抗氧剂3114合成反应热力学和动力学的研究

研究了常温溶剂法合成抗氧剂3114反应热力学和动力学过程。控制温度在117±2℃,研究结果表明,反应是零级反应,反应速率常数k=1.91×10-3/min,反应的平衡常数K=138.4(mol/L)-6,反应活化能Ea=1366.2J/mol。     

Hydrogenolysis of alkanes and olefin polymerization on the silica-supported zirconium hydrides: A comparative DFT study

The model reactions of ethylene polymerization and hydrogenolysis of linear alkanes (propane, n-butane, and n-pentane) on the silica-supported zirconium hydrides (Si–O)₃Zr^IVH, (Si–O)₂Zr^IVH₂, and (Si–O)₂Zr^IIIH were studied using the DFT approach. Catalytic processes under study were shown to occur involving different surface hydrides. The ethylene polymerization was found to proceed at comparable rates on the zirconium monohydrides, (Si–O)₃ZrH, and dihydrides, (Si–O)₂ZrH₂. Cleavage of linear alkanes on the monohydrides (Si–O)₃ZrH is thermodynamically unfavorable; however, the dihydrides (Si–O)₂ZrH₂ can act as catalysts of the process under mild conditions. Hydrides of the trivalent zirconium, (Si–O)₂Zr^IIIH, can also contribute to the hydrogenolysis reaction. A feature of all the systems studied is low regioselectivity of the corresponding processes.     

The kinetics of B‐a and P‐a type copolybenzoxazine via the ring opening process

The structure of benzoxazines is similar to that of phenolic resin through thermal self‐curing of the heterocyclic ring opening reaction that neither requires catalyst nor releases any condensation byproduct. These polybenzoxazine resins have several outstanding properties such as high thermal stability and high glass transition temperature. To better understand the curing kinetics of this copolybenzoxazine thermosetting resin, dynamic and isothermal differential scanning calorimetry measurements were performed. Three models, the Kissinger method, the Flynn–Wall–Osawa method, and the Kamal method, were used to describe the curing process. Dynamic kinetic activation energies based on Kissinger and Flynn–Wall–Osawa methods are 72.11 and 84.06 KJ/mol, respectively. The Kamal method based on an autocatalytic model results in a total order of reaction between 2.66 and 3.03, depending on curing temperature. Its activation energy and Arrhenius preexponential are 50.3 KJ/mol and 7959, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 730–737, 2005     

Modeling of metadynamic recrystallization kinetics after hot deformation of low-alloy steel Q345B

Based on the steady-state strain measured by single-pass hot compression tests, the method by a double-pass hot compression testing was developed to measure the metadynamic-recrystallization kinetics. The metadynamic recrystallization behavior of low-alloy steel Q345B during hot compression deformation was investigated in the temperature range of 1 000–1 100 °C, the strain rate range of 0.01–0.10 s⁻¹ and the interpass time range of 0.5–50 s on a Gleeble-3500 thermo-simulation machine. The results show that metadynamic recrystallization during the interpass time can be observed. As the deformation temperature and strain rate increase, softening caused by metadynamic recrystallization is obvious. According to the data of thermo-simulation, the metadynamic recrystallization activation energy is obtained to be Q _md=100.674 kJ/mol and metadynamic recrystallization kinetics model is set up. Finally, the error analysis of metadynamic recrystallization kinetics model proves that the model has high accuracy (correlation coefficient R=0.988 6).     

A new model for evaluating the electrical conductivity of nonferrous slag

Electrical conductivity of molten slag is an important physicochemical property for designing the refining process in electric smelting furnaces.Though conductivities of many slag systems have been measured,the quantitative relationships of conductivity with slag composition and temperature are still very limited.In this article,the Arrhenius law was used to describe the experimental data of conductivities for CaO-MgO-Al2O3-SiO2,CaO-Al2O3-SiO2,CaO-MnO-Al2O3-SiO2,as well as CaO-MgO-MnO-Al2O3-SiO2 systems,and...     

