CARBON 4 8 ( 2 0 1 0 ) 3 6 9 2 –3 6 9 9

available at www.sciencedirect.com

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

Role of processing on interlaminar shear strength

enhancement of epoxy/glass fiber/multi-walled carbon
nanotube hybrid composites

V.C.S. Chandrasekaran, S.G. Advani, M.H. Santare *

Department of Mechanical Engineering and Center for Composite Materials, University of Delaware, Newark, DE 19716, United States

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

Article history: Interlaminar shear strength (ILSS) of hybrid composites made from glass fiber and multi-
Received 26 March 2010 walled carbon nanotube (MWCNT) modified epoxy is compared with unmodified epoxy/
Accepted 4 June 2010 glass fiber composites (control). By combining the techniques of high speed mechanical
Available online 22 June 2010 stirring and ultrasonic agitation, 0.5% MWCNT by weight was dispersed in epoxy to prepare
a suspension. Composites were manufactured by both injection double vacuum-assisted
resin transfer molding (IDVARTM) and the flow flooding chamber (FFC) methods. Compres-
sion shear tests were conducted on the manufactured samples to determine ILSS. The
effect of processing history and batch-to-batch variability of materials – glass fiber preform,
resin and carbon nanotubes – on ILSS of samples made by both techniques was investi-
gated. Statistical analysis of the measured ILSS values for hybrid composites and their
comparison with the control specimens clearly show that hybrid composites made by
the FFC process resulted in (i) significant ILSS enhancement relative to the control and to
IDVARTM specimens and (ii) better repeatability than the IDVARTM process. A description
of both IDVARTM and FFC processes and their role in dispersing the nanotubes between the
fabric layers was discussed.
 2010 Elsevier Ltd. All rights reserved.

1. Introduction Matrix modifications include the addition of nanofillers

Fiber-reinforced laminated composites are increasingly being
used in structural applications because of their mechanical
performance and potential for significant weight reduction
relative to metals. The in-plane properties of laminated com-
posites are fiber dominated and they are sufficient for many
structural applications. The out-of-plane/through thickness
properties, such as interlaminar shear strength (ILSS), are
matrix dominated and are the limiting factor in many struc-
tural applications. ILSS has been improved by various meth-
ods such as Z pinning, stitching and matrix modifications
[1]. However, Z pinning and stitching fibers in the thickness
direction lead to significant additional manufacturing com-
plexity and cost.
such as nanoclay, nanofibers and nanotubes. The filler’s
nanometric size leads to a high specific surface area
(>1000 m2/g), and their high aspect ratio and high Young’s
modulus and strength make them attractive candidates for
polymer reinforcement. The combination of nanotube modi-
fied matrix, together with conventional fiber-reinforcements,
has led to a new generation of multiscale, multifunctional
structural materials [2]. Recently, a significant amount of re-
search [3–13] has been conducted in the area of matrix mod-
ification by nanofillers with promising outcome. Siddiqui
et al. [13] saw a 26% increase in flexural modulus of plain
woven carbon fiber epoxy composites manufactured by hand
layup process, with the addition of 3% nanoclay to the epoxy
matrix. Zhou et al. [4] reported 22.3% improvement in the

* Corresponding author: Fax: +1 302 831 3619.

