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Molecular dynamics and free volume in organic glass-formers: a series of oligomer and polymer1,4-poly(isoprene)s

Authors
Journal
Chemical Physics Letters
0009-2614
Publisher
Elsevier
Volume
602
Identifiers
DOI: 10.1016/j.cplett.2014.04.006
Keywords
  • Organics
  • Chain Length
  • Spin Probe Dynamics
  • Esr
  • Ortho-Positronium Annihilation
  • Free Volume
  • Pals

Abstract

Abstract We present a combined study of the rotational dynamics and free volume in a series of 1,4-poly(isoprene)s using ESR and PALS, respectively. The spectral parameter of mobility, 2Azz‘, of the spin probe TEMPO is related to the annihilation of the ortho-positronium (o-Ps) probe. The o-Ps lifetime τ3(T50G) ≅ const.1 and τ3(TX1fast) ≅ const.2 rules are valid independent of chain length and moreover, the T50G’s coincides with the bend effect at Tb1L’s. Finally, the new finding is that the first acceleration at TX1slow agrees with a change in the o-Ps lifetime width parameter, σ3, below the glass transition temperature.

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