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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


been synthesized such as epoxy–clay nanocomposites [4, 5],
Clay reinforced polymer composites have spurred great polyimide–clay nanocomposites [6] and polyurethane–clay
interest since nylon 6–clay nanocomposites were developed nanocomposites [7, 8], to name a few. Previous studies have
and found applications in the automotive industry by the found that nanoclay reinforced polymeric composites offer
researchers at Toyota in the early 1990s [1–3]. With many improved properties over pristine polymers in tensile
only 4.2 wt% clay dispersed in nylon 6 matrix, the modulus and strength [2, 9–11], thermal properties and heat
elastic modulus increased by as much as 100% and the distortion temperature [2, 12], resistance to flammability [13],
heat distortion temperature increased by 80 ◦ C compared and reduced permeability to liquids or gases [14]. A common
to those of the unfilled nylon 6 matrix [1, 2]. To date, observation from these studies is that the magnitude of
3 Authors to whom any correspondence should be addressed. improvement is, to a large extent, dependent upon the state
4 www.me.sc.edu/research/nano
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 of the films was calculated based on the weight lost before
the matrix, i.e. nanoclays are completely exfoliated, could and after placing in the vacuum oven at 100 ◦ C over 24 h.
the enhancement be more significant. However, the clay The water contents of pure agarose and 40% MMT/agarose
dispersion effect on the resulting mechanical properties is not films are 16.58% and 12.77% respectively. Different loadings
well understood, especially for nanocomposites with a higher (i.e. concentration) of MMT/agarose films were prepared by
clay concentration. varying the ratio of MMT to the amount of dry agarose added.
The term clay refers to a class of materials made up of The thickness of the resulting MMT/agarose films is in the
layered silicates, among which montmorillonite (MMT) is the range from 60 to 80 µm.
most commonly used clay in the synthesis of nanocomposites. For structural characterization of the nanoclays by atomic
The MMT is composed of layered, nanometre thick platelets, force microscopy (AFM), the resulting exfoliated MMT
and has the same crystalline structure as mica [15]. Although suspension was further diluted with distilled water and then a
clay has many attractive properties such as high elastic drop of solution was put onto the surface of newly cleaved mica.
modulus and wide availability at low cost, its application is
limited largely because the clay dispersion cannot be easily
2.2. Structural and mechanical characterization
achieved [16]. The full exfoliation of nanoclays in nylon 6
matrix was first achieved by Usuki et al [17] in 1993 and is The morphology of the nanoclays used in this study was
believed to be a fundamental breakthrough for utilizing clay in characterized using a Dimension 3100 AFM system (Veeco
practical applications. Metrology Group) operated in the tapping mode. Cross-
Although nanoclays have proven to be a prominent re- sections of the nanocomposite films were studied with a
inforcement, to date, only a few polymer–clay nanocompos- Philips EM 430 ST transmission electron microscope (TEM).
ites with well enhanced strength or stiffness have been re- The morphology, characteristic length and thickness of the
ported. Agarose is a naturally occurring polysaccharide and nanoclays before dispersion were investigated and compared
has been mainly used as a gel medium for the separation of with those of the clays within the nanocomposites.
DNA and protein molecules via electrophoresis [18]. With an Mechanical properties of the composites were measured
