Materials Today Communications 24 (2020) 100990

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Materials Today Communications

journal homepage: www.elsevier.com/locate/mtcomm

Influence of graphene nanoplatelets on curing kinetics and rheological T

properties of a benzoxazine resin
V. García-Martíneza,b,*,1, M. R.Gudea, S. Calvoa, M.R. Martínez-Mirandaa, A. Ureñab
a
FIDAMC, Foundation for the Research, Development and Application of Composite Materials, Avda. Rita Levi Montalcini 29, 28906, Getafe, Madrid, Spain
b
Department of Applied Mathematics, Materials Science and Engineering and Electronics Technology, Universidad Rey Juan Carlos, 28933, Móstoles, Madrid, Spain

A R T I C LE I N FO A B S T R A C T

Keywords: The effect of two types of graphene nanoplatelets on the curing kinetics, gelation and vitrification behaviour of a
Benzoxazine benzoxazine resin was investigated by means of differential scanning calorimetry and rheological experiments.
Graphene nanoplatelets The results showed that the incorporation of graphene nanoplatelets did not change the autocatalytic nature of
Curing kinetics curing reaction. However, when benzoxazine was doped with the nanofiller supplied by XG-Sciences an accel-
Vitrification
eration effect in curing reaction was observed, especially when a 2 wt.% was added. This catalytic effect was
Gelation
demonstrated by the reduction of peak temperature, apparent activation energy and the shorter gelation and
vitrification times.
Finally, the curing kinetic equation for benzoxazine and its nanocomposites was obtained by linear model-
fitting of non-isothermal experiments and it matched reasonably well with the experimental results from both
non-isothermal and isothermal tests.

1. Introduction
Benzoxazines are phenolic thermoset resins which have received
much attention due to their interesting features. Besides the unique
properties found in the traditional phenolic resins (heat resistance, fire
retardant and good electrical properties), benzoxazines also present
near-zero shrinkage, low water absorption, good thermal stability, good
fire-smoke-toxicity performance and good mechanical properties.
Furthermore, they can be obtained from inexpensive raw materials, no
strong acid catalysts are necessary for polymerization and they do not
release by-products during curing thus being a fascinating resin for
many applications [1–5]. During the last years, the addition of gra-
phene to polymers has attracted the interest of researchers in order to
improve their thermal, mechanical and electrical properties. Graphene
is an atomically thick, two-dimensional substance consisting of sp2-
hybridized carbon atoms arranged in a honeycomb structure. As a result
of its unique properties such as exceptional specific modulus, me-
chanical strength, high electrical and thermal conductivity and good
chemical resistance, graphene is potential nanofiller that could dra-
matically improve the properties of polymer-based composites at a very
low loading. These improvements strongly depend on how graphene is
distributed and oriented into polymer as well as the interfacial bonding
between them. The best properties are obtained when graphene is ex-
foliated in single layers with the highest aspect ratio.
When nanofillers are added to the polymeric matrix, the resin
curing process can change, so an understanding of curing behavior of
the nanofilled benzoxazine resin is of great interest and can provide an
improvement in design and manufacturing of composites parts [6].
One of the first studies about the curing kinetics of benzoxazine
resin was performed by Ishida et al. [7]. In recent years, other authors
have explored the benzoxazine resin polymerization mechanism
[8,9,1,10]. Wang et al. [11] studied the curing kinetics of bisphenol-AP-
based benzoxazine by isothermal differential scanning calorimetry
(DSC) experiments and kinetics parameters were determined. The cor-
responding models of the curing processes for the benzoxazine-epoxy
novolac mixtures were examined by Jubsilp et al. [12] by non-iso-
thermal DSC. They found that the autocatalytic kinetic model provided
the best description of the investigated curing reactions. The rheolo-
gical and curing behavior of high heat-resistant benzoxazine resin by
means of dynamic DSC was investigated by Zhang et al. [13]. Although
much effort has been concentrated on the study of benzoxazine resin
polymerization, no many studies have been focus on understanding the
effect of different carbon nanofillers on its curing kinetics. Zeng et al.
[14] demonstrated that the addition of graphene oxide could decrease

