POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. 13, 353362 (2002)

DOI:10.1002/pat.198

A Systematic Study of the Microwave

and Thermal Cure Kinetics of the
DGEBA/DDS and DGEBA/DDM
Epoxy-amine Resin Systems
David J. T. Hill1*, Graeme A. George2 and David G. Rogers3
1
Polymer Materials and Radiation Group, Department of Chemistry, The University of Queensland, Brisbane
4072, Australia
2
Centre for Instrumental and Developmental Chemistry, School of Physical Sciences, Queensland University of
Technology, Brisbane 4001, Australia
3
Cooperative Research Centre for Advanced Composite Structures, 506 Lorimer Street, Fishermans Bend 3207,
Australia

ABSTRACT W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W parameters, and the systems were both found to be

characterized by a negative substitution effect. Copyright
The microwave and thermal cure processes for the epoxy- 2002 John Wiley & Sons, Ltd.
amine systems (epoxy resin diglycidyl ether of bisphenol
A, DGEBA) with 4,4'-diaminodiphenyl sulphone (DDS)
and 4,4'-diaminodiphenyl methane (DDM) have been KEYWORDS: DGEBA/DDS; DGEBA/DDM; thermal
investigated for 1 : 1 stoichiometries by using fiber-optic cure; microwave cure; kinetics; mechanisms; bre-optic
FT-NIR spectroscopy. The DGEBA used was in the form FT-NIR spectroscopy
of Ciba-Geigy GY260 resin. The DDM system was
studied at a single cure temperature of 373 K and a single
stoichiometry of 20.94 wt% and the DDS system was INTRODUCTION W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
studied at a stoichiometry of 24.9 wt% and a range of
temperatures between 393 and 443 K. The best values of Thermosetting resins are among the most indust-
the kinetic rate parameters for the consumption of amines rially important materials in use today. Indeed,
have been determined by a least squares curve fit to a technology in the processing of these materials has
model for epoxy/amine cure. The activation energies for been recognized as critical to the aerospace and
the polymerization of the DGEBA/DDS system were defence industries. Epoxy resins, which are char-
determined for both cure processes and found to be 66 and acterized by the presence of the oxirane function-
69 kJ mol 1 for the microwave and thermal cure ality, are an important industrial class of
processes, respectively. No evidence was found for any thermosetting resin, due to their chemical resis-
specific effect of the microwave radiation on the rate tance, outstanding adhesive properties, good
mechanical and physical properties.
*Correspondence to: D. J. T. Hill, Polymer Materials and The curing mechanism of epoxy resins with
Radiation Group, Department of Chemistry, The University of primary amines is accepted as occurring by means
Queensland, Brisbane 4072, Australia. of three fundamental reactions: (i) the primary

