Analysis of the carbon source for diamond crystal growth

The lattice constants of diamond and graphite at high pressure and high temperature （HPHT） were calculated on the basis of linear expansion coefficient and elastic constant. According to the empirical electron theory of solids and molecules （EET）, the valence electron structures （VESs） of diamond, graphite crystal and their common planes were calculated. The relationship between diamond and graphite structure was analyzed based on the boundary condition of the improved Thomas-Fermi-Dirac theory by Cheng （TFDC）. It was found that the electron densities of common planes in graphite were not continuous with those of planes in diamond at the first order of approximation. The results show that during the course of diamond single crystal growth at HPHT with metal catalyst, the carbon sources forming diamond structure do not come from the graphite structure directly. The diamond growth mechanism was discussed from the viewpoint of valence electron structure.     

Fe,Cr及Fe（Cr ）合金磁矩的价电子结构分析

给出了确定单质或二元固溶体原子状态的简单快捷方法,应用该方法可清楚地给出固体中化学键网的分布、键强有关固体的其它特性,如熔点、电导率、磁矩、结合能、强度、韧性等,作为例子,建立了α－Fe,α-Cr和不同Cr含量F(Cr）合金的价电子结构,并对晶格常数和磁矩的实验结果给出了满意的价电子结构分析。     

WC,TiC,Fe3 C及Co2C的价电子结构与性能的分析

运用固体与分子经验电子理论计算了几种过渡族金属碳化物的价电子结构 ,发现碳化物的主要价电子结构参数主键键能与碳化物的熔点、硬度及生成焓之间存在着很好的相关性     

The valence electron structure and property analysis of TiC

The valence electron structure of TiC was calculated by using the empirical electron theory of solids and molecules. The calculated results show that with the increase of temperature the number of common electrons of TiC increases, which indicates that TiC has a good thermal stability; and there exists a close relationship between hardness and brittleness of TiC. According to the number of lattice electrons, the differences among the crystals with different structures can be explained qualitatively. Using the “bond- strengthening factor”, the differences of hardness among the crystals with different structures can also be qualitatively explained to some extent.     

Valence electron structure analysis of refining mechanism of Sc and Ti additions on aluminum

The mechanism of the difference of refining effect between Sc and Ti adding to aluminum can not be explained substantially with traditional theory. Valence electron structures of Al-Ti and Al-Sc alloys have been studied by using the empirical electron theory of solids and molecules (EET). The covalent bond electron numbers and interfacial electron density differences are calculated. The conclusion is that, in the two alloys, different covalent bond electron numbers of nucleation particles, and different electron densities on the interface between the second phase particles and the matrix, fundamentally lead to the difference of refining effect between Sc and Ti adding to aluminum. Supported by the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20050003042)     

镓酸镧基固体电解质离子导电性与价电子结构的关系

文章应用固体与分子经验电子理论计算了镓酸镧基固体电解质材料的价电子结构,计算结果表明,1/(nAnB)随x及y增加而增加。实验结果表明,当x、y小于20%时,电导率σ随x、y增加而增加,并随1/(nAnB)增加而电导率σ增加,通过价电子结构的计算,可预测不同成分的LSGM的电导率。     

N80油管钢的CO_2高温高压腐蚀电化学行为与机理研究

在高温高压釜中模拟油气井腐蚀环境 ,采用电化学交流阻抗和动电位扫描极化曲线测试技术 ,研究了N80钢在温度为 10 0℃ ,CO2 分压为 1.18MPa条件下的腐蚀电化学行为和阳极与阴极反应机理 ,实时监测了腐蚀产物膜对腐蚀行为和腐蚀反应机理的影响 .研究结果表明 :N80钢的阳极反应过程服从Bockris机理 ;N80钢的阴极反应以H2 CO3的还原为主 ;反应中间产物吸附与腐蚀产物膜覆盖的竞争导致交流阻抗谱随腐蚀时间而变化 ,影响着钢的腐蚀行为 ,产物膜对钢基体具有一定的保护作用     

富氧条件下烃类选择性催化还原NOx研究进展--金属氧化物催化剂体系及NO还原反应机理

综述了负载或非负载的金属氧化物催化剂体系上,富氧条件下NO的非选择性催化还原反应性能及反应机理.着重讨论了还原剂种类、催化剂结构与化学性质对催化反应的影响及催化剂的耐水性和耐SO2性能.探讨并总结了金属氧化物催化剂体系上NO的还原机理.     

