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A Synchrotron in situ X-ray Study on the Multiple Melting Behaviors of Isomorphous Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P(HB-co-HV)) with Middle HV Content

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Abstract

The multiple endothermic peaks without observable recrystallization phenomenon of isomorphous poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB-co-HV)] with the middle HV content of 19.4 mol% and 28.7 mol% were confirmed by differential scanning calorimetry (DSC), and the evolutions of crystal structure and lamellar morphology in the heating and melting process were tracked by in situ synchrotron wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS) techniques. The emergence of asymmetric features of both the diffraction peaks and scattering curves indicates the coexistence of different lamellar crystals with varied unit cell parameters. Based on the in situ WAXD and SAXS measurements, we calculated the evolutions of the unit cell parameters a and b as well as the long period and lamellar thickness upon heating. The comparative analysis of WAXD and SAXS data confirms that the multiple endothermic peaks of P(HB-co-19.4%HV) and P(HB-co-28.7%HV) result from the melting of different lamellae rather than the melting/recrystallization. The thinner, unstable uniform lamellae with HV counits total inclusion melt first and the thicker, stable sandwich lamellae with HV counits partial inclusion melt last. In addition, the large second melting peak in P(HB-co-19.4%HV), differing from that of samples with HV content of 28.7 mol% and 36.2 mol%, is due to the unique state of HV content leading to a transition of sandwich lamellae to uniform lamellae. The present study establishes the relationship between the different lamellae structure and multiple melting behaviors of isomorphous copolymer.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Nos. 51973097 and 51773101). We thank Shanghai Synchrotron Radiation Facility (SSRF) for supporting the WAXD and SAXS measurements.

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  1. Ningbo Key Laboratory of Specialty Polymers, State Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, 315211, China

    Hao Zhu, You Lv, Dan Shi, Yi-Guo Li, Wei-Jun Miao & Zong-Bao Wang

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  1. Hao Zhu
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  3. Dan Shi
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Correspondence to Zong-Bao Wang.

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A Synchrotron in situ X-ray Study on the Multiple Melting Behaviors of lsomorphous Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P(HB-co-HV)) with Middle HV Content

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Zhu, H., Lv, Y., Shi, D. et al. A Synchrotron in situ X-ray Study on the Multiple Melting Behaviors of Isomorphous Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P(HB-co-HV)) with Middle HV Content. Chin J Polym Sci 38, 1015–1024 (2020). https://doi.org/10.1007/s10118-020-2427-5

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