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Self-Similar Conformations and Dynamics in Entangled Melts and Solutions of Nonconcatenated Ring Polymers

机译:纠缠熔体的自相似构象和动力学以及非连接环聚合物的溶液

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摘要

A scaling model of self-similar conformations and dynamics of nonconcatenated entangled ring polymers is developed. Topological constraints force these ring polymers into compact conformations with fractal dimension df = 3 that we call fractal loopy globules (FLGs). This result is based on the conjecture that the overlap parameter of subsections of rings on all length scales is the same and equal to the Kavassalis–Noolandi number OKN ≈ 10–20. The dynamics of entangled rings is self-similar and proceeds as loops of increasing sizes are rearranged progressively at their respective diffusion times. The topological constraints associated with smaller rearranged loops affect the dynamics of larger loops through increasing the effective friction coefficient but have no influence on the entanglement tubes confining larger loops. As a result, the tube diameter defined as the average spacing between relevant topological constraints increases with time t, leading to “tube dilation”. Analysis of the primitive paths in molecular dynamics simulations suggests a complete tube dilation with the tube diameter on the order of the time-dependent characteristic loop size. A characteristic loop at time t is defined as a ring section that has diffused a distance equal to its size during time t. We derive dynamic scaling exponents in terms of fractal dimensions of an entangled ring and the underlying primitive path and a parameter characterizing the extent of tube dilation. The results reproduce the predictions of different dynamic models of a single nonconcatenated entangled ring. We demonstrate that traditional generalization of single-ring models to multi-ring dynamics is not self-consistent and develop a FLG model with self-consistent multi-ring dynamics and complete tube dilation. This selfconsistent FLG model predicts that the longest relaxation time of nonconcatenated entangled ring polymers scales with their degree of polymerization N as τrelax ~ N7/3, while the diffusion coefficient of these rings scales as D3d ~ N−5/3. For the entangled solutions and melts of rings, we predict power law stress relaxation function G(t) ~ t−3/7 at t < τrelax without a rubbery plateau and the corresponding viscosity scaling with the degree of polymerization N as η ~ N4/3. These theoretical predictions are in good agreement with recent computer simulations and are consistent with experiments of melts of nonconcatenated entangled rings.
机译:建立了自相似构象和非串联缠结环聚合物动力学的比例模型。拓扑约束迫使这些环状聚合物形成分形维数df = 3的紧凑构象,我们称其为分形环状小球(FLG)。该结果基于这样的推测,即在所有长度尺度上,环的分段的重叠参数都相同,并且等于Kavassalis-Noolandi数OKN≈10-20。纠缠环的动力学是自相似的,并且随着尺寸增大的环在其各自的扩散时间逐渐重新排列而进行。与较小的重排环路相关的拓扑约束通过增加有效摩擦系数来影响较大环路的动力学,但对限制较大环路的纠缠管没有影响。结果,定义为相关拓扑约束之间的平均间隔的管直径随时间t增大,从而导致“管扩张”。在分子动力学模拟中对原始路径的分析表明,管的完全扩张与管的直径在时间相关的特征环尺寸上有关。将时间t处的特征性循环定义为在时间t内扩散了与其大小相等的距离的环形部分。我们根据纠缠环的分形维数和基础原始路径以及表征管扩张程度的参数得出动态缩放指数。结果再现了单个非串联纠缠环的不同动力学模型的预测。我们证明了传统的将单环模型推广到多环动力学不是自洽的,并开发了具有自洽的多环动力学和完整的管扩张的FLG模型。这种自洽的FLG模型预测,未连接的纠缠环聚合物的最长弛豫时间随其聚合度N的变化而变化,其聚合度N为τrelax〜N 7/3 ,而这些环的扩散系数则随着D3d〜N < sup> −5/3 。对于环的纠缠解和熔体,我们预测了在t <τrelax处无橡胶平稳期的幂律应力松弛函数G(t)〜t −3/7 ,且相应的粘度标度为聚合N为η N 4/3 。这些理论预测与最近的计算机模拟非常吻合,并且与非连接纠缠环的熔体实验一致。

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