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121.
采用溶胶-凝胶法制备了不同纳米TiO2含量的聚砜(PSF)/TiO2杂化超滤膜, 研究了TiO2浓度对聚砜铸膜液流变学及热力学性质的影响, 构建了计算成膜过程中表观扩散系数(Da)的新方法, 求出不同TiO2浓度及温度下的Da值, 进而剖析了铸膜液流变学和热力学性质的变化对成膜动力学的影响. 并通过扫描电镜观察、杂化膜孔隙率和超滤性能的测试考察了表观扩散系数与膜结构和性能的关系. 结果表明, 加入TiO2溶胶的PSF铸膜液由牛顿流体转变为非牛顿流体, 其粘度随TiO2浓度增大而增大. TiO2的加入减小了铸膜液对非溶剂的容纳能力, 加速铸膜液的液-液相分离, 同时TiO2引起的热力学促进作用和流变学阻碍作用相互竞争, 共同影响Da的变化. 实验得出, Da随温度升高而增大, 随TiO2浓度的增大有先增大后减小的趋势. 表观扩散系数Da与膜的结构和性能具有很好的相关性并能直观地描述整个成膜过程. 相似文献
122.
Poly(3,3-dimethyl oxetane) fractions ranging in number average molecular weights from 18500 to 130000 have been isothermally crystallized from the relaxed melt state in the temperature range from 12 to 44 °C, where only the monoclinic modification is formed. The influence of molecular weight and undercooling in crystallization kinetics has been analyzed. The level of crystallinity is very slightly dependent on molecular weight but the influence of this parameter on the time scale of the crystallization is relatively pronounced. The crystallization temperature coefficient was determined and it was found a constant value of the product of the interfacial energies in the range of molecular weights which has been analyzed. Growth rate measurements were carried out for fraction ¯M
n=130000 and it was found that the temperature coefficients for overall and growth rates are equal. Finally, the comparison of the experimental results for this polymer with those reported for poly(oxetane) shows two main differences: first, the crystallization rate is slower for poly(3,3-dimethyl oxetane) and second, the temperature coefficient is smaller for this polymer. 相似文献
123.
W. Zielenkiewicz B. Golankiewicz G. L. Perlovich M. Koźbiał 《Journal of solution chemistry》1999,28(6):731-745
Solubilities of tricyclic analogs of acyclovir have been determined in water at 25, 35, and 45°C and in octanol, water-saturated octanol, and octanol-saturated water at 25°C. Octanol-water partition coefficients were determined at 25°C. Melting temperatures and molar enthalpies of fusion were measured. Activity coefficients in water, octanol, and in aqueous octanol solutions were determined and are discussed. The effect of hydrophilic and hydrophobic substituents in the tricyclic analogs on their thermodynamic properties are discussed. The standard Gibbs energy of transfer between the saturated phases were found to correlate with known values of the melting point of the solvents and the solubilities of the solute. For a number of the compounds examined, correlations between the minimum inhibitory concentration against the herpes simplex virus type 1 (HSV-1) and type 2 (HSV-2), varicella-zoster virus (VZV), thymidine kinase-deficient (TK–) strains of VZV and
were established. Detailed conclusions have been derived concerning the relationships between the structure and the thermodynamic parameters of the compounds examined. 相似文献
124.
Using well-cycled, thin composite graphite electrodes we analyze carefully the limitations of potentiostatic and galvanostatic intermittent titration techniques (PITT and GITT, respectively) for determination of the differential (incremental) intercalation capacitance, Cdif, and the chemical diffusion coefficient, D, of Li ions in these ion-insertion electrodes (IIEs). We demonstrate the superiority of the GITT over PITT to determine these quantities as the former technique allows for a more accurate determination of Cdif and hence D which closely approach to the spinodal domain related to the first-order phase transition during ion-insertion. We show that GITT is also more effective in eliminating the parasitic contributions of background currents to the total measured response. A pronounced difference in the initial, intrinsic kinetics of formation of a new phase in the bulk of the old one has been observed depending on the direction of titration (phases less saturated with Li are formed faster during deintercalation than the Li-rich phases in the course of intercalation). 相似文献
125.
B. Pateyron M. F. Elchinger G. Delluc P. Fauchais 《Plasma Chemistry and Plasma Processing》1996,16(1):39-57
In most cases the energy dissipated in plasma jets used either,for heating or spraying is varied by changing the are current, the total gas floc+rate, and composition. However, when doing so, conditions are reached where the plasma jet may become supersonic. To predict such conditions or to characterize supersonic plasma jets the knowledge of the sound velocitya is mandatory The goal of this paper is to calculatea versus plasma forming gas composition, temperature, and pressure. Rigorous calculation would imply the knowledge of the chemical reaction kinetics, sound velocity depending strongly on this. Unfortunately such kinetics are generally lolknown for plasma jet floras and the only possibility is to determine the equilibrium sound velocitya calculated through the isentropic coefficient T. This coefficient has been calculated taking into account the dissociation and ionization reactions at equilibrium for temperatures ranging from 300 to 25,000 K and pressures between 0.1 and 1 Mpa for Ar, H2, He, Ar-He, Ar-H2, O2, N2, air, .steam, and methane.a often called the frozen sound velocity, was also calculated using (ratio of specific heats) instead of . 相似文献
126.
