Iran Polym J (2012) 21:353–363
DOI 10.1007/s13726-012-0036-z
ORIGINAL PAPER
Effects of 2-ethyl-4-methylimidazole and tetraethylammonium
bromide on the fracture properties of epoxidized soybean oil
based thermoset
S. G. Tan • W. S. Chow
Received: 24 October 2011 / Accepted: 14 March 2012 / Published online: 31 March 2012
Ó Iran Polymer and Petrochemical Institute 2012
Abstract In this paper, we aim to report the effects of
catalyst (types and concentrations) on the fracture mechanics
of epoxidized soybean oil (ESO) based thermosets. ESO
resin was thermally cured using methylhexahydrophthalic
anhydride curing agent in the presence of two types of
catalysts, i.e., tetraethylammonium bromide and 2-ethyl-4-
methylimidazole (EMI). The loading of the catalysts varied
from 0.3 to 0.8 phr. The fracture behaviour of ESO thermoset
was examined on the basis of the principle of linear elastic
fracture mechanics (LEFM) and essential work of fracture
(EWF). LEFM measurements were performed using single-
edge notched tensile and double-edge notched tensile (DENT)
tests, while, EWF measurements were carried out using
DENT tests. The fracture morphologies of the ESO thermo-
sets were characterized via field emission scanning electron
microscopy. It was determined that the plane-strain fracture
toughness (KIC), the specific EWF (we), and the specific plastic
fracture work (bwp) of ESO thermosets were significantly
influenced by the types and loading of catalysts. In addition,
the fracture toughness properties were associated with the
crosslink density of the ESO thermosets. In addition, it was
found that the brittle–ductile transition of EMI-catalyzed ESO
thermosets can be assessed by the combination of LEFM and
EWF in the fracture toughness measurement.
Keywords Mechanical property  Morphology 
Renewable resources  Thermosets  Catalyst
S. G. Tan  W. S. Chow (&)
School of Materials and Mineral Resources Engineering,
Engineering Campus, Universiti Sains Malaysia,
Nibong Tebal, 14300 Pulau Pinang, Malaysia
e-mail: chowwenshyang@yahoo.com
Introduction
Developing of thermosetting materials from natural
renewable resources especially vegetable oil derivatives is
of scientific interests in the field of polymer. This is pre-
dominantly due to the environmental friendliness and cost
effectiveness of the vegetable oils. Epoxidized soybean oil
(ESO) has been predominantly used to substitute and
toughen fossil-fuel-based polymers in recent years. ESO
derived from biological origin substrates could bring along
numerous environmental advantages, because, they are
biodegradable and are neutral in the carbon dioxide cycle
during polymer biodegradation process.
Plenty of attempts have been conducted to enhance the
toughness of the polymer systems and to assess their
fracture behaviour. Linear elastic fracture mechanics
(LEFM) and essential work of fracture (EWF) are two
established and well-known approaches used to examine
the fracture characteristics of polymers. Few researchers
used the concept of LEFM and EWF to evaluate the frac-
ture behavior of different types of polymer. Barany et al.
[1] reported the concepts of EWF to examine the in-plane
(plane stress) fracture toughness of amorphous copolyes-
ters. Pfaff [2] introduced the method of EWF to study the
plane-stress fracture toughness of amine-cured epoxy
compositions. Tan et al. [3] investigated the influence of
the epoxidized palm oil (EPO) concentration on the plane-
strain fracture toughness (KIC) of epoxy-palm oil blends
based on the principle of LEFM. Beh Saleh et al. [4]
applied the LEFM concept to determine the KIC of the
diglycidyl ethers of bisphenol-A (DGEBA) thermoset
toughened with different concentration of the carbonyl-
terminated butadiene acrylonitrile copolymer liquid rubber.
Ma et al. [5] measured the KIC of the neat DGEBA epoxy
thermoset, the DGEBA/liquid rubber composites and the
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DGEBA/core–shell rubber composites according to the
principle of LEFM.
