Composites: Part B 45 (2013) 308320

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Composites: Part B
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Epoxy clay nanocomposites processing, properties and applications: A review

Asif Abdul Azeez a, Kyong Yop Rhee a,, Soo Jin Park b,, David Hui a,c
a
Department of Mechanical Engineering, College of Engineering, Kyung Hee University, Yongin 446-701, Republic of Korea
b
Department of Chemistry, Inha University, 253, Nam-gu, Incheon 402-751, Republic of Korea
c
Department of Mechanical Engineering, University of New Orleans, LA 70148, United States

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

Article history: The review renders a short background on the research work carried out on epoxy clay nanocomposites.
Received 2 February 2012 Clays are one of the ideal nano reinforcements for polymers because of their high intercalation chemistry
Accepted 12 April 2012 and aspect ratio. Epoxy clay nanocomposites are nding vast applications in various industries like aero-
Available online 27 April 2012
space, defense, automobile, etc. The physical and chemical properties of the epoxy systems are inuenced
by the processing techniques, clay modier and curing agents used for the preparation of nanocompos-
Keywords: ites. The clay morphology (intercalation/exfoliation) of the nanocomposites is also depended on the
A. Polymermatrix composites (PMCs)
above parameters. So the emphasis of the present work is to highlight these parameters on morphology
A. Nano-structures
B. Mechanical properties
and the nal mechanical, thermal and barrier properties of the nanocomposites. The proposed applica-
tions of the epoxy clay nanocomposites are also discussed.
2012 Elsevier Ltd. All rights reserved.

1. Epoxy resin
The term epoxy resin refers to both the prepolymer and its
cured resin/hardener system. The former is a low molecular weight
oligomer that contains one or more epoxy groups per molecule
(more than one unit per molecule is required if the resultant
material is to be crosslinked). The characteristic group, a three-
membered ring known as the epoxy, epoxide, oxirane, glycidyl or
ethoxyline group as shown in Fig. 1 is highly strained and therefore
very reactive. Epoxy resins can be cross-linked through a polymer-
ization reaction with a hardener at room temperature or at
elevated temperatures (latent reaction). Curing agents used for
room temperature cure are usually aliphatic amines, and for high
temperature, aromatic amines and acid anhydrides are used.
Polyfunctional amines, polybasic carboxylic acids, mercaptans
and inorganic hardeners are also used as specialized curing
agents. In general, the high temperature cured resin systems
have improved properties, such as higher glass transition temper-
ature, strength and stiffness, compared to those cured at room
temperature [15].
Among the thermoset materials, epoxy resins shows special
chemical characteristics such as absence of byproducts or volatiles
during curing reactions, low shrinkage up on curing, curing over a
wide temperature range and the control of degree of cross-linking.
Depending on the chemical structure of the curing agents and cur-
ing conditions, the properties of cured epoxy resins will vary. Epoxy
resins are versatile with excellent chemical and heat resistance,
Corresponding authors. Tel.: +82 31 201 2565; fax: +82 31 202 6693 (K.Y. Rhee).
E-mail addresses: rheeky@khu.ac.kr (K.Y. Rhee), sjpark@inha.ac.kr (S.J. Park).
high adhesive strength, good impact resistance, high strength and
hardness, and high electrical insulation [35].
2. Polymer nanocomposites
Polymer nanocomposites have attracted great interest, both in
industry and in academics, because they exhibit remarkable
improvement in material properties compared with virgin polymer
or conventional micro and macro composites [620]. Conventional
composites usually require a high content (>10%) of the inorganic
llers to impart the desired mechanical properties. Such high ller
levels increase their density of the product and can cause the dete-
rioration in properties through interfacial incompatibility between
the ller and the organic material. Besides, processability worsens
as ller content increases. In contrast, nanocomposites show
enhanced thermo mechanical properties even with a small amount
of layered silicate (65%). Polymer nanocomposites are generally
dened as the combination of polymer matrix and llers that have
at least one dimension in nanometer range. The nano llers can
be one-dimensional (layered minerals such as clay) [613],
two-dimensional (like carbon nanotube, nanowires, nanobers,
cellulose whiskers, etc.) [1416], and three-dimensional (spherical
particles include silica nanoparticles, nanowhiskers, etc.) [1720].
Polymer nanocomposites are known for its outstanding mechanical
properties like high elastic modulus [611,2124], increased
strength [611,25], barrier resistance [2630], ame retardancy
[3136], etc. with very small addition (65 wt.%) of nano particles.
This is due to the very large surface area of interaction between
polymer matrix and nano ller. Among the different nanollers,
special attention has been paid to clays in the eld of

1359-8368/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesb.2012.04.012
 A.A. Azeez et al. / Composites: Part B 45 (2013) 308320
Fig. 1. Epoxy or oxirane group.
nanocomposites. Clays (Layered silicates) are found to be one of the
ideal nano reinforcements for polymers, because of its high interca-
lation chemistry, high aspect ratio, ease of availability and low cost.
3. Clays
Clays are hydrous silicates or alumino silicates and are funda-
mentally containing silicon, aluminum or magnesium, oxygen
and hydroxyl with various associated cations. These ions and OH
groups are organized into two dimensional structures as sheets.
Clay minerals are also called layered silicates or phyllo silicates be-
cause their structural frame work is basically composed of 1 nm
thick silicate layers comprising silica and alumina sheets joined to-
gether in various proportions and stacked on top of each other in
certain way with a variable interlayer distance. The clay minerals
can be classied into three different types based on the condensa-
tion ratio of silica to alumina sheet [12,13].
3.1. 1:1 Type
It consists of one octahydral alumina sheet and one tetrahydral
silica sheet condensed in 1:1 ratio, called as dimorphic or two
sheet minerals. The sheet does not bear any charge due to the ab-
sence of isomorphic substitution in both silica and alumina sheet.
Layers are held together by hydrogen bonding between hydroxyl
group in octahedral sheets and oxygen in tetrahedral sheets. The
space between the layers is occupied by water molecules, e.g., Kao-
linite, Perlite, Hallosite, etc.
3.2. 2:1 Type
In 2:1, trimorphic or three sheet minerals, an alumina sheet is
sandwiched between two silica sheets. This type of clay belongs
to smectite family. Stacking of these layers create a Vander Waals
gap between clay layers. Isomorphic substitution of Al3+ with Fe2+,
Mg2+, Li+ in the octahedron sheets and/or Si4+ with Al3+ in the tet-
rahedron sheets gives each layer an overall negative charge, which
is counterbalanced by exchangeable metal cations such as Na+,
Ca2+, Mg2+, Fe2+, and Li+ residing in the interlayer space, e.g., mont-
morillonite (MMT), hectorite, saponite, ouro hectorite, laponite,
ouromica (somasif).
