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The Temperature Dependence of

Viscoelastic Behaviour & Polyethylene

Dynamic mechanical measurements of unoriented crystalline polyethylene
terephthalate fibres have been made over the temperature range of the glass/
rubber transition. The results have been conlpared with previously reported
creep data. A consistent representation of both sets of data can be obtained
using first-order approximation methods and defining the transition tenlperature
as that for which t a n 8 is a maximum.

DYNAMIC mechanical measurements on polyethylene terephthalate fibres
of different physical structure have been reported in a previous publication 1
which was primarily concerned with the anisotropy of elastic and visco-
elastic behaviour in oriented fibres. The present paper deals particularly
with the frequency/temperature relationships for these fibres, and the
earlier work has been extended in several ways. First, the dynamic
mechanical measurements have been extended to lower frequencies by
construction of an apparatus with a working range of 10 -:~ to 10 c/s.
Secondly, the dynamic measurements are compared with extensional creep
data obtained elsewhere 2 and previously reported dielectric loss :~ and
dilatometric measurementsL
The previous dynamic mechanical measurements 1 were restricted to a
narrow range of frequencies, and it was found adequate to describe the
frequency/temperature behaviour as that of a constant activation energy
system. The extensional creep data 2 for unoriented crystalline fibres, on
the other hand, showed shift factors which could be fitted to the Williams-
Landell-Ferry relationshipL It also appeared that the dielectric loss and
dilatometric measurements were consistent with this representation. It is,
ihowever, not easy to distinguish between the W L F representation and a
constant activation energy over a narrow range of frequencies, particularly
at high frequencies. It is therefore of interest to examine dynamic
mechanical measurements over a wide range of frequencies for crystalline
unoriented fibres, together with the creep data, to see if a consistent
representation of both can be obtained.

Preparation of samples
The fibres were made by the conventional melt-spinning process in
which molten polymer is extruded through small orifices to produce non-
crystalline fibres with a very low degree of molecular orientation. These
fibres were then subjected to a heat-crystallization process. The latter
*Present address: H. H. Wills Physics Laboratory, University of Bristol,

process is necessary to stabilize the samples before subjecting them to
the range of temperatures encountered during the dynamic mechanical

Physical characterization of samples
A detailed investigation of the molecular structure of the samples was
not undertaken. However, it was of value to obtain empirical measures
of crystallinity and molecular orientation, recognizing the arbitrary nature
of these types of measurement.
The measure of crystallinity was an X-ray diffraction method devised
by Farrow and Preston 6, which compares the integrated intensity of the
sharp X-ray reflections from crystalline material with the integrated intensity
of the diffuse reflections from the non-crystalline material.
A measure of the overall molecular orientation was obtained from the
optical birefringence. This is the difference between the refractive indices
of the fibres, along and at right angles to the fibre axis, and was measured
using polarized light and a Berek compensator.

Measurement of dynamic extensional modulus (Young's modulus)
The apparatus used in the measurement of extensional modulus is shown
diagrammatically in Figure 1. It is identical in principle to that described
in a previous publication I but possesses a wider frequency range (10 -3 to

Strain J Carrier
gauge I
Phase I Phase
Fibre [ sensitive sensitive
sample rectifier rectifier
Sine Cosine
t t
Integrator Integrator
hi ~ etement
t f

In phase Ouadrature
L . . .

• Scotch-yoke
. . . . . J

E' Ert
mechanism Outputdisplay
Figure/--Schematic diagram of the dynamic mechanical apparatus