In this present research work, ESO thermosets were
synthesized using the methylhexahydrophthalic anhydride
(MHHPA) curing agent in the presence of two types
of catalysts, i.e., 2-ethyl-4-methylimidazole (EMI) and
tetraethylammonium bromide (TEAB). In our previous
work, we have found that the flexibility and rigidity of the
ESO thermoset was influenced by the types and concen-
tration of the catalyst. In this work, the fracture behavior of
the ESO thermoset is characterized using both principles of
LEFM and EWF. It is also believed that the combination
of LEFM and EWF in fracture toughness measurement can
be a model to quantify the brittle–ductile transitions of
certain ESO thermoset.
Experimental
Materials
Epoxidized soybean oil (ESO) resin with about 6.1 wt% of
epoxy oxirane content and molecular weight of approxi-
mately 950 g/mol was supplied by Shangdong Longkou
Longda Chemical Industry (China). Industrial grade of
Table 1 ESO resin, MHHPA curing agent, EMI and TEAB catalysts used in this study
Name Molecular structure
ESO
MHHPA
EMI
TEAB
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MHHPA curing agent was purchased from CAPE Tech-
nology Sdn Bhd. (Malaysia). EMI and TEAB catalysts
were supplied by Sigma-Aldrich (USA). All the materials
used in the present work, as described in Table 1, were of
commercial grade and were used without further purifica-
tion. The material designation and composition of the ESO
thermoset are shown in Table 2.
Preparation of ESO thermoset
Methylhexahydrophthalic anhydride curing agent was pre-
mixed with EMI and TEAB catalysts at a predetermined
ratio. ESO resin and MHHPA/catalyst mixture were mixed
at the room temperature and stirred mechanically to pre-
pare a homogenous mixture. The mixture was then poured
into the cavities of mould and subjected to thermal curing
process in an oven at 140 °C for 3 h. Based on the
appearance of the cured ESO thermosets, the specimens
were homogeneous and transparent.
Fracture toughness characterization
Fracture toughness measurement was carried out according
to the principles of LEFM on the single-edge notched
tensile (SENT) and the double-edge notched tensile
Molecular
weight (g/mol)
950
168
110
210
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Table 2 Materials designation and composition of the ESO

thermoset
Material designation Composition
EMI catalyst TEAB catalyst
(phr) (phr)

EMI-catalyzed ESO thermoset

ES_0.3I 0.3 –
ES_0.4I 0.4 –
ES_0.5I 0.5 –
ES_0.6I 0.6 –
ES_0.7I 0.7 –
ES_0.8I 0.8 –
TEAB-catalyzed ESO thermoset
ES_0.3A – 0.3 Fig. 1 Schematic diagrams of SENT and DENT specimens for ESO
ES_0.4A – 0.4 thermosets
ES_0.5A – 0.5
ES_0.6A – 0.6 The measurement of total work of fracture was con-
ES_0.7A – 0.7 ducted based on the principles of EWF on the DENT
ES_0.8A – 0.8 specimens. The dimension of the DENT specimen are
60 9 20 9 3 mm3 (length 9 width 9 thickness) with the
(DENT) specimens. The dimension of the specimen are crack length-to-width ratio (a/W) of 0.2, 0.4 and 0.6. An
60 9 20 9 3 mm3 (length 9 width 9 thickness) with the initial crack was produced by sliding the notched specimen
crack length-to-width ratio (a/W ratio) of about 0.4. The with a fresh razor blade. The testing speed was set at
notched ESO specimen was then slid with a fresh razor 10 mm/min. The specific essential work and the specific
blade to initiate cracks. Experiment was conducted using plastic work can be determined from the linear plot of wf
an Instron machine (model 3366, UK) equipped with a versus L according to Eq. 3 [8].
10-kN load cell at a testing speed of 10 mm/min on five Wf
specimens. The mechanical grip distance used in the wf ¼ ¼ we þ bwp L ð3Þ
LB
present study is 40 mm.
Figure 1 shows the schematic diagrams of SENT and where wf is the maximum load applied, B is the specimen
DENT specimens for the ESO thermosets. The plain-strain thickness, W is the specimen width, a is the initial notched
fracture toughness (KIC) of the SENT specimen was length, L is the ligament length for a given specimen
determined using Eq. 1 [6], whereas the KIC of the DENT thickness; we is the failure work per unit surface area, and
specimen was determined using Eq. 2 [7]. The influence of wp is the plastic work per unit volume of the plastic
EMI concentration on KIC value of the ESO thermoset was deformation zone.
analyzed using a one-way analysis of variance (ANOVA).