E-mail address: santare@udel.edu (M.H. Santare).
0008-6223/$ - see front matter  2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2010.06.010
 CARBON 4 8 ( 20 1 0 ) 3 6 9 2–36 9 9
flexural strength of satin weave carbon fiber-reinforced epoxy
composites manufactured by the VARTM process when they
added 2% carbon nanofibers to the epoxy matrix. Gojny
et al. [5] found that non-crimp glass reinforced polymer com-
posites with 0.3% by weight of nanotubes added to the epoxy
matrix manufactured by the RTM technique resulted in a 20%
improvement in ILSS over unmodified epoxy. Beyakrova et al.
[14] found that introduction of 0.25% of MWCNT in carbon fi-
ber/epoxy composites using VARTM results in an enhance-
ment of the ILSS by 27%.
The above cited studies have shown varying amounts of
improvement in several composite properties through the
addition of various nanofillers in epoxy. In each case, differ-
ent concentrations of nanofillers are infused into different
fiber systems using different processing techniques. In this
study, we will focus on one material system and evaluate
the effects of using two different VARTM techniques on the
resulting ILSS of the composite. The material system chosen
for this study is epoxy resin, plain weave E-glass fiber and
MWCNT.
Studies of ILSS enhancement in composites from addition
of CNT to the matrix have had a mixed outcome in the liter-
ature with reports ranging from zero improvement to 27%
[5,14–16]. Apart from using different variations and batches
of materials, the reported studies use different processing
techniques for manufacturing which vary from hand layup,
VARTM, RTM and autoclave. In a series of papers by K.
Schulte’s group, they report an ILSS improvement for hybrid
composites of 20% [5], improvement of 16% [15] and no
improvement [16]. In their first two papers [5,15] they used re-
sin transfer molding (RTM) to inject the modified epoxy sus-
pension into a mold and saw similar ILSS enhancement in
those studies. In [16], they used vacuum-assisted resin trans-
fer molding (VARTM) and a different epoxy resin and saw no
improvement in ILSS. They concluded that the significance of
the effect of nanoparticles on the mechanical properties of an
epoxy resin depends on the type of resin [16]; but it is also
possible that this difference may be due to the change in
the processing method from RTM to VARTM. These two meth-
ods can cause the distribution of nanoparticles to be different
due to the different resin flow patterns.
The main challenges in exploiting the mechanical proper-
ties of carbon nanotubes (CNTs) for reinforcement of fiber
composites are obtaining good dispersion, interfacial adhe-
sion and overcoming the increased processing difficulty due
to the increase in viscosity of resin resulting from the addition
of CNT. Even if the CNT is dispersed well in a thermoset ma-
trix such as epoxy, if the suspension is not properly infused
into the spaces between glass fiber mats, we may not be able
to realize the potential improvement of ILSS. Therefore, the
appropriate choice of processing technique is essential to pro-
ducing a successful hybrid composite.
Improvement of ILSS of hybrid composites has been ex-
plored from various perspectives. However, the roles of pro-
cessing and variability of materials from one batch to the
next, while keeping the materials and CNT content the same,
have not been thoroughly examined in the reported literature.
Manufacturing inherently results in variability in composite
properties due to variations in the precursor materials, such
as the resin batch, suspension preparation methods, variation
3693
in glass fiber permeability, glass fiber sizing, and operator var-
iability. These factors can cause inconsistency in the resulting
properties and make it difficult to interpret the ILSS results re-
ported in literature. Therefore it is important to do a statisti-
cal study of the results to determine the significance of any
apparent ILSS enhancement.
The present study concentrates on manufacturing of hy-
brid composites by dispersing 0.5% by weight of multiwall
carbon nano tubes (MWCNT) in the epoxy and exploring the
role of the process and material variability on the ILSS of
the hybrid composite. In this study, the MWCNT/epoxy sus-
pension was prepared using several variations of ultrasonic
agitation. The resin was then injected into glass fiber pre-
forms using two different processes; injection double vac-
uum-assisted resin transfer molding (IDVARTM) and the
flow flooding chamber (FFC) method. The ILSS of the resulting
hybrid composites was measured using the compression
shear test (CST) method [17]. Control samples without
MWCNT were also tested. These controls were subjected to
the same suspension preparation method and manufacturing
process as the test samples to isolate the effect of MWCNT. In
addition to the influence of the manufacturing process, we
also explored the effect of batch-to-batch variability of raw
materials, such as glass fibers, MWCNT and epoxy resin, on
the ILSS. Statistical analyses were carried out to determine
the significance of each of the above factors in increasing
ILSS.
2. Experimental
2.1. Materials
