Carbon 112 (2017) 17e26

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Interlaminar microstructure and mechanical response of 3D robust

glass fabric-polyester composites modified with carbon nanofibers
T. Senthil a, Zixiang Weng a, Lixin Wu a, b, *
a
Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou 350002, China
b
Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002,
China

a r t i c l e i n f o a b s t r a c t

Article history: The present work explores new methodology of fabricating the polymer nanocomposite with improved
Received 10 June 2016 interlaminar, dynamic and micro mechanical properties. Varying amount of carbon nanofibers (CNF)
Received in revised form were filled into the glass fiber/unsaturated polyester composite using filtering membrane vacuum-
26 October 2016
assisted method. Microporous nylon membrane was used to improve the dispersion of CNF in the
Accepted 27 October 2016
Available online 28 October 2016
lamination panels. CNF reinforcement and its concentration had a significant effect on the properties of
the composites. Electron microscopy studies on delamination and nanofillers dispersion showed
improved interfacial adhesion with CNF filled composites. The end-notched flexure and short-beam
strength tests were performed to assess the effect of filling CNF on the interlaminar fracture proper-
ties of the composites. Existence of critical concentration was observed for the reinforcement of nano-
filler. The properties of the composite enhance with increase in reinforcement upto critical
concentration, beyond which it decreases. Better storage modulus (~57%) and improved interlaminar
properties (~89%) were consistently observed with 2 wt% CNF filled nanocomposite irrespective of the
glass fiber loading, besides, the thermal stability and char yield which were also improved significantly.
Nanoindentation study shows 39% and 26% increase in elastic modulus and hardness of the composite
respectively, on reinforcement of 2 wt% CNF.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction due to their excellent stiffness and strength, exceptional electrical

The demands for production of three-dimensional (3D) network
glass fiber reinforced polyester nanocomposites (GFRPC) are
increased due to their huge number of potential applications [1e3].
Many research works have been conducted to enhance the desired
properties (i.e. mechanical, electrical and thermal) of fiber rein-
forced polymer nanocomposites (FRPCs) by the incorporation of
various carbon nanofillers [4e7]. Especially the vapor grown car-
bon nanofibers (VGCNF) are promising to develop multifunctional
polymer nanocomposites. These nanocomposites are used in elec-
tromagnetic interference shielding, sensors, electrostatic discharge
protection, super capacitors, batteries and fuel cells. This is mainly
* Corresponding author. Key Laboratory of Design and Assembly of Functional
Nanostructures, Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences, Fuzhou 350002, China.
E-mail address: lxwu@fjirsm.ac.cn (L. Wu).
and thermal properties, good corrosion resistance, low cost, high
aspect ratio and larger diameters typically in the range of
50e400 nm [8e12]. Understanding the micro-buckling, fiber
rupture, crack propagation through fiber resin interfaces and failure
strain are essential to improve the performance of nanocomposites.
In general, incorporating a small quantity of VGCNF as re-
inforcements in the polymer matrices can significantly increase the
overall properties of the polymer nanocomposites. However, the
uniform dispersion of the carbon nanofibrils within the resin and
fiber interlayers limits the improvement of interlaminar properties
such as interlaminar shear strength (ILSS) and interlaminar fracture
toughness (GIIC) of FRPCs, especially at high loading of nanofibrils
[13e15]. Numerous approaches have been proposed to improve the
interlaminar properties and to enhance the delamination and crack
propagation resistance of FRPCs [16,17]. The direct infusion method
has been widely used to fabricate FRPCs filled with various nano-
fillers. However, a major drawback of this method is that, one has to
avoid the fabrication of composites with high loading of carbon

