Polymer Testing 40 (2014) 33e38

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Property modelling

On the Kissinger equation and the estimate of activation

energies for non-isothermal cold crystallization of PET
Renate M.R. Wellen a, *, Eduardo L. Canedo b
a
Federal University of Pernambuco, Recife PE, 50740-521, Brazil
b
Technological Institute of Pernambuco, Recife PE, 50740-540, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The activation energy for nonisothermal cold crystallization of polyethylene terephthalate
Received 29 June 2014 (PET) and its blends with 1% polystyrene (PS) and 1% styrene-acrylonitrile copolymer
Accepted 8 August 2014 (SAN) were measured based on differential scanning calorimetry (DSC). The Kissinger
Available online 27 August 2014
method was used to compute the activation energies in all cases, obtaining mean values of
120, 100, and 85 kJ/mole for neat PET, PET/1%PS and PET/1%SAN. A modified Kissinger
Keywords:
procedure is proposed to estimate activation energies in polymer systems in which the
Activation energy
relative crystallinity - measured at constant heating rates - can be correlated by the Ozawa
Kissinger method
Nonisothermal cold crystallization
model with a temperature-independent exponent. Values of the activation energy of 115
PET and 160 kJ/mole were obtained for cold crystallization of PET in the PET/1%PS and PET/1%
SAN blends using the modified Kissinger procedure.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction k ¼ k0 expðEa =RTÞ (1)

The activation energy of a chemical reaction is defined
as the minimum amount of energy required to activate the
molecules of the reactant to a condition in which they can
undergo the chemical transformation. In terms of the
transition-state theory, the activation energy is the differ-
ence in energy content between the activated or transition-
state configuration and the reactant their initial configu-
ration. Activation energy can be thought of as the height of
the energy barrier separating two minima of potential en-
ergy (of reactants and products of the reaction). For a re-
action to advance at a measurable rate, an appreciable
number of reactant molecules should have energy equal to
or greater than the activation energy in the conditions of
the reaction. Under these conditions, the rate constant, that
is, the factor of the reaction rate that depends on temper-
ature, and not on the concentration of reactants and
products, can be represented by an Arrhenius expression:
* Corresponding author.
E-mail address: wellen.renate@gmail.com (R.M.R. Wellen).
where k0 is a pre-exponential factor, Ea is the activation
energy (energy per mole), T is the temperature in the ab-
solute scale, and R ¼ 8,315 J/K mole is the universal gas
constant. The parameters k0 and Ea depend on the process
in question, but are independent of the temperature. These
concepts, while strictly speaking valid only for simple one-
step chemical reactions, can be generalized to complex
multistep reactions - considering the rate-controlling step -
and many physical processes. For polymeric systems, acti-
vation energy is a parameter used to investigate many
chemical and physical transformations, such as crystalli-
zation, reticulation, degradation, decomposition, etc. The
effect of additives, pigments, fillers, and other resins may
be analyzed in terms of activation energies [1e8].
Thermal analysis techniques, in particular differential
scanning calorimetry (DSC), are widely used to acquire data
of time, temperature and heat flow absorbed or released
during the process under investigation. Several procedures
have been developed to calculate activation energies [9e14].
Among them, the Kissinger method has been extensively

http://dx.doi.org/10.1016/j.polymertesting.2014.08.008
0142-9418/© 2014 Elsevier Ltd. All rights reserved.
34 R.M.R. Wellen, E.L. Canedo / Polymer Testing 40 (2014) 33e38

