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Relationship between melting behavior and morphological changes of semicrystalline polymers

Evidence from the case of poly(hexamethylene succinate)

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Abstract

The present study on the case of poly(hexamethylene succinate) is to provide a basis for a better understanding of the subtle relationship between melting behavior and morphological changes of semicrystalline polymers. The melting behavior and morphological changes of poly(hexamethylene succinate) during both isothermal secondary crystallization and annealing processes were investigated by DSC and SAXS. DSC results showed that, with increasing crystallization time or annealing time, the melting endotherm continuously shifted to higher temperature, which suggested that some minor structural or morphological changes must occur. However, almost no changes at all on the crystal thickness were observed from SAXS measurements. The observed evidence confirmed that the increase in the melting temperature is not attributed to crystal thickening but crystal perfection. More exactly, the rearrangement and smoothing of tie molecules at the folding surface result in the reduction of the fold surface free energy, which dominantly contributes to the increase in the melting peak temperature. The origin of the new endothermic peak observed after annealing at elevated temperature was also discussed. TMDSC results indicated that the annealing peak resulted from the enthalpy relaxation and devitrification transition of rigid amorphous fraction formed by the driving force of thermodynamic nonequilibrium, rather than usually regarded as the melting of thin lamellae or imperfect crystals formed by annealing secondary crystallization.

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Acknowledgements

This work was financially supported by the National Program on Key Basic Research Program of China (973 Program No. 2015CB654700 (2015CB654701)), the National Science Foundation of China (No. U1508204) and the Fundamental Research Funds for the Central Universities (No. DUT16QY38).

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Authors and Affiliations

  1. State Key Laboratory of Fine Chemicals, Department of Polymer Science and Materials, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, People’s Republic of China

    Zhiyong Wei, Yang Yu, Cheng Zhou, Xuefei Leng & Yang Li

  2. Beijing National Laboratory for Molecular Sciences, Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, People’s Republic of China

    Liuchun Zheng

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  1. Zhiyong Wei
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  2. Yang Yu
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  3. Cheng Zhou
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Wei, Z., Yu, Y., Zhou, C. et al. Relationship between melting behavior and morphological changes of semicrystalline polymers. J Therm Anal Calorim 129, 777–787 (2017). https://doi.org/10.1007/s10973-017-6255-y

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