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Free Radical Copolimerization Dispersions Glassy State Relaxation pp 149–190Cite as

Glassy state relaxation and deformation in polymers

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Part of the book series: Advances in Polymer Science ((POLYMER,volume 103))

Abstract

An overview of a nonequilibrium glass theory is presented to describe the structural relaxation and deformation kinetics of polymeric glasses, compatible blends, and particulate composites. The glassy state relaxation is a result of the local configurational rearrangements of molecular segments, and the dynamics of holes (free volumes) provide a quantitative description of the segmental mobility. On the basis of the dynamics of hole motion, a unified physical picture has emerged which enables us to discuss the structure relaxation, physical aging, and glassy state deformation. The links between the bulk and shear relaxations, the change in deformation from linear to nonlinear viscoelastic responses, and the nonlinear viscoelastic nature of plastic deformation are discussed. Theoretical expressions are presented for the determination of the PVT (pressure-volume-temperature) behavior, for the elucidation of the equilibrium and nonequilibrium nature of the glass transition, for the calculation of viscoelastic response, and for the prediction of yield behavior and stress-strain relationships of these polymeric systems.

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Abbreviations

a:

macroscopic timescale (shift factor)

A:

parameter measures volume interaction

d:

fractal dimension

D:

local diffusion constant

eij :

strain tensor

E:

relaxation modulus

f:

hole (free volume) fraction

ΔH :

activation energy

k:

Boltzmann constant

n:

number of holes

nx :

number of polymer molecules

N:

total number of lattice sites

p:

pressure

q:

cooling rate (<0)

qv :

wave number on fractal lattice

Q:

wave vector of the fluctuation

r:

spatial vector

R:

diffusion length

t:

time

T:

temperature

T r :

reference temperature

Tg :

glass transition temperature

v:

lattice volume

V:

total volume

ΔW :

external work acting on the lattice

x:

number of monomer segments/polymer

α:

= εf/kT 2

β:

stretched exponent

δ:

nonequilibrium hole fraction

εh :

= ε is the hole energy

εf :

flex energy

η:

= E/2(1 + θ) is the shear modulus

θ:

Poisson ratio

ϰ:

= E/3(1−2θ) is the bulk modulus

μ:

physical aging rate

ν:

fractal exponent

ϱ:

state density

σij :

stress tensor

σy :

yield stress

τ:

relaxation time

ϕ:

volume fraction in blends or composites

χ:

interaction parameter

ψ:

relaxation function

ω:

angular frequency

Ωij :

activation volume tensor

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Authors and Affiliations

  1. Xerox Webster Research Center, 800 Phillips Road, 114-39D, 14580, Webster, NY, USA

    T. S. Chow

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  1. T. S. Chow
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© 1992 Springer-Verlag

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Chow, T.S. (1992). Glassy state relaxation and deformation in polymers. In: Free Radical Copolimerization Dispersions Glassy State Relaxation. Advances in Polymer Science, vol 103. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0020905

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  • DOI: https://doi.org/10.1007/BFb0020905

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  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-55108-9

  • Online ISBN: 978-3-540-46727-4

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