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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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Cooperative local dynamics – the glass-transition zone

Cooperative local dynamics – the glass-transition zone

Chapter:
(p.38) 2 Cooperative local dynamics – the glass-transition zone
Source:
Viscoelastic Behavior of Rubbery Materials
Author(s):

C. M. Roland

Publisher:
Oxford University Press
DOI:10.1093/acprof:oso/9780199571574.003.0002

When the density of segments becomes sufficiently high, the motions of polymer chains are governed primarily by intermolecular cooperativity. With continued cooling or pressurization, the timescale of the motions can become so larger that relaxation is ‘arrested’, and the material transitions to a glassy state. Many plastics are glassy polymers; moreover, the glass transition is the operative mechanism in a number of applications of rubber. Nevertheless, because of the complex interplay of forces and structure, there is no comprehensive theory of the glass transition. In this chapter the diverse properties characteristic of vitrifying polymers—non-Arrhenius and non-Debye behaviors, the change in dynamics occurring above T g, dynamic heterogeneity, the Johari—Goldstein process, and various decoupling phenomena—are described. Recent developments in quantifying the role of thermal energy and density on the behavior are reviewed.

Keywords:   glass transition, segmental relaxation, decoupling, Debye–Stokes–Einstein equation, diffusion constant, equation of state, Kohlrausch function, dynamic heterogeneity, Prigogine–Defay ratio

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