Time–Temperature-Transformation (TTT) Diagram of the

Isothermal Crosslinking of an Epoxy/Amine System:

Curing Kinetics and Chemorheology

E. Mounif, V. Bellenger, A. Tcharkhtchi

LIM, ENSAM 151 Bd de l’Hôpital 75013 Paris

Received 27 October 2006; accepted 30 March 2007

DOI 10.1002/app.26612
Published online 27 February 2008 in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Rotational molding is a new process for draw the TTT diagram. We have completed this diagram
thermosets, few research works have been done on this by adding the isoviscosity curves to determine the
subject. The goal of this study is to determine the optimal available domain for rotational molding. Ó 2008 Wiley Peri-
conditions (time, temperature, viscosity, etc) of this process odicals, Inc. J Appl Polym Sci 108: 2908–2916, 2008
for an epoxy-amine system. The thermal and rheological
analysis help us to investigate the vitrification and the Key words: epoxy resin; TTT diagram; vitrification; gela-
gelation of the reactive system (DGEBA-DETDA) and to tion; rotational molding

INTRODUCTION and the shape of the part will be fixed. Depending

on the final application, the conversion ratio can be
Rotational molding of reactive systems such as ep-
increased in a later post cure. Many criteria are con-
oxy amine thermosets1 has been the subject of recent
sidered by authors to characterize the gel point (G0
work2–4 because it presents an attractive alternative
and G00 curves intersection, the point for which tan d
to the use of thermoplastic powders in the aim of
is independent of frequency, the divergence point of
optimizing cycle times thanks to gelation and open-
viscosity and so on. . .8). However, in the case of the
ing a new domain of applications. The viscosity vari-
rotational molding the processing must be finished
ation is the main phenomenon, which affects the
before the gel point and the processing has a maxi-
cycle time of rotational molding. The evolution of
mum limit of viscosity gmax after which the system
the viscosity is highly dependent on the increase of
has a solid rotation.
the molecular weights and the structure evolution of
Another important property of polymeric materi-
the reactive system during an isothermal cure.
als is the glass transition temperature Tg. The evolu-
Understanding this structure evolution allows us to
tion of this property can be linked directly to the
predict the evolution of the viscosity. Until now,
conversion ratio Tg 5 f(x) via Di-Benedetto’s equa-
there are no general kinetic schemes universally
tion.9 Kinetics investigation of chemical reactions [x
accepted5 for the crosslinking of epoxy amine sys-
5 f(t)] allows us to determine the vitrification curve
tems. In the case of aromatic amine hardeners, the
Tg 5 f(t) for an isothermal cure.
substitution effect6,7 (i.e., the formed secondary
In this article we tried to define the optimal condi-
amine are less reactive than primary amine groups)
tions of rotational molding of an epoxy-amine sys-
delays the crosslinking and the formation of the gel.
tem, by building up the well-known time-tempera-
The first formed oligomers will be linear with a few
ture transformation-diagram (TTT),10–12 and by deter-
branches which decreases the viscosity comparing
mining the kinetics parameters, which control the
with the linear oligomers of the same molecular
crosslinking process.
weight. The most important processing event of a
reactive system is the formation of a gel which is a
three dimensional, infusible, and insoluble network.
Background
The gel time is a critical point for thermosets proc-
essing because the system will not flow any more, Isothermal kinetics
Scheme 1 displays the general accepted mechanism13
Correspondence to: V. Bellenger (veronique.bellenger@paris. which was first published by Smith14 and later by
ensam.fr).
Horie and Hiura15 for the crosslinking of an epoxy
Journal of Applied Polymer Science, Vol. 108, 2908–2916 (2008) prepolymer by an amine hardener. It proposes
V
C 2008 Wiley Periodicals, Inc. mainly two ways (catalytic and noncatalytic) of ring
TTT DIAGRAM OF CROSSLINKING OF EPOXY/AMINE SYSTEM 2909

perature. The differential equation system control-

ling the concentration variation of reactive species is:

d½E

¼ k1 ½A1
½E
 k2 ½E
½A2
(1)
dt

d½A1

¼ k1 ½E
½A1
 k1c K½A1
½E
½OH
(2)
dt

d½A2

¼ k1 ½E
½A1
þ k1c K½A1
½E
½OH
 k2 ½E
½A2

dt
 k2c K½A2
½E
½OH
ð3Þ

d½OH

¼ k1 ½E
½A1
þ k2 ½E
½A2
þ 2k1c K½A1
½E
½OH
þ
dt
2k2c K½A2
½E
½OH
ð4Þ

d½EOH

¼ k1c K½A1
½E
½OH
 k2c K½E
½A2
½OH
(5)
dt

where [A1], [A2], [E], [OH], and [EOH] are respec-

tively, the concentrations of primary amine, second-
ary amine, epoxy, hydroxyl, and activated epoxy
groups. The buid-up of an epoxy-hydroxyl complex
was considered as a rapid equilibrium compared
with other steps of the mechanism and in this case
Scheme 1 Curing mechanism of an epoxy prepolymer we note the product kicK as kic.
crosslinked by a diamine. The last differential equations system can be modi-
fied to take into account the effect of evaporation of
monomers on the kinetic of crosslinking,22 but we
opening of the epoxy groups. The activation of the think that the evaporation may be neglected when
ring opening of epoxy is achieved by proton donors the crosslinking is achieved in a closed crucible
especially the produced hydroxyl groups. Both (DSC) or quartz cells (FTIR). For crosslinking tem-
hydroxyl and primary amine groups can catalyze perature close to glass transition temperature, the
the reaction via the formation of complexes like (E- process is controlled by the diffusion23–26 due to the
OH) and (E-A1). We considered only the build-up of reduced mobility of reactants in the reactive system.
epoxy-hydroxyl complexes, which has the main par- But when the crosslinking temperature (Tiso) is 308C
ticipation in the catalytic mechanism.16–18 This acti- higher than the glass transition (Tg), the effect of the
vation can be achieved by other hydrogen donors or diffusion on the crosslinking mechanism can be
impurities like HX. neglected.
Etherification or homopolymerization (Scheme 2)
can also occur at high crosslinking temperatures. It
can be catalyzed by the presence of tertiary amine
groups and when the epoxy is in excess,19 especially
when the epoxy structure contains already tertiary
amine groups like tetraglycidyl diamino diphenyl
methane (TGDDM) or N,N-diglycidyl aniline (DGA).20
The importance of the etherification depends also
on the basicity of the used amine, for instance, in
the case of the 4,40 -methylene bis(3-chloro-2,6-di-
ethylaniline) (MCDEA) hardener, the weak basicity
of MCEDA makes the etherification a competitive
reaction.21
The etherification can be neglected in our case,
because the DGEBA is not in excess, the structure of
DGEBA does not contain any tertiary amine groups
and finally crosslinking does not occur at high tem- Scheme 2 Mechanism of etherification.