http://dx.doi.org/10.1016/j.carbon.2016.10.087
0008-6223/© 2016 Elsevier Ltd. All rights reserved.
18 T. Senthil et al. / Carbon 112 (2017) 17e26
nanofibers (CNF). During the mixing process in direct infusion
method, nanofiller agglomerates may form and act as crack initia-
tion sites, leading to deteriorated performance.
Hossain et al. [18] investigated ILSS properties of a series of glass
fiber (GF)/unsaturated polyester (UP) composites reinforced with
different loading of CNF developed by vacuum assisted resin
transfer molding (VARTM). They observed that 29% increase in ILSS
of GFRPC on addition of 0.2 wt% CNF. Sadeghian et al. [19] used
VARTM to enhance the Mode-I delamination (GIC) resistance of CNF
filled glass fiber/polyester composites. Ahmadi et al. [20] noticed
that combined use of CNF and unidirectional glycidyl methacrylate
(GMA) grafted ultra-high molecular weight polyethylene
(UHMWPE) fibers leads to a significant synergy in the mechanical
properties of nanocomposites. The highest improvement in tensile
and flexural strengths was obtained on addition of 1 wt% CNF.
Literature shows high concentration of carbon nanofillers are
preferred at the neighborhood of the fiber-matrix interface to
promote the adhesion between them [21]. Consequently, it is
essential to develop new techniques for fabricating GFRPC with
uniformly dispersed high content of CNF between the fiber and
matrix, thereby mechanical, thermal and electrical properties can
be hopefully achieved.
In the present work, the applicability of filtering membrane
vacuum-assisted method (FMVAM) was investigated for the fabri-
cation of 3D robust network structures multi-plies reinforcement of
glass fiber/unsaturated polyester composites with VGCNF as the
functional carbon nanofillers. The interlaminar properties of the
composites were assessed using ILLS and GIIC tests. Besides, me-
chanical responses were studied by tensile, flexural and dynamic
mechanical analysis (DMA). To investigate interfacial bonding be-
tween the nanofillers and glass fiber/UP matrix plies fracture sur-
faces, the fractured surfaces were examined using the field
emission scanning electron microscopy (FESEM). Nano-indentation
hardness test was also performed for investigating the properties of
fiber/matrix and filler/matrix interfaces.
2. Experimental
2.1. Materials
Unsaturated phthalic-based polyester resin, glass fiber woven
fabric, vapor grown carbon nanofibers and nylon microfiltration
membrane were used for the preparation of composites. Vapor
grown carbon nanofibers (VGCFTM-H) synthesized by the gas phase
Fig. 1. FESEM images of CNF. (A colour version of this figure can be viewed online.)
method were procured from Showa Denko Japan Co., referred to as
CNF. Fig. 1 shows FESEM image of the procured CNF, an averaged
diameter of 150 nm and a length of 10e20 mm was observed. They
were randomly oriented and the average specific area was 15 m2/g
with a purity of >99%. The unsaturated phthalic-based polyester
resin (grade: Palatal P68V-994, styrene content: 40%, viscosity at
23
C: 150e180 mPa S) and hardener methyl ethyl ketone peroxide
(MEKP) were supplied by DSM, Jiangsu, China. Glass fiber woven
[0
/90
] fabric (E-LTM600/300) was bought from Bluston com-
posites material Ltd., Co., Zhejiang, China. The nylon microfiltration
membrane with a pore size of 0.45 mm was purchased from Bio-
genro biotechnology Co., Ltd., Beijing, China.
2.2. Preparation of GF/UP/VGCNF nanocomposites
Fig. 2 shows the sequential steps followed to fabricate CNF
reinforced 3D network GF/UP nanocomposites. The reinforcement
of CNF was done at the weight fractions of 0.2, 0.5, 1, 2 and 3 wt%.
The preparation of nanocomposite began with dispersion of CNF
into polyester resin using a high intensity ultrasonic atomizer probe
(20 KHZ, Scientz-Jy92-IIDN) for 60 min at room temperature. About
1.5% hardener was added into UP/CNF and then properly mixed
using a vacuum-assisted high speed mechanical stirrer at 1000 rpm
followed by degasification. In order to avoid styrene evaporation,
degassing and sonication were carried at room temperature. Sub-
sequent hand lay-up techniques followed by a FMVAM were
applied to prepare six layers of GF/UP/CNF laminate with thickness
of (3 ± 0.5) mm and a size of (200  200) mm.
The homogenized mixture obtained in the previous step was
evenly coated on the surface of bidirectional pristine glass fabrics
by a hand roller and then six layers of the coated glass fiber fabrics
were stacked together in the sequence of 0
/90
to get unique
prepreg panel. Subsequently, two nylon microfiltration membranes
were placed on top and bottom of the prepreg panel, which
reduced the flow of mixture and to prevented the carbon nano-
fillers at the maximum from resin flow. This may lead to the
accumulation of high content of CNF in the interlayer of composites.
A bleeder cloth and peel ply were also used. The entire panel was
then placed in a vacuum bag accompanied with a cold press. The
pressure of 10 MPa was applied to the prepreg panel for 24 h. It
increases the fiber volume fraction and infiltrate the CNF suspen-
sion preferentially between the fabrics gaps. The excess resin was
dragged by applying a vacuum through the vent of sealed bag.
Finally, post curing of GF/UP/CNF nanocomposites was carried out
at 80
C for 4 h.
2.3. Characterizations
The fracture surfaces of ILSS gold sputtered GF/UP composite
and GF/UP/CNF nanocomposites samples were examined by field
emission scanning electron microscope (FESEM) (JSM-7500F, JEOL,
Japan) at an accelerating voltage of 5 kV, using secondary electrons
for imaging. A transmission electron microscope (TEM) (JEOL JEM-
2010, Japan) was used to observe the dispersion of the CNF and
filler matrix interface of the nanocomposites.
Thermal stabilities of conventional and nanophased composites
were analyzed by thermogravimetric analysis (STA449C, NETZSCH,
Germany) from 25 to 800
C at a heating rate of 10
C.min1 under a
nitrogen atmosphere. Samples of about 10 mg was placed in a
thermogravimetric analysis (TGA) pan.
The storage modulus (E0 ) and tan delta (tand) of the prepared
composites were measured using dynamic mechanical analyzer
(DMA-Q800, TA, USA) under single cantilever beam mode. The
experiments were conducted at a heating rate of 5
C.min1 from
ambient to 180
C with amplitude of 20 mm and frequency of 1 Hz.
 T. Senthil et al. / Carbon 112 (2017) 17e26
Fig. 2. Schematic of the filtering membrane vacuum-assisted method. (A colour version of this figure can be viewed online.)
In-order to determine the interlaminar shear strength, speci-
mens of (22  7.2  ~3) mm with span length to thickness ratio of 4
were prepared from the composites. The test was performed in the
universal material test machine (AGX-100PLUS, Shimadzu, Japan)
at a cross-head speed of 0.5 mm min1 according to ASTM D 2344
with the short beam shear (SBS) method under three-point
bending mode. Five samples of each type were tested, and the
average and standard deviation values were determined. The
schematic of the testing setup is shown in Fig. 3a. Bernoulli-Euler
beam theory was used to calculate the ILSS of composite as given
in equation (1):
Pmax
F sbs ¼ 0:75 
bh
where Pmax indicates the maximum breaking load (N), b and h are
the width and thickness of the specimen in mm, respectively.
End-notched flexure (ENF) method was used to determine the
mode II interlaminar fracture toughness (GIIC) according to the
direct beam theory. The test was performed in a universal material
test machine (AGX-100PLUS, Shimadzu, Japan) at a cross-head
speed of 1 mm min1 and a schematic of the testing set-up is
shown in Fig. 3b. The initial pre-cracks were created at about
35 mm from the edge and at the mid-plane of the specimen using a
Teflon film. Five samples of each type were tested, and the average
and standard deviation values were determined. The direct beam
theory was used to calculate GIIC as given in Equation (2):
9a2 P d
GIIC ¼

