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21.
从现有的PCDFs分子的正辛醇 /水分配系数 (logKow)实验数据出发 ,建立定量结构 性质关系方程(QSPR) .采用G98W程序包中的PM3方法对 13 5个多氯代二苯并呋喃 (PCDFs)分子和二苯并呋喃进行了优化计算 ,作业命令为 #pPM3optfreqscf(conver =9) ,以计算所得的分子轨道能量、碳原子电荷作为PCDFs分子结构描述符 ,运用多元线性回归技术建立了PCDFs的logKow与分子结构描述符的四元方程 ,最优相关系数为 0 .95 0 7,标准偏差为 0 .173 7,经检验该模型的稳健性好 ,并对未有实验数据的 85个PCDFs的logKow进行预测 相似文献
22.
Volker John 《国际流体数值方法杂志》2004,44(7):777-788
This paper presents a numerical study of a two‐dimensional time‐dependent flow around a cylinder. Its main objective is to provide accurate reference values for the maximal drag and lift coefficient at the cylinder and for the pressure difference between the front and the back of the cylinder at the final time. In addition, the accuracy of these values obtained with different time stepping schemes and different finite element methods is studied. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
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Compared with linear polymers, more factors may affect the glass‐transition temperature (Tg) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. Tg's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of Tg to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. Tg's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. Tg values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. Tg values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of Tg versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that Tg increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004 相似文献
25.
Hidetaka Tobita 《Journal of Polymer Science.Polymer Physics》2004,42(14):2801-2812
The matrix formula developed in the context of heterochain theory, M?w = M?wp + WF ( I ? M )?1 S , was applied to describe the molecular weight development during free‐radical multicomponent polymerization. All of the required probabilistic parameters are expressed in terms of the kinetic‐rate constants and the various concentrations associated with them. In free‐radical polymerization, the number of heterochain types, N, needs to be extrapolated to infinity, and such extrapolation is conducted with only three different N values. This matrix formula can be used as a benchmark test if other approximate approaches can give reasonable estimates of the weight‐average molecular weights. The moment equations with the average pseudo‐kinetic‐rate constants for branching and crosslinking reactions may provide poor estimates when the copolymer composition drift during polymerization is very significant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2801–2812, 2004 相似文献
26.
A. Zubeldia M. Larraaga P. Remiro I. Mondragon 《Journal of Polymer Science.Polymer Physics》2004,42(21):3920-3933
The microstructure and fracture behavior of epoxy mixtures containing two monomers of different molecular weights were studied. The variation of the fracture toughness by the addition of other modifiers was also investigated. Several amounts of high‐molecular‐weight diglycidyl ether of bisphenol A (DGEBA) oligomer were added to a nearly pure DGEBA monomer. The mixtures were cured with an aromatic amine, showing phase separation after curing. The curing behavior of the epoxy mixtures was investigated with thermal measurements. A significant enhancement of the fracture toughness was accompanied by slight increases in both the rigidity and strength of the mixtures that corresponded to the content of the high‐molecular‐weight epoxy resin. Dynamic mechanical and atomic force microscopy measurements indicated that the generated two‐phase morphology was a function of the content of the epoxy resin added. The influence of the addition of an oligomer or a thermoplastic on the morphologies and mechanical properties of both epoxy‐containing mixtures was also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3920–3933, 2004 相似文献
27.
Su Nee Tan Daniel Fornasiero Rossen Sedev John Ralston 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):307-315
The foam behaviour of low molecular weight polypropylene glycols (PPG) was investigated as a function of concentration and molecular weight (190–2000 g mol−1). For each polypropylene glycol, foam stability increases with concentration and passes through a maximum, beyond which foamability is suppressed as the solubility limit of the glycol is exceeded and droplets of glycol form. Light-scattering data as well as static and dynamic surface tension results provide the key information leading to these interpretations. A maximum in foamability was observed for the PPG molecules with increasing molecular weight (caused by a change in molecular conformation at the interface). This suppresses the Marangoni effect and leads to a decrease in foam stability. 相似文献
28.
Per B. Zetterlund Kazuki Miyake Kunihiro Goto Bunichiro Yamada 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2640-2650
A detailed investigation of addition–fragmentation chain transfer (AFCT) in the free‐radical polymerization of methyl methacrylate (MMA) in the presence of methyl α‐(bromomethyl)acrylate (MBMA) was carried out to elucidate mechanistic details with efficient macromonomer synthesis as an underlying goal. Advanced modeling techniques were used in connection with the experimental work. Curve fitting of simulated and experimental molecular weight distributions with respect to the rate coefficient for addition of propagating radicals to MBMA (kadd) over 60–120 °C resulted in Eadd = 21.7 kJ mol?1 and Aadd = 2.18 × 106 M?1 s?1 and a very weak temperature dependence of the chain‐transfer constant (Eadd ≈ Ep). The rate coefficient for fragmentation of adduct radicals at 60 °C was estimated as kf ≈ 39 s?1 on the basis of experimental data of the MMA conversion and the concentration of 2‐carbomethoxy‐2‐propenyl end groups. The approach developed is generic and can be applied to any AFCT system in which copolymerization does not occur and in which the resulting unsaturated end groups do not undergo further reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2640–2650, 2004 相似文献
29.
用改进的离子束增强沉积方法和恰当的退火从V2O5粉末直接制备了VO2多晶薄膜.实验测试表明,薄膜的取向单一、相变特性显著、结构致密、界面结合牢固、工艺性能良好,薄膜的电阻温度系数(TCR)最高可达4.23%/K.从成膜机理出发,较详细地讨论了离子束增强沉积 VO2多晶薄膜的TCR高于VOx薄膜的TCR的原因.分析认为,单一取向的VO2结构使薄膜晶粒具有较高的电导激活能,致密的薄膜结构减少了氧空位和晶界宽度,使离子束增强沉积 VO2多晶薄膜结构比其他方法制备的VOx薄膜更接近于单晶VO2是其具有高TCR的原
关键词:
VO2多晶薄膜
离子束增强沉积
热电阻温度系数 相似文献
30.