Composite Structures 86 (2008) 6977

Contents lists available at ScienceDirect

Composite Structures
journal homepage: www.elsevier.com/locate/compstruct

Fracture toughness of the nano-particle reinforced epoxy composite

Byung Chul Kim, Sang Wook Park, Dai Gil Lee *
Department of Mechanical Engineering, Korea Advanced Institute of Science and Technology, ME3221, Guseong-dong, Yuseong-gu, Daejeon 305-701, Republic of Korea

a r t i c l e

i n f o

Available online 18 March 2008

Keywords:
Fracture toughness
Epoxy adhesive
Nano-particle
Carbon black
Nanoclay
Cryogenic temperatures

a b s t r a c t
Although thermoset polymers have been widely used for engineering components, adhesives and matrix
for ber-reinforced composites due to their good mechanical properties compared to those of thermoplastic polymers, they are usually brittle and vulnerable to crack. Therefore, ductile materials such as
micro-sized rubber or nylon particles are added to thermoset polymers are used to increase their fracture
toughness, which might decrease their strength if micro-sized particles act like defects.
In this work, in order to improve the fracture toughness of epoxy adhesive, nano-particle additives such
as carbon black and nanoclay were mixed with epoxy resin. The fracture toughness was measured using
the single edge notched bend specimen at the room (25 C) and cryogenic temperature (150 C). From
the experimental results, it was found that reinforcement with nano-particles improved the fracture
toughness at the room temperature, but decreased the fracture toughness at the cryogenic temperature
in spite of their toughening effect.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Thermoset polymers have been widely used for engineering
components, adhesives and matrix for ber-reinforced composites
due to their good mechanical properties compared to those of thermoplastic polymers. However, since they are usually brittle and
vulnerable to crack, ductile thermoplastic materials such as micro-sized rubber or nylon particles are added to the polymers to increase their fracture toughness, which compromises the strength
of thermoset polymers.
The addition of rigid micro-scale llers to polymers often increases its strength, but decreases the toughness since the llers
or agglomerates may induce stress concentration, which initiates
cracks and make them become larger than the critical crack size
that causes failure. Therefore, it is a good way to reinforce the polymers with nano-particles in order to increase the fracture toughness without sacricing the mechanical strength of the polymers
because well-dispersed nano-particles are much smaller than the
critical crack size to initiate failure. Thus, they provide an avenue
for simultaneously toughening and strengthening polymers [1].
Nano-particle reinforced polymer composites have been widely
studied and some researchers already studied the improvement of
the fracture toughness of polymers. Carbon nanotubes (CNT) have
shown a high potential to improve the mechanical properties of
polymers as well as electrical properties [2,3]. Gojny et al. [4] reported that DWCNT (double walled CNT) could increase both tensile strength and fracture toughness. Florian et al. [5] studied the
* Corresponding author. Tel.: +82 42 869 3221; fax: +82 42 869 5221.
E-mail address: dglee@kaist.ac.kr (D.G. Lee).
0263-8223/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compstruct.2008.03.005

inuence of different carbon nanotubes on the tensile properties

as well as fracture toughness and explained the contribution of
nanomechanical mechanisms to enhancement of the fracture
toughness. However, CNT has not been widely used to improve
the mechanical properties because of its high material cost. Since
the rst discovery by Toyota researchers on the reinforcing effect
of relatively cheap nanoclay on the polymeric material [6], many
researchers have focused on it: Weiping et al. [7] reported that
nanoclay could increase the fracture toughness of epoxy by 2.2
and 5.8 times. Lei et al. [8] studied the dependences of Youngs
modulus and fracture toughness on clay concentration using the
tensile and 3-point bending methods. Qi et al. [9] investigated
the effect of several nanoclay additives, which were mixed with
DGEBA epoxy resin using a mechanical stirrer, on tensile modulus,
tensile strength and fracture toughness of the nanocomposite. Ho
et al. [10] increased the tensile strength and Vickers hardness value of the epoxy using nanoclay mixed by mechanical stirring
method. Carbon black also has been used for reinforcement of
polymers, which has been mainly used for reinforcing elastomer
and for UV protection, electromagnetic interference shielding and
anti-static shielding of polymers [11]. Novak [12] studied the electro-conductive HDPE/CB composite with improved toughness.
However, mechanical reinforcing effects of the carbon black have
not been widely studied yet.
As mentioned above, most of researchers have been interested
in the mechanical properties of nanocomposites at the room temperature. However, only few researchers studied the cryogenic
properties of epoxy and its composite [1315].
A study on the nanocomposite is important since it can affect
the structural characteristics of a composite structure when it is