Han-Lang Wu Chen-Chi M. Ma Chia-Hsun Li Tzong-Ming Lee Chih-Yuan Chen Chin-Lung Chiang Chen Wu 《Journal of membrane science》2006,280(1-2):501-508
Poly(amide imide) (PAI) was synthesized using 1,2,4-benzenetricarboxylic anhydride (BTBA) and 4,4′-methylenebis(phenyl isocyanate) (MBPI). SPEEK/PAI blend membranes were prepared and investigated by NMR, GPC, FT-IR and AFM. The chemical structures of PAI and SPEEK were characterized by using NMR and FT-IR. The adsorption of the SPEEK/PAI blend membrane of water or methanol solution was also characterized. The significant swelling of the blend membrane in concentrated methanol solution was explained by the solubility parameter. The water diffusion coefficient (DH2O) was related to the lambda value of the membrane. The SPEEK/PAI blend membrane had a lower proton conductivity and methanol permeability than Nafion. However, the relative selectivity (proton conductivity divided by methanol permeability) of the SPEEK/PAI 70/30 (w/w) blend membrane was 3.46 × 104 S s cm−3, which is closed to that of Nafion (3.30 S s cm−3). 相似文献
127.
结合三维静电势参数研究二取代苯的定量结构-疏水性关系 总被引:1,自引:0,他引:1
对含有常见取代基的92个二取代苯化合物进行了结构优化和静电势及其导出参数的计算,运用多元线性回归方法对化合物的疏水常数与分子的结构参数进行了关联.结果表明,分子表面负静电势的加和ΣV-S、分子空间内最负的静电势Vmin、表面最大静电势Vs,max以及分子体积V、极性表面积APS和分子的偶极密度μ/V这六个参数,可以很好地用于表达这些化合物疏水性与分子结构间的定量关系,而不用具体考虑分子中极性基团间的相互作用.用建立起来的QSPR(quantitative structure-property relationship)关系式对111个类似化合物的疏水性进行了预测,获得了满意的结果. 相似文献
128.
Estimation of diffusion coefficient of Ba++ ions in silica gel from periodic precipitation of BaMoO4
Formation of Liesegang rings on the growth of BaMoO4 crystals in silica gel by single diffusion is discussed. The rhythmic precipitation is found to be influenced profoundly by (a) the molarity of inner and outerelectrolytes (b) the age of gel and (c) the pH of the gel medium. The time law, spacing law and the law relating diffusion depth and width are verified. A method to estimate the diffusion coefficient of the outer electrolyte in the gel medium is developed and calculated for Ba++ions. 相似文献
129.
Anwar Ali S.Sabir M.Tariq 《物理化学学报》2007,23(1):79-83
Measurements of density(ρ), viscosity(η), and refractive index(n), were carried out on α-amino acids, DL-solution at 298.15, 303.15, 308.15, and 313.15 K. These measurements have been carried out to evaluate some important parameters, viz., apparent molar volume (φv), partial molar volume (φv0), transfer volume (φ0v (tr)), viscosity A and B coefficients of Jones-Dole equation, free energies of activation per mole of solvent (△μ0#1) and solute (△μ0#2),enthalpies (△H*) and entropies (△S*) of activation of viscous flow, variation of B with temperature ((a)B/(a)T)P, and molar refractive index (RD). These parameters have been interpreted in terms of solute-solute and solute-solvent interactions and structure making/breaking ability of solutes in the given solution. 相似文献
130.
Dense membranes were prepared from poly(vinyl alcohol)–poly(N-vinyl pyrrolidone) (PVA–PVP) blends of different compositions and studied in swelling and dehydration by pervaporation of three organic solvents contaminated by 5 wt% water. The swelling generally increases with the PVP content. No extraction occurs in water–tetrahydrofuran (THF) and water–methyl ethyl ketone (MEK) mixtures. In ethanol containing 10 wt% of water, there is no extraction for blends containing less than 40 wt% PVP and an increasing extraction beyond this PVP content. The pervaporation flux of the water–ethanol mixture increases drastically at the same threshold whereas the water permselectivity falls to a low level. The values of the diffusion and permeability coefficients determined from transient permeation of the test water–ethanol mixture exhibit a similar sudden increase at the same PVP content threshold. This singular behavior of the blend membranes is interpreted by a strong affinity of the PVP component to ethanol, combined with a disappearance of crystallites in the blend at this threshold. Consequently the amorphous membrane can swell freely according to the affinity of the PVP component, leading to the observed behavior. 相似文献