Chen K, Saltzman E J, Schweizer K S
J Phys Condens Matter. 2009 Dec 16;21(50):503101. doi: 10.1088/0953-8984/21/50/503101. Epub 2009 Nov 23.
Recent progress in developing statistical mechanical theories of supercooled polymer melts and glasses is reviewed. The focus is on those approaches that are either explicitly formulated for polymers, or are applications of more generic theories to interpret polymeric phenomena. These include two configurational entropy theories, a percolated free volume distribution model, and the activated barrier hopping nonlinear Langevin theory. Both chemically-specific and universal aspects are discussed. After a brief summary of classic phenomenological approaches, a discussion of the relevant length scales and key experimental phenomena in both the supercooled liquid and glassy solid state is presented including ageing and nonlinear mechanical response. The central concepts that underlie the theories in the molten state are then summarized and key predictions discussed, including the glass transition in oriented polymer liquids and deformed rubber networks. Physical ageing occurs in the nonequilibrium glass, and theories for its consequences on the alpha relaxation are discussed. Very recent progress in developing a segment scale theory for the dramatic effects of external stress on polymer glasses, including acceleration of relaxation, yielding, plastic flow and strain hardening, is summarized. The article concludes with a discussion of outstanding theoretical challenges.
本文综述了过冷聚合物熔体和玻璃态统计力学理论的最新进展。重点关注那些专门为聚合物制定的方法，或者是应用更通用的理论来解释聚合物现象的方法。这些方法包括两种构型熵理论、一种渗流自由体积分布模型以及活化势垒跳跃非线性朗之万理论。文中讨论了化学特异性和普遍性两个方面。在简要总结经典唯象学方法之后，本文介绍了过冷液体和玻璃态固体中的相关长度尺度和关键实验现象，包括老化和非线性力学响应。接着总结了熔体状态下理论的核心概念，并讨论了关键预测，包括取向聚合物液体和变形橡胶网络中的玻璃化转变。非平衡玻璃中会发生物理老化，并讨论了其对α弛豫影响的相关理论。总结了在发展用于解释外部应力对聚合物玻璃产生显著影响（包括加速弛豫、屈服、塑性流动和应变硬化）的链段尺度理论方面的最新进展。文章最后讨论了悬而未决的理论挑战。
