Polymer Testing 30 (2011) 616624

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

Material Behaviour

Changes in activation energy and kinetic mechanism during EVA

crosslinking
O. Bianchi a, J. De N. Martins a, R. Fiorio a, R.V.B. Oliveira a, L.B. Canto b, *
a
b

Federal University of Rio Grande do Sul (UFRGS), Materials Science Graduate Program, 91501-970 Porto Alegre/RS, Brazil
Federal University of So Carlos (UFSCar), Materials Engineering Department (DEMa), 13565-905 So Carlos/SP, Brazil

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 22 March 2011
Accepted 3 May 2011

The activation energy and kinetic mechanism throughout the crosslinking process of
copolymer ethylene-vinyl acetate (EVA), initiated by dicumyl peroxide (DCP), were
determined in the framework of a multi-step solid-state process. Crosslinking was performed in a differential scanning calorimeter (DSC) under non-isothermal conditions. The
activation energy (E) was determined by means of the isoconversional integral method
using the Cai approach. The E values (87105 kJ mol
1) were found to be dependent on the
crosslinking conversion (a) and DCP content. Kinetic mechanisms were determined by the
Criado method from Ea(T) data through the use of the master plots of theoretical kinetic
models. At 0.1 < a < 0.5, the EVA crosslinking obeys homogeneous kinetics with ratecontrolled reactions (Fn mechanisms). At a  0.5, the medium becomes heterogeneous
and EVA crosslinking occurs through a diffusion-controlled reaction (Dn mechanisms). At
a y 0.9, the temperature increases and the EVA crosslinking follows homogeneous
kinetics with Fn mechanisms.
2011 Elsevier Ltd. All rights reserved.

Keywords:
EVA
Crosslinking activation energy
Crosslinking kinetic mechanism

1. Introduction
Crosslinked copolymers of ethylene-vinyl acetate (EVA)
are widely available. Crosslinking of EVA is commonly
performed through a thermochemical process using
dicumyl peroxide (DCP) [16]. This process follows
a mechanism where thermally decomposed peroxide
radicals abstract mainly the hydrogen bonded to the
tertiary carbon of the vinyl acetate groups, followed by
crosslinking through mutual termination of EVA macroradicals to form a network structure. Knowledge of the EVA
crosslinking kinetics can aid the tailoring of the crosslinking degree during processing, which plays a major role
in the ultimate mechanical, thermal and chemical properties. The peroxide-initiated crosslinking of EVA can be
considered as a solid-state process that takes place through

* Corresponding author. Tel.: 55 16 3351 8515; fax: 55 16 3361 5404.

E-mail address: leonardo@ufscar.br (L.B. Canto).
0142-9418/$ see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2011.05.001

the nucleation and subsequent growth of crosslinked gels

within the EVA melt [2].
Kinetic mechanisms of solid-state processes are very
often unknown or too complicated to be determined. One
simple way to deal with this is to consider that a single
mechanism governs the entire process. In this case, the
process can be described by a single kinetic model. On the
other hand, if one wishes to consider changes in the kinetic
mechanism and then in the kinetic model throughout the
process, the dependence of the activation kinetics parameters on the reaction conversion must be taken into
account. This is a difcult task because the interpretation of
this dependence is based on theoretical concepts which
prescribe that the activation parameters of an elementary
reaction step be constant [79].
Isoconversional methods are often used to solve the
dependence of activation kinetics parameters on the reaction conversion for solid-state processes. The advantage of
the isoconversional kinetics methods is that they do not
require prior knowledge of the reaction mechanism (or

O. Bianchi et al. / Polymer Testing 30 (2011) 616624

kinetic model) in order to quantify the kinetic parameters.

