4.5 Article

A Unified Thermodynamic Model of Flow-induced Crystallization of Polymer

Journal

CHINESE JOURNAL OF POLYMER SCIENCE
Volume 39, Issue 11, Pages 1489-1495

Publisher

SPRINGER
DOI: 10.1007/s10118-021-2622-z

Keywords

Flow-induced crystallization; Unified thermodynamic model; Flow-induced chain orientation

Funding

  1. National Natural Science Foundation of China [51890872, 51633009]
  2. National Key R&D Program of China [2018YFB0704200]

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The research presents a unified thermodynamic model of flow-induced crystallization of polymer, which considers conformational entropy reduction, flow-induced chain orientation, interaction of ordered segments, and free energy contribution of crystal nucleus and morphology. It clarifies the determining parameters of critical crystal nucleus size and explains the acceleration of nucleation, emergence of precursor, and different crystal morphologies induced by flow.
We propose a unified thermodynamic model of flow-induced crystallization of polymer (uFIC), which incorporates not only the conformational entropy reduction but also the contributions of flow-induced chain orientation, the interaction of ordered segments, and the free energy of crystal nucleus and crystal morphology. Specifically, it clarifies the determining parameters of the critical crystal nucleus size, and is able to account for the acceleration of nucleation, the emergence of precursor, different crystal morphologies and structures induced by flow. Based on the nucleation barrier under flow, we analyze at which condition precursor may occur and how flow affects the competition among different crystal forms such as orthorhombic and hexagonal phases of polyethylene. According to the uFIC model, the different crystal morphologies and structures in the flow-temperature space have been clarified, which give a good agreement with experiments of FIC.

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