ever-increasing demand for advanced materials, enhancing the using an UMT-2 mechanical tester (CETR Inc.). Both tensile
mechanical properties of natural polymers like agarose to make and three-point bending tests were preformed. The composite
new, high-performance composites is important and com- films were first cut into strips and then attached onto a frame,
pelling. The synthesis methods of polymer–clay nanocom- which was used for protecting the specimen from tension or
posites are generally categorized into three groups according twisting during handling. The frame was cut away once the
to the starting materials and the processing techniques: in- specimen was mounted on the tester. The instrument is capable
tercalation of polymer or pre-polymer from solution, in situ of applying up to 5000 mN force with a force resolution of
intercalative polymerization and melt intercalation [19]. 1.3 mN. The strain rate was 0.5 mm min−1 for all tensile tests.
In the present study, a group of montmorillonite- Fracture surfaces of the tensile specimens were examined using
reinforced agarose nanocomposite films with clay concentra- a Philips XL30 field emission environmental scanning electron
tion up to 80 wt% were prepared and characterized, with the microscope (ESEM) operated at 30 kV.
focus on their structural and mechanical properties. The objec- Three-point bending tests were preformed using the
tives of this study were to investigate the effects of clay concen- same tester. A high-resolution load transducer with a force
tration and dispersion on the resulting mechanical properties, resolution of 0.1 mN was used. The bending elastic modulus
and to develop a theoretical model for predicting the mechan- was calculated by
ical properties of nanoclay reinforced polymer composites. L3 d P
E= (1)
48 · I dδ
2. Experimental details 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
2.1. Sample preparation
bending load–deflection curve.
A 1 wt% solution of sodium montmorillonite (Cloisite Na + , Nanoindentation tests were performed using a Triboscope
Southern Clay Products) was dispersed in distilled water. nanomechanical testing system (Hysitron Inc.) in conjunction
The dispersion was sonicated (Branson 5510) for an hour with the Veeco AFM system. The Hysitron nanoindenter
and then centrifuged (Sorvall® Legand T) at 3500 rpm for monitors and records the load and displacement of the indenter,
75 min. The transparent supernatant solution was decanted into a diamond Berkovich three-sided pyramid, with a force
a silated container. The weight concentration of this exfoliated resolution of about 1 nN and displacement resolution of about
montmorillonite (MMT) nanoclay suspension was 0.7%. 0.1 nm. Hardness and elastic modulus were calculated from
Nanocomposites were prepared by a gelation method, the recorded load–displacement data. A typical indentation
i.e. agarose (CertifiedTM PCR) was added to the MMT experiment consists of four steps: approaching the surface;
suspension at a concentration of 1 wt%. The mixtures were loading to peak load; holding the indenter at peak load for
first heated to 100 ◦ C to dissolve the agarose and then poured 5 s; finally unloading completely. The holding segment was
into Petri dishes. Agarose gels were formed when the mixtures included to avoid the influence of creep on the unloading
were cooled to room temperature. These gels were dried characteristics since the unloading curve was used to obtain
at room temperature in the air, resulting in nanocomposite the elastic modulus of a material. For more details on
films after the gels dehydrated and collapsed. Water content nanoindentation experimental techniques, please see [20, 21].

