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1.3 M OLECULAR
BACKGROUND
1 I NTRODUCTION
/T 102 (Kg.mm2.K1)
2.5
21.5 C
40 C
60 C
80 C
1.5
100 C
120 C
140 C
Potential energy
0.5
6
Log
(b)
(a)
Figure 1.5: (a) Schematic representation of the Eyring flow theory. (b) Tensile yield stress
versus strain rate at different temperatures for polycarbonate, symbols indicate
experimental data and solid lines are fits using the Eyring-theory. Adapted from
Bauwens-Crowet et al. [30].
(/T) 10
(dynes cm
deg )
It is known that, in the linear viscoelastic range, the time dependent behaviour can
include contributions of secondary relaxation processes. It was shown by several
authors that this also holds for the tensile yield stress of these materials [30, 32].
2 C
30
40
50
60
70
80
90
0
6
Log
Figure 1.6: Tensile yield stress versus strain rate at different temperatures for polymethylmethacrylate, symbols are experimental data and solid lines are fits using the
Ree-Eyring theory. Adapted from Roetling [32].
As an example, Figure 1.6 shows the yield stress of PMMA as function of strain
rate for a large range of temperatures. With increasing strain rate the yield stress
shows a change in slope for all temperatures, the transition shifting to higher rates
with increasing temperature. The additional contribution at the higher strain rates
(i.e. shorter times, or a reduced time scale) is generally attributed to the secondary
relaxation process.
1.3 M OLECULAR
BACKGROUND
To describe this yield behaviour, a Ree-Eyring modification of the Eyring flow theory
is used. The modification consists of placing two Eyring flow processes in parallel.
This approach was also shown to be applicable for semi-crystalline materials, such
as e.g. isotactic polypropylene [33,34], while for some other materials an extra, third,
process was necessary [35, 36].
Volume
log(Compliance)
Temperature and stress both increase the molecular mobility and, consequently, accelerate the time scale at which the material deforms. From this it might be concluded
that when both are kept constant, the mobility and its resulting rate of deformation
do not change. It was, however, shown by Struik that for many polymers this is not
correct [37]. With increasing time elapsed after a (thermal) quench from above Tg , he
observed a decrease in molecular mobility: the response to linear creep experiments
at constant temperature shifts to longer loading times, see Figure 1.7(a).
Equilibrium
melt
Nonequilibrium
glass
Ageing
Equilibrium
glass
Tg
log(Time)
(a)
Temperature
(b)
Figure 1.7: (a) Schematic representation of the influence of ageing time te on the linear creep
compliance. (b) Schematic illustration of physical ageing: volume as a function of
temperature.