Engineering Fracture Mechanics 73 (2006) 23362345

www.elsevier.com/locate/engfracmech

The inuence of silicate-based nano-ller

on the fracture toughness of epoxy resin
A.J. Brunner

a,*

, A. Necola a, M. Rees a, Ph. Gasser b, X. Kornmann

R. Thomann c, M. Barbezat a

a,1

Laboratory for Materials and Engineering, Empa, Swiss Federal Laboratories for Materials Testing and Research,
CH-8600 Duebendorf, Switzerland
Laboratory for Concrete/Construction Chemistry, Empa, Swiss Federal Laboratories for Materials Testing and Research,
CH-8600 Duebendorf, Switzerland
c
Freiburg Materials Research Centre, Albert-Ludwigs-Universitat, D-79104 Freiburg, Germany
Received 29 September 2005; received in revised form 20 April 2006; accepted 5 May 2006
Available online 19 June 2006

Abstract
Dispersion of nano-sized, silicate-based ller in epoxy resin is expected to yield improved materials properties in several
areas. Various mechanical properties, specically improved fracture toughness, as well as improved ame-retardant eects
are of interest. The nal objective of the research is investigating whether a nano-modied epoxy matrix yields improved
delamination resistance in a ber-reinforced laminate compared to a laminate with neat epoxy as matrix material. As a rst
step towards this goal, the fracture toughness of nano-modied epoxy resin is compared with that of the neat resin. Fracture toughness improvement up to about 50% and energy release rates increased by about 20% are observed for addition of
10 wt.% of organosilicate clay.
 2006 Published by Elsevier Ltd.
Keywords: Fracture toughness; Silicate-based nano-scale ller; Nano-composite epoxy; Standard test procedure

1. Introduction
Nano-composites from polymeric matrix materials (thermoplasts or thermosets) reinforced with nano-sized
llers (e.g. carbon nano-tubes, nano-sized particles or intercalated layers) are an active area of research and
the number of published papers has reached a stage where rst reviews are summarizing the state of the
art [13]. The range of properties where nano-sized llers are expected to yield improvements over neat polymers is wide, improved impact properties [4,5] and re-resistance or retardance [6] can be cited as examples.

Corresponding author. Tel.: +41 44 823 44 93; fax: +41 44 821 62 44.
E-mail address: andreas.brunner@empa.ch (A.J. Brunner).
Present address: ABB Switzerland Ltd., Corporate Research, CH-5405 Baden-Dattwil, Switzerland.

0013-7944/$ - see front matter  2006 Published by Elsevier Ltd.

