Influence of concentration on the activation energy for diffusion in polymer-solvent systems

The self-diffusion of benzene, toluene, and ethylbenzene in polystyrene have been analyzed using the Vrentas/Duda free-volume diffusion model. Diffusion coefficient predictions suggest an exponential concentration dependence of the activation energy required to overcome attractive forces, E. Without the use of any diffusion data approximating E as zero over the entire concentration range yields self-diffusion coefficient predictions which are in good agreement with experimental data. © 1992 John Wiley & Sons, Inc.     

Determination of Diffusion Coefficients for Binary Nonelectrolyte Mixtures. A Free-Volume Predictive Approach

A diaphragm cell has been used to measure mutual diffusion coefficients at 25°C for four binary nonelectrolyte mixtures: ethylbenzene + n-hexane, carbon tetrachloride + ethylbenzene, cyclohexane + p-xylene, and 1,2-dichloroethane + cyclohexane. A free-volume predictive approach for binary mutual diffusion coefficients was developed and tested. Only infinite dilution diffusion coefficients, some readily available pure substance data, and UNIFAC group contribution parameters are used in the model. No binary equilibrium thermodynamic information is required. For 73 binary systems with an overall average absolute deviation of 5.2%, it has been shown that the developed method is better than two commonly available reference methods for the prediction of liquid diffusion coefficients.     

HIPS的γ辐照效应的正电子寿命谱研究

测量了高强度聚苯乙烯（ＨＩＰＳ）的正电子寿命谱随γ辐照剂量的变化，观察到自由体积孔洞的平均半径随辐照剂量的增加而基本不变，且自由体积孔洞的浓度和半径分布宽度随辐照剂量的增加而减小．这一实验结果表明，γ辐照后高强度聚苯乙烯力学性能的改善与自由体积特性的变化相关联．     

Direct measurement of free-volume hole distributions in polymers by using a positronium probe

We have directly measured the free-volume hole distributions in semicrystalline polypropylene by positron lifetime annihilation spectroscopy. A Laplace inversion technique was engaged to analyze the positron lifetime spectra measured under quasi-isotropic external pressures of 0, 4.2, and 14.7 kbar into continuous lifetime distributions. The hole radii distributions as determined from the ortho-positronium lifetime distributions are found to be between 4.0 and 0.5 Å and to have maxima at 3.0, 1.9, and 1.1 Å under the external pressures of 0, 4.2, and 14.7 kbar, respectively. © 1992 John Wiley & Sons, Inc.     

Evaluation of free-volume theories for solvent self-diffusion in polymer–solvent systems

An evaluation of free-volume theories for solvent self-diffusion is carried out using recent comprehensive data sets for penetrant self-diffusion in polymer solutions. Different theories are compared, and free-volume theories in the prediction of penetrant self-diffusion coefficients in glassy polymer systems is also evaluated. © 1993 John Wiley & Sons, Inc.     

Static correlations of higher order and diffusion in an interacting lattice gas

For a lattice gas with extended hard core interaction on a square lattice the static correlation functions of higher order, which determine the average jump rate in the diffusion process, are calculated both by the Monte Carlo method and by analytic approximations. It is found that the superposition approximation is very inaccurate for the correlation functions of third and fourth order, but gives better results for the average jump rate. Up to concentrations ofc = 0.3 better consistency with the Monte Carlo data for both quantities is obtained by treating the site occupation numbers as Gaussian random variables and accordingly expressing the correlation functions of higher order by products of averages of two particle correlations. For concentrationsc > 0.3, however, a Bethe-Peierls cluster approximation is superior to the superposition approximation.The results of this paper were presented at the I.L.L, workshop Beyond Radial Distribution, Grenoble, July 15–16, 1985.     

Thermodynamics of Organic Mixtures Containing Amines. II. Excess Molar Volumes at 25°C for Methylbutylamine + Alkane Systems and Eras Characterization of Linear Secondary Amine + Alkane Mixtures

Excess molar volumes, at 25°C and atmospheric pressure for methylbutyl amine + n-hexane; + cyclohexane; + n-octane; n-decane; + n-dodecane; + n-tetradecane, or + n-hexadecane systems are reported from densities measured with a vibrating-tube densimeter. The excess functions, molar enthalpy, and volume, for linear secondary amine + n-alkane systems are discussed in terms of interactional and structural effects. In addition, these solutions, which include amines from dimethyl to dioctylamine, are studied in the framework of the ERAS model. The corresponding ERAS parameters are reported. The agreement between experimental data and ERAS results is good for excess enthalpies, excess Gibbs energies, and excess molar volumes. The larger discrepancies are found for the excess volumes when strong free-volume effects are present in the investigated mixtures. The variation with temperature of the thermodynamic properties is well described by ERAS.     

环己烷在聚乙烯和聚异丁烯中无限稀释扩散系数 的测定

采用填充柱的反相气相色谱方法,基于Hadj-Romdhane-Danner色谱过程的数学模型,在323.2～363.2K温度范围内测定了环己烷在聚异丁烯和聚乙烯膜中的无限稀释扩散系数。从实验数据可以看出,环己烷更容易在PIB中发生扩散。对实测扩散数据进行了自由体积理论关联,结果表明,采用空穴自由体积替代Vrentas-Duda自由体积理论方程中自由体积项的修正方程能很好地描述溶剂分子扩散系数随温度的变化关系。     

Fickian diffusion in glassy polymer-solvent systems

A free-volume theory is developed for the analysis of Fickian diffusion processes in glassy polymers. Equations are presented for the prediction of mutual diffusion coefficients in concentrated glassy polymer-penetrant systems. The concentration dependence of the mutual diffusion coefficient is dependent on how much free volume the solvent contributes to the system and on how the addition of solvent affects the densification of the polymer matrix. © 1992 John Wiley & Sons, Inc.