Statistical analyses were performed at a 95 % confidence Morphological characterization
level. Data were analyzed with Design-Expert (version
6.0.6 software, Stat-Ease, Inc.). The morphology of the fractured surface of ESO thermo-
 a  a 2 setting resin was studied using field emission scanning
Fmax 1=2
KIC ¼  a  1:99  0:41 þ 18:7 electron microscopy (FE-SEM) model Supra 35VP (Zeiss,
BW W W Germany). The specimen surface was coated with gold
 a 3  a 4 
 38:48 þ53:85 ð1Þ and/or palladium prior to FE-SEM testing in order to avoid
W W electrostatic charging.
Fmax 1=2
KIC ¼ a
 BW a  a 2  a 3  Results and discussion
 1:99 þ 0:76  8:48 þ27:36 ð2Þ
W W W
LEFM
where Fmax is the maximum load applied, B is the speci-
men thickness, W is the specimen width, and a is the initial Linear elastic fracture mechanics is used in this present
notch length. study to quantify the severity of cracks in influencing the

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Fig. 2 Effect of EMI and TEAB concentrations on the plain-strain
fracture toughness of the single-edge notched tensile ESO thermosets
fracture behaviour of the ESO thermoset. According to the
principles of LEFM, it is found that the plain-strain fracture
toughness (KIC) of the EMI-catalyzed ESO thermoset
increases with increasing the EMI catalyst concentration
varying from 0.3 to 0.8 phr. However, the KIC of the TEAB-
catalyzed ESO thermoset increases with the TEAB catalyst
concentration up to 0.5 phr after which there is a drop as
shown in Figs. 2 and 3. One-way ANOVA shows that there
was statistically significant difference in the fracture
toughness average (probability \ 0.01 %) among the ESO
thermosets catalyzed with different EMI or TEAB catalyst
concentration, ranging from 0.3 to 0.8 phr. This gives us a
hint that catalyst concentration did play its role in influ-
encing the fracture toughness of ESO thermoset. The
improvement in fracture toughness of the ESO thermoset
with the catalyst concentration is attributed to the increase
in the degree of cure in the crosslinked network structure
and the concomitant reduction of the unreacted monomer
species in the thermoset. In general, degree of cure is the
extent to which curing of a thermosetting resin taken place.
At relatively low crosslink levels, the crosslinked network
in the ESO thermoset is able to absorb, transform and dis-
sipate the fracture energy through the deformation of the
molecular networks by appreciable plastic flow.
In our previous works [9, 10], it was found that the
residual monomer species, e.g., mixture of ESO and
MHHPA monomers, which did not take part during the
thermal curing reaction, are present in the ESO thermoset.
Note that these residual monomer species may plasticize
the thermoset and offer a more local flexibility to dissipate
energy. The energy dissipated by plastic deformation will
significantly increase the total energy needed for the crack
growth and this may account for the increase of KIC.
According to Cook [11], the increase in crosslink density in
the silica-filled dimethacrylate resin gives rise to an
improvement in the fracture toughness.
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Fig. 3 Effect of EMI and TEAB concentrations on the plain-strain
fracture toughness of the double-edge notched tensile ESO thermosets
Interestingly, KIC of the ESO thermoset decreases
drastically once the TEAB catalyst concentration added
into the thermosets exceeding 0.5 phr. This finding is
mainly attributed to the relatively high amount of crosslink
density in the cured TEAB-catalyzed ESO thermosets. In
general, crosslink density is the average number of cross-
links per unit volume. Instead of absorbing and dissipating
external force applied, the highly crosslinked network in
the ESO thermoset is no longer capable to dissipate sig-
nificant amounts of hysteretic strain energy in the form of
heat. The energy will eventually used to break the network
chains. In addition, the refrained monomers concentration
in the TEAB-catalyzed thermoset is found to be very low,
except for the ES_0.3A thermosets. The highly crosslinked
ESO network is unable to dissipate sufficient amount of the
applied forces to suppress the catastrophic brittle mode of
fracture even if there is a small diffuse zone of plastic
deformation ahead of the crack tips. It will eventually give
rise to the reduction in KIC in these thermosets as shown in
Figs. 2 and 3. This finding is in line to the finding reported
by Zhang [12] who found that the highly crosslinked epoxy
system commonly possesses low KIC value. It is mainly
due to the fact that the lack of post-yielding deformability
and the relatively low volume of plastic zone at the notched
tips as a result of crosslinking will result in the reduction in
KIC of the highly crosslinked thermoset. In contrast, Levita
et al. [13] determined in their study that the epoxy ther-
mosets with moderate or medium crosslink density tend to
possess higher KIC value.