2b 3a3 þ 2L3
where a is initial delamination length of pre-crack (25 mm), P is the
19
maximum load of interlaminar fracture failure, d denotes the
maximum load point displacement, b is the specimen width and L
indicates the half-span length (50 mm) of the specimen. One-way
analysis of variance (ANOVA) was performed for a better under-
standing of the effect of CNF loading on the ILSS and GIIC of the
composites. Statistical significance was determined at a probability
(P)-value < 0.05.
In-order to study the micromechanical properties of the com-
posites, nanoindentation hardness test was performed. Five sam-
ples of each type were tested, and the average and standard
deviation values were determined. For the study, samples
(20  20  3) mm were initially grounded using silicon carbide
papers of 100#, 180#, 400#, 800#, 1200# and 2500# grades and
(1) then finally polished using diamond paste suspension (0.5e5 mm
particle size) for 30 min. The nanoindentations were performed in a
nanoindenter instrument (Hysitron Inc., Tribo Indenter 750, USA)
with a three-sided pyramid Berkovich diamond indenter (radius of
the indenter probe was 50 nm). The maximum force of 300 mN was
applied at a constant rate of 60 mN S1. About 50 indentations were
performed on each samples and the distance between the two
adjacent indentations was 300 nm. In order to avoid the creep ef-
fect, dwell time was selected as 60 s. The indentations were
measured using high resolution optical microscopy. The hardness
and elastic modulus were calculated using equations (3) and (4)
[22]. The calculation of elastic modulus is related to the initial
slope of the unloading curve.
(2) Pmax
H¼ (3)
Ac
20 T. Senthil et al. / Carbon 112 (2017) 17e26