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Nanoindentation hardness is defined as the indentation particle. It is clear that the majority of clay particles are single-
load divided by the projected contact area of the indentation. layer platelets before dispersion, as shown in figure 1(e). The
It is the mean pressure that a material will support under load. average length of clay particles is 174.7 nm and the aspect ratio
From the load–displacement curve, hardness can be obtained is 108.3.
at the peak indentation load as Previous studies have shown that the interlayer spacing
is 0.96 nm for natural (unpolymerized) MMT with a platelet
Pmax
H= (2) thickness of 0.94 nm [25, 26]. According to XRD analysis,
A the interlayer spacing of intercalated MMT within the agarose
where A is the projected contact area. For an indenter with matrix is averaged to be 1.52 nm. In addition, the tensile
a known geometry such as the Berkovich tip used in this modulus of individual MMT platelets is 178 GPa and its density
study, the projected contact area is a function of contact is 2.83 g cm−3 [25].
depth, which is measured by the nanoindenter in situ during Figure 2 shows the low magnification TEM images of
indentation [20, 21]. Therefore, the projected contact area A the nanocomposites with 30, 60, and 80% clay loadings. In
can be measured and calculated directly from the indentation figure 2(b), it is shown more clearly that clay particles were,
displacement. to a large extent, dispersed uniformly and oriented randomly
The indentation elastic modulus was calculated using the within the matrix. Nevertheless, the clay particles within
Oliver–Pharr data analysis procedure [22] beginning by fitting lower clay loading nanocomposites show a slight tendency
the unloading curve to a power-law relation. The unloading of the stacked platelets to be parallel to the nanocomposite
stiffness can be derived from the slope of the initial portion film surfaces. This tendency is diminished with increasing
of the unloading curve, S = d p/dh. Based on relationships clay concentration. The higher the clay concentration, the
developed by Sneddon [23] for the indentation of an elastic smaller the deviation from uniform orientation found. When
half space by any punch that can be described as a solid the clay weight concentration is higher than 60%, thicker
of revolution of a smooth function, a geometry independent platelet stacks can be found and the clay dispersion is less
relation involving contact stiffness, contact area, and elastic uniform with further increasing the clay content. The high
modulus can be derived as follows: magnification TEM images of the nanocomposites with 0, 30,
 60, and 80% clay loadings are shown in figure 3. These images
S π demonstrate clearly that the nanoclays within the agarose
Er = (3)
2β A matrix were mainly in the form of platelet stacks composed
of approximately 11 platelets in a stack and thus existed
where β is a constant which depends on the geometry of the
as intercalated particles. According to results measured by
indenter (β = 1.034 for a Berkovich indenter) [20, 21], and E r
AFM, however, about 75% of clay particles were exfoliated
is the reduced elastic modulus which accounts for the fact that
single-layer platelets. It is evident that the pre-exfoliated
elastic deformation occurs in both the sample and the indenter.
MMT platelets were re-aggregated during the dispersion and
E r is given by
polymerization processes. The high clay concentration in the
1 1 − ν 2 1 − νi2 matrix as well as the large aspect ratio and high surface-to-
= + (4) volume ratio of the clay platelets make it difficult for the
Er E Ei
agarose to wrap the platelets and keep them apart from one
where E and ν are the elastic modulus and Poisson’s ratio for another.
the sample, respectively, and E i and νi are the same quantities The characteristic length and thickness of the nanoclays
of the indenter. For the diamond indenter, E i = 1140 GPa and within the nanocomposites were measured by TEM. Figure 4
νi = 0.07 [20, 21]. shows the histogram of particle length and number of
platelets per particle for the clay particles within the matrix.
3. Results and discussion Comparison of figure 4 with figures 1(d) and (e) shows that
both particle length and thickness are increased during the
Figure 1 shows the representative TEM and AFM images composite preparation process. As a result, the aspect ratio
as well as the morphology characteristics of the nanoclays is decreased from 108.3 down to 16.
used in this study. Direct observation of individual clay The representative tensile stress–strain curves are shown
platelets or platelet stacks confirms that MMT has the layered in figure 5. It is noted that both tensile elastic modulus
structural characteristic with an irregular shape, which is in and strength increase with an increase in clay concentration
good agreement with previous studies [24]. The measured and reach the peak values at 60% clay loading. With
platelet thickness is about 1 nm, which is also consistent with a further increase in clay concentration the modulus and
the previously published value [25, 26]. The maximum length strength decrease. The ductility decreases with increasing clay
measured is 853 nm and the maximum width 430 nm. Since concentration, as shown in figure 6, indicating an increase in
there are no standards regarding representing the length and brittleness in the high clay loading composites.
width of irregular shape, in this study, the characteristic length For a two-phase composite, there is an optimum volume
of a platelet is represented by the average of its length and fraction or volume ratio that provides good bonding between
width that were measured in two perpendicular directions and the two phases for load transfer. When clay loading is
correspond well to its shape. The histograms of platelet length higher than a critical volume/weight percentage, the direct
and thickness are shown in figures 1(d) and (f), respectively. consequence is that the clay particles within nanocomposites
Figure 1(e) shows the histogram of the number of platelets per cannot be completely exfoliated into platelets or even fully

