INSTITUTE OF PHYSICS PUBLISHING NANOTECHNOLOGY

Nanotechnology 16 (2005) 2020–2029 doi:10.1088/0957-4484/16/10/006

Structural and mechanical

characterization of nanoclay-reinforced
agarose nanocomposites
Xiaodong Li1,3,4 , Hongsheng Gao1 , Wally A Scrivens2,3 ,
Dongling Fei2 , Vivek Thakur2 , Michael A Sutton1,
Anthony P Reynolds1 and Michael L Myrick2
1
Department of Mechanical Engineering, University of South Carolina, 300 Main Street,
Columbia, SC 29208, USA
2
Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter
Street, Columbia, SC 29208, USA

E-mail: lixiao@engr.sc.edu and scrivens@mail.chem.sc.edu

Received 21 April 2005, in final form 1 June 2005

Published 3 August 2005
Online at stacks.iop.org/Nano/16/2020
Abstract
Nanoclay-reinforced agarose nanocomposite films with varying weight
concentration ranging from 0 to 80% of nanoclay were prepared, and
structurally and mechanically characterized. Structural characterization was
carried out by transmission electron microscopy (TEM), scanning electron
microscopy (SEM) and atomic force microscopy (AFM). It was found that
pre-exfoliated clay platelets were re-aggregated into particles (stacked
platelets) during the composite preparation process. Each particle consists
of approximately 11 clay platelets stacked together. The nanoclay particles
were homogeneously dispersed within an agarose matrix. The clay particles
were oriented with a slight preference of the stacked platelets being parallel
to the composite film’s surface within the low loading composite films.
Mechanical properties of the nanocomposite films were measured by tensile,
three-point bending and nanoindentation tests. Mechanical testing results
show that nanoclays provide a significant enhancement to the tensile
modulus and strength. For the 60% clay nanocomposite, its elastic modulus
increases up to 21.4 GPa, which is five times higher than that of the agarose
matrix. Based upon the structural characterization, a theoretical model has
been developed to simulate the mechanical behaviour of the
nanoclay-reinforced polymer composites.

1. Introduction various clay reinforced nanocomposites or hybrids have

Clay reinforced polymer composites have spurred great
interest since nylon 6–clay nanocomposites were developed
and found applications in the automotive industry by the
researchers at Toyota in the early 1990s [1–3]. With
only 4.2 wt% clay dispersed in nylon 6 matrix, the
elastic modulus increased by as much as 100% and the
heat distortion temperature increased by 80 ◦ C compared
to those of the unfilled nylon 6 matrix [1, 2]. To date,
3 Authors to whom any correspondence should be addressed.
4 www.me.sc.edu/research/nano
been synthesized such as epoxy–clay nanocomposites [4, 5],
polyimide–clay nanocomposites [6] and polyurethane–clay
nanocomposites [7, 8], to name a few. Previous studies have
found that nanoclay reinforced polymeric composites offer
many improved properties over pristine polymers in tensile
modulus and strength [2, 9–11], thermal properties and heat
distortion temperature [2, 12], resistance to flammability [13],
and reduced permeability to liquids or gases [14]. A common
observation from these studies is that the magnitude of
improvement is, to a large extent, dependent upon the state
of dispersion of nanoclays in the matrix. Only when clays