10 c/s). It was also found to produce results with greater accuracy and
reproducibility than had proved possible using the earlier apparatus.
The sample is subjected to a sinusoidal strain of fixed amplitude, which

is provided by a Scotch-yoke mechanism driven by a servo-controlled
motor. The stress is measured by a non-bonded strain gauge transducer
attached to the other end of the sample. Simultaneous comparison of stress
and strain is made electronically using a Servomex Transfer Function
Analyser (TFA).
The T F A provides a servo-controlled motor which, in addition to
providing a means for a sinusoidal strain, rotates a loop in a high frequency
(to~) alternating magnetic field (2kc/s). Since the loop rotates at a very
low frequency (to,D, i.e. the test frequency, this produces a carrier modu-
lated at the rotational speed of the form
K sin to,,,t cos to,,t for w, >~ w,,,
which can then be fed to the system under test. However, in our application
the mechanical signal is used and consequently the return signal presented
to the measuring system by the transducer will be of the form
K1 sin (to,,t+3)+N
where 3 is the angular phase shift produced by the system under test and
N represents unwanted elements such as harmonics, random noise, etc.
At this stage a carrier is introduced and the signal is then multiplied
simultaneously but separately by sin to,,t and cos w,,y. This multiplication
at the modulation frequency, to .... is carried out by a synchro element with
resolver type windings. This element is directly coupled to the same motor
shaft which drives the Scotch-yoke and the rotor winding is fed with the
signal from the transducer plus carrier. The two stator windings are at
90 ° to each other and from these are derived the sine and cosine functions.
These two signals after being demodulated to remove the carrier
frequency component are of the form

Ks sin (to,d+ 3) sin to,~t+N sin ¢0,,,t
= ½K2 [cos 3 - cos (2tomt + 3)] + N sin to,,y
and K2 sin (to,,,t + 3) cos to,~t + N cos to~,t
= ½K2 [sin 3 + sin (2to,,,t + 3)] + N cos to,d
These signals are then integrated over a complete cycle to remove all
unwanted terms. Two steady signals are then obtained which are propor-
tional in magnitude and polarity to the real and imaginary parts of the
system output at the fundamental frequency, i.e.
I/m m 1 ,,, m

f ~K2cos 3 a t and

It is essential that the Scotch-yoke mechanism be as free from noise as
possible and this was largely achieved by making the eccentric collar of
Nylon which, in turn, rotates in contact with polished stainless-steel
surfaces. Provision was also made for aligning the eccentric Nylon collar
with respect to the loop thereby avoiding any constant additional phase
difference between the loop and the strain.
As in the previous apparatus a sinusoidal strain of + 0 . 2 5 m m , i.e.
P. R. P I N N O C K and I. M. W A R D

,+ 0.25 per cent on the 10 cm sample, was chosen, having already established
that this is within the range of the linear viscoelastic behaviour. The sample
was also subjected to a static strain of approximately 0.25 mm to prevent
it going slack. The fibre is connected to both the Scotch-yoke mechanism
and to the strain gauge by German-silver tubing connections.
The fibre is surrounded by an annular copper can through which heated
air may be passed. The copper can in turn is insulated by a Thermos
jacket enabling the temperature of the fibre to be controlled to within
1 deg. C.
Creep measurements
The creep data discussed in this paper were all obtained in a previous
investigation which has been reported fully elsewhere 2. The creep measure-
ments were confined to unoriented monofilaments which had been heat-
crystallized by heating at 180°C for one hour. These samples were therefore
exactly equivalent to the unoriented crystalline fibres used for the dynamic
mechanical measurements.
The reader is referred to the previous publication for details, but to
summarize, the creep compliance of unoriented crystalline polyethylene
terephthalate was measured in the linear viscoelastic range from 65 to
115"5°C, isothermal creep data being obtained at nine fixed temperatures,

Linear viscoelastic behaviour
There are several equivalent ways of determining the mechanical
behaviour of a linear viscoelastic system. These are broadly of two types,
the first being the response of the system to transient stress or strain, and
the second its response to dynamic stress or strain. The results of transient
measurements define a relaxation modulus or a creep compliance and the
dynamic measurements define a complex modulus or compliance.
A convenient starting point for consideration of the transient type
measurements is the Boltzmann superposition principle. For uniaxial creep,
this relates the final strain e (t) to the elemental increments of stress do-(~-)
applied at times ~-.

e (t) = ~-0 + J (t - r) dr

where J (t) is the creep compliance, and similarly for stress relaxation

where E (t) is the stress relaxation modulus, E0 is the instantaneous elastic
modulus and de (r) are the elemental strain increments.
From the dynamic mechanical approach, consider the system to be
subjected to a sinusoidal stress
o- = o'0 sin tot