The resin used in this study is a commercially available SC-15
epoxy supplied by Applied Poleramic Inc. It is a low-viscosity,
two-phase, toughened epoxy resin system consisting of part-
A (mixture of: diglycidyl ether of bisphenol A, 60–70%, ali-
phatic diglycidylether, 10–20%, and epoxy toughener 10–
20%) and part-B (hardener, cycloaliphatic amine 70–90%, and
polyoxyl alkyl amine 10–30%). It cures at room temperature
and is commonly used to manufacture fiber-reinforced com-
posites using the vacuum-assisted resin transfer molding
(VARTM) process. We selected MWCNT to mix with the resin
due to their low cost relative to single walled nanotubes
(SWNT) or double walled nanotubes (DWNT). The MWCNT
were purchased in two batches from the ILJIN nanotech com-
pany, in Korea and Helix Material Solutions, USA, and both
were made by CVD (>95%). Their wall structure was verified
by examination under SEM and TEM. The diameters of the
nanotubes were on the order of 10–20 nm and the length
was between 10 and 50 lm. The woven glass fiber mats were
supplied by Saint-Goban Vetrotex Company and had a fiber
density of 800 g/m2.
2.2. Manufacturing
The processing of the glass fiber/epoxy/MWCNT hybrid com-
posites consists of two stages: (i) preparation of MWCNT/
epoxy suspensions and (ii) impregnation of the suspension
into a mold containing fiber preforms. The suspensions were
3694 CARBON 4 8 ( 2 0 1 0 ) 3 6 9 2 –3 6 9 9
prepared using high speed mechanical stirring for 5 min fol-
lowed by ultrasonic agitation. In this study, we looked at sev-
eral different methods for suspension preparation, and two
different VARTM impregnation methods; IDVARTM and FFC.
We will first present and discuss the various suspension prep-
aration methods, and then introduce the processing methods.
2.2.1. Preparation of MWCNT/epoxy suspensions
In this study, we used two ultrasonic agitation techniques,
bath sonication and tip sonication, and sonication times of 6
and 20 h for both agitation techniques. In addition we devel-
oped an alternate 2-min sonication with the ultrasonic horn
tip submerged in the resin, thus creating five suspension
preparation methods. All preparations contained 250 mg of
MWCNT added to 38.5 g of Epoxy SC-15 resin part-A and
11.5 g of Epoxy SC-15 resin part-B in a beaker, resulting in
0.5% by weight of MWCNT in epoxy suspensions. The beaker
was placed inside a Branson 1510 ultrasonic bath sonicator
and agitated for 6 or 20 h, to prepare the bath sonicated sus-
pensions. Similarly, the other suspensions were prepared by
agitating the suspensions for 6 h, 20 h or 2 min with a Sonics
Vibra Cell tip sonicator. The high local energy from the tip
sonicator, when the tip is submerged in the suspension, can
overheat the resin and reduce the average MWCNT length.
Therefore the tip of the sonicator was placed slightly above
the liquid surface instead of immersing it in the liquid to re-
duce overheating and shortening of MWCNT length for 6 and
20 h suspensions. For 2 min sonication, the tip was sub-
merged in the suspension. The shortened sonication time re-
duced the tendency for overheating and MWCNT breakage.
After each of the above sonication techniques, the beaker
containing the suspension was placed in a bell jar under a
vacuum for 2 h for degassing. The resin used for the control
samples without the MWCNT, was also subjected to identical
sonication processes.
2.2.2. IDVARTM process
One of the two variations of VARTM explored was the IDV-
ARTM process. In this process, eight layers of 5 cm · 5 cm wo-
ven glass fiber mat were cut and sealed under a vacuum bag.
The air was evacuated by applying a vacuum (the first vac-
uum) to the outlet port of the mold. The fiber mats compacted
under the external atmospheric pressure acting on the bag.
The vacuum line was then clamped to hold the first vacuum
and a pre-selected amount of resin (either neat epoxy or
one of the MWCNT/epoxy suspensions) was introduced
through a gate between the bag and the compacted preform.
The resin inlet was then clamped and the entire closed mold
was placed in a reservoir which was under slightly higher
vacuum than the first vacuum for 30 min. This slightly higher
second vacuum releases the external atmospheric pressure
induced by the first vacuum and allows the eight compressed
fiber mats to relax and recover some of their original thick-
ness. This recovery opens up the gaps between the glass mats
making it easier for the MWCNT/epoxy suspension to flow
into the larger channels between the glass fiber mats due to
the intrinsic capillary pressure and gravity. After the
MWCNT/epoxy suspension fills the gaps between the glass fi-
ber mats, it wicks laterally into the glass fiber mats by capil-
lary action. The second vacuum is then released to reapply
the external atmospheric pressure onto the mold for an addi-
tional 30 min to further infuse the MWCNT/epoxy suspension
into the fiber mats. After the MWCNT suspension fills the
empty regions within and in between the fiber mats, the first
vacuum line is reopened to draw off the excess MWCNT/
epoxy suspension and further compress the mold and obtain
the desired higher fiber volume fraction. The manufactured
hybrid composite samples were post-cured in oven at 100 C