doi:10.1016/j.engfracmech.2006.05.004

A.J. Brunner et al. / Engineering Fracture Mechanics 73 (2006) 23362345

2337

The eect of nano-sized llers on fracture behaviour, specically fracture toughness, has also been investigated
recently [710].
The aim of the present paper is based on the idea to use epoxy with a relatively small amount of nano-size
ller as matrix in ber-reinforced laminates [11,12]. As a rst step, neat and nano-modied epoxy specimens
without ber reinforcement have been prepared for a comparison of the fracture toughness of the matrix
material itself. By that, the applicability of the existing test procedure [13] to nano-composite thermosets is
investigated. Additional properties of the neat and nano-modied epoxy are also determined (partly taken
from [11]) and compared.
2. Experimental
Plates (nominally 200 mm 150 mm 4 mm) of epoxy resin (Araldite CY 225 resin and Aradur HY 925
hardener from Huntsman) have been manufactured by casting in an Aluminium mould both with and without
functionalized organosilicate clay based ller (10 wt.%, corresponding to about 7.2% of anorganic phase), type
and processing details are described in [11]. Two batches of neat epoxy and nano-modied epoxy have been
prepared. The plate materials have been characterized with (a) visual inspection, (b) X-ray diraction and (c)
dynamic mechanical thermal analysis (DMTA). Additional results for the second batch of nano-modied
epoxy (compared with those of a third batch of neat resin) are described in [11].
X-ray diraction (XRD) spectra have been obtained in a h2h conguration (equipment Panalytical XPert
pro), with scan steps of 0.05 and a scan speed of 0.05/5 s. The beam optics were as follows: Soller slit
0.04 rad, xed divergence slit (1/4), 10 mm mask, xed anti-scatter slit (1/2) for the incident, and xed
anti-scatter slit (1/4), Soller slit 0.04 rad, and nickel lter for the diracted beam optics. The detector (type
XCelerator) was comprised of 127 elements (each 70 lm wide) yielding an active length (240 mm goniometer
radius) of 2.1226 and a minimal step length of 0.0167.
Dynamic mechanical thermal analysis (DMTA) was performed and the properties of the neat and nano-modied epoxy have been determined between 120 C and +160 C in a three-point bending conguration under
deformation control, a forced oscillation frequency of 10 Hz, and a heating rate of 2 C/min (Eplexor 500N
from Gabo Qualimeter GmbH, Germany). A static load of nominally 1.0% strain and a superimposed sinusoidal load of nominally 0.03% strain were applied to samples of nominal size of 25 mm 15 mm 4 mm with a
span length of 20 mm and the results compared with DMTA data obtained earlier on tensile specimens [11].
Single edge notched bending (SENB) specimens have been prepared from both batches of each neat and
nano-modied epoxy. SENB specimens were nominally 63 mm long, 15 mm wide, and 4 mm thick (=plate
thickness). They were tested to determine the critical fracture toughness KIC and critical energy release rate
GIC, respectively, according to the standard test method for polymers [13] issued by the International Organisation for Standardisation (ISO). A V-shaped notch was machined to a depth of about 3.5 mm, and then
extended by knifeblade tapping to a total length around 7 mm (eectively ranging from about 6.3 to
8.3 mm). Tests have been performed with a cross-head speed of 1 mm/min at +23 C and 50% relative humidity. For the second batches of specimens, the indentation correction (see Section 5.4 of [13]) has been measured
for each specimen individually.
The fracture mechanics test data have been analysed in accordance with the prescriptions of the standard
test method [13]. Spreadsheets developed and validated at the authors laboratory in an international round
robin using poly-methyl-methacrylate (PMMA) specimens [14] were used for the data analysis. A magnifying
glass (magnication 8 times) has been used to visually determine the initial crack lengths which have been measured at ve positions across the thickness. Comparative plane strain compression testing has been performed
to determine the compressive yield stress and the compressive modulus applying a set-up and a procedure
described in [15].
After fracture testing, the fracture surfaces have been examined by scanning electron microscopy (SEM).
Images have been taken with the secondary electron detector in an environmental scanning electron microscope (type XL30 from Philips) operated in the high-vacuum mode. The specimen surfaces have been coated
with ash-evaporated carbon.
Transmission electron micrograph (TEM) images were taken with a TEM-equipment (type LEO 912
Omega from Zeiss) at an accelerating voltage of 120 kV. Preparation details are described in [11].

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A.J. Brunner et al. / Engineering Fracture Mechanics 73 (2006) 23362345

3. Results
Visual inspection showed that the nano-modied epoxy appeared less translucent and of a darker colour
than the neat epoxy, but homogeneous on a macroscopic scale.
X-ray diraction spectra of both, neat and nano-scale modied epoxy are shown in Fig. 1 for a 2-h range
between 5 and 25. The diractograms for dierent batches of each neat and nano-scale lled epoxy coincide,
and, therefore, scales have been shifted for the presentation (Fig. 1). The neat epoxy essentially yields broad,
featureless diractograms reecting the random network structure. Both batches of nano-lled epoxy, however, show a distinct peak at a 2-h value of 19.5. This is attributed to the combined (1 1 0) and (0 2 0) reections of the intercalated silicate clay, see [11] for details.
Transmission electron microscopy (TEM) images of the nano-modied epoxy of the second batch of the
present study (Fig. 2, and additional TEM shown in [11]) indicate intercalation of the silicate layers in the
epoxy with distances between silicate layers on the order of 9 nm. Homogeneously intercalated regions extend
over several hundred nano-meters up to the micrometer range (Fig. 2).
DMTA curves are shown in Fig. 3 for neat and nano-size lled epoxy in a three-point bending conguration. The data can be compared with earlier DMTA results obtained on tensile specimens, shown in [11]. A
signicant increase in the elastic modulus (around 40%) is recorded at room temperature by the addition of
nano-size ller to the neat epoxy. Considerable in-batch and batch-to-batch variations are observed in the
modulus measurements. Contrary to that, the glass transition temperatures, taken as the maxima of the
tan d curves for the dierent batches of neat epoxy, fall all into a narrow range around +134 C, basically
independent of the test conguration (bending in present paper or tensile quoted in [11]). The values for
the nano-size modied epoxies are lower than for the neat epoxy and vary, they amount to about +109 C
for the rst, and around +114 C for the second batch. The latter value again agrees with the earlier tests
reported in [11].
Loaddisplacement diagrams from the fracture toughness tests on both types of epoxy are shown in Fig. 4.
It can be noted that the nano-modied epoxy specimens yield a larger slope and hence larger stiness as well
as a larger variation in slope (both in-batch and from batch-to-batch) than the neat epoxy. Corrected displacement values to fracture according to the ISO standard [13] are about 0.16 mm for the neat and slightly less for
the nano-modied epoxy (0.130.14 mm).
The fracture data are summarized in Table 1 (fracture toughness) and Table 2 (energy release rate). For
neat epoxy, eight specimens of each batch, out of 13 and 16, respectively are valid according to the criteria