Then the sinusoidal strain produced will be given by e=e~ sin (cot-6)
where 6 defines the phase lag between stress and strain. The ratio between
strain and stress e/o- defines the complex compliance J * = J ' + i J ' . Alter-
natively, we may define the complex modulus E * = E ' + iE', from the
reciprocal ratio of stress to strain.
The mathematical relationships between the creep compliance, the
stress-relaxation modulus and the dynamic compliance and modulus, have
been discussed in detail by Gross 7 and others. These relationships are
complex and involve, for example, recourse to the methods of Fourier or
Laplace transforms to relate transient to dynamic quantities. Although it
is possible to compute exactly one quantity from another, provided that
a sufficient time-scale is covered, this is rarely profitable for considerations
of the viscoelastic behaviour of polymers. In the first place, the visco-
elastic behaviour can rarely be determined experimentally with sufficient
accuracy, and secondly the behaviour normally changes fairly slowly with
change in frequency. It is therefore often adequate to resort to approximate
methods, and these will be discussed in the next section.

Use of approximate methods
The relaxation modulus can also be expressed as

E (t)=Eo+ ( H (z)e-' ~d l n z (1)

where H (T) is a function defining the relaxation spectrum (see, for example,
ref. 8, p 41).
A similar generalization for creep gives the creep compliance in terms
of a 'retardation-time' spectrum, L (z).

Y (t)=/0+ t" L (T) (1 - e-','O d In T

where J0 is the instantaneous elastic compliance.
The real and imaginary parts of the dynamic modulus can also be
expressed in terms of H (7-).

E' (w)= E0 + . ~--ro-~ J d In ~- (2)


E" (09)=
H (r) (or ] (3)
$-~r# j d In r

The approximations to be used in this paper all derive from approximate
methods to obtain H (T).
Equation (1), which has the form of a Laplace transform, can be used
t o evaluate H (z) to various orders of approximation, as has been extensively
discussed in the literature (see, for example, ref. 8, p 44).

The first-order approximation was proposed by Alfrey and is generally
known as the Alfrey approximation.
It gives
n (~')=[-dE (t)/d ln t]t=~
and can be considered to arise by approximating the intensity function
e-t/~ which goes from 0 at ~-=0 to 1 at ~- > ~ by a step function going
from 0 to 1 at r = t.
Second-order and higher-order approximations can be obtained involving
the first derivative and higher derivatives of E (t) with respect to Int.
As discussed in detail by Staverman and SchwarzP and others the first-
order Alfrey approximations hold provided that the relaxation spectrum
or retardation spectrum do not change very rapidly with frequency. In
mathematical terms this requires that the second- and higher-order
derivatives should be small compared with the first-order derivative.
The analysis of the creep and dynamic data presented here suggests that
first-order approximations are adequate. Furthermore this will be shown
to be expected from examination of the creep data alone.
Thus we shall assume that the relaxation spectrum is given by
H (r) = [ - dE (t)/d In t]t ,.
To a similar degree of approximation equations (2) and (3) can be shown
to give
[dE' (~0) ] 2 [E" (co)]1/..... (4)

From the latter approximations it follows that
d In E' (w)/d In co= ( 2 / 7 0 tan 8 (5)
In a similar manner it can be shown that
d In J' (oJ)/d In w = (2/7r) tan 8 (6)
It is also noted that E(t)=E'(o)) and J(t)=J'(o)) for o)=l/t.

