条件下，WO₃-MCM-48和W_xC-MCM-48样品仍然保持MCM-48的三维立方有序介孔结构，n_Si/n_W=30～15时，碳化钨的物相为W₂C；n_Si/n_W=7.5时，碳化钨为W₂C和WC物相，W_xC-MCM-48催化剂表现出了良好的加氢脱硫催化性能。     

The crystal structure of the molybdenum cementite Mo12Fe22C10 (ξ-phase)

The crystal structure of molybdenum cementite Mo₁₂Fe₂₂C₁₀ (-phase) has been determined by means of a single crystal x-ray diffraction study of crystal fragments. The lattice parameters were found to be:a=10.865 (3),b=7.767 (2),c=6.559 (2) Å and =120.13 (2)°, space group C2/m;Z=1. From the analysis ofPatterson maps and differenceFourier analysis the atomic parameters were derived, yielding a residual ofR=0.059. The crystal structure contains octahedral and triangular prismatic groups which accommodate the carbon atoms in their voids, as is usually found in interstitial compounds. The octahedral building group consists of four Mo- and two Fe-atoms, the triangular prism is built up by four Fe-and two Mo-atoms. The mode of filling of the metal polyhedra is discussed.

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Die Kristallstruktur von Molybdän-Zementit, Mo₁₂Fe₂₂C₁₀ (-Phase)

Zusammenfassung Die Kristallstruktur von Molybdän-Zementit, Mo₁₂Fe₂₂C₁₀ (-Phase) wird auf Grund von Einkristall-Beugungsaufnahmen unter Anwendung vonPatterson-and DifferentialFourier-Analysen bestimmt. In der monoklinen Elementarzelle (a=1.870;b=7.67;c=6.563 Å, =120.1°) Raumgruppe C 2/m befindet sich eine Formeleinheit Mo₁₂Fe₂₂C₁₀ (oderZ=2, Mo₆Fe₁₁C₅). DerR-Wert von 6% für 1200 Reflexe unterstreicht die Richtigkeit der Struktur, die aus oktaedrischen und trigonal prismatischen Gruppen aufgebaut ist. Die Oktaedergruppe besteht aus 4 Mo- und 2-Fe-Atomen, die trigonal prismatische Gruppe aus 4 Fe- und 2 Mo-Atomen. Die Kohlenstoffatome füllen die Lücken dieser Bauelemente, wie es für typische Einlagerungscarbide (Komplexcarbide) erwartet werden kann.

     

纳米晶掺钇硬质合金粉末的制备

采用高能球磨法制备了纳米晶掺Y硬质合金粉末。用XRD，SEM和DTA等分析检测手段，研究了纳米晶掺Y硬质合金粉末的结构、形貌和相的变化。结果表明：高能球磨45h，可获得晶粒尺寸约为8nm的掺Y硬质合金粉末；微量Y的加入，有利于硬质合金粉末晶粒的细化；在25～45h范围内，随着高能球磨时间的延长，粉末晶粒尺寸减小，且掺Y硬质合金粉末的晶粒尺寸比未掺Y的硬质合金粉末晶粒尺寸要细一倍；高能球磨25h，粉末中Co的X射线衍射峰消失。高能球磨掺Y硬质合金粉末的DTA曲线在626℃出现了1个尖锐的放热峰。高能球磨掺Y硬质合金粉末固结之后，其合金晶粒细小，机械性能较好。     

First‐principles study of metal/nitride polar interfaces: Ti/TiN

We have examined the optimal interface structure, ideal work of adhesion and bonding character of polar Ti(110)/TiN(111) interfaces by first‐principles density‐functional plane‐wave pseudopotential calculations. Both Ti‐ and N‐terminated interfaces, including six different interface structures, were calculated. The interface structure for each termination, continuing the TiN crystal structure across the interface, has the largest work of adhesion. Although both terminations yield substantial adhesion energies in the range 3–7 J m^?2, the N‐terminated interface is ～4 J m^?2 stronger than the Ti‐terminated interface. Analysis of the interfacial electronic structure shows that the Ti‐terminated interface is a mixed strong, metallic and weak covalent character, whereas the N‐terminated interface is a polar covalent bond similar to the Ti/TiC interface. Further study of the separation of the optimal interface shows that the cleavages will never fracture at the interface due to the strong bonding, which is consistent with the experimental results. Copyright © 2003 John Wiley & Sons, Ltd.     

