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Coarse grained model of diffusion in entangled bidisperse polymer melts

机译:纠缠双分散聚合物熔体中的粗粒扩散模型

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摘要

Chain diffusion is studied in mixtures of bidisperse linear polymers of same chemical identity by means of simulations. The two subpopulations are moderately to highly entangled, with the shorter chain length N_S, fulfilling N_S/N_e>=5. To this end, a coarse grained model calibrated to reproduce both the structure and dynamics of chains in monodisperse entangled melts is used [A. Rakshit and R. C. Picu, J. Chem. Phys. 125, 164907 (2006)]. Its performance in reproducing chain dynamics in a polydisperse melt is tested by extensively comparing the results with those obtained from an equivalent fine scale representation of the same system (a bead-spring model). The coarse grained model is used further to investigate the scaling of the diffusion coefficient with the length of the two types of chains and its dependence on the respective fractions. The model reproduces many features observed experimentally. For example, the diffusion coefficient of one of the chain types decreases with increasing the length of the other type chains. It is shown that, in this model, this effect is not linked to constraint release. When the matrix chains become sufficiently long, their length does not influence the diffusion coefficient of the short chains anymore. The diffusion coefficient of the short chains scales with their weight fraction in a manner consistent with experimental observations. In mixtures, the dynamics of the short chains is slower and that of the long chains is marginally faster than in their respective monodisperse melts.
机译:通过模拟研究了具有相同化学特性的双分散线性聚合物混合物中的链扩散。这两个亚群被中等至高度纠缠,链长度较短N_S,满足N_S / N_e> = 5。为此,使用了经过粗化处理的模型,该模型经过校准可重现单分散缠结熔体中链的结构和动力学[A. Rakshit和R.C. Picu,J.Chem。物理125,164907(2006)]。通过将结果与从相同系统的等效精细比例表示(珠弹簧模型)中获得的结果进行广泛比较,来测试其在多分散熔体中重现链动力学的性能。粗粒度模型进一步用于研究扩散系数随两种类型链的长度及其对各个分数的依赖性的缩放。该模型再现了实验观察到的许多功能。例如,一种链条类型的扩散系数随着另一种链条的长度增加而减小。结果表明,在该模型中,这种影响与约束释放无关。当基质链变得足够长时,它们的长度不再影响短链的扩散系数。短链的扩散系数与其重量分数成比例,与实验观察结果一致。在混合物中,短链的动力学要比它们各自的单分散熔体慢,长链的动力学要快一些。

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