Composites: Part A 39 (2008) 1851–1858

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Fracture behaviour of fumed silica/epoxy nanocomposites

M. Battistella a, M. Cascione a, B. Fiedler b, M.H.G. Wichmann b, M. Quaresimin a,*, K. Schulte b
a
Department of Management and Engineering, University of Padova, Stradella San Nicola 3, 36100 Vicenza, Italy
b
Institute of Polymers and Composites, Technische Universität Hamburg-Harburg, Denickestrasse 15, D-21073 Hamburg, Germany

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

Article history: The paper shows the results of an experimental programme oriented to the manufacturing and charac-
Received 12 April 2008 terisation of nanocomposites based on epoxy resin modified with fumed silica nanoparticles (0.1, 0.3 and
Received in revised form 4 September 2008 0.5 vol.%) with different surface treatments (unmodified, AMEO and GLYMO). The resulting degree of dis-
Accepted 7 September 2008
persion and the interfacial adhesion were investigated by TEM and SEM. Previous tensile and fracture
toughness properties are discussed together with new results on the fatigue behaviour under mode I
loading. The fracture toughness KIc turned out to be significantly increased and a positive trend towards
Keywords:
the improvement in the crack propagation threshold under fatigue was observed.
A. Nano-structures
B. Fracture toughness
Ó 2008 Elsevier Ltd. All rights reserved.
B. Fatigue
Fumed silica

1. Introduction
The addition of nanoparticles has proven to exhibit a high po-
tential for significantly improving mechanical properties of poly-
mers. This behaviour justifies the great interest of the scientific
community and industry. A vast amount of experimental works
has been performed and published during recent years. Neverthe-
less, most of the available data refer to static properties while the
behaviour under cycling and dynamic loading is rarely investi-
gated. A brief overview on some of the most important work is pre-
sented below.
Siegel et al. [1] obtained an increase of 15% of the strain to fail-
ure filling an epoxy resin with 10 wt.% of nanometric TiO2 particles.
Evora et al. [2] found that adding only 1 vol.% of TiO2 nanoparticles
within unsaturated polyester resin increased the fracture tough-
ness of about 57% due to the uniform and fine dispersion of the fil-
ler within the resin at low volume contents. More significant
enhancements in fracture toughness (almost 100% at 4.5 vol.% of
Al2O3 nanoparticles in unsaturated polyester) were achieved
improving the particle-matrix adhesion through a silane surface
treatment [3].
Wetzel et al. [4] studied the effects of nano (alumina) and mi-
cro-spherical (calcium silicate) particle addition to epoxy resin
and found increases in flexural modulus (up to 35%), strength (up
to 20%) and Charpy impact energy (up to 35%). In a following, inter-
esting work [5], neat epoxy reinforced with Al2O3 nanoparticles at
different volume contents was investigated. The 10 vol.% epoxy/
Al2O3 nanocomposite exhibited significant improvements in flex-
* Corresponding author. Tel.: + 39 0444 998723.
E-mail address: marino.quaresimin@unipd.it (M. Quaresimin).
ural modulus (around 40%), strength (15%) and fracture toughness
(120%). Furthermore, the crack propagation threshold and resis-
tance turned out to be improved dramatically, with the crack prop-
agation rates for nanocomposites being orders of magnitude
slower than neat resin for the same range of SIF.
Adebahr et al. [6] proposed a novel route to prepare nanocom-
posites consisting of monodispersed SiO2 nanoparticles and reac-
tive resin. The addition of 23 wt.% of particles subjected to
thermal anhydride curing induced a 66% increase in KIC, while
UV curing led to an improvement of 82% at 50 wt.%. Lin et al. [7]
reported that tensile and impact strength of titanium dioxide and
montmorillonite filled epoxy resin reached a maximum for a filler
content of 5–8 vol.% and decreases at higher filler contents, some-
times even below the neat resin values.
Ragosta et al. [8] improved the mechanical properties of epoxy
resin adding 10 wt.% of silica particles with a diameter of 10–
15 nm. The normalized elastic modulus reached the value of 1.5,
while the normalized yield strength increased up to 1.3. The addi-
tion of silica raised the fracture energy of the epoxy matrix by a
factor of about 4, whereas the increase of KIc was twofold.
Zheng et al. [9] found that the addition of 3 wt.% of silica nano-
particles within epoxy matrix leads to an increase in tensile
strength of 115%, while the impact strength increases by 56%.
In the literature, the toughening effect due to the addition of
particles to polymers has been studied for a long time [10–12]. Dif-
ferent toughening mechanisms have been mentioned, such as the
localised inelastic matrix deformation and void nucleation, particle
debonding, crack deflection, crack pinning, crack tip blunting, par-
ticle deformation or breaking at the crack tip. However, it is still an
open question which are the effective mechanisms responsible for
toughening on nanocomposites [13]. Furthermore, experimental