used to study polymer crystallization during the heating of

substantially amorphous samples of semicrystalline poly-
mers, a process known as cold crystallization [15,16].
Recently, generalized activation energy, a function of
temperature or conversion, has been defined for complex
processes [17e19]. However, the classical concept of activa-
tion energy as a single number characterizing the process
(even if approximately so) irrespective of processing condi-
tions or extent of reaction, has not completely loss its appeal.
In the present work, the Kissinger method is applied to
the investigation of the energy barrier for the cold crys-
tallization of the semicrystalline thermoplastic poly-
ethylene terephthalate (PET) and blends of PET with small
amounts of the amorphous, immiscible polymers poly-
styrene (PS) and a copolymer of styrene and acrylonitrile
(SAN). PET is widely used in many industrial applications,
such as bottles for the packaging industry, fibers for the
clothing industry, and devices for the transport industry, in
which crystallinity developed during processing plays an
important role, PS and the SAN are polymers widely used in
the packing, micro-electronics and house devices in-
Fig. 1. Schematic DSC scans for PET, PS, and SAN heated at 10 C/min.
dustries. Experimental evidence shows that the addition of
small amounts of PS or SAN has a significant effect in
controlling the cold crystallization of mostly amorphous were prepared in a Haake Rheomix 600 laboratory internal
PET samples in a similar way as an anti-nucleating agent mixer fitted with high intensity (roller type) rotors for
does, but with no damage in the mechanical properties, any 10 minutes, with the chamber wall kept at 265 C and the
formulation that difficult the crystallization of PET, nominal speed of the rotors set at 60 rpm. Immediately
increasing the required supercooling and/or decreasing the after mixing, the melt was quenched in iced water to
crystallization rate will have a significant impact on the minimize PET crystallization and obtain substantially
operating window of process that are affected by the amorphous samples.
crystallinity of the material. Process such as blow of con- The nonisothermal cold crystallization of PET, PET/PS
tainers, extrusion film blowing, and fiber forming are ex- and PET/SAN blends with 1% of PS or SAN (by weight) was
amples of these processes [20e26]. Along with the “classic” investigated using a differential scanning calorimeter Shi-
Kissinger method, a reformulated Kissinger method is madzu DSC-50. Glassy samples, 5 to 8 mg in weight, were
suggested to obtain a modified activation energy for the heated from room temperature to 300 C at ten different
cold crystallization conducted at constant heating rates for rates: 1, 2.5, 5, 7.5, 10, 15, 20, 30, 40, and 50 C/min. All test
systems in which the experimental data can be modeled samples were wrapped in aluminum foil to get better heat
following Ozawa's theory [27]. transfer [28].

2. Experimental
2.1. Materials
Bottle grade PET, trade name Rhopet S78, was supplied
by Rhodia (Brazil) with an intrinsic viscosity [h] ¼ 0.78 dL/g
and weight-average molar mass Mw ¼ 48 kg/mol. Injection
grade PS and SAN, trade names Styron 649D and Luran
358N, were purchased from Dow (Brazil) and from BASF,
respectively. Preliminary DSC scans of the polymers in Fig. 1
showed glass transitions at 70 C, 95 C and 107 C corre-
sponding to PET, PS and SAN; an exothermic cold crystal-
lization peak at and an endothermic melting peak of PET.
Complete absence of crystallinity is observed for PS and
SAN.
2.2. Methods
Before mixing, the polymers were oven dried under
forced air circulation to remove humidity and prevent PET
degradation during processing. PET was dried at 120 C for
6 hours, and PS and SAN at 80 C for 14 hours. The blends
3. Theoretical background
Kissinger [15] developed a procedure to estimate the
activation energy in physical or chemical processes from
data obtained at several nonisothermal tests conducted at
constant heating rates (constant during each test, different
among tests). The conditions for the validity of Kissinger
approach are:
(a) The expression of the rate of reaction c as a function of
temperature T and conversion x is separable, that is,
may be written as a product of two factors: a kinetic
constant k, which is a function only of temperature, and
a function f of the conversion but not of the
temperature:



dx
c¼ ¼ k T $f x (2)
dt
(b) The kinetic constant is an exponential function of the
reciprocal of the temperature, Eq. (1).
 R.M.R. Wellen, E.L. Canedo / Polymer Testing 40 (2014) 33e38 35

