European Polymer Journal 39 (2003) 1721–1727

www.elsevier.com/locate/europolj

The enthalpy of fusion and degree of crystallinity of

polymers as measured by DSC
Y. Kong, J.N. Hay *

Department of Metallurgy and Materials, The School of Engineering, The University of Birmingham, P.O. Box 363, Edgbaston,
Birmingham B15 2TT, UK
Received 1 July 2002; received in revised form 4 October 2002; accepted 4 March 2003

Abstract
Crystalline polymers are not in thermal equilibrium and thermodynamic parameters such as enthalpy of fusion as
determined by differential scanning calorimetry from the area under the melting endotherm over a wide temperature
range have not been measured under equilibrium conditions. Accordingly measurements of the degree of crystallinity
based on the enthalpy of fusion reflect experimental conditions, are incorrect in that they do not usually agree with
those determined by other analytical procedures, such as density and WAX scattering, particularly when measured at
ambient temperatures. While this has been repeatedly pointed out procedures used to determine the fractional crys-
tallinity of polymers based on the enthalpy of fusion continue to be widely used.
Using the First Law method, the enthalpy of fusion and fractional crystallinity have been measured as a function of
temperature for metallocene polyethylene and polyethylene terephthalate during heating. The crystallinity measured on
the sample prior to heating is in good agreement with that determined by density and wide angle X-ray diffraction.