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B.C. Kim et al. / Composite Structures 86 (2008) 6977

used as a matrix of the laminates or the reinforcement of a foam

core. It was reported that the characteristics of a composite structure could be improved when the nanoclay reinforced epoxy was
used as a matrix of laminates. Antonio et al. [16] improved the
damping coefcient and the energy dissipation characteristic of
the glass/epoxy composite using nanoclay particles. Hosur et al.
[17] improved the impact characteristic of the composite sandwich
structure using the nanoclay infused foam.
In this study, carbon black and nanoclay were mixed with epoxy
to investigate their toughening effect. The fracture toughness was
measured using the single edge notched bend (SENB) specimens
with respect to the particle content at the room (25 C) and cryogenic temperature (150 C). In order to investigate their toughening mechanism, the fracture surface was also observed with SEM.

Epoxy resin
+ nanoparticles

Epoxy resin
+ nanoparticles

Hopper

2. Specimen preparation
2.1. Materials
The epoxy matrix used in this study was the modied bisphenol-A type epoxy resin (YD-114F, Kukdo Chemical, Korea) and
polyetheramine hardener (JEFFAMINE D-230, Huntsman, US) were
used as a curing agent. The proper mixing ratio was 10:3. The conductive carbon black (Ketjenblack EC-300J, Ketjen Black International Co., Japan) and the nanoclay (Cloisite 93A, Southern Clay
Products, US), which was natural montmorillonite modied with
quaternary ammonium salt, were used as reinforcements. Table 1
shows the physical properties of the nano-particles.

1st roll

3rd roll

2nd roll

Scraper

Vacuum

2.2. Dispersion method of nano-particles

As shown in Fig. 1, the mixing process consisted of three steps.
Firstly, the nano-particles were manually mixed with the epoxy resin, followed by mixing at 60 C with a magnetic stirrer for 60 min,
as shown in Fig. 1a. Secondly, 0.15 kg of the mixture was added
batch-wise to the three roll mill (Exakt 50, Exakt Vertriebs GmbH,
German) for high shear mixing, as shown in Fig. 1b. Gojny et al.
[18] and Yasmin et al. [19] reported that the three roll mill provided a good dispersion of DWCNTs and carbon blacks in an epoxy
resin. The gap size between the ceramic rolls of the diameter of 50
mm was 5 lm. The rotational speeds of the rst roll, second roll,
and third roll were set to 60, 120 and 240 rpm, respectively. The
maximum shear rate could be obtained between the second and
the third roll, which was 6.28  104 m/m s. The collected suspension was put into the roll mill repeatedly until uniform dispersion
was achieved. Five time repeating was required to achieve saturated mechanical properties, as explained in the following section
of experimental results. Finally, the dispersed suspension was
mixed with the hardener in vacuum using a magnetic stirrer for
30 min, as shown in Fig. 1c. After hardener mixing, the mixture
was cured for 2 h at 125 C.

