Composites: Part A 40 (2009) 463–468

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

Preparation and characterization of epoxy/c-aluminum oxide nanocomposites

Cheng-Ho Chen a,b,*, Jian-Yuan Jian a, Fu-Su Yen c
a
Department of Chemical and Materials Engineering, Southern Taiwan University, No. 1 Nan-Tai Street, Yong-Kang, Tainan 710, Taiwan
b
Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan, Taiwan
c
Department of Resources Engineering, National Cheng Kung University, Tainan, Taiwan

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

Article history: Epoxy/c-Al2O3 nanocomposites were prepared with a homogenizer and followed by a stepwise thermal
Received 28 August 2008 curing process in this study. The dispersion of c-Al2O3 nanoparticles was examined with a transmission
Received in revised form 8 January 2009 electron microscopy (TEM). Meanwhile, the effects of c-Al2O3 nanoparticles on thermal, dynamic
Accepted 17 January 2009
mechanical and tensile properties of epoxy/c-Al2O3 nanocomposites were also investigated and dis-
cussed. When the c-Al2O3 content was increased from 1phr to 5phr, results revealed that c-Al2O3 nano-
particles were effective to enhance both the stiffness and toughness of epoxy resin. Meanwhile, the
Keywords:
maximum properties of glass transition temperature (Tg), Td5%, storage modulus, tensile modulus, and
A. Thermosetting resin
Particle-reinforcement
elongation at break were observed in the epoxy/5phr c-Al2O3 nanocomposite.
B. Thermal properties Ó 2009 Elsevier Ltd. All rights reserved.
B. Mechanical properties
B. Strength

1. Introduction the mechanical and thermal properties of polymers, such as clay

[2], silica [3], calcium carbonate (CaCO3) [4–6], and aluminum
Conventional polymer microcomposites generally contain with oxide (Al2O3) [7]. The improved properties include toughness, stiff-
large amounts of inorganic fillers (more than 20 wt%) in order to ness, damping, chemical resistance, heat resistance, thermal con-
achieve enhanced properties of stiffness and glass transition tem- ductivity, coefficient of thermal expansion, and electrical
perature (Tg). The fabrication of cheaper microcomposites is feasi- properties.
bly made by replacing the expensive resins with low cost inorganic Epoxy resins have been widely used in many industrial applica-
fillers. However, these gains are usually offset by losses in ductility tions, such as adhesives, construction materials, composites, lami-
and toughness. Large amount of filler additions would also detri- nates, and coatings due to their excellent mechanical properties,
mentally affect the processability of the polymers and then in- low cost, ease of processing, fine adhesion to many substrates,
crease the wear rate of processing facilities. In contrast, and good chemical resistance. However, the inherently brittle nat-
nanoparticles such as calcium carbonate and silica filled polymers ure of epoxy has been an important issue and largely limited its
possess significant improvements in both rigidity and toughness of application in some areas. Toughening epoxy with organic addi-
the resulted composites. Therefore, polymer nanocomposites have tives, such as rubber, has been proved to be an effective and widely
been paid great attention because these materials often exhibit used method [8,9]. However, the disadvantage of this approach is
much better properties than polymers or polymers filled with that it may sacrifice the stiffness of epoxy significantly. In addition,
micrometer-size inorganic fillers. The degree of dispersion and the incorporation of rubber would decrease the Tg of epoxy, which
the type of nanoscale fillers are two key factors to manipulate determines the upper limit of application temperature for epoxy
the properties of nanocomposites. By only adding 2–5 wt% nano- resins.
scale fillers, the enormous enhancement in properties of a polymer In order to increase the Tg and improve the mechanical prop-
nanocomposite can be observed. Furthermore, the weight of fin- erties of epoxy resin, epoxy nanocomposites have attracted con-
ished polymer nanocomposites can be obviously reduced by com- siderable attention from both fundamental research and
paring with those of the conventional polymer microcomposites application points of view over the past 10 years [10–30]. Nano-
[1]. Various nanoscale fillers have been studied in order to improve composite means that at least one solid phase dimension in the
composite is in the nanometer scale. The inclusion of nanorigid
particles with relatively huge surface area in an epoxy matrix
* Corresponding author. Address: Department of Chemical and Materials Engi- leads to increase the particle–matrix interactions. This effort re-
neering, Southern Taiwan University, No. 1 Nan-Tai Street, Yong-Kang, Tainan 710,
sulted in significant improvements in mechanical properties
Taiwan. Tel.: +886 6 3010001; fax: +886 6 2425741.
E-mail address: [email protected] (C.-H. Chen). [10–17] and flame retardency of the composite [18]. Generally