0957-4484/05/102020+10$30.00 © 2005 IOP Publishing Ltd Printed in the UK 2020

 Structural and mechanical characterization of nanoclay-reinforced agarose nanocomposites
are homogeneously dispersed and randomly orientated within
the matrix, i.e. nanoclays are completely exfoliated, could
the enhancement be more significant. However, the clay
dispersion effect on the resulting mechanical properties is not
well understood, especially for nanocomposites with a higher
clay concentration.
The term clay refers to a class of materials made up of
layered silicates, among which montmorillonite (MMT) is the
most commonly used clay in the synthesis of nanocomposites.
The MMT is composed of layered, nanometre thick platelets,
and has the same crystalline structure as mica [15]. Although
clay has many attractive properties such as high elastic
modulus and wide availability at low cost, its application is
limited largely because the clay dispersion cannot be easily
achieved [16]. The full exfoliation of nanoclays in nylon 6
matrix was first achieved by Usuki et al [17] in 1993 and is
believed to be a fundamental breakthrough for utilizing clay in
practical applications.
Although nanoclays have proven to be a prominent re-
inforcement, to date, only a few polymer–clay nanocompos-
ites with well enhanced strength or stiffness have been re-
ported. Agarose is a naturally occurring polysaccharide and
has been mainly used as a gel medium for the separation of
DNA and protein molecules via electrophoresis [18]. With an
ever-increasing demand for advanced materials, enhancing the
mechanical properties of natural polymers like agarose to make
new, high-performance composites is important and com-
pelling. The synthesis methods of polymer–clay nanocom-
posites are generally categorized into three groups according
to the starting materials and the processing techniques: in-
tercalation of polymer or pre-polymer from solution, in situ
intercalative polymerization and melt intercalation [19].
In the present study, a group of montmorillonite-
reinforced agarose nanocomposite films with clay concentra-
tion up to 80 wt% were prepared and characterized, with the
focus on their structural and mechanical properties. The objec-
tives of this study were to investigate the effects of clay concen-
tration and dispersion on the resulting mechanical properties,
and to develop a theoretical model for predicting the mechan-
ical properties of nanoclay reinforced polymer composites.
2. Experimental details
2.1. Sample preparation
A 1 wt% solution of sodium montmorillonite (Cloisite Na + ,
Southern Clay Products) was dispersed in distilled water.
The dispersion was sonicated (Branson 5510) for an hour
and then centrifuged (Sorvall® Legand T) at 3500 rpm for
75 min. The transparent supernatant solution was decanted into
a silated container. The weight concentration of this exfoliated
montmorillonite (MMT) nanoclay suspension was 0.7%.
Nanocomposites were prepared by a gelation method,
i.e. agarose (CertifiedTM PCR) was added to the MMT
suspension at a concentration of
1 wt%. The mixtures were
first heated to 100 ◦ C to dissolve the agarose and then poured
into Petri dishes. Agarose gels were formed when the mixtures
were cooled to room temperature. These gels were dried
at room temperature in the air, resulting in nanocomposite
films after the gels dehydrated and collapsed. Water content
of the films was calculated based on the weight lost before
and after placing in the vacuum oven at 100 ◦ C over 24 h.
The water contents of pure agarose and 40% MMT/agarose
films are 16.58% and 12.77% respectively. Different loadings
(i.e. concentration) of MMT/agarose films were prepared by
varying the ratio of MMT to the amount of dry agarose added.
The thickness of the resulting MMT/agarose films is in the
range from 60 to 80 µm.
For structural characterization of the nanoclays by atomic
force microscopy (AFM), the resulting exfoliated MMT
suspension was further diluted with distilled water and then a
drop of solution was put onto the surface of newly cleaved mica.
2.2. Structural and mechanical characterization
The morphology of the nanoclays used in this study was
characterized using a Dimension 3100 AFM system (Veeco
Metrology Group) operated in the tapping mode. Cross-
sections of the nanocomposite films were studied with a
Philips EM 430 ST transmission electron microscope (TEM).
The morphology, characteristic length and thickness of the
nanoclays before dispersion were investigated and compared
with those of the clays within the nanocomposites.
Mechanical properties of the composites were measured
using an UMT-2 mechanical tester (CETR Inc.). Both tensile
and three-point bending tests were preformed. The composite
films were first cut into strips and then attached onto a frame,
which was used for protecting the specimen from tension or
twisting during handling. The frame was cut away once the
specimen was mounted on the tester. The instrument is capable
of applying up to 5000 mN force with a force resolution of
1.3 mN. The strain rate was 0.5 mm min−1 for all tensile tests.
Fracture surfaces of the tensile specimens were examined using
a Philips XL30 field emission environmental scanning electron
microscope (ESEM) operated at 30 kV.
Three-point bending tests were preformed using the
same tester. A high-resolution load transducer with a force
resolution of 0.1 mN was used. The bending elastic modulus
was calculated by
L3 d P
E= (1)
48 · I dδ
where L is the suspended length and I is the second moment
of inertia. d P/dδ is the slope of the initial linear portion of the
bending load–deflection curve.
Nanoindentation tests were performed using a Triboscope
nanomechanical testing system (Hysitron Inc.) in conjunction
with the Veeco AFM system. The Hysitron nanoindenter
monitors and records the load and displacement of the indenter,
a diamond Berkovich three-sided pyramid, with a force
resolution of about 1 nN and displacement resolution of about
0.1 nm. Hardness and elastic modulus were calculated from
the recorded load–displacement data. A typical indentation
experiment consists of four steps: approaching the surface;
loading to peak load; holding the indenter at peak load for
5 s; finally unloading completely. The holding segment was
included to avoid the influence of creep on the unloading
characteristics since the unloading curve was used to obtain
the elastic modulus of a material. For more details on
nanoindentation experimental techniques, please see [20, 21].
2021
X Li et al
Nanoindentation hardness is defined as the indentation
load divided by the projected contact area of the indentation.
It is the mean pressure that a material will support under load.
From the load–displacement curve, hardness can be obtained
at the peak indentation load as
Pmax
H= (2)
A the interlayer spacing of intercalated MMT within the agarose
where A is the projected contact area. For an indenter with
a known geometry such as the Berkovich tip used in this
study, the projected contact area is a function of contact
depth, which is measured by the nanoindenter in situ during
indentation [20, 21]. Therefore, the projected contact area A
can be measured and calculated directly from the indentation
displacement.
The indentation elastic modulus was calculated using the
Oliver–Pharr data analysis procedure [22] beginning by fitting
the unloading curve to a power-law relation. The unloading
stiffness can be derived from the slope of the initial portion
of the unloading curve, S = d p/dh. Based on relationships
developed by Sneddon [23] for the indentation of an elastic
half space by any punch that can be described as a solid
of revolution of a smooth function, a geometry independent
relation involving contact stiffness, contact area, and elastic
modulus can be derived as follows:

60, and 80% clay loadings are shown in figure 3. These images
S π
Er = (3)
2β A
where β is a constant which depends on the geometry of the
indenter (β = 1.034 for a Berkovich indenter) [20, 21], and E r
is the reduced elastic modulus which accounts for the fact that
elastic deformation occurs in both the sample and the indenter.
E r is given by
1 1 − ν 2 1 − νi2
= + (4)
Er E Ei
where E and ν are the elastic modulus and Poisson’s ratio for
the sample, respectively, and E i and νi are the same quantities
of the indenter. For the diamond indenter, E i = 1140 GPa and
νi = 0.07 [20, 21].
3. Results and discussion
Figure 1 shows the representative TEM and AFM images
as well as the morphology characteristics of the nanoclays
used in this study. Direct observation of individual clay
platelets or platelet stacks confirms that MMT has the layered
structural characteristic with an irregular shape, which is in
good agreement with previous studies [24]. The measured
platelet thickness is about 1 nm, which is also consistent with
the previously published value [25, 26]. The maximum length
measured is 853 nm and the maximum width 430 nm. Since
there are no standards regarding representing the length and
width of irregular shape, in this study, the characteristic length
of a platelet is represented by the average of its length and
width that were measured in two perpendicular directions and
correspond well to its shape. The histograms of platelet length
and thickness are shown in figures 1(d) and (f), respectively.
Figure 1(e) shows the histogram of the number of platelets per
2022
particle. It is clear that the majority of clay particles are single-
layer platelets before dispersion, as shown in figure 1(e). The
average length of clay particles is 174.7 nm and the aspect ratio
is 108.3.
Previous studies have shown that the interlayer spacing
is 0.96 nm for natural (unpolymerized) MMT with a platelet
thickness of 0.94 nm [25, 26]. According to XRD analysis,
matrix is averaged to be 1.52 nm. In addition, the tensile
modulus of individual MMT platelets is 178 GPa and its density
is 2.83 g cm−3 [25].
Figure 2 shows the low magnification TEM images of
the nanocomposites with 30, 60, and 80% clay loadings. In
figure 2(b), it is shown more clearly that clay particles were,
to a large extent, dispersed uniformly and oriented randomly
within the matrix. Nevertheless, the clay particles within
lower clay loading nanocomposites show a slight tendency
of the stacked platelets to be parallel to the nanocomposite
film surfaces. This tendency is diminished with increasing
clay concentration. The higher the clay concentration, the
smaller the deviation from uniform orientation found. When
the clay weight concentration is higher than 60%, thicker
platelet stacks can be found and the clay dispersion is less
uniform with further increasing the clay content. The high
magnification TEM images of the nanocomposites with 0, 30,
demonstrate clearly that the nanoclays within the agarose
matrix were mainly in the form of platelet stacks composed
of approximately 11 platelets in a stack and thus existed
as intercalated particles. According to results measured by
AFM, however, about 75% of clay particles were exfoliated
single-layer platelets. It is evident that the pre-exfoliated
MMT platelets were re-aggregated during the dispersion and
polymerization processes. The high clay concentration in the
matrix as well as the large aspect ratio and high surface-to-
volume ratio of the clay platelets make it difficult for the
agarose to wrap the platelets and keep them apart from one
another.
The characteristic length and thickness of the nanoclays
within the nanocomposites were measured by TEM. Figure 4
shows the histogram of particle length and number of
platelets per particle for the clay particles within the matrix.
Comparison of figure 4 with figures 1(d) and (e) shows that
both particle length and thickness are increased during the
composite preparation process. As a result, the aspect ratio
is decreased from 108.3 down to 16.
The representative tensile stress–strain curves are shown
in figure 5. It is noted that both tensile elastic modulus
and strength increase with an increase in clay concentration
and reach the peak values at 60% clay loading. With
a further increase in clay concentration the modulus and
strength decrease. The ductility decreases with increasing clay
concentration, as shown in figure 6, indicating an increase in
brittleness in the high clay loading composites.
For a two-phase composite, there is an optimum volume
fraction or volume ratio that provides good bonding between
the two phases for load transfer. When clay loading is
higher than a critical volume/weight percentage, the direct
consequence is that the clay particles within nanocomposites
cannot be completely exfoliated into platelets or even fully
 Structural and mechanical characterization of nanoclay-reinforced agarose nanocomposites