Received 13 January 2001

Copyright 2002 John Wiley & Sons, Ltd. Accepted 25 June 2001
354 / Hill et al.
amine-epoxy ring opening reaction which results in
the formation of a secondary amine and a hydroxyl
group; (ii) the secondary amine-epoxy reaction
results in the formation of a tertiary amine and a
second hydroxyl group; (iii) an etherification
reaction, which occurs via a reaction between one
of the pendant hydroxyl groups and the oxirane
functionalities in the epoxy resin.
The conventional process of thermoset curing of
composites involves subjecting the material to
temperature and pressure cycles in an autoclave.
Problems with this conventional curing technique
are related to the length, cost and complexity of the
autoclave curing cycle, which, depending on the
material being cured, can take several hours and
involve several temperature ramping and de-
ramping steps [1]. The major difficulty with
temperature ramping in conventional curing tech-
niques is related to the slow response of the
autoclave.
The inherent difficulties and inefficiencies in-
volved in conventional curing techniques have led
researchers to explore other ways of facilitating the
cure process which could save time and energy, as
well as possibly lead to the formation of materials
with unique and desirable mechanical properties.
A number of alternatives to the conventional
technique of autoclave cure have been suggested.
One of the more promising of these is microwave
induced curing, which has a number of possible
advantages over conventional techniques and has
often been suggested as a cost-effective alternative
to conventional heating procedures [2].
Microwave heating is a direct form of heating,
compared with conventional heating techniques
which are based on conduction of heat through a
material. Since microwave radiation generates heat
within materials, sample temperatures are poten-
tially able to be changed and controlled more
readily. Any increase in input power or improve-
ment in the tuning of a microwave oven immedi-
ately results in an increase in temperature of
the material undergoing cure. Microwave energy
affects only the material being processed, and is
therefore inherently more energy efficient than
thermal heating, which also heats the walls of the
oven and the air surrounding the process material.
A definite potential advantage of microwave
heating over conventional techniques is thus lower
production costs as a consequence of its greater
energy efficiency. Another potential advantage is
related to the greater controllability of microwave
heating, which offers the possibility of more easily
producing materials with unique physical and
mechanical properties.
Recently, several reports have suggested that
there are fundamental differences between the
mechanisms of microwave and conventional heat-
ing, and that these can affect their respective
kinetics of polymerization or curing [35]. Workers
studying these reactions have thus concentrated
their efforts on investigating the possibility of
reduced processing time with the use of microwave
radiation compared with conventional thermal
Copyright 2002 John Wiley & Sons, Ltd.
curing techniques. In addition, a substantial
amount of research work has been devoted to
identifying any differences in the physical and
mechanical properties of microwave and thermally
processed materials. We have previously reported
analyzes of the kinetics of the cure of several epoxy-
amine systems [615].
The epoxy resin diglycidyl ether of bisphenol A
(DGEBA) is one of the most commonly used in
industry. An industrial formulation of this epoxy
resin, Ciba-Geigy GY260, was used in this work.
These epoxy resins are typically cured with the aid
of amine crosslinking agents. In this work, two of
the most common amine based crosslinking agents
were employed, 4,4'-diaminodiphenyl sulphone
(DDS) and 4,4'-diaminodiphenyl methane (DDM).
In order to gain an understanding of the cure of
composite materials, it is necessary to first under-
stand the kinetics of the reactions occurring during
the cure. In this study we have examined the
kinetics of the amine reactions for GY260 cured
with DDS and DDM for both thermal and micro-
wave processing, with a view to examining
whether there are any fundamental differences
between the two processes.
EXPERIMENTAL W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
The experimental procedures adopted have been
described in detail previously [79]. The thermal
and microwave cure of the samples were mon-
itored using FT-NIR spectroscopy. The thermal
cure reactions were carried out in 3 mm id pyrex
tubes containing approximately 0.2 g of sample.
The samples were cured in a preheated aluminum
block thermostatt with temperature control to
within 0.1 C and the FT-NIR spectra were
obtained in real time by transmission using a
PerkinElmer 1600 spectrometer fitted with an
external bench on which the heater block was
mounted. The microwave cure reactions were
carried out in a single mode, tunable, cylindrical
cavity operating at a frequency of 2.45 GHz. The
cavity was fitted with a Teflon, cylindrical,
approximately 5 g sample compartment and silica
fibre-optics, with a 200 mm fiber diameter, for
acquiring the real-time FT-NIR spectra in the center
of the sample using with an optical path length of
approximately 2 mm [9]. The temperature of the
sample within the optical path was monitored by
an adjacent fiber-optic temperature probe and
controlled to within 0.2 C by variation of the
microwave power to the cavity [9]. The FT-NIR
signal to noise ratios for the thermal cure reactions
were greater than those which were obtainable for
the microwave cure reactions, because of the fiber-
optic monitoring used in the latter experiments,
and hence the concentration and rate data for the
former studies are subject to smaller experimental
errors.
The experimental techniques used to obtain the
time dependence of the functional group concen-
trations of the primary and secondary amine
Polym. Adv. Technol., 13, 353362 (2002)
 Epoxy-amine Resin Systems / 355