含合金元素γ-Fe晶胞价电子结构及其对相变过程的影响

利用固体与分子经验电子理论,对奥氏体中含合金元素γ-Fe晶胞的价电子结构进行了计算分析.结果表明,合金元素溶入γ-Fe晶胞后,其价电子结构发生了较大变化,Fe原子杂化态向较高杂阶迁移,其相结构因子均有不同程度的增加.同时晶胞内形成了由强键组成的八面体结构,阻碍了原子的移动,使得γ-Fe晶胞在相变过程中产生"类拖曳效应",提高过冷奥氏体的稳定性,亦会延缓马氏体相变的进程.     

叠合梁叠合面抗剪机理分析及抗剪强度计算

本文充分利用已有的研究成果，分析了叠合面的抗剪破坏机理及其影响因素，并列举比较部分规范和研究者的叠合面计算方法，提出今后需要进一步研究的建议．     

无机改性蒙脱石的EET计算及其与PMMA复合

 采用固体与分子经验电子理论(EET)对自制的钾蒙脱石(K-MMT)和镁蒙脱石(Mg-MMT)的层间作用力进行计算与分析,并对乳液插层聚合法制备的PMMA/K-MMT和PMMA/Mg-MMT复合材料进行XRD表征.EET研究结果表明,K-MMT和Mg-MMT中,片层表面与其吸附的K⁺和Mg²⁺之间的结合能分别为92.32 kJ/mol和0.06 kJ/mol,相对于K-MMT而言,Mg-MMT更容易以片层形式分散到聚合物基体中.XRD表征结果表明,K-MMT以团聚形式分散在PMMA基体中,而Mg-MMT均匀分散于PMMA基体中,验证了EET分析所得结论.     

高压喷雾射流雾化及水雾捕尘机理的拓展理论分析

通过对射流扰动控制方程、射流色散方程解算结果的分析,基于两相流的喷雾概念模型,引入了空穴、湍流和空气动力共同作用的雾化模型。认为高压喷雾时,喷嘴内部形成的空穴和湍流作用主导喷嘴出口附近的一次雾化,而空气动力则控制着此后的二次雾化过程。提出以临界韦伯数作为射流是否发生二次雾化的判据。根据对液滴破碎方式的分析,认为液流完全分裂成雾滴的射流临界初速度为60 m/s,且射流破碎一般发生在一次雾化中,薄膜破碎一般发生在二次雾化中。基于液滴对尘粒的主动碰撞理论,对典型喷雾降尘机理进行了改进,认为当含尘气体处于非饱和状态且温度高于液体温度时,捕集率与液滴粒径间存在一个最佳组合;在相同的液气比,相同的液滴喷入时,降低气流速度有利于微细液滴对细小尘粒的捕集。     

一种新型噻唑盐的微波辅助合成及对安息香缩合的催化作用

以4-甲基-5-羟乙基噻唑和对氰基氯化苄为原料微波合成一种新型噻唑盐,3-(对氰基苄基)-4-甲基-5-(2-羟乙基)噻唑氯化物,再用此噻唑盐替代VB1作为安息香缩合反应的催化剂,检验其催化性能,发现催化苯甲醛得苯偶姻收率为74.5％、催化糠醛得糠偶姻收率为76.1％,此噻唑盐不仅具有天然VB1的无毒性,且可回收利用;考察了物质的量投料比、反应时间、反应温度及微波反应器功率对此噻唑盐收率的影响;并用HPLC测定产物的纯度,通过熔点、元素分析、IR及LC-MS对噻唑盐性质和及苯偶姻结构进行了表征.     

CH3Br和CH3I分子价轨道电子动量分布的理论计算

基于Hartree-Fock和密度泛函理论,用几种不同水平的基组对CH3Br和CH3I分子价轨道电子动量分布进行了计算,并与Minchinton等人的实验和理论进行了比较.得到的计算结果有很大的改善,与Minchinton等人的实验符合较好.对CH3Br分子,计算结果的改善主要是使用了有极化、弥散函数的大基组.对于CH3I分子,则主要是来自考虑了相对论效应的LANL2DZ基组.     