Figure 1. Representative (a) TEM and (b) AFM images of the nanoclays before dispersion, (c) cross-section of a clay platelet, (d) histogram
of particle length before dispersion, (e) histogram of platelet number per particle, and (f) histogram of particle thickness before dispersion.
(This figure is in colour only in the electronic version)

Figure 2. Low magnification TEM images of nanocomposites with (a) 30% clay, (b) 60% clay, and (c) 80% clay concentration.

intercalated. TEM observation of the high clay loading
composites has proven that when the clay concentration
is higher than 60% there is less available agarose matrix
material for intercalating into the nanoclays. Thus good
bonding between the clay and agarose matrix can hardly be
formed for these nanocomposites. Therefore, the agarose–
clay nanocomposites with clay loading higher than 60% have
no practical meaning unless better dispersion techniques are
developed.
Figure 7 shows the representative load–deflection curves
of three-point bending tests. The load was normalized
with respect to the cross-section area of the specimen. By

2023
X Li et al

Figure 3. High magnification TEM images of (a) agarose matrix and nanocomposites with (b) 30% clay loading, (c) 60% clay loading, and
(d) 80% clay loading.

0.15 200
(a)
Total clay number =378
Average length =236.61 nm
0.1 150
Frequency

Stress (MPa)

100
0.05
0% clay
50 30% clay
0 60% clay
40 100 160 220 280 340 400 460
80% clay
Particle length (nm)
0
0.5 0 0.05 0.1 0.15 0.2
(b) Strain (mm/mm)
Total number =378
Average number per particle
Figure 5. Representative stress–strain curves of nanocomposites
n=11.13
with 0, 30%, 60%, and 80% clay in the matrix.
Frequency

0.25

increases with an increase in clay concentration and reaches

0 concentration.
7 9 11 13 15 17
No. of platelets per particle
Figure 4. Histogram of (a) length of clay particles and (b) number
of platelets per particle.
normalizing, the slope of the load–deflection curve is directly
correlated to the magnitude of the tensile modulus. It
can be seen that the elastic modulus of the nanocomposite
the maximum value at 60% clay concentration. Then the
elastic modulus decreases with a further increase in clay
19
The elastic moduli as functions of clay concentration
measured by tensile and bending tests are plotted in figure 8(a).
It is clear that the elastic moduli measured by tensile and
bending tests are in good agreement for the nanocomposites
with clay concentrations less than 60%. The elastic modulus
reaches the maximum value of 21.4 ± 2.5 GPa at 60% clay
loading, which is increased sixfold compared with that of
the agarose matrix. It has been reported that human bone

