Physical gelation and macromolecular mobility of sustainable polylactide during isothermal crystallization |
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| Authors: | Huagao Fang Qizheng Xie Haibing Wei Pei Xu Yunsheng Ding |
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| Institution: | Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Provincial Key Laboratory of Advanced Functional Materials and Devices, Hefei University of Technology, Hefei, Anhui Province, People's Republic of China |
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| Abstract: | The mobility of free macromolecular chains is of importance to the growth of crystallites in a crystallizing sustainable polylactide (PLA), which was scarcely explored by rheology. In this study, the time‐resolved rheological properties for PLA during isothermal crystallization were investigated first, showing that the storage and loss modulus experience 2–3 decades of increase. The Avrami analysis reveals that the crystallization kinetics in rheological measurement protocol follows the homogeneous nucleation and three‐dimensional growth mechanism. The linear viscoelastic properties in the vicinity of physical gelation point were then studied at the inverse quenching temperature of 165 °C. The results show that physical gelation occurs when the critical absolute crystallinity reaches 13% as determined by the rheological method. Relaxation time spectra reveal that the interfacial relaxation is greatly retarded but the presence of growing spherulites possesses little constraint on the mobility of free chains in matrix especially before physical gelation point. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1235–1244 |
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| Keywords: | Avrami analysis crystallization liquid– solid transition relaxation viscoelastic properties |
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