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

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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


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

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Structural and mechanical characterization of nanoclay-reinforced agarose nanocomposites

0.25 40
Tensile tests

Elastic modulus (GPa)


0.2 Bending tests
30

0.15
Ductility

20
0.1
10
0.05
0
0 0 20 40 60 80 100
0 20 40 60 80 100
Clay concentration (wt. %)
Clay concentration (wt. %)
250
Figure 6. Ductility (percentage elongation at failure) as a function
of clay concentration.

Tensile stress (MPa)


200

150
100
0 % clay
Normalized load (mN/mm2 )

30 % clay 100
80
60 % clay
80 % clay 50
60
0
0 20 40 60 80 100
40 Clay concentration (wt. %)

Figure 8. (a) Elastic modulus as a function of clay concentration


20
obtained by tensile and three-point bending tests, and (b) tensile
strength as a function of clay concentration.
0
0 0.01 0.02 0.03 0.04
Displacement (mm)
every 20th deposition cycle and other solutions also refreshed
Figure 7. Representative normalized load–deflection curves of
appropriately. A thickness of 4.9 µm was obtained for the
bending tests.
typical 200-multilayer films. The measured elastic moduli of
the artificial nacres were 10 ± 2 and 13 ± 2 GPa for 100-
has an elastic modulus of 11.4–21.2 GPa [27–29]. The and 200-layered films, respectively. The maximum tensile
nanoclay reinforced agarose nanocomposites have comparable strength of these films was 109 MPa and was reported to have
mechanical properties with human bone. This may extend the approached that of real nacre. By comparison of the elastic
application of agarose-based material to orthopaedic and other modulus of the artificial nacre and the nanocomposite films
bioengineering areas. in this study, it is quite clear that the mechanical properties
The tensile strength, for the composites with clay loading of the agarose–clay composite films are superior to those
ranging from 40 to 60%, is increased by as much as 50% of the artificial nacre. From a synthesis point of view, the
compared with that of agarose matrix, as shown in figure 8(b). easy and simple route for the preparation of agarose–clay
The maximum tensile strength was found to be 183 MPa for nanocomposites used in the present study has profound merits,
the nanocomposite with about 50–60% clay loading. Noting, which should find more industrial applications.
the wide range of clay loadings is very useful for tailoring the Figure 9 shows the representative SEM images of fracture
mechanical properties according to the design requirements. surfaces of the nanocomposites with 0, 40, 60, and 80% clay
When clay concentration is higher than 60%, however, both loadings. It can be seen that the fracture surface became
elastic modulus and tensile strength decrease drastically with increasingly rougher with an increase in clay concentration.
a further increase in clay concentration, indicating unfeasible For the composites with clay concentrations less than 60%, no
volume fraction and poor interfaces between the agarose matrix debris particles were found on the fracture surfaces, indicating
and clay particles. a strong bonding between the clay particles and the matrix.
Tang et al [30] developed the nanostructured polymer Clay-like debris particles were found on the fracture surfaces
clay films, named artificial nacre, using a layer-by-layer of the 80% clay composite. This further confirms that the
assembly process in which 5 min adsorption of organic layers agarose matrix is less available to intercalate into nanoclays for
(polyelectrolytes) and 10 min dispersion of inorganic layers the 80% clay nanocomposite, thereby resulting in poor bonding
(clay MMT) were processed sequentially with a rinsing process between the nanoclay particles and the agarose matrix.
in deionized water between every two sequences. The 2 min Figure 10 shows the hardness and elastic modulus of the
rinsing processes were used to remove the irregular adsorbed nanocomposites measured by nanoindentation tests. Both the
platelets loosely attached to the clay layer in order to obtain a nanoindentation hardness and elastic modulus decrease in a
better interface between the organic layer and inorganic clay random manner as clay concentration is increased. It should
platelets. During this process, the clay solution was refreshed be noted that the tensile and three-point bending tests measured

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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 and its individual components. For conventional composite