3.3. 2:2 Type
The layer structure of 2:2 type, known as tetramorphic of four
sheet minerals, is formed by the alternate condensation of silica
tetrahedron sheets and alumina or magnesium octahedron sheets,
e.g., Chlorite.
4. Montmorillonite
Among the different types of clay minerals, montmorillonite is
the most commonly used for the preparation of polymer clay nano-
composites [613]. Montmorillonite owes special attention among
the smectite group due to its ability to show extensive inter layer
expansion or swelling, because of its peculiar structure as shown in
Fig. 2.
309
The crystal structure of montmorillonite consists of layers
formed by sandwiching an edge shared octahedral sheet of alu-
mina between two silica tetrahedral sheets, so that the apical oxy-
gen atoms of the tetrahedral sheets are all shared with the
octahedral sheet. Isomorphous substitution of aluminum for sili-
con in the tetrahedral sheet and iron or magnesium for aluminum
in the octahedral sheet provides an overall negative charge to the
crystal lattice. As the surface between the layers is negatively
charged it attracts cations such as Fe2+, Ca2+ or Na+. They form a
positively charged layer between the negatively charged surfaces
of the clay layers. Such layers extend continuously in the plane
constituted by the x and y axes and are stacked up in the z axis,
forming the whole crystal structure. The silicate layers of MMT
are planar, stiff about 1 nm in thickness with high aspect ratio
and large active surface area (700800 m2/g). These layers organize
themselves in a parallel way to form stacks with a regular van der
Waals gap in between them, called as interlayer or gallery. The
sum of the single layer thickness and the interlayer is called d-
spacing or basal spacing. The total quantity of the absorbed cations
(K+, Na+, Ca2+, and Mg2+) in the inter gallery of clay layers at a PH
value of 7 is referred as the cation exchange capacity (CEC) of clay
minerals. It is measured by the unit mill mol/100 g of layered sili-
cate (or MMT). Higher the value of negative charge, the stronger is
the capacity for hydration, swelling and dispersion.
5. Organic modication of clay
Generally clays are hydrophilic in nature. In order to make com-
patible with organic polymers, the surface of the clay minerals
should be modied to organophilic prior to its use. Organic cations
such as an ammonium ion or phosphonium ion are the commonly
used organic modiers for clay minerals [611,37,38]. Modication
involves the exchange of interlayer inorganic cations with organic
onium salts. The organic modication causes the expansion of the
interlayer space and thereby increases the d spacing to certain ex-
tent (normally over 2 nm). Thus the organic modication favors
the diffusion of polymer or its precursor into the interlayer space.
Fig. 3 shows the schematic representation of the organic modica-
tion of clay. Alkyl ammonium ions are most popular since they can
easily be exchanged with the ions situated between the layers.
Depending on the layer charge density of the clay, the alkyl ammo-
nium ions may adopt different structures between the clay layers.
Alkyl ammonium ions reduce the electrostatic interactions be-
tween the silicate layers thus facilitate diffusion of the polymer
into the galleries. In general, the longer the surfactant chain length,
the more will be the d spacing of the clay layers [9].
6. Structure of polymer clay nanocomposites
Depending on the nature of the components, processing condi-
tion and strength of the interfacial interactions between polymer
and layered silicates (modied or unmodied), either conventional
composites or nanocomposites can be formed as shown in Fig. 4
[611,24]. In a conventional composite, the polymer cannot diffuse
between the clay layers and the clay particles exist in their original
aggregated state. Properties of these composites are similar to the
micro particle lled composites. An improvement in modulus is
normally achieved in conventional clay composite but this rein-
forcement benet is usually accompanied with a deciency in
other properties such as strength or toughness. If there is a favor-
able condition for the mixing of clay minerals with polymer, two
extremes of nanocomposites are formed, i.e., intercalated and exfo-
liated nanocomposites. In intercalated nanocomposites, the clay
layers retain the well ordered multi structure of alternating poly-
meric and clay layers with a d spacing of 2030 A. On the other
310 A.A. Azeez et al. / Composites: Part B 45 (2013) 308320

Fig. 2. Structure of montmorillonite.

Fig. 3. Organic modication of clay.
hand, in exfoliated nanocomposites, the individual clay layers are
well separated and randomly distributed in the continuous poly-
mer matrix with a d spacing of more than 50 A. The intercalation
and exfoliation of the clay layers in the polymer matrix can be
identied through wide angle X-ray diffraction (WAXD) and Trans-
mission Electron Microscopy (TEM). The characteristic WAXD of
unmodied clay (Cloisite Na), organically modied clay (Cloisite
30B and clay 3) and organically modied clays swelled by epoxy
resin is shown in Fig. 5 [39]. Here it is clear that the d spacing in-
creases with the organic modication of clay and it further in-
creases when it swelled in epoxy resin. After curing, the epoxy
clay nanocomposites can give either intercalated or exfoliated
structure, where the d spacing will be increased further for interca-
lated structure or the peak corresponding to the d spacing in the
WAXD will be disappeared in exfoliated structures as shown in
the case of epoxy-5 wt.% Cloisite 30B (clay 1) mixtures cured at
different temperatures (Fig. 6) [39]. Lingaiah et al. suggested that
air plasma etching followed by scanning electron microscopy
(SEM) imaging is a promising technique for visualizing the exfoli-
ation and dispersion of inorganic nanollers like clay and CNT in
polymer nanocomposites [40].
7. Preparation of nanocomposites
There are several methods to prepare clay based polymer nano-
composites. These include in situ polymerization, melt intercala-
tion and solution casting.

Fig. 4. Types of polymer clay nanocomposites [9,24].

 A.A. Azeez et al. / Composites: Part B 45 (2013) 308320
Fig. 5. The characteristic WAXD of (a) unmodied clay (Cloisite Na), (b and c)
organically modied clay (Cloisite 30B (b) and clay 3 (c)) and (d) organically
modied clays swelled by epoxy resin (Epon 828) [78].
Fig. 6. WAXD patterns showing (a) intercalated and (b) exfoliated clay structures
obtained by curing Epon 8285 wt.% clay 1(Cloisite 30B) mixtures using Jeffamine
D230 respectively at 50 C for 5 h and at 100 C for 2 h [78].