during the cure of these epoxy systems have been MY721. In the case of GY260, there could be no
described in our previous papers [68]. Data for the differentiation of E0 and E1 groups, since the epoxy
formation of tertiary amine were obtained using the molecule is difunctional, with well separated
mass balance assumption below, as described by St oxirane groups. Therefore a modification to eq. (1)
John and George [1012]. was made in which the total epoxy concentration
was used for the hydroxyl catalyzed reaction,
PA0 PAt SAt TAt instead of being divided into the E0 and E1
components. This modified equation is shown in
where [PA]t, [SA]t and [TA]t are the concentrations eq. (2).
of primary, secondary and tertiary amine at time t,
respectively, and [PA]0 is the initial concentration d[PA]/dt k1 [EP][PA]2 k2 [PA][EP][OH] 2
of primary amine.
The experimental data were analyzed for the Equation (2) was used to fit the rate curves for
kinetic models using the least squares curve fitting primary amine consumption versus time for the
routine found in SigmaPlot for Windows version GY260/DDS/DDM systems. However, the fit
2.0, which is based on the MarquardtLevenberg afforded by this model was found to be poor for
algorithm [8]. In each case the fitted data were both the thermal and microwave processes. The
checked for the presence of a global minimum, so extent of the deviations between fitted and raw rate
that the values of the kinetic rate parameters curves for amine consumption using this model, in
obtained from the fit were best values. fact, suggested that the proposed mechanistic
scheme was incorrect.
RESULTS AND DISCUSSION W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W Kozielski et al. [12] have reported a detailed NIR
study of the cure kinetics of DDS with two
Industrial epoxy resins based on the DGEBA industrial epoxy resins, Dow Tactix 742 and Shell
structure have been widely studied due to their 1153, which have similar structures to the DGEBA
applicability to composite materials. Significantly, resin studied here. In their NIR study of the
the DGEBA/DDS system has been the system most reaction kinetics of the thermal cure of these resin
commonly studied in the past by workers compar- systems, they fitted the primary amine rate curve
ing thermal and microwave cure kinetics. In using an equation of the form of eq. (2), but with an
this respect, it is the system for which most of additional term to account for the possibility of
the disagreement regarding differences between tertiary amine catalysis, as shown in eq. (3).
microwave and thermal cure kinetics has been
reported. Hedrick et al. [3, 16] and Wei et al. [17] d[PA]/dt k1 PA2 EP k2 [PA][EP][OH]
3
both found a microwave induced enhancement of k3 [PA][EP][TA]
the cure reaction of this system, while Mijovic et al.
[4] observed a slight microwave induced retarda-
tion or no change [18, 19] when compared with the
conventional curing process. The objective of GY260 Cured with DDS
studying this system was to directly compare the
thermal and microwave cure processes and to Figure 1 shows selected FT-NIR spectra obtained
derive a model to explain the amine cure kinetics. during the course of the cure of GY260/DDS 24.9
We have recently reported a study of the wt% at 423 K. The peaks at 5067 cm 1 arise from the
kinetics and mechanisms of the thermal and primary amine groups, at 6060 cm 1 from the
microwave cure of the tetraglycidyldiaminodiphe- oxirane groups, at 6678 cm 1 from both the primary
nyl methane (TGDDM) epoxy resin, Ciba Giegy amine and secondary amine groups and from
MY721, with DDM and DDS [8]. The modeling of 7000 cm 1 from the hydroxyl groups. The concen-
the consumption of primary amine in these resin tration of the primary amine during the cure can be
systems was based in the use of eq. (1), which was conveniently obtained from the band at 5067 cm 1.
introduced by St John and George [11, 15] Figure 2 shows a typical curve for the time
dependence of the primary amine concentration for
the cure of GY260/DDS 24.9 wt% at 393 C obtained
d[PA]/dt k1 [EP][PA]2 k2a [PA][E0][OH] from the in situ monitoring of the FT-NIR spectrum.
1
k2b [PA][E1][OH] Differentiation of this curve with respect to time
then provides information about the rate of
where [E0] and [E1] represent the concentrations of consumption of primary amine across the cure
epoxy groups in TGDDM which are adjacent to process. Typical curves showing the rate of primary
unreacted (E0) and reacted (E1) epoxy groups, amine consumption as a function of time and
respectively. This recognizes the difference in the primary amine concentration, obtained from the
reactivity of these groups due to the intramolecular data in Fig. 2, are shown in Fig. 3(A) and 3(B),
catalytic effect of the adjacent hydroxyl group (OH) respectively.
in the case of the E1 functional groups. Information with respect to the rate of con-
The exact form of the model of St John and sumption of primary amine was then tested against
George could not be applied to the GY260 resin, the proposed rate equations for various models.
due to the structural differences between it and Samples of the quality of fit afforded by eq. (3) to

Copyright 2002 John Wiley & Sons, Ltd. Polym. Adv. Technol., 13, 353362 (2002)
356 / Hill et al.

