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Effects of urea and glycerol mixture on morphology and molecular mobility in thermoplastic starch/montmorillonite-type nanofiller composites studied using XRD and NMR

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Abstract

Starch-based polymer systems have attracted a great deal of interest as a potential alternative to conventional plastics for packaging applications. Mechanical and thermal properties of these systems strongly depend on their local structure and molecular dynamics. In this study, the effects of urea and glycerol mixtures on structure and molecular mobility in thermoplastic starch/montmorillonite-type nanofiller composites were investigated using X-ray diffraction and nuclear magnetic resonance spectroscopy (27Al, 13C, and 1H). The X-ray diffraction patterns indicate intercalation of plasticizer molecules and starch chains inside the montmorillonite particles in all composites. The urea crystallites in most urea-containing composites and starch retrogradation in all composites with glycerol-plasticized starch were also deduced from X-ray diffractions. Changes in the 27Al NMR spectra measured on the studied samples were related to the amount of plasticizer molecules available for interaction with exfoliated and reassembled MMT platelets. The 1H NMR spectra shapes indicate that increased glycerol content results in greater molecular mobility, which causes starch retrogradation during sample ageing, inferred from T1(13C) spin–lattice relaxation times and the change in C1 resonance shape in the 13C NMR spectra respectively. Starch retrogradation was not detected in the composites with urea-plasticized starch due to their rigid structure reflected in relatively long T1(13C) spin–lattice relaxation times.

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Acknowledgements

This research was supported by the Slovak Grant Agency through VEGA project no. 1/0751/21.

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Authors and Affiliations

  1. Department of Physics, Faculty of Electrical Engineering and Informatics, Technical University of Košice, Park Komenského 2, 042 00, Košice, Slovakia

    Anton Baran, Oľga Fričová, Peter Vrábel, Mária Hutníková & Mária Kovaľaková

  2. Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 842 36, Bratislava, Slovakia

    Hamed Peidayesh & Ivan Chodák

  3. Institute of Metallurgy, Faculty of Materials, Metallurgy and Recycling, Technical University of Košice, Letná 9, 042 00, Košice, Slovakia

    Ľuboš Popovič

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  1. Anton Baran
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Baran, A., Fričová, O., Vrábel, P. et al. Effects of urea and glycerol mixture on morphology and molecular mobility in thermoplastic starch/montmorillonite-type nanofiller composites studied using XRD and NMR. J Polym Res 29, 257 (2022). https://doi.org/10.1007/s10965-022-03110-6

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