Intensity [arbitrary units]

a)

c)

b)

d)

5000

8000

4500

7000

4000
6000
3500
3000

5000

2500

4000

2000

3000

1500
2000
1000
1000

500
0

0
5

11

13

15

17

19

21

23

25

2- []
Fig. 1. X-ray diraction spectra of neat and nano-size lled epoxy, 2-h range from 5 to 25, (a) neat epoxy rst batch, (b) neat epoxy
second batch, (c) nano-modied epoxy rst batch, (d) nano-modied epoxy, second batch; (a) and (c) left hand scale, (b) and (d) right hand
scale (shift between the scales to show the curves without overlap). The peak at 19.5 in the nano-modied epoxy is attributed to the
combined (1 1 0) and (0 2 0) reections, indicating a spacing of the silicate layers of about 8.8 nm, for details see [11].

A.J. Brunner et al. / Engineering Fracture Mechanics 73 (2006) 23362345

2339

Fig. 2. Transmission electron micrograph (TEM) taken at low magnication on a specimen from the second batch of nano-modied
epoxy (additional TEM shown in [11]).

Fig. 3. Dynamic mechanical thermal analysis of neat and nano-size lled epoxy, three-point bending conguration, temperature range
120 to +160 C tested at 10 Hz, (a) neat epoxy rst batch, (b) neat epoxy second batch, (c) nano-modied epoxy rst batch, (d) nanomodied epoxy, second batch. The shift in Tg indicates a lower cross-link density for the nano-modied epoxy, the width of the peak is
discussed in [11].

p
dened in [13]. Averaging over all valid specimens from both batches yields a KIC of 0.740 0.140 MPa m,
2
and a GIC of 134 24pkJ/m for the neat epoxy. The KIC average values for batch 1 and 2, respectively, are
0.750 and 0.730 MPa m with standard deviations of 12.5% and 24.9%. Corresponding GIC values are 132.6

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A.J. Brunner et al. / Engineering Fracture Mechanics 73 (2006) 23362345

60

50

Load [N]

40

30

20

10

0
0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

Corrected Displacement [mm]

Fig. 4. Comparison of typical loaddisplacement diagrams from fracture toughness tests for neat and nano-modied epoxy. The four
curves with maximum loads above 40 N (black) are from nano-modied epoxy, the others (grey) from neat epoxy (rst batch bold, second
ne lines, rst specimen solid, second specimen dashed line). There is little in-batch and batch-to-batch variation for the neat epoxy, but
considerable in-batch and batch-to-batch variation for the nano-modied epoxy.
Table 1
Fracture toughness results on neat and nano-modied epoxy resin, only specimens fullling all validity criteria specied in the standard
procedure [13] are used to calculate the averages and standard deviations (s.d.)
Epoxy

Batch

Valid tests

Total tests

Average KIC
p
(MPa m)

s.d.
p
(MPa m)

s.d.
(%)

Min.
p
(MPa m)

Max.
p
(MPa m)