7.1. In situ polymerization
In this method, the liquid monomers or prepolymers (epoxy
resin) are intercalated into clay layers and polymerizes within
the clay layers resulting the expansion of the interlayer distance
(d spacing). Polymerization can be initiated by heat or a suitable
initiator. Most of the exfoliated nanocomposites are produced by
this method because it provides to select suitable reagents and
polymerization routes resulting a good afnity between clay and
polymer. In situ polymersiation technique has been used for the
preparation of nanocomposites based on polyamide (PA) [30],
poly(e-caprolactone) [41], polystyrene (PS) [42], polyoleen (PP
and PE) [4345] polyethylene terephthalate (PET) [46], epoxy
[6,10].
7.2. Melt intercalation
The melt intercalation involves the blending of clay with the
polymer matrix in molten state. If the layer surfaces have sufcient
afnity with the polymer, the polymer can diffuse between the
clay layers and form either an intercalated or an exfoliated nano-
composite. Melt intercalation technique is used for the preparation
of nanocomposites based on polyamide such as nylon 6 [47] and
nylon 66 (PA66) [48], and polyethylene terephthalate (PET) [49].
This method is more economical and simpler than other methods.
The melt intercalation process has become increasingly popular
because of its great potential for application with rapid processing
311
methods such as injection molding [50] and twin screw extrusion
[51]. Melt blending technique is more efcient and produces nano-
composites with improved mechanical properties when it is pro-
cessed under the aid of super critical carbon dioxide [52].
7.3. Solution casting
In the solution method, polymer clay nanocomposites are
prepared by using a suitable solvent such as water, acetone, and
chloroform, in which the polymer is soluble and the clay is dispers-
ible. When the polymer solution and the clay-dispersed solution
are mixed, the polymer chains will be intercalated between the
clay layers by replacing the solvent molecules. Intercalated poly-
mers will remain in the clay layers upon the removal of solvent.
It is reported that the increase in entropy by desorption of solvent
molecules is the driving force for the intercalation of polymer from
solution [53]. Water soluble polymers such as poly (ethylene
oxide) [54], and poly(ethylene vinyl alcohol) [55] have been inter-
calated between the clay layers by this method. Nanocomposites
based on cellulose [56], high-density polyethylene [57], polyimide
[29], etc. have been synthesized by this method using non-aqueous
solvents. The major advantage of this method is that it offers the
possibility to synthesize intercalated nanocomposites based on
polymers with low or even without polarity.
8. Epoxy clay nanocomposites
Among polymer layered silicate (clay) nanocomposites, epoxy
based systems has been reported in detail, due to the ease of
processing as well as its versatile applications in various elds.
The structure and properties of epoxy clay nanocomposites are
inuenced by the curing agents, clay modier and processing
method.
9. Curing agents
In epoxy clay systems, there have been used amine and anhy-
dride based curing agents, which rendered different properties
and morphology to the epoxy systems. It was found that when
anhydride was used as curing agent, an exfoliated morphology
while diamino diphenyl methane (DDM) gave an intercalated mor-
phology, since anhydride is a liquid and can easily diffuse into the
clay gallery unlike DDM which is a solid [58]. Similar observations
were made by Xu et al. [59] for diethylenetriamine and tung oil
anhydride. Kornman et al. [60] found that aliphatic amine cured
epoxy produced an exfoliated morphology compared to cyclo ali-
phatic amine cured epoxy because of the higher reactivity of for-
mer. The diffusion rate and reactivity of the curing agent also
inuence the exfoliation of clay. Chin et al. [61] reported that an
exfoliated nanocomposites is formed when the DGEBA epoxy with
octadecyl ammonium modied MMT is cured with less than stoi-
chiometric amount of meta-phenylene diamine (MPDA) or with
autopolymerization without curing agent. On other hand an inter-
calated nanostructure is formed when it is cured with equimolar of
higher concentration of MPDA. Extragallery cross linking has been
dominated in the case of higher concentration of curing agent,
resulting in intercalated nanocomposites. Kong et al. [62] studied
the exfoliation behavior of epoxy clay nanocomposites varying
the electro negativities of the aromatic diamine curing agent and
curing temperatures. Epoxy clay nanocomposites based on DGE-
BA/PDA and DGEBA/MDA systems produced an intercalated struc-
ture due to the high reactivity of the curing agents which induces
faster gelation in the extragallery region, while DGEBA/DDS system
gave exfoliated structure due to the low reactivity of the curing
agent thereby slowed down the extragalley gelation and provides
312 A.A. Azeez et al. / Composites: Part B 45 (2013) 308320
enough time for intragallery polymerization. The TEM pictures
showing the exfoliation and intercalation of DGEBA-MDA system
and DGEBA-DDS system are shown in Fig. 7a and b, respectively
[62].
McIntyre et al. [63] has reported that the storage modulus and
Tg of the nanocomposites were increased with the addition of Cloi-
site 30B for DGEBA epoxy cured by tryethylenetetramine (TETA),
DDS and DDM while a lowering of Tg was observed for TGDDM/
DDS system. Among the DGEBA system, DDS cured system showed
improved Tg and modulus compared to other curing agents. All
composites have not shown any signicant improvement in the
thermal stability by the addition of clay particles. Zilg et al. [64]
found higher toughness for an intercalated structure and higher
modulus (stiffness) for completely exfoliated structure for nano-
composites based on anhydride cured DGEBA epoxy.
10. Clay modier
Generally based on the organic modier used in the modica-
tion clay, the structure and properties of the nanocomposites var-
ies considerably. Intercalated nanocomposite is generally produced
with quaternary and tertiary alkyl ammonium surfactants due to
low bronsted acidity of the surfactants. The xed layer separation
of clay layers is unable to provide optimum level of reinforcement.
Exfoliated nanocomposite is produced with primary and secondary
alkyl ammonium surfactants or quaternary surfactants containing
hydroxyl groups due to the high bronsted acidity of the surfactants.
In exfoliated nanocomposites, the clay layers will be sufciently
separated and randomly oriented to allow full interfacial bonding
with matrix resin to improve the properties of nanocomposites.
In the case of primary and secondary ammonium modied clay,
the rate of intragallery polymerization occurs at a faster rate com-
pared to extragallery polymerization leading to an exfoliated struc-
ture while the extragallery polymerization is in faster rate in the
case of tertiary and quaternary ammonium modied clay results
an intercalated morphology. It is also reported that as the chain
length of alkyl ammonium (clay modier) increases, the morphol-
ogy changes from intercalation to exfoliation morphology [65].
