Thermochimica Acta 595 (2014) 22–27

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

The curing kinetics and thermal properties of epoxy resins cured by

aromatic diamine with hetero-cyclic side chain structure
Xuhai Xiong a , Rong Ren a , Siyang Liu a , Shaowei Lu a , Ping Chen a,b, *
a
Liaoning Key Laboratory of Advanced Polymer Matrix Composites Manufacturing Technology, Shenyang Aerospace University, Shenyang 110136, China
b
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China

A R T I C L E I N F O A B S T R A C T

Article history: The use of novel aromatic diamine containing phthalide structure (BAPP) as curing agent of
Received 18 May 2014 diglycidylether of bisphenol A (DGEBA) epoxy resin has been studied. BAPP can react with epoxy
Received in revised form 28 July 2014 monomers by an epoxy-amine condensation mechanism, which renders phthalide cardo incorporate
Accepted 29 July 2014
into the network structure of the thermoset. The curing behavior and kinetics have been investigated by
Available online 1 August 2014
differential scanning calorimetry (DSC) and the kinetic analysis of non-isothermal cure shows that
autocatalytic model is suitable to describe the cure mechanism. The thermal–mechanical properties have
Keywords:
been determined with dynamic mechanical analysis (DMA) and the activation energies for relaxation
Aromatic amine
Phthalide structure
were calculated according to the Arrhenius law. Thermogravimetric analysis exhibits a lower initial
Epoxy resin decomposition temperature, decreased rate of decomposition and higher char yield compared with
Curing kinetics DGEBA cured with commercially available 4,40 -diaminodiphenylsulfone (DDS).
Thermal–mechanical properties ã 2014 Published by Elsevier B.V.

1. Introduction increasing molecular chain of curing agent will reduce crosslinked

Curing agents play an important role in determining the practical
use of epoxy resin [1–3]. The excellent properties, such as mechanical
strength, heat resistance, durability and adhesiveness, are obtained
by reacting the linear epoxy resin with suitable curatives to form
three-dimensional crosslinked thermoset networks [4,5]. Therefore,
design and development of novel curing agent is one of effective
methods to improve properties of epoxy resin [2,5–8].
Despite the fact that epoxy resins could be cured by many types of
hardeners, aromatic amines retain a prominent position in high-tech
fields [9,10]. Epoxy resins cured with aromatic amine generally
provide enhanced environmental (hydrolytic) stability, outstanding
heat-resistant and mechanical properties [5,9]. 4,40 -diaminodi-
phenyl methane (DDM), m-phenylene diamine (m-PDA) and
4,40 -diaminodiphenylsulfone (DDS) are principal commercial
aromatic-amine curing agents. These traditional aromatic amines
with low molecular weight, however, bring on highly crosslinked
materials, which are seized of greater brittleness. Generally,
* Corresponding author at: Liaoning Key Laboratory of Advanced Polymer Matrix
Composites Manufacturing Technology, Shenyang Aerospace University, No. 37,
Daoyi South Avenue, Daoyi Development District, Shenyang 110136, China. Tel.: +86
24 89723970.
E-mail addresses: xiongxuhai@126.com (X. Xiong), chenping_898@126.com
(P. Chen).
density and further improve the toughness of network, but heat
resistance is decreased [6]. Therefore, the chain-extended aromatic
amines with multiaryl skeleton may provide a good balance
between mechanical and thermal properties.
Phthalide moieties are the ever-popular hetero-cyclic side
cardo groups and incorporated into polymer main chains to
improve solubility, heat resistance and thermal oxidative stability
[11–13]. Phenolphthalein and its derivations have been used
largely as aromatic bisphenol monomers for preparing high-
performance thermoplastics and thermosetting resins. According-
ly, phthalide-containing epoxy compounds were designed and
synthesized, and various epoxy resin systems modified by
polymers with phthalide cardo structure were developed
[14–16]. Although phthalide-modified epoxy systems show a lot
of advantages, a more cost-effective approach to introduce
phthalide moiety into epoxy networks using phthalide-contained
aromatic amine curing agents, which are of large molecular weight
and have the potential to overcome the defects of traditional
aromatic amines, has been not paid more attention.
The present work aims to investigate the curing kinetics and
mechanism of diglycidylether of bisphenol A (DGEBA) epoxy resin
cured with aromatic diamine containing phthalide structure
(BAPP) by using the non-isothermal DSC. The thermal properties
including thermal mechanical and thermal stability of cured
material will be also studied by means of DMA and TGA.