2024

0.25
0.2
0.15
Ductility
0.1
0.05
0 0
0 20 40 60
Clay concentration (wt. %)
Figure 6. Ductility (percentage elongation at failure) as a function
of clay concentration.
100
0 % clay
Normalized load (mN/mm2 )
30 % clay
80
60 % clay
80 % clay
60
40
20
0
0 0.01 0.02
Displacement (mm)
Figure 7. Representative normalized load–deflection curves of
bending tests.
has an elastic modulus of 11.4–21.2 GPa [27–29]. The
nanoclay reinforced agarose nanocomposites have comparable
mechanical properties with human bone. This may extend the
application of agarose-based material to orthopaedic and other
bioengineering areas.
The tensile strength, for the composites with clay loading
ranging from 40 to 60%, is increased by as much as 50%
compared with that of agarose matrix, as shown in figure 8(b).
The maximum tensile strength was found to be 183 MPa for
the nanocomposite with about 50–60% clay loading. Noting,
the wide range of clay loadings is very useful for tailoring the
mechanical properties according to the design requirements.
When clay concentration is higher than 60%, however, both
elastic modulus and tensile strength decrease drastically with
a further increase in clay concentration, indicating unfeasible
volume fraction and poor interfaces between the agarose matrix
and clay particles.
Tang et al [30] developed the nanostructured polymer
clay films, named artificial nacre, using a layer-by-layer
assembly process in which 5 min adsorption of organic layers
(polyelectrolytes) and 10 min dispersion of inorganic layers
(clay MMT) were processed sequentially with a rinsing process
in deionized water between every two sequences. The 2 min
rinsing processes were used to remove the irregular adsorbed
platelets loosely attached to the clay layer in order to obtain a
better interface between the organic layer and inorganic clay
platelets. During this process, the clay solution was refreshed
Structural and mechanical characterization of nanoclay-reinforced agarose nanocomposites
40
Tensile tests
Elastic modulus (GPa)
Bending tests
30
20
10
0
20 40 60 80 100
80 100
Clay concentration (wt. %)
250
Tensile stress (MPa)
200
150
100
50
0
0 20 40 60 80 100
Clay concentration (wt. %)
Figure 8. (a) Elastic modulus as a function of clay concentration
obtained by tensile and three-point bending tests, and (b) tensile
strength as a function of clay concentration.
0.03 0.04
every 20th deposition cycle and other solutions also refreshed
appropriately. A thickness of 4.9 µm was obtained for the
typical 200-multilayer films. The measured elastic moduli of
the artificial nacres were 10 ± 2 and 13 ± 2 GPa for 100-
and 200-layered films, respectively. The maximum tensile
strength of these films was 109 MPa and was reported to have
approached that of real nacre. By comparison of the elastic
modulus of the artificial nacre and the nanocomposite films
in this study, it is quite clear that the mechanical properties
of the agarose–clay composite films are superior to those
of the artificial nacre. From a synthesis point of view, the
easy and simple route for the preparation of agarose–clay
nanocomposites used in the present study has profound merits,
which should find more industrial applications.
Figure 9 shows the representative SEM images of fracture
surfaces of the nanocomposites with 0, 40, 60, and 80% clay
loadings. It can be seen that the fracture surface became
increasingly rougher with an increase in clay concentration.
For the composites with clay concentrations less than 60%, no
debris particles were found on the fracture surfaces, indicating
a strong bonding between the clay particles and the matrix.
Clay-like debris particles were found on the fracture surfaces
of the 80% clay composite. This further confirms that the
agarose matrix is less available to intercalate into nanoclays for
the 80% clay nanocomposite, thereby resulting in poor bonding
between the nanoclay particles and the agarose matrix.
Figure 10 shows the hardness and elastic modulus of the
nanocomposites measured by nanoindentation tests. Both the
nanoindentation hardness and elastic modulus decrease in a
random manner as clay concentration is increased. It should
be noted that the tensile and three-point bending tests measured
2025
X Li et al
Figure 9. Representative SEM images of the fracture surfaces of (a) agarose matrix and nanocomposites with (b) 40% clay, (c) 60% clay,
and (d) 80% clay.
2 10
Hardness
Elastic modulus
Hardness (GPa)
1.5
1
0.5
0 0
0 20 40 60
Percentage of clay
Figure 10. Nanoindentation hardness and elastic modulus as a
function of clay concentration.
the modulus in the direction parallel to the nanocomposite
films, whereas the nanoindentation tests measured the elastic
modulus in the direction perpendicular to the composite films.
The nanoindenter probed a small volume of material and
the indenter tip might or might not encounter the nanoclay
particles; even if the indenter tip encountered the nanoclay
particles, the nanoclay particles beneath the indenter tip might
be bent down together with the indenter [31]. On the other
hand, the nanoindentation elastic/plastic deformation zone is
much smaller compared with that of the global tensile and
bending tests, and there were no or only a few nanoclay
particles in the nanoindentation deformation zone. Long-range
load transfer was limited.
4. Modelling of elastic modulus
The overall strategy in developing a model is to establish
the relation of the physical properties between a composite
2026
and its individual components. For conventional composite
systems, the theoretical frameworks have been well developed
Elastic modulus (GPa)
8 for predicting various properties of a composite based on the
properties of its individual components. These theories are
6
useful for evaluating the contribution of individual components
4
and for optimizing the overall performance of a composite
based on the matrix and filler moduli, volume fraction, filler
aspect ratio and orientation etc. In all these theories, the
2
underlying assumptions are (1) all components in a composite
will act independently and (2) the interaction or bonding
80 100
between the matrix and fillers is strong enough for load transfer.
The two well known composite theories are Halpin–
Tsai theory [32–34] and Mori–Tanaka theory [35]. Both
theories have received considerable attention in the composite
community [25, 26, 36–40]. However, none of them can
be applied directly to the nanoclay reinforced nanocomposite
materials, in which the roles of aspect ratio, dispersion, and
orientation of the fillers are more critical compared with
conventional composites.
Halpin theory [32–34] has been widely used for
predicting the elastic modulus of unidirectional fibre reinforced
composites as functions of the fibre volume fraction and aspect
ratio. The longitudinal and transverse elastic moduli, i.e. E 11
and E 22 , as shown in figure 11, are expressed in a general form:
E 1 + ξ ηVf
= (5)
Em 1 − ηVf
where E and E m are the elastic moduli of the composite and
the matrix, respectively. Vf is the volume fraction of the filler.
η is given by
Ef
E
−1
η = Emf (6)
Em
+ξ