Similarly Wang et al. [66] also reported that the curing speed of
the intra and extra layer epoxy amine reaction is the key factor
for the synthesis of exfoliated epoxy clay nanocomposites.
Park et al. [39] investigated a mechanism of nanoclay exfolia-
tion in epoxy clay nanocomposites. The complete exfoliation of
clay layers from the intercalated tactoids can be produced if the
ratio of shear modulus to complex viscosity is maintained at or
Fig. 7. Transmission electron micrographs of (a) DGEBA-MDA-C18 clay (10 phr)
and (b) DGEBA-DDS-C18 clay (10phr). Scale bar indicates 20 nm [68].
above 24 1/s, such that elastic forces inside the galleries outweigh
the viscous forces offered by the extragallery epoxy. So the elastic
force exerted by the cross-linking epoxy molecules inside the clay
galleries pushed out the outermost clay layers from the tactoids
against the opposing forces arising from electrostatic and van der
Waals attraction and shear, the latter due to motion of clay sheets
during exfoliation as shown Fig. 8. Contrary to earlier reports
[65,66], they [39] found that the faster intragallery polymerization,
though accelerated the exfoliation process, was not necessary for
exfoliation. It was also observed that clays containing hydroxylated
quaternary ammonium ions and quaternary ammonium ions with
no polar functional groups produced exfoliated structures equally
easily, provided the ratio of storage modulus to complex viscosity
was maintained above 24 1/s. Higher curing temperature as well
as the presence of organically modied clay particles accelerated
the formation of gels, and the gel time presented an upper bound
of time available for exfoliation.
Pluart et al. [67] demonstrated that adequate compatibilisation
of montmorillonite followed by swelling of clay galleries by epoxy
was necessary to obtain intercalated/exfoliated nanocomposites. In
another study [68], they correlated the morphology and mechani-
cal properties of epoxy clay nanocomposites and observed an
improvement in stiffness for exfoliated nanocomposites. However,
a very interesting stiffness/toughness balance was shown by the
intercalated nanostructures without lowering their Tg. Lakshmi et
al. [69] investigated the thermal stability and structural character-
istics of different epoxy clay nanocomposites using hexadecyl
ammonium and phosphonium clay and DDS as hardener. The
ammonium modied clay epoxy system showed appreciable
mechanical and glass transition temperature properties while
phosphonium modied clay epoxy system exhibited highest ther-
mal resistance properties compared with unmodied epoxy sys-
tems. Similarly, the higher thermal resistance properties of the
alkyl phosphonium clay epoxy nanocomposites were reported by
Wei et al. [70].
Inuence of clay surface modication on the structure of the
epoxy clay nanocomposites using a hardener of polyoxypropylen-
ediamine have been investigated by Ryznarova et al. [71]. They
observed that the difference between the curing rates inside and
outside clay gallery was crucial for achieving intercalation/exfolia-
tion of the prepared nanocomposites. Protonated and functional-
ized clay modiers catalyzed the intragallery polymerization of
epoxy resulted in the reduction in gelation times, gradual increase
in d spacing during curing and high degree of dispersion leading to
increased elongation at break and toughness. In contrast, non
functionalized alkyl ammonium ions were unable to catalyze the
intragallery polymerization resulted in the faster extragallery poly-
merization leading to only partially intercalated nanocomposites.
Kornman et al. [72] also studied the inuence of the nature of
the clay on the structure of epoxy clay nanocomposites. Organic
modied montmorillonite clay with a low CEC showed an exfoli-
ated structure compared to clay with high CEC, which showed an
intercalated structure during the swelling of clay in the epoxy resin
for 24 h prior to curing. This is due to the low amount of organic
modier (octadecyl ammonium chloride) present in the former
clay provides more space for DGEBA molecules. So the self poly-
merization of epoxy can occur in large extent and causes the diffu-
sion of new DGEBA molecule between the clay layers leading to the
exfoliation of clay. Triantafyllidis et al. [73] reported that the epoxy
clay nanocomposites prepared by the incorporation of homoionic
organic clays exchanged with relatively short chain di- or tri-
amines and mixed-ion organic/inorganic clays partially exchanged
(35%) with long chain diamines modied by di- or tri-amines re-
sulted in intercalated structures with improved youngs modulus
and storage modulus. On the other hand, homoionic organic clays
exchanged with long chain diamines and triamines resulted in
 A.A. Azeez et al. / Composites: Part B 45 (2013) 308320
Fig. 8. Schematic illustration of the intercalated state and exfoliation process showing the forces acting on a pair of clay layers (a) organically modied clay, (b) epoxy
intercalated state, and (c) forces acting on a two-particle tactoid [76].
exfoliated nanocomposites, but with compromised mechanical
properties especially reduced Tg due to the plasticizing effect of
the long chain amine modiers.
Ha et al. modied the nanoclay using 3-amino propyl triethoxy
silane and studied the wear [74], tensile [75] and fracture [76]
properties of silane-treated clay/epoxy nanocomposites. The frac-
ture, tensile and wear properties of the nanocomposites increased
for the silane treated clay, due to the good dispersion of clay in
epoxy as well as the improved interfacial adhesion between epoxy
and clay layers. They also investigated the temperature effects on
the tensile and fracture properties of silane treated epoxy clay
nanocomposites [77]. Recently, Xu et al. [78] reported the effect
of curing reaction and thermal properties of the epoxy clay
nanocmposites made of different polymerically-modied clays.
They found an exfoliated morphology by XRD for (polystyrene-
co-acrylic acid) PSAA modied clayepoxy with improved thermal
properties due to the reaction occurred between epoxy groups and
carboxylic acid in the inter-gallery of PSAA which could facilitate to
clay dispersion in the epoxy matrix.
