链多分散性对无序聚合物网络弹性的影响。

Effect of Chain Polydispersity on the Elasticity of Disordered Polymer Networks.

作者信息

Sorichetti Valerio, Ninarello Andrea, Ruiz-Franco José M, Hugouvieux Virginie, Kob Walter, Zaccarelli Emanuela, Rovigatti Lorenzo

机构信息

Laboratoire de Physique Théorique et Modéles Statistiques (LPTMS), CNRS, Université Paris-Saclay, F-91405 Orsay, France.

Laboratoire Charles Coulomb (L2C), University of Montpellier, CNRS, F-34095 Montpellier, France.

出版信息

Macromolecules. 2021 Apr 27;54(8):3769-3779. doi: 10.1021/acs.macromol.1c00176. Epub 2021 Apr 14.

Abstract

Due to their unique structural and mechanical properties, randomly cross-linked polymer networks play an important role in many different fields, ranging from cellular biology to industrial processes. In order to elucidate how these properties are controlled by the physical details of the network (e.g., chain-length and end-to-end distributions), we generate disordered phantom networks with different cross-linker concentrations and initial densities ρ and evaluate their elastic properties. We find that the shear modulus computed at the same strand concentration for networks with the same , which determines the number of chains and the chain-length distribution, depends strongly on the preparation protocol of the network, here controlled by ρ. We rationalize this dependence by employing a generic stress-strain relation for polymer networks that does not rely on the specific form of the polymer end-to-end distance distribution. We find that the shear modulus of the networks is a nonmonotonic function of the density of elastically active strands, and that this behavior has a purely entropic origin. Our results show that if short chains are abundant, as it is always the case for randomly cross-linked polymer networks, the knowledge of the exact chain conformation distribution is essential for correctly predicting the elastic properties. Finally, we apply our theoretical approach to literature experimental data, qualitatively confirming our interpretations.

摘要

由于其独特的结构和力学性能,随机交联聚合物网络在从细胞生物学到工业过程等许多不同领域中发挥着重要作用。为了阐明这些性能是如何由网络的物理细节(例如链长和端到端分布)控制的,我们生成了具有不同交联剂浓度和初始密度ρ的无序虚拟网络,并评估它们的弹性性能。我们发现,对于具有相同的网络,在相同链浓度下计算的剪切模量,它决定了链的数量和链长分布,强烈依赖于网络的制备方案,这里由ρ控制。我们通过采用一种不依赖于聚合物端到端距离分布具体形式的聚合物网络通用应力-应变关系来解释这种依赖性。我们发现网络的剪切模量是弹性活性链密度的非单调函数,并且这种行为具有纯粹的熵起源。我们的结果表明,如果短链丰富,这对于随机交联聚合物网络来说总是如此,那么精确的链构象分布知识对于正确预测弹性性能至关重要。最后,我们将我们的理论方法应用于文献实验数据,定性地证实了我们的解释。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11af/8154883/926e4e45f627/ma1c00176_0002.jpg

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