It is believed that the crosslink density is one of the
factors influencing the fracture toughness of the thermo-
setting materials. Correlation between the fracture tough-
ness and the crosslink density of the epoxidized vegetable
oils-based thermosets is shown in Fig. 4. The crosslink
density measurements of the EMI-catalyzed and TEAB-
catalyzed ESO thermosets were conducted using the
Iran Polym J (2012) 21:353–363
Fig. 4 Correlation of fracture toughness and crosslink density for
epoxidized vegetable oil based thermosets (data from [3], [14], [15]
are plotted as comparison)
dynamic mechanical analyzer (DMA) as described in our
previous works [9, 10]. It can be seen that the fracture
toughness of the thermoset is affected by the crosslink
density; both in the case of current study (i.e., ESO with
TEAB catalyst and ESO with EMI catalyst) and epoxy/
epoxidized vegetable oil blends (i.e., [3, 14, 15]).
Similar trend was also reported by Cho et al. [16] who
found that the fracture toughness of the diallylterephthalate
resin increases with molecular weight between crosslinks
(i.e., decreasing the crosslink density) up to the optimum
level after which there is a significant drop. Another report
for the liquid crystalline epoxy also displayed that the
fracture toughness does not increase monotonically with
increasing the molecular weight between crosslinks, but
drops off when the optimum fracture toughness is achieved
[17]. One possible explanation to these findings can be
related to the crosslink network structures in the epoxidized
vegetable oils-based thermosets.
Presence of a number of unreacted monomer species in
the epoxy network due to the incomplete cure reaction as in
the case of the EMI-catalyzed systems gives rise to low KIC
value. This is mainly attributed to the fact that the unre-
acted monomer species will induce non-uniform stress
distribution and consequently give rise to microscopic
stress concentration [18]. These undesirable stress con-
centration areas will make the breakage of the chains
around the unreacted site easier. Hence, a low KIC value is
obtained. The progressively improvement in the KIC values
up to an optimum level is believed to be due to the alle-
viation of the stress concentration as the degree of curing is
increased. When the cure reaction is almost complete, the
effect of the unreacted group remained in the network
structure becomes insignificant effect on the KIC, and
therefore the effects of crosslink become dominant.
Ability of the crosslinks in the epoxy thermosets with
moderate crosslink density to dissipate the fracture energy
357
along the entire molecular chains accounts for the increase in
KIC values to an optimum level. However, the highly cross-
linked network losses its ability to dissipate the fracture
energy by plastic deformation as the development of the local
plastic zone at the crack tip is strictly limited [19]. Considering
these facts, a reduction in KIC value is detected as the crosslink
density was further increased as shown in Fig. 4.
The fracture toughness measurement of the ESO ther-
moset is evaluated using both SENT and DENT methods in
the present study. SENT is selected for the toughness
measurement since it is feasible to examine the ductile and
brittle fracturing polymers due to the appropriate defor-
mation mode during fracture [20]. DENT is chosen in
assessing the fracture behavior of the ESO thermosets due
to the symmetry of its specimens which will avoid the
distortion of specimens during deformation [8]. It is noted
in Figs. 2 and 3 that the KIC obtained from the SENT and
DENT specimens are different. This difference is attributed
to the different crack deformation mode taken place during
the fracture process. SENT specimen experiences propa-
gation ahead of the notched-tip whereas each notched-tip in
the DENT specimen propagates until they meet halfway
along the ligament length.