11. Processing method
Processing methods inuence the clay morphology. The usual
processing methods to disperse the clay layers in epoxy matrix
are mechanical stirring, ultrasound sonication [79,80], high shear
mixing [81,82], ball milling [83], etc. Lam et al. [79] reported that
10 min ultrasonication result an optimum micro-hardness at
4 wt.% clay containing epoxy nanocomposite. Zunjarro et al. [80]
reported that high speed shear mixing yielded better mechanical
properties compared to ultrasonication, even though both methods
gave exfoliated morphology. Yasmin et al. [81] found that epoxy
clay nanocomposites processed by three roll mill is efcient in
achieving high levels of exfoliation and dispersion of clay particles
within a short period of time. The modulus of the nanocomposites
313
found to increase with increase in clay concentration. However, the
tensile strength was decreased with addition of clay particles com-
pared to pure epoxy due to the occasional occurrence of nano to
micro sized voids in the microstructure. They observed that effec-
tive degassing during processing will enhance the tensile strength
of the resultant nanocomposites. Chen et al. [84] prepared a fully
exfoliated layered silicate epoxy nanocomposites by the combina-
tion of high shear mixing and ultrasonication in the presence of
acetone. Lu et al. [83] observed a decrease in impact strength
and exural strength for 4,40 -diamino diphenyl sulfone (DDS)
cured epoxy clay nanocomposites processed by mechanical stirrer
as well as high speed emulsifying and homogenizing mixer
(HEHM) where as processing by HEHM followed by ball milling im-
proved the mechanical properties. It was reported that epoxy
DDSclay nanocomposites processed by high pressure mixing
method showed dramatic increase in fracture toughness compared
to direct mixing method [85]. However, the glass transition
temperature decreases as the clay content increases. Liu et al. stud-
ied [86,87] the effect of mixing method to improve the dispersion
of clay in epoxy and observed a signicant improvement in frac-
ture toughness at 1 wt.% of clay loading for tetraglycidyl diamino
diphenyl methane (TGDDM) epoxy-DDS-clay nanocomposites syn-
thesized with high pressure mixing method compared to direct
mixing method. The Tg of the nanocomposites is found to decrease
with increase in clay content. The effect of temperature, speed and
time at the pre-mixing step during dispersion on intercalation and
exfoliation of clay in the epoxy resin have been studied by Ngo et
al. [88]. Even though the above premixing parameters have not any
signicant effect on the intercalation of organoclay at the pre-mix-
ing step, they have a positive effect on the intercalation/exfoliation
of nanoclay at the curing step.
The effect of processing variables on the mechanical properties
of clay/epoxy nanocomposites produced in a centrifuge has been
studied by varying processing conditions such as centrifuge rotor
314 A.A. Azeez et al. / Composites: Part B 45 (2013) 308320
speed and curing temperature, including different types of clay
[89]. As the amount of clay is increased, the elastic modulus of
epoxyclay nanocomposites increased up to a maximum of 6% clay
.The tensile strength and energy to failure continually increase
with clay quantity all the way up to 10%. The amount of increase
in a particular property depends on the type of clay used and the
surface treatment of that clay. For the rotor speed, the slower
speeds were found to be the best, while the higher speeds caused
the properties to deteriorate with the critical speed being around
3000 rpm. After 3000 rpm the higher speeds caused the clay layers
to actually break rather than separate, making the layers ineffec-
tive as nanocomposite llers. The curing temperature again
showed best results at lower temperature, but with higher temper-
atures causing specimen brittleness and deterioration of its prop-
erties. The optimum temperature range was about 80100 C.
Wang et al. [90,91] developed a new method, namely slurry
compounding for the preparation of highly exfoliated epoxy clay
nanocomposites using pristine clay, which involved the transfer
of clay water suspension to epoxy resin by solvent exchange step
and silane modication step. The important feature of the tech-
nique was that very little amount of organic modiers was enough
to facilitate the exfoliation of clay, in contrast to conventional orga-
noclays, which normally contains at least 2545% of organic sur-
factants. The resultant nanocomposites showed improvement in
fracture toughness, youngs modulus, storage modulus and Tg.
The formation of a large number of microcracks and the increase
in fracture surface area due to crack deection are the major
toughening mechanism in the nanocomposites. Wang et al. [92]
investigated the effect of clay concentration on the morphology
and properties of epoxy clay nanocomposites prepared by in situ
polymerization under mechanical stirring followed by ultrasonica-
tion and observed a decrease in layer space along with aggregation
of clay particles with increase in clay concentration due to the in-
crease in viscosity. Thermal decomposition temperature remained
unchanged and the Tg decreased, whereas the storage modulus in-
creased with increase in clay concentration. According to them, the
improved storage modulus is due to the stiff ller reinforcement
with partial exfoliation.
12. Properties of epoxy clay nanocomposites
Epoxy clay nanocomposites show enhanced thermo mechanical
properties even with a small amount of layered silicate (65%).
Improvements comprise higher modulus, increased strength, heat
resistance, decreased gas permeability, reduced coefcient of ther-
mal expansion and decreased ammability. The main reason for
this improved property in nanocomposites is the large interfacial
interaction between the matrix and layered silicate and also the
high aspect ratio of the dispersed clay particles.
13. Mechanical properties
Mechanical properties of polymerclay nanocomposites depend
on the microstructure in which how the clay layers are dispersed in
the polymer matrix. Generally the well dispersion of the clay par-
ticles in the polymer matrix yields enhanced tensile modulus, stor-
age modulus and tensile strength. Even though, the tensile
strength and modulus tend to increase with increasing clay con-
tent, the increasing trend is more noticeable for the tensile modu-
lus. The reinforcing effect of clay layers on the tensile modulus is
mainly due to the high modulus and high aspect ratio of the dis-
persed clay layers. This will provide large interfacial interaction be-
tween clay layers and polymer matrix. Chan et al. [93] has
investigated the reinforcing mechanism of the epoxy clay nano-
composites, particularly the interaction between nanoclay and sur-
rounding matrix. They observed 34% and 25% increase in Youngs
modulus and tensile strength respectively with the incorporation
of 5 wt.% of nanoclay to the epoxy matrix, as compared with a pris-
tine sample. The reinforcing mechanism is proved to be the exis-
tence of interlocking and bridging effects. Nanoclay clusters with
the diameter of 10 nm could enhance the mechanical interlocking
inside the composites and thus, breaking up the crack propagation.
The formation of boundaries between the nanoclay clusters and
epoxy can rene the matrix grains and further improve the exural
strength of the composites.
Basara et al. observed 17.2% increase in tensile modulus when
7 wt.% of Cloisite 30B was incorporated to epoxy matrix [94].
Yasmin et al. [81] reported that the tensile modulus (stiffness)
increases with increase in clay loadings as shown in the stress
strain behavior of epoxy clay nanocomposites (Fig. 9). But the ten-
sile strength and strain to failure are found to decrease as the clay
content decreases.