1359-835X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2009.01.010
464 C.-H. Chen et al. / Composites: Part A 40 (2009) 463–468

speaking, there are three types of nanofillers in terms of their at 80 °C for 24 h and weighed again. The curing level was deter-
shapes. These are spherical filler (three-dimension), sheet-like mined by the following equation:
filler (two-dimension), and rod-like filler (one-dimension). In re-
AB
cent years, many researchers focused on the use of sheet-like Curing level ð%Þ ¼ 100
A
nanoclays as fillers to modify epoxy [10–25]; however, only a
few reports were related to the studies of spherical nanoparticles where A represents the weight of neat epoxy or epoxy/c-Al2O3
[30,31]. Incorporation of rigid spherical nanoparticles into epoxy nanocomposite before immersed in MEK and B represents the
brings less perturbing effects and this task does not decrease weight of neat epoxy or epoxy/c-Al2O3 nanocomposites after im-
the crosslink density of epoxy significantly. Thus, using spherical mersed in MEK for 24 h and dried in an oven at 80 °C for 24 h.
fillers may be a promising approach to toughen epoxy without
sacrificing the resulted product’s glass transition temperature 2.4. TEM examination
and stiffness. Furthermore, investigation in nanocomposites with
spherical nanoparticles will bring new insights in the study of Ultrathin sections (about 80 nm) were cut from rectangular
polymer nanocomposites. blocks of the epoxy and epoxy/c-Al2O3 nanocomposites by an
Aluminum oxide (Al2O3) has good physical properties, such as ultramicrotome (RMC MT-X, RMC Instruments Corp., USA). The
abrasion resistance, corrosion resistance, thermal stability, electri- c-Al2O3 nanoparticle and its dispersion in the nanocomposites
cal insulation, and high mechanical strength, etc. Therefore, in or- were directly observed by using a TEM (JEM-1230, JEOL Ltd., Japan)
der to increase Tg and enhance mechanical properties of the epoxy with an acceleration voltage of 100 kV. The filament type of TEM is
resin, c-Al2O3 nanoparticles were added into the epoxy resin in this LaB6.
study. Meanwhile, in order to increase the toughness of epoxy re-
sin, the rubber (carboxylterminated butadiene acrylonitrile 2.5. TGA analysis
(CTBN)) was used. The effects of various c-Al2O3 contents on the
properties of epoxy/c-Al2O3 nanocomposites were examined and A thermogravimetric analyzer (TGA; Perkin–Elmer, model: TGA
discussed. In addition, the dispersion of c-Al2O3 nanoparticle was 7, USA) was conducted to analyze the thermal degradation charac-
examined with a transmission electron microscopy (TEM). Further- teristics of the epoxy and epoxy/c-Al2O3 nanocomposites in the
more, the effects of c-Al2O3 nanoparticle on thermal, dynamic temperature ranged from 50 to 800 °C with a heating rate of
mechanical and tensile properties of epoxy/c-Al2O3 nanocompos- 10 °C/min under a nitrogen stream. The thermal degradation onset
ites were also investigated. temperature and the thermal degradation weight loss of the sam-
ples were recorded and analyzed, respectively.
2. Experimental
2.6. DMA analysis
2.1. Materials
The samples were cut into rectangular bars with dimensions of
The epoxy used in this study was a widely used bifunctional 6.0 mm 3.0 mm 0.7 mm. A dynamic mechanical analyzer
