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Composites: Part A 39 (2008) 540554

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Interlaminar shear strength of glass ber reinforced epoxy

composites enhanced with multi-walled carbon nanotubes
Zhihang Fan, Michael H. Santare, Suresh G. Advani *
Department of Mechanical Engineering and Center for Composite Materials, University of Delaware, Newark, DE 19716, USA

Received 8 May 2007; received in revised form 20 November 2007; accepted 23 November 2007

Abstract

In this study, we examine the interlaminar shear strength (ILSS) of traditional glass ber reinforced epoxy composites enhanced by
strategically injecting multi-walled carbon nanotube (MWNT)epoxy suspensions into stationary glass ber mats. The suspensions were
prepared by combining the techniques of high-speed mechanical stirring, ultrasonic agitation and acid oxidation. Two types of process
designs were introduced to fabricate the hybrid MWNT/glass/epoxy composites and their relative merits were discussed. Short beam
shear (SBS) and compression shear tests (CST) were conducted on the manufactured components to characterize the inuence of the
process and the weight percentage of nanotubes on the ILSS. The results show that the introduction of MWNT into the composite
increased the ILSS by up to 33%. The preferential orientation of the MWNTs in the thickness direction was found to contribute to
the increase in the interlaminar shear properties.
2007 Elsevier Ltd. All rights reserved.

Keywords: A. Preform; A. Nano structures; B. Interface/interphase; B. Mechanical properties; Capillary ow

1. Introduction Many researcher have explored other ways to improve

While laminated ber reinforced polymermatrix
composite materials have been used successfully in many
industries such as aerospace, automobile, marine, military,
etc., their interlaminar shear strength (ILSS) is usually a
limiting design characteristic. This is because conventional
manufacturing techniques do not produce reinforcing
bers oriented in the thickness direction to sustain trans-
verse load [1]. Improving ILSS has long been an important
goal in the ber reinforced composites eld, and to this
end, dierent approaches have been tried. Some of the
more eective attempts have been weaving bers in the
thickness direction or using Z-pins to connect the laminae
[27]. However, these techniques are labor intensive and
require additional manufacturing processes that can
greatly increase the cost of the resulting components [8].
*
Corresponding author.
E-mail address: advani@udel.edu (S.G. Advani).
the ILSS by using nanoparticles and carbon nanotubes
(CNT) [917]. Zhou et al. [10] found that adding 2 wt%
carbon nanobers (CNF) into glass ber reinforced
epoxy composites increased the ILSS by 22.3%. In 2005,
Gojny et al. [16] gained 20% improvement in ILSS by add-
ing 0.3 wt% double-walled carbon nanotube (DWNT) into
ber reinforced epoxy composites. Wichmann et al. [11]
also got similar enhancement of ILSS, as well as electrical
conductivity by using the DWNT. Yokozeki et al. [12]
found that carbon ber reinforced composites can benet
from dispersion of cup-stacked carbon nanotubes
(CSCNTs) between ber mats and that these can delay
the onset of matrix cracking. Siddiqui et al. [13] found that
adding organoclay nanoparticles increases both crack
growth resistance and fracture toughness in carbon ber
reinforced polymer composites. Zhu et al. [18] proposed
an innovative way to create CNT/ber/polymer compos-
ites by coating SWNTs on the surface of glass bers before
lling the mold with vinyl ester and got 35% enhancement
in ILSS. Veedu et al. extended this method by growing