2003 Elsevier Ltd. All rights reserved.

Keywords: Enthalpy of fusion; Crystallinity; First Law method

1. Introduction crystallisation mechanism, there is general disagreement

The fractional crystallinity of a semi-crystalline poly-
mer is one of its most important physical parameters in
that it reflects the morphology and determines me-
chanical properties, in that the Young modulus, yield
stress, fatigue response and impact strength increase
progressively with crystallinity [1]. There is also a gen-
eral tendency to become more brittle and the fracture
mechanism changes from ductile yielding to craze initi-
ation of cracks. While differential scanning calorimetry
(DSC) is widely used to characterise semi-crystalline
polymers by determining melting characteristics and
*
Corresponding author. Tel.: +44-121-414-4544; fax: +44-
121-414-5232.
E-mail address: j.n.hay@bham.ac.uk (J.N. Hay).
0014-3057/03/$ - see front matter
2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0014-3057(03)00054-5
on how the fractional crystallinity should be measured
by this technique and also whether the measured value
has any real significance [2–8]. The fractional crystal-
linity determined by DSC differs substantially from that
determined by other analytical techniques and to such
an extent that it is considered that DSC fractional
crystallinity is defined differently from that determined
by wide angle X-ray diffraction (WAXD) and density
measurements, fold surface effects and the invalidity of
the two phase model of crystalline polymers being in-
voked most frequently.
Most DSC methods rely on measuring the heats of
fusion and melting temperatures of crystalline sam-
ples and comparing these directly [9–20]. The tempera-
ture range observed depends on the thermal stability
of the lamellae present in the sample, and to their
thickness distribution. Thickening of the lamellae with
time isothermally or on heating makes the observed
1722 Y. Kong, J.N. Hay / European Polymer Journal 39 (2003) 1721–1727
melting endotherms heating rate dependent and melt-
ing occurs over a wide range of temperature [21]. It
is not uncommon to observe multiple melting endo-
therms, crystallisation exotherms and shifts of the en-
dotherm to higher temperatures with heating rate [22,
23].
Enthalpy is a fundamental thermodynamic of mate-
rials; it is temperature dependent and any change in
enthalpy accompanying a phase change is also temper-
ature dependent [24]. Equilibrium thermodynamic pro-
cedures adopted for low molar mass materials are
assumed to apply to polymers and these produce errors
in the measurement of fractional crystallinity by ther-
mal analysis [9–20]. Highly viscous melts means that
polymer crystallisation is limited by kinetic rather than
thermodynamic parameters. Due to dynamic chain
entanglements not all of the molecular segments crys-
tallise, defects are present in the crystals and the di-
mensions of the critical nuclei limit the lamellar crystal
thickness [25]. Accordingly these lamellae undergo re-
organisation and progressive thickening on heating. The
rate of heating and annealing alter the observed enth-
alpy of fusion and the temperature range over which
melting is observed [2,25]. Accordingly, unlike low mo-
lecular weight materials, polymer crystals melt over a
wide range of temperature and the temperature depen-
dence of the enthalpy of fusion cannot be neglected [26].
The observed melting endotherms reflect the thermal
stability of the lamellae present as melting is approached
and not in the initial sample prior to heating [22]. The
melting enthalpies are not comparable directly unless
they are measured over the same temperature range
[3,7].
Assumptions have been adopted for convenience in
using DSC to measure the fractional crystallinity of
polymers; one involves measure the enthalpy of fusion
from the area of the endotherm above an arbitrarily
drawn baseline. The errors involved in doing this can be
large [25,27]. S
egu
ela [6] has correctly stated that the
correct baseline for such analysis is given by:
Cp;b ðT Þ ¼ Cp;c Xc ðT Þ þ Cp;a ð1  Xc ðT ÞÞ ð1Þ
where Cp;b ðT Þ is the heat capacity of the semi-crystalline
sample at temperature T , Cp;c and Cp;a are the heat ca-
pacity of the completely crystalline and amorphous
phase respectively and Xc ðT Þ is the weight fraction of
crystallinity at temperature T . However, all of these
parameters are temperature dependent and it is impos-
sible to determine the theoretical baseline unless Xc ðT Þ
and the heat capacity values are known.
An alternative more thermodynamically correct pro-
cedure, since it relies on the application of the First Law
of Thermodynamics, has been used previously [7]. In this
paper a comparison is made between the fractional
crystallinities measured by this method and other ana-
lytical techniques on the same polymer samples.
2. Experimental
Poly(ethylene terephthalate), PET, was supplied by
DuPont Ltd as moulding pellets. It has a number aver-
age molecular weight of 19.6 kg mol1 and weight av-
erage of 36.4 kg mol1 . PET was dried in a vacuum oven
at 100 C for 12 h and pressed at 280 C for 2 min at a
pressure of 7.5 MN m2 into 100 mm · 100 mm · 0.8 mm
plaques. These plaques were quenched in ice water to
obtain amorphous sheets.
Metallocene polyethylene (m-PE) was purchased from
Exxon Chemical Co. France, as an Exact grade 3009. It
is a copolymer of ethylene and hexene-1, whose number
and weight average molecular weight are 40 and 100
kg mol1 respectively. The m-PE was moulded at 160 C
for 5 min under the same pressure. The plaques were
slowly cooled in the hydraulic press to room tempera-
ture in 5 h.
A Perkin–Elmer DSC, DSC-2, interfaced to a PC was
used to measure the thermal properties of the moulded
samples. The calorimetry was operated under a nitrogen
flow 20 cm3 min1 . The temperature of the calorimeter
was calibrated from the observed melting points of
ultra-pure materials––stearic acid, indium, tin and lead
at the heating rates of 10, 5 and 2.5 K min1 and then
extrapolated to zero heating rate to correct for thermal
lag. The procedure used in DSC was the same as de-
scribed previously [7].
Densities were measured on moulded specimens by
ArchimedesÕ method by weighing in air and in n-heptane
at 296 K and averaged over at least three specimens
taken from the same sample. The weight fraction crys-
tallinity is given by
ðq  qa Þqc q
Xc ¼ ¼ Xc;v c ð2Þ
ðqc  qa Þq q
where qc and qa are the densities of crystalline and
amorphous regions. The values used for PET were 1.515
and 1.335 g cm3 respectively [28]. Xc;v is the volume
fraction crystallinity and q is the density of the sample
measured.
WAXD experiments were carried out using a Philips
XÕPert vertical diffractometer interfaced to a PC. The
diffractometer was operated with CuKa radiation and
wavelength of 0.1542 nm at 40 keV and 50 mA. The
diffraction intensities were recorded as a function of
increasing scattering angle 2h, which was in the range 5–
80 with a step angle of 0.02 and the scan time of 1 s per
step. The volume crystallinity was calculated from the
ratio of the areas under the crystalline peak to the total
 Y. Kong, J.N. Hay / European Polymer Journal 39 (2003) 1721–1727 1723

