Delayed classification model for free-Surface suppression of tg in polymer glasses

Scott T. Milner, Jane E.G. Lipson

Research output: Contribution to journalArticlepeer-review

32 Scopus citations

Abstract

Suppression of the glass transition by some tens of degrees within a few tens of nanometers of a free surface in a polymer film is a technologically important, commonly observed, as-yet poorly understood phenomenon. We construct a quantitative theory of the influence of the free surface via transmission of "kinks" or "free volume" along the backbone of loops starting and ending at the free surface, following a proposal by de Gennes. Using our delayed glassification (DG) model, we predict depth-dependent values of the local Tg for both semi-infinite and freestanding film geometries, for both infinite and finite molecular weights. The qualitative features of our results are in reasonable agreement with experiment, but the averaging process inherent in connecting our results to macroscopic observations raises further issues, which we treat in the following paper.

Original languageEnglish (US)
Pages (from-to)9865-9873
Number of pages9
JournalMacromolecules
Volume43
Issue number23
DOIs
StatePublished - Dec 14 2010

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

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