1359-835X/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2007.11.013
 Z. Fan et al. / Composites: Part A 39 (2008) 540554
Fig. 1. Schematic of CNTs distributed between glass ber layers which could enhance the interlaminar shear strength (ILSS).
MWNTs on the SiC woven fabrics to make 3D hybrid
composites and achieved remarkable improvement in inter-
laminar fracture toughness (424%), hardness, delamination
resistance, and thermal and electrical conductivities [17].
All these results have shown an encouraging path toward
CNT application in ber reinforced structure composites
and suggest that distributing a carbon nanotube (CNT)/
epoxy suspension between layers, as shown in Fig. 1A
may improve the ILSS of ber reinforced laminated com-
posites. Further, if the CNT suspension is guided to ow
in the thickness direction, the CNT in the suspension might
orient in the thickness direction due to shear [19] as shown
schematically in Fig. 1B. The preferentially orientated CNT
between glass ber layers in the thickness direction could
enhance the ILSS more eectively if the load from the
matrix can be transferred eectively to the nanotubes.
To test this hypothesis, we fabricated glass/epoxy compos-
ites with a small quantity of oxidized multi-walled carbon
nanotubes (OMWNT) dispersed in the epoxy. The
OMWNT/epoxy suspension was injected into the glass pre-
forms using the vacuum assisted resin transfer molding
(VARTM) method and a newly developed injection and double
vacuum assisted resin transfer molding (IDVARTM) method.
The interlaminar shear strength (ILSS) of the composite was
measured using the short beam shear (SBS) and compression
shear test (CST) methods. Control samples were manufactured
in the same manner but using neat epoxy to compare the ILSS
of unenhanced composites with composites containing
OMWNT at 0.5, 1 and 2 wt%. Statistical analysis was carried
out to determine the level of statistical signicance of the results.
2. Experiments
2.1. Materials
In an attempt to keep the material costs relatively low,
multi-walled carbon nanotubes (MWNT) were chosen over
541
single-walled carbon nanotubes (SWNT are still very expen-
sive). The MWNT were made by CVD (>95%) and pur-
chased from the ILJIN nanotech Company, Korea. The
diameters of the nanotubes were of the order of 1020 nm
and the length was between 0.5 and 15 lm. The woven glass
ber mats were supplied by Saint-Goban Vetrotex Com-
pany and had a ber density of 800 g/m2. The resin used
was epoxy SC-15 from Applied Polymetric Inc.
2.2. Preparation of MWNT suspensions
Much research has been conducted to develop methods
to separate MWNT and disperse them in various polymer
melts [18,2030]. In this study, we used a technique com-
bining high-speed mechanical stirring, ultrasonic agitation
and acid oxidation to create a well dispersed MWNT
suspension.
First, approximately 1.2 g of MWNT was oxidized by
reuxing in 48 ml of a 3:1 mixture of sulfuric and nitric acid
for 30 min at 140 C and then ltering with distilled water
(3000 ml) to wash away any acidic residue from the nano-
tubes surfaces. Then the oxidized MWNTs (OMWNTs)
were placed in acetone and agitated in an ultrasonic water
bath for 1 h. A predetermined amount of epoxy (depending
on desired OMWNT concentration) was added and the
mixture was agitated for another 1 h. Finally, the mixture
of MWNT, epoxy and acetone was placed into a water
bath at 80 C and continuously stirred by a high-speed
magnetic stirrer for 4 h to fully evaporate the acetone. This
method generated a nearly uniformly separated MWNT/
epoxy suspension as shown in Fig. 2. Although there were
still a number of 0.51 lm MWNT aggregates in the sus-
pension, the fraction of separated, single MWNT bers
was signicant. However, the oxidizing process results in
the attrition of MWNT (OMWNT) length to an average
of about 500 nm from the original MWNT length of about
542 Z. Fan et al. / Composites: Part A 39 (2008) 540554
15 lm. due to the strong acid reaction with the open molec-
ular chains on the MWNT surfaces [20,21,31].
2.3. Manufacturing process
2.3.1. Vacuum assisted resin transfer molding (VARTM)
VARTM is a well-established method for fabricating
glass or carbon ber epoxy composites with 5055% ber
volume fractions. Distribution-media-assisted VARTM
has an additional advantage in that the suspension will
ow across the ber mat in the thickness direction. Because
OMWNT typically align in the shearing direction [19], it is
possible that the resin ow in the thickness direction will
help to create preferential orientation of OMWNT in the
thickness direction. Thus, we rst attempted the conven-
tional distribution-media-assisted VARTM method to
manufacture the hybrid OMWNT/glass/epoxy composites.
Eight layers of the glass ber fabric were stacked
together and a distribution media was placed on the top
as shown in Fig. 3. A vacuum was applied to the stack to
provide the pressure gradient needed to inltrate the sus-
pension into the preform. Another consequence of the
applied vacuum is that the stacked ber mats compress
due to the external atmospheric pressure on the sealed
bag, increasing the ber volume fraction. The OMWNT/
epoxy suspension was drawn through a tube into the mold.
Because the distribution media had much higher perme-
ability than the glass ber mats [32], the OMWNT suspen-
sion preferentially lls the distribution media rst before
owing across the ber layers in the thickness direction.
As soon as the suspension arrives at the vent located at
the bottom, the injection is discontinued but the vacuum
is maintained. After the suspension cures, the vacuum is
discontinued and the hybrid OMWNT/glass/epoxy com-
posite part is de-molded.
One disadvantage of this VARTM process is that the
permeability of the compressed ber preforms is an order
of magnitude lower than the uncompressed ber performs
(Kalong_compress = 7.9  1012 m2 along ber direction and
Kacross_compress = 1.39  1013 m2 across ber direction).
Fig. 2. Transmission electron microscope (TEM) image of OMWNTs in suspension.
The vacuum-induced compression reduced the total thick-
ness of the eight glass ber mats from 8.4 to 4.4 mm, result-
ing in a higher ber volume fraction and consequently a
reduced spacing between the bers. The reduced spacing
between glass bers was observed to be of the order of
5 nm to 10 lm [19]. This intra-ber spacing is small enough
to lter OMWNT from the suspension during the infusion.
Therefore, the concentration of OMWNT increases on the
upstream side as the suspension ows through the ber
mat. This increases the viscosity of the suspension and
reduces the ow into the fabric signicantly [21,28,33,34].
Thus, the driving pressure becomes insucient to over-
come this ltering and viscous resistance eect and the
OMWNT suspension fails to penetrate the glass ber mats
at concentrations higher than 0.5%.
For suspensions with higher concentrations, the
OMWNT blocked the ow at the top few ber layers
and the suspension was not able to wet the fabric com-
pletely. Gojny et al. [16] did not notice such ltering eect,
which might be due to the larger spacing between bers in
their RTM method as compared to our VARTM method.
But they also found that it would be very dicult to man-
ufacture a sample containing more than 0.5 wt% CNT in
the polymer because of the much higher viscosity of the
suspension.
Transmission electron microscopy (TEM) was used to
characterize the OMWNT orientations between the ber
mats for the 0.5% suspension. Since there will be many
bers or nanotubes at a selected location as shown in
Fig. 4, it will be important to use a description that can
embody many dierent directions. Thus, we chose a second
order orientation tensor method using image analysis [19].
An ellipse derived from the orientation tensor was drawn
for each image to indicate the orientation state of all
MWNTs in that image. An elongated ellipse signies a high
degree of preferential orientation in the direction of the
major axis as shown in Fig. 4, whereas a circle will signify
no particular preference of orientation. More details of this
method can be found in the reference by Fan and Advani
[19]. Due to the existence of the glass bers in the matrix,
 Z. Fan et al. / Composites: Part A 39 (2008) 540554 543