Fig. 3. Digital image and schematic of a) SBS tests, and b) ENF tests. (A colour version of this figure can be viewed online.)

pffiffiffiffiffi
dP 2Er Ac
S¼ ¼ pffiffiffi
dH p may be due to aggregation of CNF at 3 wt%. It indicates the exis-
where Pmax is the maximum applied load, Ac (Ac ¼ 24.56h2c ) is the
projected contact area calculated at the depth of indentation (h), S
and Er denote the contact stiffness and reduced elastic modulus,
respectively. The Er can be calculated from the following Eq. (5):
1 1  n2s
¼ (5)
Er Es
where Es signify young's or specimen modulus and ns represents
Poisson's ratio of the specimen.
3. Results and discussion
3.1. Effects of CNF on ILSS and mode II interlaminar fracture
toughness of nanocomposites
The results of three points end notch test could be utilized to
understand the lamination failure mechanisms between the layers
of composites. Generally, the lamination failure depends on the
states of materials (i.e. defects in the laminate, nature of the poly-
mer matrix, fiber volume fraction, so on), interface bonding
strength and dispersion of the nanofillers. Fig. 4a compares the ILSS
of UP/GF composite prepared with different weight fractions of CNF
and indicates the significant effect of the reinforcement of CNF and
its concentration on ILSS of UP/GF composite. The ILSS values of
30 ± 1.09, 35 ± 0.33, 41 ± 2.89, 46 ± 1.67, 57 ± 0.96 and
42 ± 0.67 MPa were obtained for 0, 0.2, 0.5, 1, 2 and 3 wt% CNF
reinforcement, respectively. The maximum increment of about 89%
in ILSS was observed for UP/GF composite on reinforcement of 2 wt
% CNF. It was observed that the ILSS of UP/GF composite increased
with increase in concentration of CNF upto 2 wt%. The further in-
crease in concentration of CNF decreased the value of ILSS, which
(4)
tence of critical weight fraction upto which uniform distribution of
reinforcement of CNF results in enhancement of ILSS. The similar
trend was also observed by Ma et al. [21] with CNF reinforced
polymer composites (CFRP). The increments in ILSS value of 15, 36,
54 and 89% were obtained for 0.2, 0.5, 1 and 2 wt% CNF reinforce-
ment, respectively. This is mainly due to the stress transfer capa-
bility of CNF at the interfacial vicinity of resin and fiber region.
One-way ANOVA method was used to study the significant ef-
fects and interactions of various CNF loading. Tukey's honestly
significant difference method was used for all post hoc analysis to
identify the significant difference between each set of test. Signif-
icance level greater than 0.05 was observed for 0 and 0.2 wt%, 0.5
and 3 wt%, 1 and 3 wt% comparisons, whereas all other compari-
sons were found to be statistically significant. As shown in Fig. 4a,
addition of 0.2 wt% of CNF resulted in a slight increase of ILSS but it
was not considerable compared to the control. Similar observation
was found in between 0.5 and 3 wt% and, also 1 and 3 wt% CNF
loaded composites. At the same time, as the CNF content was
increased from 0.2 to 2 wt%, the ILSS of the nanocomposite was also
increased to a great extent, when compared to control and other
filler loaded composites, thus confirms that the observed values are
statistically significant (P < 0.05; R2 ¼ 0.9697 (Table 1)).
Fig. 5 shows the SEM micrographs of the fractured surfaces of
UP/GF composites at different CNF reinforcements. The fractured
surfaces reveal the interfacial adhesion between the fibers and
matrix. It is observed to be a favorable mechanical interlocking
between the nanofillers and surface of the glass fibers. Typical load-
displacement curves and the corresponding fractographs of the
neat UP/GF and UP/GF with 0.2e3 wt% CNF composites are shown
in Fig. 6. It is worthwhile to note that, initially all the laminates
show an increase in load up to the maximum level because of the
 T. Senthil et al. / Carbon 112 (2017) 17e26 21

Fig. 4. Variations in (a) ILSS and (b) ENF of GFRPC as a function of different wt% of CNF. Symbols (*, **, þ) indicate pairwise comparisons that were statistically not different
(P  0.05), whereas all other comparisons were different (P < 0.05). (A colour version of this figure can be viewed online.)

