Pillai2 2012

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CHAPTER 2
Chitosan-based Nanocomposites
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a
a,b
SREEJARANI K. PILLAI* AND SUPRAKAS S. RAY

a
DST/CSIR Nanotechnology Innovation Centre, National Centre for

Nano-Structured Materials, Council for Scientic and Industrial Research,
Pretoria 0001, Republic of South Africa; b Department of Chemical
Technology, University of Johannesburg, Doornforntein 2018, Johannesburg,
Republic of South Africa
*Email: [email protected]
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2.1 Introduction
In the area of nanotechnology, polymer matrix-based nanocomposites have
generated a considerable amount of attention in the recent literature. This area
has emerged with the recognition that nano-sized reinforcement materials, due
to their high surface area, aspect ratio, and dispersion, could yield signicant
property enhancement in polymeric systems when compared to large-scale
particulate reinforcement.1,2 In the past half century, although synthetic petroleum-based polymers have been widely used in composite preparation for a
variety of applications, they have become a major source of waste disposal
problems due to their poor biodegradability.3 As a result of the increasing
awareness concerning human impact on the environment and constant
increases in fossil resources prices, the last decade has seen the development of
ecient solutions to produce new environmentally friendly materials. Particular attention has been paid to the replacement of conventional petroleumbased plastics with materials based on biopolymers, such as biodegradable
polyesters,47 proteins,810 or polysaccharides.1114 Within this strategy, polysaccharides are vital candidates because of their renewable and recyclable
nature and their biodegradable character, together with the fact that they
RSC Green Chemistry No. 17

Natural Polymers, Volume 2: Nanocomposites
Edited by John J Maya and Thomas Sabu
r The Royal Society of Chemistry 2012
Published by the Royal Society of Chemistry, www.rsc.org
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Chapter 2
represent the most abundant fraction of biomass. Chitosan is one of the most
widely exploited polysaccharides in various applications owing to its properties
that depend on environmental variables such as pH, ionic strength, and electric
eld.15
Nano-biocomposites, obtained by adding nanollers to biopolymers like
chitosan, result in very promising materials since they show improved properties with preservation of the material biodegradability without eco-toxicity.
Such materials are mainly destined for biomedical applications and dierent
short-term applications, e.g. packaging, agriculture, and hygiene devices. They
thus represent a strong and emerging answer for improved and eco-friendly
materials.
This chapter reviews the recent developments in the area of chitosan-based
nanocomposites, with a special emphasis on clay-containing nanocomposites of
chitosan. It describes various nano-sized reinforcements, preparation and
characterization of the nanocomposites, their properties and applications.
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2.2 Structure and Properties of Chitosan

Chitin, poly[b-(1-4)-N-acetyl-D-glucosamine], is a natural polysaccharide of
major importance, rst identied in 1684 (see Figure 2.1). This biopolymer is
synthesized by an enormous number of living organisms, such as arthropods,
fungi, and yeast, and from other biological sources; considering the amount of
chitin produced annually in the world, it is the most abundant polymer after
cellulose. The most important derivative of chitin is chitosan. Contrary to
chitin, chitosan is not widespread in the nature. It is found in some mushrooms
(zygote fungi) and in the termite queens abdominal wall. It is industrially
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(a)
30
OH
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(b)
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Figure 2.1
Chemical structures of (a) chitin and (b) chitosan.
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obtained by (partial) deacetylation of chitin in the solid state under alkaline

conditions (concentrated NaOH) or by enzymatic hydrolysis in the presence of
chitin deacetylase. Its chemical structure, presented in Figure 2.1, is a random
linear chain of N-acetyl-D-glucosamine units (acetylated unit) and D-glucosamine (deacetylated unit) joined by b-(1-4) linkages.16 Conventionally, the
distinction between chitin and chitosan is based on the degree of acetylation
(DA), with chitin having DA values higher than 50% and chitosan having
lower percentages. It follows that there is no unique polymer structure for
chitosan, which gives this material properties which depend on its DA, as well
as on its molecular weight.15 According to the bioresource, industrial chitosan
shows molecular weights ranging from 5 to 1000 kg mol1. In the solid state,
chitosan is a semicrystalline polymer, and it can exist in dierent allomorphs
depending on its DA, distribution of the acetyl groups along the carbohydrate
chain, and the chitosan preparation procedure. Chitin and chitosan are biocompatible, biodegradable, and non-toxic polymers.17
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2.2.1 Importance of Chitosan