Fig. 3. Schematic of OMWNT/glass/epoxy composite being processed by the VARTM method to create preferentially oriented OMWNTs in the
thickness direction.

Fig. 4. TEM images of OMWNT orientation state (A) preferential orientation in the thickness direction between glass ber mats and (B) preferential
orientation in ow direction between two bers. The major axis of the ellipse signies the strength of the orientation state of the OMWNT while its
direction signies the direction of preferential orientation [19].

it is dicult to achieve successful sections for TEM to
observe the OMWNT orientation states between the glass
ber mats. But we did observe preferentially orientated
patterns of MWNTs in the thickness direction from all
the microtome sections taken. Under TEM, we observed
appreciable preferential orientation of the OMWNT
between the mats in the thickness direction, as shown by
the elongated ellipse in Fig. 4A. Examining the ow
through the gaps between the bers, OMWNT were also
found to be preferentially orientated in the ow direction
as shown in Fig. 4B.
Although the ow speed across the thickness direction is
low, the spaces between glass bers in a compacted
VARTM mold is much smaller than the spaces between
544 Z. Fan et al. / Composites: Part A 39 (2008) 540554
mats, on the order of 5 nm to 10 lm. Therefore, the shear
rate and the high viscosity can generate sucient shear
stress to aect the orientation state of the OMWNTs, as
we observed in Fig. 4 and in Ref. [19]. As discussed in that
paper, Brownian motion was found to have little eect on
the MWNT orientation state during the curing process
[19]. Fig. 4 shows that the orientation state of OMWNTs
is essentially the same after 24 h of curing.
Due to the limitations of the VARTM process discussed
above, processing of hybrid OMWNT/glass/epoxy com-
posites with OMWNT concentrations higher than 0.5%
requires the development of a modied process design.
2.3.2. Injection and double vacuum assisted resin transfer
molding (IDVARTM) method
To increase the concentration of OMWNT, we devel-
oped a new variation of the VARTM method, which we
term: injection and double vacuum assisted resin transfer
molding (IDVARTM). The IDVARTM method is similar
to the conventional distribution-media-assisted VARTM
method, but takes advantage of the capillary action of
the ber tows for enhanced infusion. With this method
we were able to inject suspensions of epoxy containing up
to 2 wt% concentration of OMWNT into the ber mats.
As depicted in Fig. 5, the procedure can be described in
the following steps:
Fig. 5. Schematic of injection and double vacuum assisted resin transfer molding (IDVARTM) manufacturing process.
Step (1) Eight layers of 5 cm  5 cm woven glass ber mat
are sealed with a vacuum bag and the air is evac-
uated by applying the rst vacuum, which is con-
nected to the outlet of the mold; the thickness of
ber mats shrinks from 8.4 mm down to 4.4 mm
due to the compression from the external atmo-
spheric pressure.
Step (2) The outlet is clamped to discontinue the rst vac-
uum and the OMWNT/epoxy suspension is
injected into the closed mold; excess suspension
is injected to over saturate the space between the
bag and the preform.
Step (3) The inlet is clamped and the entire closed mold is
placed into a second vacuum chamber for 30 min.
This releases the external atmosphere pressure
induced by the rst vacuum and allows the eight
compressed ber mats to recover some of their
original thickness, increasing the thickness back
to 6.8 mm. The recovery expands the gaps
between the glass mats making it easier for the
OMWNT/epoxy suspension to infuse into the lar-
ger channels between the glass ber mats by
intrinsic capillary pressure.
Step (4) After the OMWNT/epoxy suspension lls the
gaps between the glass ber mats, it starts to
infuse across into each glass ber mat by capillary
pressure.
 Z. Fan et al. / Composites: Part A 39 (2008) 540554 545

