Polymer Testing 22 (2003) 689–697

www.elsevier.com/locate/polytest
Material Behaviour
Cure kinetics of epoxy-based nanocomposites analyzed by
Avrami theory of phase change
D.Z. Chen, P.S. He ∗, L.J. Pan
Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, 230026, Anhui, China

Received 10 October 2002; accepted 13 December 2002

Abstract

The effect of montmorillonite on the cure kinetics and the structure of epoxy resin/organo-montmorillonite (Org-
MMT)/methyltetrahydrophthalic anhydride (MeTHPA)/2-ethyl-4-methyl-imidazole (2,4-EMI) nanocomposites are
investigated by X-ray diffraction (XRD) and the dynamic torsional vibration method (DTVM). The XRD result indicates
that an exfoliated nanocomposite was obtained. The experimental data obtained from DTVM are explained by the
Avrami theory of phase change, and show that the theoretical prediction is in good agreement with the experimental
results. No special formation mechanism for epoxy resin/Org-MMT/MeTHPA/2,4-EMI nanocomposite is observed. The
addition of Org-MMT reduces the gelation time tg, and increases the rate of the curing reaction and the value of the
kinetic constant k. The half-time t1/2 of cure after the gel point decreases with increasing cure temperature, while the
values of kinetic constant k rise as the cure temperature increases. The nanocomposite has a larger value of k and
smaller value of n comparing with the epoxy resin/MeTHPA/2,4-EMI system without Org-MMT.
 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Epoxy resin; Nanocomposite; Montmorillonite; Dynamic torsional vibration method

1. Introduction these resin-based nanocomposites generally have two

Epoxy resin-layered silicate nanocomposites are new
hybrid materials of polymers with nanometer-sized inor-
ganic particles which have recently been widely studied,
principally due to the far-ranging application potential of
epoxy resin in many fields. The high aspect ratio and
high strength of the nano-scaled layered silicate plays a
key role in the improvement of the properties of nanoc-
omposites [1]. Because of the unique nanometer-size dis-
persion of the inorganic particles in the polymer matrix,
these materials generally exhibit significant improve-
ments in mechanical properties [2–4], thermal stability
[5], flame retardancy [6] and dielectric properties [7] etc.,
compared with the base polymer at very low loading lev-
els. Like other polymer-layered silicate nanocomposites,
∗ to penetrate the epoxy swollen galleries and initiate intra-
Corresponding author. Tel.: 86-551-3601714.
E-mail address: hpsm@ustc.edu.cn (P.S. He).
distinctive morphologies: (a) intercalated composites, in
which the matrix polymer is interclated between the sili-
cate layers and the expanded silicate layers are still in
order; (b) exfoliated nanocomposite, in which the indi-
vidual 1-nm thick silicate layers are completely dispersed
in a polymer matrix and the gallery structures are com-
pletely destroyed.
The nature and mechanism of the exfoliation process
of the surface modified layered-silicate nanoparticles in
the crosslinking epoxy network have been of recent
interest. Lan [8] demonstrated that the exfoliation of the
clay is not only dependent on the reactivity of the epoxy
system but also on the rate of intercalation of epoxy and
curing agent. Kornmann [9] compared the effect of ali-
phatic diamine and cycloaliphatic diamines on the struc-
ture of a nanocomposite, finding that although the former
gave the slowest cure rate it allowed more curing agent
gallery polymerization leading to better exfoliation,

