The startup and steady shear flow properties of an entangled, monodisperse polyethylene liquid (C1000H2002) were investigated via virtual experimentation using nonequilibrium molecular dynamics. The simulations revealed a multifaceted dynamical response of the liquid to the imposed flow field in which entanglement loss leading to individual molecular rotation plays a dominant role in dictating the bulk rheological response at intermediate and high shear rates. Under steady shear conditions, four regimes of flow behavior were evident. In the linear viscoelastic regime (), orientation of the reptation tube network dictates the rheological response. Within the second regime (), the tube segments begin to stretch mildly and the molecular entanglement network begins to relax as flow strength increases; however, the dominant relaxation mechanism in this region remains the orientation of the tube segments. In the third regime (), molecular disentangling accelerates and tube stretching dominates the response. Additionally, the rotation of molecules become a significant source of the overall dynamic response. In the fourth regime (), the entanglement network deteriorates such that some molecules become almost completely unraveled, and molecular tumbling becomes the dominant relaxation mechanism. The comparison of transient shear viscosity, , with the dynamic responses of key variables of the tube model, including the tube segmental orientation, , and tube stretch, , revealed that the stress overshoot and undershoot in steady shear flow of entangled liquids are essentially originated and dynamically controlled by the component of the tube orientation tensor, rather than the tube stretch, over a wide range of flow strengths.
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机译:通过使用非平衡分子动力学的虚拟实验,研究了纠缠的单分散聚乙烯液体(C1000H2002)的启动和稳态剪切流动特性。模拟揭示了液体对施加流场的多方面动力学响应,其中导致单个分子旋转的缠结损失在决定中等和高剪切速率下的总体流变响应中起着主导作用。在稳定剪切条件下,明显表现出四种流动特性。在线性粘弹性状态下(<数学xmlns:mml =“ http://www.w3.org/1998/Math/MathML” id =“ mm1”溢出=“ scroll”> γ mi> ˙ mo> mover> / mo> τ mi> d mi > − mo> 1 mn> mrow> msubsup> mrow> mrow> math>),the管网络的方向决定了流变反应。在第二种机制内(展开▼