Step (5) The second vacuum is released to reapply atmo-
sphere pressure to the mold for 30 min to further
squeeze the OMWNT/epoxy suspension into the
ber mat. Although some OMWNTs are still
being ltered at this stage, this turns out to be
an advantage because the higher concentration
OMWMT/epoxy suspension will remain between
the ber mats where it is most needed to improve
the ILSS.
Step (6) After the OMWNT suspension lls the empty
regions within and between the ber mats, the rst
vacuum is reapplied to draw o the excess
OMWNT/epoxy suspension and recompress the
mold to obtain the desired higher ber volume
fraction.
posite manufactured using the traditional distribution-
media-assisted VARTM method in which, due to ltering,
the OMWNT did not penetrate through all the layers.
Fig. 6B shows a cross-section of a composite made using
the IDVARTM method. Notice that in Fig. 6B, the
OMWNT appear to be uniformly distributed between the
glass ber mats, as opposed to Fig. 6A where they do
not. To observe the OMWNTs in the hybrid composites
made from IDVARTM, we examined a fracture surface
of the sample under SEM. In Fig. 6C, OMWNTs are
clearly seen embedded in the matrix surrounding the glass
ber surface, which indicates that OMWNTs had success-
fully infused into the glass ber mats.
2.4. Interlaminar shear strength (ILSS) characterization

With the IDVARTM method, we successfully manufac-
tured OMWNT/glass/epoxy composites with up to 2 wt%
OMWNT concentration in the suspension without creation
of any dry regions or voids. Subsequent microscopy
showed the presence of nanotubes in the regions in the
interlaminar spaces between the ber mats. Fig. 6A shows
the cross-section of a hybrid OMWNT/glass/epoxy com-
When the transverse shear load experienced by a lami-
nated composite exceeds the interlaminar shear strength
(ILSS), a delamination failure will occur between the layers
of reinforcing bers. To measure the ILSS of a composite
directly, a pattern of pure shear stress should be generated
between laminae to induce an interlaminar shear failure.
Any normal loads introduced perpendicular to ber layers

