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基于非平衡态热力学的简单、准确且用户友好的缠结聚合物熔体和溶液流变学微分本构模型。

Simple, Accurate and User-Friendly Differential Constitutive Model for the Rheology of Entangled Polymer Melts and Solutions from Nonequilibrium Thermodynamics.

作者信息

S Stephanou Pavlos, Ch Tsimouri Ioanna, G Mavrantzas Vlasis

机构信息

Department of Chemical Engineering, Cyprus University of Technology, 30 Archbishop Kyprianou Str., Limassol 3036, Cyprus.

Department of Materials, ETH Zürich, CH-8093 Zürich, Switzerland.

出版信息

Materials (Basel). 2020 Jun 26;13(12):2867. doi: 10.3390/ma13122867.

Abstract

In a recent reformulation of the Marrucci-Ianniruberto constitutive equation for the rheology of entangled polymer melts in the context of nonequilibrium thermodynamics, rather large values of the convective constraint release parameter had to be used in order for the model not to violate the second law of thermodynamics. In this work, we present an appropriate modification of the model, which avoids the splitting of the evolution equation for the conformation tensor into an orientation and a stretching part. Then, thermodynamic admissibility simply dictates that ≥ 0, thus allowing for more realistic values of to be chosen. Moreover, and in view of recent experimental evidence for a transient stress undershoot (following the overshoot) at high shear rates, whose origin may be traced back to molecular tumbling, we have incorporated additional terms into the model accounting, at least in an approximate way, for non-affine deformation through a slip parameter . Use of the new model to describe available experimental data for the transient and steady-state shear and elongational rheology of entangled polystyrene melts and concentrated solutions shows close agreement. Overall, the modified model proposed here combines simplicity with accuracy, which renders it an excellent choice for managing complex viscoelastic fluid flows in large-scale numerical calculations.

摘要

在非平衡热力学背景下,对马尔鲁奇 - 亚尼鲁贝托缠结聚合物熔体流变学本构方程的最新重新表述中,为使模型不违反热力学第二定律,不得不使用相当大的对流约束释放参数值。在这项工作中,我们提出了该模型的一种适当修正,它避免了将构象张量的演化方程拆分为取向部分和拉伸部分。然后,热力学可容许性简单地规定(\xi \geq 0),从而允许选择更现实的(\xi)值。此外,鉴于最近有实验证据表明在高剪切速率下存在瞬态应力下冲(跟随上冲),其起源可追溯到分子翻滚,我们已将额外的项纳入模型,至少以近似方式通过滑移参数(\beta)考虑非仿射变形。使用新模型来描述缠结聚苯乙烯熔体和浓溶液的瞬态和稳态剪切及拉伸流变学的现有实验数据显示出密切的一致性。总体而言,这里提出的修正模型将简单性与准确性相结合,这使其成为在大规模数值计算中处理复杂粘弹性流体流动的绝佳选择。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6354/7345944/9dafa147a918/materials-13-02867-g001.jpg

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