Hardness systems, the theoretical frameworks have been well developed
Elastic modulus (GPa)

Elastic modulus 8 for predicting various properties of a composite based on the


Hardness (GPa)

1.5
properties of its individual components. These theories are
6
useful for evaluating the contribution of individual components
1
4
and for optimizing the overall performance of a composite
based on the matrix and filler moduli, volume fraction, filler
0.5 aspect ratio and orientation etc. In all these theories, the
2
underlying assumptions are (1) all components in a composite
0 0 will act independently and (2) the interaction or bonding
0 20 40 60 80 100
Percentage of clay between the matrix and fillers is strong enough for load transfer.
The two well known composite theories are Halpin–
Figure 10. Nanoindentation hardness and elastic modulus as a Tsai theory [32–34] and Mori–Tanaka theory [35]. Both
function of clay concentration. theories have received considerable attention in the composite
community [25, 26, 36–40]. However, none of them can
the modulus in the direction parallel to the nanocomposite be applied directly to the nanoclay reinforced nanocomposite
films, whereas the nanoindentation tests measured the elastic materials, in which the roles of aspect ratio, dispersion, and
modulus in the direction perpendicular to the composite films. orientation of the fillers are more critical compared with
The nanoindenter probed a small volume of material and conventional composites.
the indenter tip might or might not encounter the nanoclay Halpin theory [32–34] has been widely used for
particles; even if the indenter tip encountered the nanoclay predicting the elastic modulus of unidirectional fibre reinforced
particles, the nanoclay particles beneath the indenter tip might composites as functions of the fibre volume fraction and aspect
be bent down together with the indenter [31]. On the other ratio. The longitudinal and transverse elastic moduli, i.e. E 11
hand, the nanoindentation elastic/plastic deformation zone is and E 22 , as shown in figure 11, are expressed in a general form:
much smaller compared with that of the global tensile and
bending tests, and there were no or only a few nanoclay E 1 + ξ ηVf
= (5)
particles in the nanoindentation deformation zone. Long-range Em 1 − ηVf
load transfer was limited.
where E and E m are the elastic moduli of the composite and
the matrix, respectively. Vf is the volume fraction of the filler.
4. Modelling of elastic modulus η is given by
Ef
E
−1
The overall strategy in developing a model is to establish η = Emf (6)
the relation of the physical properties between a composite Em

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Structural and mechanical characterization of nanoclay-reinforced agarose nanocomposites

Fibre 1 Clay platelet 1 to construct the model. AFM observation of the nanoclays
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
2 2 of clay fillers, aspect ratio R and shape parameter ξ should be
3 3 calculated by the average length and thickness, as given by
Loading direction Composite modulus Shape parameter
 ¯
l
Fibres Platelets Fibres Platelets ξ = 2R = 2 · (9)
1 E11=Ep E11=Ep ξ =2(l/d) ξ =2(l/t)

