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Breakdown of time-temperature superposition: From experiment to the coupling model and beyond

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Abstract

We studied chain and segmental relaxation in polyisoprene using broadband dielectric and light scattering spectroscopy. Our results demonstrate different temperature dependence of these processes (i.e. failure of the time-temperature superposition) in the entire temperature range studied. Segmental relaxation varies with temperature faster than chain relaxation at low temperatures while reverse is observed at high T. The transition between two regimes seems to occur around the dynamic crossover temperature. It appears that non-entangled and slightly entangled polymers exhibit the same behavior. The results are compared to predictions of the coupling model. We emphasize that current models cannot describe the data consistently.

Original languageEnglish
Pages (from-to)3838-3844
Number of pages7
JournalJournal of Non-Crystalline Solids
Volume353
Issue number41-43
DOIs
StatePublished - Nov 1 2007
Externally publishedYes

Funding

The authors thank Kia Ngai for many stimulating and encouraging discussions and Ken Schweizer for helpful comments and discussion. The work is supported by the ACS Petroleum Research Fund. We also acknowledge funding of the dielectric spectrometer acquisition by the Ohio Board of Regents Action Fund, by The University of Akron and by the National Science Foundation.

Keywords

  • Fragility
  • Glass transition
  • Polymers and organics
  • Rheology

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