1359-835X/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2008.09.010
1852 M. Battistella et al. / Composites: Part A 39 (2008) 1851–1858
techniques and descriptive models are based on macro-mechanical
concepts. Thus, their application to nanocomposites is not straight-
forward and indeed questionable. Particle-matrix debonding and
localized deformations in the process zone ahead of the crack tip
are probably responsible of the considerable toughening effect
brought by nanomodification. Recent experimental investigations
by Johnsen et al. on silica nanoparticle reinforced epoxy polymers
confirm these assumptions [14]. Because of the very high specific
surface area, even very low filler contents can significantly contrib-
ute to matrix reinforcement. Especially interface related effects,
such as debonding mechanisms and void nucleation could play a
significant role even at low volume contents. Although classical
mechanical theories concerning particle toughening sometimes
even predict a decrease of toughening contribution with decreas-
ing particle size, the increasing amount of interfacial area and
absolute number of particles in the process zone can be reasons
for the experimentally observed increases in KIc [15].
Xie et al. [16] reported the improvement of the mechanical
properties of PVC with the addition of CaCO3. At 5 vol.%, optimal
performances were achieved in Young’s modulus, tensile yield
strength, strain to failure and Charpy impact energy. The filler en-
abled ductile fracture caused by elevated triaxial stresses at the
neck region and consequently debonding at the particle-matrix
interface. Increasing the load, the ligaments between the voids
were stretched increasing the energy consumption.
Lazzeri et al. [17] showed that the addition of 10 vol.% of un-
coated CaCO3 led to an increase in Young’s modulus and yield
stress and to a decrease in impact strength. On the other hand, if
the particles were covered with stearic acid, the tensile properties
slightly dropped and the impact strength linearly increased with
the stearic acid surface concentration. The fracture surface analysis
showed cavities and voids due to debonding and deformation
bands in the stress whitened areas. As demonstrated in [18], the
void formation allows for a plastic deformation of the interparticle
ligaments, which is assumed to be main absorbing energy
mechanism.
Yang et al. [19] investigated the fracture behaviour of polyam-
ide 66 filled with TiO2 nanoparticles. With the increase of the
TiO2 content from 1 to 3 vol.%, the plastic zone around the crack
tip decreased and the density of dimples near the pre-notched area
increased. Thus, the energy absorbed during crack propagation
should be higher for the nanoreinforced matrix than for the pure
polyamide.
In the last decades the greatest part of the researches carried
out on nanomodification was oriented to thermoplastic matrix
nanocomposites, however the attention of the scientific commu-
nity has recently moved to the nanomodification of thermosetting
resins, in view of their possible application as matrix for ternary,
fibre reinforced laminates. Because of their size in the nanometre
regime, nanoparticles are small enough to penetrate the fibre rov-
ings and to act as matrix reinforcement in FRP laminates.
Chisholm et al. [20] investigated the influence of a nanocom-
posite matrix on a laminate composite. The presence of 1.5 wt.%
of SiC nanoparticles within the epoxy resin increased the tensile
modulus of the nano-modified matrix of 44% and the tensile
strength of 15%. The tensile modulus of the corresponding lami-
nate increased of 23.5% and the tensile strength of 11%. Also in
the flexural test the laminate containing 1.5 wt.% of SiC in the ma-
trix showed improvements (39% in strength and 12% in modulus).
However, when the nano-reinforcement was increased from 1.5%
to 3%, a worsening of both tensile and flexural properties of the
composite was observed.
Kinloch et al. [21] investigated the fracture behaviour of GFRP
laminates with a nano-modified epoxy matrix and found consider-
able increase in GIc and GIIc when using silica nanoparticles alone
and in combination with a CTBN toughening.
From the previous discussion, the beneficial effects of nanopar-
ticles in improving the mechanical properties are evident even at
low filler contents. However, most of the work has been done on
the investigation of static properties, while few papers
[5,22,23,29] can be found about the effects of nanofillers on the fa-
tigue behaviour of polymers. Blackman et al. [23] observed an in-
crease of KIc in an epoxy matrix, using nanoscaled silica particles.
The KIc improvement ranged from 27% at 4.0 wt.% of nano-SiO2
up to 73% at 20 wt.%. Moreover, they observed an improvement
in fatigue behaviour, as DKth was increased significantly. A correla-
tion between KIc and DKth was found.
In the present work attention will be focused on the crack prop-
agation resistance under cyclic loading. Indeed, the few previous
investigations seem to suggest that nanomodification is able to sig-
nificantly enhance the fatigue performance of polymers. If this
beneficial effect is confirmed, it will be another interesting feature
of polymer nanocomposites.
2. Experimental
2.1. Materials
The epoxy matrix investigated was a modified bis-phenol-A-
based epoxy resin (MGS L135i) together with an amine curing
agent H137i, both supplied by the Bakelite MGS Kunstharzpro-
dukte GmbH. Since this system is characterized by a low viscosity