Fibre 1 Clay platelet 1 to construct the model. AFM observation of the nanoclays
2 2
3 3
Loading direction Composite modulus Shape parameter
Fibres Platelets Fibres
1 E11=Ep E11=Ep ξ =2(l/d)
2 E 22=Et E22=Ep ξ =2
3 E 33=Et E33=Et ξ =2
Figure 11. Illustration of the fibre and platelet filler and shape
parameters for each case for Halpin composite theory. E p and E t are
the moduli in directions parallel (longitudinal direction) and
perpendicular (traverse direction) to the major axis of the fillers,
respectively. l is the length of the fibre or platelet, d is the diameter
of the fibre, and w and t are the width and thickness of the clay
platelet.
where E f is the elastic modulus of the filler. The tensile
modulus of an individual MMT platelet is 178 GPa [25] and the
measured elastic modulus of agarose polymer was 3.5 GPa. ξ is
the shape parameter depending on filler geometry and loading
direction, as shown in figure 11. Ashton et al [34] found that
ξ = 2(l/d) can be used to calculate the longitudinal modulus
E 11 , where l and d are the characteristic length and diameter
of the fibre, respectively. When ξ = 2, on the other hand,
the same equation can be applied for evaluating the transverse
modulus E 22 [34].
Halpin–Tsai composite theory is consistent with the rules
of composites in specific cases such as isostrain and isostress.
For example, when ξ → ∞, equation (5) reduces to the rule
of mixtures for the isostrain case, i.e.
E = Vf E f + Vm E m
where Vm is the volume fraction of the matrix and Vf + Vm = 1.
Conversely, when ξ → 0, equation (5) reduces to the inverse
rule of mixtures for the isostress case, i.e.
1 Vf Vm
= + . (8)
E Ef Em
More conveniently, the Halpin equations retain the same
form for discontinuous cylindrical fibres and platelet fillers.
The shape parameter, ξ , however, is required to change from
2(l/d) to 2(l/t) for the platelet filler, where l is the length of
the fibre or the platelet, d is the diameter of the fibre and t
the thickness of the platelet. According to the characteristic
differences between fibre and platelet, it is evident that the
fibre reinforces only in the longitudinal direction while the
platelet can reinforce in directions that are parallel to the
platelet surface. Figure 11 illustrates the fibre and platelet
filler and shape parameters for each case when the Halpin–
Tsai composite theory is applied.
The clay fillers, which may be in the forms of platelets
or platelet stacks (particles), were often simulated by lamellar
squares or circular discs with varying thickness [25, 37–39]. In
fact, clay platelets cannot be simply represented by any shape,
as shown in the AFM image in figure 1. Nevertheless, it is
required to represent clay platelets by a proper shape in order
Structural and mechanical characterization of nanoclay-reinforced agarose nanocomposites
shows that the rectangular shape with the length to width ratio
of about 1.5 could best represent clay platelets.
In general, for nanocomposite systems with large quantity
of clay fillers, aspect ratio R and shape parameter ξ should be
calculated by the average length and thickness, as given by
 ¯
l
Platelets ξ = 2R = 2 · (9)
ξ =2(l/t)
t¯
ξ =2(w/t)
ξ =2 where l¯ and t¯ are the average length and thickness of clay fillers,
respectively.
Both l¯ and t¯ can be evaluated by statistically analysing
the TEM images of the composites. In general, TEM images
with magnifications in the range of 60 000× to 80 000× can
provide data accurate enough to represent the length and
thickness of the clay particles within the matrix [25, 41]. The
evaluation could be done manually or with the help of some
specific software. In either way, the clay platelets or particles
shown in the TEM images are numbered and with all their
information such as length, orientation, number of platelets
per particle or thickness collected. Thus, the histogram plots
of particle length and platelet numbers per particle can be
plotted, as shown in figure 4. Alternatively, the averaged clay
particle thickness can also be measured by x-ray diffraction
(XRD) [42–44]. Nevertheless, it is difficult to measure the
full widths at half-maximum of the 001 reflection accurately
