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Influence of steric and intramolecular inductive effects on the variable trends in R-X (R=Alkyl) bond dissociation energy

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science china Chemistry 2009年第7期52卷 943-951页

作者： CAO ChenZhong school of Chemistry and Chemical engineering, hunan university of science and technology, xiangtan 4112.1, china school of Chemistry and Chemical engineering Hunan University of Science and Technology Xiangtan 411201 China

The question "why are the variation trends of R-X bond dissociation energy different?" is answered. The R-X bond dissociation energy (BDE) may be influenced by three main factors: the C-X intrinsic bond energy, the 1,3 geminal repulsion, and the intramolecular charge-induced dipole. In the presence of atom X, the variation trend of BDE in R-X (R= Me, Et, i-Pr, t-Bu) is dominated by two factors, the 1,3 geminal repulsion and the intramolecular charge-induced dipole. The former decreases the R-X BDE, and the latter either increases or decreases the R-X BDE. For the series of R-X with the R-C bond (such as R-Me, R-CH == CH2, R-C≡CH, and R-CN), the 1,3 geminal repulsion decreases the R-X BDE, and the variation trends of R-C BDE decrease from Me to t-Bu. As regards the series of R-X (such as R-H, R-BH2, and R-SiH2) in which the electronegativity of atom X is smaller than that of the carbon atom, the above two factors decrease the R-X BDE, and the variation trends of the R-X BDE decrease from Me to t-Bu. As to the series of R-X (such as R-F, R-OH, R-Cl, R-Br, R-I, and R-NH2) in which the electronegativity of atom X is larger than that of the carbon atom, the 1,3 geminal repulsion decreases the R-X BDE, while the intramolecular charge-induced dipole increases the R-X BDE. In this case, the variation trends of R-X BDE depend on the competition of the two factors. As a result, some of them (e. g., R-F, R-OH) increase from Me to t-Bu, some (e. g., R-I) decrease from Me to t-Bu, and some (e. g., R-Br) change very little.

关键词： bond dissociation energy charge-induced dipole geminal repulsion ionic configuration

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Novel nanoporous binary Ag-Ni electrocatalysts for hydrazine oxidation

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Rare Metals 2010年第1期29卷 26-31页

作者： YI Qingfeng, LI Lei, YU Wenqiang, LIU Xiaoping, ZHOU Zhihua, and NIE Huidong school of Chemistry and Chemical engineering, hunan university of science and technology, xiangtan 4112.1, china school of Chemistry and Chemical engineering Hunan University of Science and Technology

From an aqueous mixture of Ag（I）-EDTA complex and Ni（II） nitrate, silver and nickel particles were co-deposited on the surface of titanium substrates by the hydrothermal method using hydrazine hydrate as a reduction agent. The prepared titanium-supported nano-scale Ag and Ag-Ni particles （nano Ag/Ti, nano Ag86Ni14/Ti, nano Ag77Ni23/Ti, and nano Ag74Ni26/Ti） exhibit nanoporous 3D network textures. Their electrocatalytic activity towards hydrazine oxidation in alkaline solutions was evaluated by cyclic voltammetry and chronoamperometry. The results show that the four samples present a low onset potential of ca. -0.60 V vs. SCE and considerably high and stable anodic current densities for hydrazine oxidation. Among them, the nano Ag86Ni14/Ti electrode exhibits the highest anodic current density towards hydrazine oxidation, showing an increment of electro-active sites on the nano Ag86Ni14/Ti due to the addition of Ni to Ag particles.

关键词： electrocatalyst silver hydrazine oxidation fuel cell

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Application of the annexation principle to the study of thermodynamic properties of ternary metallic melts In-Pb-Ag and In-Bi-Sb

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Rare Metals 2002年第2期21卷 142-151页

作者： ZHANG JianMetallurgical engineering school.university of science and technology Beijing, Beijing 100083, china Metallurgical engineering school University of Science and Technology Beijing 北京 100083

Based on the phase diagrams, measured activities an the annexationprinciple, the calculating models of mass action concentrations forin-Pb-Ag and In-Bi-Sb ternary metallic melts have been *** results of calculation both agree with practice, and obey the lawof mass action, showing that the models formulated can reflect thestructural reality of the corresponding melts and the annexationprinciple is applicable to the them.