0142-9418/03/$ - see front matter  2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0142-9418(03)00002-3
690 D.Z. Chen et al. / Polymer Testing 22 (2003) 689–697
which may be attributed to its characteristic of a more
highly flexible backbone than the cycloaliphatic ones.
Russell [10] found that for the m-phenylenediamine
(MPDA) cured epoxy system, exfoliated nanocomposites
were formed with epoxy resin cured with less than an
equal-molar concentration of MPDA or with auto-poly-
merization of the epoxy resin without curing agent,
whereas the intercalated structure was only observed
with too much curing agent. This indicated that excessive
curing agent resulted dominantly in the rapid rate of
extragallery crosslinking in comparison to the slower
intragallery diffusion, which suppressed the exfoliation.
All of these publications about epoxy-clay nanocompos-
ites concentrated on their formation mechanism, struc-
ture, as well as induced applied properties. In this presen-
tation, the emphasis is placed on the cure kinetics of
epoxy resin-layered silicate nanocomposites and also the
effect of Org-MMT on the cure behavior of epoxy sys-
tems.
Curing of a resin system is the critical and productivity
controlling step in the fabrication of thermosetting-
matrix composites. The cure process of an epoxy resin
is the crosslinking of linear macromolecules with a com-
plicated mechanism. As soon as the crosslinking forms,
the resin will not be dissolved and melted. Usually,
chemical analysis, Fourier transformed infrared spec-
troscopy (FT-IR) [11] and differential scanning calor-
imetry (DSC) [12] for detecting the degree of conversion
of reactive groups have been the common analytical
techniques in the attempt to study the cure process.
Recently, DTVM monitoring of the change of mechan-
ical properties during the curing process developed in
our laboratory has been successfully used to study the
cure process of the epoxy resin-BF3-MEA system [13]
and the epoxy resin-triethanolamine system [14], and
was proved to be an efficient research method for the
cure of thermosets [15]. Compared with other methods,
the advantage of DTVM is that it supports the novel
technique to monitor the cure process continuously in
situ, even at the last stage of cure in which the method
still retains a measurable sensitivity.
The kinetics and mechanisms of the curing of epoxy
resins by cyclic anhydrides have been extensively inves-
tigated during the past three decades. Such great atten-
tion derives from the multiple applications of these
materials in the electrical industry. Similarly, as happens
with other thermosetting polymers, the study of the cure
kinetics contributes both to a better knowledge of the
process development and to improving the quality of the
final product.
In general, kinetic expressions include two kinds of
models: phenomenological and mechanistic. The kinetics
of the epoxy-anhydride system used to be studied
through phenomenological models: the nth-order reac-
tion [16] and auto-catalytic model [17]. In this paper,
another phenomenological model-Avrami theory of
phase change will be introduced. As we have known,
Avrami theory was originally used to describe the kinetic
process of polymer crystallization. However, many mol-
ecular aggregates (microgels) or high-molecular-weight
particles have been observed during an infinite network
formation as a result of crosslinking [18], Lu et al. [19]
considered that in a broad sense, crystallization can be
considered as a physical form of crosslinking, and in
some aspects the behavior of amorphous crosslinked
polymers at a higher degree of curing reaction is similar
to that of crystallization. Therefore it is possible to pre-
dict the cure process of thermosets using the Avrami
equation.
Recently, Kim and his coworkers have attempted to
study the kinetics of epoxy-methylene dianiline (MDA)
and epoxy-carboxyl-terminated butadiene-acrylonnitrile
copolymer (CTBN)-MDA systems by means of the
Avrami theory in both isothermal [20] and nonisothermal
[21] conditions based on DSC results. A systematical
consistent method of kinetic analysis was applied and
the results showed that the model of Avrami phase
change theory is another convenient phenomenological
model for the description of thermosets curing. The criti-
cal objective of this presentation is to study the curing