and converted into the weight fraction crystallinity by If a two-phase model [3,27] is adopted for semi-crys-
using the above equation. talline polymers, the enthalpy of the partially crystalline
sample at temperature T is H ðT Þ, i.e.
HðT Þ ¼ Xc ðT ÞHc ðT Þ þ ð1  Xc ðT ÞÞHa ðT Þ ð6Þ
3. DSC analysis
On heating, the rate of heat flow into the sample is then
3.1. Conventional method
dH =dt ¼ ðdH =dT ÞðdT =dtÞ ¼ Cp b ð7Þ
In DSC, the weight fraction crystallinity is conven- where dH =dt is the heat flow, Cp ¼ dH =dT the sample
tionally measured by divided the enthalpy of fusion at apparent heat capacity [27] and b the heating rate. This
the different temperature, i.e. heat capacity has two components, arising from the heat
capacities of the crystalline and amorphous fractions of
Xc ðT Þ ¼ DHf ðT3 ! T4 Þ=DHf0 ðTm0 Þ ð3Þ
the sample and also that arising from any change in
crystallinity, dXc ðT Þ, i.e.,
where Xc ðT Þ is the weight fraction crystallinity,
DHf ðT3 ! T4 Þ is the enthalpy of fusion of the sample Cp ¼ dH =dT
between T3 and T4 as illustrated in Fig. 1, and DHf0 ðTm0 Þ is
dXc ðT Þ
the enthalpy of fusion of the totally crystalline at the ¼ ½Cp;c Xc ðT Þ þ Cp;a ð1  Xc ðT ÞÞ  DHf0 ðT Þ
dT
equilibrium temperature, Tm0 . This is obviously wrong
dXc ðT Þ
since the measurement should be done in the same ¼ Cp;b  DHf0 ðT Þ ð8Þ
temperature, i.e. dT

where Cp;c ¼ dHc ðT Þ=dT and Cp;a ¼ dHa ðT Þ=dT are the
Xc ðT Þ ¼ DHf ðT Þ=DHf0 ðT Þ ð4Þ
heat capacity of completely crystalline and amorphous
in which, materials, dXc ðT Þ=dT is the crystallinity change with
temperature. The first term on the right hand side is the
DHf0 ðT Þ ¼ Ha ðT Þ  Hc ðT Þ ð5Þ change in heat capacity on heating the sample and the
second is the excess heat capacity [4] due to any change
where DHf ðT Þ and DHf0 ðT Þ are the enthalpy of fusion of in crystallinity.
the measured sample and 100% crystalline material at Eq. (8) can be rearranged to
temperature T . Ha ðT Þ and Hc ðT Þ are the enthalpies of the
100% crystalline and amorphous phases at temperature Cp  Cp;b
dXc ðT Þ ¼ dT ð9Þ
T . Apparently, DHf0 ðT Þ is temperature dependent. DHf0 ðT Þ
endothermic

∆Hf

T1 T2 T3 T4
Heat capacity

∆Hc
exothermic

Temperature
Fig. 1. A schematic representation of the enthalpy changes on heating an amorphous crystallisable polymer. Dash baseline drawn
arbitrarily.
1724 Y. Kong, J.N. Hay / European Polymer Journal 39 (2003) 1721–1727

12 0.6

0.5

Fractional crystallinity / wt
10

Heat capacity / J g-1K-1

0.4
8

0.3
6

0.2
4

0.1
2
Liquid
T1 T2 0.0
0
250 300 350 400 450

Temperature / K

Fig. 2. DSC trace of the melting of m-PE and the change in fractional crystallinity with temperature. Liquid amorphous specific heat
extrapolated from the molten state.

If a sample of initial crystallinity, X0 , is melted from T1 served melting occurs over a narrow temperature range
to T2 , as shown in Fig. 2, it is clear that at temperature T1 [29]. Then it can be assumed that DHf0 ðT 0 Þ is independent
the fractional crystallinity is the initial value X0 , while at of temperature, and Eq. (10) reduces to,
T2 the fractional crystallinity is 0. On integrating the Z T2
above Eq. (9) from T1 to T2 gives 1 DHf
X0 ¼ ðCp  Cp;b Þ dT ¼ ð13Þ
Z T2 DHf0 T1 DHf0
Cp  Cp;b
X0 ¼ Xc0 ðT1 Þ ¼ dT ð10Þ where
T1 DHf0 ðT Þ
Z T2
This equation clearly indicates that if the conventional DHf ¼ ðCp  Cp;b Þ dT
method––what might be called ‘‘the baseline procedure’’–– T1

