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COMPOSITES
SCIENCE AND
TECHNOLOGY
Composites Science and Technology 68 (2008) 718726
www.elsevier.com/locate/compscitech

Understanding the eect of nano-modier addition upon the


properties of bre reinforced laminates
Marino Quaresimin a, Russell J. Varley
a

b,*

Department of Management and Engineering, University of Padova, 36100 Vicenza, Italy


CSIRO Manufacturing and Materials and Technology, Clayton South 3168, Australia

Received 27 February 2007; received in revised form 23 August 2007; accepted 13 September 2007
Available online 20 September 2007

Abstract
This work presents a survey of the eect of three dierent commercially available nano-modiers on the mechanical properties of an
epoxy/anhydride unidirectional carbon bre reinforced laminates. The nano-modiers consisted of an organo-modied layered silicate,
vapour grown carbon bre (VGCF) and a triblock copolymer (SBM). The work has shown that tensile modulus exhibited little dierence
between the unmodied laminates while a modest decrease was observed for the tensile strength. Properties related to the toughness of
the matrix, demonstrated improvements compared to the unmodied laminate such as the notch sensitivity under compression, ILSS and
GIIC performance. The improvement of the GIIC for the VGCF modier in particular was found to be over 100%. It was suggested that
high aspect ratio of the nano-additive helped to constrain the growth of the micro-cracks which in turn delayed failure. Mode I GIC
performance however, was found to decrease as a result of the bre tows preventing optimum dispersion of the modier. The eect
of this was a very high eective clay concentration in the interlayer resin rich regions and a less than optimum bre dispersion, results
in promotion of the propagating crack rather than inhibition.
 2007 Elsevier Ltd. All rights reserved.
Keywords: A. Particle reinforced composites; B. Fracture toughness; A. Layered Structures

1. Introduction
The use of nano-additives, such as organo-modied layered silicates, carbon nanobres or nanotubes and others,
to reinforce epoxy resins has generated signicant interest
both academically and commercially in recent times [14].
This interest is primarily a result of the concurrent
improvements in mechanical properties such as toughness,
strength and modulus, as well as improvements and thermal properties such as re performance, degradation and
glass transition temperatures (amongst others), at low levels of addition that allows the use of existing processing
methods. It has been well documented however, that to
achieve these property improvements, the nano-additive

Corresponding author. Tel.: +61 3 9545 2491; fax: +61 3 9544 1128.
E-mail address: russell.varley@csiro.au (R.J. Varley).

0266-3538/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2007.09.005

must be suciently dispersed and compatible with the


epoxy resin. Depending upon the nano-additive in question, this brings a range of associated challenges unique
to the material. In the case of layered silicates, the lateral
dimensions of the clay platelets are of the order of microns
in area, around 1 nm thick and arranged in stacks known
as tactoids [5]. Complete exfoliation, therefore requires
the separation of the tactoids from the primary particle,
followed by the destruction of the order or the clay platelets within the tactoids. Although it is widely reported that
full exfoliation of the clay platelets will maximise the
improvement in strength, modulus and toughness [4,6], it
has also been suggested that a balance between an exfoliated and intercalated structure may be preferable to maximise modulus and toughness enhancements in epoxy resin
matrices [7]. Boo et al. [8] reached similar conclusions that
toughening mechanisms in nano-platelet reinforced
composites, such as crack deection or crack pinning, are

