Theory of glassy dynamics in conformationally anisotropic polymer systems

Folusho T. Oyerokun, Kenneth S Schweizer

Research output: Contribution to journalArticle

Abstract

A mode coupling theory for the ideal glass transition temperature, or crossover temperature to highly activated dynamics in the deeply supercooled regime, Tc, has been developed for anisotropic polymer liquids. A generalization of a simplified mode coupling approach at the coarse-grained segment level is employed which utilizes structural and thermodynamic information from the anisotropic polymer reference interaction site model theory. Conformational alignment or/and coil deformation modifies equilibrium properties and constraining interchain forces thereby inducing anisotropic segmental dynamics. For liquid-crystalline polymers a small suppression of Tc with increasing nematic or discotic orientational order is predicted. The underlying mechanism is reduction of the degree of coil interpenetration and intermolecular repulsive contacts due to segmental alignment. For rubber networks chain deformation results in an enhanced bulk modulus and a modest elevation of Tc is predicted. The theory can also be qualitatively applied to systems that undergo nonuniversal local deformation and alignment, such as polymer thin films and grafted brush layers, and large elevations or depressions of Tc are possible. Extension to treat directionally dependent collective barrier formation and activated hopping is possible.

Original languageEnglish (US)
Article number224901
JournalJournal of Chemical Physics
Volume123
Issue number22
DOIs
StatePublished - Jan 1 2005

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Polymers
alignment
polymers
coupled modes
coils
Liquid crystal polymers
Rubber
Brushes
Polymer films
brushes
liquids
Elastic moduli
bulk modulus
rubber
Thermodynamics
glass transition temperature
Thin films
crossovers
retarding
Liquids

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Theory of glassy dynamics in conformationally anisotropic polymer systems. / Oyerokun, Folusho T.; Schweizer, Kenneth S.

In: Journal of Chemical Physics, Vol. 123, No. 22, 224901, 01.01.2005.

Research output: Contribution to journalArticle

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