Epoxy resin
+ nanoparticles
+ hardener

Fig. 1. Dispersion process of nano-particles: (a) mixing with a magnetic stirrer at

60 C, (b) mixing with a three roll mill, (c) hardener mixing in vacuum with a
magnetic stirrer.

52.8

1
12

10

2.3. Specimen fabrication

The single edge notch bend (SENB) specimens were used to
determine the fracture toughness, KIc, as shown in Fig. 2, which satTable 1
Physical properties of nano-particles

48

Physical properties

Ketjenblack EC-300J

Cloisite 93A

Porosity (%)
Density (g/cm3)
Surface area (m2/g)
Particle size (lm)
d-spacing, d001 ()

69.3
2.1
950
0.035

1.88
800
213
24

Fig. 2. Dimension of the SENB (single edge notched bending) specimen and the
xture for the exural test (dimensions in mm).

ised the requirements of ASTM D5045-99 [20]. In order to get

accurate KIc values, it is important to make a very sharp pre-crack
and eliminate residual stress around the crack tip. In this work, the

B.C. Kim et al. / Composite Structures 86 (2008) 6977

71

Impactor

Guide bearing

Razor blade
Fig. 3. Drop weight tapping machine for making a pre-crack of SENB specimens.

Fig. 4. Pre-crack generated by tapping with a fresh razor blade: (a) pre-crack
generated at the end of the notch, (b) magnied crack tip.

notch tip in Fig. 4a was machined using a rotating saw. The precrack was generated by tapping a fresh razor blade into the notch
tip with a drop weight shown in Fig. 3. After fabricating SENB specimens, the crack tip was observed using SEM.

Fig. 5. Effect of the residual stress around the crack tip and the crack length: (a) KQ
vs. displacement before and after relaxation, (b) KIc with respect to the a/W ratio.

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B.C. Kim et al. / Composite Structures 86 (2008) 6977

Since machining and tapping process induced residual stress

around the crack tip, each specimen was kept in an oven at 60 C
for 30 min for relaxation. After relaxation, the crack tip was found
to be closed, whose radius was smaller than 500 nm, as shown in
Fig. 4b.
3. Experiments
The mode I fracture toughness, KIc, was determined by the 3point bending method with SENB specimens and the xture as
shown in Fig. 2. The tests were performed using INSTRON 5583
(INSTRON corp., MA, USA) equipped with an insulation chamber.
The crosshead speed was 10 mm/min as recommended by ASTM
D5045-99, which was fast enough to prevent the viscoelastic
behavior of the epoxy [20].
The KIc values were determined using the following relationship
[20]:


PQ
KQ
f x; W 2B
1
1=2
BW
2
1:99

x1

x2:15

3:93x

2:7x

; x a=W 2
f x 6x1=2
1 2x1  x3=2
 2
KQ
3
B; a; W  a P 2:5
rYS

where KQ is a provisional fracture toughness, f the shape factor, PQ

the peak load, B the specimen thickness (6 mm), W the specimen
width (12 mm), a the crack length, rYS the yield strength.
Eq. (3) was satised for the dimensions of fabricated SENB specimens. The tests were performed with respect to the particle content at the room (25 C) and cryogenic (150 C) temperature.
Also, the fracture surfaces were observed with SEM.

4. Experimental results and discussion

4.1. Effect of the residual stress around the crack tip and the crack
length
ASTM recommends either inserting a fresh razor blade by tapping or sliding a new razor blade across the notch root to initiate
a pre-crack [20]. However, it can generate large amount of residual
stress around the crack tip. Though many researchers have suggested the fracture toughness of polymeric materials, they have
not inspected the crack tip visually or investigating the effect of
the residual stress. In addition, it is not easy to make the specimen
with the same crack length. In order to get valid fracture toughness
values, some experiments with epoxy specimens were performed
before testing the effect of nano-particles.

1
Fracture toughness, K Ic (MPa m1/2)

0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Neat epoxy

2.0wt% CB
(5 times)

100nm

2.0 wt% CB
(10 times)

100nm

Fig. 6. The effect of the circulation time during mixing: (a) the fracture toughness with respect to the circulation time, (b) TEM images of the epoxy reinforced with 2.0 wt% of
the carbon black and nanoclay (left: CB, right: nanoclay).