⁎
Corresponding author at: FIDAMC, Foundation for the Research, Development and Application of Composite Materials, Avda. Rita Levi Montalcini 29, 28906,
Getafe, Madrid, Spain.
E-mail address: Vanessa.Garcia.External@fidamc.es (V. García-Martínez).
1
Web page: http://www.fidamc.es.

https://doi.org/10.1016/j.mtcomm.2020.100990
Received 10 December 2019; Accepted 7 February 2020
Available online 08 February 2020
2352-4928/ © 2020 Elsevier Ltd. All rights reserved.
V. García-Martínez, et al.
the cure temperature of benzoxazine resin whereas the polymerization
of benzoxazine monomer was delayed by to some extent in the presence
of graphite. Bandeira et al. [15] observed that the incorporation of
carbon nanotubes (CNTs) into neat benzoxazine affected the cure ki-
netic of nanostructured composites, since the values of enthalpy in-
creased and the activation energy decreased. The incorporation of the
functionalized multiwall carbon nanotubes (MWCNTs) displayed good
acceleration effects and the activation energy was lower than that of
neat benzoxazine throughout the whole curing process as Lin et al.
showed [16].
In this work, the influence of two graphene nanoplatelets types on
the curing behaviour and rheological properties of benzoxazine-based
resin has been evaluated. Heat of reaction, peak temperature, and ac-
tivation energy as well as vitrification time were evaluated by differ-
ential scanning calorimetry. In addition, reaction rate equations were
obtained for neat resin and its nanocomposites. Gelation times were
determined by rheological experiments and then, the activation energy
for the gelation was calculated.
2. Experimental
2.1. Materials
An industrial benzoxazine-based resin supplied by Henkel
Corporation (Loctite BZ 9102) has been used for this study. It is a one
component matrix which can be stored for up-to six months at room
temperature and it has been formulated to be used in liquid resin
technologies, including resin transfer molding (RTM) and vacuum as-
sisted resin infusion molding (VARIM).
Two different types of GNPs produced by thermal reduction were
acquired to Avanzare (Avangraphene-2) and XG-Sciences (xGnP®
Graphene Nanoplatelets, Grade M) and their main features, given by
the suppliers, are shown in Table 1.
2.2. Nanocomposites preparation
The dispersion of GNPs into the benzoxazine matrix was performed
by means of a three roll mill EXAKT 80E (Exakt Advanced Technologies
GmbH) in seven steps. The gap between rolls was reduced in every step
(between 120 μm and 15 μm) [17] to achieve a mixture in which
graphene was exfoliated and uniformly distributed. Then, all mixtures
were degassed in vacuum at 105 °C for 15 min. Nanocomposites with
0.5 wt.% and 2 wt.% of both graphene types (GrXg and GrAv) were
prepared and designated: BzGrXg-0.5, BzGrXg-2, BzGrAv-0.5 and
BzGrAv-2 respectively.
2.3. Experimental methods
The commercial GNPs purity was analysed by Infrared Spectroscopy
(FTIR) and thermogravimetric analysis (TGA). Infrared spectra of all
GNPs in KBr were obtained in a Thermo Scientific Nicolet spectrometer
in the range between 500 and 4000 cm−1. TGA measurements were
made with a TA Instruments Q500 thermogravimetric analyser, scan-
ning from room temperature to 800 °C at a rate of 10 °C/min in nitrogen
atmosphere.
Morphology of composites was evaluated using a Philips CM200
transmission Electron Microscope (TEM) equipped with a SuperTwin
Table 1
Main features of graphene nanoplatelets given by the supplier.
Graphene identification Supplier Oxigent content (%) Average flake thickness (nm)
GrXg XG-Sciences <1 < 6
GrAv Avanzare 0.5-1.5 < 2
*Not indicated in the data sheet.
2
Materials Today Communications 24 (2020) 100990
objective lens and LaB6 filament of 200 kV. Before TEM observation,
samples were prepared by cryomicrotomy cutting.
The curing kinetics of GNPs/benzoxazine nanocomposites were
studied with a TA Instruments Q2000 differential scanning calorimeter
(DSC). The curing reaction of these nanocomposites has been studied by
means of several isothermal and non-isothermal experiments. The
heating rates employed for the non-isothermal experiments were 2, 5,
10 and 15 °C/min from room temperature to 330 °C. In addition,
temperatures of 170, 190 and 210 °C were chosen for isothermal tests.
Then, samples were cooled to room temperature and a new heating
ramp at 10 °C/min was performed in order to determine their glass
transition temperature and the heat of any possible residual reaction.
The extent of cure (α) has been determined as the quotient between the
residual heat of reaction and the average cure enthalpy obtained in the