http://dx.doi.org/10.1016/j.tca.2014.07.027
0040-6031/ ã 2014 Published by Elsevier B.V.
 X. Xiong et al. / Thermochimica Acta 595 (2014) 22–27 23

2. Experimental

2.1. Materials

Commercially available diglycidylether of bisphenol A

(DGEBA)-based epoxy resin, with an epoxy equivalent of about
185–210 and average equivalent weight of 196, was supplied by
Wuxi Resin Works, China, and dried at 100  C in vacuum for 1 h
before use. The hardener, 3,3-bis[4-(4-aminophenoxy)phenyl]
phthalide (BAPP), was synthesized according to the reported
method [17]. The molecular structures of chemical structures
DGEBA and BAPP are illustrated in Scheme 1.

2.2. Preparation of DGEBA/BAPP blend

The prepolymer DGEBA/BAPP was prepared by mixing

stoichiometric DGEBA and BAPP at 90  C under vigorous mechani-
cal stirring for about 5 min, and then a homogeneous, visually
transparent mixture was obtained. The mixture was poured
directly into preheated teflon mold and then the mold was
transferred into an oven at 100  C under vacuum for 5 min to drive
off entrapped bubbles. The following temperature programs were
used to finish the cure process in an air convection oven at 120  C
for 1 h, 160  C for 2 h plus a post-cure period at 180  C for 4 h.
Finally, the casting was removed from the mold and characterized.
2.3. Characterization
Differential scanning calorimetry (DSC) measurements were
conducted with a PerkinElmer Diamond DSC instrument. The
DGEBA/BAPP mixture (about 7–9 mg mass) was loaded into sealed
aluminum pan. All DSC experiments were performed under N2
protection and run twice, the first scan was conducted from 25 to
300  C at different heating rates of 5, 7.5, 10 or 15  C/min and the
second scan was conducted from 25 to 200  C at a heating rates of
20  C/min.
Dynamic mechanical analysis (DMA) was done on a TA
Instruments Q800 DMA with an amplitude of 20 mm and a
temperature ramp rate of 3  C/min. The scanning temperature was
from 25 to 200  C and the driving frequencies were 1.0, 2.0, 5.0, 10
and 20 Hz. The cured DGEBA/BAPP specimens were cut to
dimensions of 30 mm  6 mm 1 mm for the tension mode.
Thermogravimetric analysis (TGA) was performed on a Perki-
nElmer TGA-7 thermal analyzer and the cured DGEBA/BAPP sample
(around 5 mg) was heated from 25 to 700  C at a heating rate of
20  C/min under the purified nitrogen flow rate of 60 mL/min.
Fig. 1. Non-isothermal DSC thermographs of DGEBA/BAPP reactions.
3. Results and discussion
3.1. DSC analysis
3.1.1. Reactivity of DGEBA/BAPP
The non-isothermal curing reactions of DGEBA/BAPP were
studied using DSC at a heating rate of 5, 7.5, 10 and 15  C/min and
the dynamic DSC thermograms and characteristic parameters are
shown in Fig. 1 and Table 1, respectively. It can be seen that there is
a single exothermic peak in each DSC curves and heating rate has a
great influence on the shape of the exothermic curves. The
exothermic peak is shifted to higher temperature and peak width is
extended with increasing heating rate. In addition, the total heat
release of cure reaction is independent of heating rate. In order to
determine the glass transition temperature (Tg) of DGEBA/BAPP,
the cured samples were carried out the second DSC test at a
heating rate of 20  C/min. As seen from Fig. 2, Tg value shows a
strong dependence on the heating rate of the first DSC test and
decreases by about 10  C with shifting of heating rate from 5 to
15  C/min (see Table 1). The believable cause is that the increasing
heating rates reduce the network chains packing density, resulting
in a decrease of steric hindrance to molecular motion.
3.1.2. Activation energy of the non-isothermal cure
The curing of epoxy resins is a multi-step chemical process that
is complicated by the physical processes of gelation and vitrifica-
tion [9,10]. Fortunately, the isoconversional analysis is a powerful

Scheme 1. Chemical structure of DGEBA and BAPP.