epoxy resin, diglycidyl ether of bisphenol-A (DGEBA) with epoxy (DMA; Perkin–Elmer, model: DMA 7e, USA) was conducted to mea-
equivalent weight of 450–500 g/eq. The curing agent used in this sure the thermal dynamic mechanical properties of the neat epoxy
study was 4,4-diaminodiphenyl sulfone (DDS). The rubber used and epoxy/c-Al2O3 nanocomposites. The sample was two-stage
in this study was CTBN with molecular weight of 3150 g/mol. DGE- heated. First, the sample was heated from 0 to 100 °C with a heat-
BA, DDS, and CTBN were all kindly provided by the Microcosm ing rate 5 °C/min and then cooled to 0 °C in order to release the
Technology Co., Ltd., Taiwan. Methyl ethyl ketone (MEK) was pur- internal stress of the sample. Second, the sample was heated from
chased from the Kanto Chemical Co., Inc, Japan. The c-Al2O3 nano- 0 to 160 °C with operation conditions of heating rate 5 °C/min,
particles were purchased from the Degussa Co., Germany. amplitude 10 lm, and tension 105%. The storage modulus and tan d
curves were recorded and analyzed. The peak position of tan d
2.2. Preparation of epoxy/c-Al2O3 nanocomposites curve was regarded as the Tg of the sample. To ensure a consistency
in the results, three samples from each specimen were taken for
DGEBA and CTBN were dissolved in 100 ml of MEK and then test.
various c-Al2O3 contents were added into the DGEBA/CTBN solu-
tions to form mixtures. In order to let the c-Al2O3 nanoparticle well 2.7. Mechanical properties analysis
dispersed in the solution, the rotor speed and stirring time were set
as 5000 rpm and 15 min, respectively. Then, curing agent (DDS) Tensile strength and elongation at break were examined with a
was added into the mixture while stirring for additional 15 min universal testing machine (Model: Shimadzu 10KN; AG-IS, Shima-
in order to ensure that DDS was fully dissolved in the solution. dzu Instruments Co., Japan) at a crosshead speed of 10 mm/min.
The standard curing cycle for the resulted nanocomposite was indi- Test specimens were rectangular bars with dimensions of
cated as following: heating to 45 °C and then holding for 1 h, a sub- 10.0 mm 50.0 mm 0.7 mm. Six different specimens were sam-
sequent heating to 80 °C and then holding for 5 h, a subsequent pled from neat epoxy or each nanocomposite for measurement.
heating to 140 °C and then holding for 6 h, a subsequent heating The six testing results were averaged and then reported.
to 170 °C and then holding for 5 h, and then cooling the resulted
material down to the ambient temperature. In order to remove
3. Results and discussion
residual MEK, all nanocomposites were vacuum dried at 50 °C for
24 h. Finally, the epoxy/c-Al2O3 nanocomposites were obtained.
Fig. 1 showed the influence of various c-Al2O3 contents on the
curing level of epoxy in epoxy/c-Al2O3 nanocomposites. For neat
2.3. Curing level analysis
epoxy, the result indicated that the curing level was up to 99.99%
after the curing process. As the amounts of c-Al2O3 nanoparticle
The weighed neat epoxy or epoxy/c-Al2O3 nanocomposite was
were increased to 1phr, 3phr, and 5phr, the curing levels of epoxy
immersed in MEK and stirred for 24 h. After 24 h, the undissolved
in epoxy/c-Al2O3 nanocomposites were 99.9%, 99.8%, and 98.2%,
neat epoxy or epoxy/c-Al2O3 nanocomposite was dried in an oven
C.-H. Chen et al. / Composites: Part A 40 (2009) 463–468 465