Fig. 6. Cross-section of (A) OMWNT composite manufactured with conventional distribution-media-assisted VARTM process in which OMWNTs were
ltered and (B) OMWNT composite manufactured using IDVARTM in which the OMWNTs are distributed evenly between glass ber layers. (C) SEM
images of OMWNTs embedded in matrix on the glass ber surface after fracture of hybrid composite sample made from IDVARTM.
546 Z. Fan et al. / Composites: Part A 39 (2008) 540554
can alter the failure process, making it impossible to deter-
mine an accurate value for the ILSS.
A number of dierent tests (Fig. 7) have been developed
for the purpose of characterizing the ILSS. These experi-
ments are designed to load the specimen so that it fails in
interlaminar shear and the shear stress at failure is 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. 7A. The main drawback
of this test is that not all specimens fail in transverse shear.
Some fail by crushing at the load point or exure due to the
bending, or by a combination of these with transverse
shear. Several test methods (Fig. 7B and C) use axial tensile
or compressive loading to fail the sample in shear. In these
methods, the expected failure plane is actually loaded in
tension or compression simultaneously with the shear.
Therefore, the failure is a mixed-mode type of failure and
does not necessarily correspond to the ILSS. The curved-
double-cantilever-beam (CDCB) method characterizes
ILSS by recording the strength to tear the laminates apart
following an initial pre-crack between laminates (Fig. 7D).
The interlaminar loading pattern in this experiment starts
out as tension and gradually becomes shear making it ques-
tionable as a measure of the static shear strength. The com-
pression shear test (CST) is designed to create direct shear
Fig. 7. Geometry of the dierent experimental interlaminar shear tests [35,36].
load along the laminate interface and force the specimen to
break apart in pure shear (Fig. 7E). The advantages and
disadvantages of each method have been reviewed and dis-
cussed in the previous literature [1,3639] and we will not
attempt to reproduce that discussion here. In the present
work, we selected the short beam shear (SBS) and compres-
sion shear test (CST) methods to measure the ILSS of our
samples of glass ber reinforced composites made by the
IDVARM method.
2.4.1. Short beam shear (SBS) test
The short beam shear (SBS) test is designed to generate
interlaminar shear indirectly through bending and is the
most popular method to characterize the apparent inter-
laminar shear strength of unidirectional, ber-reinforced
composites (ASTM D 2344). As shown in Fig. 8, the spec-
imen is placed on two cylindrical supports and a cylindrical
head is moved down to apply a force at the center and gen-
erate an increasing transverse load until the rst failure is
recorded. The load at failure is then used to determine
the apparent interlaminar shear strength of the composite.
2.4.2. Compression shear test (CST)
We built a compression shear test (CST) device similar
to the one described in the paper by Schneider et al. [36],
with some minor modications. As shown in Fig. 9, in
the CST test, a specimen is placed between two clamps.
 Z. Fan et al. / Composites: Part A 39 (2008) 540554 547

Fig. 8. Picture of short beam shear (SBS) (ASTM D 2344).

Fig. 9. Picture of compression shear test (CST).

The left clamp contacts the left half of the top surface,
which is perpendicular to the laminate planes. Symmetri-
cally, the right clamp contacts the right half of the bottom
surface of the specimen. Two vertical guides support the
left and right sides of the specimen to prevent it from rotat-
ing or moving horizontally. The right clamp is xed in posi-
tion, and the left clamp moves down to generate direct
interlaminar shear along the central plane of the specimen
until failure. The load on the specimen at failure is divided
by the area of the failure plane to determine the interlam-
inar shear strength (ILSS) of the specimen.
3. Results and discussion
3.1. Short beam shear (SBS) test
In the SBS test, the determination of ILSS is based on
classical (BernoulliEuler) beam theory. For a beam of
rectangular cross-section loaded in three-point bending,
the maximum interlaminar shear stress occurs at the mid-
thickness of the beam between the center and end supports
and is calculated to be
3 PB
s  1 icant damage before the specimen fails by shear.
4 wt
where PB is the maximum load and w and t are the width
and the thickness of the beam, respectively. We selected a
span to thickness ratio for the samples of w/t = 4 as recom-
mended by the ASTM standards (ASTM D 2344). During
bending in SBS, the load increases proportionately with
deformation, until a peak load is reached. If the load drops
by 30% or more immediately after the peak load is reached,
it is assumed that the specimen failed in laminar shear and
the peak load is then used to determine the apparent ILSS.
The main advantage of the SBS is its simplicity. The
specimens are relatively easy to prepare and the test itself
is simple to conduct and requires little xturing. However,
the SBS gives an accurate measure of the ILSS value only if
pure interlaminar shear failure takes place. Many doubts
have been raised regarding the accuracy and reliability of
the SBS. The most common criticism is that in the SBS,
the specimen usually encounters other types of damage
before or concurrent with interlaminar shear failure, caus-
ing the specimen to fail by other than pure interlaminar
shear [8,40,41].
In Fig. 10A, the shear stress eld in half of a curved SBS
specimen is shown as calculated by nite element modeling
[1]. We can see from the gure, that the maximum shear
stress does not occur in the middle of the section; instead,
it occurs closer to the surface where the load is applied.
Additionally, a highly concentrated compressive stress
can be seen near the loading point. This compression is
in the transverse direction where the strength is not as high
as it is in the ber direction and therefore can cause signif-
In the present study, our tests were further complicated
due to the fact that we used woven glass ber reinforced
epoxy composites. These materials have a relatively tough
matrix and non-planar (undulating) interlaminar regions
and therefore can experience a variety of dierent failure
and damage modes before interlaminar shear failure occurs
under SBS loading. Fig. 11 shows a number of experimen-
548 Z. Fan et al. / Composites: Part A 39 (2008) 540554

Fig. 10. Contours of shear stress in specimen of (A) short beam shear and (B) compression shear test [1].