Journal of Applied Polymer Science DOI 10.1002/app

2910 MOUNIF, BELLENGER, AND TCHARKHTCHI

Determination of the chemical kinetic constants TABLE II

Initial Concentrations of Different Functional Groups
In phenomenological or empirical models, parame-
[E]0 [A1]0 [A2]0 [A3]0 [OH]0
ters have not necessarily physical meanings. In this
research, our aim is to obtain the best parameters for Concentration (mol kg21) 4.36 2.24 0 0 0.134
the proposed mechanism which can describe ele-
mentary steps taking place and explain the observed
experimental results. parallel plates with a 0.5–1 mm spacing and a 50-
The numeric integration of the last differential equa- mm diameter. The reactive mixture is added quickly
tion system [eqs. (1)–(5)] is achieved using home- on the preheated plate and a time sweep is started
made Matlab programming code based on 4th order when the temperature equilibrium was reached
semi-implicit Runge–Kutta method.27 To get the best again. A time ramp at a multifrequency mode is
fit for the primary amine and epoxy group conversion used to determine the gel time considering the loss
ratios, we have started with an initial estimate of factor independence of frequency as a criterion of
kinetics parameters (Table I) and then a constrained gel point.
optimization process based on the direct search
method (Nelder–Mead Simplex Method28) is used to Thermal analysis
get the best set of parameters. We support the hypoth-
esis that relative reactivity ratio of secondary amines The cure of investigated systems is studied by
to primary amines, via noncatalytic way (r 5 k2/k1) is means of a differential scanning calorimeter DSC-
equal to the catalytic one (rc 5 k2c/k1c). This ratio is Q10 from TA instruments, using aluminum hermetic
equal to 0.5 for equal reactivities (Table I) of the pri- crucibles. The DSC is calibrated in enthalpy and
mary (always interfered as 2 3 NH) and secondary temperature scales by using a high purity indium
amine ( NRH) groups. Table II contains the initial sample.
concentration of different reactive functions. Isothermal crosslinking is achieved by three ways:
a. One sample is placed in the preheated DSC cell,
and time scan is started when the temperature
EXPERIMENTAL
equilibrium was regained until the base line is
Materials reached again.
b. Interrupted crosslinking was achieved in situ in
Diglycidyl ether of bisphenol A (DGEBA) with an
the DSC cell in sealed aluminum crucibles.
epoxy equivalent weight of 178 g mol21, from Fluka
Crosslinking is quenched by a rapid cooling
is used. Diethyl toluene diamine (DETDA) or Etha-
when the desired crosslinking time is reached.
cure100 from Safic Alcan exists as a mixture of 2,4
c. Isothermal crosslinking of the reactive system
and 2,6 isomers with an NH equivalent mass of 45
was achieved also in a steel beaker heated by
g mol21 and is added as a hardener for epoxy resin.
an oil bath under mechanical stirring, samples
Scheme 3 represents the structures of both compo-
were taken at different times and quenched by
nents. To prepare the thermoset system, hardener is
cooling in an ice bath.
added to DGEBA in stoichiometric ratio. To obtain a
homogenous mixture, the components are mixed at
558C in an oil bath and degassed under vacuum for
20 min at 408C.

Methods
Rheological analysis
Rheological properties are measured using an ARES
Rheometer from TA instrument equipped with

TABLE I
Initial Estimate and Intervals for the Kinetic Parameters
Minimum Maximum
Initial accepted accepted
Kinetic parameter estimate value value
k1 (kg mol21 min21) 0.1 1028 1
k1c (kg2 mol22 min21) 0.1 1028 1 Scheme 3 Chemical structures of prepolymer and hard-
r 0.25 1028 0.5 ener. [Color figure can be viewed in the online issue,
which is available at www.interscience.wiley.com.]

Journal of Applied Polymer Science DOI 10.1002/app

TTT DIAGRAM OF CROSSLINKING OF EPOXY/AMINE SYSTEM 2911

When samples with various thicknesses are ana-

lyzed, a reference band has to be considered. Phenyl
groups absorption bands (4623, 4681, 4065 cm21) are
widely used in the literature.29 In our case the same
cell is used for all experiments; therefore we applied
the simple equation: xNIR ¼ 1  A A0 , to quantify the
1

epoxy conversion ratio; At/A0 is the ratio of actual

area of peak with respect to initial one.