A three phase model of epoxy, exfoliated clay layers and nano-
layer clusters was developed by Luo and Daniel [95] to characterize
and model the youngs modulus of the nanocomposites. The Mori
Tanaka method was used to evaluate the youngs modulus of the
system as a function various parameters such as exfoliation ratio,
clay layer and clay cluster aspect ratios, d spacing and intragallery
modulus, matrix modulus and matrix poissons ratio. Relevant vol-
ume ratios of the clays have been calculated from the weight ratio
(w), matrix density (qm) and clay particle density (qc). Without
intercalation or exfoliation, the clay particle volume ratio, Vc can
be calculated as
w=qc
Vc
w=qc 1  w=qm
The actual silicate material volume ratio V 0c
t
V 0c V c
do
where t is the layer thickness and do is the initial layer spacing.
After processing, resulting in partial exfoliation and intercala-
tion, the volume ratio, Ve of the exfoliated fraction, re of the clay
particle is
V e V c r e t=do
The volume ratio Vi of the intercalated cluster is
d d
V i v 0c 1  r e v c 1  r e
t do
where d is the layer spacing in the intercalated clusters.
The effective stiffness tensor C of the composite is calculated
by MoriTanakas method
Fig. 9. Stressstrain behavior of clay nanocomposites [81].
 A.A. Azeez et al. / Composites: Part B 45 (2013) 308320
C  C 1 V 2 fc2  c1 Ag
where C1 is the matrix phase stiffness tensor, C2 is the inclusion
stiffness tensor, and V2 the inclusion volume ratio. The concentra-
tion tensor A is given by
A Adil V 1 I V 2 fAdil g1
and
Adil I SC 1
1 C 2  C 1 
1
where I is the fourth order unit tensor, S is the fourth order Eshel-
bys tensor, and V1 the matrix volume ratio
For comparison purposes, the stiffnesses computed by the Voigt
and reuss models are
C Voigt V 1 C 1 V 2 fC 2 g;
1 1
C Reuss V 1 C 1
1 V 2 fC 2 g
Interestingly, the model predictions as shown in the Fig. 10 were in
good agreement with experimental results. From the above model,
it was concluded that (1) the composite modulus of the system in-
creases with increase in the degree of dispersion, (2) exfoliation ra-
tio has a decisive role in the enhancement of modulus, (3) high
aspect ratios of the single clay platelet as well as clay clusters are
desirable in stiffness enhancement, and (4) larger d spacing is pre-
ferred along with high cluster aspect ratio for large improvement in
composite modulus.
The study on the morphology and mechanical properties of
epoxy system with octadecylammonium ion-modied MMT
showed an improvement in modulus and fracture toughness (KIC)
and exhibited a mixed intercalated/exfoliated structure by Becker
et al. [96]. Pluart et al. [68] also reported similar improvements in
the tensile strength and stiffness as well as fracture toughness of
DGEBA resin resulting from clay additions. Zhang et al. [97] found
88% and 21% improvement in impact strength and tensile strength
respectively for epoxy clay nanocomposites having 3 wt.% organo-
clay. Ingram et al. [98] observed an increase in storage modulus
for DDS and DDM cured DGEBA epoxy clay nanocomposites. Similar
observations are made by Hussain et al. [99] for aromatic amine
cured DGEBF epoxy clay nanocomposites. The storage modulus
and fracture toughness were found to increase with increase in clay
concentration for epoxy clay nanocomposites cured by diethyltolu-
enediamine [100].
Lin [101] has studied the effect of exfoliated nanoparticles on
the epoxy matrix to mechanical properties using organically trea-
ted Na-montmorillonite (Cloisite 30B) and titanium dioxide nano-
particles. It is found that the compression strength, fracture
strength and Youngs modulus for both reinforced nanocomposites
Fig. 10. Predicted and experimental results for Youngs modulus of epoxy/clay
nanocomposite as a function of clay concentration (DER 331 epoxy matrix) [95].
315
are much higher than that of pure epoxy matrix which is attributed
to the vein shape and the ductile dendrite phase occurred in the
matrix during the compressive deformation. The friction coef-
cient and wear coefcient of Cloisite 30B nanocomposites were
effectively reduced with rising ller content which should be
attributed to the improved dispersion of the nano particles. They
also assumed that the wear rate of Cloisite 30B nanocomposites
may improve nearly 30% due to its large agglomerated particle
which will prevent the entrapping of nanoparticle and epoxy deb-
ris between two sliding materials.
However, many authors [9,102104] have reported a reduction
in tensile strength, impact strength, fracture toughness as well as
the strain at break of the polymer clay nanocomposites with the
addition of clay particles. There are several reasons to explain the
decrease in properties as clay content increases .One reason is
the stress concentration effect of agglomerated clay particles at
higher clay loadings. The agglomeration of clay particles at higher
clay concentration also results lower in mechanical properties due
to lowering of ller surface area and lower polymer/clay surface
interaction. Another reason is that as clay content increases, the
viscosity of the system increases resulting in heterogeneity and
nanovoids formation due to the entrapment of air bubbles during
sample preparation. Miyagawa et al. [105,106] have observed a de-
crease in impact strength with increase in clay content for anhy-
dride and amine cured epoxy nanocomposites.
The durability studies of epoxy montmorillonite clay nanocom-
posites under room temperature, in hot and cold conditions
showed that the mechanical properties were found to decrease
with increase in time. 2 wt.% clay lled epoxy nanocomposites
showed enhancement in properties with relatively less number
of cracks and better interfacial bonding in all conditions over its
neat counterpart [107]. Qi et al. [108] reported 25% improvement
in fracture toughness with the incorporation of 5% Cloisite 30B in
epoxy matrix.
Cluster size effect in the hardness and interlaminar shear prop-
erties of nanoclay/epoxy composites with different amount of
nanoclay contents were examined [109]. It is found that the mi-
cro-hardness of the composites was enhanced with the addition
of small amount of nanoclay into the epoxy. However, there was
an optimal limit in which the hardness was dropped by continu-
ously increasing the nanoclay content. This might be due to the size
of the clusters reaching a crucial limit and therefore the reinforcing
function of the nanoclays decreased. Interlaminar shear test
showed the short beam shear strength of the epoxy decreased after
adding few percents of nanoclay particles. Microscopic observation
using SEM on the fracture surfaces showed that the size of the clus-
ters varied with the amount of nanoclays used in the composites. It
is reported that the exfoliation and dispersion of nanollers in
nanocomposites can be effectively visualized by air plasma etching
followed by scanning electron microscope (SEM) imaging
technique [40]. The method was applied to study MMT clay in vinyl
ester, MMT/epoxy and carbon nanotube (CNT) in vinyl ester
nanocomposites. This technique provides microscopic to submicro-
scopic 3-D details of the inorganic llers in a polymer composite.