(c) Tests are conducted at constant heating rate F ¼ dT/ Eq. (6) correspond to a first-order process for which
dt > 0; the method cannot be applied to processes that q ¼ 1. Eq. (7) involves the so-called Avrami-Efremov ki-
occur during cooling [9]. netics [10,11] for which q z 1; for example, for a sym-
metric peak (xp ¼ 0.5), q ¼ 1.13 for m ¼ 1 and q ¼ 1.03 for
(d) The rate of reaction at constant heating rate F as a m ¼ 4. For constant Ozawa exponent equations (6) and (7)
function of temperature has a relative maximum in the are in accordance with Kissinger conditions (a), (c), (d) and
interval under study; that is, there is a peak tempera- (e); agreement with condition (b) is checked a posteriori: a
ture Tp for which dc/dT ¼ 0 and d2c/dT2 < 0. It is open to linear relationship in the plot of Kissinger is taken as proof.
question how to treat systems that for some values of Eq. (6) suggests an alternative way to estimate an acti-
heating rate show multiple peaks and for others single vation energy. The equivalent of Kissinger's Eq. (3) for a
peaks. process modeled according to Ozawa and conducted at
(e) The rate or variation of the kinetic function f(x) at the constant heating rate is:
peak is a negative constant q ¼ (df/dx)p < 0.

fEa0 0 1m Ea0
¼ k 0 f exp  (8)
Under these conditions, Kissinger demonstrated that, RTp2 RTp
for a series of nonisothermal tests:
where k'0 and E'a are defined by the expression:


fEa Ea

¼ qk exp  (3) dk 
RTp2
0
RTp ¼ k0 exp  E0 RT (9)
dT 0 a

or:
 . 
d ln f Tp2 E
   ¼ a
d 1 Tp R d ln fm Tp2 E0
According to Eq. (4), a plot of lnðf=Tp2 Þ versus 1/Tp(Kis-
singer plot) leads to a straight line with slope equal to Ea/
R. Kissinger method is strictly valid only if all five condi-
tions above, (a) to (e) are met. Frequently, compliance is
assumed or proven to be only approximate. In usual ap-
plications, peak temperatures Tp are obtained directly from
the output of DSC tests conducted at different constant
heating rates F. The Kissinger method provides a simple
and direct (model-free) way to estimate the activation
energy Ea for the nonisothermal cold crystallization of
polymers.
Ozawa [27] proposed a model to correlate the relative
crystallinity x during nonisothermal crystallization of a
polymer from a series of tests conducted at different (but
constant during each test) heating or cooling rates F ¼ jdT/dtj:
 
x ¼ 1  exp kfm
where the Ozawa parameter k is a function of temperature,
k ¼ k(T), and the Ozawa exponent m is a constant, inde-
pendent of the temperature. In addition to having some
theoretical foundation (it can be obtained from Nakamura's
isokinetic assumption [9,28] as the limiting case for con-
stant heating rate), Ozawa's model has the unique charac-
teristic among other macrokinetic nonisothermal models
of having the parameter as a function of temperature.
The differential form of Ozawa's model, the crystalliza-
tion rate corresponding to Eq. (4) is:
dx dk 1m
¼ f ð1  xÞ
dt dT
This may further developed expressing F as a function
of k and x according to Eq. (4):

11=m
dx d ln k
¼ k1=m ð1  xÞ ln 1
dt dT 1x
The equivalent of Eq. (4) is now:
 . 
(4)
   ¼ a (10)
d 1 Tp R
According to Eq. (10), a plot of ln ðf m = Tp2 Þ versus 1/Tp
should lead to a straight line with slope equal to Ea0 =R. The
parameter E'a is a modified activation energy, different, in
general, from activation energy Ea.
If Ozawa exponent is a function of temperature, the
differential form of Ozawa's model is not separable; for
example, the equivalent of Eq. (6) in this case is:


dx dk dm
¼ k ln f f1m ð1  xÞ (11)
dt dT dT
Eq. (11) cannot be separated into the product of two
functions, one of temperature alone and the other of con-
version (relative crystallinity) alone. The Kissinger method
(5) should not be applied in this case.
Finally, while using Kissinger procedure to estimate the
activation energy for cold crystallization of polymers, the
following considerations must be taken under advice:
 Activation energies may be estimated by other pro-
cedures, even if the data fail to meet Kissinger condi-
tions. The Kissinger method is a very convenient way to
estimate it, but the concept of activation energy is far
more general than the limited assumptions of this
particular method.
 Complex processes such as polymer crystallization may
not be well represented by a single activation energy,
(6)
which assumes that the same mechanism prevails from
the onset (x z 0) to the end of the process (x z 1).
4. Results and discussion
(7)
DSC raw data in the form of heat flow (J) versus time (t)
or temperature (T) were integrated in the time interval
36 R.M.R. Wellen, E.L. Canedo / Polymer Testing 40 (2014) 33e38

