高分子流体的黏弹性质是高分子科学和工程中一个非常重要的研究领域.与简单黏性液体和弹性固体不同,外场作用下缠结高分子流体呈现出复杂的黏弹性行为,例如应力不仅仅与应变幅度或应变速率有关,还与整个形变历史相关.近半个世纪以来,人们建立了很多描述这些复杂黏弹性质的模型和理论,其中一类是基于连续性介质力学原理的唯象模型,例如:Maxwell模型、Voigt-Kelvin模型和在时空上所有参数为常量的连续性模型;另一类是瞬态网络模型,该模型把缠结点考虑成瞬态交联点,高分子链看成珠簧链;还有一类是微观分子理论,其中最著名的是"管子模型".本文首先介绍缠结高分子流体的线性黏弹性响应和Boltzmann叠加原理的基本概念,然后,重点综述描述高分子黏弹性质仍非常有实际应用价值的3个经典唯象模型,包括Maxwell模型、Voigt-Kelvin模型和瞬态网络模型,特别是这些理论的详细推导和存在的主要问题.关于高分子黏弹性的微观理论将在其它综述中单独介绍.
Viscoelastic properties of entangled polymer fluids have been an important research area in polymer science and engineering. Unlike elastic solids or simple viscous liquids,entangled polymer fluids exhibit very complicated viscoelastic behavior in an external field,which indicates that the stress is a function of the whole deformation history rather than just of strain amplitude or of strain rate. In the recent half century,plenty of models and theories have been made to understand these viscoelastic properties. Some are based on the principles of continuum mechanics,such as the Maxwell model,the Voigt-Kelvin model,and the various constitutive models,all of which have parameters that are constant in space and time. An alternative model of polymer dynamics and rheology is modeled by a transient network where the entangled points are considered to act as temporary crosslinks and polymer chains are represented by beads and springs. The rheological behavior of the system depends on the kinetics of breakage and reformation of the network made of interacting polymer molecules. Others are microscopic theories for an entangled polymer fluids. One of the most famous and successful molecular theories is the tube theory. In this review article,we first introduce the basic concepts of the linear response of viscoelasticity and the Boltzmann 's superposition principle. Then,we focused on the three classical phenomenological models,including the Maxwell model,the Voigt-Kelvin model,and the transient network model,which are still popularly employed in the field of entangled polymers and other viscoelastic materials. In particular,the detailed derivation and critical issues for these models are discussed.Microscopic theories of viscoelasticity will be detailedly and thoroughly introduced in other reviews.