透形状对聚合物和网络中激活动态和选择性的影响,这些影响基于自相一致的合作跳跃理论
Baicheng Mei1,2, Kenneth S Schweizer1,3,4,2
1Department of Materials Science, University of Illinois, Urbana, IL 61801, USA. kschweiz@illinois.edu.
Soft matter
|November 8, 2023
概括
分子形状显著影响聚合物的透动力学,特别是在玻璃过渡附近. 一个新的理论解释了非球形形状如何影响跳跃率,为放松时间创建主曲线.
科学领域:
- 聚合物物理 聚合物物理
- 材料科学 材料科学 材料科学
- 化学工程是化学工程的重要组成部分.
背景情况:
- 了解聚合物的透动态对于材料设计和应用至关重要.
- 现有的理论经常简化分子形状,限制它们对复杂系统的适用性.
- 非球形分子形状对激活动态的影响仍然是一个悬而未决的问题.
研究的目的:
- 概括和应用微观自相一致的合作跳跃理论,以研究非球形分子形状在聚合物动态中的作用.
- 为了隔离分子形状对透动力学的明确影响,在广泛的温度范围内,直到动力玻璃过渡温度.
- 开发一个理论框架,涉及分子结构,动力约束和透跳跃行为.
主要方法:
- 微观自相一致的合作跳跃理论的概括.
- 在聚合物融和交联网络中分析激活的透动态.
- 引入一个尺寸比变量来描述透的形状影响.
主要成果:
- 预计在超冷的状态下,对于对聚合物矩阵类型 (融化与交联) 敏感的较大的透物,会产生高度形状依赖的激活放松.
- 对较小的分子或在更高的温度下,透形状的影响较弱.
- 拟议的尺寸比变量将放松时间组织成主曲线,统一形状效应.
- 融体与网络的相对透放松时间显示出相反的趋势,取决于比较基础 (绝对温度与T_g的固定距离).
结论:
- 非球形的分子形状在激活的透动力学中起着关键作用,特别是在深度超冷状态下.
- 开发的理论提供了一个定量框架,用于理解和预测形状依赖的动态,通过实验扩散数据验证.
- 这些发现对设计具有量身定制的运输特性的聚合物有影响,包括选择性膜应用.
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