FIGURE 1. Selected FT-NIR spectra obtained during the

thermal cure of GY260/DDS 24.9 wt% at 423 K. Spectra
from top to bottom are for cure times of 4, 12, 20, 40, 60
and 80 min.

the experimental data for rate of consumption of

primary amine for both the thermal and microwave
curve of GY260/DDS 24.9 wt% at 393 and 423 K are
demonstrated in Fig. 4(A) and 4(B) and Fig. 5(A)
and 5(B), respectively. As can be seen, the quality of
fit is very good for both cure processes at both
temperatures, which suggests that the mechanistic
model described by eq. (3) provides a good
representation for the curve of this resin system.
Similar observations were made across the whole
range of cure temperatures investigated. The best
values obtained for the kinetic rate parameters for
the thermal cure processes at 403, 423 and 443 K

FIGURE 3. The variation of the rate of consumption of

primary amine for GY260/DDS 24.9 wt% at 393 K with
(A) time and (B) primary amine concentration.

are presented in Table 1, along with the values

FIGURE 2. The dependence of the concentration of
primary amine with time for the thermal cure of GY260/
DDS 24.9 wt% at 393 K.
reported by Kozielski et al. [12] for the analogous
Shell 1153/22 wt% DDS resin system. The kinetic
parameters obtained in the two studies are of
similar magnitudes and follow similar trends.
The time taken for the resin system to reach the
cure temperature differed between the thermal and
microwave cure processes, with a significant time
lag being observed for the microwave process, as
was reported previously for the MY721/DDS cure
processes [8]. As a result, the observed initial
reaction rates for the two processes differ some-
what, as shown in Figs 4 and 5. In addition, the time
taken to reach the maximum rate of cure, and the
maximum rate itself, differed for the two processes.
However, if the rate of primary amine consumption
is compared with the instantaneous primary amine
concentration, there is much better agreement

Copyright 2002 John Wiley & Sons, Ltd. Polym. Adv. Technol., 13, 353362 (2002)
 Epoxy-amine Resin Systems / 357

FIGURE 4. The rate of consumption of primary amine with

time for GY260/DDS 24.9 wt% at 393 K for (A) thermal FIGURE 5. The rate of consumption of primary amine with
and (B) microwave cure. Line shows tted curve. time for GY260/DDS 24.9 wt% at 423 K for (A) thermal
and (B) microwave cure. Line shows tted curve.

between the two process, as demonstrated in Fig. 6
for the cure at 393 K. Again, similar observations
were reported for the MY721/DDS systems [8]. The
small differences between the two curves in Fig. 6
arise from unavoidable small differences between
the cure temperatures of the two samples which are
cured in separate experiments. The good agree-
ment between the two curves is indicative of there
being no fundamental difference between the
reaction mechanism for the two cure methods;

TABLE 1. Kinetic Rate Parameters for the Thermal Cure of the GY260/DDS 24.9 wt% System at 403, 423 and 443 K,
Together with the Corresponding Data for the Shell 1153/DDS 22 wt% System Reported by Kozielski et al.[12]

Rate parameter
(kg2 mol 2 min 1) GY 260 (403 K) GY260 (423 K) 1153 (423 K) GY260 (443 K) 1153 (443 K)
4 3 3 3 3
k1 6.56  10 1.77  10 2.51  10 1.08  10 6.80  10
3 3 2 2 2
k2 3.49  10 6.66  10 1.23  10 2.23  10 3.02  10
1 1 2 2 2
k3 1.09  10 1.59  10 4.18  10 5.20  10 1.98  10