from those wide-angle XRD curves in this study. Thus, the
characteristic length, thickness and aspect ratio of the clay
particles were measured by TEM observation.
In addition to the aspect ratio and shape parameter,
orientation of the clay particles has a significant effect on
modulus. Practically, almost all composites have some
extent of filler misalignment. Previous studies have revealed
(7) that the deviation from unidirectional reinforcement would
result in sizable reductions in composite modulus. van Es
et al [45] studied the nanocomposites reinforced by both
fully exfoliated fibre and platelet fillers, and established the
following equations to quantitatively calculate the elastic
moduli:
fibres
E composites = 0.184E p + 0.816E t (10)
platelets
E composites = 0.49E p + 0.51E t (11)
where E p and E t are the composite moduli in the directions
parallel and perpendicular to the major axis of the filler,
respectively. These two equations show clearly that for
completely exfoliated nanocomposites the platelet filler
provides higher reinforcement than the fibre filler.
As mentioned above, the aspect ratio of clay particles can
be measured by either TEM observation or XRD. For the fully
exfoliated polymer–clay nanocomposites, the thickness of the
clay fillers is the thickness of the MMT platelet. However,
the complete exfoliation of clay particles is hard to achieve
as with the present study, in which almost all clay particles
exist as intercalated platelet stacks within the matrix. The
number of clay platelets and measured particle thickness tc
can be calculated by
tc − tp
n= +1 (12)
d001
2027
X Li et al
30
(a)
Aspect ratio
20
10
0 each sub-model can be evaluated accurately. In the second
0 20 40
Clay concentration (wt.%)
40
(b)
Elastic modulus (GPa)
30
20
10
0 loading higher than 30% need to be corrected according to
0 20 40
Clay concentration ( wt.%)
Figure 12. (a) Plot of clay aspect ratio as a function of clay
concentration, and (b) elastic modulus as a function of clay
concentration obtained by tensile tests, three-point bending tests,
and theoretical modelling results.
where n is the number of platelets per particle and d001 is the
interlayer spacing of the clay particle, which may be evaluated
from high resolution TEM images. Otherwise, wide-angle
XRD analysis can accurately measure the interlayer spacing
of intercalated clay within nanocomposites. tp = 0.94 nm is
the MMT platelet thickness [25].
According to the data from TEM observation, the aspect
ratios of clay particles within the nanocomposites were
evaluated to be 16.27, 15.08, and 8.83 for the nanocomposites
with 30, 60, and 80% clay loadings, respectively. Since
the aspect ratio decreases linearly with increasing clay
concentration in the range from 30 to 60%, the linear
interpolation was applied to estimate the aspect ratio of clay
particles for the nanocomposites with 5–30% clay loadings.
Figure 12(a) shows the curve of the aspect ratio as a function of
clay concentration. Note that the aspect ratio decreases sharply
when the clay loading is higher than 60%, which indicates the
deterioration of clay enhancement and is consistent with the
sharp decrease in mechanical properties.
Based on structural characterization, the composites
studied can be modelled by a three-phase composite system,
i.e. the clay platelet stacks, the agarose intercalated into
these platelet stacks and agarose matrix. For different clay
loadings, only the density of the MMT platelet stacks is
changed. This model can be solved in two steps. The
platelet stacks and agarose intercalated within these stacks
can be first regarded as localized two-phase composites or as
equivalent reinforcements, whose elastic modulus is given by
equation (7). Then, the equivalent reinforcements and agarose
2028
matrix could compose of the resulting two-phase composites.
Halpin–Tsai composite theory and equation (11) can be applied
to the second two-phase composite model. It should be noted
that the simulated elastic moduli are available only for the
nanocomposites with clay loadings up to 60%. When clay
loading is beyond 60%, the interface between the nanoclay and
agarose matrix will be degraded and hence cannot be simulated
by any existing model.
