Liebetreu Maximilian, Ripoll Marisol, Likos Christos N
Faculty of Physics, University of Vienna, Boltzmanngasse 5, 1090 Vienna, Austria.
Forschungszentrum Jülich, Institute of Complex Systems, Theoretical Soft Matter and Biophysics, 52425 Jülich, Germany.
ACS Macro Lett. 2018 Apr 17;7(4):447-452. doi: 10.1021/acsmacrolett.8b00059. Epub 2018 Mar 22.
The behavior of unknotted and trefoil-knotted ring polymers under shear flow is here examined by means of mesoscopic simulations. In contrast to most polymers, ring polymers in a hydrodynamic solvent at high shear rates do not get shortened in the vorticity direction. This is a consequence of the backflow produced by the interaction of the sheared solvent with the end-free polymer topology. The extended structures of the ring in the vorticity-flow plane, when they are aligned in a constant velocity plane, favor ring contour fluctuations. This variety of conformations largely suppresses the tank-treading type of rotation with extended conformations in favor of the tumbling type of rotations, where stretched and collapsed conformations alternate. The extension of trefoil knots is also enhanced, so that the knots become delocalized. We anticipate that these effects, which disappear in the absence of hydrodynamic interactions, will have a crucial impact on the rheological properties of concentrated ring solutions, and will also influence the behavior of more complicated systems such as mixtures of polymers with different topologies.
本文通过介观模拟研究了无结和三叶结环状聚合物在剪切流作用下的行为。与大多数聚合物不同,在高剪切速率下处于流体动力学溶剂中的环状聚合物在涡度方向上不会缩短。这是由于剪切溶剂与无端基聚合物拓扑结构相互作用产生的回流所致。当环状聚合物在涡度流平面中的伸展结构在恒定速度平面中排列时,有利于环状聚合物轮廓的波动。这种多样的构象在很大程度上抑制了具有伸展构象的“坦克履带”式旋转,而有利于“翻滚”式旋转,即伸展和收缩构象交替出现。三叶结的伸展也会增强,从而使结变得离域。我们预计,这些在没有流体动力学相互作用时会消失的效应,将对浓环状聚合物溶液的流变性质产生关键影响,并且还会影响更复杂体系的行为,例如不同拓扑结构聚合物混合物的行为。