24 X. Xiong et al. / Thermochimica Acta 595 (2014) 22–27

Table 1
DSC analysis of DGEBA/BAPP resin at different heating rates.

b (K/min) Tonseta ( C) Tpeakb ( C) Tendc ( C) 4Hd (J/g) Tge ( C)

5 131.7 170.5 221.3 212.6 157.1
7.5 133.8 178.6 230.2 221.4 153.4
10 136.1 185.8 238.9 217.5 151.2
15 142.2 196.1 260.4 228.4 147.8
a
The onset cure temperatures.
b
The peak exothermic temperature.
c
The end cure temperatures.
d
Total heat of cure reaction.
e
Glass transition temperature measured by DSC.

tool to explore the evolvement of cure mechanism by monitoring

the variations in the effective activation energy with the extent of
curing [18–21]. To perform isoconversional analysis, the original
DSC data on exothermic peak were transformed into the fractional
conversion (a) versus temperature curves at various heating rates,
and the corresponding plots are shown in Fig. 3. The a values were
obtained by the integration of the exothermic peak based on the
following equation:
a ¼ Ha =Htotal
where Ha is the fractional enthalpy and Htotal is the total enthalpy
of the cure reaction.
It is clear from Fig. 3 that all a values increase very slowly at the
beginning of curing and when the samples were heated to given
temperatures, the a values show a sharply increase and then level
off. Moreover, to obtain the same a value, the required temperature
is increased with increasing heating rate.
A modified integral method proposed by M.J. Starink based on
Kissinger–Akahira–Sunose method, which is of more accurate, was
used to estimates the activation energies (Ea) for different
conversion levels (a). Starink equation is expressed as follows [22]:
lnðb=T 1:92
a Þ ¼ const  1:0008  ðEa =RT a Þ
where b is the heating rate, R is the universal gas constant, Ta is the
absolute temperature at a fixed value of the variable a.
The activation energy can be calculated from the slope of the
linear plot of ln(b/Ta1.92) against 1/Ta. The resulting Ea-dependen-
cies are shown in Fig. 4. It can be seen that the Ea values are around
47.5–60.9 kJ/mol, the average value is 56.1 kJ/mol, which is quite
typical for epoxy/aromatic amine copolymerizations [6,19]. In the
interval 0.05  a  0.6, the Ea values are practically constant which
Fig. 3. Conversion degree as a function of temperature.
suggests that the process follows a single step kinetic model. After
(1)
a > 60%, the values of Ea decrease gradually to as low as 50 kJ as
the degree of conversion increases. The same phenomenon was
observed in the non-isothermal or isothermal cure of DGEBA/1,3-
phenylenediamine (m-PDA) using Vyazovkin method [19]. The
decrease in Ea may indicate a change of the reaction mechanism.
However, decreased amplitude of the Ea value is smaller than that
reported in the other works [18,19]. The reason may be that when
a > 60% epoxy curing system in the present consideration has
passed the gel point and loses the ability to flow. In other hand,
from Figs. 2 and 3 it is known the actual experimental temperature
(a > 60%) is always above the glass transition temperature, hereat,
the mixture of polymer network and monomer is not frozen and
capable of engaging in further polymerization. Based on the
aforementioned facts, it is reasonable to expect that the decrease in
(2)
Ea results from increasing diffusion control.
3.1.3. Model-fitting kinetic analysis
Reaction rate equation for thermosetting system is generally
expressed
da Ea
¼ Aexpð Þf ðaÞ (3)
dt RT

Fig. 4. Variation of effective activation energy calculated based on Starink method

Fig. 2. Tgs of cured DGEBA/BAPP measured by DSC at a heating rate of 20 K/min. with conversion.
 X. Xiong et al. / Thermochimica Acta 595 (2014) 22–27 25

Fig. 5. Plots of normalized y(a) and z(a) against a.

