Nonmonotonic Stress Overshoot in Entangled Polymer Melts under Two-step Shear

Yong-Jin Ruan; Ya-Qing Chang; Jiang-Yang Mo; Bai-Cheng Mei

doi:10.1007/s10118-025-3481-9

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Nonmonotonic Stress Overshoot in Entangled Polymer Melts under Two-step Shear

RESEARCH ARTICLE | Updated：2026-01-13

- Nonmonotonic Stress Overshoot in Entangled Polymer Melts under Two-step Shear
- Nonmonotonic Stress Overshoot in Entangled Polymer Melts under Two-step Shear
- Chinese Journal of Polymer Science 2026年44卷第1期页码：268-277
- Affiliations：
  
  a.State Key Laboratory of Polymer Science and Technology, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  b.School of Science, Changchun Institute of Technology, Changchun 130012, China
  c.Shandong Key Laboratory of Biophysics, Institute of Biophysics, Dezhou University, Dezhou 253023, China
  d.Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
- Author bio：
  
  yjruan@ciac.ac.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 22341303, 22103079, and 22503003) and the Shandong Provincial Natural Science Foundation (No. ZR2023QB232). B.M. acknowledges the Beijing Institute of Technology Research Fund Program for Young Scholars (No. RCPT-6120250009).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3481-9.
- DOI：10.1007/s10118-025-3481-9
  中图分类号：
- 收稿：2025-09-12，
  
  录用：2025-10-13，
  
  网络首发：2025-12-18，
  
  纸质出版：2026-01-15
- Accepted：
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Ruan, Y. J.; Chang, Y. Q.; Mo, J. Y.; Mei, B. C. Nonmonotonic stress overshoot in entangled polymer melts under two-step shear. Chinese J. Polym. Sci. 2026, 44, 268–277

Yong-Jin Ruan, Ya-Qing Chang, Jiang-Yang Mo, et al. Nonmonotonic Stress Overshoot in Entangled Polymer Melts under Two-step Shear[J]. Chinese Journal of Polymer Science, 2026, 44(1): 268-277.
Ruan, Y. J.; Chang, Y. Q.; Mo, J. Y.; Mei, B. C. Nonmonotonic stress overshoot in entangled polymer melts under two-step shear. Chinese J. Polym. Sci. 2026, 44, 268–277 DOI： 10.1007/s10118-025-3481-9.

Yong-Jin Ruan, Ya-Qing Chang, Jiang-Yang Mo, et al. Nonmonotonic Stress Overshoot in Entangled Polymer Melts under Two-step Shear[J]. Chinese Journal of Polymer Science, 2026, 44(1): 268-277. DOI： 10.1007/s10118-025-3481-9.

摘要

Molecular dynamics simulations uncover the microscopic origin of the second stress overshoot

2max

in two-step shear. The nonmonotonic

2max

results from coupled variations of tube orientation and entanglement number

highlighting the need for a unified theoretical framework.

Abstract

Shear stress overshoot in entangled polymer rheology is a hallmark of transient dynamics

but its microscopic origin remains under debate. Using molecular dynamics simulations

we investigate a two-step shear protocol consisting of successive startup shears separated by a waiting period

with the first shear interrupted before the overshoot. In the homogeneous flow

the GLaMM theory captures the stress response during the first shear

but fails to reproduce the nonmonotonic dependence of the second stress overshoot (

2max

) on the waiting time. Contrary to the prediction of a nonmonotonic normal stress component

during the waiting period

our simulations show that

like the tube segment orientation (

)

the contour length of the primitive chain (

)

and the entanglement number per chain (

)

relaxes monotonically toward equilibrium. At the strain corresponding to

2max

both the tube segment orientation and the entanglement number per chain exhibit a nonmonotonic dependence on the waiting time that closely mirrors the behavior of

2max

indicating that both factors play significant roles in governing

2max

. Our findings are consistent with the interpretation of Ianniruberto and Marrucci [

ACS Macro. Lett.

2014

552

]

for orientation effects and with the viewpoint of Wang

et al

. [

Macromolecules

2013

3147

]

for entanglement effects

although the two explanations are rooted in distinct physical pictures. These results provide new insights into the stress responses of entanglement polymer fluids and underscore the need for a more unified theoretical framework.

关键词

Keywords

references

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