kinetics of the prepared epoxy resin/anhydride/Org-
MMT nanocomposites by DTVM under isothermal con-
ditions. Through the application of the Avrami method,
a good agreement between theoretical predictions and
experimental DTVM data was achieved, and the corre-
sponding kinetic parameters of the cure process, such as
the rate constants, the Avrami exponents and the appar-
ent activation energies, etc., were obtained.
2. Experimental
2.1. Materials
Epoxy resin E51 used, the diglycidyl ether of
bisphenol A (denoted EP) with a epoxy value 0.48–0.54
and average epoxy equivalent 196, was a commercial
product, derived from Shanghai Resin Factory (China).
Methyltetrahydrophthalic anhydride (MeTHPA), CP,
used as the curing agent was kindly supplied by the Fine
Chemistry and Engineering Factory of Shanghai Jingshi
(China). 2-ethyl-4-methyl-imidazole (2,4-EMI), AR, pur-
chased from the Development Center of Special Chemi-
cal Agents in Huabei Region, acted as a catalyst. Na+-
montmorillonite with the cation exchange capacity
(CEC) value of about 100 mmol/100 g, was purchased
from Qingshan Chemistry Agent Factory in Lin’an
(China). (CH3)3(CH2)16NH4Br, the surfactant of clay,
was purchased from the Research Institute of Xinhua
Active Material in Changzhou. The organo-montmoril-
lonite (Org-MMT) was prepared by an ion exchange
reaction. For the isothermal cure experiment, epoxy resin
 D.Z. Chen et al. / Polymer Testing 22 (2003) 689–697
(EP), the curing agent (MeTHPA) and the catalyst (2,4-
EMI) were mixed in the stoichiometric ratio of 100:80:2
(by weight). The loadings of filled Org-MMT were 0, 5
and 10 phr (parts per hundred resins), respectively.
2.2. Dynamic torsional vibration method and
experimental curve analysis
As all the original experimental data of this paper are
given by DTVM, it is quite necessary to illustrate the
experimental setup and its principle of use. Dynamic tor-
sional vibration is a non-resonant forced vibration [13–
15]. The schematic diagram of a homemade experi-
mental setup — HLX-I Resin Curemeter is shown in Fig.
1. The lower mold 3 having a heater within it and used
as the torsional vibrator is filled with the resin materials.
When the motor 6 is switched on, the upper mold 2 also
having a heater within it comes down, and the molds
close with a gap that can be adjusted. The cure tempera-
ture is controlled with thermistors. Thus, the isothermal
cure process can be performed. As soon as the upper and
lower molds close, the motor 5 is on, and the lower mold
starts a torsional vibration with a frequency of 0.05 Hz
at an angle below 1°, which also can be adjusted accord-
ing to the hardness of cured resin materials, by means
of an eccentric disc 4 on the speed change gear 7. The
torque amplitude of the torsional vibration is transformed
into electronic signals by means of the strain gauge load
cell 1, amplified through the amplifier 10 and recorded
by the recorder 11.
The resin system with a different degree of cure has
a different torque (or modulus, viscosity etc). Therefore,
the change in the mechanical properties, i.e. the degree
of cure of the resin system, can be monitored and
Fig. 1. Schematic representation of the dynamic torsional
vibration apparatus. (1) strain gauge load cell; (2) upper mold;
(3) lower mold; (4) eccentric disc; (5) motor for torsional
vibration; (6) motor for closing molds; (7) speed change gear;
(8) amplifier; (9) temperature controller; (10) recorder; (11)
power supporter.
691
determined by measuring the changes in torque, and a
continuous curve reflecting the whole cure process can
be obtained. A typical experimental curve obtained by
DTVM is shown in Fig. 2. The abscissa is the curing
time and the ordinate is the torque required to turn the
resin system with a small angle, which corresponds to
the modulus or viscosity of the resin system, and can be
thought of as a relative parameter of the degree of cure.
The time of closure of the molds is taken as the starting
time of cure point O. In the range OA of the curing time
the network structure formed during the cure reaction is
not enough to cause forced vibration of the upper mold.
As a result, the strain gauge load cell will not have any
signal to input, so that the experimental curing curve is
linear corresponding to the abscissa. At the point A, the
viscosity of the resin system is high enough (i.e. the net-