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B.C. Kim et al. / Composite Structures 86 (2008) 6977

To check the effect of the residual stress, two SENB specimens

were prepared. The one was kept in an oven at 60 C for 30 min
for relaxation, while the other was left at the room temperature
of 25 C after generating a pre-crack. Fig. 5a shows the temporary
fracture toughness change during the exural test for both the
specimens. The compressive load was replaced by the temporary
fracture toughness since it was dependent on the specimen geometry. For the specimen without relaxation, a brittle fracture occurred due to residual stress around the crack tip, which was
followed by ductile crack propagation. However, after relaxation,
a ductile fracture was observed from the initiation in the specimen.
From this result, it was concluded that the fracture toughness
might be overestimated without eliminating the residual stress
around the crack tip. Consequently, it has been concluded that a
valid fracture mode could not be observed if the specimen is not
relaxed after generation of pre-crack. Fig. 5b shows the measured
fracture toughness with respect to a/W ratio. Since the KIc value increased as the a/W ratio was increased, the a/W ratio should be
carefully selected to get a valid KIc. Therefore, all the specimens
were relaxed before experiments and a/W ratios were checked to
satisfy the dimensional requirement, 0.45 < a/W < 0.55, after each
experiment [20].

4.2. Effect of the mixing time on the dispersion state

In order to get a uniform dispersion state, the collected nanoparticle/resin suspension was put into the three roll mill repeatedly. As shown in Fig. 6a and b, ve times was enough to get a reasonably uniform dispersion and a saturated fracture toughness.
High shear mixing was effective to disperse carbon black (CB) particles in the viscous resin.
4.3. Effect of nano-particles on the fracture toughness
Fig. 7b shows the fracture toughness with respect to CB content.
The CB of more than 3.0 wt% was not uniformly dispersed due to
the nonlinear increase of viscosity of the resin/CB suspension. As
the CB content was increased, the KIc value gradually increased.
Fig. 7a shows the typical KQ vs. displacement curves for each content. The fracture modes were ductile when the CB content was
less than 2.0 wt%. When the CB content was 2.0 wt%, the fracture
toughness was improved by 18% on the average and the fracture
mode was still ductile. When the CB content was 3.0 wt%, the fracture mode changed from ductile to brittle with the fracture toughness increase by 23% on the average.

1.2

1
Neat epoxy
1.0wt%CB
2.0wt%CB
3.0wt%CB

0. 9

0. 7

1/2

K Q (MPa m )

1/2

K Q (MPa m )

0. 8

Neat epoxy
0. 5wt%NC
1. 0wt%NC
2. 0wt%NC

0. 6
0. 5
0. 4
0. 3
0. 2

0.8
0.6
0.4
0.2

0. 1
0

0.1

0.2
0.3
0.4
Displacement (mm)

0.5

0.6

0.1

0.2

0.3

0.4

0.5

0.6

2.5

Displacement (mm)

1.2

(M Pa m 1/2)

1/ 2

K Ic (M Pa m )

1.1

0.9

Ic

0.8

0.7

1
0.9
0.8
0.7

0.6

0.5

1
1.5
2
CB content (wt%)

2.5

Fig. 7. Effect of CB particles on the fracture toughness at the room temperature

(25 C): (a) KQ vs. displacement curve, (b) fracture toughness with respect to carbon
black (CB) content.

0.6

0.5

1
1.5
2
Nanoclay content (wt%)

Fig. 8. Effect of nanoclay particles on the fracture toughness at the room temperature (25 C): (a) KQ vs. displacement curves, (b) fracture toughness with respect to
the nanoclay content.