2 E 22=Et E22=Ep ξ =2 ξ =2(w/t)
3 E 33=Et E33=Et ξ =2 ξ =2 where l¯ and t¯ are the average length and thickness of clay fillers,
respectively.
Figure 11. Illustration of the fibre and platelet filler and shape Both l¯ and t¯ can be evaluated by statistically analysing
parameters for each case for Halpin composite theory. E p and E t are
the TEM images of the composites. In general, TEM images
the moduli in directions parallel (longitudinal direction) and
perpendicular (traverse direction) to the major axis of the fillers, with magnifications in the range of 60 000× to 80 000× can
respectively. l is the length of the fibre or platelet, d is the diameter provide data accurate enough to represent the length and
of the fibre, and w and t are the width and thickness of the clay thickness of the clay particles within the matrix [25, 41]. The
platelet. 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
where E f is the elastic modulus of the filler. The tensile information such as length, orientation, number of platelets
modulus of an individual MMT platelet is 178 GPa [25] and the per particle or thickness collected. Thus, the histogram plots
measured elastic modulus of agarose polymer was 3.5 GPa. ξ is of particle length and platelet numbers per particle can be
the shape parameter depending on filler geometry and loading plotted, as shown in figure 4. Alternatively, the averaged clay
direction, as shown in figure 11. Ashton et al [34] found that particle thickness can also be measured by x-ray diffraction
ξ = 2(l/d) can be used to calculate the longitudinal modulus (XRD) [42–44]. Nevertheless, it is difficult to measure the
E 11 , where l and d are the characteristic length and diameter full widths at half-maximum of the 001 reflection accurately
of the fibre, respectively. When ξ = 2, on the other hand, from those wide-angle XRD curves in this study. Thus, the
the same equation can be applied for evaluating the transverse characteristic length, thickness and aspect ratio of the clay
modulus E 22 [34]. particles were measured by TEM observation.
Halpin–Tsai composite theory is consistent with the rules In addition to the aspect ratio and shape parameter,
of composites in specific cases such as isostrain and isostress. orientation of the clay particles has a significant effect on
For example, when ξ → ∞, equation (5) reduces to the rule modulus. Practically, almost all composites have some
of mixtures for the isostrain case, i.e. extent of filler misalignment. Previous studies have revealed
E = Vf E f + Vm E m (7) that the deviation from unidirectional reinforcement would
result in sizable reductions in composite modulus. van Es
where Vm is the volume fraction of the matrix and Vf + Vm = 1. et al [45] studied the nanocomposites reinforced by both
Conversely, when ξ → 0, equation (5) reduces to the inverse fully exfoliated fibre and platelet fillers, and established the
rule of mixtures for the isostress case, i.e. following equations to quantitatively calculate the elastic
moduli:
1 Vf Vm
= + . (8)
fibres
E composites = 0.184E p + 0.816E t (10)
E Ef Em
platelets
More conveniently, the Halpin equations retain the same E composites = 0.49E p + 0.51E t (11)
form for discontinuous cylindrical fibres and platelet fillers. where E p and E t are the composite moduli in the directions
The shape parameter, ξ , however, is required to change from parallel and perpendicular to the major axis of the filler,
2(l/d) to 2(l/t) for the platelet filler, where l is the length of respectively. These two equations show clearly that for
the fibre or the platelet, d is the diameter of the fibre and t completely exfoliated nanocomposites the platelet filler
the thickness of the platelet. According to the characteristic provides higher reinforcement than the fibre filler.
differences between fibre and platelet, it is evident that the As mentioned above, the aspect ratio of clay particles can
fibre reinforces only in the longitudinal direction while the be measured by either TEM observation or XRD. For the fully
platelet can reinforce in directions that are parallel to the exfoliated polymer–clay nanocomposites, the thickness of the
platelet surface. Figure 11 illustrates the fibre and platelet clay fillers is the thickness of the MMT platelet. However,
filler and shape parameters for each case when the Halpin– the complete exfoliation of clay particles is hard to achieve
Tsai composite theory is applied. as with the present study, in which almost all clay particles
The clay fillers, which may be in the forms of platelets exist as intercalated platelet stacks within the matrix. The
or platelet stacks (particles), were often simulated by lamellar number of clay platelets and measured particle thickness tc
squares or circular discs with varying thickness [25, 37–39]. In can be calculated by
fact, clay platelets cannot be simply represented by any shape,
as shown in the AFM image in figure 1. Nevertheless, it is tc − tp
n= +1 (12)
required to represent clay platelets by a proper shape in order d001

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X Li et al

30 matrix could compose of the resulting two-phase composites.