corresponding to the cold crystallization event, from a start

point (t1) to end point (t2) (visually determined and using a
straight virtual baseline (J0) between them) to obtain the
relative crystallinity x (fraction crystallized) and the crys-
tallization rate (normalized peak) c computed as:

dx jJ  J0 j
c¼ ¼ (12)
dt E0
where E0 is the gross latent heat of crystallization:

Zt2
E0 ¼ jJðt 0 Þ  J0 ðt 0 Þjdt 0 (13)
t1

Relative crystallinities and crystallization rates may be

expressed as functions of time or temperature, taking into
consideration that, at constant heating rate (F ¼ dT / dt),
temperature is a linear function of time.
Fig. 2 shows the normalized nonisothermal cold crys-
tallization peaks of PET, PET/1%PS and PET/1%SAN deter-
mined at different heating rates [30e36]. Addition of a
small amount of amorphous immiscible polymer results in
a delay of cold crystallization of the matrix. Thus, PS and
SAN behave as anti-nucleant or retardant agents as far as
the cold crystallization of PET is concerned. While the de-
gree of crystallinity is not significantly affected by the
addition of PS or SAN, the rate of crystallization diminishes,
resulting in broader and shorter cold crystallization peaks
when compared with the neat PET crystallization peaks
[20e22,25]. Even although PS is an apolar and SAN a polar
polymer, both have the same effect on the cold crystalli-
zation of PET, at least at the low level, 1%, tested in this
work. Table 1 lists the peak crystallization temperature for
all heating rates tested.
Fig. 3 presents the Kissinger plots based on the data of
Table 1. From the slope of the straight lines in the plots, the
following values of the activation energy were obtained:
Ea ¼ 120 ± 12 kJ/mole for neat PET, Ea ¼ 100 ± 14 kJ/mole for
PET/1%PS, and Ea ¼ 85 ± 8 kJ/mole for PET/1%SAN. The
expected uncertainty of the activation energy is in the
range of 9.5e13%, an acceptable level, as the repeatability
and reproducibility of DSC measurements is not better than
6 and 8%, respectively [1,2]. Fig. 2. Crystallization rate versus temperature for nonisothermal cold
However, the data in Fig. 3 are not well represented by crystallization of PET at several heating rates (indicated). Notice the differ-
straight lines and the linear Kissinger relationship was ences in vertical scale.

forced upon them. The slopes in Fig. 3 increase as the

temperature decreases (or Tp1 increases), suggesting a
variable, temperature dependent activation energy. For Table 1
example, for neat PET crystallization at 110e120 C an Peak temperature for non isothermal cold crystallization of PET.
activation energy of 165 kJ/mole may be more appropriate
PET PET/1%PS PET/1%SAN
than the average value of 120 kJ/mole estimated over the
temperature interval 110e140 C, while at 130e140 C a F ( C/min) Tp ( C) F ( C/min) Tp ( C) F ( C/min) Tp ( C)