non-isothermal tests. The glass transition temperature (Tg) has been
calculated as the half-width point.
In addition, modulated differential scanning calorimetry (MDSC)
experiments at 170, 180, 190 and 200 °C have been carried out to study
the vitrification time, with modulation amplitude of 1 °C and 60 s of
period. The vitrification time has been calculated as the inflexion point
of the reversing Cp signal [18].
The rheological properties of nanocomposites have been studied
with a TA Instruments AR-G2 rheometer (25 mm parallel plate as-
sembly) in oscillation and flow mode. The evolution of viscosity with
temperature was evaluated by non-isothermal flow tests from 50 °C to
250 °C at angular velocity of 1.5 rad/s. To determine the linear vis-
coelasticity range, strain sweeps at several isothermal temperatures and
frequencies was carried out. Isothermal experiments at temperatures
between 170−200 °C were performed at fixed frequency of 1 rad/s and
0.1–100 % strain with a gap lower than 1 mm. The evolution of storage
modulus (G’) and loss modulus (G’’) were register as function of reac-
tion time to calculate the gelation time and the apparent activation
energy for the gelation.
3. Results and discussion
3.1. GNPs characterization
Thermally reduced GNPs usually contain some residual oxygen
functional groups at their edges and in the basal plane due to the oxi-
dation process [19]. TGA is a valuable tool to characterize the quantity
of organic substance covalently attached to the surface of graphene-
based materials because they are thermally removed in the range of
temperatures between 200 and 800 °C [20]. TGA results of GNPs
(Fig. 1a) showed a total weight loss of 1.8 % for GrAv and 5.3 % for
GrXg which confirmed a major number of residual oxygen functional
groups for graphene nanoplatelets supplied by XG-Sciences. This
oxygen content obtained by thermogravimetric analysis was very si-
milar to the indicated by the supplier (0.5–1.5 %) for GrAv while a
much higher oxygen content was obtained regarding to the manu-
facturer specification (< 1 %) for GrXg. The FTIR analysis (Fig. 1.b)
was developed to evaluate the nature of these oxygen functional groups
present in GNPs. The same peaks were obtained for both graphene
nanoplatelets at 1068, 1365, 1624, 1726 and 3451 cm−1 proved the
presence of CO (epoxide), CH (bending vibration), CC (deoxidised
graphitic domain), CO and the broadened peak corresponding to the
stretching vibrations of OHee]]e bonds [21]. Bellow 200 °C the
Specific surface area (m2/g) Average particle lateral dimension (μm)
120-150 15
* 20
V. García-Martínez, et al.
Fig. 1. (a) TGA thermograms, (b) FTIR spectra for both types of GNPs.
majority of the water molecules and OeH groups are stripped off,
whereas the residual hydroxyl and epoxide groups are progressively
eliminated at temperatures between 600 and 1000 °C [22]. The FTIR
results were in accordance with the spectra found by other authors for
thermally reduced graphene nanoplatelets [19,21]. According with the
TGA thermograms of GNPs (Fig. 1a) the major weight loss happened at
temperatures higher than 200 °C which indicated the presence of re-
sidual hydroxyl and epoxy groups especially in GrXg.
3.2. Morphology of GNPs/benzoxazine nanocomposites
It is well known that the dispersion degree of graphene nanoplate-
lets into polymer matrix has a strong influence in the final properties of
the nanocomposites. The major improvements in mechanical, thermal
and electrical performance are obtained with low thickness of GNPs.
Nevertheless, the physic-chemical and mechanical properties of these
nanocomposites will be examined in a near future work.
In order to evaluate the morphology of nanocomposites containing a
2 wt.% of both graphene nanoplatelets, they were observed by TEM
(Fig. 2). Clusters of GNPs which comprise a few number of graphene
layers are randomly dispersed in benzoxazine resin. This suggests that
not a complete exfoliation was achieved. When these areas were ex-
amined at higher magnifications, the wrinkling and rolled structure of
graphene layers can be clearly appreciated (Fig. 2c-d). This effect was
also observed by Zaman et al. [23] in epoxy nanocomposites. In ac-
cordance with these authors, during the curing process the GNPs scroll
and roll to reduce their configurational entropy. In addition, the thinner
nanoplatelets, the more scrolls created. Fig. 2e-f displays nanoplatelets
with different number of graphitic layers, near to 10–25 layers in both
nanocomposites which confirmed a similar dispersion and exfoliation