Copyright 2002 John Wiley & Sons, Ltd. Polym. Adv. Technol., 13, 353362 (2002)
358 / Hill et al.
FIGURE 6. The rate of consumption of primary amine with
primary amine concentration for GY260/DDS 24.9 wt% at
393 K for thermal (&) and microwave (*) cure. Line shows
tted curve.
namely conventional thermal cure and microwave
cure, across the whole range of cure temperatures
studied.
The apparent activation energy for the primary
amine reaction was measured by plotting the
maximum rate of cure versus the reciprocal of the
temperature, as shown in Fig. 7 for the thermal and
microwave cure processes. The activation energies
obtained for the two cure methods were in good
agreement, as demonstrated in Table 2, and also
agreed with values reported by Kozielski et al. [12]
which were in the range 5973 kJ mol 1.
The DGEBA/DDS system has been the most
common of those reported in the literature with
respect to comparisons between microwave and
thermal cure kinetics. Some of this literature has
indicated that microwave radiation is able to
significantly accelerate the reactivity of this
epoxy-amine system over conventional curing
techniques, as discussed earlier. In a study of this
system Marand et al. [5] reported that the reactiv-
ities of the secondary amine- and primary amine-
epoxy were approximately the same for microwave
cure process. In the light of the previous studies, it
is important to study closely the secondary amine-
epoxy reaction and to compare its rate parameters
with those of the primary amine-epoxy reaction.
TABLE 2. Arrhenius Parameters for the GY260/DDS
24.9 wt% System for Thermal and Microwave Cure
Processes
Parameter Thermal Microwave
1
Ea (kJ mol ) 69.0 65.7
1 1
Ln (Rate/mol kg min ) 16.5 15.5
Copyright 2002 John Wiley & Sons, Ltd.
FIGURE 7. Arrhenius plots for the cure of GY260/DDS
24.9 wt% by thermal (&) and microwave (*) cure.
We have previously shown that for the thermal
and the microwave cure of the MY721/DDS system
[8], the kinetics for the reaction of the secondary
amine can be modeled using a relationship based
on the model proposed by St John and George
[12, 15], given in eq. (4).
d[SA] d[TA] k4 [SA][EP][OH]
dt dt 1 expC 1
4
k5 [SA][EP][TA]
1 expC 2
In eq. (4), k4 and k5 are the rate parameters for the
reactions catalyzed by hydroxyl group and tertiary
amine, respectively, a is the degree of cure, a1 and
a2 are the critical extents of cure for hydroxyl group
and tertiary amine catalyzed reactions, respec-
tively, and represent the conversions above which
diffusion begins to become important and C is a
fitted constant related to the degree of diffusion
control. In the curve fit, a1 and a2 were constrained
to the range 01 and k4 and k5 were constrained to
positive values. C was left unconstrained.
Figure 8(A) and 8(B) show the rate curves of
tertiary amine formation versus time, and the
corresponding curve fits obtained from eq. (4), for
the thermal and microwave cure reactions of
GY260/24.9% DDS at 443 K. The same data plotted
against primary amine concentration are shown in
Fig. 9. These plots show the level of agreement
between the experimental data and the model.
Although there are some small differences, most
likely due to uncertainties in the calculation of the
tertiary amine concentration, the agreement is
good. Certainly, the discrepancies observed be-
tween the rates of tertiary amine formation in the
thermal and microwave cure reactions of this resin
system are not sufficiently large as to indicate a
Polym. Adv. Technol., 13, 353362 (2002)
 Epoxy-amine Resin Systems / 359

FIGURE 9. The rate of formation of tertiary amine versus

primary amine concentration for GY260/DDS 24.9 wt% at
443 K for thermal (*) and microwave (&) cure.

reason for this discrepancy in the reported rate of

the secondary amine-epoxy reaction is unknown,
although it could possibly be related to the
confounding effects of temperature gradients on
the observed microwave cure kinetics, which we
have previously reported [7]. However, in the
present study these temperature gradients, which
are related to the nature of the microwave field
gradients within the cavity, have been eliminated

FIGURE 8. The rate of formation of tertiary amine with time

for GY260/DDS 24.9 wt% at 443 K for (A) thermal and (B)
microwave cure. Line shows tted curve.

difference of an order of magnitude in reactivity

between the two curing procedures.
As observed in the MY721/DDS system [8], the
average ratios of k4/k2 and k5/k3 were found to be
less than unity for both the thermal and microwave
cure processes, with their values being 0.23 and
0.22; and 0.19 and 0.25, respectively. This would
indicate that a negative substitution effect (i.e. a
lower rate of reaction of the secondary amine
compared to the primary amine with the epoxy
group) exists in both the thermal and microwave
cure reaction of this epoxy-amine system. The
values of these ratios are similar to those reported
by Kozielski et al. [12], which were in the range
0.180.20 for the hydroxyl catalyzed reaction for the
industrial DGEBA resins which were investigated. FIGURE 10. Selected FT-NIR spectra obtained during the
This result is clearly at odds with that reported by thermal cure of GY260/DDM 20.94 wt% at 373 K.
Marand et al. [5] in their study of the thermal and Spectra from top to bottom are for cure times of 2, 10, 20,
microwave cure kinetics of the same system. The 30, 40 and 50 min.