work formation is completed enough) for the gelation in
the resin system to occur, and the torque appears and the
strain gauge load cell inputs some signal. Thus, the point
A is the gel point and the time corresponding to OA is
the gel time tg for the system. After point A the torque
increases with increasing curing time. The increasing
amplitude of the torque (slope of the curve) reflects the
rate of the curing reaction. The increasing trend of the
torque tends to steady with increasing curing time, and
the equilibrium torque G⬁ is thus reached (point B). In
the meantime, the curing reaction is completed and a
cup-like experimental curve is obtained. The time corre-
sponding to OC is the full curing time. The envelope
of the experimental curve corresponds to the change of
mechanical behavior of the resin system during cure.
Since the cup-like experimental curve is symmetric to
the time axis, for convenience we can just take the upper-
half of the envelope as the isothermal cure curve to ana-
lyze the cure process.
Fig. 2. The general analysis for experimental isothermal cure
curve. O: starting the reaction; A: gel point, the torque is
appeared; OA: gelation time, tg ; AB: rate of curing reaction
(tanq); C: cure is completed and the torque become constant;
CD: maximum torque, relative degree of cure; OD: full curing
time, tc; OABC: outer envelop curve, i.e. isothermal cure curve.
692 D.Z. Chen et al. / Polymer Testing 22 (2003) 689–697
2.3. X-ray diffraction (XRD)
X-ray diffraction patterns were recorded by monitor-
ing the diffraction angle 2q from 1.5–10° on a Rigaku-
D/max-γA X-ray diffractometer. The diffractometer was
equipped with a CuKa (l = 0.1542 nm) radiation source
operated at 40 kV and 100 mA. The scanning speed and
the step size used were 2°/min and 0.02°, respectively.
3. Results and discussion
3.1. XRD analysis
The XRD analysis was used to characterize the struc-
ture of epoxy resin E51/Org-MMT nanocomposites. The
XRD patterns of E51-clay composites containing
(CH3)3(CH2)16NH4+ -montmorillonite cured at 110 °C
were shown in Fig. 3. As reported [22], when polymer
chains are inserted into the galleries of montmorillonite,
the lattice spacing is enlarged. With the proceeding of
the interclation and polymerization, the lattice spacing
continues to increase, and once the spacing becomes so
large as to result in disappearance of Bragg diffraction,
the so-called exfoliated nanocomposite is formed. As
shown in Fig. 3, the (001) diffraction peak of the com-
posites does not exist for both 5 and 10 phr filler contents
in comparison with the montmorillonite modified with
CH3(CH2)15N+(CH3)Br, suggesting that the lattice spac-
ing of montmorillonite has been expanded large enough
by the driving force of polymerization and the exfoliated
nanocomposites of epoxy resin E51/Org-
MMT/MeTHPA/2,4-EMI were formed. At the other
angle, the result gives another illustration that as soon
as the appropriate cure agent and experimental con-
Fig. 3. The XRD characterization for epoxy resin E51/organo-
montmorillonite Org-MMT/MeTHPA/2,4-EMI nanocomposit-
es.
ditions are adopted, the montmorillonite treated with ter-
tiary onium ions can also be used to successfully prepare
the epoxy resin-based nanocomposite, which is in
accordance with Qi’s results [23,24].
3.2. Isothermal cure curves for epoxy cure systems
Fig. 4 is the typical isothermal cure curves (G⫺t) for
epoxy resin E51 systems with and without organo-mont-
morillonite at 90 °C obtained by the DTVM. The curves
are similar in shape for various Org-MMT loadings. The
initial torque G0 is zero because the curve at the range
of time from 0 to tg is identical to abscissa. After the gel
point, the torque appears and the amplitude of torque
increases with increasing temperature. Since the slope of
the curve after gel times tg reflects the cure rate, it means
that the cure rate increases with increasing cure tempera-
ture. All these facts agree with the general law of rate
dependence on temperature. The time reaching the
maximum or equilibrium torque G⬁ is the full cure time
tc and it decreases with increasing of the temperature,
but G⬁ is almost the same for these four temperatures.
The gel times tg can be easily read from the curves
directly. It is clear according to Fig. 4, that the values
of tg for E51/Org-MMT nanocomposites are very close
at a given temperature, and are all smaller than that of