Table 1
Results of analysis of variance (ANOVA) for ILSS.

Source Degree of freedom (DF) Sum of square (SS) Mean square (MS) F-value P-value

Model 5 1328.33408 265.66682 76.86617 1.08602  108

Error 12 41.47471 3.45623 e e
Total 17 1369.80879 e e e

Fig. 5. FESEM fractographs (at a magnification of 1000 and scale bar ¼ 50 mm) of (a) 0 wt%, (b) 0.2 wt%, (c) 0.5 wt%, (d) 1 wt%, (e) 2 wt%, and (f) 3 wt% CNF filled GFRPC. (A colour
version of this figure can be viewed online.)

homogeneity of the composites signifies the good dispersion of
nanofillers in the resin (Fig. 8). The homogeneous dispersion of CNF
in UP/GF composite resulted in increase of load from zero to
maximum value. However, the initiation of crack growth between
the lamination layers led to sudden decrease in load with further
elongation (Fig. 6). Among the various concentration of CNF re-
inforcements, the significant effect on shear strength was observed
with 2 wt% loaded CNF.
The de-bonding, agglomerates, crack deflection, nanofillers
pull-out and crack bridging defects played a prominent role in
determining the toughness of FRCs, as observed from the literature
[14e18,23]. Fig. 4b shows typical interlaminar fracture toughness of
UP/GF composite at different CNF loadings. A number of tough-
ening methods, such as braiding, matrix modifications, 3D fabric
architecture, embroidery, Z pinning, microscale particles or fibers
and stitching was developed to enhance the interlaminar shear
strength and fracture toughness, nevertheless at the cost of in-
plane mechanical properties [4,15]. Here, delamination resistance
was employed using CNF in order to improve the experimental
results without compromising other composites properties. The
GIIC value increased with increase in concentration of CNF upto 2 wt
% and decreases with further increase in concentration of CNF. For
22 T. Senthil et al. / Carbon 112 (2017) 17e26
Fig. 6. Load versus displacement graphs of neat and different wt% of CNF filled GFRPC.
(A colour version of this figure can be viewed online.)
higher weight fraction, a significant reduction was observed at 3 wt
%, it is due to the unsatisfactory dispersion of CNF and agglomerates
of the nanofillers can be formed between the laminates. Moreover,
the higher amount of nanofillers into resin attributed to crack
propagation near the laminates, because of the resin dispersion
saturation limit. This results in decrement of ILSS and GIIC of UP/GF
composite beyond the critical weight fraction CNF reinforcement.
Hossain et al. [18] report nucleation of crack initially at polymer
matrix, when the load is applied to the multi-scale reinforcement
composite structures. The stress is transferred from the inferior
modulus matrix to long fiber via nanofillers by crack bridging effect
in the interfacial region. At a critical CNF weight fraction of 2 wt%,
the fracture toughness reached a maximum GIIC value of
1139.22 J m2 with a high standard deviation (P < 0.05), which
indicates that UP/GF laminates can sustain a high-fracture tough-
ness value with presence of CNF at the maximum load. Herein, the P
values of control and 2 wt%, 0.2 and 2 wt%, 3 and 2 wt% composite
comparisons are statistically significant (<0.05), whereas all other
comparisons were found to be statistically insignificant (Table 2).
This observation is in good agreement with the fact that are pre-
sented in the previous discussion.
The fracture toughness values of 726 ± 25.82, 803 ± 80.73,
872 ± 102.89, 922 ± 54.49, 1139 ± 134.96 and 861 ± 45.32 J m2
were obtained for 0, 0.2, 0.5, 1, 2 and 3 wt% CNF reinforced UP/GF
composite, respectively. The increases in GIIC upon addition of CNF
indicate improved capabilities of UP/GF laminates to resist the
crack growth. This is mainly due to the enhancement in interfacial
adherent between the matrix and glass fiber on addition of CNF
which is supported by SEM micrograph (Fig. 7). Further, the high
aspect-ratio of CNF favors to upsurge the absorption of the applied
energy. Godara and coworkers [24] observed a substantial
improvement in interlaminar fracture toughness for the carbon-
epoxy composites with the addition of carbon nanofillers. It has
been shown that CNT-bridging in the laminate regions could be
delaying the crack initiation and propagation by crack bridging