Neat
Neat
Neat
Nano
Nano
Nano

1
2
1+2
1
2
1+2

8
8
16
4
5
9

13
16
29
10
5
15

0.750
0.730
0.740
0.936
1.133
1.045

0.094
0.182
0.140
0.098
0.157
0.163

12.5
24.9
18.9
10.5
13.9
15.6

0.605
0.420
0.420
0.843
0.977
0.843

0.916
1.019
1.019
1.074
1.382
1.382

Table 2
Energy release rate results on neat and nano-modied epoxy resin, only specimens fullling all validity criteria specied in the standard
procedure [13] are used to calculate the averages and standard deviations (s.d.)
Epoxy

Batch

Valid tests

Total tests

Average
GIC (J/m2)

s.d.
(J/m2)

s.d.
(%)

Min.
(J/m2)

Max.
(J/m2)

Neat
Neat
Neat
Nano
Nano
Nano

1
2
1+2
1
2
1+2

8
8
16
4
5
9

13
16
29
10
5
15

132.6
135.9
134.2
135.8
160.9
149.7

11.9
33.0
24.0
13.5
23.5
22.8

9.0
24.3
17.9
10.0
14.6
15.2

120.8
115.7
115.7
120.7
133.3
120.7

149.9
183.9
183.9
147.4
197.9
197.9

and 135.9 J/m2 with standard deviations of 9.0% and 24.3%, respectively. For the nano-modied
epoxy, the
p
two batches yield clearly diering results. KIC average values are 0.936 and 1.133 MPa m with standard deviations of 10.5% and 13.9%, and GIC average values 135.8 and 160.9 J/m2 with standard deviations of 10.0%

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2341

Table 3
Comparison of properties of the neat and nano-lled epoxy (average values from both batches with standard deviations, except where
noted for the nano-modied epoxy), quantities marked with * are from [11] determined on a third batch for the neat and from the second
batch for the nano-modied epoxy
Property

Neat epoxy

Nano-modied epoxy

Density/specic gravity [g/cm3]

Silicate content [wt.%]a
Tensile modulus [MPa] *
Tensile strength [MPa] *
Elongation at break [%] *
Compressive modulus [MPa]
Compressive yield strength [MPa]
p
Fracture toughness KIC [MPa m]
2
Energy release rate GIC [J/m ]
Glass transition temperature [C]

1.2115 0.0004

3100 50
80.3 0.8
7.4 1.7
2300 120b
92 1.2d
0.740 0.140f
134 14h
+134

1.2602 0.0061 (+4.0%)

7.2 0.02
4700 130 (+52%)
51.5 1.4 (36%)
1.2 0.1 (84%)
3600 160c (+56%)
108 1.5e (+17%)
1.133 0.160g (+53%)
161 24i (+20%)
+109/+114j

Determined as ignition residue according to EN 60 (losses on ignition).

Average for two batches with ve measurements each, values for rst and second batch, respectively are 2370 85 MPa and
2200 90 MPa.
c
Average for two batches with eight and four measurements, values for rst and second batch, respectively are 3660 145 MPa and
3470 100 MPa.
d
Average for two batches with ve measurements each, values for rst and second batch, respectively are 93 0.1 MPa and
91 0.6 MPa.
e
Average for two batches with eight and four measurements each, values for rst and second batch, respectively are 108 1.1 MPa and
106 0.3 MPa.
f
Average for two batches with eight and seven measurements each, values for rst and second batch, respectively are
p
p
0.750 0.09 MPa m and 0.730 0.18 MPa m.
p
g
Average for second batch with ve measurements, rst batch average is 0.936 0.1 MPa m, however, there is evidence of eects from
residual stresses in the rst batch.
h
Average for two batches with eight and seven measurements each, values for rst and second batch, respectively are 133 12 J/m2 and
136 33 J/m2.
i
Average for second batch with ve measurements, rst batch average is 136 14 J/m2; however, there is evidence of residual stresses in
the rst batch.
j
Values for rst and second batch, respectively, there is evidence for eects from residual stresses in the rst batch.
b