According to Strandberg [21], the DENT specimens will
only undergo the state of pure tension along the ligament
during the fracture process, whereas the SENT specimens
will experience a combination of tension and bending as a
result of its asymmetric geometry. Hashemi [22] found that
the net-section stress for the SENT specimen is different
than that of the DENT specimen even if both specimens
possess the similar crack length-to-width ratio. Kim et al.
[23] reported that these SENT and DENT specimens need
different crack opening stresses to initiate the crack
deformation during the fracture process.
EWF
The concept of EWF is used in the present study to
determine the specific EWF (we) and specific plastic frac-
ture work (bwp) of the ESO thermosets. This approach can
be utilized to overcome the limitations of LEFM, in which
the LEFM fails to accurately measure the fracture tough-
ness, i.e., fracture is preceded by the deformation which is
not linearly elastic under the plane stress condition [24]. It
is shown in Table 3 that we of the EMI-catalyzed ESO
thermoset increases with increasing the EMI concentration,
whereas bwp demonstrates the opposite trend. For the
TEAB-catalyzed ESO thermoset, we increases with the
TEAB concentration up to 0.5 phr after which there is a
drop. However, bwp of the ESO thermoset decreases with
increasing the TEAB concentration.
What is worthwhile to note in Table 3 is that we of the
ESO thermoset increases as the amount of the EMI and the
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Table 3 The specific essential work of fracture and the specific density on the size of the plastic zone in front of the crack
plastic fracture work of ESO thermoset tips. In addition, Bos et al. [29] mentioned that plastic zone
ESO thermoset Specific essential work Specific plastic fracture size reduces as the crosslink density in the crosslinked
of fracture, we (J/m2) work, bwp (J/m2) network increases.
Barany et al. [8] stated that bwp represents the material
EMI-catalyzed
resistivity against crack propagation. Hence, it is strongly
ES_0.3I 6,546.1 3,707.5
believed that ESO thermoset catalyzed with lower EMI and
ES_0.4I 9,755.9 3,431.5
TEAB catalyst concentration possesses higher resistivity
ES_0.5I 10,176.0 1,128.3
against crack propagation. The negative value of the bwp
ES_0.6I 21,620.0 1,046.3
indicates the sign of non-applicability for the EWF
ES_0.7I 22,381.0 1,038.7
approaches to assess the plane-stress fracture toughness of
ES_0.8I 32,152.0 -956.3
the ESO thermosets which had experienced a transition
TEAB-catalyzed from ductile to brittle. According to Mouzakis et al. [30],
ES_0.3A 9,925.1 712.0 the non-EWF will never be negative and a ductile–brittle
ES_0.4A 10,914.0 404.2 transition in the crack propagation phase associated to the
ES_0.5A 11,630.0 353.9 change in plane-stress or plane-strain condition has been
ES_0.6A 2,072.5 123.4 taken place.
ES_0.7A 1,900.5 -28.4
ES_0.8A 1,654.1 -95.0 LEFM and EWF fracture characterization
of ESO thermoset

TEAB catalyst concentration increase up to 0.8 and
0.5 phr, respectively. The increase in we gives us a hint that
the crack initiation resistivity of the ESO thermosets
against the fracture energy improves. This improvement is
mainly attributed to the increase in crosslink density of the
ESO thermoset. According to Chen et al. [25], we is
directly proportional to the crosslink density. Karger-
Kocsis et al. [26] also reported that we of polymeric system
is highly dependence on the molecular entanglement net-
work density. However, it is found that we of the TEAB-
catalyzed ESO thermoset reduces sharply when the TEAB
concentration is increased beyond 0.5 phr. The intense
crosslinking formed beyond the limits for the ESO ther-
mosets to fully dissipate fracture energy effectively gives
rise to the reduction in we.
Similar finding was reported by Gencur et al. [27] who
mentioned that thermosets with highly crosslinked epoxy
network possess low ability to resist crack inception and
propagation. It is due to the fact that highly crosslinked
network which is unable to dissipate the fracture energy
applied in hysteresis form tends to fully transfer the energy
into breaking the polymeric chains and subsequently
reduce the crack resistivity of the thermoset.