Preparation and electrochemical characterization of activated carbons by chemical-physical activation

A process was proposed based on the combination of chemical and physical activation for the production of activated carbons used as the electrode material for electric double layer capacitor (EDLC). By material characterization and electrochemical methods, the influences of the activitation process on the specific surface area, pore structure and electrochemical properties of the activated carbons were investigated. The results show that specific surface area, the mesopore volume, and the specific capacitance increase with the increase of the mass ratio of KOH to char (m(KOH)/m(char)) and the activation time, respectively. When m(KOH)/m(char) is 4.0, the specific surface area and the mesopore volume reach the maximum values, i.e. 1 960 m²/g and 0.308 4 cm³/g, and the specific capacitance is 120.7 F/g synchronously. Compared with the chemical activation, the activated carbons prepared by chemical-physical activation show a larger mesopore volume, a higher ratio of mesopore and a larger specific capacitance. Foundation item: Project(2007BAE12B01) supported by the National Key Technology Research and Development Program of China     

Hydrogen sorption properties of nanocrystalline Mg2FeH6-based complex and catalytic effect of TiO2

The diversities of hydrogen sorption properties of Mg₂FeH₆-based complexes with and without TiO₂ were investigated. Mg₂FeH₆-based complexes with and without TiO₂ were synthesized respectively by reactive mechanical alloying, and hydrogen sorption properties of the complexes were examined by Sieverts-type apparatus. The results show that the sample without TiO₂ releases 4.43 % (mass fraction) hydrogen in 1.5 ks at 653 K under 0.1 MPa H₂ pressure and absorbs 90% of the total 4.43 % (mass fraction) hydrogen absorbed in 85 s at 623 K under 4.0 MPa H₂ pressure. But for the sample with TiO₂ addition under the same condition, it only needs 400 s to release all of the stored hydrogen and 60 s to absorb 90% of the total hydrogen absorbed. The activation energies for desorption process of the samples with and without TiO₂ are determined to be 71.2 and 80.3 kJ/(mol·K), respectively. The improvement in hydrogen sorption rate and and reduction in activation energy can be attributed to the addition of TiO₂.     

一种新的混沌神经网络及其应用

提出一种新的混沌神经元模型,该神经元的激励函数由复合正弦函数和Sigmoid函数构成,通过分叉图及Lyapunov指数的计算,分析了其动力学特征.基于该模型构造了一种新的暂态混沌特征神经网络,并将其应用于组合优化问题.仿真实验结果表明了该算法的有效性与可行性.     

激活能测试装置设计及微晶硅薄膜激活能测试

为了分析微晶硅薄膜的本征特性,设计了激活能测试装置。测试装置包括测试平台、真空系统和加热控制系统。同时给出激活能计算方法,并对不同电压、不同取点个数对激活能测试的影响进行分析。分析结果表明,不同测试电压对激活能测试结果影响很小,不同取点个数计算的激活能差别也很小。     

水热温度对玻璃纤维增强HAp-CS涂层的影响

为了制备出结合强度较好的生物涂层,采用水热电泳法在碳/碳复合材料表面成功制备了玻璃微纤维增强的羟基磷灰石——壳聚糖(g(f)/HAp-CS)复合涂层,用x-射线衍射仪、透射电子显微镜、扫描电子显微镜、能谱分析仪、红外傅里叶变换分析仪等测试手段对涂层进行了测试和表征,主要研究了水热沉积温度对复合涂层中HAp晶相和涂层显微结构的影响以及HAp涂层的沉积动力学.结果表明:采用玻璃微纤维增强的HAp-CS涂层,致密性和均匀性有了很大提高,显著减少了复合涂层表面的裂纹;随着水热温度的升高,涂层中HAp的衍射峰逐渐增强,表面形貌得到了有效改善,涂层的致密性和均匀性显著提高;涂层的沉积速率随水热温度的升高而加快,其沉积活化能为14.63kJ/mol.