degree in all the samples.
3.3. Non-isothermal DSC experiments
Dynamic thermograms at heating rates of 2 °C/min for pure ben-
zoxazine and its nanocomposites with a 0.5 wt.% and 2 wt.% of both
types of GNPs are shown in Fig. 3. All curves presented a single exo-
thermic peak of the curing reaction, so it was assumed that there was a
single chemical process occurring. The heat of reaction (ΔH), onset
temperature (Tonset), peak temperature (Tpeak), glass transition tem-
perature (Tg) and average heat of reaction (ΔHmean) of all samples were
collected in Table 2 (nanocomposites enthalpy values were normalized
to the neat amount of resin). It can be appreciated that both Tonset and
Tpeak remained nearly constant in all nanocomposites excepting for
BzGrXg-2 where a slight decrease in the onset and peak temperature
was observed. The same trend was appreciated when other heating
ramps (5, 10 or 15 °C/ min) were employed. This accelerating effect
could be initially associated with the notably high thermal conductivity
of GNPs. However, taking into account that only nanocomposites with a
2 wt.% of GrXg presented this accelerating effect, the catalytic behavior
3
Materials Today Communications 24 (2020) 100990
may be partially attributed to the higher presence of hydroxyl and
epoxide groups in the surface of GrXg (as TGA and FTIR results showed)
which might act as a catalyst for oxazine-ring polymerization reaction
[24]. Lin et al. detected that the incorporation of nanoclays in ben-
zoxazine delayed the curing reaction, while the addition of MWCNTs
showed a good catalytic effect that may be due to their higher con-
centration of functional groups and larger specific surface area [16]. A
similar catalytic effect has been reported in CNT/ polybenzoxazine for
Kaleemullah et al. [25]. Other authors have found that the presence of
GNPs (5 wt.%) in epoxy resin also accelerated the curing reaction which
was attributed to the high thermal conductivity of GNPs [26].
The average heat of reaction, ΔHmean, for each GNPs/benzoxazine
mixture slightly increased with the addition of both types of graphene
nanoplatelets, especially when a 2 wt.% of GrXg is introduced in neat
resin. This could suggest that benzoxazine matrix in the nanocompo-
sites reached a higher cross-linking degree than in the neat resin. Two
opposite effects of nanofillers on total heat of reaction of epoxy resin
have been reported in the literature: (1) a decrease in ΔH which might
be related to the proportional reduction of epoxy concentration in the
nanocomposite or the increased viscosity caused by the presence of
nanofiller which hindered the mobility of the reactive species [27], (2)
an increase in the total heat release could indicate that the extent of
cure in the matrix doped with nanofiller is larger compared with neat
resin [28].
The Tg values of the cured samples obtained in the second scan were
lower in nanocomposites manufactured with Avanzare’s graphene
which could be related with a more imperfect network constructed
during the curing reaction. However, when the graphene supplied by
XG-Science is added to neat resin, the glass transition temperature was
relatively higher at heating rates of 2 and 5 °C/min or it remained
constant at higher heating rates. The Tg was increased by hindering
segmental motions of polymer chain via mechanical interlocking of
GNPs [14].
Fig. 4 shows the extent of conversion (α) as a function of tem-
perature for neat benzoxazine and its nanocomposites at heating rate of
10 °C/min. It can be appreciated that all curves show a sigmoidal form,
which indicated that the curing reaction of GNPs/benzoxazine nano-
composites is autocatalytic in agreement with our previous study for
benzoxazine resin [29]. Although the incorporation of graphene na-
noplatelets has no influence on curing mechanism of benzoxazine, it
was quite evident that the extent of cure shifted to lower temperatures
in nanocomposites manufactured with GrXg and this effect was more
pronounced for 2 wt.% of this nanofiller. These results supported the
catalytic effect of GrXg in benzoxazine curing reaction. The acceleration
of curing process imparted by this type of graphene nanoplatelets could
have a positive effect on the processing of carbon fibre composites by
reducing the time needed for cure and from saving energy [6].
For further understanding about the influence of graphene on ben-
zoxazine curing, the apparent activation energy (Ea) has been calcu-
lated by using the Kissinger method and the isoconversional Flynn-
V. García-Martínez, et al. Materials Today Communications 24 (2020) 100990