M. Quaresimin, R.J. Varley / Composites Science and Technology 68 (2008) 718726

promoted when intercalated tactoids or even agglomerates


are present. As well it was suggested that fully exfoliated
nanocomposites would if fact possibly reduce fracture
toughness. Carbon based nanotubes are another class of
nano-additives which show signicant potential provided
they can be adequately dispersed within an epoxy matrix.
Diculties in complete dispersion however, arise from electrostatic attractive forces between the tubes causing them
to exist in agglomerated bundles. A variety of methods,
reviewed elsewhere [9] have been investigated, which particularly highlights the diculty of reducing the electrostatic
forces while not degrading the bre and hence compromising the composite properties. Other nano-additives that
have shown signicant improvement in improving the
mechanical properties of epoxy resins, are triblock copolymers. These additives can self assemble through thermodynamic processes to form unique nanostructures within
reactive epoxy matrices [10,11] that promote unique toughening mechanisms arising from the unique morphologies.
However, the eect upon viscosity and the tendency to
micro-phase separate tends to inhibit the benets of the
nano-additive.
The application of toughening polymer matrices to a
bre reinforced composite however, creates further complexities in optimising the performance of the resin dominated composite properties. While the constraining
nature of bre reinforcement can minimise the eectiveness
of rubber additives in carbon bre composites [12], it is
suggested here that alternative toughening mechanisms of
nano-additives may overcome these limitations. It is important to note here that that comparatively weak out of plane
inter-laminar properties have the greatest potential (and
indeed need) for improvement, while it is unlikely (and
equally less important) that the in-plane bre dominated
properties would be able to be signicantly improved.
The research performed to date, aimed at translating resin
properties to the bre reinforced composite, has met with
mixed results. Rice et al. [13] reported a 12% improvement
in modulus at 2 wt% of organosilicate for aerospace composite materials while reporting no improvement in other
mechanical properties. Timmerman et al. (2002) [14],
reported negligible improvements in mechanical properties,
although they did report a signicant reduction in transversal microcracking during cryogenic cycling of nanoclay
composites compared to traditional composites, and indicating the need for careful selection of nanoclay concentration and surface modication. Becker et al. (2003) [15] have
shown that improvements in crack opening fracture toughness can be achieved at low levels of clay addition. This was
explained as being due to the formation of a crack bridging
mechanism and the supplementary reinforcement provided
by the clay. Although the matrix was not epoxy based, an
AS-4/PEEK composite modied with SiO2 nanoparticles
has been shown by Jen et al. (2004) [16] to synergistically
improve mechanical properties in unidirectional laminates.
They found that a 1 wt% addition of nanoparticles
improved strength and modulus by 12% and 19%, respec-

719

tively in quasi-isotropic laminates while cross-ply laminates


produced smaller increases. Additionally they found that
the nano-modied laminates had little eect upon the tensile fatigue performance. The use of glass bre as the reinforcement however, has yielded improved results compared
to carbon. Improvements in strength (compressive [17] and
exural [18,19]) of the order of 25% have been reported at
low levels of addition. The work by Haque and Shamsuzzoha [18] also reported large improvements in the ILSS
and fracture toughness. The level of improvement has been
attributed by Kornmann et al. (2005) [19] to the anity
between the silicate organoclay and the silicate glass bres
and enhancing the bre matrix adhesion. It is of interest to
note that for the abovementioned reasons the substantial
improvements reported in the bre dominated properties
(i.e. tensile and bending) are considered to warrant more
research in this area.
This paper therefore seeks to further understand the
eect of nano-modiers similar to those discussed above
on the properties of an epoxy anhydride carbon bre laminate. Some benets of using nano-modiers are highlighted, while also presenting and justifying some
deleterious eects arising from specic diculties in relation to processing the composite. Three commercially
available nanomodifers are used in this work, namely organo-modied layered silicate (nanoclay), vapour grown
carbon bre (VGCF) and an organic triblock copolymer
system. All three systems were fabricated into carbon bre
reinforced composites and a range of mechanical properties
were determined. Scanning electron and optical microscopic techniques were used to provide an explanation
for the results obtained.
2. Experimental
2.1. Materials
The polymeric matrix consisted of a blend of the diglycidyl ether of bisphenol A (DGEBA) under the trade name
of D.E.R. 331 (DOW, USA) and the epoxy novolac resin
under the trade name of D.E.N. 431 (DOW,USA), The
anhydride hardener was a hexa-hydrophthalic anhydride
(XD5200) supplied by Ciba Specialty Chemicals (Australia). The composition of the base matrix formulation was
as follows: 29 phr of DER331 resin, 27 phr of DEN431
resin, 44 phr of the hardener XD5200 and 0.5 phr of the
accelerator, 1-methyl-imidazole. The nanoclay used here
was Cloisite 30B supplied by Southern Clay Products
(USA). They are surface modied lamellae of montmorillonite 1 nm thick and with lateral dimensions from 70 to
150 nm according to the product data sheet supplied. The
vapour grown carbon nanobers (VGCF) were obtained
from Applied Sciences under the trade name of Pyrograf-III PR24-PS. They have a diameter of 200 nm and
their length can range between 30 and 100 lm, with a specic surface area of 5053 m2/g. The triblock copolymer
used was an acrylic block copolymer poly styrene butadi-