Whereas chitin is insoluble in most solvents and dicult to process into useful
materials, chitosan is readily soluble in dilute aqueous acidic solutions and is
easily processed because of the amino groups present. Other advantages of this
polymer include availability, low cost, high biocompatibility, biodegradability,
antimicrobial property, ease of chemical modication, and excellent lmforming ability.18 Chitosan also possesses properties including its high viscosity, charge distribution, and release mechanisms, making it particularly suitable
as a carrier. Because of its unique properties, chitosan has attracted scientic
and industrial interest in several elds, such as biotechnology, pharmaceutics,
biomedicine, packaging, wastewater treatment, cosmetics, and food science.19
Since chitosan is a haemostatic from which blood anticoagulants and antithrombogenics have been formed and can be easily processed into dierent
forms such as gels, membranes, beads, micro-particles, nano-bres, scaolds, or
sponges, it nds a variety of biomedical applications in tissue engineering,
wound healing, drug delivery, etc.2024 Research into the chemical properties
of chitosan has demonstrated its suitability for the preparation of enzymatic
biosensors for the analysis of metallic elements, proteins, and lipids.25,26
Chitosan has also been used as a coating for textile bre protection and
resistance and in paper and paperboard coating, e.g. for food packaging.27
In spite of the numerous advantages and unique properties of chitosan-based
materials, they are not widely used to replace synthetic polymers because of
their poor mechanical properties and moisture sensitivity. Moreover, its
inherent properties, such as thermal stability, rigidity, and gas barrier properties, are often insucient to meet the requirements of a number of applications. Consequently, to make them more suitable and competitive, both
chemical and physical treatments of the materials are required.28
Many research studies have focused on improving the physical properties of
chitosan materials by decreasing the hydrophilicity and improving the
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Chapter 2
mechanical properties. Hydrophobic materials, such as neutral lipids, fatty

acids, or waxes, have been added to improve the moisture barrier properties of
chitosan lms.29,30 One of the earliest methods to stabilize chitosan was to
cross-link it with reagents like glutaraldehyde or to apply g-irradiation.3133
The development of multiphase materials, e.g. blends or composites, where a
reinforcing phase is added to chitosan, also represents a viable method of
stabilization and improvement of properties.3436 Traditionally, micro-sized
mineral llers like silica, talc, and clay are added to reduce the cost and improve
chitosans performance in some way. However, the mechanical properties such
as elongation at break and tensile strength of these composites decrease with
the incorporation of these llers.
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2.2.2 Chitosan-based Nanocomposites

A new class of chitosan composite materials has emerged recently, based on the
incorporation of reinforcing llers with dimensions in the nanometric scale
(nanollers with at least one dimension within 100 nm).11,3739 Depending on
the nature and surface functionality of the nanollers, nanocomposites could
exhibit modications in their properties, such as improved mechanical and
barrier properties, higher transparency,4043 etc. Such property enhancements
rely on their nanoscale dispersion, even with a very low level of nanoller
incorporation (r5 wt%), which results in a high aspect ratio and high surface
area. The reinforcement eciency of nanocomposites can match that of conventional composites with 4050% of loading with classical llers.40 Nanocomposites with chitosan as the matrix and nano-sized reinforcements result in
more stable and stronger materials. In these cases the percentage of reinforcing
phase is normally low (510 wt%), to make the chitosan proportion relatively
high. This results in products that closely resemble the matrix in terms of
biocompatibility and bioactivity.
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2.2.3 Importance of Chitosan-based Nanocomposites

