Capaccioli S, Ngai K L
Dipartimento di Fisica and INFM (UdR Pisa), Università di Pisa, Largo B. Pontecorvo 3, I-56127 Pisa, Italy.
J Phys Chem B. 2005 May 19;109(19):9727-35. doi: 10.1021/jp044893j.
The coupling model was applied to describe the alpha-relaxation dynamics of each component in perfectly miscible mixtures A(1-x)B(x) of two different glass-formers A and B. An important element of the model is the change of the coupling parameter of each component with the composition, x, of the mixture. However, this change cannot be determined directly from the frequency dispersion of the alpha-relaxation of each component because of the broadening caused by concentration fluctuations in the mixture, except in the limits of low concentrations of either component, x --> 0 and x --> 1. Fortunately, the coupling model has another prediction. The coupling parameter of a component, say A, in the mixture determines tau(alpha)/tau(JG), the ratio of the alpha-relaxation time, tau(alpha), to the Johari-Goldstein (JG) secondary relaxation time, tau(JG), of the same component A. This prediction enables us to obtain the coupling parameter, n(A), of component A from the isothermal frequency spectrum of the mixture that shows both the alpha-relaxation and the JG beta-relaxation of component A. We put this extra prediction into practice by calculating n(A) of 2-picoline in binary mixtures with either tri-styrene or o-terphenyl from recently published broadband dielectric relaxation data of the alpha-relaxation and the JG beta-relaxation of 2-picoline. The results of n(A) obtained from the experimental data show its change with composition, x, follows the same pattern as assumed in previous works that address only the alpha-relaxation dynamics of a component in binary mixtures based on the coupling model. There is an alternative view of the thrust of the present work. If the change of n(A) with composition, x, in considering the alpha-relaxation of component A is justified by other means, the theoretical part of the present work gives a prediction of how the ratio tau(alpha)/tau(JG) of component A changes with composition, x. The data of tau(alpha) and tau(JG) of 2-picoline mixed with tri-styrene or o-terphenyl provide experimental support for the prediction.
耦合模型被用于描述两种不同玻璃形成体A和B的完全互溶混合物A(1-x)B(x)中各组分的α弛豫动力学。该模型的一个重要元素是各组分的耦合参数随混合物组成x的变化。然而,由于混合物中浓度波动导致的展宽,除了在两种组分中任一组分的低浓度极限情况(x→0和x→1)外,无法直接从各组分α弛豫的频率色散确定这种变化。幸运的是,耦合模型还有另一个预测。混合物中某一组分(如A)的耦合参数决定了该组分A的α弛豫时间τα与约哈里 - 戈尔茨坦(JG)二级弛豫时间τJG的比值τα/τJG。这一预测使我们能够从显示组分A的α弛豫和JGβ弛豫的混合物等温频谱中获得组分A的耦合参数n(A)。我们通过根据最近发表的2-甲基吡啶的α弛豫和JGβ弛豫的宽带介电弛豫数据,计算2-甲基吡啶与三苯乙烯或邻三联苯的二元混合物中的n(A),将这一额外预测付诸实践。从实验数据获得的n(A)结果表明,其随组成x的变化遵循与先前仅基于耦合模型处理二元混合物中某一组分α弛豫动力学的工作中所假设的相同模式。对于本工作的主旨还有另一种观点。如果通过其他方式证明在考虑组分A的α弛豫时n(A)随组成x的变化是合理的,那么本工作的理论部分给出了组分A的τα/τJG比值如何随组成x变化的预测。2-甲基吡啶与三苯乙烯或邻三联苯混合时的τα和τJG数据为该预测提供了实验支持。