RESULTS AND DISCUSSION

Effect of various crosslinking conditions
Figure 2 shows the results of thermal analysis of the
three last crosslinking ways. Conversion ratio versus
Figure 1 NIR spectrum of the isothermal crosslinking of cure time curves in isothermal curing conditions are
the reactive system of DGEBA-DETDA. [Color figure can obtained by normalizing the integral heat flow
be viewed in the online issue, which is available at
www.interscience.wiley.com.] curves with respect to the total enthalpy of reaction
of fully reacted samples. A good agreement is
noticed between experimental results of various
Running integral of the Universal analysis soft- types of curing conditions. The use of running inte-
ware (from TA instrument) was used to get the con- gral for one sample isothermal curing allows deter-
version ratio in the first case (a) and a dynamic scan mining quickly the conversion ratio versus the cure
(58C min C21 ) of partly cured samples was done to time or the heat flow versus the conversion ratio.
measure the residual enthalpy and glass transition The heat flow is supposed to be proportional to reac-
temperature Tg (b and c). tion rate dQ
dt ¼ DHtot dt , the extrapolation of the baseline
1 dx
Working at high heating rates shifts the reaction to to t 5 0 min is more difficult at high temperature
higher temperature and in this case it would not be (Fig. 3) due to the difficult stabilization of temperature
easy to neglect side reactions. The choice of the heat- in the sample at the beginning of the experiment.
ing rate was optimized to get a good estimate of The average reaction enthalpy of the equimolar
glass transition temperature. mixtures (DHtot 5 92 J/epoxy equivalent) was in
The total heat of reaction, DHtot, is estimated from agreement with those reported in literature30–32 for
nonisothermal experiments. In these experiments, similar reactive systems. It should be noticed that in
sample is heated from initial temperature Tini to final our case, conversion ratios determined by DSC and
temperature Tf, with linear heating rates of 2, 5, 7,
and 108C min21. DHtot is calculated by drawing a
linear baseline and integrating the area under the
peak. The heat of isothermal reaction is estimated by
extrapolating the final baseline. Dynamic DSC
experiments are also performed to determine the
glass transition temperature, of an uncured Tg0, and
completely cured material Tg1. The glass transition
temperature is taken as the inflection point of the
second order endothermic transition.

Near infra red (NIR) spectroscopy

Fourier transform NIR spectroscopy is performed
using Bruker IFS28 spectrophotometer, equipped
with a Globar source, KBr beam splitter, and DTGS
detector. All spectra (Fig. 1) were collected in the
near infra red domain (7500–4000 cm21) at a 4 cm21
resolution and 32 scans per sample. For thermal con-
trol, a temperature controller is used (Specac). The Figure 2 Comparison between different kinds of curing
conditions (T 5 1408C, (^): Sample Crosslinked in oil bath
reactive mixture is injected with a syringe in the cell (*): Sample Crosslinked in the DSC cell, (—): running in-
(Quartz with 2-mm pathlength) when the controller tegral) (T 5 1308C (^): Sample Crosslinked in oil bath, (—):
showed the programmed temperature. running integral).

Journal of Applied Polymer Science DOI 10.1002/app

2912 MOUNIF, BELLENGER, AND TCHARKHTCHI

Figure 3 Heat flow for different conditions of isothermal

cure 1308C (*), 1408C (&), and 1508C (~). Figure 5 Conversion ratio of primary amine (*) and ep-
oxy (*) groups during a cure at 1308C and Matlab
numeric solution (—). [Color figure can be viewed in the
NIR spectroscopy (Fig. 4) are no more comparable online issue, which is available at www.interscience.wiley.
com.]
after the gel point. In fact the sharp increase of the
viscosity at the gel point and the consumption of re-
active species lower the reaction rate. Concerning, for the cure temperatures T 5 1308C and T 5 1408C.
the DSC measurement, the heat flow decreases and Table III shows the numeric values of the catalytic
heat dissipation becomes more difficult to detect. and noncatalytic parameters, obtained by the last
When one considers conversion ratio obtained by optimization. Obviously, the reaction occurs mainly
NIR spectroscopy (xNIR), the chemical absorbance by a catalytic mechanism and the contribution of a
also decreases and integrating the absorption band noncatalytic mechanism can be neglected.
was not easy due to the weak measured energy; so The reactivity ratio increases with temperature,
both methods of characterization become less effi- which means that primary amines are still more re-
cient. We were interested in characterizing the reac- active at high temperature than secondary ones. Sup-
tive system before gelation, where the process is con- posing that all kinetics parameters follow Arhennius
trolled by chemical kinetics. Law, k 5 A exp(Ea/RT), one can estimate (Table IV)
the corresponding activation energies (Ea) and the
Kinetics parameters pre-exponential factors (A). As expected, catalytic
activation energies are lower than those of noncata-
A good agreement is noticed between the numeric
lytic reactions and higher than those obtained by
solution and the experimental data (Figs. 5 and 6)