[gRT = 250 mPa s], it can be used in LCM manufacturing processes.
The nanofiller used was AEROSILÒ 380, a hydrophilic fumed sil-
ica with a specific surface area of 380 m2/g and an average primary
particle diameter of 7 nm. The AEROSIL 380 was provided by De-
gussa AG, Germany. The surface of the fumed silica was chemically
modified with two different coupling agents: 3-aminopropyltrime-
thoxysilane (Dynasylan AMEO) and 3-glycidyloxypropyltrimeth-
oxy-silane (Dynasylan GLYMO), both supplied by Degussa AG,
Germany.
The surface modification process as well as the manufacturing
parameters are reported elsewhere [24].
Nine different nanocomposites were produced and analysed
since three different fumed silica volume fractions (0.1, 0.3,
0.5 vol.%) and three different chemical modification conditions
(non-treated fumed silica, AMEO-modified and GLYMO-modified
fumed silica) were considered.
The fatigue performances of nanocomposites were then com-
pared with those of the neat epoxy.
2.2. Morphological analysis
The degree of dispersion of the filler within the matrix was ana-
lysed by TEM and SEM investigations. The SEM analysis was car-
ried out without any gold sputtering, because the presence of the
gold-layer on the specimen surface could lead to the loss of impor-
tant information about the filler dispersion, since it has the same
dimensions of the particles diameter.
From TEM analysis only qualitative results can be gained about
the dispersion and distribution of the nanofiller. In general, it can
be said that the treatment with AMEO and GLYMO resulted in only
slight differences regarding the state of dispersion. A generally
good state of dispersion was found for all three systems investi-
gated. Both, the unmodified and the GLYMO-modified fumed silica
particles showed a comparable fine degree of dispersion and the
resulting fine network structure caused by the high attractive
forces between the particles.
Fig. 1 shows a TEM micrograph of non-modified fumed silica at
0.1 vol.%. It reveals the tendency of fumed silica nanoparticles to
create small clusters within the matrix. These aggregates tend to
 M. Battistella et al. / Composites: Part A 39 (2008) 1851–1858
Fig. 1. TEM analysis on the 0.3% unmodified fumed silica nanocomposite.
attract each other forming greater structures called agglomerates,
which have a chain-like branched structure. In general, these
aggregates consist of several tens of primary particles and exhibit
dimensions of several ten to one hundred nanometres.
The dispersion achieved with the GLYMO-modified silica parti-
cles is shown in Fig. 2. It shows a very fine and uniform distribution
comparable to that of unmodified silica particles. The same sizes
were found for the aggregate substructures in these nanocompos-
ites. Figs. 1 and 2 are representative for the overall morphology of
these nanocomposites, as the structure and size of nanoparticle
clusters observed in all the TEM specimens were very similar.
These findings were confirmed by the rheological results: in fact,
GLYMO-modified silica particles had shown the lowest value of
viscosity (compared to the neat resin) and which can be attributed
to the presence of few small aggregates and the reduced attractive
interparticle forces.
Analysing the AMEO-modified silica particles distribution, the
overall dispersion was comparable to the other two systems. How-
ever, certain larger clusters and agglomerates were observed,
exhibiting diameters of several hundreds of nanometres, disturb-
ing the generally fine state of dispersion (Fig. 3). This phenomena
may be related to the fact that during calandering AMEO-modified
silica particles, which have the NH2 groups on their surface, started
cross-linking with the epoxy matrix due to the high pressure in the
calander gap. Due to this effect, a layer of crosslinked molecules
Fig. 2. TEM analysis on the 0.5% GLYMO-modified fumed silica nanocomposite.
1853
Fig. 3. TEM analysis on the 0.5% AMEO-modified fumed silica nanocomposite.
surrounds these clusters of aggregates and are therefore not dis-
persible anymore since they are already chemically bonded. In fact,
during the following period of curing, the matrix can react only
with the functional groups which cover the surface of these aggre-
gates, encapsulating them within the matrix itself. Fig. 4 reports an
SEM analysis on the 0.5% AMEO-modified fumed silica nanocom-
posite. Aggregates and agglomerates are clearly visible on the frac-
ture surface of the tensile test specimens after testing.
2.3. Tensile and fracture toughness results
In our previous work [24], the results of the static tests for the
mechanical characterisation have already been reported, including
DMTA. The results of tensile and fracture toughness tests are sum-
marised here again to give an overall view of the mechanical per-
formances of the materials.
Tensile tests were performed on dog-bone specimens
(L0 = 20 mm, thickness>=2 mm) using a Zwick Z010 universal test-
ing machine according to DIN EN ISO 527 with a crosshead speed
of 1 mm/min. The elongation of the specimen was measured using
a long distance encoder with a gauge length of 25 mm (Zwick Multi
Sense).
Tensile properties are shown in Figs. 5–7. The addition of the fil-
ler to the epoxy resin does not significantly affect the strength of
the material. Unmodified fumed silica particles slightly decrease
Fig. 4. SEM analysis on the tensile fracture surface of a 0.5% unmodified fumed
silica specimen.
1854 M. Battistella et al. / Composites: Part A 39 (2008) 1851–1858

