Elevation of the glass transition temperature in flexible-chain semicrystalline polymers

Christopher K. Yee-Chan, Robert C. Scogna, Richard A. Register

Research output: Contribution to journalArticlepeer-review

5 Scopus citations


In the idealized two-phase model of a semicrystalline polymer, the amorphous intercrystalline layers are considered to have the same properties as the fully-amorphous polymer. In reality, these thin intercrystalline layers can be substantially influenced by the presence of the crystals, as individual polymer molecules traverse both crystalline and amorphous phases. In polymers with rigid backbone units, such as poly(etheretherketone), PEEK, previous work has shown this coupling to be particularly severe; the glass transition temperature (Tg) can be elevated by tens of degrees celsius, with the magnitude of the elevation correlating directly with the thinness of the amorphous layer. However, this connection has not been explored for flexible-chain polymers, such as those formed from vinyl-type monomers. Here, we examine Tg in both isotactic polystyrene (iPS) and syndiotactic polystyrene (sPS), crystallized under conditions that produce a range of amorphous layer thicknesses. Tg is indeed shown to be elevated relative to fully-amorphous iPS and sPS, by an amount that correlates with the thinness of the amorphous layer; the magnitude of the effect is severalfold less than that in PEEK, consistent with the minimum lengths of polymer chain required to make a fold in the different cases.

Original languageEnglish (US)
Pages (from-to)1198-1204
Number of pages7
JournalJournal of Polymer Science, Part B: Polymer Physics
Issue number10
StatePublished - May 15 2007

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Polymers and Plastics
  • Materials Chemistry


  • Glass transition
  • Isotactic
  • Polystyrene
  • Semicrystalline
  • Syndiotactic


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