mechanism. Reinforcement of 0.2 and 0.5 wt% CNF showed only a
small increase in ILSS and GIIC of UP/GF composite. This result
suggests that the interfacial adherent between the matrix and glass
fiber was weak at lower CNF loading (0.5 wt%). Further, only small
Table 2
Results of analysis of variance (ANOVA) for ENF.
Source Degree of freedom (DF) Sum of square (SS)
Model 5 295623.31357
Error 12 123030.88848
Total 17 418654.20205
surface area of the GF was reinforced with CNF and more micro
cracked GFs were appeared. On the other hand, significant increase
in ILSS and GIIC of UP/GF composite was obtained with 1 and 2 wt%
CNF reinforcement. Therefore, the sufficient amount of CNF rein-
forcement was expected to improve the bonding between the fi-
bers and resin due to CNF-bridging and elimination of micro cracks
on GFs by complete reinforcement.
Further, microstructural homogeneity and less aggressive ag-
glomerates of CNF in the interfacial region was noticed (Fig. 5),
probably due to the weak secondary force (van der Waals) of the
individual carbon nanofibers. As a consequence, improved crack
growth resistance and substantial improvement in mechanical
properties of the composites were achieved. There was a significant
reduction in GIIC of composite on addition of 3 wt% CNF. The excess
reinforcement of CNF beyond its critical fraction resulted in for-
mation of agglomerates at interlamination layers and pullout of
CNF. Strong van der Waals interactions of nanofibers result in
stiffened interfacial adhesion network between the resin matrix
and fibers. This makes them rigid leading to break the laminates
one by one rapidly along the fiber direction and easy the crack
growth. Note that the dispersed carbon nanofibers behaved as van
der Waals bonding and mechanical interlocking between the resin
matrix and fiber which could reduce fiber-bridging effect and the
deflected fracture failure. Herein, adding the higher amount of CNF
into the glass fiber interlayers showed enhancement of GIIC, which
was not appeared in any open literature.
3.2. Effects of CNF on the viscoelastic behavior of nanocomposites
Figs. 9 and 10 show the variations of storage modulus (E0 ) and
tan d as a function of temperature, respectively. As expected, the
storage modulus increased for a critical CNF loading of 2 wt% at
below the glass transition temperature (Tg) because of the rein-
forcement effect added by the nanofillers and also degree of crys-
tallinity in the nanocomposite, as shown in Fig. 9. Here, the E0 value
of each sample decreased step by step (i.e. glassy regime to rubbery
regime) when temperature increased from 25 to 180
C. It is
noteworthy that the E0 of UP/GF composite increased by 49% on
reinforcement of 2 wt% CNF and it is reduced to about 28% with
3 wt% CNF reinforcement. The reduction E0 was attributed to the
agglomeration of CNF at the fiber interface which led to a decrease
in strengthening of the composite structures. Similar trend was also
observed in literature [18], in which the incorporation of CNF
drastically reduced the E0 of nanocomposite.
Furthermore, a linear increase in modulus was found to be 15,
23 and 37% for the 0.2, 0.5 and 1 wt% CNF filled GFRPC, respectively.
It indicates that CNF could act as a percolating network in the vi-
cinity of the interphase and consequently transfer the load. In short,
both the enhanced bonding strength and higher cross-link den-
sities can be the reason for linear improvement and, the addition of
CNF efficiently absorb a substantial amount of energy during
damping thereby restricting mobility of polymer molecules. The
variance of modulus with temperature was associated to the
energy-absorbing mechanism and extensive polymer matrices
transition.
Fig. 10 shows the temperature dependence of the tan d of UP/GF
composite with and without reinforcement of CNF. As shown in
Mean square (MS) F-value P-value
59124.66271 5.76681 0.00612
10252.57404 e e
e e e
 T. Senthil et al. / Carbon 112 (2017) 17e26 23

Fig. 7. FESEM micrographs (at a magnification of 500 and scale bar ¼ 100 mm) of the fracture surface of (a) 0 wt%, (b) 0.2 wt%, (c) 0.5 wt%, (d) 1 wt%, (e) 2 wt%, and (f) 3 wt% CNF
filled GFRPC. (A colour version of this figure can be viewed online.)