p
and 14.6%, for batch 1 and 2, respectively. Taking the averages of 1.133 MPa m and of 161 J/m2 (nano-modied epoxy, batch 2), the addition of 10 wt.% of nano-ller to the epoxy yields an increase of about 50% in
fracture toughness and of about 20% in energy release compared with neat epoxy. Additional properties of
the neat and nano-modied epoxy, partly taken from [11], are compared in Table 3.
Fig. 5 shows selected SEM images of fracture surfaces of neat and nano-modied epoxy. The neat epoxy
shows comparatively smooth and featureless surfaces at all magnications (up to 51 200). Nevertheless, a
low-contrast texture is recognizable at higher magnications (beyond about 15 000), oriented roughly parallel
to the crack propagation. The nano-modied epoxy, on the other hand, shows a platelet-type, fairly corrugated surface even at low magnications (6500). No crack propagation oriented features have been observed
for the nano-modied epoxy. SEM images taken at higher magnications (>20 000) indicate distinct features
in the sub-micrometer range on the individual platelets of the nano-modied epoxy.
4. Discussion
The increase of roughly 40% in modulus upon modication by nano-size ller observed in the DMTA
three-point bending experiments compares quite well with data obtained from the static plain-strain compression tests (increase around 55%, see Table 3). The relatively high absolute values obtained compared with the
earlier DMTA tests on tensile specimens [11] are quite likely induced by the sample geometry used (low span
to thickness ratio in the bending tests). The glass transition temperature (Tg) appears to be lowered by about
2025 C upon introducing the nano-size ller into the base system. Simultaneously, the width of the tan d
peak is increasing. This indicates a probable change in the cross linking density and homogeneity of the resin

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A.J. Brunner et al. / Engineering Fracture Mechanics 73 (2006) 23362345

Fig. 5. Selected SEM-images of the fracture surfaces of neat (left), and nano-modied epoxy (right) at increasing magnication (top to
bottom). The neat resin yields at and virtually featureless surfaces (except for a ne texture roughly oriented parallel to the crack
propagation), while the nano-modied epoxy shows a platelet-like structure with distinct features ranging down to 200400 nm.

network due to the interaction between resin and functionalized ller. These results are consistent with the
DMTA data obtained previously on this system [11].
The width of the transition peak for both batches of nano-modied epoxy is comparable. However, there is
a dierence in Tg determined from DMTA between the two batches. The rst batch yields the lower value
(around +109 C), indicating a lower cross-linking density than in the second batch (Tg around +114 C).
It is expected that this would yield a slightly higher fracture toughness, contrary to what is eectively observed.
Compared with neat resin, the width of the transition peak is increased for both batches of nano-modied
epoxy. This could be interpreted as a larger range of cross-linking density in the nano-modied materials, consistent with the dispersion of regions of nano-intercalated silica in the epoxy.
Comparing the overall averages of the fracture mechanics data (averaging over valid specimens only) indicates that the addition of 10 wt.% of functionalized nano-scale ller changes the fracture toughness KIC by
about 50% and the energy release GIC by about 20%. When the data are analysed with respect to the dierent
batches (plates), the batch-to-batch variation for the neat epoxy is clearly within one standard deviation. The
average values for the two batches of nano-modied epoxy do dier somewhat more (see Tables 1 and 2). The
formation of pre-cracks initially deviating from the plane of symmetry as visually observed during blade tapping of the rst batch of nano-modied epoxy points toward residual stresses from manufacturing. This was