The isoconversional methods are, thus, modelindependent techniques or model-free kinetics (MFK) for
determining the activation parameters. Once these values
are determined, the kinetic model can be reconstructed
and the kinetic mechanism can be determined [10,11].
In a previous paper [2] we used the kinetic models of
Avrami, Ozawa and Avrami-Ozawa to gain insight into the
crosslinking kinetics of EVA initiated by DCP. We also used
the isoconversional method of Flynn-Wall-Ozawa (FWO)
with the Doyle approximation to determine the dependence
of the activation energies on the crosslinking conversion.
Plots were constructed of the crosslinking conversion values
obtained from the dynamic heating of EVA/DCP samples in
a differential scanning calorimeter (DSC). The Avrami model
allowed the determination of the rate constant (k) and halflife time (t1/2), and indicated that the growth of crosslinks is
sporadic and spherical, and occurs from nuclei. Systematic
changes observed in the values for the activation energy (E)
(FWO analysis), Ozawa exponent (m) and F(T) parameter
(Avrami-Ozawa model) indicated that the EVA crosslinking
mechanism changes with the degree of conversion during
the process. However, despite the progress made in
obtaining these kinetic parameters, the kinetic mechanisms
that govern each step of the solid-state crosslinking process
of EVA remain unclear.
The aim of this study is to determine the activation
energies and kinetic mechanisms taking place throughout
the EVA crosslinking process initiated by DCP from nonisothermal differential scanning calorimeter (DSC) analysis. The dependence of the activation energy on the
crosslinking conversion (Ea(T)) was determined by means of
the isoconversional integral method applying the approach
proposed by Cai [12], using the nonlinear least-squares
method of the Levenberg-Maquard Algorithm [13,14]. The
kinetic mechanisms occurring throughout the EVA crosslinking process were then identied from Ea(T) data by
means of the Criado method, using a suitable approximation for the Arrhenius integral, by comparing the similarities of the experimental plots with master curves obtained
using theoretical kinetic models.

1.1. Theoretical background

The differential expression for the reaction rate (da/dt)
of a single-step solid-state process has the following
general form:

da
kT$f a
dt

(1)

In Eq. (1), a is the conversion degree (extent of reaction), t

is the reaction time, k is the rate (kinetic) constant which is
dependent on the absolute temperature (T), and f(a) is
a kinetic model function dependent on the conversion (a)
which describes the kinetic mechanism of the process.
The kinetic model can be obtained in the differential
form by rearrangement of Eq. (1):

1 da
f a
kT dt

(2)

617

Eq. (2) can be rearranged to give:

da
kT$dt
f a

(3)

The kinetic model can be obtained in integral form (g(a))

by integration of Eq. (3) between the limits a 0 at t 0
and a a at t t:

ga

a
0

Z t
da
dt kT$t
kT$
f a
0

(4)

The dependence of the rate constant (k) on the temperature (T) can be expressed by the Arrhenius equation:

E


kT A$e RT

(5)

In Eq. (5), A is the pre-exponential factor, E is the activation energy, R is the universal gas constant, and T is the
absolute temperature.
Therefore, Eq. (3) can be rewritten as:

E


da
A$e RT $dt
f a

(6)

If the reaction is carried out under a linear heating rate

(T T0 f$t), where T0 is the onset temperature, T is the
temperature at which a given conversion a is reached and
fdT/dt is the heating rate, and considering that da/
dt da/dt$dT/dtf$da/dt, Eq. (6) becomes:

E
da
A

$e RT $dT
f
f a

(7)

Thus, the kinetic model (g(a)) can be obtained by integration of Eq. (7) between the limits a 0 at T T0 and
a a at T T:

ga

a
0

da
A
$
f
f a

E


e RT $dT

(8)

T0

The value of the integral between 0 and T0 of the function

e
E/RT is usually considered to be negligible (relative to the
integral between 0 and T), which is an acceptable simplication if the reactivity is not too high (i.e., if the temperatures involved in the process are signicantly higher than
the onset temperature) [15]. Therefore, one can write:

ga

A
$

E


e RT $dT

(9)

The integral of Eq. (9) is called the temperature integral

or Arrhenius integral. It has no analytical solution. The
numerical solution of Eq. (9) can be represented by:


ga

AE

fR

x

$e

px
x

(10)

In Eq. (10), p(x) is an approximation of the Arrhenius

integral obtained by integration of the conversion (a) over
the temperature (T) and x E/RT.