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M. Quaresimin, R.J. Varley / Composites Science and Technology 68 (2008) 718726

ene methyl methacrylate (SBM), supplied by Arkema,


under the trade name of AF-X E20. The unidirectional carbon bers Tenax G30-700 12K HTA-7C by Toho-Tenax
America Inc. was used. In this work, the following laminates containing 5 wt% of nanoclay, 7.5 wt% of VGCF
and 10 wt% of SBM were prepared for evaluation and
compared to an unmodied laminate. The concentrations
for each additive were specically chosen so as to have
the greatest potential for exhibiting improvement in the
laminate properties while minimising any deleterious
consequences.
2.2. Nanocomposite formation
The nano-additives were dispersed in the resin systems
prior to application onto the unidirectional bre as follows.
The organoclay was dispersed through a shear mixing process where the epoxy resins were heated to 130 C and the
clay added while mixing at a rate of 1000 rpm. This was
continued for 1 h until the hardener was added and the
resin was cooled to room temperature. The VGCF was dispersed in the epoxy resin system according to an attrition
milling process. The VGCF was placed in a container along
with milling balls and solvent and stirred at 1000 rpm for
1hr. After this time the balls were removed and the VGCF
and solvent were added to the epoxy resin. The solvent was
concentrated to a specic volume and then pre-pregged by
applying a known quantity of resin onto the carbon bre.
The triblock copolymer was formed by dissolving in acetone along with the epoxy resin formulation and then
pre-pregged in a similar manner to the VGCF.
2.3. Sample Fabrication
Prepregs were prepared according to a hand lay-up process at room temperature of around 22 C and ambient
humidity. In the case of the unmodied and the nanoclay
modied resins, a solventless melt process was used to
apply the resin evenly. In the case of the VGCF and triblock copolymer systems, a solvent based process whereby
the solution was applied to the carbon bre using a paint
brush. The solvent was allowed to evaporate overnight
where the temperature varied from 22 C to 12 C and
ambient humidity before fabrication was commenced. In
all cases, care was taken to ensure that similar quantities
of resin were applied to the bre. The prepreg was then
cut out and fabricated according to the test being performed. A teon lm of thickness 5 lm was inserted as
the crack starter for the mode I and II lay-up sequence.
In the case of the mode I and II samples, [0]24 sequence
was used, a [0]10 sequence was used for the compressive
and tensile properties while a [0]6 sequence was used for
the impact testing. Curing for all systems unmodied and
nano-modied was performed using a vacuum bag conguration between a platen press and the cure prole was as
follows: 3080 C at 5 C/min under vacuum and 1.4 bars
of additional pressure, hold at 80 C for 2 h and under vac-

