支化高分子熔体流变本构模型的研究进展

熊钟强; 俞炜

doi:10.14028/j.cnki.1003-3726.2024.24.271

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支化高分子熔体流变本构模型的研究进展

专论 | 更新时间：2025-01-23

- 支化高分子熔体流变本构模型的研究进展
- Progress on Rheological Constitutive Models for Branched Polymer Melts
- 高分子通报 2025年38卷第2期页码：265-283
- 作者机构：
  
  1.中国科学院大学温州研究院，温州 325000
  2.上海交通大学化学化工学院，流变学研究所，上海 200240
- 作者简介：
  
  *熊钟强，E-mail: zhongqiangxiong@ucas.ac.cn；俞炜，E-mail: wyu@sjtu.edu.cn
- 基金信息：
  
  国家自然科学基金(52333001;12247174;22403021)
- DOI：10.14028/j.cnki.1003-3726.2024.24.271
  中图分类号：
- 收稿日期：2024-09-16，
  
  录用日期：2024-11-07，
  
  网络出版日期：2024-12-18，
  
  纸质出版日期：2025-02-20
- 稿件说明：
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熊钟强, 俞炜. 支化高分子熔体流变本构模型的研究进展. 高分子通报, 2025, 38(2), 265–283

Xiong, Z. Q.; Yu, W. Progress on rheological constitutive models for branched polymer melts. Polym. Bull. (in Chinese), 2025, 38(2), 265–283
熊钟强, 俞炜. 支化高分子熔体流变本构模型的研究进展. 高分子通报, 2025, 38(2), 265–283 DOI： 10.14028/j.cnki.1003-3726.2024.24.271.

Xiong, Z. Q.; Yu, W. Progress on rheological constitutive models for branched polymer melts. Polym. Bull. (in Chinese), 2025, 38(2), 265–283 DOI： 10.14028/j.cnki.1003-3726.2024.24.271.

摘要

分子本构模型的构建是理解微结构动力学和宏观流变行为关系的重要途径。从非平衡态统计物理的角度出发，流变学本构模型的研究已经取得显著的进展。计算的分子结构包括但不限于线型链、星型链、H型链、绒球链、梳型链、瓶刷链、树型链、随机支化链等。本文综述的高分子流变本构模型，虽然由于历史原因，模型之间的命名并不相关，但其解决的问题是一脉相承，由简入繁的。我们将从Onsager变分原理的角度开始，介绍每个线性黏弹性模型针对的问题和假设，使得模型发展的路径呈现得更加清晰。线性黏弹性模型的成功，使我们能够深刻地认识结构性能之间的关系，为非线性黏弹性模型的构建打下坚实的基础。通过结合线性黏弹性谱和非线性松弛机理，构建的非线性模型能够在实验中的振荡剪切、启动剪切/拉伸、阶跃剪切等流变测试模式下得到很好的验证。同时也由于分子间动态相互作用和非线性耦合的复杂性等问题，对于链吸附、动态反应、滑环滑动等结构的动态性，模型的构建目前仍然存在很大的挑战。

Abstract

The construction of molecular constitutive models is an important way to understand the relationship between microstructure dynamics and macroscopic rheological behavior. From the perspective of non-equilibrium statistical physics

significant p

rogress has been made in the study of rheological constitutive models. The calculated molecular structures include but are not limited to linear chains

star chains

H chains

pom-pom chains

comb chains

bottle-brush chains

tree-like chains

and randomly branched chains

etc

. The rheological constitutive models of polymers reviewed in this article

although the names of these models are not related due to historical reasons

models themselves are developed from simplicity to complexity. We will start from the perspective of the Onsager variational principle to introduce the problems and assumptions addressed by each linear viscoelastic model

in order to present the development path of the model more clearly. The success of linear viscoelastic models enables us to deeply understand how structure affects performance

laying a solid foundation for the construction of nonlinear viscoelastic models. By combining linear viscoelastic spectra with nonlinear relaxation mechanism

the constructed nonlinear model can be well validated in rheological testing

such as oscillatory shear

start-up shear/extension

and step shear in experiments. However

due to the complexity of dynamic intermolecular interactions and nonlinear coupling

there are still significant challenges in constructing models for the dynamics of structures

such as chain adsorption

dynamic reactions

and slide-ring sliding.

关键词

Keywords

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