Fig. 11. Two typical curves of load vs. deection for a short beam shear specimen (A) and (B).

tal curves of SBS load vs. deformation for several speci- loaddeection behaviors in the gure. In Fig. 11A, the
mens cut from the same sample. We see two typical curve rises gradually and then drops suddenly showing a
 Z. Fan et al. / Composites: Part A 39 (2008) 540554 549

Fig. 12. SEM images of (A) interlaminar shear failure mode; (B) resin microcracks caused by compression; (C) indentation failure mode in SBS.

distinct failure load developed in the sample, while in Table 1

Fig. 11B, the curve rises, attens for some time and then Interlaminar shear strength (ILSS) of OMWNT/glass/epoxy composites
measured by short beam shear (SBS)
shows a small drop.
We found that in the case of the specimen generating a Specimen number ILSS (MPa)
curve such as Fig. 11A, we were able to observe a clear 0 wt% 0.5 wt% 1 wt%
interlaminar shear failure in the sample, as shown in 1 30.17 47.95 42.09
Fig. 12A. However, in case of Fig. 11B, we observed micro- 2 32.89 28.77 34.80
cracking of the resin inside the glass ber tows as shown in 3 41.21 29.09 35.31
4 31.58 31.55 41.07
Fig. 12B. It appears that this damage was caused by com- 5 31.03 26.31 35.50
pression in the glass ber tow. Some indentation failure, as 6 27.83 37.79 45.28
shown in Fig. 12C, was also observed for the specimens 7 31.37 39.57 36.09
that resulted in the type of curves shown in Fig. 11B. 8 33.86 27.22 37.03
Therefore, for specimens exhibiting shear load curves such Average 32.49 33.53 38.40
as Fig. 11B, we assumed that some other damage modes Standard deviation (%) 12.2 22.6 10.1
contributed to the failure. The calculated ILSS therefore p-Value 0.09
represented ultimate failure under a combination of dier-
ent failure modes in the tested specimen, for example, resin
microcracks, indentation and interlaminar shear. This type
of combined failure was found in 90% of the tested speci- analysis. From a statistical viewpoint, if the p-value is less
mens resulting in a large standard deviation in the measure- than 0.05, the data from dierent groups can be considered
ment data as shown in Table 1 and Fig. 13. Although, the statistically distinct, otherwise they are assumed to belong
average ILSS as measure by SBS, of the composites to the same population. The smaller the p-value, the more
improved 3.2% by adding 0.5 wt% OMWNT in epoxy, signicant the dierences among dierent groups. The
and 18.2% for 1 wt% OMWNT, the standard deviation p-value for the data from the SBS test was 0.09 (higher
of each group of specimens was 1022.6%, as shown by than 0.05). Therefore, the ILSS values determined by the
error bars in Fig. 13. Because the deviation among speci- SBS test for samples containing dierent OMWNT concen-
men groups is not much dierent from the deviation within trations were not statistically dierent. Put another way,
each group, we applied the analysis of variance (ANOVA) based on this statistical analysis, we could not distinguish
method to statistically analyze the dierence. For the a dierence in the interlaminar shear strength of dierent
details of ANOVA, see for example, [42]. Only the single hybrid MWNT/glass/epoxy composites using the short
p-value derived from all the data was calculated for this beam shear (SBS) test.
550 Z. Fan et al. / Composites: Part A 39 (2008) 540554

Fig. 13. Chart of ILSS of the hybrid OMWNT/glass/epoxy composites at dierent OMWNT concentrations in epoxy resin measured using the SBS
method.

3.2. Compression shear test (CST)
The advantage of the CST method is that it can create
pure interlaminar shear stress between ber planes and
therefore minimizes the inuence of other possible failure
modes, such as compression, indentation and exure.
Fig. 10B shows the shear stress eld in a specimen loaded
in CST as calculated by the nite element method [39].
One can easily identify the maximum interlaminar shear
stress along the middle plane, which will cause interlaminar
shear failure. Similar to the stress contours for the SBS test,
we can still observe stress concentration at the surface where
the load is applied. However, this stress concentration is
directed along the ber direction and because the strength
is higher in this direction, the incidence of compressive
failure will be minimized. Thus, the CST is seen to be a more
reliable method to characterize the interlaminar shear
strength (ILSS) [39]. Further analysis and more detailed
discussion have been reported in the literature [1,36,39,43].
Fig. 14 shows typical loaddeection curves recorded
during CST testing. The load increases proportionately
with deection until it reaches a peak followed by a sharp
drop of at least 50%. This type of sharp drop is taken as an
indication that a pure interlaminar shear failure has
occurred in the CST test. The calculated values for the
ILSS determined from this test did not dier by more that
10% for specimens cut from a single manufactured part.
Considering the variations in the sample size and the mate-
rial and the local heterogeneities in the process, this varia-
tion is rather small.
Fig. 15 shows an SEM image of the failure plane from a
specimen tested in CST. Interlaminar shear failure can
clearly be observed along the axis of the specimen.
3.3. Eect of OMWNTs on ILSS of composites
3.3.1. ILSS of glass ber reinforced composites fabricated by
IDVARTM
As stated earlier, using the injection and double vacuum
assisted resin transfer molding (IDVARTM) method, we
fabricated four types of hybrid composite samples by infus-
ing eight layers of 5 cm  5 cm woven glass ber mats with