The reduction in bwp with increasing the EMI and the
TEAB catalyst concentrations as illustrated in Table 3 is
due to the increase in crosslink density in the ESO ther-
mosets. This is confirmed by the fact that there is a reverse
relationship between bwp and crosslink density [28]. The
reduction in the plastic zone size with increasing crosslink
density gives rise to the reduction of bwp. Cho et al. [16]
reported in their study that there is a significant effect of
the molecular weight between crosslinks and the crosslink
Plenty of linear and non-linear fracture mechanics, espe-
cially the LEFM and the EWF, have been widely utilized to
characterize the fracture behavior of polymers. However,
there are limitations for each of the fracture concepts used
to assess the actual fracture characteristics of the polymeric
materials accurately. LEFM is inapplicable to be used to
assess the fracture toughness of the ductile polymers
exhibiting relatively large plastic zone in a plane-stress
condition at the notched-tip [1]. Mouzakis et al. [30] also
found that LEFM is not appropriate to determine the
toughness of tough polymers due to the restriction of the
sample geometry. EWF concepts are only applicable to
those polymers that experience complete ligament yielding
before crack growth initiation [31]. Haughie et al. [32]
reported that EWF method is invalid to examine the frac-
ture behavior of polymers that fails in the dual ductile/
brittle mode. Similar finding was reported by Mouzakis
et al. [30] who mentioned that EWF is non-applicable for
polymers showing ductile–brittle transition during fracture.
Based on these facts, it can be concluded that neither
LEFM nor EWF can be utilized to assess the fracture
characteristics of polymeric materials that exhibit different
toughness and brittleness, owing to their polymeric struc-
ture, flexibility and rigidity, degree of curing, crosslink
density, etc. Thus, a tool to study the transitions of ESO
thermoset as a function of catalyst concentration is devel-
oped based on the combination of two approaches (i.e.,
LEFM and EWF) in the study. There is a must to take into
considerations the fracture behavior of the ESO thermosets
(i.e., brittle, ductile or brittle-ductile) to make sure the
basic requirements of the particular fracture mechanics
approaches are met and to prevent wrong conclusions.

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Fig. 5 Fracture toughness studies on the EMI-catalyzed ESO
thermoset by the LEFM and the EWF approaches
The fracture toughness and the specific EWF of ESO
thermosets against the EMI catalyst concentration obtained
on the basis of the principles of LEFM and EWF, respec-
tively, are shown in Fig. 5. It is clearly shown in Fig. 5 that
the EMI-catalyzed ESO thermosets experience a transition
from ductile to brittle as the EMI concentration is increased
from 0.3 to 0.8 phr. Interestingly, it is found that the ESO
thermoset catalyzed with 0.5 phr EMI concentration shows
a likely brittle–ductile transition. At this particular EMI
concentration, the slopes of the LEFM and EWF curves
start to deviate from linear behavior. This deviation may
indicate that the lack of suitability of the fracture
mechanics approach to predict and to assess the fracture
behavior of the ESO thermosets with that particular EMI
catalyst concentration. The less accuracy in toughness
assessment for those ESO thermosets varying from flexible
to rigid is assumable to be due to the limitations and the
assumptions made when formulating these fracture
mechanics.
At EMI catalyst concentration lower than 0.5 phr, EWF
is the most appropriate technique to assess the toughness of
the ESO thermosets which are ductile in nature. Beyond
0.5 phr, the toughness of ESO thermosets can be success-
fully characterized on the basis of the concepts of LEFM.
In addition, it is noticed that both slopes of LEFM and
EWF curves can be likely superimposed. Therefore, it is
believed that brittle–ductile transition of the ESO thermo-
sets could possibly be assessed by the combination of
LEFM and EWF approaches. In addition, the combination
of both LEFM and EWF theories could be a model for
researchers to study and evaluate the brittle–ductile tran-
sitions of the polymeric materials.