for 4 h. Fig. 1 shows the important processing steps of the
IDVARTM process and Fig. 2 shows an example of the manu-
factured sample.
2.2.3. Manufacturing by FFC
The flow flooding chamber (FFC) process is another varia-
tion of the standard VARTM manufacturing technique. The de-
tails of the process and its advantages and disadvantages
compared with the VARTM process are discussed in Alms
and Advani [18]. In this process, as with IDVARTM, eight layers
of 5 cm · 5 cm woven glass fiber mat are cut and sealed with a
vacuum bag and the air is evacuated by applying the first vac-
uum to the outlet of the mold which compacts the fiber mats
under the external atmospheric pressure. The vacuum line is
then clamped just below the mold to hold the first vacuum.
Before the MWCNT/epoxy suspension is injected into the
closed mold, an outer chamber is formed above the bagging
film by placing a foam rubber frame which is covered by an ac-
rylic top sheet. A regulated higher vacuum is drawn into this
outer chamber, which pulls the bagging material away from
the woven glass fiber mats, creating an empty space between
the vacuum bag and the top layer of the glass mats. As soon as
the resin is introduced through the inlet, it immediately
rushes into this empty space. Once the top layer of the glass
mats is covered with resin, the resin supply is cut off and
the second vacuum, which is slightly higher than the first vac-
uum is held to continue relaxing the preform. This relaxation
expands the gaps between the glass mats making it easier for
the MWCNT/epoxy suspension to wick into the larger
a b Atmospheric Pressure
c Second Vacuum – Bell Jar d Atmospheric Pressure
Fig. 1 – Schematic of IDVARTM process (a) fiber mats
compacted and sealed under the bag with first vacuum
applied at the vent. (b) MWCNT suspension injected into the
mold using Omega tubing. (c) Second vacuum applied by
keeping the mold under a bell jar. Suspension infuses into
the preform. (d) Second vacuum removed. Suspension
squeezes into the preform under atmospheric pressure.
 CARBON 4 8 ( 20 1 0 ) 3 6 9 2–36 9 9
Fig. 2 – Hybrid composite sample, of thickness 0.2 in.
channels between the glass fiber mats due to the intrinsic cap-
illary pressure. The fact that the first vacuum line is clamped
helps in keeping the MWCNT suspensions between the cham-
ber and the mold for some time, facilitating percolation rather
than allowing flow through the outlet tube into the vacuum
bucket. After the MWCNT/epoxy suspension fills the gaps be-
tween the glass fiber mats, it starts to wick laterally into the
glass fiber mats by capillary pressure. The second vacuum is
then released after 30 min to reapply atmospheric pressure
onto the mold, and squeeze the MWCNT/epoxy suspension
into the fiber mat. The first vacuum is then reapplied to draw
off the excess MWCNT/epoxy suspension and recompress the
fabric and obtain the desired higher fiber volume fraction for
the composite. The manufactured hybrid composite samples
were post-cured in an oven at 100 C for 4 h. Fig. 3 schemati-
cally shows the FFC process.
2.3. Interlaminar shear strength characterization
In this study, we used the compression shear test to measure
the ILSS of the manufactured composites as a means to quan-
tify the effects of the addition of MWCNT to the resin [17].
When the transverse shear load experienced by a lami-
nated composite exceeds the interlaminar shear strength
(ILSS), a delamination failure will occur. To measure the ILSS
of a composite directly, a pattern of pure shear stress should
be generated between laminae to induce a pure interlaminar
shear failure. Any normal loads introduced perpendicular to
the fiber layers can alter the failure process, making it difficult
to determine an accurate value for the ILSS. A number of dif-
ferent tests have been developed for the purpose of character-
izing the ILSS. These experiments are designed to load the
Fig. 3 – Schematic of flow flooding chamber (FFC) process.
3695
specimen to failure in interlaminar shear and the average
shear stress across the failure surface is then taken as the
ILSS. Comparing the available methods, the short beam shear
(SBS) method is the simplest and therefore most commonly
used in practice. Based on classical beam theory, it causes
transverse shear failure through three point bending as
shown in Fig. 4a. The main drawback of this test however, is
that not all specimens fail in transverse shear. Some fail by
crushing at the load point or flexure due to the bending, or
by a combination of these mechanisms together with trans-
verse shear. The compression shear test (CST), Fig. 4b is de-
signed to create direct shear load along the inter-laminate
interface and force the specimen to break apart in pure shear
[19]. FE modeling of both SBS and CST by Rosselli and Santare
[20] clearly shows that the CST gives a simpler and more well
defined shear stress distribution compared to SBS. For SBS,
the shear stress distribution is not uniform and the maxi-
mum shear stress occurs near the loading nose. In the case
of CST, the shear stress distribution is almost uniform
through the thickness with two peaks near the loading sur-
face edges. Further comparison of these two methods and