14. Thermal properties
Polymer clay nanocomposites are known for its high thermal
stability and ame retardancy. The improved thermal stability is
attributed to the action of clay layers as superior insulator and
mass transport barrier to the volatile products generated during
decomposition as well as assisting in the formation of char after
thermal decomposition [6,110112]. The slowing down of the es-
cape of the volatile products in nanocomposites is because of the
labyrinth effect of the silicate layers in the polymer matrix
316 A.A. Azeez et al. / Composites: Part B 45 (2013) 308320
[113,114]. The improved thermal stability of the polymer clay
nanocomposites has been reported for various types of organoclays
and polymer matrices. Zhang et al. [97] reported that the heat dis-
tortion temperature and thermal decomposition were heightened
from 124 C and 348 C to 133 C and 373 C, respectively for epoxy
clay nanocomposites with 5 wt.% clay compared to pristine epoxy
matrix.
Lakshmi et al. [69] compared the thermal stability of unmodi-
ed epoxy (UME) systems and clay modied epoxy (CME) systems
by using different epoxy resins such as bisphenol A diglycidyl ether
(BDGE), bisphenol A propoxylate diglycidyl ether (BPDG), bisphe-
nolAbrominated diglycidyl ether (BBDG) and tetraglycidyl of
diaminodiphenylmethane (TGDDM) and different clay modies
such as hexadecyltrimethylammonium (HDTMA) modied clay
(MMT) and hexadecyltriphenylphosphonium(HDTPP) modied
clay as shown in Fig. 11a and b. The initial decomposition temper-
ature (IDT) of the CME is found to be higher than any of the UME
systems. Among the clays HDTTP modied systems showed high
IDT. The improved thermal stability of the clay modied epoxy sys-
tems are attributed to barrier action of hard MMT-Clay nanolayers,
which protect from volatilizing epoxy polymer chains present in
between them and also restrict the segmental motion of the poly-
mer networks. The enhanced thermal stability of the nanocompos-
ites may also be due to the presence of inorganic phases like, SiO2,
Al2O3, and MgO in clay particles, high temperature resistant moie-
ties like, phenyl units and/or bromine atoms present in the epoxy
Fig. 11. Thermal properties of (a) unmodied epoxy systems (UME) and (b) clay
modied epoxy (CME) systems [69].
and the triphenylphosphine unit in the HDTPP-MMT clay. A signif-
icant improvement in thermal stability has also been reported on
epoxy clay nanocomposites prepared with reactive phosphorous
containing organo clay (RPC) by the evaluation of activation energy
and integral procedural decomposition temperature [115].
Wang et al. [115] has reported large increment in limiting oxy-
gen index (LOI) with the incorporation of 5 wt.% of RPC to the
epoxy resin indicating the extraordinary improvement in ame
retardancy, which is ascribed to the synergistic effect of phospho-
nium ions and silicate layers in the clay as well as enhanced sur-
face area by the exfoliation of clay layers. The improved ame
retardancy of the polymer clay nanocomposites may be attributed
to the formation of thermal insulating and low permeable char res-
idue of clay layers at the outer surface of the nanocomposite during
combustion and acts as a protective barrier by reducing the heat
and mass transfer between the ame and polymer. The char resi-
due of clay layers will also reduce the oxygen uptake and the es-
cape of volatile gases produced by polymer degradation [116].
Camino et al. [117] reported the mechanism of the improved re
retardany of epoxy clay nanocomposites cured by methyl tetrahy-
dropthalein anhydride. This is due to the formation of protective
skin created by ablative reassembling of the clay layers as well
as the chemical structure of the clay. An improved re resistance
was also observed in the case of epoxy carbon ber composites
with the addition of nanoclay and graphene nanosheets [118].
Gu and Liang [119] reported that thermal stability of the epoxy
clay nanocomposites were inuenced by the clay loading, structure
and nature of the purge gas. The thermal degradation behavior was
found to be in three steps in air and two steps in nitrogen for the 2
and 10 wt.% of clay loading to the epoxy. In addition, the improved
thermal stability was observed for 2 wt.% clay loading due to its
exfoliated structure, while lowest thermal stability observed for
10 wt.% systems with an intercalated structure in nanocomposites.
Further, among the systems, the 10 wt.% clay incorporated system
showed better ame retardancy due to high char yield and low
maximum degradation rate temperature.
Kaya et al. [120,121] reported that the incorporation of unmod-
ied clay (MMT) into the epoxy resin did not affect the Tg value,
while the addition of 3 wt.% of organically modied clay (OMMT)
increased the Tg by about 15 C due to the better exfoliation of clay
in the epoxy matrix. It is also observed that the epoxy clay nano-
composites containing OMMT clay particles exhibited better opti-
cal transparency than those with MMT. Flame retardancy of the
epoxy was increased by the addition of clay particles and the burn-
ing rate is decreased by 38% and 58% for MMT and OMMT nano-
composites respectively for 10% clay loading.
Many investigators reported that the Tg of the polymer either
increase or decrease with the addition of clay particles. The in-
crease in Tg is attributed to the slower segmental motion due the
polymer chains being anchored to the surface of the clay. Lu et
al. [122] and Miyagawa et al. [123] observed an increase in Tg with
the addition of clay particles to epoxy resin. Liu et al. [100] ob-
served a decrease in Tg with increase in clay content. This was
attributed to the plasticizer effect of the clay modier.
Temperature effects on the fracture behavior and tensile prop-
erties of silane-treated clay/epoxy nanocomposites were investi-
gated [77]. Tensile tests were performed at 30 C, 25 C, 40 C,
and 70 C. Tensile strength and elastic modulus were greater than
those of unmodied samples for all temperatures except 70 C.
However, the tensile properties decreased as temperature in-
creased. In particular, at 70 C, the tensile properties were less than
10% of the original value at room temperature, independent of sur-
face treatment. The fracture and tensile properties of silane-treated
clay/epoxy nanocomposites increased due to good dispersion of
the clay in epoxy and improvement in interfacial adhesive strength
between epoxy and clay layers.