Fig. 8. TEM micrographs of polyester/CNF nanocomposite sample. (A colour version of this figure can be viewed online.)

Fig. 10, increase in Tg (118
C) by increasing high aspect-ratio of CNF

Fig. 9. Temperature dependence of storage modulus for both neat and CNF filled
GFRPC. (A colour version of this figure can be viewed online.)
content upto 2 wt% and then slight decrease in the value of Tg
(114
C) with further incorporation of CNF (3 wt%) which agrees
well with earlier reasoning. The decrease height of the tan d peak at
a higher temperature indicates the occurrence of plastic deforma-
tion and reduction in interfacial strength between primary fibers
and CNF phase. Numerous studies have been executed to investi-
gate the effect of carbon nanofillers on nanocomposite damping
factor [23,25]. The Tg peak gradually shifted to a higher temperature
with increasing CNF loading, which indicated improved adhesion
between the fiber and resin matrix. The reinforcement of CNF
increased the Tg value of composite by 6
C and no significant
change in onset temperature.
The introduction of CNF filled the free volume of the matrix
network and decreased the segmental motion of the polymer
chains. Accordingly, stronger fiber-polymer-nanofiller interactions,
presence of crystallinity and higher cross-linking density aided in
24 T. Senthil et al. / Carbon 112 (2017) 17e26

a indicates decomposed fraction, Et is the activation energy for

decomposition, R is the gas constant, and q ¼ T e Tmax. Using this
equation, with some exceptions, one can say that the increase in
activation energy leads to stress transfer between the resin and
fiber, as well as an increase in the thermal stability.
The plots of ln[ln(1-a)1] versus q is shown in Fig. 12. The slope
of the curve gives the value of Et. The values of the Tmax, IDT and Et of
the UP/GF composite with different weight fraction of CNF are lis-
ted in Table 3. Lower values of Tmax and IDT and higher value Et were
obtained for the composite with 2 wt% of CNF, which indicates that
higher energy was required to initiate the thermal decomposition
when the composite is reinforced with CNF. It confirms that CNF
had greater effect on the thermal stability of the composite, causing
a high energy requirement to attain the motions of the chain
segments.

Fig. 10. Variation of tand as a function of temperature for both neat and CNF filled 3.4. Effects of CNF on indentation modulus and hardness of
GFRPC. (A colour version of this figure can be viewed online.)
nanocomposites

achievement of high E0 and marginally increased level of Tg of the
composite on reinforcement of CNF.
3.3. Effects of CNF on thermal stability of nanocomposites
Thermogravimetric analysis was carried to better understand
the effect of nanofiller reinforcement on thermal behavior of
composite. Fig. 11 shows the TGA graph of composite with and
without nanofiller reinforcement. From the graph, temperature of
maximum rate of degradation (Tmax) and initial decomposed tem-
peratures (IDT) were identified. The temperature region between
40 and 350
C showed the removal of unreacted polyester resin and
other unexpected impurities and the temperature region above
350
C showed the thermal degradation of the composite. The
reinforcement of CNF shows enhanced char yield of composite at
800
C. Evidently from Fig. 11, increase in CNF content increased the
thermal stability of the composite, which was similar to the results
shown by Hossain et al. [18]. The activation energy for decompo-
sition (Et) of the composite was determined by the Horowitz and
Metzger equation, as shown in Eq. (6) [26,27]:
h i Et q
ln lnð1  aÞ1 ¼ 2
(6)
RTmax
In general, nanoindentation is one of the improved and
advanced method to determine the micromechanical behavior
such as hardness, plastic and elastic modulus of variety of materials
in nanoscale [28]. Moreover, the nanoindentation has been widely
used to study the interphase region and their stability or stiffness
(S) formed between the fibers and polymer matrix. Using this
method, the contact damping (uC) along the indentation can also
be calculated for a single loading/unloading cycle. Fig. 13 illustrates
the hardness and reduced elastic modulus of the UP/GF composite
with different amount of CNF. The hardness steadily increased with
increasing the filler content due to the occurrence of the substantial
cross-linking density and indentation size effect (ISE). By adding
0.5 wt% CNF into neat polyester resin the hardness increased by
16%, whereas the nanophased composite containing 0.2 wt%
nanofiller was 8%. Interestingly, in the nanocomposite containing

where Tmax is the temperature at the maximum rate of weight loss,

Fig. 12. Typical plots of ln[ln(1a)1] versus q (TTmax) for both neat and CNF filled
GFRPC. (A colour version of this figure can be viewed online.)

