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Dynamics and rheology of wormlike micelles emerging from particulate computer simulations

机译:从颗粒计算机模拟中产生的蠕虫状胶束的动力学和流变学

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摘要

We perform coarse-grained computer simulations of solutions of semidilute wormlike micelles and study their dynamic and rheological properties, both in equilibrium and under shear flow. The simulation model is tailored to the study of relatively large time and length scales (micrometers and several milliseconds), while it still retains the specific mechanical properties of the individual wormlike micelles. The majority of the mechanical properties (persistence length, diameter, and elastic modulus of a single worm) is determined from more detailed atomistic molecular dynamics simulations, providing the link with the chemistry of the surfactants. The method is applied to the case of a solution containing 8% (by weight) erucyl bis(hydroxymethyl)methylammonium chloride (EHAC). Different scission energies ranging from 15.5kbT to 19.1kBT are studied, leading to both unentangled and entangled wormlike micelles. We find a decrease in the average contour length and an increase in the average breaking rate with increasing shear rate. In equilibrium, the decay of the shear relaxation modulus of the unentangled samples agrees with predictions based on a theory of breakable Rouse chains. Under shear flow, transient over- and undershoots are measured in the stress tensor components. At high shear rates we observe a steady-state shear stress proportional to 1/3, where is the shear rate. This is confirmed by our high shear rate experiments of real EHAC in a parallel-plate geometry.
机译:我们对半稀释蠕虫状胶束的溶液进行了粗粒度的计算机模拟,并研究了它们在平衡流动和剪切流动下的动力学和流变特性。该仿真模型是为研究相对较大的时间和长度范围(微米和几毫秒)而量身定制的,同时仍保留了各个蠕虫状胶束的特定机械性能。大多数机械性能(单个蠕虫的持续长度,直径和弹性模量)由更详细的原子分子动力学模拟确定,提供了与表面活性剂化学性质的联系。该方法适用于含有8重量%的芥酸双(羟甲基)甲基氯化铵(EHAC)的溶液的情况。研究了范围从15.5kbT到19.1kBT的不同断裂能量,导致无缠结和缠结的蠕虫状胶束。我们发现,随着剪切速率的增加,平均轮廓长度减小,平均断裂速率增加。在平衡状态下,未缠结样品的剪切松弛模量的衰减与基于易碎罗斯链理论的预测一致。在剪切流下,在应力张量分量中测量瞬态过冲和下冲。在高剪切速率下,我们观察到与1/3成比例的稳态剪切应力,其中为剪切速率。这通过我们在平行板几何形状中对真实EHAC的高剪切速率实验得到了证实。

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