pure epoxy resin, probably because the treating agent of
montmorillonite has some catalysis function on the ring-
opening of epoxy [25]. While comparing the two systems
containing various Org-MMT contents, it can be found
that the case of 5 phr loading has a faster curing speed.
This phenomenon (which can also be seen from Fig. 4)
should arise from a combination of two influencing fac-
tors. On the one hand, just as described above, MMT
modified with organic ammonium has certain catalysis
to the cure of epoxy resin system. On the other hand, the
multilayer silicate structure may act as a mass transport
barrier. In addition, the cure reaction after the gel point
is dominantly controlled by diffusion, and so the sheets
of MMT inevitably restrict the crosslinking reactions
between the galleries. Which factor is dominant deter-
mines the trend of the change of total cure rate. Evi-
dently, when the Org-MMT loading is up to 10 phr, the
retardant effect plays the main role.
Due to the torque of the cure curve after the gel point
at any time is proportional to the degree of cure reaction
of the resin system, it is convenient to introduce a new
parameter of relative degree of cure a at any time as fol-
lowing:
G(t)
a⫽ (1)
G⬁
where G(t) is the torque at time t. Based on the a defi-
nition, therefore, the isothermal cure curve of G⫺t can
be easily converted to the plot of a–t which directly
reflects the relation between the relative cure degree and
 D.Z. Chen et al. / Polymer Testing 22 (2003) 689–697
Fig. 4. The isothermal cure curves of torque vs. time for E51/Org-MMT/MeTHPA/2,4-EMI nanocomposites filled with 0, 5 10 phr
Org-MMT at 90 °C.
the cure time. The plot of a⫺t is another expression of
the isothermal cure curve. The relative degree of cure a
as the function of curing time for different systems is
shown in Fig. 5. From a⫺t plots, the gelation time, and
even the relative cure speed after the gel point can be
observed or compared directly. The values of tg for dif-
ferent systems are listed in Table 1. As can be seen
clearly from Fig. 5 and Table 1, the higher the curing
temperature, the shorter the values of tg and tc for the
systems. On the other hand, in the case of the effect of
Org-MMT on crosslinking reactions, the values of tg and
tc of the formed nanocomposites have an obvious
decrease compared with the pure epoxy system (for
Fig. 5. The uncured fraction of cure as a function of time for
the systems at different temperatures and filler loadings. (a) 0
phr; (b) 5 phr; (c) 10 phr.
693
example, for the case of 5 phr loading at 100 °C the
gelation time tg is 5.3 min smaller than that of epoxy
resin without Org-MMT), and correspondingly an
increased slope of the cure isotherms is shown, meaning
that the Org-MMT filler accelerates the curing rate.
3.3. The application of Avrami model
The Avrami equation has a classical form
a ⫽ 1⫺exp[⫺k’tn] (2)
where a is the relative degree of cure; t the cure time;
tg the gel time; n the Avrami exponent that is a reflection
of nucleation and growth mechanism; and k a tempera-
ture dependent kinetic constant.
Due to the cure curve being the same as the abscissa
before gelation time tg, the isothermal cure data obtained
by the DTVM can be analyzed using the following modi-
fied Avrami equation [26]:
a ⫽ 1⫺exp[⫺k(t⫺tg)n] (3)
or
ln[⫺ln(1⫺a)] ⫽ lnk ⫹ nln(t⫺tg) (4)
Eq. (4) can be used to get the kinetic parameters from
the cure curves at different temperatures. The units of k
and t or tg are (min)⫺n and min, respectively. A best fit
line of the plot of ln[⫺ln(1⫺a)] vs. ln(t⫺tg) will provide
parameter n from the slope and k from the intercept. Fig.
6 is a typical plot of the above equation for the cure
process of the epoxy resin E51/Org-MMT/MeTHPA/2,4-
EMI. The kinetic parameters obtained by the Avrami
theory are listed in Table 1. The good linearity indicates
that it is valid to illustrate the cure process after the
gel point.
The apparent rate constant k determines the rates of
the nucleation and growth processes that control the cur-
ing rate. As seen from Table 1, the apparent rate constant
k retains a remarkable sensitivity to the cure temperature.
Values of k rise with increasing cure temperature, that
is, the higher the temperature, the faster the cure rate.
At any curing temperature, the case of E51/Org-
694 D.Z. Chen et al. / Polymer Testing 22 (2003) 689–697

