New Kinetics Equation for Stress Relaxation of Semi-crystalline Polymers below Glass Transition Temperature

Cheng Zhang; Li-Hai Cai; Bao-Hua Guo; Bing Miao; Jun Xu

doi:10.1007/s10118-022-2749-6

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New Kinetics Equation for Stress Relaxation of Semi-crystalline Polymers below Glass Transition Temperature

RESEARCH ARTICLE | Updated：2022-11-16

- New Kinetics Equation for Stress Relaxation of Semi-crystalline Polymers below Glass Transition Temperature
- New Kinetics Equation for Stress Relaxation of Semi-crystalline Polymers below Glass Transition Temperature
- 高分子科学（英文版） 2022年40卷第12期页码：1662-1669
- Affiliations：
  
  a.Advanced Materials Laboratory of Ministry of Education, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
  b.Tsinghua Innovation Center in Dongguan, Dongguan 523808, China
  c.Center of Materials Science and Optoelectronics Engineering, College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China
- Author bio：
  
  jun-xu@mail.tsinghua.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 21873054, 21774131 and 21544007). B. H. Guo thanks the National Natural Science Foundation of China (Nos. U1862205 and 51673110) and China Petroleum & Chemical Corporation for financial support.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-022-2749-6.
- DOI：10.1007/s10118-022-2749-6
  中图分类号：
- 收稿：2022-01-25，
  
  修回：2022-3-18，
  
  录用：2022-4-8，
  
  网络首发：2022-06-28，
  
  纸质出版：2022-12-01
- Accepted：
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Zhang, C.; Cai, L. H.; Guo, B. H.; Miao, B.; Xu, J. New kinetics equation for stress relaxation of semi-crystalline polymers below glass transition temperature. Chinese J. Polym. Sci. 2022, 40, 1662–1669

Cheng Zhang, Li-Hai Cai, Bao-Hua Guo, et al. New Kinetics Equation for Stress Relaxation of Semi-crystalline Polymers below Glass Transition Temperature[J]. Chinese Journal of Polymer Science, 2022, 40(12): 1662-1669.
Zhang, C.; Cai, L. H.; Guo, B. H.; Miao, B.; Xu, J. New kinetics equation for stress relaxation of semi-crystalline polymers below glass transition temperature. Chinese J. Polym. Sci. 2022, 40, 1662–1669 DOI： 10.1007/s10118-022-2749-6.

Cheng Zhang, Li-Hai Cai, Bao-Hua Guo, et al. New Kinetics Equation for Stress Relaxation of Semi-crystalline Polymers below Glass Transition Temperature[J]. Chinese Journal of Polymer Science, 2022, 40(12): 1662-1669. DOI： 10.1007/s10118-022-2749-6.

摘要

A new kinetics equation is proposed to quantitatively describe the two-step mechanism of stress relaxation in Nylon 1010

which consists of stress biased Eyring-like local activation at short time scale and a cooperative excitation process with the excitation size proportional to the reciprocal of stress at long time scale.

Abstract

The stress relaxation of semi-crystalline nylon 1010 cannot be fitted by the Kohlrausch-Williams-Watts formula when the experiments were performed at pre-yielding regime below the glass transition temperature. We study this problem and identify the two-step mechanism of stress relaxation. At short time scale

relaxation is fast

dominated by stress biased thermal fluctuation with a fixed short-range length scale (activation volume). At long time scale

relaxation is slow due to the emergence of a cooperative long-range length scale determined by the stress fluctuation. The cooperative length scale is proportional to the reciprocal of stress and the amplitude of stress fluctuation is the product of stress and activation volume. Based on this two-step mechanism

we propose a new kinetics equation to capture the stress relaxation effectively

where the short time relaxation is described by an Eyring-like local activation and the long-time relaxation is captured by a cooperative excitation process resorting to an extension from the random first order transition theory. Our equation fits the experimental data well and can serve as a model to guide the related experiments of relaxation processes in crystalline solids.

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references

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