Fig. 14. Deection load curves recorded in compression shear test (CST).
 Z. Fan et al. / Composites: Part A 39 (2008) 540554 551

Fig. 15. SEM image of interlaminar shear failure mole in compression shear test (CST).

Fig. 16. Interlaminar shear strength (ILSS) of hybrid OMWNT/glass/epoxy composites made by injection and double vacuum assisted resin transfer
molding (IDVARTM) method.

0, 0.5, 1 and 2 wt% OMWNT/epoxy suspensions, respec- Table 2

tively. We found that adding OMWNT to the resin Interlaminar shear strength (ILSS) of hybrid OMWNT/glass/epoxy
increased the ILSS of these hybrid OMWNT/glass/epoxy composites made by IDVARTM and measured by CST method
composites. Fig. 16 shows the average ILSS for the various Specimen number ILSS (MPa)
OMWNT percentages as determined by the CST device. 0 wt% 0.5 wt% 1 wt% 2 wt%
The results show that 0.5, 1, 2 wt% OMWNT in epoxy 1 25.79 28.05 28.01 31.01
increased the ILSS by 9.7%, 20.5% and 33.1%, respectively, 2 25.52 29.34 30.21 31.46
with respect to the neat epoxy (0 wt%). Table 2 shows the 3 26.75 27.18 31.37 35.41
actual ILSS test data of each group of OMWNT/glass/ 4 25.83 26.76 32.88 36.78
5 24.77 29.96 31.23 33.59
epoxy specimens as well as a single p-value derived for this 6 24.36 26.22 30.92 32.55
group taken as a whole. The very small p-value, 2.35  7 25.43 27.90 30.21 34.00
1011 conrms that adding OMWNT aects the ILSS of 8 24.90 27.77 30.34 35.87
glass ber reinforced composites in a statistically signicant Average 25.42 27.90 30.65 33.83
way. Standard deviation (%) 2.9 4.5 4.5 6.2
p-Value 2.35  1011
3.3.2. Eect of preferentially orientated OMWNT on ILSS
of glass ber reinforced composites
Using the conventional distribution-media-assisted OMWNT in the thickness direction between glass ber
VARTM method, we were able to make hybrid OMWNT/ layers was observed. As described in the earlier section of
glass/epoxy composites that contained 0.5 wt% OMWNT the paper, the 0.5 wt% OMWNT/epoxy suspension was also
in epoxy. As shown in Fig. 4, preferential orientation of used to make a hybrid composite by the IDVARTM
552 Z. Fan et al. / Composites: Part A 39 (2008) 540554

Fig. 18 shows the ILSS improvement of glass ber rein-

Fig. 17. Random OMWNT orientation state in a sample made by
IDVARTM.
method. Because the IDVARTM method does not generate
shear ow in the thickness direction, OMWNTs did not
show any preferential alignment in any particular direction,
as shown in Fig. 17. Thus, we have two types of 0.5 wt%
OMWNT/glass/epoxy composites: one that contains prefer-
entially orientated OMWNTs in the thickness direction and
one in which the MWNTs exhibit random orientation state.
Comparing the ILSS of these two composites should help us
determine the eect of the OMWNT orientation on the inter-
laminar shear properties.
forced epoxy composites using the 0.5 wt% OMWNT/
epoxy suspension relative to unenhanced specimens: one
sample was made by IDVARTM method resulting in no
preferential OMWNT orientation in the thickness direction
and the other sample was manufactured by distribution-
media-assisted VARTM resulting in preferentially orien-
tated OMWNTs in the thickness direction. The sample
containing the preferentially orientated OMWNTs had a
12.2% higher ILSS as compared to the control sample
without nanotubes made by VARTM while the sample
containing randomly oriented OMWNTs fabricated by
IDVARTM showed an improvement of 9.7% over the con-
trol sample made using the same IDVARTM process.
Because the OMWNTs are preferentially orientated in
the thickness direction during VARTM, it is highly likely
that these oriented OMWNTs have a slightly greater eect
in improving the ILSS as compared to the non-preferential
orientation resulting from the IDVARTM. Since the
improvement was measured by comparing VARTM
(without nanotubes) to VARTM (with nanotubes) and
IDVARTM (without nanotubes) to IDVARTM (with
nanotubes) samples, the improvement dierences of 9.7%
and 12.2% cannot be attributed to the thickness or volume
fraction variations between VARTM and IDVARTM.
However, it is possible that other factors during processing,
for example, compaction and ow path, may have also
contributed to the dierences in the magnitude of orienta-
tion state observed. The 9.7% and 12.2% improvements are
average results obtained from testing eight samples from
dierent laminates fabricated using both VARTM and
IDVARTM processes. For higher than 0.5% MWNT con-
tent in the epoxy, the ltering eect was prominent in the
VARTM method, hence it was not possible to investigate