value of 85 kJ/mole may be better, supported by the 1 110.3 1 120.9 1 118.1

experimental data (broken lines in Fig. 3). Since the relative 2.5 112.4 2.5 124.7 2.5 125.0
5 117.7 5 130.2 5 131.2
crystallinity increases with the temperature during the cold
7.5 120.4 7.5 137.2 7.5 135.5
crystallization process, the effective activation energy may 10 124.4 10 140.6 10 139.7
be considered as a function of the conversion, as suggested 15 128.6 15 147.6 15 146.9
in the literature [37e46]. 20 131.9 20 140.2 20 150.4
The DSC data for the cold crystallization of PETand the two 30 137.4 30 163.5 30 160.6
40 142.6 40 167.4 40 169.6
blends at different heating rates were correlated according to
50 148.6 50 159.5 50 178.2
the Ozawa model, Eq. (5), to obtain the corresponding
 R.M.R. Wellen, E.L. Canedo / Polymer Testing 40 (2014) 33e38
Fig. 3. Plots of Kissinger to evaluate the activation energy Ea for the non-
isothermal cold crystallization of PET, PET/1%PS, and PET/1%SAN. Solid lines
correspond to mean values; broken lines correspond to low and high tem-
perature fittings for neat PET.
parameters as functions of temperature in the intervals of
120e135 C for neat PET, 120e145 C for the blends. The re-
sults may be found elsewhere [20e22,25]. Fig. 4 shows
Ozawa's exponent m as a function of temperature.
Fig. 4 shows neat PET Ozawa's exponent is strongly
dependent on temperature for the whole interval tested,
being four times higher at 120 C (m ~ 1) than at 135 C. On
the other hand, Ozawa's exponent for the cold crystalliza-
tion of PET in the blends, while showing a drop at on the
lower temperatures tested, display an (approximately)
constant exponent for T > 130 C: m z 1.53 for PET/1% PS
and m z 2.27 for PET/1% SAN.
According to the equivalence between isothermal
Avrami and nonisothermal Ozawa models [29,30], the
Fig. 4. Ozawa exponent m versus temperature, estimated throughout the cold
crystallization temperature interval at heating rates from 1 C/min to 50 C/min.
37
Fig. 5. Modified Kissinger plot to evaluate the activation energy E'a for the
nonisothermal cold crystallization of PET/1%PS and PET/1%SAN (heating
rates from 5 C/min to 50 C/min).
Ozawa exponent m describes some characteristics of crys-
talline entities during the crystallization. If homogeneous
nucleation and diffusion controlled crystal growth are
assumed the value of m z 1.53 for PET/PS blends suggests
one-dimensional crystal growth geometry and the value of
m z 2.27 suggests two or tri-dimensional crystal geometry.
Fig. 5 presents plots of ln fm = Tp2 versus 1 / Tp for the two
blends using only tests in which Tp > 130 (heating rates
greater than 5 C/min), a condition in which the Ozawa's
exponent may be assumed approximately constant, inde-
pendent of temperature. From the slope of the straight lines
in the plots, the following values of the modified activation
energy were obtained: E'a ¼ 115 ± 20 kJ/mole for PET/1%PS
and E'a ¼ 160 ± 28 kJ/mole for PET/1%SAN.
5. Final considerations
The Kissinger method has been applied to obtain the
activation energy for the cold crystallization of PET in neat
resin, and in blends with small amounts of PS and SAN. A
modification of the classic procedure was presented, appli-
cable to processes conducted at constant heating rates that
can be modeled according to Ozawa procedure, in systems
with little secondary crystallization and narrow variation of
the morphological structure of the crystallites, leading to
almost constant values of the m exponent. The Kissinger is a
very simple and fast method to obtain mean activation en-
ergies, useful in comparative studies, specifically those
taking place during constant heating rates with a defined
peak temperature. An analysis of Kissinger plots may also
show the activation energy dependence on temperature,
and allows computing local values of the activation energy
for different stages of the process. In this way, it may be a
simpler alternative to complex isoconversional kinetic
analysis, which is related to the extent of phase trans-
formation, valid at least for a preliminary screening. Iso-
conversional methods lead to temperature dependent
38 R.M.R. Wellen, E.L. Canedo / Polymer Testing 40 (2014) 33e38
activation energy. Some researchers believe that the acti-
vation energy should be a constant, independent of tem-
perature, in order to be a meaningful kinetic parameter [6,7].
Acknowledgments
The authors wish to thanks Rhodia (presently M&G)/
Brazil for providing the PET, and CNPq/Brazil (MCTI/CNPq
N 14/2012) and FACEPE/PE/Brazil for the financial support.
RMRW thanks Dr. Holger Warth, Director of Material Sci-
ence at SABIC, for discussions related to this subject.
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