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O. Bianchi et al. / Polymer Testing 30 (2011) 616624

Cai et al. [12] obtained approximation constants for the

Arrhenius integral based on the Pattern Search numeric
solution method considering one degree rational:

px

x 0:66691
x 2:64943

(11)

The Cai approximation shows a low percentage deviation

when compared to other methods proposed in the literature [15].
Substituting Eq. (11) into Eq. (10), and solving the
exponential equation by the taking natural logarithm of
both sides, one obtains an equation for the evaluation of
non-isothermal kinetic parameters [12]:

ln





ga
AR E 0:66691$RT
E


ln
$
2
fE E 2:64943$RT
T
RT

(12)

Eq. (12) describes the behavior of a single-step solid-state

process where the activation energy (E) and the preexponential factor (A) are independent of the conversion
(a). However, for a multi-step solid-state process like
crosslinking, the Arrhenius parameters are dependent on a.
Isoconversional methods allow complex multi-step
solid-state processes to be solved by evaluation of the
dependence of E on a or T. The advantage of the isoconversional kinetics methods under non-isothermal
conditions is that they do not require prior knowledge of
the kinetic model in order to quantify the Arrhenius
parameters. These isoconversional methods are, thus,
kinetic model-independent techniques or model freekinetics (MFK) for determining the Arrhenius parameters.
The isoconversional methods are based on the principle
that the unknown form of g(a) may be eliminated by
comparing the data for a set of isoconversional temperatures obtained from various heating rates. Since at a xed

value of a the f(a) function holds for any temperature or

temperature regime, the isoconversional method is applicable to each conversion and to the temperature interval
(DT) related to this conversion. Thus, the isoconversional
method can describe the kinetics of a solid-state process by
using multiple single-step kinetic equations, each of which
is associated with a given conversion (a) [10,11].
Through the use of the isoconversional method, Eq. (12)
can be rearranged as:

6
7
f
7
ln6
4
5
E

0:66691$RT
a
a
T
T
Ta2Ta $
EaT 2:64943$RTaT


AaT $R
EaT


ln
EaT $ga
RTaT

(13)

The subscript a(T) of Eq. (13) refers to a given conversion

(a). The rst term on the right side of Eq. (12) can be
considered to be an adjustable parameter. Thus, from Eq.
(13), the dependence of E on a can be obtained by integral
methods using non-linear approximations from the
dependence of the reaction rate (da/dt) on temperature (T)
obtained from a set of kinetic runs at linear heating rates.
The evaluation is carried out for each conversion (a).
Criado et al. [16,17] obtained a method to determine the
kinetic mechanisms of multi-step solid-state processes
based on the comparison of an experimental function
called Z(a(T)) obtained from Ea(T) with the master curves
obtained for the theoretical kinetic models f(a) and g(a)
describing the kinetic mechanisms that govern each step of
a solid-state process. This method has been successfully
used in kinetic studies on the thermal degradation of
polymers [18].

Table 1
Kinetic mechanisms of solid-state processes and the corresponding algebraic expressions for the kinetic models f(a) and g(a).
Kinetic mechanisms

Kinetic models
f a

Nucleation and grown

A2: Avrami-Erofeev
A3: Avrami-Erofeev
A4: Avrami-Erofeev
Geometrical
R1: Phase boundary-controlled reaction (linear contraction)
R2: Phase boundary-controlled reaction (contracting area)
R3: Phase boundary-controlled reaction (contracting volume)
Reaction-order
F1: 1st order (random nucleation with one nucleus on the individual particle)
F2: 2nd order (random nucleation with two nuclei on the individual particle)
F3: 3rd order (random nucleation with three nuclei on the individual particle)
Diffusion
D1: One-dimensional
D2: Two-dimensional (Valensi equation)

D3: Three-dimensional (Jander equation)

D4: Three-dimensional (Ginstling Brounshtein equation)

1 da
kT dt

ga

R a da
kT$t
0
f a

21
a
ln1
a1=2
31
a
ln1
a2=3
41
a
ln1
a3=4

ln1
a1=2

ln1
a1=3

ln1
a1=4

1
21
a1=2
31
a2=3

1
a
1
a2

ln1
a
1
a
1 
1

1
a3

1=21
a
2 
1

1=2a
1

ln1
a

a2

31
a2=3
21
1
a1=3 
3
21
a
1=3
1

1
1
a1=2
1
1
a1=3

1
a,ln1
a a
1
1
a1=3 2
1
2a=3
1
a2=3

O. Bianchi et al. / Polymer Testing 30 (2011) 616624

Fig. 1. DSC scans of EVA samples.