UNMOD. FS The strain to failure of the three types of nanocomposites shows

FS-AMEO an improvement, which is highest for the AMEO-modified silica
2800 FS-GLYMO particles, with an increase of 20% compared to the neat epoxy. This
Young's Modulus [MPa]

also demonstrates the capability of the nanofiller to increase

2600
toughness at low volume fractions.
2400 The fracture toughness test was performed on CT specimens
(width 33 mm and thickness 5 mm) according to ASTM 5045/99
2200 by using an MTS 858 testing machine. The pre-crack was intro-
duced by manual tapping with a razor blade and the crosshead
2000 speed was set at 10 mm/min.
The results of the fracture toughness test are shown in Fig. 8.
1800
The main effect of the nanofiller addition is the improvement of
1600 the fracture toughness for all the nanocomposites produced. In
particular, GLYMO-modified silica particles at 0.5 vol.% show a KIC
0 of 1.34 MPa m0.5, which means an increase of the 54% compared
0.1 0.3 0.5
to the neat epoxy (KIC = 0.87 MPa m0.5). It is worth noting that mor-
Volume Content [%] phological analyses indicated the GLYMO-modified silica particles
as those with the finest and most uniform dispersion also with a
Fig. 5. Tensile test: Young’s modulus for all the nanocomposites. (Values for the
neat epoxy are given by the dashed lines) strong adhesion with the matrix.