Results revealed that the aggregation phenomenon of c-Al2O3

100 nanoparticles was significantly increased as the amount of c-
Al2O3 nanoparticles was increased. For epoxy/1phr c-Al2O3 and
90 epoxy/5phr c-Al2O3 nanocomposites, the aggregation phenome-
non of c-Al2O3 nanoparticles was not significant. Moreover, some
c-Al2O3 nanoparticles can be well dispersed in the epoxy matrix.
Curing level (%)

80
This observation was due to the high stirring speed, i.e.
5000 rpm, resulting in high shear force during mixing process.
70
Thus, the agglomerates can be destroyed or reduced in sizes. This
phenomenon is illustrated in Scheme 1.
60 For epoxy/9phr c-Al2O3 nanocomposite, the aggregation phe-
nomenon of c-Al2O3 nanoparticles was much more significant than
50 those of epoxy/1phr c-Al2O3 and epoxy/5phr c-Al2O3 nanocompos-
ites. As results indicated in Fig. 3, the size of incompact c-Al2O3
40 clusters was approximately ranged from 100 to 600 nm. The aggre-
0 2 4 6 8 gation of c-Al2O3 nanoparticles might result from their huge spe-
γ-Al2 O3 content (phr) cific surface area and high surface energy.
Fig. 4 showed TGA curves of neat epoxy, epoxy/5phr c-Al2O3,
Fig. 1. Effect of the c-Al2O3 content on the curing level of epoxy/c-Al2O3 and epoxy/9phr c-Al2O3 nanocomposites. Fig. 5 illustrated the
nanocomposites. influence of c-Al2O3 contents on the Td5% of the epoxy/c-Al2O3
nanocomposites. It was found that the Td5% of neat epoxy was
379 °C. Further, increasing the amount of c-Al2O3 nanoparticles
respectively. These values were close to the reported curing level
up to 5phr in the epoxy resin, the Td5% of the nanocomposite could
of neat epoxy. However, as the amounts of c-Al2O3 nanoparticles
be increased up to 392 °C, which was about 13 °C higher than that
were increased up to 7phr and 9phr, the curing levels of epoxy in
of neat epoxy. These phenomena were resulted from the addition
the nanocomposites were decreased down to 93.1% and 92.4%,
of c-Al2O3 nanoparticles which might act as the thermal stabilizer
respectively. Thus, this observation revealed that adding too
in the epoxy nanocomposite. However, when adding c-Al2O3 nano-
many c-Al2O3 nanoparticles during the formation of the nano-
particles up to 7phr and 9phr into the epoxy matrix, the curing lev-
composite may block the curing reaction between DGEBA and
els of epoxy nanocomposites were decreased to 93.1% and 92.4%,
DDS. Therefore, the curing reaction cannot be executed com-
respectively. Thus, the Td5% of epoxy/7phr c-Al2O3 and epoxy/
pletely [32].
9phr c-Al2O3 nanocomposites was dramatically down to 215 and
Fig. 2 showed the morphology of spherical c-Al2O3 nanoparti-
201 °C, respectively.
cles which were examined with TEM. It showed that the spherical
DMA was employed to evaluate the effects of c-Al2O3 nanopar-
c-Al2O3 nanoparticles strongly intended to aggregate together due
ticles on dynamic response of epoxy under a given set of condi-
to their huge specific surface area and high surface energy. It also
tions. The applied displacement and the resulting load were
revealed that the size of the c-Al2O3 nanoparticle was ranged from
measured in both amplitude and relative phase, which gave both
10 to 30 nm and the size of c-Al2O3 clusters was ranged from 100
an elastic storage and a viscous loss modulus. Storage modulus di-
to 500 nm. Fig. 3(a) was the TEM images of neat epoxy. The disper-
rectly associated with elastic response of epoxy nanocomposites.
sion of c-Al2O3 nanoparticles in epoxy was also examined through
Fig. 6 showed the storage modulus curves of neat epoxy and
TEM. Fig. 3(b)–(d) showed the TEM images of epoxy/1phr c-Al2O3,
epoxy/c-Al2O3 nanocomposites. For epoxy/5phr c-Al2O3 nanocom-
epoxy/5phr c-Al2O3, and epoxy/9phr c-Al2O3, respectively.
posite, the storage modulus of epoxy nanocomposite was signifi-
cantly improved at the temperature ranged from 0 to 80 °C as
compared with those of the neat epoxy and other epoxy/c-Al2O3
nanocomposites. Fig. 7 showed the storage modulus and tan d
curves of the epoxy/5phr c-Al2O3 nanocomposite. The peak posi-
tion of tan d curve can be regarded as the Tg of epoxy/5phr
c-Al2O3 nanocomposite.
Fig. 8 illustrated the effect of various c-Al2O3 amounts on the Tg
of the epoxy/c-Al2O3 nanocomposites. For neat epoxy, the Tg was
about 83 °C. A maximum Tg was observed at 5phr c-Al2O3 content.
The Tg of the epoxy/5phr c-Al2O3 nanocomposite was 96 °C, which
was about 13 °C higher than that of neat epoxy. Result indicated
that the Tg of the epoxy nanocomposite can be increased by
increasing the amount of c-Al2O3 nanoparticles in the resulted
product. This observation was due to the increasing inorganic filler
resulted in decreasing the free spaces among molecules and fur-
ther increasing the difficulty for epoxy molecules to either rotate
or move. However, when the c-Al2O3 content was increased up
to 9phr, Tg of the resulted product was decreased down to 80 °C.
This phenomenon might be resulted from uncompleted curing
reaction between DGEBA and DDS since too many c-Al2O3 nano-
particles were added into the epoxy resin during the formation
of the nanocomposite [33].
It can be concluded that the Tg of epoxy/c-Al2O3 nanocomposite
was affected by two factors. The first factor was the curing level of
Fig. 2. TEM image of c-Al2O3 nanoparticles. epoxy. The second factor was the c-Al2O3 content. For epoxy/5phr
466 C.-H. Chen et al. / Composites: Part A 40 (2009) 463–468