Fig. 18. Percentage improvement in interlaminar shear strength (ILSS) of two types of glass ber reinforced epoxy composites containing 0.5 wt%
OMWNT/epoxy, as compared to the unenhanced composite: one sample contains no preferentially orientated OMWNT in the thickness direction and the
other sample contains preferentially orientated OMWNTs in the thickness direction.
 Z. Fan et al. / Composites: Part A 39 (2008) 540554
the inuence of preferential MWNT orientation in the
thickness direction on the ILSS of the composite.
4. Conclusions
This study was conducted to determine if we could
improve the ILSS of glass ber reinforced composites by
reinforcing them with carbon nanotubes in the regions
between the fabric layers. When the concentration of
OMWNT in the Epoxy was lower than 0.5 wt%, the tradi-
tional distribution-media-assisted VARTM method could
be used to make hybrid OMWNT/glass/epoxy composites
with preferential orientation of OMWNT in the thickness
direction between the glass ber layers. However, in case
of OMWNT suspensions with concentrations higher than
0.5 wt%, ltering and low permeability across the ber lay-
ers, caused this method to break down. The low permeabil-
ity and resulting ltering were caused, at least partly, by the
compaction of the preform under the application of the
vacuum. A novel injection and double vacuum assisted
resin transfer molding (IDVARTM) method was designed
to reduce the eects of compaction. This method allows
capillary pressure to assist the infusion. Using this method,
hybrid OMWNT/glass/epoxy composites were made suc-
cessfully with a relatively uniform distribution of OMWNT
between the layers, using suspensions of up to 2 wt%
OMWNT epoxy.
The short beam shear test was found to not be reliable in
characterizing the interlaminar shear strength (ILSS) of the
hybrid composites because failures occur by a combination
of dierent modes: compression, indentation, exure and
laminar shear. The compression shear test (CST) minimizes
the inuence of other failure modes, generating a nearly
pure interlaminar shear failure and allowing for consistent
evaluation of the ILSS of hybrid OMWNT/glass/epoxy
composites. The results show that the addition of OMWNT
improved the ILSS in these composites made by both the
distribution-media-assisted VARTM and IDVARTM
methods. For the 0.5 wt% samples, the improvement seen
using the distribution-media-assisted VARTM process
was greater than that using IDVARTM process, which we
suspect is due to the preferentially orientated OMWNT in
the former case. However, we were not able to manufacture
composites with more than 0.5 wt% OMWNT using the dis-
tribution-media-assisted VARTM process. The IDV-
ARTM allowed us to fabricate composites with 0.5, 1 and
2 wt% OMWNT/epoxy resin composites in which the ILSS
increased by 9.7%, 20.5% and 33.1%, respectively, with
respect to the unreinforced resin. Considering that the
weight fraction of resin in the composites is about 50%,
the OMWNT weight fraction in the hybrid composites as
a whole, is much lower, ranging from 0.25 to 1 wt%. This
shows that a very small amount of MWNT can enhance
the ILSS eectively by using IDVARTM processing
method. Suspensions containing more than 2% OMWNT
were too viscous to penetrate the ber mats using either
manufacturing technique.
553
Acknowledgements
The authors gratefully acknowledge the support pro-
vided by the National Science Foundation under Grant
DMI- 0115127. Additional appreciation goes to Dr. Lauke
for generously providing information on design of CST de-
vice and Dr. Chao-Ying Ni for his TEM expertise. Thanks
also to Dr. D.J. Pochan and Mr. Frank Friss for micro-
tome sectioning the suspensions.
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