2.4. Fatigue results

UNMOD. FS
70 FS-AMEO Fatigue tests were performed using an MTS 858 testing ma-
FS-GLYMO chine, according to procedures reported for metals in the ASTM E
65 647-00. CT specimens (width 33 mm and thickness 5 mm) were
pre-cracked by tapping using a razor blade. The length of the
60 pre-crack was about 2 mm. Then a sine wave cyclic load with
UTS [MPa]

R = 0.1 and f = 15 Hz was applied. The crack tip area was magnified
55 by a travelling microscope connected to a digital camera. Through
a specific acquisition software the image of the crack could be sent
50 from the digital camera to a computer and displayed on the mon-
itor. The crack length was measured with an accuracy of about
45 0.01 mm. The crack growth was regularly detected and the crack
length as a function of the number of cycles was reported. With
40 this acquisition method, regular and smooth crack length vs. num-
0
0.1 0.3 0.5 ber of cycles curves can be produced. The a-N plots exhibited an
Volume Content [%] exponential increase, with the crack growing very slowly in the
first thousands of cycles and then growing faster and faster. A typ-
Fig. 6. Tensile test: tensile strength for all the nanocomposites. (Values for the neat ical a-N curve is shown in Fig. 9 for a 0.3 vol.% AMEO-fumed silica
epoxy are given by the dashed lines) specimen.
The incremental polynomial method was implemented accord-
ing to ASTM E 647-00 and used to evaluate the crack growth rate
UNMOD. FS da/dN. Figs. 10–17 show the Paris curves of each nanocomposite
FS-AMEO compared to that of the reference epoxy.
7 FS-GLYMO In some cases at the DK value chosen for the beginning of the
Strain to failure ε [%]

test, the crack was already in the Paris regime, where the crack
6 growth rate linearly increases with DK. Thus, the crack propagation

UNMOD. FS
5 FS-AMEO
1.4
FS-GLYMO
4 1.2
KIc [MPa*m^0.5]

1.0
3 0.8
0.0
0.1 0.3 0.5
0.6
Volume Content [%]
0.4
Fig. 7. Tensile test: strain to failure for all the nanocomposites. (Values for the neat
epoxy are given by the dashed lines) 0.2
0.0
0.1 0.3 0.5
the strength, while modified fumed silica particles lead to re- Volume fraction [%]
stricted benefits to the tensile parameters. The strength decrease
can be explained by the tendency of the filler to clustering which Fig. 8. Fracture toughness test: KIC for all the nanocomposites. (Values for the neat
leads to weaken the matrix. epoxy are given by the dashed lines)
 M. Battistella et al. / Composites: Part A 39 (2008) 1851–1858 1855

-2
22 0.3vol% AMEO-modified FS sp.1 10
AMEO mod. FS - 0.1%
20
crack length, a [mm]

-3

da/dN [mm/cycle]
10
18
16 10
-4

14
-5
10
12
10 10
-6

8
0 150000 300000 450000 600000 10
-7

No. cycles 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0.5
Δ K [MPa*m ]
Fig. 9. Crack length vs fatigue life for a 0.3% AMEO-fumed silica specimen.
Fig. 12. Paris curves for 0.1% AMEO-modified fumed silica nanocomposite and neat
epoxy. (Yellow symbols and dotted lines are for the neat epoxy, red symbols and
-2 lines for the nanocomposite).
10
UNMOD. FS - 0.3%
-3
10
da/dN [mm/cycle]

-2
10
AMEO mod. FS - 0.3%
-4
10 10
-3

da/dN [mm/cycle]
-5 -4
10 10

-6 -5
10 10

-7 -6
10 10
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1
0.5
Δ K [MPa*m ] -7
10
Fig. 10. Paris curves for 0.3% unmodified fumed silica nanocomposite and of the 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
0.5
neat matrix. (Yellow symbols and dotted lines are for the neat epoxy, blue symbols Δ K [MPa*m ]
and lines for the nanocomposite).
Fig. 13. Paris curves for 0.3% AMEO-modified fumed silica nanocomposite and neat
epoxy. (Yellow symbols and dotted lines are for the neat epoxy, red symbols and
-2
lines for the nanocomposite).
10
UNMOD. FS - 0.5%
-3
10 -2
da/dN [mm/cycle]