A.J. Brunner et al. / Engineering Fracture Mechanics 73 (2006) 23362345

2343

not observed for the second batch that yielded higher average values of KIC and GIC. The eect of residual
stresses could hence explain the lower fracture toughness of the rst batch of nano-modied epoxy (in spite
of the lower cross-link density). The second batch only is, therefore, taken for quoting fracture toughness data
for nano-modied epoxy.
The at and relatively featureless fracture surface of neat epoxy resin specimens is consistent with a relatively brittle fracture mechanism. The comparatively strong corrugation of the fracture surfaces of the
nano-modied epoxy, on the other hand, is consistent with the measured, improved fracture toughness and
energy release rate compared with the neat epoxy. For the nano-modied epoxy, there are distinct structural
features on the surface of the platelets with sizes of 500 nm or less. Considering the silica-intercalated regions
with diameters of up to 1000 nm or more indicated by TEM images on the second batch of nano-modied
epoxy (Fig. 2) it can be speculated that these features in the SEM images could be due to fracture between
such intercalated regions and neat epoxy surrounding them. Such a mechanism would explain the corrugated
fracture surfaces as well as the improved fracture toughness compared with neat epoxy resin. It has to be noted
that no distinct dierence has been observed so far between the fracture surfaces of the dierent batches of the
nano-modied epoxy.
It can be added that there is a relatively large number of invalid tests if all criteria, including initial crack
length specimen width (a/w)-ratio and modulus dierence, of the standard analysis [13] are applied. 16 out of
29 (55%) for neat and 9 out of 15 (60%) of the tests were valid. a/w-ratios outside the recommended limits of
0.45 (lower) and 0.55 (upper) were the most frequently violated criterion (eight neat and one nano-modied
specimen), while pre-crack length variation exceeding 10% across the specimen width yielded invalid results
for two neat and one nano-modied specimen.
The KIC and GIC data can also be analysed with respect to various parameters. The correlation of KIC with
(a/w)-ratio (Fig. 6) is discussed as an example. For both types of epoxy, an apparent trend for increasing KIC
values with increasing a/w-ratio is observed. This trend persists, even if only values for a/w within the recommended limits (0.450.55) are considered.
The scant literature data on eects of nano-scale llers on the fracture toughness of epoxy indicates an
increase in fracture toughness for the nano-composite but the magnitude of the eect quite likely depends
on the weight fraction of the nano-scale ller [710]. For a heavily lled epoxy with 60 wt.% of conventional
p
(not nano-dispersed) quartz ller the supplier data sheet [16] indicates values of KIC and GIC (1.82.0 MPa m

Fig. 6. KIC values of neat and nano-modied epoxy plotted as function of the ratio between initial crack length, a, and specimen width, w.
Both batches of nano-modied epoxy are shown. Note the trend for increasing KIC with increasing a/w (see text for details).

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A.J. Brunner et al. / Engineering Fracture Mechanics 73 (2006) 23362345

and 300350 J/m2, respectively) that are higher than those obtained for epoxy with 10 wt.% nano-intercalated
silicate clay.
From an application point of view, it will be even more interesting to see whether or by how much the fracture toughness and other properties are changed if the matrix in a bre-reinforced laminate is replaced by the
nano-modied epoxy. Improvements in various properties have been observed when a glassber laminate
with nano-modied epoxy matrix is compared with a laminate with neat epoxy matrix: averages of exural
modulus (+5.7%), of exural strength (+27.5%), and of exural strain (+23.5%) are all increased [11]. This
raises the expectation that the improved fracture properties of the nano-modied epoxy reported in the present
paper can also be transferred to bre-reinforced laminates. The ESEM images shown in [11] do yield indications of improved bre-matrix adhesion when nano-modied epoxy is used as matrix in a glassbre laminate
(compared with a neat epoxy matrix laminate). Combined with some improvement of the fracture toughness
of the matrix, this could well result in a considerably improved delamination resistance.
5. Conclusions
An increase between about 40 and 50% in fracture toughness and around 1020% in energy release has been
observed relative to the neat epoxy for nano-modied epoxy prepared by addition of 10 wt.% of functionalized
organosilicate clay. Scanning electron microscopy images indicate considerable dierences in the fracture surfaces of neat and nano-modied epoxy, consistent with the measured fracture data. Various other properties
are improved in the nano-modied epoxy, e.g. a considerable increase in tensile and compressive modulus by
more than 50% is observed. The most noteworthy exceptions known to date are ultimate tensile strength, elongation at break, and glass transition temperature, which are all reduced.
In principle, the standardized ISO test procedure for fracture toughness measurements of polymers [13] can
be applied to the nano-modied epoxy. A considerable percentage of tests (between 40% and 45%) have been
found to be invalid according to the criteria of the standard test procedure and it is recommended to prepare
more than the minimum number of ve specimens per material.
The nano-modied epoxy hence shows potential for improving delamination resistance when used as
matrix in bre-reinforced laminates, analogous to the improvement of other mechanical properties reported
in the present paper and in [11].
Acknowledgements
Mr. U. Gfeller provided XRD data, and Mr. K. Ruf DMTA results. Specimen preparation has been performed by Mr. D. Volki and a rst series of fracture tests been conducted by Mr. M. Heusser.
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