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Wall boundary model for primitive chain network simulations

机译:用于原始链网络仿真的墙边界模型

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摘要

In condensed polymeric liquids confined in slit channels, the movement of chains is constrained by two factors: entanglement among the chains and the excluded volume between the chains and the wall. In this study, we propose a wall boundary (WB) model for the primitive chain network (PCN) model, which describes the dynamics of polymer chains in bulk based on coarse graining upon the characteristic molecular weight of the entanglement. The proposed WB model is based on the assumptions that (i) polymers are not stuck but simply reflected randomly by the wall, and (ii) subchains below the entanglement length scale behave like those in bulk even near the wall. Using the WB model, we simulate the dynamics of entangled polymer chains confined in slit channels. The results show that as the slit narrows, the chains are compressed in the direction normal to the wall, while they are expanded in the parallel direction. In addition, the relaxation time of the end-to-end vector increases, and the diffusivity of the center of mass decreases. The compression in the normal direction is a natural effect of confinement, while the expansion is introduced by a hooking process near the wall. The trends revealed that the relaxation time and diffusivity depend on the increase in friction due to an increased number of entanglements near the wall, which is also associated with the hooking process in the PCN model. These results are expected within the assumptions of the PCN model. Thus, the proposed WB model can successfully reproduce the effects of wall confinement on chains.
机译:在限制在狭缝通道中的冷凝聚合物液体中,链的运动受到两个因素的限制:链之间的缠结以及链​​与壁之间的排他体积。在这项研究中,我们为原始链网络(PCN)模型提出了一个壁边界(WB)模型,该模型描述了基于缠结特征分子量的粗粒度的散装聚合物链的动力学。提出的WB模型基于以下假设:(i)聚合物不会被粘住,而只会被壁随机反射,并且(ii)缠结长度尺度以下的子链的行为类似于散装的那些,甚至在壁附近。使用WB模型,我们模拟了限制在狭缝通道中的纠缠聚合物链的动力学。结果表明,随着缝隙变窄,链条在垂直于壁的方向上被压缩,而在平行方向上扩展。另外,端到端矢量的弛豫时间增加,质心的扩散率降低。法向压缩是自然的限制作用,而膨胀是通过壁附近的钩挂过程引入的。趋势表明,松弛时间和扩散率取决于壁附近纠缠次数的增加而导致的摩擦力的增加,这也与PCN模型中的挂钩过程有关。这些结果是在PCN模型的假设范围内预期的。因此,提出的WB模型可以成功地再现壁约束对链的影响。

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