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COMPOSITES
SCIENCE AND
TECHNOLOGY
Composites Science and Technology 68 (2008) 718726
www.elsevier.com/locate/compscitech
b,*
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
719
720
721
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.
722
150000
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
0.05
0.1
0.15
0.2
0.25
diameter/width
0.3
0.35
2000
1800
1600
1400
1200
1000
800
600
400
200
0
unmodified
resin
organo-clay
SBM
VGCF
-800
-700
un-modified resin
nano-clay
SBM
-600
VGCF
-500
-400
0.60
-300
initiation
0.50
-200
propagation
-100
plain
4mm
8 mm
12mm
GIC [kJ/m2]
0.40
0
0.30
0.20
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).
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]
1.2
0.8
Si
0.4
Al
0.0
0
0.5
1.5
2.5
E [keV]
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
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ILSS [MPa]
50
40
30
20
10
0
un-modified organo-clay
resin
SBM
VGCF
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.
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
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
725
726
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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