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Viscoelastic Behavior of Rubbery Materials$
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C. Michael Roland

Print publication date: 2011

Print ISBN-13: 9780199571574

Published to Oxford Scholarship Online: September 2011

DOI: 10.1093/acprof:oso/9780199571574.001.0001

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Confinement effects on polymer dynamics

Confinement effects on polymer dynamics

(p.298) 10 Confinement effects on polymer dynamics
Viscoelastic Behavior of Rubbery Materials

C. M. Roland

Oxford University Press

When a polymer is constrained to spatial dimensions less than roughly 100 nm, its glass-transition temperature often becomes lower than T g for the bulk state. This effect is well established for free-standing films and often occurs with supported films and material confined within nanopores. The mechanism for the T g reduction appears to be the enhanced mobility of surface molecules, a result of fewer intermolecular constraints and greater unoccupied volume. However, this explanation cannot account for many details of the phenomenon—the magnitude of the effect depends on the nature of the confining surface, the chemical structure and even tacticity of the material, and its molecular weight. This chapter reviews how spatial confinement affects segmental and chain mobilities, showing how the effects can be dramatic, yet are complex and unaccounted for by any model.

Keywords:   confinement, surface mobility, Tg depression, constraints, radius of gyration, thin film, nanofillers

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