As illustrated in Fig. 6, the brittle–ductile transition
trend as observed in the EMI-catalyzed ESO thermoset is
not observable in the TEAB-catalyzed systems. This result
is interesting that increasing the amount of catalyst con-
centration does not simply induce the brittle–ductile
359
Fig. 6 Fracture toughness studies on the TEAB-catalyzed ESO
thermoset by the LEFM and the EWF methods
transition phenomenon. Instead of undergoing this transi-
tion, the slopes of LEFM and EWF curves increase with
increasing the TEAB concentration up to 0.5 phr after
which there is a drop. One possible reason why the brittle–
ductile transition was not detectable is tight crosslinking
and rigid crosslink network formed in the TEAB-catalyzed
ESO thermoset.
As reported in our previous works [9, 10], it is found
that the degree of conversion of the TEAB-catalyzed ESO
thermoset approaches 99 % and the refrained monomer
concentration is found to be very low. Beyond the limits to
dissipate the fracture energy applied in hysteresis form, the
TEAB-catalyzed ESO thermosets are prone to brittle
fracture at relatively low strain via bond ruptures if sub-
jected to a large external stress. It is also confirmed by the
fact that the ESO specimens with no or very limited flex-
ible chain segments has no way to dissipate and absorb the
force applied effectively through a large-scale of irrevers-
ible plastic deformation when high breaking force is
applied. In other words, all the TEAB-catalyzed ESO
thermosets including those catalyzed with low TEAB
concentration (i.e., 0.3 phr) do not deform in a ductile
manner before eventually fracturing and therefore, no
transition trend from ductile to brittle is obtained as the
TEAB concentration is increased from 0.3 to 0.8 phr as
shown in Fig. 6. Thus, LEFM could be the most suitable
approach to assess the toughness of the TEAB-catalyzed
ESO thermosets which are brittle in nature.
Morphology characterization
FE-SEM technique is used in this study to characterize the
fractured surfaces of the ESO thermosetting materials and
to correlate the morphology to their fracture behavior.
Figures 7 and 8 show the fractured surfaces of the ESO
thermosets catalyzed with different EMI and TEAB cata-
lyst concentration, varying from 0.3 to 0.8 phr. The SEM
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Fig. 7 SEM micrographs of the fractured surfaces of a ES_0.3I, b ES_0.4I, c ES_0.5I, d ES_0.6I, e ES_0.7I, and f ES_0.8I samples
micrographs of the EMI-catalyzed ESO thermosets, as
shown in Fig. 7, show tortuous cracks and increased
number of ridges with increasing EMI catalyst concentra-
tion. These observations indicate an improvement in the
deformation resistance and crack propagation of the
material, which is accounted for the increased in KIC value
of the ESO thermosets as shown in Fig. 2. In addition, the
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depth of the ridges on the fractured surface is detected to be
increased with increasing the EMI concentration. These
ridge depths are the products of the fracture, showing the
ability of the ESO thermoset to hinder the fracture forces
during fracture deformation. Therefore, increased fracture
energy is required to initiate the crack growth and to
fracture the ESO thermoset with higher EMI concentration.
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Fig. 8 SEM micrographs of the fractured surface of a ES_0.3A, b ES_0.4A, c ES_0.5A, d ES_0.6A, e ES_0.7A, f ES_0.8A samples
In addition, it is noticed that ESO thermoset catalyzed
with low EMI concentration (i.e., 0.3–0.4 phr) undergoes a
ductile mode of fracture. Presence of several shear defor-
mations and crack deformation lines on the fractured sur-
face of ES_0.3I and ES_0.4I indicate the ESO specimens
experience a ductile mode of failure. Identical observation
was reported by Gupta et al. [33] who observed that the
fracture surface morphology of the soybean-based epoxy
361
thermoset fractured in a ductile manner consists of several
crack arrest lines.
Furthermore, the morphological fibrous patterns and
many river markings on the fractured surface of ES_0.3I
and ES_0.4I also reveal a ductile fracture mechanism has
taken place. The presence of these characteristics features
indicates the evidence of ductile fracture involving a rel-
atively stable crack growth [34]. The ductile fracture of
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ESO thermosets gradually changes into brittle mode of
fracture if the EMI catalyst concentration was increased to
0.8 phr. The waviness and closely placed line patterns on
the fractured surface of ES_0.7I and ES_0.8I indicates a
brittle fracture deformation has occurred. Biju et al. [35]
also found that similar brittle fracture deformation behavior
on the fractured surface of rigid poly(vinyl chloride).