Fig. 3. TEM images of epoxy/c-Al2O3 nanocomposites: (a) neat epoxy, (b) epoxy/1phr c-Al2O3, (c) epoxy/5phr c-Al2O3, and (d) epoxy/9phr c-Al2O3.

100
a b
Shear force
c
80

60
Weight %

Scheme 1. Break up of large agglomerate into each individual or finer ones due to
the shear force.
40

c-Al2O3 nanocomposite, the curing level was 98.2% which was b

close to that of neat epoxy. Therefore, its Tg was higher than that 20
of neat epoxy. For epoxy/9phr c-Al2O3 nanocomposite, the curing c
level was 92.4%. Therefore, its Tg was slightly lower than that of a
0
neat epoxy, although its c-Al2O3 content was 9phr.
100 200 300 400 500 600 700 800
Fig. 9 revealed the effects of amount of c-Al2O3 nanoparticles on
Temperature (°C)
storage moduli of epoxy/c-Al2O3 nanocomposites at various tem-
peratures, i.e. 0, 20, 40, 60, and 80 °C. Fig. 9 was plotted for Fig. 4. TGA curves of the epoxy/c-Al2O3 nanocomposites: (a) neat epoxy, (b) epoxy/
epoxy/c-Al2O3 nanocomposites with various c-Al2O3 contents as 5phr c-Al2O3, and (c) epoxy/9phr c-Al2O3.
indicated on Fig. 6. From data shown on Fig. 9, a maximum storage
modulus appeared at 5phr c-Al2O3 content. At 0, 20, 40, and 60 °C,
the storage modulus of neat epoxy was the lowest as compared uli of the neat epoxy and epoxy/c-Al2O3 nanocomposites. The first
with those of other samples with c-Al2O3 nanoparticles. However, factor was c-Al2O3 content in epoxy/c-Al2O3 nanocomposites. The
at 80 °C, the storage modulus of epoxy/9phr c-Al2O3 nanocompos- second factor was Tg of epoxy/c-Al2O3 nanocomposites. At lower
ite was the lowest as compared with those of other samples with temperature, i.e. 0, 20, 40, and 60 °C, which were lower than the
c-Al2O3 nanoparticles. From the observed results, it can be con- Tg s of neat epoxy and epoxy/c-Al2O3 nanocomposites, both c-
cluded that there were two major factors to affect the storage mod- Al2O3 content and Tg can simultaneously affect the storage moduli
C.-H. Chen et al. / Composites: Part A 40 (2009) 463–468 467

500

450 100

400

350 90
Td5%(°C)

Tg(°C)
300

250 80

200

150 70

100

50 60
0 2 4 6 8 0 2 4 6 8 10
γ-Al2O3 content (phr) γ-Al2 O3 content (phr)

Fig. 5. Effect of the c-Al2O3 content on Td5% of epoxy/c-Al2O3 nanocomposites (Td5% Fig. 8. Effect of various c-Al2O3 contents on Tg of epoxy/c-Al2O3 nanocomposites.
stands for the temperature which the sample remains 95 wt% during the TGA test).