justification for using CST as the more appropriate method
is presented in Rosselli and Santare [20].
The CST samples were cut from the manufactured com-
posite laminates described in the earlier sections of this pa-
per. The shear test fixture and the approximate size of the
samples (0.4 in. in length, 0.2 in. in width and 0.15 in. in thick-
ness), are shown in Fig. 5a and b, respectively. The left loading
surface contacts the left half of the top surface, which is per-
pendicular to the laminate planes and the right loading sur-
face contacts the right half of the bottom surface of the
specimen. Two vertical guides support the left and the right
sides of the specimen to prevent it from rotating or moving
horizontally. The right loading surface is fixed in position,
and the left loading surface moves down under the applied
load, to generate a direct interlaminar shear stress along
the central plane of the specimen until failure. The shear
force applied to the specimen at failure is then divided by
the area of the failure plane to determine the average shear
stress at failure, which is reported as the interlaminar shear
strength (ILSS) of the specimen.
3. Results and discussion
3.1. IDVARTM
Fig. 6 shows the ILSS results for the various composite lami-
nates manufactured with the IDVARTM process. For each
manufacturing process 17–20 samples were tested. The aver-
age value for ILSS is reported with the standard deviation
shown by the error bars. The first two bars are for samples
prepared with resin subjected to 20 h of bath sonication.
The control (the left bar of the two) has no MWCNT while
the test specimen (the right of the two) has 0.5% MWCNT by
weight. Similarly, the second set of two bars is for samples
prepared with resin subjected to 6 h of bath sonication. The
third set of bars is for samples prepared with resin subjected
to 20 h of tip sonication. The fourth set of bars is for samples
prepared with resin subjected to 6 h of tip sonication. The
next to last set of bars are for samples prepared with 2 min
3696 CARBON 4 8 ( 2 0 1 0 ) 3 6 9 2 –3 6 9 9
Fig. 4 – (a) Short beam shear (three point bending) test. (b) Compression shear test.
Fig. 5 – (a) Compression shear test fixture with sample loaded. (b) Typical test sample with dimensions.
Fig. 6 – The ILSS comparison for control and 0.5% MWCNT
specimens manufactured using the IDVARTM process
subjected to different sonication cycles. The number of
samples tested for each case were between 17 and 20.
of tip sonication. The last bar represents the average ILSS for
samples prepared with unmodified resin (resin not subjected
to sonication).
From Fig. 6, we notice that the unmodified epoxy compos-
ite samples (the right-most bar) gave a lower ILSS than the
samples that were subjected to sonication (all the other bars).
However, by comparing the bars in each set of two, the results
also show that in each case, the sonicated resin performed
about equally well, with or without the addition of nanotubes.
This indicates that the increase in ILSS relative to unmodified
resin is more likely caused by sonication rather than by the
addition of nanotubes. Among the different suspension prep-
aration methods, we see that composites prepared using 20-h
bath and 6-h tip sonication show no significant ILSS enhance-
ment due to MWCNT while 6-h bath sonication shows a slight
decrease in ILSS and 20-h tip sonication shows a larger reduc-
tion in ILSS. In addition, we found that a resin suspension
sonicated for 2 min with an immersed tip, gave nearly the
same ILSS as the 20-h bath. Statistically there is no significant
difference between ILSS for these two cases. The immersed
tip method also gave a very low standard deviation of about
5%. It is important to note, that if a researcher had performed
this experiment without subjecting the unreinforced epoxy to
the sonication processes, they might have drawn the conclu-
sion that the nanotubes had led to the enhancement of the
ILSS rather than the sonication process.
To determine the effectiveness of adding 0.5% MWCNT for
enhancing ILSS of hybrid composites made using IDVARTM,
we performed a statistical analysis to compare all control
samples containing only the resin subjected to different sus-
pension preparation methods to the 0.5% MWCNT epoxy sub-
jected to the same suspension preparation methods. The
overall average for the ILSS of 0.5% MWCNT loaded compos-
ites was 30.09 ± 5.04 MPa compared to the average for the con-
trol samples of 31.84 ± 4.24 MPa, a decrease of 5.8% in ILSS for
MWCNT hybrid composites. We performed a Student’s t-test
 CARBON 4 8 ( 20 1 0 ) 3 6 9 2–36 9 9
to determine the statistical significance of the difference and
a single p-value was derived from all the data collected. From
a statistical viewpoint, if the p-value is less than 0.05, the data
from different groups can be considered statistically distinct
at the 95% confidence level, otherwise they are assumed to
belong to the same population. The smaller the p-value, more
significant is the difference among groups. The p-value for
this data is 0.026 hence the data from these two groups are
statistically distinct at the 95% confidence level. The statisti-