Fig. 2. TEM images of nanocomposites with a 2 wt.% of GrXg (a,c,e) and GrAv (b,d,f) at different magnifications.

Table 2
Non-isothermal cure data for benzoxazine and its nanocomposites.
Sample Heating rate Tonset (ºC) Tpeak (ºC) ΔH Tg (ºC) ΔHmean
(ºC/min) (J/g) (J/g)

Bz 2 203 213 452 180 441

5 223 233 434 181
10 238 248 435 183
15 243 257 442 183
BzGrXg-0.5 2 201 212 452 198 448
5 221 231 439 195
10 236 248 451 180
15 245 258 449 181
BzGrAv-0.5 2 202 212 442 177 448
5 222 232 463 178
10 237 248 440 182
15 246 258 449 180
BzGrXg-2 2 199 210 463 193 452
5 219 230 451 195
10 234 245 449 183
Fig. 3. Dynamic DSC curves for neat resin and its nanocomposites at heating 15 243 256 443 183
rate of 2 °C/min. BzGrAv-2 2 201 212 454 178 443
5 221 232 450 172
10 237 248 434 172
Wall-Ozawa (FWO) method [30]. Both methods allow calculating the 15 246 258 435 172
activation energy of the curing reaction without prior knowledge of
reaction mechanism which is a great advantage. However, conversely
to Kissinger method, the isoconversional method admits that activation

4
V. García-Martínez, et al. Materials Today Communications 24 (2020) 100990

Fig. 4. Extent of conversion (α) as a function of temperature for neat benzoxazine and GNPs/benzoxazine nanocomposites at heating rate of 10 °C/min: (a) general
graph; (b) magnification of the marked area.

where n and m are the reaction orders. Combined with Eqs. (1) and (2)
results Eq. (3):
dα −E
= Aexp ⎛ a ⎞ α m (1 − α )n
dt ⎝ RT ⎠ (3)
By rearranging and taking logarithms in both sides of Eq. (3), the
following expression, which is based in the combined kinetic analysis
[33], is achieved:

dα 1 ⎤ = ln (A) − Ea
ln ⎡ m n
⎢
⎣ dt α (1 − α ) ⎥⎦ RT (4)
From the simultaneous treatment of various kinetics curves under
different heating rates, the kinetic triplet (E, A and f(α)) can be de-
termined. The best fit values of the parameters are assumed to be those
Fig. 5. Activation energy obtained by Kissinger and FWO methods.
that return the best linearity of the plot of the left hand side of Eq. (4)
against the reciprocal absolute temperature. The numerical optimiza-
energy varies with the conversion and Eα can be determined form slope tion of the parameters m and n enables to calculated the coefficient of
of Ln (β) versus (1/T) curves at several heating ramps. The evolution of linear correlation maximum which allows evaluating the best linearity
benzoxazine Ea values with graphene addition estimated by Kissinger [34]. The linear fitting was limited to the range of α = 0.05 - 0.85 to
and FWO (calculated as the average of Eα for conversions between 0.1 minimize the experimental error in kinetic data.
and 0.9) were displayed in Fig. 5. From the results it can be noted that The curing kinetic equation of the benzoxazine resin and GNPs/
the addition of GNPs caused a decrease in apparent activation energy in benzoxazine nanocomposites obtained from the results of the model-
GNPs/benzoxazine nanocomposites [31]. fitting was collected in Table 3.
The reduction in activation energy barrier with the introduction of To validate the kinetic model parameters for each system, the ex-
GNPs in the benzoxazine resin was also accompanied by an increase in perimental results were compared with those predicted for the equa-
enthalpy values of these nanocomposites as it was previously explained, tions. Fig. 6 shows the experimental and predicted curves of dα/dt
confirming the catalytic nature of GNPs plays in the curing reaction of against the temperature for all graphene-benzoxazine nanocomposites.
benzoxazine, especially with a 2 wt.% of GrXg is added to neat resin It was noticeably appreciated that the modelled curves fitted well with
[15]. the experimental data for all the samples and the best fitting was ob-
tained at low heating rates (2 and 5 °C/min). The pre-exponential factor
3.4. Kinetic model for GNPs/ benzoxazine nanocomposite (A) decreased with the addition of GNPs (especially for BzGrAv-0.5 and
BzGrXg-2) while de overall reaction order (m + n) remained almost
The following general expression is commonly employed for de- constant for Bz and its nanocomposites (≈ 2.9) so it was not influenced
scribing the kinetic analysis of thermosetting polymers: by the addition of GNPs. The activation energy was lower in GNPs/
benzoxazine nanocomposites compared with neat Bz and the lowest
dα −E
= k f (α ) = Aexp ⎛ a ⎞ f (α )
dt ⎝ RT ⎠ (1)
Table 3
where A is the pre-exponential factor, Ea is the activation energy, R is Reaction rate equations for neat benzoxazine and GNPs/benzoxazine nano-
the universal gas constant (8.314 J.mol.K−1) and T is the absolute composites.
temperature. System Reaction rate equation
The autocatalytic nature of curing reaction for benzoxazine resin
Bz
was demonstrated in our previous study as it was mentioned above dα
dt
= (2.81x1010) exp ( −97540
RT )α1.2 (1 − α )1.7
[29]. The identical S-shape form for the curves of conversion versus BzGrXg-0.5
= (9.02x10 ) exp ( )α
dα 9 −92566 1.2 (1 − α )1.7
dt RT
temperature for GNPs/benzoxazine nanocomposites allowed con-
BzGrAv-0.5
= (6.33x10 ) exp ( )α
dα 9 −91126 1.2 (1
firming the same autocatalytic curing mechanism. The truncated − α )1.7
dt RT
Sestak-Berggren model is a trustworthy method for autocatalytic kinetic BzGrXg-2
= (7.67x10 ) exp (
dα
dt
9 −91883
RT )α1.2 (1 − α )1.8
and it is described by the following equation [32]: BzGrAv-2
= (1.22x10 ) exp ( )α
dα 10 −93829 1.2 (1 − α )1.8
dt RT
f (α ) = α m (1 − α )n (2)

5
V. García-Martínez, et al.
Fig. 6. Comparison of experimental data (symbols) and calculated values (solid lines) for curing reaction of GNPs/benzoxazine nanocomposites.
values were obtained for BzGrAv-0.5 and BzGrXg-2 as it was observed
in the previous calculated Ea values by means of Kissinger and FWO
methods.
3.5. Isothermal DSC measurement of curing process
Isothermal DSC experiments for all the samples were performed in
order to further investigation the effect of GNPs presence in benzox-
azine curing reaction. Fig. 7 shows curves of conversion versus time at
170 °C and 210 °C for all the samples. The autocatalytic nature of
polymerization reaction for GNPs/benzoxazine nanocomposites was
also reasserted because the curves of conversion which showed an in-
flexion point when plotted versus time and α reached its maximum at
conversions around 0.4 [7]. As it was expected the maximum conver-
sion increased with the isothermal temperature. It was eventually
Fig. 7. Conversion against time for Bz and its nanocomposites at 170 °C and 210 °C.
6
Materials Today Communications 24 (2020) 100990
observed that the initial reaction rates were altered, depending on the
type of GNPs incorporated into benzoxazine resin. At 170 °C the con-
version of BzGrXg-2 increased very quickly compared with other sam-
ples and the final extent of conversion was also higher for this nano-
composite. However, at 210 °C this effect was not so pronounced and α
of BzGrXg-2 increased only faster than other samples until α≈0.6.
Afterwards, the extent of conversion for neat benzoxazine at this tem-
perature was higher than its nanocomposites.
Isothermal tests for all GNPs/benzoxazine nanocomposites were
also carried out in order to verify the kinetic triplet extracted from the
constant heating rates because a reliable model should simultaneously
fit dynamic and isothermal runs with the same kinetic parameters. A
comparison of the experimental reaction rate versus time and the pre-
dicted data was made in Fig. 8 for all the samples at different isothermal
temperatures. The modelled values matched really well with the
V. García-Martínez, et al. Materials Today Communications 24 (2020) 100990