Frequency/temperature equivalence and the definition of 'transition
The discussion has so far only been concerned with the variation of
mechanical properties with time or frequency at a fixed temperature. This
paper is, however, primarily concerned with the temperature dependence
of the viscoelastic behaviour. With transient measurements, it is fairly
straightforward to obtain the frequency/temperature dependence by
comparison of data obtained at different fixed temperatures. The procedure
is to obtain a 'master creep curve' or a 'master stress-relaxation curve' by
superposition of the isothermal data. The linear frequency shifts corres-
ponding to shifts in temperature are thus obtained directly.
It is, however, not so obvious how to obtain shift factors directly from
the dynamic mechanical data, obtained at constant frequency over a range
of temperatures, because each set of data for the real and imaginary parts

of the modulus or compliance does not in itself define a particular tem-
perature. Strictly, the measurements of E' and E " at constant frequency
over a range of temperatures should be used to construct plots of E ' and
E " at constant temperature for a series of frequencies. These plots can
then be superimposed to obtain the shift factors. A similar procedure.
of course, can be applied to measurements of J' and J" at constant
frequency, with an identical result.
A somewhat simpler procedure has been used in this paper, which will
be shown to be adequate. It is based on the following considerations.
The previous dynamic mechanical measurements ~ showed that to a
first approximation change in temperature produced a uniform shift on a
logarithmic time scale. However, the creep data show that this is not
strictly true over a wide time scale, since the so-called W L F equation
gives a better fit to the shift factors than one with a constant activation
energy. However, the difference between these two representations is not
large for a restricted time scale.
It follows from equation (4) that a peak in the relaxation spectrum
(which will correspond to a 'transition') occurs when dE' (6o)/d In ~o and
E"Io~) have a m a x i m u m value. In a system with a constant activation
energy A then time is related to temperature 0 by the equation
r ( 0 ) = r (0) exp CA/RO)
Hence for measurements at constant frequency a passible definition of
the transition temperature is the temperature at which dE'(O)/dO and
E " ( 0 ) have a m a x i m u m value. For reasons of experimental convenience,
this definition was adopted in one of our previous publicationd and used
to define transition temperatures for extensional and torsional viscoelastic
behaviour. Similarly an alternative definition can be the temperature when
d J ' (0)/d0 and J'" C0) have a maximum value. A further definition, following
from equation (5) and (6), is that the transition temperature is the tempera-
ture for a m a x i m u m value of tanS, which is equivalent to that for a
m a x i m u m in d In E' (0)/d0 and d In J' (0)/d0.
These three definitions of transition temperature give appreciably
different values for that temperature. This was remarked in the previous
paper', and shown to follow very simply from the standard linear solid
representation which was considered adequate for the previous investigation
in a very narrow frequency range. In particular, it is to be expected that
the m a x i m u m in tan 8 will occur at a temperature intermediate between
the m a x i m u m in dE' (0)/d0 or E " (0) and that in dJ' (O)/dO or J " (0).
The aim of our simplified procedure can now be defined. It is to select
one point from the E'(O), E"(O), J'(O), J"(O) or t a n 8 (0) results and
observe how this point shifts with change of frequency. Since our frequency
shifts must be identical whether we use modulus or compliance results it
would suggest the best approximation will be obtained by defining the
transition temperature as the temperature of the maximum in either tan 8,
d In E" (O)/dO or d In J ' (0)/d0.
Typical results for the variation of the measured quantities E ' and E " are
P. R. P I N N O C K and I. M. W A R D

2.5 - 0.25

2-0 - 0.20
- 0

•EuE 1"5 -0.15
£ 1-0 0.I0 ~o

0.5 0"05

I I I I I I I I I 0
20 30 40 50 60 70 80 90 100 110 120
Temperature, °C
0.25 r-

0.20 !


r- q22
0,10 t°I EP

0.05 -

(13) I I " I (I yneslcm 2 °C)
0.0 30 40 50 60 70 80 90 100 110 120
Temperature, °C
Figure 2--Typical measurements made at 0"1 c/s ~a) E ' and E", (b) t a n & dE'/dO
and d log U/dO

Table 1. Transition temperatures for unoriented crystalline PET fibres

I Temperature, °C for maximum Dynamic
ence % E" dE" / dO tan8 d log E ' / d 0 c/s
33 ---7¢- T t 92 92 0"01
33 86 88] 97 96 0"1
33 89 [93 103 100 1
33 95[95 I 110 104 10


shown in Figures 2(a) and 2(b), together with the derived quantities
dE'/dO, tan 6 and d In E/dO. Values of the transition temperatures defined
by the temperature at which these quantities have a m a x i m u m value are
given in Table 1 for various frequencies. Table 1 also includes the X-ray