1800

1500 1600
d
1400
1250 e
storage modulus (MPa)

f (a)
Storage modulus (MPa)

1200
c (b)
1000
b 1000 (c)
(d)
750 a 800

600
500
400

250 200 (e)

0 2 4 6 8 10
0
γ-Al2 O3 content (phr)
0 20 40 60 80 100 120 140
Temperature (°C) Fig. 9. Effects of various c-Al2O3 contents on storage moduli of epoxy/c-Al2O3
nanocomposites at various temperatures: (a) 0 °C, (b) 20 °C, (c) 40 °C, (d) 60 °C, and
Fig. 6. DMA curves of the epoxy/c-Al2O3 nanocomposites: (a) neat epoxy, (b)
(e) 80 °C.
epoxy/1phr c-Al2O3, (c) epoxy/3phr c-Al2O3, (d) epoxy/5phr c-Al2O3, (e) epoxy/
7phrc-Al2O3, and (f) epoxy/9phr c-Al2O3.

of the epoxy/c-Al2O3 nanocomposites. Therefore, the storage mod-

ulus of epoxy/9phr c-Al2O3 nanocomposite was higher than those
of neat epoxy, epoxy/1phr c-Al2O3, and epoxy/3phr c-Al2O3 nano-
1600
composites, although the Tg of epoxy/9phr c-Al2O3 nanocomposite
1400 was lower than those of neat epoxy, epoxy/1phr c-Al2O3, and
epoxy/3phr c-Al2O3 nanocomposites.
1200 At higher temperature, i.e. 80 °C, which were close to the Tg of
Storage modulus (MPa)

neat epoxy or epoxy/c-Al2O3 nanocomposites, the second factor

1000 dominated the storage moduli of the epoxy/c-Al2O3 nanocompos-
ites. Therefore, the storage modulus of epoxy/9phr c-Al2O3 nano-
Tan δ

800
composite was the lowest as compared with neat epoxy and
600 other epoxy/c-Al2O3 nanocomposites. It can be concluded that
the influence of Tg on the storage modulus of epoxy/c-Al2O3 nano-
400 composite was more important than that of c-Al2O3 content at the
temperature close to Tg.
200 Fig. 10 illustrated the effects of the c-Al2O3 content on tensile
modulus and elongation at break of epoxy/c-Al2O3 nanocompos-
0 ites. It was observed that both tensile modulus and elongation at
0 20 40 60 80 100 120 140
break of epoxy/c-Al2O3 nanocomposites were increased as the c-
Temperature (°C)
Al2O3 contents were increased from 0phr to 5phr in the epoxy
Fig. 7. Effect of temperature on storage modulus and tan d of the epoxy/5phr nanocomposites. At 5phr c-Al2O3 content, the tensile modulus
c-Al2O3 nanocomposite. and elongation at break of epoxy nanocomposite can be increased
468 C.-H. Chen et al. / Composites: Part A 40 (2009) 463–468

10 found that both tensile modulus and elongation at break of

1700 epoxy/c-Al2O3 nanocomposites were increased with the c-Al2O3
content increased from 0phr to 5phr. It also revealed that c-
8 Al2O3 nanoparticles were effective to enhance both the stiffness
1600
and toughness of epoxy resin. Among various contents of c-

Tensile modulus (MPa)

Elongation to Break (%)

Al2O3 in the nanocomposites, epoxy/5phr c-Al2O3 nanocomposite

1500 had the maximum Tg, Td5%, storage modulus, tensile modulus, and
6
elongation at break. When the c-Al2O3 content in the nanocom-
posite was increased up to 7phr or 9phr, not only the coagulation
1400
phenomena of c-Al2O3 nanoparticles were significantly observed,
4 but also resulted in decreasing of thermal stability of the epoxy
1300 nanocomposites.

2 1200 Acknowledgments
0 2 4 6 8 10
γ-Al2 O3 content (phr) The authors appreciate the finance supports from the Project
No. 96-EC-17-A-08-S1-023 supplied by the Ministry of Economics
Fig. 10. Effects of various c-Al2O3 contents on elongation at break and elastic Affairs and the Project No. was NSC 94-2216-E-218-003 supplied
modulus of epoxy/c-Al2O3 nanocomposites.
by the National Science Council, Taiwan, ROC.

up to about 32% and 39%, respectively. It revealed that c-Al2O3 References

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