is used to measure the crystallinity, the temperature de-

This is the only situation that observed enthalpy of fu-
pendence of each parameter must be incorporated into
sion of a semi-crystalline polymer can be directly related
the integration equation. Polymer crystals melt over a
to the fractional crystallinity. Although Eq. (13) has a
wide temperature range and drawing an arbitrary base-
similar form to (3), the two enthalpies have been defined
line between two set temperatures, and integrating the
differently. Recently Qiu et al. [8] concluded that the
enclosed area cannot measure the heat of fusion. Instead
degree of crystallinity measured by DSC is equal to the
since [24]
initial crystallinity plus an increment due to heat ca-
Z T2
pacity change, i.e.
DHf ðT2 Þ ¼ DHf ðT 0 Þ þ DCp ðT Þ dT ð11Þ
T0
Xcdsc ¼ X0 þ DXc ð14Þ
0
where DHf ðT2 Þ and DHf ðT Þ are the changes of the
as the temperature dependence of the enthalpy of fusion
enthalpy of fusion at temperature T2 and any other
was not considered and the baseline was incorrectly
temperature T 0 respectively, and DCp ðT Þ is the difference
constructed.
of heat capacity as function of temperature, then
Alternative methods are required to determine the
Z Tm0 fractional crystallinity more correctly.
DHf0 ðT 0 Þ ¼ DHf0 ðTm0 Þ  DCp;c dT ð12Þ
T0
3.2. The First Law method
where DHf0 ðT 0 Þ is the enthalpy of fusion of 100% crys-
talline at any other melting point T 0 , DCp;c is the heat The First Law method is an application of the First
capacity difference between the completely amorphous Law of Thermodynamics to the heating and cooling of a
and crystalline phases. polymer sample in a calorimeter. The detailed descrip-
Only when the polymer sample has been crystallised tion of the method can be found in a previous paper [7].
at high temperature over a long period time is it ob- It involves heating a crystalline sample between two set
 Y. Kong, J.N. Hay / European Polymer Journal 39 (2003) 1721–1727 1725

temperatures, T1 and T2 , and returning the amorphous Combining with Eqs. (4), (12) and (19) gives
sample from T2 back to T1 without crystallisation oc-
R T2
curring. The net change in enthalpy between the two is 0 T0
ðCp  Cp;a Þ dT
the residual enthalpy, DHR , and is measured at T1 . The Xc ðT Þ ¼ R T0 ð20Þ
DHf0 ðTm0 Þ  T 0m DCp;c dT
residual enthalpy is used to measure the crystallinity of
the sample at T1 . The procedure can also be used to
measure the crystallinity of the sample at any interme- The fractional crystallinity of the sample can thus be
diate temperature during heating to melting. determined at any temperature on melting.
At T1 , the crystallinity of the sample is expressed as The essential difference between the ‘‘baseline’’ and
the First Law method is that: in the latter the enthalpies
X0 ðT1 Þ ¼ DHf ðT1 Þ=DHf0 ðT1 Þ ¼ DHR =DHf0 ðT1 Þ ð15Þ of fusion are correct at each temperature and have
where DHf ðT1 Þ and DHf0 ðT1 Þ
are the enthalpies of fusion thermodynamic significance.
of the partially and completely crystalline polymer at T1 .
Similarly at any other temperature T 0 the enthalpy of
fusion is the difference of enthalpy change between the
4. Results and discussion
heating from T 0 to T2 and the cooling amorphous from
T2 to T 0 , i.e.
4.1. The change crystallinity of m-PE on melting
DHf ðT 0 Þ ¼ DH ðT 0 ! T2 Þ þ DH ðT2 ! T 0 Þ ð16Þ
Fig. 2 shows the melting endotherm of the m-PE
in which sample and the resulting change in fractional crystal-
Z T2
linity on heating. m-PE is reasonably thermal stable to
DH ðT 0 ! T2 Þ ¼ Cp dT ð17Þ decomposition above Tm and amorphous heat capacity
T0 can be determined over a significant temperature range
such that it can be extrapolated to ambient temperature
and
with reasonable certainty. The heat of fusion of crys-
Z T0 talline PE was taken directly from Ref. [30]. It is clear
DH ðT2 ! T 0 Þ ¼ Cp;a dT ð18Þ that up to about 300 K the fractional crystallinity of
T2
m-PE is constant, at a value of 0.54 consistent with
On simplifying Eq. (16) becomes those of 0.57 and 0.54 measured by density and WAXD,
Z T2 respectively. On heating above 300 K the fractional
DHf ðT 0 Þ ¼ ðCp  Cp;a Þ dT ð19Þ crystallinity of the sample begins to decrease with tem-
T0 perature and drops progressively to zero at 400 K. The

Amorphous
383K*2h
4
Heat capacity / J g-1K-1

448K*18h

Liquid T2
T1
1

0
350 400 450 500 550

Temperature / K
Fig. 3. DSC analyses in PET amorphous and crystallised at 383 K for 2 h and at 448 K for 18 h on heating. Liquid amorphous line
extrapolated from post-Tg .
1726 Y. Kong, J.N. Hay / European Polymer Journal 39 (2003) 1721–1727

0.4
Amorphous
383K*2h

Fractional crystallinity / wt
0.3 448K*18h

0.2

0.1

0.0

350 400 450 500 550

Temperature / K
Fig. 4. The temperature dependence of the fractional crystallinity of PET on heating––amorphous, crystallised at 383 K for 2 h and
448 K for 18 h.

