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首页> 外文期刊>Macromolecular symposia >Influence of Chain Structure and Swelling on the Elasticity of Rubbery Materials: Localization Model Description
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Influence of Chain Structure and Swelling on the Elasticity of Rubbery Materials: Localization Model Description

机译：链结构和溶胀对橡胶材料弹性的影响：局部化模型描述

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Classical network elasticity theories are based on the concept of flexible volumeless network chains fixed into a network in which there are no excluded volume, or even topological, interactions between the chains and where the chains explore accessible configurations by Brownian motion. In this type of 'classical' model of rubber elasticity, the elasticity of the deformed network derives from the entropic changes that arise from a deformation of the network junction positions. The shortcoming of this approach is evident from the observation that unswollen rubbery materials are nearly incompressible, reflecting the existence of strong intermolecular interactions that restrict the polymer chains to the exploration of their local tube-like molecular environments along their chain contours. The imposition of a deformation of these solid rubbery materials then necessitates a consideration of how the local molecular packing constraints become modified under deformation and the impact of these changes in chain confinement on the macroscopic elasticity of the material as a whole. Many researchers have struggled with this difficult many-body problem. The present paper focuses on the simple 'localization model' (LM) of rubber elasticity of Gaylord and Douglas (GD), which provides a simple minimal model for the network elasticity of rubbery materials in the dense polymer state. Particular emphasis in the present paper is given to the implications of this model for describing how network elasticity changes with solvent swelling, a phenomenon for which large deviations from classical elasticity have been observed and a situation highly relevant to numerous applications that involve rubbery materials. We also discuss the physical nature of 'entanglement' based on the same molecular packing picture and deduce general conditions for entanglement in terms of molecular parameters. Our predictions accord rather well with experimental correlations relating chain molecular structure to the entanglement molecular mass, changing elasticity with swelling, etc.
机译：经典的网络弹性理论基于固定在网络中的灵活无量网络链的概念，在该网络中，链之间没有排除的体积甚至拓扑相互作用，并且链通过布朗运动探索可访问的配置。在这种类型的“经典”橡胶弹性模型中，变形网络的弹性源自网络连接位置变形引起的熵变。从观察中可以明显看出这种方法的缺点，即未溶胀的橡胶状材料几乎不可压缩，反映出存在强烈的分子间相互作用，这种相互作用限制了聚合物链只能沿着其链状轮廓探索其局部管状分子环境。然后，对这些固体橡胶状材料施加形变，就必须考虑在形变下如何改变局部分子堆积约束，以及这些链约束变化对整个材料的宏观弹性的影响。许多研究人员一直在努力解决这个难题。本文关注的是盖洛德和道格拉斯（GD）橡胶弹性的简单“局部化模型”（LM），它为致密聚合物状态下橡胶材料的网络弹性提供了一个简单的最小模型。本文特别强调了该模型的含义，该模型用于描述网络弹性如何随溶剂溶胀而变化，已经观察到与经典弹性有较大偏差的现象以及与涉及橡胶材料的众多应用高度相关的情况。我们还将基于相同的分子堆积图讨论“纠缠”的物理性质，并根据分子参数推导纠缠的一般条件。我们的预测与链式分子结构与纠缠分子质量，随着膨胀而改变弹性的实验相关性非常吻合。

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