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Material Behaviour
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 mol1) 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
da
kT$f a
dt
(1)
1 da
f a
kT dt
(2)
617
da
kT$dt
f a
(3)
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)
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
ga
A
$
E
e RT $dT
(9)
ga
AE
fR
x
$e
px
x
(10)
618
px
x 0:66691
x 2:64943
(11)
ln
ga
AR E 0:66691$RT
E
ln
$
2
fE E 2:64943$RT
T
RT
(12)
6
7
f
7
ln6
4
5
E
0:66691$RT
a
a
T
T
Ta2Ta $
EaT 2:64943$RTaT
AaT $R
EaT
ln
EaT $ga
RTaT
(13)
Table 1
Kinetic mechanisms of solid-state processes and the corresponding algebraic expressions for the kinetic models f(a) and g(a).
Kinetic mechanisms
Kinetic models
f a
1 da
kT dt
ga
R a da
kT$t
0
f a
21 aln1 a1=2
31 aln1 a2=3
41 aln1 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 a1 1
1 a3
1=21 a2 1
1=2a
1
ln1 a
a2
31 a2=3
21 1 a1=3
3
21 a1=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
619
Fig. 2. Crosslinking conversion (a(T)) vs. crosslinking time (t) for EVA
samples.
620
ZaT f a$ga
(14)
da T
ZaT
$ $px
dt f
(15)
px
R T dH
dT
T0
dT
aT R
TN dH
dT
T0
dT
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
(17)
(16)
T T0
(18)
2. Experimental
2.1. Materials
Fig. 3. Activation energies (E) vs. crosslinking conversion (a(T)) for EVA
samples.
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.
622
Fig. 4. (continued)
623
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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