cal analysis is summarized in Table 1. The statistical analysis
shows that the 0.5% MWCNT epoxy composites manufac-
tured by IDVARTM actually have lower ILSS than the control
samples. The results shown in Fig. 6 indicate that the addition
of 0.5% MWCNT into the resin has a small negative effect on
the ILSS of the composites manufactured using the IDVARTM
method. In addition, the results indicate that 2-min tip soni-
cation is as effective as the 20-h bath sonication method for
improving the ILSS. From IDVARTM we found that of all the
sonication methods, 2-min tip and 20-h bath sonication are
the most effective suspension preparation methods.
Fundamentally, FFC and IDVARTM are very similar manu-
facturing techniques and both are based on vacuum-assisted
resin transfer molding (VARTM) process with slight varia-
tions. So, we concluded that the results from IDVARTM exper-
iment for suspension preparation could be applied for FFC. To
confirm this, in a separate experiment, we prepared 2-min tip
sonication and 20-h bath sonication suspensions and infused
them via FFC process. We found that ILSS of samples pre-
pared by the two sonication methods were similar. Therefore,
for the FFC manufacturing method (discussed below) we will
use only the 2-min tip sonication, significantly reducing the
time required for the suspension preparation.
3.2. FFC
To explore the possibility that the effectiveness of adding
MWCNT to enhance ILSS could be influenced by the manufac-
turing method, we prepared another set of composite speci-
men using the FFC method. Modified epoxy glass fiber
hybrid composites containing 0.5% MWCNT and control sam-
ples (without the addition of nanotubes) were both prepared
by the FFC method using the 2-min tip agitation suspension
preparation method. We measured the ILSS using the CST
on 54 samples of Control and 43 samples of 0.5% hybrid com-
posite and performed a statistical analysis to compare all the
control samples to the 0.5% MWCNT epoxy composites to
determine if the addition of MWCNT had an effect on the
Table 1 – Summary of Student’s t-test for samples prepared
by IDVARTM method.
Statistical parameter IDVARTM
Control 0.5%
Number of samples 69 73
Mean (MPa) 31.84 30.09
Standard deviation (MPa) 4.24 5.04
Estimate for difference (MPa) 1.751
95% CI for difference (MPa) ( 3.294, 0.208)
p-Value 0.026
3697
ILSS. We found that the overall average for the ILSS of 0.5%
MWCNT loaded composites was 32.82 ± 3.87 MPa compared
to average for the control samples of 27.07 ± 3.99 MPa, an in-
crease of 21.3%. A Student’s t-test shows that for the FFC
manufacturing process, the addition of MWCNT significantly
increased the ILSS. The statistical analysis is summarized in
Table 2.
In IDVARTM, there is initially flow across the preform due
to line injection. After application of the second vacuum,
there is an increase in permeability due to preform relaxation.
In spite of the high permeability, there is sometimes incom-
plete saturation of the fiber tows because of the highly vis-
cous nature of the resin. When the percentage of nanotubes
is increased, they may be filtered out before reaching the bot-
tom fiber mat. Due to this incomplete saturation, nanoparti-
cles may not be present in sufficient numbers in between
the preform in certain areas, resulting in lower ILSS.
In FFC, the vacuum bag is raised more than in IDVARTM.
This results in better relaxation of the preform and higher per-
meability. When the resin is injected by a single port, it goes to
the top of the mat and starts to percolate downward with the
help of capillary action and gravity. Apart from this higher
permeability; the tool is heated and maintained at 40 C to
keep the viscosity of the nanotubes suspension relatively
low. This helps the resin to flow through the preform more
easily and saturate the fiber tows. Better flow of nanoparticles
in between fiber mats helps increase ILSS enhancement.
3.3. Material variability
To explore the influence of material variability, we manufac-
tured and performed the CST test on composites prepared
from two different batches of resin and fibers. The same ap-
proach was followed, in which the control samples and 0.5%
MWCNT loaded composites were made with FFC and IDV-
ARTM methods and all were subjected to the 2-min tip agita-
tion suspension preparation method. Fig. 7 shows that for the
most part, there is a batch-to-batch variability in ILSS of both
control and 0.5% MWCNT loaded samples made using both
IDVARTM and FFC. The single exception is the last pair of bars
on the right of the figure, indicating that changing the nano-
tube vendor did not significantly affect the ILSS. Another re-
sult to note is that the ILSS of the control samples reduced
as we changed batches of resin and glass fiber for both the
FFC and IDVARTM process. The ILSS of 0.5% MWCNT loaded
epoxy made from IDVARTM also reduced as we changed the
Table 2 – Summary of Student’s t-test for samples prepared
by FFC method.
Statistical parameter FFC
Control 0.5%
Number of samples 54 43
Mean (MPa) 27.07 32.82
Standard deviation (MPa) 3.99 3.87
Estimate for difference (MPa) 5.745
95% CI for difference (MPa) (4.152, 7.338)
p-Value 0.0002
3698 CARBON 4 8 ( 2 0 1 0 ) 3 6 9 2 –3 6 9 9