 A.A. Azeez et al. / Composites: Part B 45 (2013) 308320
15. Barrier properties
Clay layers in the polymer matrix can act as an effective barrier
to the penetrants. The enhanced barrier property of polymer nano-
composites is due to the labyrinth or tortuous path (Fig. 12) that
retards the diffusion of gas molecules through the polymer matrix.
Neilsons equation is proved to be a reliable estimate [124] of
gas permeability of polymer-layered silicate nanocomposite sys-
tems. The Neilsons equation is as follows:
Pn 1  /


Pm 1 a2/
where Pn represents the permeability of the resulting nanocompos-
ite and Pm represents the permeability of the matrix polymer, / is
the volume fraction of clay platelets, a Lt, is the aspect ratio of
the clay layers and L and t are the length and thickness of clay layers
respectively. Due to the mismatch of the experimental values with
theoretical predictions, the tortuosity factor was corrected by the
modied Neilsons model to include the orientation factor as pro-
posed by Bharadwaj [27].
According to Bharadwaj, the permeability of a nanocomposite
(Pn) containing clay stacks of length (L) (L also being the length
of the individual clay platelets) and thickness (t) is related to the
permeability of the pure matrix (Pm) by
Pn 1  /

2

ability with increase in clay content for epoxy clay nanocompos-
Pm 1 L/
2t 3
S 12
where / is the volume fraction of clay platelets, S is dened as an
order parameter (S 12 3 cos2 h  1) representing the orientation
Fig. 12. Zigzag diffusion (tortuous) pathway of a gas through clay-based polymer
nanocomposites [29].
Fig. 13. Order parameter of the clay layers [27].
317
of the tactoids in the matrix and h represents the angle between
the direction of preferred orientation (n) and the sheet normal (p)
unit vectors as shown in Fig. 13. The order parameter (S) can range
from 1 to 1/2. If S = 1(h = 0), the tactoids will be aligned perpendic-
ular to the gas ow direction (in this case, the model is equivalent to
Neilsons model). When S = 0 (h = 57), the tactoid will be distributed
randomly and if S = 1/2 (h = p/2), the tactoids will be aligned in the
gas ow direction. From Bharadwajs model, it can be concluded
that both aspect ratio and order parameter of the clay platelets
inuence the permeability of nanocomposites.
Hydrogen gas permeability has been reduced to 70% for epoxy
clay nanocomposites compared to base epoxy resin and observed
vefold decrease in helium leak rate for the lament wound carbon
ber reinforced cryo tanks made with the above nanocomposites
[125]. Mittel [126] observed 30% reduction in O2 gas permeability
for 3.5 vol.% of organically modied vermiculite clay incorporated
epoxy systems. He also noticed a substantial decrease in water per-
meation in the above epoxy clay systems. But for the unmodied
system (Na vermiculite clay),the water permeation is found to in-
crease indicating that the polarity of the hydrophilic interlayers is
signicantly reduced after the organic modication, but interlayers
are still partially polar to attract the molecules of water. Further
improvement in barrier property can be achieved by introducing
much longer alkyl chains as well as increasing the grafting density
in the ammonium ions.
Kim et al. [127] reported a gradual decrease in moisture perme-
ites, agreeing the prediction based on tortuous path model.
Among the different organically modied clay, he observed better
moisture barrier properties for nanocomposites in which the clay
particles with larger interlayer distance between the individual
clay layers and more uniform distribution. Bagherzadeh et al.
[128] found an increase in the barrier and anti-corrosive properties
with increase in clay loading. Nanocomposite coating with 1 wt.%
clay loading showed about 70% reduction in water uptake and
the best anti-corrosive performance of coatings was obtained at
3 and 5 wt.% clay concentrations. In another report, the barrier ef-
ciency of epoxy/montmorillonite nanocomposite coating to H2S
was substantially increased under high temperature and pressure
oilgas environment compared to pure epoxy coating [129].
16. Applications
Because of the large improvement observed in the mechanical,
thermal and barrier properties, epoxy clay nanocomposites can be
318 A.A. Azeez et al. / Composites: Part B 45 (2013) 308320
used for many specic applications in aerospace, defense and auto-
mobile industries. These composites are also used in high perfor-
mance structural and functional applications such as laminates
and composites, adhesives, sealants, tooling, molding, casting,
electronics and construction.
Epoxy clay nanocomposites reinforced with a high strength car-
bon/glass ber have the greatest potential for commercial applica-
tions within the automotive and aircraft industries [130], due to
their ability to reduce component weight and enhance mechanical
properties. Filament wound carbon ber reinforced cryotanks
made with epoxy nanocomposite had a vefold lower helium leak
rate than the corresponding tanks made without clay [125]. The
prominent reduction in leak rate may be due to the ow induced
alignment of the clay layers during processing. Use of these ad-
vanced, high barrier composites would eliminate the need for a
liner in composite cryotanks, thereby simplifying construction
and reducing propellant leakage. Fatigue crack propagation behav-
ior of epoxy composites have great importance in engineering
components that are subjecting to cyclic loading. Khan et al.
[131] observed a signicant improvement (74%) in fatigue life with
the incorporation of 3 wt.% nanoclay to epoxy CFRP composite .The
enhanced fatigue life of clay-CFRP hybrid composites is due to
toughening mechanisms induced by the improved ber/matrix
interfacial bond and nanoclay induced dimples.
Since epoxy clay nanocomposites provide improved anticorro-
sion protection [126], it can nd new applications in modern air-
craft anticorrosion coatings. Epoxy clay nanocomposites have
been extensively used for the structural adhesive applications,
due to its potential improvement in adhesive properties with prac-
ticality and low cost. Recently, it was reported that the bulk adhe-
sive strength of the epoxy resin could be improved with the
addition of nanoclay [132].
17. Conclusion
Epoxy nanocomposites are highly versatile polymer systems for
the new era of making lighter structural composites for various
aerospace and automobile applications. The nal morphology,
physical, chemical and barrier properties of the nanocomposites
were inuenced by processing method, clay modier and curing
agents. Epoxy clay nanocomposites showed remarkable improve-
ment in tensile, exural and fracture toughness properties. Thermal
stability and barrier properties were signicantly improved by the
incorporation of clay particles to epoxy systems. CTE and water per-
meation of the nanocomposite were reduced considerably.
Acknowledgements
This work was supported by the Center for Science &
Technology Research (CSTR) grant funded by the Korea govern-
ment (MEST) (CSTR-002-100701-03) and Basic Science Research
Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education, Science and Technology
(2010-0023106).
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