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A model for relaxation in supercooled liquids and polymer melts

机译:过冷液体和聚合物熔体松弛模型

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摘要

A new model for molecular rearrangements in liquids is proposed. The liquids are regarded as dense ensembles of vibrating molecules satisfying the exluded volume condition. A Continuity condition is applied on the molecular scale of such systems and is regarded as controlling rearrangements leading to translations of molecules beyond the range of their vibration amplitude. It results in cooperative rearrangements which are considered as taking place in systems with fluctuating density. rates of rearrangements are considered as being controlled by thermal activation with activation energy barriers dependent on local density. Various dependencies of the activation energy abrriers on local density are examined. It is shown, that the model is able to reproduce the extremal cases of temperature dependencies of relaxation times represented on one edge by the Arrhenius relation and on the other edge by the Vogel-Fulcher-Tamman relation. The model can, however, provide a broad spectrum of other dependencies filling the gap between these extremes. All cases are based on the uniform microscopic picture of cooperative molecular rearrangements resulting from system continuity. The mdoel is implemented as a simulation algorithm (Dynamic Lattice Liquid - DLL algorithm) which is used to simulate dynamic properties of liquids and polymer melts. Simulation results obtained for polymers are compared with experimental results obtained by means of the dynamic mechanical measurements on polysobutylene samples with various molecular weights.
机译:提出了一种液体分子重排的新模型。液体被认为是满足排除体积条件的振动分子的密集集合体。连续性条件应用于此类系统的分子规模,并被视为控制重排,导致分子平移超出其振动幅度范围。这导致协作重排,这被认为在密度波动的系统中发生。重排的速率被认为是由热活化控制的,活化能势垒取决于局部密度。检查了活化能消减剂对局部密度的各种依赖性。结果表明,该模型能够再现弛豫时间与温度相关性的极端情况,其在一个边缘上由阿伦尼乌斯(Arrhenius)关系表示,而在另一边缘上由Vogel-Fulcher-Tamman关系表示。但是,该模型可以提供广泛的其他依赖关系,填补了这些极端之间的空白。所有情况均基于系统连续性导致的合作分子重排的统一微观图像。 mdoel被实现为一种模拟算法(动态晶格液体-DLL算法),用于模拟液体和聚合物熔体的动态特性。将聚合物获得的模拟结果与通过动态机械测量对各种分子量的聚丁烯样品获得的实验结果进行比较。

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