论文标题
热力学一致的本构方程描述了流量下的聚合物脱离
A thermodynamically consistent constitutive equation describing polymer disentanglement under flow
论文作者
论文摘要
我们得出了一个热力学一致的框架,用于将纠缠动力学纳入流动聚合物熔体的本构方程。我们使用它将Ianniruberto-Marriccui的对流约束释放(CCR)动力学结合到Rolie-Poly模型的有限扩展版本中,还包括Giesekus模型中的各向异性迁移率。可逆动力学是从自由能中获得的,该自由能既描述了有限延伸的构象张量和沿链条纠缠的理想气体。耗散动力学产生了构象张量和纠缠的动力学方程,其耦合术语描述了剪切诱导的分离。构象张量的弛豫动力学遵循光泽和rolie-poly模型,并解释了仓库,缩回和CCR。我们建议,纠缠恢复的放松时间$τ_ν$与控制管中聚合物伸展的Rouse Time $τ_r$成正比。这与最近的分子动力学模拟相匹配,并且对应于整个聚合物各向异性之前放松纠缠数量,这在较长的回转时间$τ_d$上放松了。我们的模型表明,在步骤构技术实验中,声称在繁殖时间缓慢重新输入的签名可以解释为源自振兴动力学中各向异性的签名。
We derive a thermodynamically consistent framework for incorporating entanglement dynamics into constitutive equations for flowing polymer melts. We use this to combine the convected constraint release (CCR) dynamics of Ianniruberto-Marriccui into a finitely-extensible version of the Rolie-Poly model, and also include an anisotropic mobility as in the Giesekus model. The reversible dynamics are obtained from a free energy that describes both a finitely-extensible conformation tensor and an ideal gas of entanglements along the chain. The dissipative dynamics give rise to coupled kinetic equations for the conformation tensor and entanglements, whose coupling terms describe shear-induced disentanglement. The relaxation dynamics of the conformation tensor follow the GLaMM and Rolie-Poly models, and account for reptation, retraction and CCR. We propose that the relaxation time $τ_ν$ for entanglement recovery is proportional to the Rouse time $τ_R$ which governs polymer stretch within the tube. This which matches recent molecular dynamics simulations, and corresponds to relaxing the entanglement number before the entire polymer anisotropy has relaxed on the longer reptation time $τ_d$. Our model suggests that claimed signatures of slow re-entanglement on the reptation time in step-strain experiments may be interpreted as arising from anisotropies in reptation dynamics.