论文标题

伸展流动中环线性混合半二元溶液的动力学和流变学:建模和分子模拟

Dynamics and Rheology of Ring-Linear Blend Semidilute Solutions in Extensional Flow: Modeling and Molecular Simulations

论文作者

Young, Charles D., Zhou, Yuecheng, Schroeder, Charles M., Sing, Charles E.

论文摘要

我们使用布朗动力学(BD)模拟和单分子实验来研究拓扑约束和水动力相互作用对重叠浓度下环线性聚合物混合物溶液的动力学和流变学的影响。我们发现模拟与实验之间的一致性在溶液混合物中表现出较大的构象波动,包括​​在流动启动以及在稳态下滚动和坦克进入的延伸。环聚合物的波动随线性聚合物的混合分数而增加,并在环weissenberg数字$ \ textrm {wi} _r \ of tem上达到峰值。相反,纯溶液中的线性和环聚合物在关键的线圈 - 脱离weissenberg数字$ \ textrm {wi} = 0.5 $处的波动峰值。 BD模拟表明,流动启动的扩展是由于流动诱导的分子环线性聚合物钩子引起的,而稳态的波动依次由分子间流体动力学相互作用(HI)主导。这是由Bidisperse线性聚合物溶液混合物的模拟支持的,该材料在环和线性聚合物之间具有相似的轮廓长度的构象动力学趋势。与BD模拟相比,单分子实验显示出较大的波动,这可能是因为在具有更强拓扑约束的较高分子量聚合物上进行实验。为此,我们提出了对拓扑相互作用和分子间HI对半硅环线性聚合物混合溶液动力学的影响的理解。

We use Brownian dynamics (BD) simulations and single molecule experiments to investigate the influence of topological constraints and hydrodynamic interactions on the dynamics and rheology of solutions of ring-linear polymer blends at the overlap concentration. We find agreement between simulation and experiment in that rings in solution blends exhibit large conformational fluctuations, including extension overshoots in the startup of flow and tumbling and tank-treading at steady state. Ring polymer fluctuations increase with blend fraction of linear polymers and are peaked at a ring Weissenberg number $\textrm{Wi}_R \approx 1.5$. On the contrary, linear and ring polymers in pure solutions show a peak in fluctuations at the critical coil-stretch Weissenberg number $\textrm{Wi} = 0.5$. BD simulations show that extension overshoots on startup of flow are due to flow-induced intermolecular ring-linear polymer hooks, whereas fluctuations at steady state are dominated by intermolecular hydrodynamic interactions (HI). This is supported by simulations of bidisperse linear polymer solution blends, which show similar trends in conformational dynamics between rings and linear polymers with a matched contour length. Compared to BD simulations, single molecule experiments show quantitatively larger fluctuations, which could arise because experiments are performed on higher molecular weight polymers with stronger topological constraints. To this end, we have advanced the understanding of the effects of topological interactions and intermolecular HI on the dynamics of semidilute ring-linear polymer blend solutions.

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