Dynamic mechanical data
The results in Table 1 show that, to a good approximation, the maxima
in dE'/dO and E " occur at the same temperature and similarly the maxima
in d in U/dO and tan 6 also occur at the same temperature, although the
latter temperature is appreciably higher than the former. These similarities
in temperature substantiate to a large extent the approximations made
earlier which resulted in equations (4), (5) and (6).
The transition temperatures which are defined as the temperatures for
m a x i m u m tan 6 have been plotted as a function of log frequency in Figure 3
in a way suitable for fitting to the W L F equation. The value of T,, needed
to give agreement between these data and the equation (also shown in
Figure 3) is 79°C. As will be remembered this form of the W L F universal
equation was formulated such that the fitting temperature T, should be
similar to the dilatometrically-measured transition temperature. This is
certainly verified here where previous dilatometric measurements 4 gave a
value of 81°C for crystalline polyethylene terephthalate polymer. It should
also be noted that it was not possible to fit the temperatures for maximum
E " to the W L F equation.

Further justification for use of first-order approximations
Further justification for the use of the first-order approximations can
be obtained directly from the creep data.

z~ --WLF equation, log ar -- 17'~ (r-Tq)
51.6-(r-r9 )
(D Dynamic mechanical data
0 (11 Dietectric data


-12 -
I I I I I 1 I I I
60 70 80 90 100 110 120 130 140 150 160
Temperature, °C
Figure 3--Temperatures for (tan 6)nl~x. at various frequencies fitted to th
WLF equation

The master creep compliance curve (Figure 4 in Ward ~) shows that the
creep compliance J (t) is, to a good approximation, a linear function of
In t over the time range l0 s to 1014sec. This range corresponds to creep
data obtained in the time interval 10 to 10' sec over the temperature range
84.4 ° to 115.5°C. Over this range it therefore follows that dJ ( 0 / d l n t is
approximately constant and that dZJ ( t ) / d l n t2 and higher derivatives are
zero, giving direct justification for the first-order approximation.
Outside this range, i.e. from 10 -4 to 105 sec on the master curve, the
first-order approximation is not satisfactory, particularly at the lowest
times. This range covers creep data obtained at the three lowest tempera-
tures only (65.0°C, 70°C and 76.6°C). It will be noted that the shift factors
from these results do not, in fact, fit on to the W L F curve (Figure 5 in
Ward2). Over the central and higher range of the creep data, however,
where the link with the dynamic data is being established, the approxi-
mation holds and a good fit is obtained to the W L F equation.

Comparison of dynamic mechanical and creep data
Using the approximations described earlier it is possible to check the
internal consistency of the dynamic mechanical data and the previously
published creep data. F r o m the creep measurements (Figure 3 in Ward ~)
E ' was computed over a range of temperatures at a number of fixed
frequencies (times) by assuming that E'(oJ, O)=l/J(t,O) with t=llto.
These derived dynamic data are given in Figure 4 where log E ' (co) is shown
as a function of temperature for four frequencies, viz. 10 -4, 10 -3, 10 -5,
10 - l c / s . The transition temperatures which are defined as those at the
point of m a x i m u m d ln E'/dO are also included in the figure. Comparison
of these with corresponding dynamic data of Table 1 shows reasonable
agreement confirming the equivalence of the creep and dynamic mechanical
measurements and the validity of the approximate procedures.
Figures 5(a) and 5(b) show the shift factor a~ as a function of temperature,
these data being obtained from the previous creep measurements. The
curve shown in Figure 5(a)is similar to that obtained in the previous work
where no correction was made for changes in the unrelaxed modulus (or
the factor pT/poTo) with temperature. Although such factors are extremely
small in polyethylene terephthalate where the creep compliance changes
markedly with temperature recent work by Morris and McCrum 9 prompted
us to attempt such a correction. On the basis of the high frequency results
of Thompson and Woods I° it was estimated that the change in the unrelaxed
modulus was approximately 0-2 per cent per deg. C. New shift factors were
then obtained from the previous data, taking into account this correction
factor. The data can again be fitted to the W L F equation, and the value
of T~, is slightly reduced, to 82°C from 85°C [Figure 5(b)].
This value of 82°C is in excellent agreement with both the dynamic To
of 79°C and the dilatometric transition temperature of 81 °C. This confirms
the expectations of the theoretical discussion that definition of dynamic
transition temperature as that for the m a x i m u m in tan 6 is necessary to
produce a consistent shift factor for both creep and dynamic data.
Over this wide frequency range, there is a definite divergence of the