WC—Co硬质合金刀片热丝法金刚石薄膜涂层附着力

用热丝法研究了ＷＣ－６％Ｃｏ硬质合金刀片金刚石薄膜涂层附着力。结果表明：采用温度为８０℃,（ＨＣｌ：ＨＮＯ３：Ｈ２Ｏ）（体积比）为１∶１∶１溶液对硬质合金刀片表面去Ｃｏ１５ｍｉｎ后,经４０ｕｍ金刚石粉及１．５ｕｍ金刚石加２０ｕｍＴａＣ混合粉进行超声预处理,结果表明,沉积的金刚石薄膜与硬质合金刀片基底具有良好的附着力,而经４０ｕｍ金刚石粉处理的薄膜涂层组织与附着力要好一些。     

Ultrafine molybdenum carbide nanoparticles supported on nitrogen doped carbon nanosheets for hydrogen evolution reaction

Nitrogen doped carbon nanosheets supported molybdenum carbides nanoparticles (Mo_xC/NCS) have been synthesized by tuning the mass ratio of melamine and ammonia molybdate. The Mo₂C/NCS-10 exhibits superior electrocatalytic performance and stability for HER, which was attributed to N-doped carbon nanosheets, small particle size, mesoporous structure, and large electrochemical active surface area.     

Pore formation during the pyrolysis of C-Nb2O5 and C-Ta2O5 xerogels

Binary organic-inorganic gels have been prepared by mixing a carbonaceous hydrosol and a Nb₂O₅ or Ta₂O₅ sol derived by hydrolysis of the alkoxides. The gels are pyrolyzed under an inert atmosphere into precursors in which carbon and the metal oxides are mixed very intimately. High temperature treatment converts the precursors into the cubic face centered carbides. The precursors as well as the carbides have been shown to be micro- and mesoporous materials. Measurements of nitrogen adsorption reveal a characteristic change of the shapes of the isotherms (Type I Type IV) and of the hysteresis loops (H4H2H1) during the thermal processes. Pore widening has been observed with rising temperature. The phenomena of crystallization, carbothermal reduction and sintering were found to control the pore shape and size. The results of the adsorption measurement correlate well with those of the thermoanalytical and X-ray diffraction studies.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

UCr4C4 with filled MoNi4 type structure

The title compound was prepared by arc melting coldpressed pellets of the elemental components with subsequent annealing at both 800°C or 1100°C. UCr₄C₄ crystallizes tetragonal, space group I4/m,a=0.79363 (4) nm,c=0.30754 (3) nm,V=0.19370 nm³ withZ=2 formula units per cell. The structure was determined from single-crystal X-ray data and refined to a residual ofR=0.027 for 16 variable parameters and 279 structure factors. The positions of the metal atoms correspond to those of the MoNi₄ type structure. The carbon atoms occupy octahedral voids formed by four chromium and two adjacent uranium atoms. Chemical bonding in UCr₄C₄ and in other interstitial compounds is briefly discussed. The average valence electron number of the metal atoms is usually greater for the unfilled (host) structure than for the corresponding filled structure.Dedicated to Prof. Dr.Kurt Komarek and to Prof. Dr.Adolf Neckel on the occasion of their 60th birthdays.     

基体的梯度结构对涂层硬质合金性能的影响

通过控制烧结气氛制备了均质和梯度结构的硬质合金基体，并用化学气相沉积制成涂层硬质合金及切削刀片。采用光学显微镜和扫描电镜观察，通过显微硬度抗弯测试和切削试验对均质基体和梯度基体的涂层硬质合金的组织特征与性能进行对比研究。研究结果表明，梯度结构的硬质合金基体可以提高涂层硬质合金的抗弯强度；相对于均质基体的涂层硬质合金刀片，梯度基体的涂层硬质合金刀片在保持耐磨性能的同时能显著提高抗冲击性能。基体涂层合金的组织结构及断口特征显示，梯度基体表层韧性区可阻碍裂纹的扩展。     

硬煤截齿刀头硬质合金的热疲劳失效分析

对硬煤综采机的易损件——截齿进行了系统的失效分析．研究中发现，热疲劳所引发的早期疲劳破坏——崩块、剥落是制约其使用寿命的重要原因．采用中等Ｃｏ含量和粗粒度的ＷＣ硬质合金，对抗热疲劳从而提高截齿使用寿命有利