关键词： activity mass action concnetration th annexation principle In-PB-Ag

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Nonlinear Theory on Dynamic Controlling Interface Patterns DuringSolidification of a Dilute Binary Alloy

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International Journal of Minerals,Metallurgy and Materials 1999年第4期13卷 253-258页

作者： Zidong Wang Hanqi Hu(Material science and engineering school, university of science and technology Beijing, Beijing 100083, china) Material science and engineering school University of Science and Technology Beijing Beijing 100083 China

In non-equilibrium nonlinear region, the nonlinear equations of time dependence of perturbation amplitude at the solid/liquidinterface during solidification of a dilute binary alloy are established on the base of assuming that there is local equilibrium at the solid/liquid interface and considering that curvature, temperature and composition at the solid/liquid interface which are related to the perturbation amplitude are nonlinear. As a result, patterns at the solid/liquid interface during solidification process, which is from nonsteadystate to steady state can be controlled by these nonlinear equations.

关键词： nonlinearity solidification, dilute binary alloy, dynamic control

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Preparation of semi-solid AlSi7Mg alloy slurry with big capability

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Rare Metals 2010年第6期29卷 642-645页

作者： LI Sha and MAO Weimin school of Materials science and engineering,university of science and technology Beijing,Beijing 100083,china school of Materials science and engineering University of Science and Technology Beijing Beijing China

Semi-solid AlSi7Mg alloy slurry was prepared by low superheat pouring and weak traveling-wave electromagnetic *** effects of pouring temperature and stirring power on the microstructure of AlSi7Mg alloy slurry were *** results show that the semi-solid AlSi7Mg alloy slurry of 5 kg can be *** new technology can save energy and make the pouring process *** the pouring temperature is decreased at a stirring power of 0.41 kW,the shape of primary α-Al grains gradually changes from dendritic-like to *** the alloy melt is poured at the temperature（630°C） with a certain superheat,the pouring process becomes easier,and the spherical microstructure of AlSi7Mg alloy slurry can be prepared by the weak traveling-wave electromagnetic *** the pouring temperature is 630°C,increasing the stirring power appropriately can result in better spherical primary α-Al grains,but if the stirring power is increased to a certain value（1.72 kW）,the shape of primary α-Al grains does not obviously improve when the stirring power is continually increased.

关键词： aluminum alloys metal forming semisolid slurry electromagnetic stirring microstructure

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β-Sialon Produced by Carbon Thermal Nitriding Reaction of Bauxite

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International Journal of Minerals,Metallurgy and Materials 2000年第3期14卷 209-213页

作者： Jun Wang, Nan Li, Caicheng Shi, Chengchang Jia ( Material science and engineering school, university of science and technology Beijing, Beijing 100083, china Material science and engineering school, Wuhan university of science and technology, Wuhan 430 Material science and engineering school University of Science and Technology Beijing Beijing 100083 China Material science and engineering school Wuhan University of Science and Technology Wuhan 430081 China

β-Sialon was produced by carbon thermal nitriding reaction in N_2 gas atmosphere when the mixtures of bauxite and anthracite were put into vertical furnace. According to the mass loss of raw materials and the result of X-ray diffration (XRD) of products, the influences of the process parameters on the compositions and relative contents of products, such as the fixed carbon content, the flow of N2, the soaking time and the temperature, were researched.