uum and 1.4 bars of pressure for a further 70 min, release


vacuum while increasing pressure to 5.5 bars, heat from
80 to 180 C at 5 C/min with pressure at 5.5 bars, hold
at 180 C at 5.5 bars for 2 h and nally cool down to room
temperature overnight. The bre volume fractions of the
laminates prepared for the unmodied resin, the clay, the
VGCF and the SBM modied resin were found to be
69 vol%, 63 vol%, 65 vol% and 54 vol%, respectively.
2.4. Mechanical properties
Mechanical properties were evaluated using an MTS 809
axial/torsion test system with load cell of 10/100 kN. For
the tensile testing measurements, samples were machined
to the following dimensions: 2 15 110 mm. Tabs were
applied to the specimens in order to improve the grip in
the clamps. The crosshead speed was set at 2 mm/min
and three specimens were tested for each material conguration. An MTS 632.85F-14 extensometer was used for
determination of tensile modulus. Compressive properties
were investigated both on plain and notched samples to
emphasise the matrix contribution. Plain samples were
cut in the size of 2 24 110 mm and tested with an unsupported length of 20 mm. Open hole compressive (OHC)
properties were determined using samples of dimensions
2 36 300 mm with holes of dierent size, namely 4, 8
and 12 mm, to investigate also the notch size eect. Holes
were carefully drilled undersize and then reamed to nal
dimensions. To avoid sample buckling notched samples
were tted with an anti-buckling xture according to
ASTM D6484. The crosshead speed used for all compressive samples was set at 2 mm/min and the test was repeated
on at least three specimens for each material conguration.
The interlaminar shear strength (ILSS) was determined
according to ASTM D2344 using samples of the following
dimensions, 12 4 30 mm. The crosshead speed was set
at 1 mm/min and six specimens were tested for each material conguration.
Mode I testing was carried out according to ASTM
D5528. Three double cantilever beam (DCB) specimens
for each material conguration were tested, with the following dimensions: width 25 mm, thickness 4 mm, length
75 mm. Steel hinges (25 50 mm) were applied to the specimens to ensure that the specimen is always vertically
loaded. An auxiliary load cell of 1 kN was tted to testing
machine and the crack propagation was monitored visually
with a travelling microscope. The crosshead speed was set
at 0.5 mm/min. The reported GIC values were calculated
using the compliance calibration method (MCC) and the
initiation values were determined by visual observation.
Mode II testing was determined using end notched exure method (ENF) according to DIN EN6034. Specimen
dimensions consisted of width 25 mm, thickness 4 mm
and length 130 mm. Three specimens were tested under
three point bending for each material conguration and
the crosshead speed was set at 1 mm/min. The distance
between the lower rolls was 100 mm and the initial crack

M. Quaresimin, R.J. Varley / Composites Science and Technology 68 (2008) 718726

length 25 mm. Mode II strain energy release rate, GIIC, was


calculated according to beam theory.
The impact test was carried out according to ASTM
D5628 standard using a CEAST Fractovis Plus 7520 falling
mass impact tester. A strain gauge striker with a hemispherical head of diameter 12.7 mm was used.
3. Results and discussion
3.1. Laminate morphology
A selection of SEM micrographs are shown in Fig. 1 at
low magnication to highlight the laminate morphology
produced in each of the laminates prepared. The characteristic layering of the plies is observed with each of the laminates which highlights a thin strip of a resin rich layer in
between the carbon bre tows. It is worth noting here that
the quality of the laminate of the SBM triblock system is
clearly inferior to the other laminates with signicant numbers of voids apparent. In addition to this, in the resin rich
layer it can be seen that phase separation of the SBM has
occurred producing particles of the order of a few microns
in diameter. This suggests that in the case of the SBM
nano-additve there has been little if any nanostructure formation. The reason for this is expected to be a result of the
entrapment of residual solvent caused by the increase in

721

viscosity. This would be expected to impact the mechanical


properties measured for this system.
3.2. Tensile Properties
The eect of the dierent nano-additives upon the composite tensile moduli are shown in Fig. 2. As can be seen
there is little eect upon properties as would be expected
given the bre dominated nature of the test performed
here. The SBM system however, is seen to decrease significantly, in accord with the reduced bre volume fraction
and lower quality of the laminate, although the elastomeric
nature of the additive may also be contributing to this large
decrease. The results of the tensile strength measurements
shown in Fig. 3, highlight a modest decrease in performance compared to the unmodied laminate for the range
of nano-modied used here. Again, for the SBM system,
lower volume fraction and laminate quality induced the
lowest strength value.
3.3. Compressive properties
The compressive properties determined here are shown
in Fig. 4. The poor performance of the SBM system is
clearly evident and can again be attributed to the extent
of voids in the laminates prepared. In fact, the reduction

Fig. 1. Scanning electron micrographs at a magnication of 200 showing the consolidation and layered morphology of the unidirectional laminates
prepared for the (a) unmodied (b) nanoclay modied, (c) VGCF modied and (d) SBM modied laminates.

