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无规共聚物熔体的积分方程理论:分子内和分子间相关性的自洽处理。

Integral equation theory of random copolymer melts: self-consistent treatment of intramolecular and intermolecular correlations.

作者信息

Sung Bong June, Yethiraj Arun

机构信息

Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.

出版信息

J Chem Phys. 2005 Jun 15;122(23):234904. doi: 10.1063/1.1931649.

Abstract

A self-consistent integral equation theory is presented for the conformational properties and spinodal lines of random copolymer melts. The theory combines field-theoretic methods with the polymer reference interaction site model (PRISM) theory. The many-chain problem is replaced by a single chain where the sites interact via a bare plus a self-consistently determined medium-induced potential, and the conformational properties are obtained using a variational method. The theoretical prediction for the spinodal line is qualitatively similar to that of non-self-consistent PRISM theory. The theory predicts macroscopic phase separation for all values of the monomer correlation strength, lambda. The inverse spinodal temperature is a nonmonotonic function of lambda with a maximum at lambda(max). For large values of lambda( approximately 1), the values of spinodal temperatures are almost identical to those of non-self-consistent PRISM theory. For low values of lambda, however, the theory predicts higher values for spinodal temperatures than non-self-consistent PRISM theory. The theory predicts significant changes in the mean-square end-to-end distance as the temperature is decreased.

摘要

提出了一种自洽积分方程理论,用于研究无规共聚物熔体的构象性质和旋节线。该理论将场论方法与聚合物参考相互作用位点模型(PRISM)理论相结合。多链问题被单个链问题所取代,其中位点通过裸势加上自洽确定的介质诱导势相互作用,并使用变分方法获得构象性质。旋节线的理论预测在定性上与非自洽PRISM理论相似。该理论预测了单体相关强度λ的所有值下的宏观相分离。逆旋节温度是λ的非单调函数,在λ(max)处有最大值。对于较大的λ值(约为1),旋节温度的值几乎与非自洽PRISM理论的值相同。然而,对于较低的λ值,该理论预测的旋节温度值比非自洽PRISM理论更高。该理论预测,随着温度降低,均方末端距会发生显著变化。

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