Copyright 2002 John Wiley & Sons, Ltd. Polym. Adv. Technol., 13, 353362 (2002)
360 / Hill et al.
FIGURE 11. The rate of consumption of primary amine
with time for GY260/DDM 20.94 wt% at 373 K for (A)
thermal and (B) microwave cure. Line shows tted curve.
by precise monitoring the temperature of the small
sample of resin under study [7].
GY260 Cured with DDM
A study was undertaken to compare the micro-
wave and thermal cure kinetics of GY260 with the
highly reactive DDM crosslinking agent. The
microwave cure of this system was studied semi-
quantitatively by Beldjouri et al. [20]. However,
their work was concerned with phenomenological
microwave induced temperature rises in these
resins, and they did not describe any of the
fundamental chemical reactions. In the present
study the thermal and microwave cure kinetics for
this resin system are compared on the basis of the
results of a mechanistic model.
Stoichiometric mixtures of GY260 and DDM
Copyright 2002 John Wiley & Sons, Ltd.
FIGURE 12. The rate of consumption of primary amine
versus primary amine concentration for GY260/DDM
20.94 wt% at 373 K for thermal (&) and microwave (*)
cure. Line shows tted curve.
were prepared by adding 20.94 wt% of the cross-
linker. Figure 10 shows selected FT-NIR spectra
obtained during the course of the cure of GY260/
DDM 20.94 wt% at 373 K. The rate of consumption
of primary amine groups was obtained in the same
manner as that for the GY260/DDS system, and
modeling of the rate versus time was performed
using eq. (3). Figure 11(A) and 11(B) show the
quality of fit afforded by this equation when
applied to the rate curves of primary amine
consumption versus time at a temperature of
373 K.
The best fit of the data to eq. (3) was found for
the thermal process to be for k1 equal to 1.0  10 3
kg2 mol 2 min 1 and k2 equal to 2.8  10 2 kg2
mol 2 min 1. The hypersurface for the curve fit to
the data for microwave cure reaction was shallow
and poorly defined. A best value for k1 of 4.0  10 3
kg2 mol 2 min 1 was obtained, but a range of k2
values provided equally good fits to the experi-
mental data. This situation arises because of the
lower accuracy of the microwave data by compari-
son with the thermal data, as mentioned above. For
this reason, the values of these rate parameters
could not be used definitively as a basis for a
quantitative comparison between the kinetics of
thermal and microwave cure reactions in this
system.
Figure 12 shows plots of the rate of primary
amine consumption versus primary amine concen-
tration for the thermal and microwave cure reac-
tions of GY260/20.94% DDM at 373 K. The data
indicate that the two rates are different in the early
stages of cure, but by only a small amount (10%)
at the maximum. These differences arose because of
the different heating rates in the microwave and
thermal curing experiments. However, there is
certainly no evidence of a large microwave induced
Polym. Adv. Technol., 13, 353362 (2002)