619

Fig. 2. Crosslinking conversion (a(T)) vs. crosslinking time (t) for EVA
samples.

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O. Bianchi et al. / Polymer Testing 30 (2011) 616624

Criado et al. [16,17] assumed the Z(a(T)) master curves to

be a convolution function of f(a) and g(a):

ZaT f a$ga

(14)

The experimental Z(a(T)) function can be obtained from

Eq. (14) by combining Eqs. (6) and (10):

da T
ZaT
$ $px
dt f

(15)

Criado et al. [16,17,19] proposed the resolution of the

experimental Z(a(T)) function (Eq. (15)) using the approximation of Senum and Yang, which is based on an eight
degree rational expression for p(x):

px

2.4. Determination of crosslinking conversions

The crosslinking conversions (a(T)) were obtained from
DSC measurements as being proportional to the enthalpies
of the exothermic events in the range of 150220  C,
according to the following equation:

 
R T dH
dT
T0
dT
aT R  
TN dH
dT
T0
dT

In Eq. (17), dH/dT is the crosslinking enthalpy at an

innitesimal temperature, T0 and TN are, respectively, the

x7 70x6 1; 886x5 24; 920x4 170; 136x3 577; 584x2 844; 560x 357; 120
x8 72x7 2; 024x6 28; 560x5 216; 760x4 880; 320x3 1; 794; 240x2 1; 572; 480x 403; 200

According to Flyn et al. [20] and Perez-Maqueda et al.

[21], the percentage deviation resulting from the use of the
Senum and Yang approximation is less than 10
11% when
x > 20.
Equation (15) can be solved from a set of experimental
da=dtjaT values by using Ea(T) data obtained from Eq. (13)
and the p(x) approximation of Eq. (16).

(17)

(16)

onset and end crosslinking temperatures, and T is the

instantaneous temperature.
Crosslinking reaction times (t) were obtained through
Eq. (18):

T
T0

(18)

2. Experimental
2.1. Materials

2.5. Determination of crosslinking activation energies

The copolymer ethylene-vinyl acetate (EVA), supplied

by Poletilenos Unio S/A (UE1866), contains 18 wt% of vinyl
acetate, as determined by thermogravimetric analysis
(TGA), and has a weight-average molecular weight (Mw) of
225,000 g mol
1 and a polydispersity (Mw/Mn) of 12, as
determined by gel permeation chromatography (GPC). The
dicumyl peroxide (DCP) (Aldrich, 98% of purity) was used as
received.

The dependency of the activation energy on crosslinking

conversion (Ea(T)) was determined by means of the isoconversional integral method with the approach proposed
by Cai [12], from a(T) (Eq. (17)) and t (Eq. (18)) experimental
data. Eq. (13) was solved using the nonlinear least-squares
method of the Levenberg-Maquard Algorithm (LMA)
[13,14]. Correlation coefcients were found to be above 0.98.

2.2. EVA/DCP compounding

EVA was compounded with 1, 2 or 4 wt% of dicumyl
peroxide (DCP), which represents [VAc]/[peroxide radical]
molar ratios of 28, 14 and 7, respectively. These are typical
amounts used in industry. The compounding was performed on a two-roll mill at 100  C for 15 min. Under these
conditions, homogeneous dispersions of DCP in EVA were
produced, and the formation of the peroxide radical was
largely avoided.
2.3. DSC analysis
Heat ows as a function of temperature (or time) at
constant heating rates were recorded using a Shimadzu DSC50 instrument. Samples (ca. 10 mg) were cut from the
previously compounded materials. The samples were heated
from 25 to 280  C, at ve different heating rates (2.5, 5, 10, 20
and 40  C min
1), under N2 atmosphere (50 mL min
1).