onset of melting in m-PE early in the heating process corresponding to a minor endotherm which has been
makes the choice of a baseline for integration difficult attributed to the melting of secondary lamellae [31]. In
and a wrong choice will undoubtedly lead to errors from all cases the greatest decreases of crystallinity was due to
the use of the ‘‘baseline method’’ of analysis. the final endotherm above 500 K corresponding to the
melting of annealed or primary lamellae.
During heating to determine the fractional crystal-
4.2. The change crystallinity of PET on melting
linity of a polymer, crystallisation, melting, re-crystalli-
sation, lamellae thickening and final melting have been
The crystallisation and melting of PET samples can be
observed. The fractional crystallinity is not constant
seen in Fig. 3. The samples prior to heating were crys-
with temperature or even time at constant temperature
tallised to different extents at different temperatures,
[4]. By using the First Law method it is possible to
such that the samples are both amorphous and partially
measure the fractional crystallinity of a sample at any
crystalline. Well crystalline samples do not show any
temperature.
apparent crystallisation exotherm, while poorly crystal-
The fractional crystallinity measured by other ana-
line samples show one but which is obviously less than
lytical techniques, such as WAXD and density, are
that of the amorphous samples. Although crystallisation
normally carried out at ambient temperature. Therefore,
conditions were varied this did not prevent annealing
and change of crystallinity occurring on heating. As
mentioned earlier [7], an extrapolated post-Tg specific
heat–temperature dependence was chosen for the liquid
amorphous line owing to degradation of PET above Tm . Table 1
Weight fraction crystallinity of PET measured by different
The change in fractional crystallinity of the above
techniques
PET samples during the heat scan can be seen in Fig. 4.
For amorphous PET the value is zero until above the PET sample Weight fraction crystallinity
glass transition where it increases rapidly from 420 to Density DSC ± 0.02 WAXD
450 K corresponding to the crystallisation exotherm. Amorphous 0.01 0.00 0
The maximum fractional crystallinity reached was about 373 K, 1 h 0.09 0.10 0.11
0.25. Poorly crystallised materials further crystallised at 373 K, 2 h 0.13 0.16 0.17
higher temperatures with the fractional crystallinity in- 373 K, 5 h 0.19 0.20 0.19
creasing on heating. The maximum crystallinity reached 398 K, 18 h 0.25 0.26 0.27
is similar to that of the amorphous samples. In the well 423 K, 18 h 0.27 0.28 0.28
crystalline PET, the crystallinity was almost constant up 448 K, 18 h 0.29 0.31 0.30
473 K, 18 h 0.35 0.36 0.37
to 450 K, but there after it decreased by a small amount
 Y. Kong, J.N. Hay / European Polymer Journal 39 (2003) 1721–1727
in comparing the fractional crystallinity measured by
DSC it must be carried out at the same temperature. In
amorphous PET samples crystallisation occurs at 50 K
above the glass transition temperature, and it is rea-
sonable to consider that the fractional crystallinity
measured at 375 K does not change until this tempera-
ture is exceeded. The original fractional crystallinity of
PET samples, crystallised at different temperatures and
times, as measured by the First Law method, density
and WAXD are compared in Table 1. There is sufficient
agreement between the various methods to suggest that
there is nothing unique about the crystallinity measured
by DSC.
5. Conclusions
Due to the temperature dependence of the enthalpies
of crystallisation and fusion, and to the presence of
annealing and lamellae thickness on heating, the frac-
tional crystallinity of a polymer should not be measured
from the melting endotherm at the observed melt-
ing point. If this is done the values obtained will
not compare with those determined by other analyti-
cal techniques measured at room temperature. As an
alternative, the First Law method of measuring the frac-
tional crystallinity has been proposed. It determines the
fractional crystallinity of the polymer at any tempera-
ture, and comparisons can then be made with other
analytical techniques. No difference in the crystallin-
ities will then be observed and there is no reason to
suggest that DSC is measuring a different average
crystallinity.
The original crystallinity present in the sample mea-
sured by DSC agrees with that determined by other
analytical methods.
Acknowledgements
One of the authors, Y. Kong, acknowledges the award
of a research scholarship from the ORS Committee and
the School of Engineering (Metallurgy and Materials)
during the tenure of this work.
The authors are grateful to Mr. M. Razavi-Nouri
for providing m-PE samples and measuring the frac-
tional crystallinities of m-PE by density and WAXD.
The authors would also like to express their appreci-
ation to Mr. F. Biddlestone for technical support and
assistance.
1727
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