105 F '10- second' modulus
'102- second ' modulus
104 ~- ID '10a-second' modutus
'104- second' mod u{ u s
103~ -{-- Temperature for maximum
d tog E
102~ de

uj 1001- @

~ 9.9


951 I I I 1_
6O 70 80 90 100 110
Temperature, °C
Figure 4 -Modulus measurements at different times and temperatures derived
f r o m previous creep data

frequency/temperature behaviour of the dynamic data from that of a
constant activation energy system. The fit to a WLF equation for the
dynamic data alone is probably not completely conclusive, but it would
certainly appear that this representation gives a consistent fit for both
dynamic and transient data.

Comparison with dielectric measurements
In the paper on creep measurements, it was noted that the dielectric
loss measurements were consistent with the WLF equation. The shift
factors were obtained by Reddish 3 from the dielectric data by measuring
the frequency at which the tan 6 maximum occurs at a given temperature
and are also plotted in Figure 3. The consistency of the dielectric and
mechanical data is further confirmed by the present work, although it may
be possible that the best fit for the dielectric data does involve a small
vertical displacement with respect to the dynamic data. This displacement
would not affect the choice of the T,,, although it is to be noted that there
is not a significant difference between the WLF equation and a constant
activation energy at high frequencies.

]it is concluded that dynamic mechanical data on polyethylene terephthalate
are consistent with the WLF equation relating time-temperature equiva-
lence. Consistency between our previous creep data and the dynamic results

2 (a)


_12 / I I [ I I I

~.- - 2

-12 I I I [ I I I
Y3 70 80 90 100 110 120 130

Figure 5--Shift factors obtained from creep data
fitted to WLF equations, (a) uncorrected data,
(b) data corrected to account for the change in
the unrelaxed modulus with temperature

can be o b t a i n e d if the transition t e m p e r a t u r e is defined f r o m the d y n a m i c
d a t a by the t e m p e r a t u r e at w h i c h tan ~ is a m a x i m u m .

Research Department,
I m p e r i a l C h e m i c a l Industries Fibres L i m i t e d ,
Harrogate, Y o r k s h i r e
( R e c e i v e d D e c e m b e r 1965)

1PL~NOCK, P. R. and WARD,I. M. Proc. phys. Sac. 1963, 81, 260
WARD, I. M. Polymer, Lond. 1964, 5, 59
a REDDISH,W. Trans. Faraday Sac. 1950, 46, 459
4 KOLB, H. J. and IZARD, E. F. J. appl. Phys. 1949, 20, 564
5WILLIAMS, M, L., LANDELL,R. F. and FERRY, J. D. ]. Amer. chem. Sac. 1955,
77, 3701
6 FARROW,G. and PRESTON,D. Brit. ]. appl. Phys. 1960, 11, 353
~GRoss, B. Mathematical Structure of the Theories of Viscoelasticity. Hermann:
Paris, 1953
s STAVERMAN, A. J. and SCHWARZL, F. Die Physik der Hochpolymeren, Band IV.
(F_.d.H.A. STUART),Springer: Berlin, 1956
9 MORRIS,E. L. and McCRuM, N. G. ]. Polym. Sci. B, 1963, l, 393
I0 THOMPSON,A. B. and WooDs, D. W. Trans. Faraday Soc. 1956, 52, 1383