M. Quaresimin, R.J. Varley / Composites Science and Technology 68 (2008) 718726


notched/plain compressive strength (MPa)

722
150000

Tensile modulus E [MPa]

140000
130000
120000
110000
100000
90000
80000
70000

1.2
un-modified resin
1.1
VGCF

nanoclay

0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2

60000

0
un-modified organo-clay
resin

SBM

VGCF

Fig. 2. Eect of nano-modier addition upon the tensile modulus.

0.05

0.1

0.15
0.2
0.25
diameter/width

0.3

0.35

Fig. 5. Eect of nano-modier addition on the normalised compressive


strength as a function of the normalised notch size.

2000

Tensile strength [MPa]

1800
1600
1400
1200
1000
800
600
400
200
0
unmodified
resin

organo-clay

SBM

VGCF

Fig. 3. Eect of nano-modier addition upon the tensile strength.

Compressive Strength (MPa)

-800
-700

un-modified resin
nano-clay
SBM

-600

VGCF

the plain specimens against normalised hole diameter. The


results obtained from the SBM laminates are not presented
due to the poor compressive values for the plain samples
which makes the comparison unrealistic. It can be suggested therefore that the addition of both VGCF and nanoclay provide the laminate with an increased resistance to
the presence of notches compared to the unmodied base
laminates. The brittle nature of epoxy resins, and their corresponding notch sensitivity is an inherent aspect of epoxy
resin which is always taken into account during design. The
reduction in notch sensitivity for nanoclay and VGCF
modied systems therefore, has the potential to increase
exibility during the design of epoxy composites. These
results complement those of Subramaniyan and Sun
(2006) [17,20] who observed maximum improvements in
compressive strength to be of the order of 25% for a wet
lay-up method similar to that used here. When they used
a VARTM methods however, they reported a decrease
in compressive strength, and attributed this to the

-500
-400
0.60
-300

initiation
0.50

-200

propagation

-100
plain

4mm

8 mm

12mm

Fig. 4. Eect of nano-modier addition upon the compressive strength for


plain and notched laminates.

GIC [kJ/m2]

0.40
0

0.30

0.20

in strength for SBM laminates is far larger than that


expected on the basis of the lower content of reinforcement. Furthermore, although in the presence of a signicant scatter, the results indicate a trend of relative
improvement in strength for both the VGCF and nanoclay
as the hole size increases. This result is highlighted further
in Fig. 5 which plots the normalised strength compared to

0.10

0.00
un-modified organo-clay
resin

SBM

VGCF

Fig. 6. Eect of nano-modier addition upon the initiation and propagation mode I interlaminar fracture toughness (DCB).

M. Quaresimin, R.J. Varley / Composites Science and Technology 68 (2008) 718726

723

Fig. 7. Optical micrographs at two magnications, illustrating the ltering eect of the carbon bre tows preventing nanomodifer from penetrating the
bre rich regions for the (a) nanoclay (on the left) and (b) VGCF (on the right).

