Dielectric relaxation of polymer networks built from macromolecules with dipole moment directed along the end-to-end chain vector

Authors

  • Yuli Ya. Gotlib,

    Corresponding author
    1. Institute of Macromolecular Compounds of the Russian Academy of Sciences, Bolshoi Prospect 31, St. Petersburg, 199004, Russia
    • Institute of Macromolecular Compounds of the Russian Academy of Sciences, Bolshoi Prospect 31, St. Petersburg, 199004, Russia
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  • Andrei A. Gurtovenko

    1. Institute of Macromolecular Compounds of the Russian Academy of Sciences, Bolshoi Prospect 31, St. Petersburg, 199004, Russia
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Abstract

The dielectric relaxation properties are considered for polymer networks built from polar macromolecules with the dipole moment directed along the end-to-end chain vector. The viscoeleastic cubic model of a regular network is used. The fixed average volume of a polymer network is ensured by the effective internal pressure. The dynamic models of polymer networks with external and interchain friction are studied. Two cases are considered: (1) polar chains cross-linked in a network at their ends, and (2) a densely cross-linked network with many network junctions per polar chain. The expressions for the autocorrelation functions of the total dipole moment of a network, which determine the dielectric susceptibility, are calculated. The relaxation spectrum of the autocorrelation function consists of two regions: the high-frequency relaxation spectrum of a chain fragment between two neighbouring junctions (intrachain relaxation spectrum) and the lowfrequency interchain relaxation spectrum. The interchain relaxation spectrum is determined by cooperative motions of chains which form a network. The characteristic time of this spectrum for networks of type (1) is the relaxation time of a chain between junctions τmin. For networks of type (2) a second time scale τ1 exists, which corresponds to motions inside the volume occupied by a single long polar chain included in a network. It leads to different time behaviour of the autocorrelation functions for both network models. The existence of only interchain friction in the network model leads to a cut-off of the relaxation spectrum at the time τmax depending on the volume of viscous interchain interactions.

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