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B.C. Kim et al. / Composite Structures 86 (2008) 6977

Fig. 8b shows the fracture toughness with respect to the nanoclay content. When the nanoclay content was less than 1.5 wt%, the
KIc value gradually increased. When the nanoclay content was
1.5 wt%, the fracture toughness was improved by 46% on the average. The nanoclay is much more effective than the carbon black.
Only 0.5 wt% of nanoclay could improve the fracture toughness
by 20%. As the nanoclay content increased over 1.5 wt%, the aver-

90

Cryogenic temperature(150 C)

80
70
Stress (MPa)

60
50

Room temperature(25 C)

40
30
20
10
0

20000

40000

60000

80000

100000

-6

Strain ( 10 )

2
-150 C

1.8

1/2

K Q (M Pa m )

1.6
1.4
1.2
1
0.8

25 C

0.4

0.1

0.2
0.3
Displacement (mm)

In order to investigate the effect of the nano-particles on the

fracture toughness at several low temperatures including cryogenic temperature of 150 C, exural tests were performed.
Fig. 9a and b shows the stressstrain relationships and the KQ vs.
displacement curves of the epoxy. The modied BPA epoxy had
ductile behavior at the room temperature. However, at the cryogenic temperature (150 C) it became brittle and the modulus
and strength increased by 160% and 90%, respectively. In the case
of steels, the fracture toughness decreases due to their increased
brittleness as the environmental temperature decreases [21].
Though the epoxy became brittle, the fracture toughness increased
signicantly at the cryogenic temperature (150 C). Nishijima
et al. [22] reported that the epoxy with free space, which was dened as the unoccupied space within the molecules, could have
high fracture toughness at the cryogenic temperature since the free
space still existed and the intermolecular forces between shrunk
networks increased. As shown in Fig. 9c, the fracture toughness
of the epoxy increased as the temperature was decreased, where
the fracture toughness at 150 C was 2.3 times higher than that
at the room temperature.
Fig. 10 shows the fracture toughness of the epoxy lled with the
nano-particle at the cryogenic temperature (150 C) with respect
to the particle content. As the amount of nano-particles was increased, the value of KIc decreased. From the results of Fig. 10, it
might be conjecture that the mixed nano-particles prevented the
shrinkage of the polymer networks, which interfered with the
intermolecular force at the low temperatures.

In order to nd the toughening mechanism of nano-particles in

the epoxy, fracture surfaces were observed using SEM. Fig. 11
shows the SEM photographs of the crack tip area.
Fig. 11a shows the fracture surfaces of the epoxy. Since the
epoxy was ductile at the room temperature, smooth fracture sur-

0.2
0

4.4. Effect of nano-particles on the fracture toughness at the cryogenic

temperature

4.5. Fracture surface observation and discussion

0.6

age fracture toughness became saturated. As shown in Fig. 8a,

the ductile-brittle fracture mode transition was observed in the
range of from 0.5 wt% to 1.0 wt%. When the nanoclay content
was 3.0 wt%, the maximum KIc value was achieved, which was
50% higher than that of the epoxy.

0.4

CB

1.6

Na no cl ay

1.8
1.4

K Ic (M Pa m1/ 2)

Fracture toughness, KIc (MPa m1/2)

1.8

1.2
1

1.6
1.4
1.2
1

0.8

0.8
0.6
-150

-120

-90
-60
-30
Temperature (C)

30

Fig. 9. Fracture toughness of the epoxy with respect to the environmental temperature: (a) stressstrain relationships, (b) KQ vs. displacement curves, (c) the KIc
value with respect to the environmental temperature.

0.6

1
2
Nanoparticle content (wt%)

Fig. 10. Fracture toughness at the cryogenic temperature (150 C) with respect to
the nano-particle content.

B.C. Kim et al. / Composite Structures 86 (2008) 6977

75

Fig. 11. Fracture surfaces of the specimens tested at (left: 25 C, right: 150 C): (a) epoxy, (b) 2.0 wt% of CB reinforced epoxy, (c) 2.0 wt% of nanoclay reinforced epoxy.

Fig. 12. Fracture surfaces of the CB reinforced specimens tested at (left: 25 C, right: 150 C): (a) 1.0 wt%, (b) 2.0 wt%, (c) 3.0 wt%.