Table 3
Thermal stability behavior of control and CNF filled GFRPC obtained from TGA
thermograms.

CNF content (wt%) Et (kJ/mol) IDT (
C) Tmax Char yield (%)

0 109 311.11 350.23 57.72

0.2 114 354.93 384.22 73.07
0.5 118 354.93 385.09 73.39
1 120 355.05 386.52 77.90
2 122 344.61 375.20 78.58
Fig. 11. Typical TGA curves of neat and CNF filled GFRPC. (A colour version of this
3 116 342.61 372.85 79.49
figure can be viewed online.)
 T. Senthil et al. / Carbon 112 (2017) 17e26
Fig. 13. Variations in hardness and reduced elastic modulus of neat and nano-
composites filled with various CNF content. Surface topography and optical micro-
graphs of indent composite samples under a maximum load of 300 mN. (A colour
version of this figure can be viewed online.)
2 wt% CNF the hardness was 9.98 ± 0.56 GPa, showing a 26%
enhancement, however, the hardness decreased about 20% by
further adding 3 wt% of CNF. As evidenced by microstructure ana-
lyzes, the addition of CNF content beyond the critical concentration
interrupted the bonding strength between the fiber, matrices and
nanofillers.
Fig. 13 shows the reduced elastic modulus of the composite as
function of CNF content, the measured values of Er confirm that the
increase in filler content increased elastic modulus of the com-
posite as expected. For instance, the nanocomposite containing
0.2 wt% CNF value was higher than neat GFRPC, with
92.9 ± 0.75 GPa and 84.9 ± 1.33 GPa, respectively, though there was
no much difference observed between them. Subsequently, the
measured indentation modulus for 1 and 2 wt% CNF filled GFRPC
were 107.8 ± 2.88 GPa and 118 ± 1.65 GPa, respectively, which
represents improved elastic modulus by the effect of CNF content.
As the Er was reduced, the resistance of the composites to inden-
tation slowly decreased due to the plasticizing effect. This result is
in highly agreement very well with the previous studies [29]. In
fact, the aggregation significantly increased with increasing filler
content, suggesting that nanofillers does not fully dispersed and
interact with the polyester resin, thus leading to the reduced
hardness as well as lower modulus.
4. Conclusions
New approach of combined hand lay-up techniques followed by
a filtering membrane vacuum-assisted method were explored to
fabricate the three-dimensional robust nanocomposite of glass fi-
ber/unsaturated polyester filled with carbon nanofibers. The
interlaminar properties, viscoelastic behavior and micromechanical
behavior of the composite were studied at varying concentration of
CNF reinforcement. Results showed the existence of critical con-
centration for the reinforcement of nanofiller within which prop-
erties of the composite enhanced with increase in reinforcement.
Beyond the critical concentration, the properties of the composite
decreased with increase in concentration of nanofiller reinforce-
ment. The critical concentration of 2 wt% CNF reinforcement was
observed for UP/GF composite. The ILSS and GIIC were improved by
about 89% and 57%, respectively for the critical filler weight fraction
of 2 wt%. Electron microscopy studies showed uniform dispersion
of nanofillers without agglomeration and strong interfacial adhe-
sion between the interlamination layers within critical concentra-
tion of CNF reinforcement. The excessive amount of CNF
25
reinforcement resulted in agglomeration of nanofillers and stiff-
ened interlamination layers. The microfiltration nylon membrane
was effectively utilized to intercept the CNF which in turn resulted
in the formation of laminate panels with a high content of CNF at
the interface. The composite with 2 wt% of CNF also exhibit
enhanced storage modulus and hardness to about 49% and 26%,
respectively. We demonstrated that the microporous membrane
vacuum-assisted methodology was an appropriate method to
fabricate improved interlaminar, viscoelastic and micro mechanical
properties of nanocomposites.
Acknowledgements
This research was financially supported by the China Post-
doctoral Science Foundation (Grant No.:2016M592098) and the
National Natural Science Foundation of China (Grant No.:
U1205114). Mr. Xiangyu Dong is gratefully acknowledged for his
kind assistance in nanoindentation.
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