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Rouse Mode Analysis of Chain Relaxation in Homopolymer Melts

机译:均聚物熔体链松弛的唤醒模式分析

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We use molecular dynamics simulations of the Kremer- Grest (KG) bead-spring model of polymer chains of length between 10 and 500, and a closely related analogue that allows for chain crossing, to clearly delineate the effects of entanglements on the length-scale-dependent chain relaxation in polymer melts. We analyze the resulting trajectories using the Rouse modes of the chains and find that entanglements strongly affect these modes. The relaxation rates of the chains show two limiting effective monomeric frictions, with the local modes experiencing much lower effective friction than the longer modes. The monomeric relaxation rates of longer modes vary approximately inversely with chain length due to kinetic confinement effects. The time-dependent relaxation of Rouse modes has a stretched exponential character with a minimum of stretching exponent in the vicinity of the entanglement chain length. None of these trends are found in models that allow for chain crossing. These facts, in combination, argue for the confined motion of chains for time scales between the entanglement time and their ultimate free diffusion.
机译:我们使用Kremer-Grest(KG)长度为10至500的聚合物链的Kremer-Grest(KG)珠-弹簧模型的分子动力学模拟,以及允许链交叉的密切相关的类似物,来清楚地描述缠结对长度尺度的影响聚合物熔体中依赖链的松弛。我们使用链的Rouse模式分析了产生的轨迹,发现纠缠强烈地影响了这些模式。链的松弛率显示出两个有限的有效单体摩擦,局部模式的有效摩擦比较长模式的有效摩擦低得多。由于动力学限制效应,较长模式的单体弛豫速率与链长成反比。随时间变化的Rouse模态具有拉伸的指数特征,在纠缠链长度附近具有最小的拉伸指数。在允许链交叉的模型中找不到这些趋势。这些事实加在一起,证明了链在纠缠时间和最终自由扩散之间的时间尺度内的局限运动。

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