Fig. 8. Comparison of the experimental reaction (symbols) rate versus time and the predicted data (solid lines) for GNPs/benzoxazine at different isothermal
temperatures.

experimental ones at high temperatures (190 and 200 °C) while at 170 the change from the liquid to the solid state [37].
°C a slight deviation between experimental and calculated data ap- Up to now, much effort has been focused on studying polymer li-
peared. quid-gel transitions because the adequate knowledge of this phenom-
enon is crucial in manufacturing process such as VARIM. Rheology is a
3.6. Study of viscosity and gelation/vitrification phenomena powerful tool to determine viscosity and elasticity changes at the time
when the infinite network appears. Among the different methods pro-
It is well known that the addition of nanofillers to polymeric ma- posed for determining the gel point in thermosetting resins, in this work
trices produces a rise in their viscosity. The best dispersion degree the the gel point was calculated as the cross-over point of the store modulus
higher increase in this property because a larger surface area is avail- (G’) and loss modulus (G’’) during the isothermal experiments. Gelation
able to interact with the matrix [35].Taking into account that the is a phenomenon strictly material dependent, so this criterion is not
benzoxazine employed in this work was intended for infusion processes, accurate because of the dependence of cross-over time on the frequency
it is important to consider the consequences of GNPs addition on its at which it is measured [38]. However, the main objective of this work
processability. According to the resin manufacturer, the recommended is to study the effect of GNP addition on the gel time of Bz resin, so this
infusion temperature is 110 ± 10 °C, so the value of viscosity was method for the determination of gel point is sufficient to define the
measured at this temperature (Table 4). The results showed an increase vicinity in which gelation occurs. Storage modulus (G’) and loss mod-
(one order of magnitude) with a 2 wt.% of GNPs, being this effect more ulus (G’’) curves for BzGrXg-2 and BzGrAv-2 at 180 °C were compiled in
accused when GrXg nanoparticles were employed. Despite of this in-
crement, the viscosity values were close to the recommended values for
vacuum assisted resin infusion molding for high temperatures (500
mPa.s) [36]. Nevertheless, a slight additional reduction in these values
may be appropriated to guarantee a correct impregnation of carbon
fabric.
During the cross-linking reaction, quick changes are induced in the
polymer molecular structure and properties. When the curing reaction
progresses the polymer molecules increase in size and form a three-
dimensional network is built. Gel point can be defined as the moment of
the apparition of the infinite three dimensional network which marks

Table 4
Viscosity of Bz and its nanocomposites at 110 °C.
Sample Viscosity (mPa.s)

Bz 73
BzGrAv-0.5 112
BzGrXg-0.5 94 Fig. 9. Curves of G’ and G’’ versus time for nanocomposites with a 2 wt.% of
BzGrAv-2 658
graphene nanoplatelets at 180 °C: BzGrXg-2 (dash line); BzGrAv-2 (continuous
BzGrXg-2 273
line).

7
V. García-Martínez, et al. Materials Today Communications 24 (2020) 100990

Table 5 Table 6
Gel times for Bz and GNPs/benzoxazine determined from the isothermal Vitrification time for Bz and its nanocomposites at several isothermal tem-
rheological experiments. peratures.
Sample Gel time, tgel (min) Sample Vitrification time, tvit (min)

170 °C 180 °C 190 °C 200 °C 170 °C 180 °C 190 °C 200 °C

Bz 63.0 37.2 24.0 12.0 Bz 149.0 91.5 60.3 44.0

BzGrAv-0.5 59.2 37.8 21.2 11.6 BzGrAv-0.5 149.8 92.9 62.1 43.5
BzGrXg-0.5 59.4 36.9 22.2 12.1 BzGrXg-0.5 153.2 96.4 62.9 44.3
BzGrAv-2 59.5 36.0 23.4 11.9 BzGrAv-2 143.1 86.8 59.0 42.1
BzGrXg-2 49.4 32.5 19.4 10.7 BzGrXg-2 155.7 98.7 64.5 43.9