关键词： β-Sialon bauxite anthracite carbon thermal nitriding processing parameter vertical furnace

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Relationship between Low Temperature Toughness and Microstructure in Low Activation Fe-Cr-Mn(W,V)Steel for Fusion Reactors

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International Journal of Minerals,Metallurgy and Materials 1999年第2期13卷 111-115页

作者： Benfu Hu Chengchang jia(Material science and engineering school, university of science and technology Beijing, Beijing 100083, china) Material science and engineering school University of Science and Technology Beijing Beijing 100083 China

Fe-Cr-Mn (W, V) austenite steel was researched in order to supply a theory base for the first wall materials of fusion *** included vacuum melting, forging, annealing, solution treatment, Charpy impact tests and microstructure observation. Theresults show that the imped value decreases with the test temperature decreasing. In this system, there is ductile/brittle transition. Themechanism of this decrease of the impact value is considered to be due to γ - ε transformation in sub-stable austenite steel and stoppingoverlapping sacking fault by grain boundaries in stable austenite steel.

关键词： fusion reactor first wall materials low temperature toughness Fe-Cr-Mn system

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Sol-gel Preparation and Infrared Radiation Property of Boron-substituted Cordierite Glass-ceramics

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Journal of Materials science & technology 2010年第5期26卷 445-448页

作者： Shuming Wang and Fenghua Kuang school of Materials science and engineering,university of science & technology Beijing,Beijing 100083,china [a] school of Materials science and engineering university of science & technology Beijing Beijing 100083 china

Boron for aluminum substitution in the cordierite structure has been examined by sol-gel preparation of different samples along the compositional junction Mg2Al4-xBxSi5O18 with x=0,0.5,1,*** increasing the x value from 0 to 1.5 the crystallization behavior changed *** amount B2O3 doping can promote the sintering of amorphous cordierite gel,effectively restrain the precipitation of μ-cordierite and enhance the crystallization of α-*** substitution of B3＋ for Al3＋ in cordierite crystal structure can effectively improve the near-infrared spectral emissivity of this cordierite based glass-ceramics.

关键词： Sol-gel Glass-ceramics Infrared radiation B3+ substitution Solid solution

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Performance Modeling and Approximate Analysis of Multiserver Multiqueue Systems with Poisson and Self-similar Arrivals

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Journal of university of science and technology Beijing 2001年第2期8卷 145-151页

作者： Zhiguang Shan, Chuang Lin, Yang Yang, Yan Wang (Information engineering school, university of science and technology Beijing, Beijing 100083, china) (Department of computer science and technology, Tsinghua university, Beijing 100084, china) Univ Sci & Technol Beijing Informat Engn Sch Beijing 100083 Peoples R China Tsinghua Univ Dept Comp Sci & Technol Beijing 100084 Peoples R China

The problem of state space explosion is still ran outstanding challenge in Markovian performance analysis for multiserver multiqueue (MSMQ) systems. The system behavior of a MSMQ system is described using stochastic high-level Petri net (SHLPN) models, and an approximate performance analysis technique is proposed based on decomposition and refinement methods as well as iteration technique. A real MSMQ system, Web-server cluster, is investigated. The performance of an integrated scheme of request dispatching and scheduling is analyzed with both Poisson and self-similar request arrivals. The study shows that the approximate analysis technique significantly reduces the complexity of the model solution and is also efficient for accuracy of numerical results.

关键词： multiserver multiqueue (MSMQ) system Web-server cluster performance analysis stochastic high-level Petri net (SHLPN) request dispatching request scheduling

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Dislocation Densites of Deformed Steel Sheets Based on Positron Annihilation

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International Journal of Minerals,Metallurgy and Materials 1998年第1期12卷 47-50页

作者： Yonglin Kang Xianjin Wang (Materials science and engineering school, university of science and technology Beijing, Beijing 100083, china) Materials science and engineering school University of Science and Technology Beijing Beijing 100083 China

The variation regularity of dislocation densites of some deformed steel sheets under three kinds of strainpaths as uniaxial tension, plane strain and equal biaxial stretching was investigated by means of positron lifetimespectrum and Doppler-broadening techniques. The results show that the increasing rate of dislocation densites isrelated to the plastic strain path. A relationship between the increasing rate of micro-defects, macro-instability andforming limits during the process of steel sheet forming was got based on analyzing the mechanism of dislocationdensity increasing under different stress-strain condihons.

关键词： positron annihilation dislocation steel sheet strain path

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