Fig. 6. Plots of ln[y(a)] versus ln[ap(1  a)].

where f(a) is the reaction model. Curing reaction of epoxy/amine

examination shows that the values of am, ap1 and ap (the
system is assumed to follow autocatalytic reaction model (two-
conversion degree on the maximum of curing exothermic peak)
parameter SB model) [5,23,24]:
satisfy the conditions: 0 < am < ap < ap1 and ap1 6¼ 0.632, which
da Ea strongly indicate that the reactions of DGEBA/BAPP follow
¼ Aexpð Þam ð1  aÞn (4)
dt RT autocatalytic reaction model.
where f ðaÞ ¼ am ð1  aÞn , m and n are reaction orders. When m = 0, The kinetic exponents n and m and the pre-exponential factor A
Eq. (4) is transformed into n-order model. were obtained according to Eq. (8). The parameters, p, were first
Kinetic parameters (m, n) of the cure reaction were estimated determined from the values of am and then a series of the plots of
using the Málek method [24–26]. In this method two parameters ln[y(a)] with respect to ln[ap(1  a)] at different heating rates
am and ap1, which are the maximum of y(a) and z(a), respectively, were constructed and shown in Fig. 6. These data show good
are first obtained based on Eqs. (5) and (6). linearity. The values of n, m and ln A were calculated from the slope
and intercept of fitting straight lines. The constant kinetic
da parameters thus were determined and listed in Table 2. Then,
yðaÞ ¼ ð ÞexpðxÞ (5)
dt the averaged m, n and ln A along with previously calculated Ea are
introduced into Eq. (4), and eventually the explicit reaction rate
equation can be obtained as Eq. (9):
da T
zðaÞ ¼ pðxÞð Þ (6)
dt b da 56100 0:232
¼ 8:86  105 expð Þa ð1  aÞ1:265 (9)
where x is the reduced activation energy, x ¼ Ea =RT; pðxÞ was dt RT
calculated using the numerical approach of Senum–Yang Eq. (7): In Fig. 7, a comparison between experimental and theoretical
values is presented to check the predictability of Eq. (9). Obviously,
x3 þ 18x2 þ 88x þ 96 the predicted rate is in fair accordance with the experimental rate.
pðxÞ ¼ (7)
x4 þ 20x3 þ 120x2 þ 240x þ 120 This demonstrates the autocatalytic reaction model is suitable to
By combining Eqs. (4) and (5) and yields Eq. (8)

ln½yðaÞ ¼ lnA þ nln½ap ð1  aÞ (8)

where p ¼ m=n ¼ am =ð1  am Þ
The average Ea value calculated by the Starink method was
introduced into Eqs. (5) and (6) and and function curves of y(a),
which were normalized in order to simplify, and z(a) could be
constructed, as shown in Fig. 5. This figure clearly indicates that
conversion am associated with the peak values of y(a) curves are
located in 0.10–0.18, and the z(a) curves show a “C” shaped contour
experiencing a practically isoconversional peak value conversion,
ap1, within 0.50–0.54. The values am and ap1 corresponding to
different heating rates are shown in Table 2. A more detailed

Table 2
Characteristic peak conversion values and calculated kinetic parameters for SB
model at different heating rates.