10
AMEO mod. FS - 0.5%
-4 -3
10 10
da/dN [mm/cycle]

-5 -4
10 10

-6 -5
10 10

-7 -6
10 10
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0 .9 1 1.1
0.5
Δ K [MPa*m ] -7
10
Fig. 11. Paris curves for 0.5% unmodified fumed silica nanocomposite and neat 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
0.5
epoxy. (Yellow symbols and dotted lines are for the neat epoxy, blue symbols and Δ K [MPa*m ]
lines for the nanocomposite).
Fig. 14. Paris curves for 0.5% AMEO-modified fumed silica nanocomposite and neat
epoxy. (Yellow symbols and dotted lines are for the neat epoxy, red symbols and
threshold could not always be clearly detected. A more accurate lines for the nanocomposite).
procedure to determine the DKth could be a DK-decreasing test.
However, the testing machine software needs a crack opening dis-
placement input in order to perform a DK-controlled test and the the COD device could damage the specimens before applying the
available COD device exerted a too high force in the notch of the testing load. Thus, a DK-decreasing approach could not be applied
small CT specimens used in this work. There was the risk that in this case.
1856 M. Battistella et al. / Composites: Part A 39 (2008) 1851–1858

10
-2 AMEO-modified fumed silica nanocomposite (Fig. 14). Moreover,
GLYMO mod. FS - 0.1% for some specimens an increase in the crack propagation threshold
-3
was observed, even if in the presence of a large scatter in the
da/dN [mm/cycle]

10 threshold values. Indeed, both in the 0.5% AMEO-modified

(Fig. 14) and in the 0.3% GLYMO-modified (Fig. 16) nanocomposites
10
-4
one specimen seemed to suggest a high crack propagation thresh-
old (around DK = 0.4 MPa m1/2) , while another specimen of the
-5 same material showed propagation also at lower DK values.
10
However, the improvement in the crack propagation threshold
is clearly related to the increase in fracture toughness observed
-6
10 for all the nanocomposites. A possible explanation for the higher
crack propagation resistance of the AMEO- modified composites
-7 could be the following: the presence of slightly larger agglomerates
10
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 with respect to the more finely dispersed GLYMO particles could
0.5
Δ K [MPa*m ] induce a more significant crack path deflection, thus resulting in
a higher resistance to crack propagation.
Fig. 15. Paris curves for 0.1% GLYMO-modified fumed silica nanocomposite and This tendency towards an improvement in the crack propaga-
neat epoxy. (Yellow symbols and dotted lines are for the neat epoxy, green symbols tion resistance is promising since it suggests that a further increase
and lines for the nanocomposite).
in filler content can lead to more significant enhancements in the
fatigue behaviour.
-2
The fracture surfaces of some nanocomposites were observed
10 through SEM and typical features like river-lines were detected
GLYMO mod. FS - 0.3%
in the region where the crack propagated under fatigue. As a rep-
-3
resentative example, the fracture surface of a specimen of the
da/dN [mm/cycle]

10
0.5% AMEO-modified fumed silica nanocomposite is displayed in
-4 Fig. 18. On the upper part of the SEM image the small smooth area
10
corresponds to the pre-cracking, while river-lines are visible on the
whole fatigue crack propagation area. The fracture surface be-
-5
10 comes again smooth where the DK approached to the KIC value
and the crack propagated statically.
-6
10

-7
10
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
0.5
Δ K [MPa*m ]
Fig. 16. Paris curves for 0.3% GLYMO-modified fumed silica nanocomposite and
neat epoxy. (Yellow symbols and dotted lines are for the neat epoxy, green symbols
and lines for the nanocomposite).

-2
10
GLYMO mod. FS - 0.5%
-3
10
da/dN [mm/cycle]

-4
10

-5
10

-6
10

-7
10
0.2 0.4 0.6 0.8 1 1.2 1.4
0.5
ΔK [MPa*m ]
Fig. 17. Paris curves for 0.5% GLYMO-modified fumed silica nanocomposite and
neat epoxy. (Yellow symbols and dotted lines are for the neat epoxy, green symbols
and lines for the nanocomposite).