(a) 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
Aspect ratio

20
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
10
by any existing model.
This approach should be more reasonable because all
phases within nanocomposites were represented properly and
0 each sub-model can be evaluated accurately. In the second
0 20 40 60 80 100
Clay concentration (wt.%) step, the Halpin–Tsai equations were applied by substituting
all the data corresponding to the equivalent reinforcement, such
40
(b) as η , ξ  aspect ratio R  , volume fraction Vf , and resulting E f
Tensile tests
of the equivalent reinforcement. However, further exploration
Elastic modulus (GPa)

Bending tests
30 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
20
nanocomposites, the simulation results were increasingly
higher compared with the tensile and bending test results,
10 which are in good agreement with each other. Therefore, the
final simulation results for those nanocomposites with clay
0 loading higher than 30% need to be corrected according to
0 20 40 60 80 100 the experimental results. The correction factor was fitted to
Clay concentration ( wt.%) be a function of the clay volume fraction, i.e. f = (1 − Vf )
Figure 12. (a) Plot of clay aspect ratio as a function of clay for all nanocomposites with clay weight concentration higher
concentration, and (b) elastic modulus as a function of clay than 30%, in this study. The correction factor is interpreted to
concentration obtained by tensile tests, three-point bending tests, compensate the incompleteness of intercalation caused by the
and theoretical modelling results. combination of high surface-to-volume ratio of clay platelets
and the high clay concentration.
Finally, the elastic moduli simulated, as well as those
where n is the number of platelets per particle and d001 is the measured by tensile and bending tests, are plotted in
interlayer spacing of the clay particle, which may be evaluated figure 12(b).
from high resolution TEM images. Otherwise, wide-angle If the clay weight concentration is less than about 5%, it
XRD analysis can accurately measure the interlayer spacing is possible that the nanoclays exist as fully exfoliated platelets
of intercalated clay within nanocomposites. tp = 0.94 nm is or as the combination of exfoliated platelets and intercalated
the MMT platelet thickness [25]. platelet stacks. It is easy to model the completely exfoliated
According to the data from TEM observation, the aspect nanocomposites. For the polymer–clay nanocomposites with
ratios of clay particles within the nanocomposites were mixed morphology, i.e. the combination of exfoliation and
evaluated to be 16.27, 15.08, and 8.83 for the nanocomposites intercalation, theoretically, it can be analysed as multiphase
with 30, 60, and 80% clay loadings, respectively. Since composites. Firstly, the composite system is required to
the aspect ratio decreases linearly with increasing clay evaluate the degree of exfoliation by TEM and XRD analysis.
concentration in the range from 30 to 60%, the linear Secondly, the exfoliated clay platelets and matrix can form a
interpolation was applied to estimate the aspect ratio of clay two-phase composite as the equivalent matrix phase. Thirdly,
particles for the nanocomposites with 5–30% clay loadings. the intercalated platelet stacks and the polymer intercalated
Figure 12(a) shows the curve of the aspect ratio as a function of within these stacks are treated as previously for the equivalent
clay concentration. Note that the aspect ratio decreases sharply reinforcing phase. Finally, the resulting two phases are
when the clay loading is higher than 60%, which indicates the composed of the final composites.
deterioration of clay enhancement and is consistent with the
sharp decrease in mechanical properties. 5. Conclusion
Based on structural characterization, the composites
studied can be modelled by a three-phase composite system, Nanoclay-reinforced agarose nanocomposite films with
i.e. the clay platelet stacks, the agarose intercalated into varying weight concentration ranging from 0 to 80% of
these platelet stacks and agarose matrix. For different clay clay were prepared and characterized. The pre-exfoliated
loadings, only the density of the MMT platelet stacks is clay platelets were re-aggregated into clay particles during
changed. This model can be solved in two steps. The the composite preparation process. Each particle consists
platelet stacks and agarose intercalated within these stacks of approximately 11 clay platelets stacked together. The
can be first regarded as localized two-phase composites or as nanoclay particles were largely homogeneously dispersed
equivalent reinforcements, whose elastic modulus is given by within the agarose matrix. The clay particles were oriented
equation (7). Then, the equivalent reinforcements and agarose with a slight preference of the stacked platelets being

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Structural and mechanical characterization of nanoclay-reinforced agarose nanocomposites

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