Table 1
The kinetic parameters of cure for the epoxy resin/MeTHPA/2,4-EMI systems filled or unfilled with Org-MMT

Loadings (phr) T (°C) tg (min) t1/2 (min) k (s⫺n) k (s-n)(cal)a n

0 90 40.30 8.98 2.56×10⫺5 2.61×10⫺5 1.62

100 24.23 4.99 1.09×10⫺4 1.26×10⫺4 1.51
110 9.89 3.12 7.82×10⫺4 1.23×10⫺3 1.21
120 5.12 3.05 7.95×10⫺3 6.72×10⫺3 0.89
5 90 34.69 8.97 5.55×10⫺5 6.29×10⫺5 1.48
100 18.93 6.49 4.11×10⫺4 4.51×10⫺4 1.23
110 9.06 3.69 2.25×10⫺3 2.66×10⫺3 1.03
120 5.06 2.12 8.03×10⫺3 9.28×10⫺3 0.89
10 90 33.39 11.69 3.26×10⫺5 3.98×10⫺5 1.49
100 17.06 6.32 9.21×10⫺5 1.09×10⫺4 1.50
110 8.63 4.43 9.50×10⫺4 1.07×10⫺3 1.16
120 4.64 2.60 2.66×10⫺3 3.28×10⫺3 1.06