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B.C. Kim et al. / Composite Structures 86 (2008) 6977

Fig. 13. Fracture surfaces of the nanoclay reinforced specimens tested at (left: 25 C, right: 150 C): (a) 1.0 wt%, (b) 2.0 wt%, (c) 3.0 wt%.

faces with occasional river patterns were observed. However, a

very smooth mirror-like surface was observed in the epoxy fractured at the cryogenic temperature though the fracture toughness
was much higher than that at the room temperature. From the results of Fig. 11a, it might be concluded that intermolecular forces
between polymer networks dominated the toughening mechanism
at the cryogenic temperature.
Fig. 11b shows the fractured surfaces of the epoxy reinforced
with 2.0 wt% of carbon black. As shown in the left gure, the increase in crack branching and pinning around the particles were
observed, which might increase the fracture toughness at the room
temperature. However, at the cryogenic temperature, any crack
branching or plastic deformation could not be observed. In spite
of the reinforcement with carbon blacks, the carbon black might
obstruct the intermolecular forces, which resulted in the low fracture toughness as shown in Fig. 10.
Fig. 11c shows the fractured surfaces of the epoxy reinforced
with 2.0 wt% of nanoclay. At the room temperature, the fracture
surface was much rougher than that of carbon black reinforced
epoxy, which might be due to the ake shape of nanoclay. At the
cryogenic temperature, the roughness of the fractured surface became smaller than that at the room temperature. Although the
fractured surface of the nanoclay reinforced epoxy had highest
roughness at the cryogenic temperature, the fracture toughness
was much less than that of the epoxy because the intermolecular
forces might dominate the reinforcing effect.
Fig. 12 shows the fracture surfaces of the CB reinforced epoxy.
At the room temperature, an increase of crack pinning was observed as the CB content was increased, which improved the fracture toughness by nano-scale toughening effect as shown in

Fig. 11b. However, the shape of fracture surfaces with a few shallow river patterns changed little at the cryogenic temperature.
Fig. 13 shows the fracture surfaces of the nanoclay reinforced specimens. At the room temperature, as the nanoclay content was increased, the fracture surface became rougher with much tearing
effect. At the cryogenic temperature, the fracture surface of the
specimen with higher nanoclay content was rougher with less
tearing effect than that at the room temperature. However, the
nanoclay reinforced epoxy still had lower fracture toughness than
the epoxy, as shown in Fig. 10. It might be concluded that intermolecular forces might dominate the reinforcing effect of the
nanoclay.

5. Conclusion
In this work, the toughening effect of carbon black (Ketjenblack
EC-300J, Ketjen Black International Co., Japan) and nanoclay (Cloisite 93A, Southern Clay Products, US) on the modied bisphenol-A
type epoxy resin (YD-114F, Kukdo Chemical, Korea) was investigated at the room (25 C) and cryogenic (150 C) temperatures.
At the room temperature, the carbon black (CB) of 3.0 wt% could
increase the KIc value by 23% on the average due to the toughening
mechanisms of nano-scale crack branching and pinning effects.
At the room temperature, the nanoclay of only 0.5 wt% could increase the KIc value by 20%, while, the nanoclay of 3.0 wt% could increase the KIc value by 50% on the average, which was due to the
tearing effect by the ake shape of nanoclay.
At the cryogenic temperature, the fracture toughness of the
epoxy was 2.3 times higher than that at the room temperature.

B.C. Kim et al. / Composite Structures 86 (2008) 6977

The nano-particles in the epoxy resin, decreased the fracture

toughness of the composite although the fracture surface was
much rougher than that of the epoxy, from which it might be concluded that the intermolecular forces between polymer networks
of the epoxy were much dominant than the toughening effect of
the mixed nano-particles at the cryogenic temperature.
If the nano-particle reinforced matrix is used for a composite
laminate, the interlaminar fracture toughness and the impact characteristic can be improved at the room temperature. However, at
the cryogenic temperature, un-reinforced epoxy may be able to
provide better structural characteristics.
Acknowledgements
This work has been supported by Ministry of Science and Technology in part by NRL (TBP), and BK21. Their supports are gratefully acknowledged.

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