Figure 6 Conversion ratio of primary amine (*) and ep-

oxy (*) groups during a cure at 1408C and Matlab
Figure 4 Comparison between conversion ratios of epoxy numeric solution (—). [Color figure can be viewed in the
groups obtained by DSC and NIR methods. Experimental online issue, which is available at www.interscience.wiley.
results (&) and linear fit (—). com.]

Journal of Applied Polymer Science DOI 10.1002/app

TTT DIAGRAM OF CROSSLINKING OF EPOXY/AMINE SYSTEM 2913

TABLE III
Kinetics Parameters of the Crosslinking Reaction
Between DGEBA and DETDA at 1308C and 1408C Cure
Temperature
1308C 1408C
21 21 24
k1 (kg mol min ) 1.6 3 10 7.6 3 1024
k2 (kg mol21 min21 ) 4.8 3 1025 2.6 3 1024
k1c (kg2 mol22 min21) 7.0 3 1023 1.1 3 1022
k2c (kg2 mol22 min21) 2.0 3 1023 3.8 3 1023
r 0.29 0.35

Uhlherr and coworkers6 who considered only the

catalytic mechanism.

Vitrification
Figure 7 Glass transition temperature as a function of
When the increasing Tg value approaches the iso- DSC conversion ratio. Experimental results (Y) and Di
thermal cure temperature, the molecular mobility is Benedetto fit (—). [Color figure can be viewed in the
strongly reduced and the reaction becomes diffusion online issue, which is available at www.interscience.wiley.
com.]
controlled and eventually breaks off. The variation
of the glass transition temperature (Tg) versus the for partly cured sample (Figs. 9 and 10). The same
crosslinking ratio, determined by DSC (x-DSC) is value for the pregel viscosity is founded and values
found to follow Di Benedetto equation: diverge only in the vicinity of the gel point because
of nonlinear effects of the built up network. The
lðTg1  Tg0 Þx
Tg ¼ Tg0 þ ; rheological behavior of different epoxy-amine reac-
1  ð1  lÞx tive systems in terms of scaling laws is studied in
details in literature.33–35 In our case we focused our
With k ¼ ðDC1 p =DCp Þ heat capacity change ratio. It is
0
interest on two essential phenomena: gelation and
measured through the glass transition for uncured vitrification.
and fully cured system by DSC. The measured value
of k 5 0.27 is different from that found by O’Brien
and White7 (i.e., k 5 0.392) but it is in good agree- Gelation
ment with the best fit obtained parameter (k 5 0.28) The gel point was obtained by considering the time
(Fig. 7). Until the gel point, the glass transition tem- to reach a value independent of the frequency (Fig.
perature Tg is smaller than the curing temperature 11), using multi-frequency experiments. One must
Tcure, which means that the gelation takes place
before the vitrification. The curve of Tg 5 f(x) is a
good tool to get the time to vitrification and to estab-
lish finally the vitrification curve (see TTT diagram).

Rheological analysis
The measurement of the rheological properties is
done using auto strain mode. The strain increases at
the beginning of the crosslinking till its maximum
allowed value and decreases at gel point to avoid
the breaking of the formed network (Fig. 8). To ver-
ify the linear viscoelasticity of the system and to see
the influence of this mode on the rheological proper-
ties, we have carried out a dynamic strain sweeps

TABLE IV
Activation Energies as Estimated from NIR Measurement
for Catalytic and Noncatalytic Mechanisms
k1 k2 k1c k2c Figure 8 Experimental curves of the real part of dynamic
ln A) 55 61 13 19 viscosity h0 (~), and strain g_ (&) versus time during
Ea (kJ mol21) 213 237 61 85 isothermal crosslinking of the DGEBA-DETDA reactive
system.