a
k (cal) = ln2 / t n1 / 2

tative information on the nature of the nucleation and the

Fig. 6. Plots of lnk vs.1/T for epoxy resin E51/Org-
MMT/MeTHPA/2,4-EMI nanocomposites.
MMT/MeTHPA nanocomposites has a larger value of k
and smaller value of n than that of E51/MeTHPA system
without Org-MMT (expect the case of 10 phr cured at
120 °C which has a relatively high n value). This
phenomenon may exist because the Org-MMT particles
plays a role of speeding up the heterogeneous nucleation
during curing. However, when comparing different filler
loadings, a feature that the system with 10 phr loading
has a lower k value still occurs; the reason has been dis-
cussed above.
The values of Avrami exponent n, describing the iso-
thermal cure, depend on the cure temperatures for
E51/Org-MMT/MeTHPA systems. Similar results are
obtained in E51/MeTHPA systems without Org-MMT.
As we have known, the Avrami exponent provides quali-
growth process in the crystallization of a polymer and
can change. The fact of change in n may imply that a
change occurs in the cure mechanism when using a lower
cure temperature, although the formation and growth of
microgels (i.e. molecular aggregates) is essentially dif-
ferent from those of crystals [21,27]. After the gel point,
the cure reaction is predominantly diffusion-controlled,
as the retardation of viscosity and a mass dispersion limi-
tation eventually sets in, the microgel particles are forced
to impinge on one another, and phase inversion may
occur. From Table 1 we can see that, as the temperature
increased, n values decrease in turn, and E51/MeTHPA
systems without Org-MMT always have higher n values.
According to the discussion above, we may conclude that
it is less of a mass transfer limitation at lower cure tem-
peratures or with less Org-MMT loadings that leads to
the relatively higher values of n. A similar result was
observed for a zeolite-filled epoxy system by Lu et al.
[28].
From Figs. 4 and 5, the half-time of cure, t1/2, namely,
the time at which 50% degree of cure is completed, can
be read directly. According to Eq. (3), the rate constants,
k can be described as follows
ln2
k⫽ (5)
(t⫺tg)n1/2
Since the Avrami exponents are included in the rate
constants, as can be seen from Eq. (3), the recalculated
constants of curing rate can be obtained based on the
observed half-time of cure, t1/2, and corresponding values
of n. The experimental data and theoretical results calcu-
lated from Eq. (5) based on the obtained values of t1/2
and n for each case are reported in Table 1. Obviously,
the experimental data and calculated results match very
well.
 D.Z. Chen et al. / Polymer Testing 22 (2003) 689–697
Fig. 7. The typical Avrami plots for the nanocomposite with
5 phr Org-MMT.
3.4. Activation energy
With the calculation of the rate constants, we assume
an Arrhenius temperature dependence to obtain the
values of the activation energy and frequency factor, i.e
k ⫽ Aexp(⫺Ea / RT) (6)
where Ea is the overall activation energy, A is an overall
frequency factor; and R is the universal gas constant.
This is a common method of analysis of isothermal data.
If the Arrhenius relation is obeyed, the overall activation
energy and frequency factor can be determined from the
slope and intercept, respectively, of the best-fit line. Fig.
7 is the plot of lnk vs. 1/T for various Org-MMT load-
ings. The good linear correlation obtained has supported
the above assumption. Values of Ea are shown in Table
2. We can see from Table 2 that the activation energies
are very close for the systems with and without Org-
MMT, indicating that the addition of montmorillonite
has little influence on the cure mechanism of epoxy resin
[29]. Based on the calculated kinetic parameters of A
(min⫺n) and Ea (kJ/mol), the relationship between the
Table 2
The activation energies for the cure systems of the epoxy resin
Loadings (phr) Ea1 (kJ/mol) Ea2 (kJ/mol)
0 106.7 84.0
5 101.7 77.3
10 105.1 78.4
Ea1, Ea2 are the activation energies calculated from the Avrami
model and Flory’s gelation theory, respectively.
695
rate constant k (min⫺n) and temperature T (K) from Eq.
(6) has a more concrete form for different systems as fol-
lows.
For pure epoxy system:
lnk ⫽ 30.64⫺1.28 ⫻ 104 / T (7)
and for the nanocomposite with 5 phr Org-MMT load-
ing:
lnk ⫽ 29.57⫺1.22 ⫻ 104 / T (8)
and for the nanocomposite with 10 phr Org-MMT load-
ing:
lnk ⫽ 31.48⫺1.26 ⫻ 104 / T (9)
To evaluate the activation energy, the gelation time
obtained by the DTVM is also used to calculate the Ea.
According to Flory’s gelation theory [30], the chemical
conversion at the gel point of the resin system is constant
and is not related to the reaction temperature and experi-
mental conditions. As a result, the apparent activation
energy Ea of cure reaction can be calculated from the
gel time tg.
lntg ⫽ C ⫹ Ea / RT (10)
where R is the gas constant, T the absolute temperature
of cure and C a constant. Fig. 8 shows a plot of lntg (see
Table 1) against 1/T for various loadings of Org-MMT
of 0, 5 and 10 phr. The good linear relationship indicates
that the relationship between tg and 1/T has good agree-
ment with Flory’s gelation theory. The best-fit lines are
nearly parallel to each other, suggesting that the values
of Ea for the epoxy resin E51/Org-MMT/MeTHPA/2,4-
EMI nanocomposites with different loadings of the Org-
MMT are very close. The apparent activation energies
can be calculated from the slopes of the lines and have
Fig. 8. Plots of lntg vs. 1/T for the epoxy resin E51/Org-
MMT/MeTHPA/2,4-EMI nanocomposites.
696 D.Z. Chen et al. / Polymer Testing 22 (2003) 689–697
the values of 78-84 kJ/mol. The cure kinetic parameters
of E51/ MeTHPA/accelerator system without Org-MMT
have been obtained using a DSC method by some inves-
tigators. The data about the activation energy are 70.8–
78.6 kJ/mol [31] and 60–84 kJ/mol [32]. As expected,
and previously reported in literature, the kinetic para-
meters obtained by different DSC methods do not match
very well. The difference might be caused by different
chemical composition of epoxy resin and different tech-
nological prescription (e.g. various weight ratios of the
three components and various cure accelerators) used in
the system. For example, the activation energy usually
decreases when the content of curing agent is increased.
4. Conclusions
The cure behavior of exfoliated epoxy resin/organo-
montmorillonite (Org-MMT)/MeTHPA/2,4-EMI nanoc-
omposites has been continuously in situ monitored by
DTVM. The cure data obtained from DTVM were suc-
cessfully analyzed with the Avrami theory of phase
change and the theoretical prediction was identical to the
experimental results. The addition of the Org-MMT has
no special cure mechanism for the epoxy resin-based
nanocomposite. The filled Org-MMT reduces the gel-
ation time tg, and increases the rate of the curing reaction
and the value of the kinetic constant k. The half-time t1/2
of cure after the gel point, which can be used to calcu-
lated the rate constant, decreases with increasing cure
temperature, and the values of kinetic constant k increase
as the cure temperature rise, that is, the higher the tem-
perature, the faster the cure rate. In addition, commonly,
a larger value of k and smaller value of n are found for
the nanocomposite system at a given cure temperature.
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