b (K/min) ap am ap1 p m n ln A
5 0.508 0.159 0.535 0.189 0.260 1.202 13.64
7.5 0.479 0.123 0.516 0.140 0.216 1.271 13.76
10 0.484 0.155 0.516 0.183 0.181 1.162 13.57
15 0.471 0.136 0.508 0.157 0.273 1.424 13.81
Mean 0.486 0.143 0.519 0.168 0.232 1.265 13.70 Fig. 7. Comparison of predicted autocatalytic reaction model with experimental
data.
26 X. Xiong et al. / Thermochimica Acta 595 (2014) 22–27
Fig. 8. DMA thermograms of cured DGEBA/BAPP systems.
describe the progress of the non-isothermal curing reaction of
DGEBA/BAPP system.
3.2. Dynamic mechanical thermal analysis
The DMA curves conducted at a driving frequency of 1.0, 2.0, 5.0,
10 and 20 Hz for the DGEBA/BAPP networks are demonstrated in
Fig. 8. Generally, peak temperature for tan d or loss modulus is
identified as the glass transition temperature (Tg) and the area of
peak is associated with the amount of energy loss caused by
molecular motion. Seen from Fig. 8, tan d curves show single peak
at a temperature range from 140 to 200  C, which is an indication
that DGEBA/BAPP networks have homogeneous microstructure.
Besides, it is obvious that storage modulus, loss modulus and
relaxation peak express strong frequency dependency. As loading
frequency increases, the network becomes somewhat stiffer. This
is because the motion of network segments can follow the change
of driving force when smaller frequency is employed. The
increasing frequency also leads to a shift of loss modulus peak
and tan d peak to a higher temperature and the shift of two peaks
shows strong regularity. Herein, the Arrhenius law is adopted to
correlate this interrelationship for calculating the activation
energy of relaxation [26]. The activation energies of relaxation
were determined based on Eq. (10).
Fig. 9. Plots of ln f versus 1/Tg.
Fig. 10. TGA thermograms of cured DGEBA/BAPP systems.
dln f
DE ¼ R (10)
dð1=T g Þ
where 4E is the activation energy for specific relaxation, Tg denotes
the corresponding relaxation temperature, R is the universal gas
constant, and f is the loading vibration frequency.
A series of f and Tg was obtained from the multi-frequency DMA
measurements under fixed heating rate and the typical kinetic
plots of ln f versus 1/Tg were drawn. According to the plots shown
in Fig. 9, ln f against 1/Tg presents a good linear correlation and 4E
was calculated from the value of the slope. As a result, the
activation energy values calculated based on loss modulus peak
temperature and tan d peak temperature are 638.8 and
587.9 kJ/mol, respectively. The results are higher than the 4E
values (563 and 538 kJ/mol) for glass transition of cured DGEBA/
DDM system estimated by Raditoiu et al. [27]. This may be ascribed
to more rigid molecular segment of BAPP than that of DDM.
3.3. Thermogravimetric analysis
The thermal stability of the cured DGEBA/BAPP was assessed
with TGA and compared with that of DGEBA cured with 4,40 -
diaminodiphenylsulfone (DDS), which was obtained from the
literature [16]. Fig. 10 compares the thermal degradation behavior
of DGEBA/BAPP and DGEBA/DDS in nitrogen atmosphere. DGEBA/
BAPP system exhibits a lower temperature of initial decomposition
(Ti), slower rate of weight loss and higher char yield. The decreased
Ti may be attributed to the lower crosslinking density and the
relatively weaker tertiary amine crosslinks because of stronger
basicity of BAPP than that of DDS [28]. On the other hand, the
present of more aromatic structure may be the most significant
factor contributing to the lower rate of weight loss and higher char
yield. The latter indicates that the DGEBA/BAPP system is of higher
limiting oxygen index (LOI) and better flame-retardant property
according to the method of van Krevelen and Nijenhuis [29].
4. Conclusions
A novel epoxy system was developed using aromatic amine
containing phthalide cardo structure as curing agent. The curing
behavior and kinetics were studied in detail by non-isothermal
DSC. The average values of the apparent activation energy obtained
by Starink equation were 56.1 kJ/mol. Model-fitting kinetic analysis
showed the
curing mechanism of DGEBA/BAPP system followed autocata-
lytic model. The viscoelastic properties of the cured material were
 X. Xiong et al. / Thermochimica Acta 595 (2014) 22–27
characterized by DMA and single peak appeared in tan d curve at a
temperature range from 140 to 200  C. Activation energies for the
glass transition determined from tan d and loss modulus peaks are
638.8 and 587.9 kJ/mol, respectively. The results obtained from
TGA analysis indicated the cured material was provided with a
decreased rate of thermal decomposition and a higher char yield.
Acknowledgements
The financial supportfrom NationalNatural Science Foundation of
China (No. 51303107), National Defense 12th Five-Year Fundamental
Research Program (No. A352*******) and program for Liaoning
Excellent Talents in University (No. LR2013002) is gratefully
acknowledged.
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