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Elucidating the impact of extreme nanoscale confinement on segmental and chain dynamics of unentangled poly(cis-1,4-isoprene)

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Abstract.

Broadband dielectric spectroscopy is employed to probe dynamics in low molecular weight poly(cis-1,4-isoprene) (PI) confined in unidirectional silica nanopores with mean pore diameter, D, of 6.5 nm. Three molecular weights of PI (3, 7 and 10 kg/mol) were chosen such that the ratio of D to the polymer radius of gyration, Rg, is varied from 3.4, 2.3 to 1.9, respectively. It is found that the mean segmental relaxation rate remains bulk-like but an additional process arises at lower frequencies with increasing molecular weight (decreasing D/Rg. In contrast, the mean relaxation rates of the end-to-end dipole vector corresponding to chain dynamics are found to be slightly slower than that in the bulk for the systems approaching D/Rg ∼ 2, but faster than the bulk for the polymer with the largest molecular weight. The analysis of the spectral shapes of the chain relaxation suggests that the resulting dynamics of the 10kg/mol PI confined at length-scales close to that of the Rg are due to non-ideal chain conformations under confinement decreasing the chain relaxation times. The understanding of these faster chain dynamics of polymers under extreme geometrical confinement is necessary in designing nanodevices that contain polymeric materials within substrates approaching the molecular scale.

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Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of Tennessee, 37996, Knoxville, TN, USA

    Thomas Kinsey, Emmanuel Mapesa, Tyler Cosby & Joshua Sangoro

  2. Center for Nanophase Materials Science, Oak Ridge National Laboratory, 37831, Oak Ridge, TN, USA

    Youjun He, Kunlun Hong & Yangyang Wang

  3. National Research and Development Institute for Cryogenic and Isotopic Technologies, ICSI Rm. Valcea, Rm. Valcea, Romania

    Ciprian Iacob

  4. Karlsruhe Institute of Technology (KIT), Institute for Chemical Technology and Polymer Chemistry, 76128, Karlsruhe, Germany

    Ciprian Iacob

Authors
  1. Thomas Kinsey
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  2. Emmanuel Mapesa
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  3. Tyler Cosby
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  4. Youjun He
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  5. Kunlun Hong
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  6. Yangyang Wang
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  7. Ciprian Iacob
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  8. Joshua Sangoro
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Correspondence to Joshua Sangoro.

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Elucidating the impact of extreme nanoscale confinement on segmental and chain dynamics of unentangled poly(cis-1,4-isoprene)

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Kinsey, T., Mapesa, E., Cosby, T. et al. Elucidating the impact of extreme nanoscale confinement on segmental and chain dynamics of unentangled poly(cis-1,4-isoprene). Eur. Phys. J. E 42, 137 (2019). https://doi.org/10.1140/epje/i2019-11907-7

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