This approach should be more reasonable because all
phases within nanocomposites were represented properly and
60 80 100
step, the Halpin–Tsai equations were applied by substituting
all the data corresponding to the equivalent reinforcement, such
as η , ξ  aspect ratio R  , volume fraction Vf , and resulting E f
Tensile tests
of the equivalent reinforcement. However, further exploration
Bending tests
Simulation of this approach revealed that the final modelling results can
only predict the elastic modulus for the nanocomposite with
clay weight concentration up to 30%. For higher clay loading
nanocomposites, the simulation results were increasingly
higher compared with the tensile and bending test results,
which are in good agreement with each other. Therefore, the
final simulation results for those nanocomposites with clay
60 80 100 the experimental results. The correction factor was fitted to
be a function of the clay volume fraction, i.e. f = (1 − Vf )
for all nanocomposites with clay weight concentration higher
than 30%, in this study. The correction factor is interpreted to
compensate the incompleteness of intercalation caused by the
combination of high surface-to-volume ratio of clay platelets
and the high clay concentration.
Finally, the elastic moduli simulated, as well as those
measured by tensile and bending tests, are plotted in
figure 12(b).
If the clay weight concentration is less than about 5%, it
is possible that the nanoclays exist as fully exfoliated platelets
or as the combination of exfoliated platelets and intercalated
platelet stacks. It is easy to model the completely exfoliated
nanocomposites. For the polymer–clay nanocomposites with
mixed morphology, i.e. the combination of exfoliation and
intercalation, theoretically, it can be analysed as multiphase
composites. Firstly, the composite system is required to
evaluate the degree of exfoliation by TEM and XRD analysis.
Secondly, the exfoliated clay platelets and matrix can form a
two-phase composite as the equivalent matrix phase. Thirdly,
the intercalated platelet stacks and the polymer intercalated
within these stacks are treated as previously for the equivalent
reinforcing phase. Finally, the resulting two phases are
composed of the final composites.
5. Conclusion
Nanoclay-reinforced agarose nanocomposite films with
varying weight concentration ranging from 0 to 80% of
clay were prepared and characterized. The pre-exfoliated
clay platelets were re-aggregated into clay particles during
the composite preparation process. Each particle consists
of approximately 11 clay platelets stacked together. The
nanoclay particles were largely homogeneously dispersed
within the agarose matrix. The clay particles were oriented
with a slight preference of the stacked platelets being
 Structural and mechanical characterization of nanoclay-reinforced agarose nanocomposites
parallel to the composite film surfaces within the low loading
composite films.
It is concluded that the nanoclay gives a remarkable
enhancement to the elastic modulus in the direction parallel to
the nanocomposite film surfaces. A sixfold increase in elastic
modulus has been achieved for the nanocomposite with 60%
clay concentration. The tensile strength increased by as much
as 50% over that of the agarose matrix for the nanocomposite
with 40–60% clay concentration. Nevertheless, the ductility
decreases as clay concentration is increased. The methodology
for modelling polymer–clay nanocomposites with different
morphologies such as the combination of exfoliation and
intercalation of nanoclays has been developed. The developed
nanoclay-reinforced agarose nanocomposites should find more
applications.
Acknowledgments
Financial support for this study was provided by the National
Aeronautical and Space Administration through grants NASA
NCC5-174 and NASA NAG-1-03017, the University of South
Carolina NanoCenter, NASA/EPSCoR grant, and the National
Science Foundation (grant number EPS-0296165 and CMS-
0201345). The content of this information does not necessary
reflect the position or policy of the Government and no official
endorsement should be inferred.
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