Dual Cold Crystallization Kinetics of Heterogeneous Amorphous Structure in Poly(<sub>L</sub>-lactide) upon Extensional Flow

Jie Zhang; Xin-Rui Gao; Zhi-Kang Ni; De-Zhuang Jia; Hao Lin; Hua-Dong Huang; Gan-Ji Zhong; Zhong-Ming Li

doi:10.1007/s10118-025-3331-9

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Dual Cold Crystallization Kinetics of Heterogeneous Amorphous Structure in Poly(_L-lactide) upon Extensional Flow

RESEARCH ARTICLE | Updated：2025-07-15

- Dual Cold Crystallization Kinetics of Heterogeneous Amorphous Structure in Poly(_L-lactide) upon Extensional Flow
- Dual Cold Crystallization Kinetics of Heterogeneous Amorphous Structure in Poly(_L-lactide) upon Extensional Flow
- 高分子科学（英文） 2025年43卷第7期页码：1231-1239
- Affiliations：
  
  a.College of Polymer Science and Engineering, National Key Laboratory of Advanced Polymer Materials, Sichuan University, Chengdu 610065, China
  b.West China Hospital/West China School of Medicine, Sichuan University, Chengdu 610041, China
- Author bio：
  
  ganji.zhong@scu.edu.cn (G.J.Z.)
  zmli@scu.edu.cn (Z.M.L.)
- Funds：
  
  This study was financially supported by the National Natural Science Foundation of China (Nos. U23A20583, 52033005, U21A2090, and 52173040), and Department of Science and Technology of Sichuan Province (No. 2024NSFTD0003). The authors also thank beamline BL16B1 at the Shanghai Synchrotron Radiation Facility for their kind support with the synchrotron WAXD and SAXS experiments.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3331-9.
- DOI：10.1007/s10118-025-3331-9
  中图分类号：
- 收稿：2025-01-24，
  
  修回：2025-02-23，
  
  录用：2025-03-05，
  
  网络首发：2025-05-06，
  
  纸质出版：2025-07-01
- Accepted：
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Zhang, J.; Gao, X. R.; Ni, Z. K.; Jia, D. Z.; Lin, H.; Huang, H. D.; Zhong, G. J.; Li, Z. M. Dual cold crystallization kinetics of heterogeneous amorphous structure in poly(_L-lactide) upon extensional flow. Chinese J. Polym. Sci. 2025, 43, 1231–1239 DOI: 10.1007/s10118-025-3331-9.

Jie Zhang, Xin-Rui Gao, Zhi-Kang Ni, et al. Dual Cold Crystallization Kinetics of Heterogeneous Amorphous Structure in Poly(_L-lactide) upon Extensional Flow[J]. Chinese Journal of Polymer Science, 2025, 43(7): 1231-1239. DOI: 10.1007/s10118-025-3331-9.
Zhang, J.; Gao, X. R.; Ni, Z. K.; Jia, D. Z.; Lin, H.; Huang, H. D.; Zhong, G. J.; Li, Z. M. Dual cold crystallization kinetics of heterogeneous amorphous structure in poly(_L-lactide) upon extensional flow. Chinese J. Polym. Sci. 2025, 43, 1231–1239 DOI: 10.1007/s10118-025-3331-9. DOI：

Jie Zhang, Xin-Rui Gao, Zhi-Kang Ni, et al. Dual Cold Crystallization Kinetics of Heterogeneous Amorphous Structure in Poly(_L-lactide) upon Extensional Flow[J]. Chinese Journal of Polymer Science, 2025, 43(7): 1231-1239. DOI: 10.1007/s10118-025-3331-9. DOI：

摘要

Poly(L-lactide) suffers from slow crystallization and poor heat-resistance

limiting applications. This study reveals that extensional flow induces a heterogeneous amorphous phase

enhancing oriented crystallization

and modulating α/α' polymorphism. A dual cold-crystallization behavior during heating is identified

advancing insights into poly(L-lactide)’s non-isothermal crystallization and heat-treatment strategy for improved performance.

Abstract

Poly(

-lactide) (PLLA)

a leading biodegradable polyester

has demonstrated potential as a sustainable alternative

owing to its excellent biodegradability and rigidity. However

their slow crystallization kinetics and poor heat resistance limit their application scope. Recent advances have highlighted that the combination of extensional flow and thermal fields can achieve toughness–stiffness balance

high transparency

and good heat resistance. However

the effect of extensional flow on the post-non-isothermal crystallization of PLLA during heating and the resulting crystalline texture remains unclear. In this study

PLLA with a heterogeneous amorphous structure and oriented polymorph was prepared by extensional flow. The effect of heterogeneous amorphous structures on non-isothermal crystallization kinetics during the heating process was studied by thermal analysis

polarized optical microscopy

infrared spectroscopy

and

ex situ

in situ

X-ray characterization. These results clearly illustrate that extensional flow enhances the formation of oriented crystalline structures

accelerates non-isothermal crystallization

and modulates the polymorphic composition of PLLA. Moreover

an unexpected dual cold-crystallization behavior is identified in ordered PLLA samples upon extensional flow

which is from the extensional flow-induced heterogeneous amorphous phase into

α'

phase (low-temperature peak) and the pristine amorphous phase into

phase (high-temperature peak). The extensional flow primarily promotes the formation of the more perfect

and

α'

phases

but has a negative e

ffect on the final content of

phase formed after cold crystallization and

α'-

-α

phase transformation. The findings of this work advance the understanding of PLLA non-isothermal crystallization after extensional flow and offer valuable guidance for high-performance PLLA upon heat treatment in practical processing.

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Keywords

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Dual Cold Crystallization Kinetics of Heterogeneous Amorphous Structure in Poly(L-lactide) upon Extensional Flow

Dual Cold Crystallization Kinetics of Heterogeneous Amorphous Structure in Poly(L-lactide) upon Extensional Flow

DOI：10.1007/s10118-025-3331-9

摘要

Abstract

关键词

Keywords

references

Dual Cold Crystallization Kinetics of Heterogeneous Amorphous Structure in Poly(_L-lactide) upon Extensional Flow

Dual Cold Crystallization Kinetics of Heterogeneous Amorphous Structure in Poly(_L-lactide) upon Extensional Flow