FIGURE 13. The rate of formation of tertiary amine versus
time for GY260/DDM 20.94 wt% at 373 K for (A) thermal
and (B) microwave cure. Line shows tted curve.
acceleration in the reaction rate for this epoxy-
amine system.
The rate of formation of tertiary amine groups
versus time for the thermal and microwave cure
reactions of GY260/DDM 20.94 wt% at 373 K, along
with their corresponding fits using eq. (4), are
shown in Fig. 13(A) and 13(B). The deviation
between the fitted curves and the experimental
data was larger than observed when fitting the rate
curves for primary amine consumption, which is
attributed to the greater level of uncertainty
involved in calculating the concentration of tertiary
amine groups. The shapes of the curves are
fundamentally alike, which suggests that the
mechanisms of reactions occurring during thermal
and microwave cure of this epoxy-amine system
are identical. There is no evidence in these plots to
support the proposal that the secondary amine-
Copyright 2002 John Wiley & Sons, Ltd.
Epoxy-amine Resin Systems / 361
epoxy reaction is measurably accelerated by the use
of microwave radiation.
The ratios of apparent rate parameters k4/k2 and
k5/k3 were found to be 0.21 and 0.19 in the thermal
and 0.25 and 0.20 in the microwave cure reactions,
respectively. These ratios suggest that there is a
negative substitution effect for the GY260/DDM
system which is related to the fundamental reaction
mechanism and is unaffected by the microwave
energy field.
CONCLUSIONS W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
The kinetics of the polymerizations of GY260 with
DDS and DDM have been studied. The rates of the
reactions of primary amine and secondary amine
have been found to be similar for microwave and
thermal cure processes. Best values of the kinetic
rate parameters for the amine reactions have been
determined based upon the model proposed by St
John and George [11, 15] for the MY721/DDM
system. The kinetic parameters revealed no evi-
dence for any specific effects of microwave radia-
tion on either the primary amine or secondary
amine reactions. The GY260/DDS and GY260/
DDM systems both displayed evidence for catalysis
by tertiary amine and a negative substitution effect
for the secondary amine reactions, with the reduc-
tion in the rate constants of the secondary amines to
about 20% of the values of the primary amine. The
activation energy for the polymerization of the
GY260/DDS system was determined, being in the
range 6669 kJ mol 1 and within experimental
uncertainty, the same for both cure processes.
ACKNOWLEDGEMENTS W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
The financial support for this project was obtained
from the Australian Research Council and the
University of Queensland.
REFERENCES W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
1. Metaxas AC, Meredith RJ. Industrial Microwave
Heating. Peter Peregrinus Publishers: London, 1983;
305.
2. Cabibsky I. Symp. Proc. Matl. Res. Soc. 1988; 124: 17.
3. Hedrick JC, Lewis DA, Ward TC, McGrath JE. Polym.
Prepr. 1988; 29: 363.
4. Mijovic J, Fishbain A, Wijaya J. Macromolecules 1992;
25: 986.
5. Marand E, Baker KR, Graybeal JD. Macromolecules
1992; 25: 2243.
6. George GA, Cole-Clarke P, St John NA, Friend G. J.
Appl. Polym. Sci. 1991; 42: 643.
7. Rogers DG, Marand E, Hill DJT, George GA. High
Perform. Polym. 1999; 11: 27.
8. Rogers DG, Hill DJT, George GA. Polym. Adv. Technol.
2001; 12: 169.
9. Rogers DG, Bialkowski ME, Hill DJT, George GA.
High Perform. Polym. 1998; 10: 341.
10. St John NA, George GA, Cole-Clarke PA, Mackay
ME, Halley PJ. High Perform. Polym. 1993; 5: 21.
11. St John NA, George GA. Progr. Polym. Sci. 1994; 29:
755.
Polym. Adv. Technol., 13, 353362 (2002)
362 / Hill et al.
12. Kozielski KA, George GA, St John NA, Billingham
NC. High Perform. Polym. 1994; 6: 263.
13. George GA, Cole-Clarke PA, St John NA, Friend G. J.
Appl. Polym. Sci. 1991; 42: 643.
14. George GA, Cole-Clarke PA, St John NA. Materials
Forum 1990; 14: 203.
15. St John NA, George GA. Polymer 1992; 33: 2679.
16. Hedrick JC, Lewis DA, Lyle GD, Wu SD, Ward TC,
McGrath JE. Polym. Mat. Sci. Eng. 1989; 60: 438.
Copyright 2002 John Wiley & Sons, Ltd.
17. Wei J, Hawley MC, De Long JD. Polym. Eng. Sci. 1993;
33: 1132.
18. Mijovic J, Andjelic S, Winnie Yee GF, Bellucci F,
Nicholas L. Macromolecules 1995; 28: 2797.
19. Mijovic J, Corso WV, Nicholas L, d'Ambrosio G.
Polym. Adv. Technol. 1998; 9: 231.
20. Beldjouri N, Bouazizi A, Douibi D, Gourdenne A.
Eur. Polym. J. 1988; 24: 53.
Polym. Adv. Technol., 13, 353362 (2002)