The results of all the above statistical analyses show that

although there is a significant difference in the value of the
ILSS measured as one changes the resin and the fiber batch,
for both batches, the addition of MWCNT increases the ILSS
if the composites are manufactured using the FFC method
and does not increase ILSS if they are manufactured using
IDVARTM.

4. Conclusions

As originally conceived, this study was conducted to deter-

mine if the ILSS of glass fiber-reinforced composites could
be increased by adding a 0.5% weight fraction of carbon nano-
tubes to the resin and to what extent any enhancement effect
is influenced by resin processing history, variability in raw
materials, and the manufacturing process. When 0.5%
Fig. 7 – Summary of results showing the effect of MWCNT modified epoxy glass fiber hybrid composites were
manufacturing process, batch variability of resin and glass made by the IDVARTM process, we did not see any improve-
fiber; and change of MWCNT manufacturer on ILSS. ment in ILSS due to the addition of MWCNT regardless of
the suspension preparation method. From this result, we
hypothesize that in many instances in the literature,
resin and glass fiber but the ILSS of 0.5% MWCNT samples
researchers have neglected to subject the control samples of
made by FFC increased as we changed the batch of materials.
unreinforced resin to the same identical process history as
The results in Table 3 clearly show a significant influence on
the resin suspension containing the nanotubes. When this
ILSS by changing the resin and fibers from one batch to another
is the case, any improvements seen in the ILSS for hybrid
while no influence was found due to the change in MWCNT
composites may be the result of sonication which brings a
manufacturer (from ILJIN to Helix). For specifics regarding the
change in the viscosity and surface tension of the epoxy sys-
materials and suppliers, please refer Section 2.1.
tem affecting the ILSS, rather than the addition of nanotubes,
As an overall test of the effectiveness of using MWCNT to
as seen in Fig. 6. One possible explanation for this is that
enhance ILSS, all the control samples and all the 0.5%
when we sonicate the epoxy resin, bubbles form in the resin
MWCNT modified epoxy glass fiber hybrid composites made
system due to small scale cavitation. With additional ultra-
by FFC process were grouped together, irrespective of fiber, re-
sonic energy, these bubbles are alternately compressed and
sin or nanotube batch, and analyzed. We found a 41.6% in-
enlarged. At some point, they collapse giving rise to a local-
crease in ILSS from an average value of 25.21 MPa of the 90
ized bursts of energy which heats the resin resulting in a sig-
control samples with a standard deviation of 4.55 MPa to an
nificant decrease in the viscosity [21] and lowering of the
average value of 35.76 MPa for the 99 hybrid composite sam-
surface tension. When the surface tension of the resin system
ples containing 0.5% MWCNT with a standard deviation of
is reduced, wettability is increased thus potentially increasing
4.58 MPa. The Student’s t-test showed that the difference
the interfacial strength between the matrix and fibers [22].
was significant as the p-value calculated was very low. From
The decrease in viscosity and surface tension of the epoxy re-
Table 3, we see that ILSS of control samples made by IDV-
sin system due to ultrasonic agitation may result in better re-
ARTM is higher than for those made by FFC. Due to the appli-
sin infiltration into the preform and a better fiber–matrix
cation of higher second vacuum in FFC, the vacuum bag is
interface improving the ILSS properties. A statistical analysis
significantly raised as compared to IDVARTM case. This can
of the different suspension preparation methods indicated
upset the nesting of the fabric layers in the control samples
that 2-min tip sonication method and 20-h bath sonication
made by FFC and could explain the higher ILSS in IDVARTM
method were the best of the suspension preparation methods
than FFC for the control samples.
and gave comparable results for the ILSS of the composite,