基于厌氧微生物的碳链延长合成高价值化学品反应机理及研究进展：不同电子供体

近年来,世界各国对能源的需求及依赖日益剧增。与此同时,为了实现社会的可持续发展和生态系统的健康稳定,可再生能源及化学品受到了极大的关注。厌氧发酵系统可以在缓解废弃物对环境造成污染的同时生产生物燃料和化学品,逐渐成为一大研究热点。基于厌氧微生物的碳链延长生产中链脂肪酸（C₆-C₁₂）,可比制备传统厌氧发酵产品（CH₄）获得更高的附加值,而与采用传统的化工方法生成中链脂肪酸相比可节省更多成本。中链脂肪酸可以通过短链有机酸的碳链延长得到,这个过程需要电子供体和电子受体的共同参与。电子供体作为驱动碳链延长的主要动力,其种类和性质会直接影响碳链延长的途径,最终产物的类型、产量和产率。因此,本文综述了乙醇、乳酸、H₂和CO等作为电子供体的链延伸机理、主要微生物和研究现状,并给出厌氧微生物利用不同电子供体实现碳链延长制取高附加值化学品的优缺点,提出有待解决的问题和发展前景。     

New structure model of oxygen-evolving center and mechanism for oxygen evolution in photosynthesis

So far, many important questions and problems concerning the structure and mechanism of photosynthetic oxygen evolution are still unsolved. On the basis of recent achievements in this field, a new structure model is proposed whereby two H2O molecules bind asymmetrically to two manganese ions (Mn1Ⅱ and Mn4Ⅲ) at the open end of "C" shaped cluster and keep rather large distance. Two histidine residues coordinate to the other two manganese ions in higher oxidation state (Mn2Ⅳ and Mn3Ⅳ ) through their nitrogen atoms of the imidazole. Cl bound as terminal ligand to Mn4Ⅲl is connected to Ca, and the latter is needed to maintain the special configuration of two Mn2O2 units by bridged-oxo and bridged-carboxylate ligands. The whole structure of oxygen evolution center is asymmetry. A new mechanism for oxygen evolution invokes predictions of asymmetric oxidation of two H2O molecules, dynamic structural changes of oxygen e-volving center and indirect proton transport, etc. Only in S2 state, could Mn1Ⅳ = O. intermediate with high oxidation potential be formed. The S2→S3 process occurs with significant structural changes, as well as intramolecular and intermolecular hydrogen transfer. The S3 state corresponds to intermediate of Mn1Ⅳ-O… H… O-Mn4Ⅳ . During S3→ [S4] →S0, the O-O bond is formed only in S4 state. The change of nucleophilic interaction between Cl and manganese ions different oxidation states has consequence for the significant structural changes in H2O oxidation process.     

基于异型部件装配的位姿调整机构设计及自由度分析

针对异型金属壳体和防热套部件精确装配的特殊要求,分析确定了用于装配精确定位的位姿调整机构的基本组成,以及3R-P-2R2T位姿调整机构的自由度组合方案.重点对2R2T金属壳体位姿调整机构进行了设计与分析,提出了一种新型4-UPS/UPP对称位姿调整并联机构,完成相应的支链结构配置,并利用螺旋理论对机构自由度进行计算.结果表明:所提新型机构能够满足金属壳体的位姿调整要求.     

New concept on coal structure and new consideration for the generation mechanism of oil from coal

The traditional two_phase structural model of coal based on the chemical covalence bonding has to be revised since recent discoveries of powerful mixed solvent such as CS-2/C-5H-9N, giving extra high yields in coal extraction at room temperature. It is believed that the physically associated interactions play important roles in the structure of coal. A composite model of coal is suggested. The organic matter of coal is mainly composed of some parts: the rigid 3_D macromolecules linked with chemical bonds; the polar molecules of high and moderate molecular weights, corresponding to asphaltenes and resins; the hydrocarbons with lower molecular weights. The polar molecules are associated by physical interactions (such as hydrogen bonding, charge transfer interactions, π_π interactions of aromatic sheets, etc.) each other and with macromolecules to form the network structure, in which some smaller nonpolar molecules are trapped. Based on the new concept of the composite coal model, some considerations for the generation mechanism of oil from coal have approached. Since the energy level of physical association is much lower than the chemical covalent bonding, the upper threshold of oil window for the generation of oil from coal seems not to be limited strictly after the theory of oil generation at the latter stage of the kerogen maturation. It looks reasonable to pay more attention to the geological conditions including the salt, water, minerals and environments of the sedimentation. The evolution process of physically associated interactions in the composite structure of coal and the generation of oil is thought to be intimately influenced by these factors.