Fig. 3. Activation energies (E) vs. crosslinking conversion (a(T)) for EVA
samples.

O. Bianchi et al. / Polymer Testing 30 (2011) 616624

621

Fig. 4. Plots of experimental Z(a(T)) vs. crosslinking conversion (a(T)) for EVA samples superimposed on master curves of kinetic models f(a) and g(a) shown in
Table 1.

2.6. Determination of crosslinking kinetic mechanisms

The crosslinking kinetic mechanisms were determined
by means of the Criado method [16,17] from Ea(T) data.

Experimental Z(a(T)) plots (Eqs. (15) and (16)) were

superimposed on theZ(a(T)) master curves obtained from
Eq. (14) using the theoretical kinetic models f(a) and g(a) to
describe the most common solid-state kinetic mechanisms

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O. Bianchi et al. / Polymer Testing 30 (2011) 616624

Fig. 4. (continued)

(Table 1). By comparing the similarity of these curves the

kinetic mechanisms occurring throughout the EVA crosslinking process can be identied.
3. Results and discussion
The DSC curves for EVA samples compounded with
different amounts of DCP (1, 2 and 4 wt%) scanned at
three different heating rates (2.5, 10 and 40  C min
1) are
shown in Fig. 1. In these curves the EVA crosslinking
appears as an exothermal event. Crosslinking peak
temperatures are shifted to higher temperatures and
crosslinking enthalpies (H) become higher as the DCP
content and/or the heating rate increase. This increase in
H is the result of more favorable conditions for the EVA
crosslinking. The higher crosslinking peak temperatures
observed for samples with increased DCP content and/or
scanned at higher heating rate is an indication that the
increase in bulk viscosity with the conversion restricts
the EVA crosslinking process.
Fig. 2 shows the curves for the crosslinking conversion
(a(T)) as a function of crosslinking time (t) for the EVA
samples of Fig. 1. All curves presented a sigmoid shape,
indicating a fast primary crosslinking process during the

initial stages and a slower secondary process during the

later stages. As expected, the crosslinking performed at
slower heating rates resulted in longer times for the reaction induction. However, the shape of the curves remained
practically unaltered with changes in the heating rate and
DCP content in the samples.
The activation energies (E) as a function of crosslinking
conversion (a(T)) for samples containing different amounts
of DCP are shown in Fig. 3. The Ea(T) values were found to be
in the range of 87105 kJ mol
1. These values are of the
same order of magnitude as those obtained by other
methods [1,2]. The evaluation of the dependence of E on
a is more realistic than the determination of a single activation energy value. Moreover, the use of the model-free
isoconversional method is considered to be more deterministic and to provide reliable values for the dependence
of E on a [10,18]. For the EVA sample with the lowest DCP
content (1 wt%), the E values decreased and then increased
and nally leveled-off with a(T). For the EVA sample with
intermediate DCP content (2 wt%), the E values decreased
and then leveled-off and nally decreased with a(T). For the
EVA sample with the highest DCP content (4 wt%) the E
values increased and then leveled-off and nally decreased
with a(T). Also, the Ea(T) values were found to be higher for