Fig. 9, and the gel time (tgel) data for all the samples studied at different
isothermal temperatures was shown in Table 5.
As expected, all the samples reached the gel point faster at higher
curing temperatures. In general, the gel time decreases with the in-
corporation of graphene nanoplatelets, being this reduction more pro-
nounced when a 2 wt.% of GrXg was added. In the case of nano-
composites manufactured with GrAv, gel times were lower that neat
resin especially for low temperatures (170−180 °C) while at higher
curing temperatures they had similar gel times than Bz [31]. A re-
markable shortening in gel time was detected by Visco et al. when a 0.5
wt.% of not chemically treated MWCNT was introduced into epoxy
resin [39]. Abdalla et al. observed a reduction in tgel of epoxy resin
when a 1 wt.% of uniformly dispersed fluorinated MWCNT was added,
while no gel time decreasing was found by the addition of 1 wt.% of
carboxylated MWCNT [40].
It has been reported that apparent activation energy for the gelation
(Egel) can be calculated from knowledge of gel time at different tem-
peratures according with the following equation [41,42]:
Egel
lnt gel = φ+
RT (5)
where tgel is the gelation time at the isothermal temperature, T is the
curing temperature, R the universal gas constant and φ is a temperature
dependent constant.
Activation energy was lower for all GNPs/benzoxazine samples
except BzGrAv-0.5 whose value was slightly superior (Fig. 10). The
addition of GrXg to Bz produced a great reduction in Egel, more pro-
nounced when the amount of nanofiller added was higher. This result
was in agreement with the more brief gel time for nanocomposite
manufactured with a 2 wt.% of this type of graphene because the lower
activation energy for gelation the shorter gel time. As a matter of fact, it
was expected a reduction in both parameters (tgel and Egel) for this
nanocomposite due to the acceleration effect of GrXg in curing reaction
observed by DSC experiments.
The molecular mobility during the cure process has also been
studied by the measurement of the heat capacity [43]. Vitrification is
related to the reversing heat capacity (Cp-rev) evolution and, thus, vi-
trification studies should be based on that magnitude [44]. In this si-
tuation, the movement of polymer chains is restricted and the curing
reaction is limited by the diffusion of reactive species, so the conversion
seems to tend to a nearly restricting value, as shown in Fig. 7 for dif-
ferent curing temperatures. The vitrification time, tvit, was taken from
the inflection point of the Cp-rev curve against time in MDSC tests. The
vitrification times for BzGrXg-2 were shorter than for neat benzoxazine
at every evaluated temperature (Table 6), while for the rest of the
samples this phenomenon happened at larger times. The acceleration of
the occurrence of vitrification at the later curing stage would produce a
positive effect on the processing of carbon fiber composites since they
would need shorter post-cure times or lower post-cure temperatures.
Zhou et al. evaluated the effect of MWCNT on the curing reaction of
epoxy and they reported that these nanofillers prevented from the vi-
trification phenomena at the later curing stage [24]. An identical be-
havior was observed by Montazeri et al. when MWCNT was added to
epoxy resin [45].
4. Conclusions
The effect of different GNPs on the cure behavior of benzoxazine
resin was studied by DSC and rheological experiments. The results
showed that GrXg acted as catalyst and facilitated the curing reaction.
This accelerating effect was more noticeable when a 2 wt.% of nano-
filler was added to neat benzoxazine, because a reduction of the peak
time, activation energy as well as gel time and vitrification time was
observed.
The addition of GNPs did not change the autocatalytic nature of
curing reaction, but increased the overall heat of reaction and the ex-
tent of cure shifted to lower temperatures in nanocomposites manu-
factured with GrXg.
The curing kinetic equations for benzoxazine and its nanocompo-
sites were obtained and results showed that modelled curves fitted well
both in dynamic and isothermal experiments.
For the development of carbon fiber composites, the acceleration
effect caused by GrXg could produce a positive effect on the processing
of these composites since they would need shorter curing and post-
curing times.

Declaration of Competing Interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.

Acknowledgments

The authors thank Henkel Corporation for supplying the benzox-

azine resin employed in this study. They also acknowledge the technical
Fig. 10. Activation energy for the gelation in benzoxazine and its nano- support of Dr. C.A. Gracia from TA Instruments.
composites. The raw/processed data required to reproduce these findings cannot

8
V. García-Martínez, et al.
be shared at this time as the data also forms part of an ongoing study.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.mtcomm.2020.
100990.
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