Absence of fine fibrils on the fractured surface of ES_0.7I
and ES_0.8I again proves that the fracture behavior of ESO
thermosets follow brittle fracture mechanism.
At 0.5-phr EMI catalyst concentration, ES_0.5I experi-
ences a brittle–ductile transition. This conclusion is made
since the fracture morphology of ES_0.5I observed by
SEM consists of both ductile and brittle characteristics
features. Closely placed line pattern (found on brittle
materials) as well as the fibrous and river pattern (found on
ductile materials) is observable on the SEM fractured
surface of ES_0.5I. Therefore, based on these observations
and the findings illustrated in Fig. 7, it can be concluded
that a brittle-ductile transition of ESO thermoset takes
place at EMI concentration of 0.5 phr.
Apart from that, from Fig. 8, it could be seen that there
are multilevel fracture paths with wavy crests and
increased number of irregular ridges on the fracture sur-
faces of TEAB-catalyzed ESO thermoset with increasing
the TEAB concentration up to 0.6 phr. Particularly, these
observed fractured features are identical to that of the ESO
thermosets catalyzed with a relatively high EMI concen-
tration as shown in Fig. 7. The presence of these charac-
teristic fractured features as shown in Fig. 8 indicates a
distinguished symbolic of increased energy absorption on
large scale of deformation [36], which could be correlated
to the KIC results as shown in Fig. 2. In addition, these
deformation features indicate the ESO thermoset experi-
enced a brittle fracture.
On the other hands, it is observed in Fig. 8 that the SEM
morphology of the fractured surfaces in ES_0.7A and
ES_0.8A shows a smooth glassy surface and their fracture
paths are straight. In addition, waviness and closely placed
line patterns are found on the SEM fractured surface of
ES_0.7A and ES_0.8A. This is the other common case of
brittle fracture, which accounts for the poor capability of a
material to resist crack initiation and propagation [36, 37].
Identical findings were reported by Ratna [38] and Situ
et al. [39] who also agreed that brittle fracture will result in
poor fracture properties. It is attributed to the fact that the
regular cracks in the fractured surface show the incapa-
bility of the ESO thermosets to resist crack initiation and
deformation effectively when an external mechanical force
is applied onto it. Based on the SEM fractured surface
morphology, the low KIC value of ESO thermoset catalyzed
with high TEAB catalyst concentration can be further
justified.
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Iran Polym J (2012) 21:353–363
Conclusions
Based on the work devoted to study the influences of EMI
and TEAB catalysts on the fracture toughness of epoxi-
dized soybean oil thermosets, the following conclusions
can be drawn.
Fracture toughness of the ESO thermoset increased with
increasing the concentration of EMI catalyst. A reduction
in the fracture toughness of the TEAB-catalyzed ESO
thermosets was found if the amount of the TEAB catalyst
concentration exceeded 0.5 phr. The specific EWF (we) of
the ESO thermoset indicated a direct relationship with the
concentration of EMI and TEAB catalyst. Again, we of the
TEAB-catalyzed ESO thermosets decreased significantly as
the TEAB catalyst concentration was increased exceeding
0.5 phr. Tortuous crack and higher number of ridges were
observed on the fractured surface of ESO thermoset cata-
lyzed with higher EMI concentration. The plane stress
fracture toughness of the ESO thermosets could be assessed
with the EWF approaches whereas the plain-strain fracture
toughness could be examined according to the principle of
LEFM. The combination of LEFM and EWF approaches
could be a tool to assess the brittle–ductile transition of the
ESO thermoset as a function of EMI concentration, which
varies from flexible to brittle behavior.
Acknowledgments Authors would like to express their appreciation
to Universiti Sains Malaysia for the Incentive Grant (8021013) and
Research University Postgraduate Research Grant Scheme (USM-
RU-PRGS 8043019). S.G. Tan also thanks the Ministry of Science,
Technology and Innovation, Malaysia (MOSTI) for the National
Science Foundation (NSF) fellowship.
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