O. Bianchi et al. / Polymer Testing 30 (2011) 616624

EVA samples with increasing DCP contents. Clearly, it can

be seen that the dependence of E on a is driven by more
than one effect. Considering that in dynamically heated
low-viscosity (diluted) systems the activation energy
increases with conversion (due to increased temperature),
and taking into account the behavior of the systems under
study (Fig. 3), it is clear that the effect of increased viscosity
with crosslinking conversion is signicant, and of course
this effect is more evident for EVA samples with increasing
DCP content. Therefore, the dependency of E on a (Fig. 3)
suggests that the kinetics of the EVA crosslinking process
changes from rate-controlled to diffusion-controlled as the
viscosity increases with the crosslinking conversion. The
dependency of E on a provides a starting point to identify
the kinetic mechanisms occurring throughout the crosslinking process of EVA.
Fig. 4 shows the experimental Z(a(T)) plots for the EVA
samples superimposed on the master curves obtained
using the kinetic models f(a) and g(a) of Table 1. The kinetic
mechanisms occurring throughout the crosslinking process
of EVA can be obtained by comparing the similarity of these
curves. It can be observed that the experimental Z(a(T))
plots of all the EVA samples match the Fn mechanisms
(chemically controlled reactions) and Rn (phase boundarycontrolled reactions) between 0.1 and 0.2 of conversion
completion, whatever the DCP content and heating rate
used. Between 0.3 and 0.4 of conversion completion, all the
samples match the Fn mechanisms. For a  0.5, there is
a gradual change to Dn mechanisms (diffusion-controlled
reaction) for all the systems. EVA samples containing any
DCP content crosslinked at the lower (2.5  C min
1) and
higher (40  C min
1) heating rates show Dn mechanisms up
to 0.9 of conversion completion; on the other hand, EVA
samples containing any DCP content crosslinked at the
intermediate (10  C min
1) heating rate gradually change
to Fn mechanisms from 0.8 up to 0.9 of conversion
completion.
These results conrm our assumption that thermal
crosslinking of EVA initiated by DCP behaves as a multistep solid-state reaction. At the beginning (0.1 < a < 0.5),
the crosslinking involves rate- or chemically-controlled (Fn
mechanisms) reactions. The reaction-order models (Fn
mechanisms) are similar to those used in homogeneous
kinetics, where the reaction rate is proportional to the
reactant concentration and the reactivity (kinetic constant).
Hence, instantaneous random nucleated macroradicals
react to form ever larger chains. The explanation for the
matching of the Rn mechanisms at the very beginning of the
reaction (0.1  a  0.2) is associated with the fact that these
kinetic mechanisms assume that nucleation occurs rapidly
in addition to the bulk contraction and density increase
that occurs due to crosslinking. As the crosslinking
proceeds (a  0.5), a volume of the high viscosity gel phase
is reached which is sufcient to make the medium
heterogeneous. Hence, the reaction rate becomes
controlled not only by the concentration and reactivity of
the macroradicals but also by their movement across the
interface and, therefore, the crosslinking becomes
diffusion-controlled (Dn mechanisms). For higher conversion degrees (a y 0.9), the temperature increases (note
that the crosslinking is performed under constant heating

623

rate) and thus the medium starts to behave with a lower

degree of heterogeneity and, therefore, the crosslinking
reactions become chemically-controlled (Fn mechanisms).
This interpretation indicates that a transition state
according to the Boltzmann distribution (homogeneous
kinetics) cannot fully explain the EVA crosslinking reactions since they behave as heterogeneous reactions as the
conversion increases [22].
4. Conclusions
The activation energy and kinetic mechanism
throughout the crosslinking process of the copolymer
ethylene-vinyl acetate (EVA) initiated by dicumyl peroxide
(DCP) under controlled heating in a differential scanning
calorimeter (DSC) were determined in the framework of
a multi-step solid-state process. Activation energies (E)
were obtained from DSC data using the Cai method.The E
values (87105 kJ mol
1) were found to be dependent on
the crosslinking conversion and DCP content in the EVA
samples. From the dependence of the activation energy on
the crosslinking conversion (Ea(T)), the kinetic mechanisms
were determined using the Criado method through
comparison of the experimental plots with the master
curves of theoretical kinetic models. At the beginning of the
reaction (0.1 < a < 0.5), the EVA crosslinking obeyed
a homogeneous kinetics with rate-controlled reactions (Fn
mechanisms). As the crosslinking proceeds (a  0.5), the
medium becomes heterogeneous and EVA crosslinking
occurs through diffusion-controlled reactions (Dn mechanisms). In the latter stages, for higher conversion degrees
(a y 0.9), the temperature increases and the crosslinking
kinetics becomes homogenous with chemically-controlled
reactions (Fn mechanisms).

Acknowledgments
The authors are thankful to Dr. Junmeng Cai from
Shanghai Jiao Tong University for explanations regarding
some of the algebraic expressions used in this study.

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