2.0

1.6

Fiber-rich region

Counts

GIIC [kJ/m2]

Resin-rich region (interlayer)

1.2

0.8

Si
0.4
Al

0.0
0

0.5

1.5

2.5

E [keV]

Fig. 8. Electrodispersive spectroscopic elemental analysis of the nanoclay


composite quantifying the inhomogeneous dispersion of the layered
silicate in the interlayer region and between the bers.

consequences of the nanoclay being ltered during the process and therefore not being evenly dispersed.
3.4. Fracture properties
Given the positive eect upon notch sensitivity of nanoclay and VGCF it was expected that the mode I crack
opening strain energy release rate GIC, would also be
improved. Fig. 6, which shows the initiation and propagation GIC results, all show large decreases in fracture tough-

un-modified organo-clay
resin

SBM

VGCF

Fig. 9. Eect of nano-modier addition upon the mode II fracture


toughness (ENF).

ness, particularly for the organo-clay and the VGCF


additives. The poor performances particularly for the organo-clay and the VGCF can be explained by examining
both the SEM images shown in Fig. 1 as well as the optical
micrographs in Fig. 7. Fig. 7 shows that for both the
VGCF and nanoclay systems, even though apparently well
dispersed within the interlayer resin rich region, there is
negligible infusion of nano-additives into the bre rich
regions. As a result the nano-additive is not evenly dispersed throughout the composite and eectively ltered
out by the bres. In addition, the micrographs shown
in Fig. 1, show that this resin rich region is actually a

724

M. Quaresimin, R.J. Varley / Composites Science and Technology 68 (2008) 718726


60

ILSS [MPa]

50
40
30
20
10
0
un-modified organo-clay
resin

SBM

VGCF

Fig. 10. Interlaminar shear strength (ILSS), as determined for the


dierent nano-modied laminates.

relatively small fraction of the area of the composite compared to the bre rich region. The result of this is that the
concentration of the nano-additive is therefore much
higher than the nominal 5 and 7.5 wt% of nanoclay and
VGCF, respectively. At such high concentrations the quality of the dispersion is compromised, increasing the
agglomeration and clustering in the resin rich regions such

that the nano-modier actually provides points of weakness rather than reinforcement, and thus decreasing toughness [21,22]. Fig. 8 provides further evidence of this
ltration of the nano-modier from the bre rich regions
for the nanoclay system, showing electro-dispersive spectroscopy analysis of the interlayer region and between the
bres. A lack of any Si and Al between in the bre rich
region is a clear indication of the lack of any nanoclay present. Again the poor performance of the SBM laminate can
be attributed to the lower quality of the laminates.
Although the SBM GIC is poor, it remains signicantly
higher than the VGCF and nanoclay systems. This complements the above discussion in that no ltering occurs for
these samples and the SBM GIC is well above that of the
VGCF and nanoclay. The actual extent to which a nanocomposite was formed either during the prepreg fabrication stage or after cure, was not specically measured in
this work. Thus this result highlights that the observed
improvements in properties, or in this case the deleterious
eects that can arise when the additive is acting as a ller.
In contrast to the poor performance of the mode I crack
opening behaviour, failure through shear loading displayed
improvements with the addition of VGCF and nanoclay
compared to the unmodied laminates. The results are

Fig. 11. Comparison of the fracture surfaces at magnications of 1500 for the (a) unmodied laminate (b) VGCF modied laminate and (c) nanoclay
laminates.