From Figs. 10–17 it can be seen that for the low filler contents
(0.1 and 0.3%) the nanomodification seems to have almost no effect
on the fatigue behaviour, but increasing the fumed silica loading, Fig. 18. SEM view of the fatigue fracture surface for a 0.5% AMEO-fumed silica
some improvements become apparent, particularly for the 0.5% specimen.
 M. Battistella et al. / Composites: Part A 39 (2008) 1851–1858
2.5. Discussion
The addition of very low volume contents of fumed silica parti-
cles led to significant improvements in the fracture toughness
behaviour of epoxy as already shown in [23]. On the other hand,
for cyclic loading some enhancements were achieved, but not as
high as in the static case. This fact could be a hint for further
increasing the filler contents in order to follow the positive trend
of the fatigue behaviour and to achieve more appreciable
improvements.
Wetzel et al. [5] measured the fatigue performance of alumina-
epoxy nanocomposites and carried out an interesting investigation
on the possible mechanisms leading to an improved fracture
toughness as well as to a higher fatigue resistance. Nanoparticles
were believed to induce toughening mechanisms such as crack
deflection, plastic deformation and crack pinning.
Nevertheless, the contrasting static and dynamic behaviour
observed in the present work seems to suggest that different
crack resistance mechanisms should act in the two cases. Thus,
different dispersion levels could be the most appropriate to im-
prove fatigue behaviour or static fracture toughness. This idea is
not supported in the literature by experimental evidences for
spherical nanoparticles, but a similar concept is proposed in the
field of clay nanocomposites, where an intercalated structure is
suggested to be in some cases preferable to completely exfoliated
clays.
Miyagawa et al. [25] studied biobased epoxy/clay composites
and found that intercalated nanocomposites led to higher fracture
toughness than exfoliated clay. Single nanoplatelets did not seem
to be strong enough to prevent crack from propagating, while
the aggregates of intercalated clays deflected crack on the micro-
metre scale and led to a rougher fracture surface and to a higher
critical strain energy release rate. Crack deflection at agglomerates
of intercalated clays in the micron range is proposed as main
toughening mechanism also in [26], where improvements in
fracture toughness up to almost 60% were detected in MMT-epoxy
nanocomposites. An exfoliated structure seems to favour high
modulus, whereas an intercalated structure leads to high
toughness.
Similar results were found in [27] with strongly intercalated
organoclay aggregates inducing fracture toughness improvements
of 55% with respect to neat epoxy.
Blends of intercalated and exfoliated organoclay layers are re-
ported [28] to lead to improvements both in tensile modulus (up
to 20% of increase with 10% of organoclay loading), in fracture
toughness (up to 100%) and in another case [29] also in the fatigue
strength of organoclay/epoxy nanocomposites.
The fatigue behaviour of clay/polypropylene nanocomposites
was investigated in [22] and an improvement of 13% in the fatigue
strength coefficient with respect to the neat PP was found. Failure
was initiated at agglomerates of several nanoplatelets, which in-
duced crazing on the polypropylene matrix and caused a large
number of dimples on the fracture surface.
A hypothesis could be that also in the nanocomposites of the
present study at some extent a slightly agglomerated structure
could be preferable to improve some mechanical properties, partic-
ularly the fatigue behaviour. In the fracture process under quasi
static loading once the crack nucleates, it suddenly propagates,
thus the resistance to crack nucleation is important and a fine dis-
persion on the nanoscale could be useful or even necessary to pre-
vent crack from initiating. On the other hand, in cyclic loading a
large part of the fatigue life can be spent to propagate the crack
up to a critical length and therefore a slightly coarser dispersion
can provide a higher resistance to crack propagation. However, this
hypothesis should be confirmed by further experimental
investigations.
1857
2.6. Conclusions
Three different surface modification conditions have been
tested for fumed silica/epoxy nanocomposites. The morphology
analysis with TEM and SEM showed that the best dispersion was
achieved with GLYMO-modified nanoparticles, while AMEO-modi-
fied and untreated fumed silica were slightly more agglomerated.
The strain to failure was generally improved through the
nanomodification with enhancements up to 20%, whereas the ulti-
mate tensile strength was not significantly affected by the fumed
silica particles.
The most important improvements were achieved in fracture
toughness, up to an increase of 54% at 0.5 vol.% of AMEO-fumed sil-
ica, thus indicating a strong effect on crack propagation resistance
already at the low filler contents of the present work. In the fatigue
test, some enhancements were visible only at 0.5 vol.%, but not so
significant. The different behaviour in static and dynamic loading
seems to suggest that different toughening mechanisms could act
in the two cases.
Further developments will include a deeper investigation on the
toughening mechanisms in nanocomposites and a shift towards
higher filler contents to achieve more appreciable improvements
also in the fatigue performance.
Acknowledgements
Part of the activity reported 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 financial
support.
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