Table 3 – Summary of Student’s t-test for samples made by FFC and IDVARTM with first and second batch of materials; last
two columns show samples made by FFC with second batch of materials using nanotubes from Iljin and Helix.
Statistical parameter IDVARTM FFC FFC-II batch
Control 0.5% Control 0.5% Iljin Helix
I batch II batch I batch II batch I batch II batch I batch II batch

Number of samples 69 37 73 37 54 36 43 29 29 27
Mean (MPa) 31.84 27.32 30.09 26.23 27.07 22.41 32.82 38.83 38.8 37.15
Standard deviation (MPa) 4.24 3.40 5.04 3.75 3.99 3.89 3.87 3.90 3.9 3.42
Estimate for difference (MPa) 4.514 3.853 4.664 6.015 1.68
95% CI for difference (MPa) (3.008,6.020) (2.159,5.547) (2.979,6.348) ( 7.885, 4.146) ( 0.23, 3.65)
p-Value 0.0002 0.0002 0.0002 0.0002 0.092
 CARBON 4 8 ( 20 1 0 ) 3 6 9 2–36 9 9
with or without nanotubes. Therefore, to reduce the suspen-
sion preparation time without compromising the quality of
dispersion, we chose 2-min tip sonication for the rest of the
experiments reported in this study.
Unlike IDVARTM when 0.5% MWCNT and control samples
were manufactured using the FFC, the average ILSS increased
from 27.07 to 32.82 MPa (a 21.3% improvement). This suggests
that the manufacturing process may play a critical role in
MWCNT distribution and hence ILSS enhancement. The pri-
mary difference between FFC and IDVARTM is that the FFC
process offers the operator more control to regulate the vac-
uum and temperature as compared to IDVARTM. Heating of
the mold plate in FFC reduces the viscosity of the 0.5%
MWCNT loaded epoxy resin promoting the suspension flow
in between the fiber mats. Permeability of the mats is also in-
creased due to a higher second vacuum applied locally by the
chamber on top of the fiber mats. Injection by a port on the
side of the glass fiber mats in FFC allows the resin to flood
the top of the glass fiber mats and start percolating by gravity
and capillary action compared to line injection through the
omega tube in IDVARTM where the driving force is mainly
the pressure difference. Consequently, better flow and satura-
tion of fiber tows results in FFC than IDVARTM and contribute
towards the increase in the ILSS of the hybrid composites
made using the FFC method. For these reasons, FFC is a more
conducive manufacturing process in terms of increasing the
ILSS of hybrid composites.
The batch-to-batch variability of raw materials also influ-
enced the ILSS. This reinforces the conclusion of Boeger
et al. [16] that the batch-to-batch variability of raw materials
such as resin and glass fiber mat, can have a significant influ-
ence on ILSS. Our results support the hypothesis that the var-
iation in ILSS enhancement reported in literature from 0% to
27% can be attributed, at least in part, to the different type of
raw materials and manufacturing processes used to make the
hybrid composites.
Acknowledgements
The authors wish to acknowledge the help of K. Schneider
and B. Lauke of the Institute of Polymer Research, Dresden,
Germany for providing the information on design of the CST
fixture. We also thank Pau Geli, University of Delaware for
his help in developing the FFC manufacturing set up and Dr.
Chaoying Ni and Frank Kriss for their SEM expertise.
R E F E R E N C E S
[1] Fan ZH, Santare MH, Advani SG. Interlaminar shear strength
of glass fiber reinforced epoxy composites enhanced with
multi-walled carbon nanotubes. Compos Pt A: Appl Sci
Manuf 2008;39(3):540–54.
[2] Schadler LS, Giannaris SC, Ajayan PM. Load transfer in
carbon nanotube epoxy composites. Appl Phys Lett
1998;73(26):3842–4.
[3] Hsiao KT, Alms J, Advani SG. Use of epoxy/multiwalled
carbon nanotubes as adhesives to join graphite fibre
reinforced polymer composites. Nanotechnology
2003;14(7):791–3.
3699
[4] Zhou YX, Pervin F, Rangari VK, Jeelani S. Fabrication and
evaluation of carbon nano fiber filled carbon/epoxy composite.
Mater Sci Eng A: Struct Mater Prop Microstruct Process
2006;426(1–2):221–8.
[5] Gojny FH, Wichmann MHG, Fiedler B, Bauhofer W, Schulte K.
Influence of nano-modification on the mechanical and
electrical properties of conventional fibre-reinforced
composites. Compos Pt A: Appl Sci Manuf 2005;36(11):1525–35.
[6] Gojny FH, Wichmann MHG, Kopke U, Fiedler B, Schulte K.
Carbon nanotube-reinforced epoxy-composites: enhanced
stiffness and fracture toughness at low nanotube content.
Compos Sci Technol 2004;64(15):2363–71.
[7] Yokozeki T, Iwahori Y, Ishiwata S. Matrix cracking behaviors in
carbon fiber/epoxy laminates filled with cup-stacked carbon
nanotubes (CSCNTs). Compos Pt A: Appl Sci Manuf
2007;38(3):917–24.
[8] Veedu VP, Cao AY, Li XS, Ma KG, Soldano C, Kar S, et al.
Multifunctional composites using reinforced laminae with
carbon-nanotube forests. Nat Mater 2006;5(6):457–62.
[9] Zhu J, Peng HQ, Rodriguez-Macias F, Margrave JL,
Khabashesku VN, Imam AM, et al. Reinforcing epoxy
polymer composites through covalent integration of
functionalized nanotubes. Adv Funct Mater 2004;14(7):643–8.
[10] Calvert P. Nanotube composites – a recipe for strength.
Nature 1999;399(6733):210–1.
[11] Thostenson ET, Ren ZF, Chou TW. Advances in the science
and technology of carbon nanotubes and their composites: a
review. Compos Sci Technol 2001;61(13):1899–912.
[12] Njuguna J, Pielichowski K, Alcock JR. Epoxy-based fibre
reinforced nanocomposites. Adv Eng Mater 2007;9(10):835–47.
[13] Siddiqui NA, Woo RSC, Kim JK, Leung CCK, Munir A. Mode I
interlaminar fracture behavior and mechanical properties of
CFRPs with nanoclay-filled epoxy matrix. Compos Pt A: Appl
Sci Manuf 2006;38:449–60.
[14] Beyakrova E, Thostenson ET, Yu A, Kim H, Gao J, Tang J.
Multiscale carbon nanotube-carbon fiber reinforcement for
advanced epoxy composites. Langmuir 2007;23:3970–4.
[15] Wichmann MHG, Sumfleth J, Gojny FH, Quaresimin M, Fiedler
B, Schulte K. Glass–fibre-reinforced composites with
enhanced mechanical and electrical properties – benefits and
limitations of a nanoparticle modified matrix. Eng Fract Mech
2006;73(16):2346–59.
[16] Boeger L, Wichmann MHG, Meyer LO, Schulte K. Load and
health monitoring in glass fibre reinforced composites with
an electrically conductive nanocomposite epoxy matrix.
Compos Sci Technol 2008;68(7–8):1886–94.
[17] Lauke B, Beckert W, Schneider K. Interlaminar shear strength
evaluation of curved composite samples. Appl Compos Mater
1994;1:267–71.
[18] Alms J, Advani SG. Simulation and experimental validation of
flow flooding chamber method of resin delivery in liquid
composite molding. Compos Pt A: Appl Sci Manuf
2007;38(10):2131–41.
[19] Schneider K, Lauke B, Beckert W. Compression shear test (CST)
– a convenient apparatus for the estimation of apparent shear
strength of composite materials. Appl Compos Mater
2001;8:43–62.
[20] Rosselli F, Santare MH. Comparison of the short beam shear
(SBS) and interlaminar shear device (ISD) tests. Compos Pt A:
Appl Sci Manuf 1997;28(6):587–94.
[21] Liu L, Huang YD, Zhang ZQ, Jiang B, Nie J. Ultrasonic
modification of aramid fiber–epoxy interface. J Appl Polym Sci
2001;81(11):2764–8.
[22] Huang YD, Liu L, Qiu JH, Shao L. Influence of ultrasonic
treatment on the characteristics of epoxy resin and the
interfacial property of its carbon fiber composites. Compos Sci
Technol 2002;62:2153–9.