M. Quaresimin, R.J. Varley / Composites Science and Technology 68 (2008) 718726

shown in Figs. 9 and 10 for the mode II ENF and interlaminar shear (ILSS), respectively. During the interlaminar
shear tests all the specimens failed by delamination. Reasonably similar trends in the mode II and ILSS results
can be seen, although it is clear that the eect of VGCF
addition is signicantly higher than that of the nanoclay.
An interesting aspect of this work therefore is the decoupling of the relationship between the tensile (mode I) failure and failure through shear processes. It is typically
expected that if the toughness of a polymer composite is
increased, improvements in both mode I and II deformations should be evident. However here, the ltration eect
that reduces the crack opening GIC has not had the same
eect for the shear failure mode GIIC. Mode II occurs via
the development of a series of sigmoidal shaped matrix
micro-cracks ahead of the crack tip with an orientation
of approximately 45 to the bre direction. In a brittle
matrix, these micro-cracks grow during loading and eventually coalesce and then fail catastrophically. The fracture
surface contains many zipper looking facets, usually
called hackles as can be seen from the SEM fracture surfaces shown in Fig. 11a for the unmodied laminate at a
magnication of 1500. Fig. 11b and c show scanning electron micrographs of the fracture surfaces of the VGCF and
nanoclay modied systems at 1500, respectively. The
micrographs show clear evidence of modication of the
mechanism by both of the nano-additives. For both
nano-modiers, the hackles are less well dened compared
to the unmodied laminate and appear closer together or
smaller. This has lead us to suggest that improved shear
performance may be related to ability of the high aspect
ratio additives to eectively anchor the micro-cracks
together, (despite their eective higher concentration) by
the VGCF bres (in particular) delaying their growth, coalescence and thus laminate failure. Therefore, the better
performance of the VGCF is likely to be a result of their
higher aspect ratio and the presence of more well dispersed
bres compared to the nanoclay. Again in both ILSS and

absorbed to impact energy ratio

0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
un-modified organo-clay
resin

SBM

VGCF

Fig. 12. Comparison of the absorbed to impact energy ratio for


unmodied and nano-modied laminates prepared.

725

mode II failure, the poor results obtained from the SBM


laminates, can be related to the lower quality of the laminate prepared, since in these cases the results are mainly
matrix-controlled and the bre content has less inuence.
3.5. Impact
The eect of nano-addition upon the energy absorption
capability of the laminates under impact loading has been
determined here. Although the [0]6 sequence is not ideal
for impact design application, it was chosen to emphasise
the contribution of the matrix in terms of energy absorption. Therefore the results of the impact testing in Fig. 12
are represented as the ratio of the absorbed to impact
energy. As can be seen, the absorption capability of both
the organoclay and the VGCF are above that of the
unmodied laminate. The observation that damage mainly
occurred through splitting, conrms the primary contribution of the matrix to the increased performance. In addition, the similarity of the impact behaviour to the GIIC
suggests it can be used as a representative parameter to
describe the matrix contribution to impact performance.
4. Conclusions
In summary, this paper has presented a short survey of
the eect of three dierent nano-modiers upon key
mechanical properties of carbon bre reinforced laminates.
With the exception of the triblock SBM laminates, good
quality laminates were prepared. The higher void content
was discussed in terms of the viscosity increase arising from
the use of SBM and the corresponding entrapment of solvent. This in turn had a deleterious eect upon mechanical
properties.
The work has shown that tensile modulus exhibited little
dierence between the unmodied laminates while a modest decrease was observed for the tensile strength for the
VGCF and nanoclay modied systems. In contrast however, properties dominated by the matrix contribution,
demonstrated signicant improvements compared to the
unmodied laminate. The notch sensitivity under compression was shown to be improved when nanoclay and VGCF
was added. The shear behaviour as evidenced, via ILSS and
GIIC was also improved, particularly for the VGCF modier which was found to improve GIIC by over 100%. It was
suggested that high aspect ratio of the nano-additive helped
to constrain the growth of the micro-cracks which in turn
delayed failure. This decrease in brittle behaviour evidenced by improvements in notched sensitivity, GIIC and
ILSS, were not however, translated into improved GIC performance as may have been expected. Substantial decreases
in mode I crack opening behaviour were observed and were
shown to be a result of the bre tows preventing optimum
dispersion of the modier by ltration. The result being
that the eective clay concentration in the interlayer
resin rich regions was much higher than the nominal
nano-additive concentration.

726

M. Quaresimin, R.J. Varley / Composites Science and Technology 68 (2008) 718726

Acknowledgements
The activity was carried out in the frame of the project
A methodology for the integrated design and development of nanocomposite products CPDA055157 funded
by University of Padova, Marino Quaresimin warmly
acknowledge the nancial support. Russell Varley would
also like to gratefully acknowledge the support of the Australian Academy of Science in carrying out this work.

[11]

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