Journal of Applied Polymer Science DOI 10.1002/app

2914 MOUNIF, BELLENGER, AND TCHARKHTCHI

Figure 9 Experimental curves of the real part of dynamic

viscosity (h0 ) measured by strain sweeps at 1308C. Each Figure 11 Loss factor (tan d) versus time for DGEBA-
strain sweep was done after different curing times: 10 min DETDA system cured at 1308C, measured at three frequen-
(^), 23 min (^), 29 min (~), 33 min (n), 36 min (), 39 cies 2 Hz (~), 5 Hz (n), and 10 Hz (l).
min (l), 41 min (1), 44 min (~), and 46 min (^).

with the gel time. The Arrhenius plot of the gel times
pay attention to the minimal frequency value (fmin) listed in the Table V is shown in Figure 12.
which can be used; this value depends on the curing
temperature (Tcure). In fact, at every frequency, the E
tgel ¼ AeRT
reaction rate has to be low during measurements.
We considered the condition proposed by Izuka where Ea is the activation energy, T is the absolute
et al.36: (1/G*) (@ G*/@ t) (2p/x) < 0.1. In our case, temperature of reaction, and R is the universal
the gel times measured by different rheological crite- gas constant. The activation energy of the reaction is
ria are almost the same. The gel times of the DGEBA- equal to 60 kJ mol21, which is a reasonable value
DETDA system for several isothermal conditions are compared with the one of bisphenol A type epoxy
summarized in Table V. Measuring the gel time at resin and aromatic amine compounds.37 When com-
higher temperatures is inaccurate because the temper- paring the gel point as measured by the parallel
ature stabilization time is considerable compared plate rheometry for different temperatures, we found
that the critical conversion ratio as measured by
DSC was about x 5 0.70 which is different from
the theoretic critical value calculated by Flory rela-
tionship. In the case of our system [tetra functional
hardener (diamine) 1(bi functional epoxy)], the
calculated critical value xgel is equal to 0.58. The
main reason for this is the difference in reactivity
(substitution effect delays the gel point38) between
primary and secondary amines groups.

Time-temperature-transformation (TTT) diagram

The Diagram Time-Temperature-Transformation is
established experimentally. For each isothermal cur-
ing temperature we determined the times it takes to
gelation (tgel) and to vitrification. We notice that the
vitrification takes place after gelation and the cross-

TABLE V
Figure 10 Dynamic viscosity of reactive system measured Gel Times for Different Isothermal Cure Temperatures
by strain sweeps at various times of the crosslinking. The Curing temperature (8C) 120 130 135 140 150
different parts of Figure 9 were connected considering the Gel time (min) 100 63 46 42 29
elapsed curing time.

Journal of Applied Polymer Science DOI 10.1002/app

TTT DIAGRAM OF CROSSLINKING OF EPOXY/AMINE SYSTEM 2915

CONCLUSIONS
The kinetic parameters of a DGEBA-DETDA thermo-
set crosslinking are identified. A catalytic and nonca-
talytic mechanism is considered for modeling the
evolution of epoxy and amine conversion ratios ver-
sus time. The gelation of the reactive system is stud-
ied in isothermal curing conditions. The gel time is
determined as a congruency in the time evolution of
the tan d curves obtained at different frequencies.
The variation of glass transition temperature versus
conversion ratio is found to be in a good agreement
with Di Benedetto equation. Finally the TTT diagram
is established coupling the thermal and rheological
measurements.
Our next work is to couple these interfered phe-
nomena: chemical reaction and heat conduction to
predict the flow of the reactive fluid.
Figure 12 Arhennius plot of gel times.
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Journal of Applied Polymer Science DOI 10.1002/app