Incorporation of nano-reinforcements into the chitosan matrix has been
demonstrated as a powerful strategy to overcome the conventional drawbacks
of the biopolymer. Nanocomposites of chitosan are potentially functional in a
number of areas, including medicine, cosmetics, biotechnology, food industry,
agriculture, environmental protection, paper industry, textiles, etc.
Chitosan can form nanocomposites with montmorillonite (MMT) clay, and
there are several reports about the drug release behaviour from the chitosan/
MMT nanocomposite lms, scaolds, and hydrogels.4448 Recent research
studies have shown that chitosan/MMT composites represent an innovative
and promising class of sorbent materials.49,50 The use of chitosan-based
nanocomposite coatings and lms in the packaging industry has become a topic
of great interest because of their potential for increasing the shelf-life of many
food products.5153 The mechanical properties of composite scaolds of
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chitosan can be improved by the addition of nano-hydroxyapatite, bioactive

glass ceramics which are widely used in tissue engineering.54,55 A number of
studies have reported recently on the use of chitosan nanocomposite scaolds
and membranes containing silver and gold nanoparticles to treat patients with
deep burns, wounds, etc., using their antimicrobial properties.56,57 In the last
few decades, the biosensor performance of chitosan materials has been signicantly enhanced by the introduction of nanomaterials in the sensing layer,
such as carbon nanotubes (CNTs),58 nanowires,59 and nanoparticles.60 In
addition to the enhancement in electrode and sensing abilities of chitosan
materials, CNTs are reported to improve physical and mechanical properties,
as well as the electric conductivities of the prepared chitosan/CNT nanocomposites.61 The unique reinforcing behaviour of graphene sheets was also
investigated in detail in chitosan biopolymers. Recent reports showed that the
incorporation of 1 wt% graphene oxide improved the tensile strength and
Youngs modulus of graphene oxide/chitosan nanocomposites by 122% and
64%, respectively.62,63 Currently, research on the composites of chitosan
and metal oxide nanoparticles has focused on TiO2 and ZnO, since they have
excellent photocatalytic performance and are stable in acidic and alkaline
solvents.64,65 A combination of chitosan and magnetic nanoparticles such as
Fe3O466 and CoFe2O467 are used in bio-applications, e.g. the immobilization of
proteins, peptides, and enzymes, bio-anity adsorbents, drug delivery, biosensors, and so on.6870 In summary, the emergence of nanotechnology is
opening new horizons to chitosan-based materials, where nanoparticles have
been utilized as stabilizing agents to improve their biocompatibility, lmforming ability, nontoxicity, and high mechanical strength. The nano-sized
particles oer distinctively dierent physiochemical, magnetic, and optical
properties compared to their bulk phase.
2.2.4 Types of Chitosan-based Nanocomposites

As mentioned above, chitosan nanocomposite properties depend on the type of
nanollers used, which in turn depend signicantly on their shape, size, surface
characteristics, and degree of dispersion in the chitosan matrix. To full the
denition of nanoller, at least one of the particle dimensions has to be at
nanometre scale (r100 nm). The dierent nanollers can be classied
depending on their aspect ratio and geometry, such as (i) platelet or layered
particles (e.g., clay, graphene), (ii) spherical (e.g., silica or metal nanoparticles),
or (iii) acicular or brous ones (e.g., whiskers, carbon nanotubes).39 The aspect
ratio (ratio of particle length to thickness) is a key factor in dening the ability
of a nanoller to enhance the composite properties. For various nanollers the
aspect ratio increases in the following order: particles, platelets, and bres, as
demonstrated in Figure 2.2.
For example, nanoclay platelets have thickness in the range of 1 nm and a
relatively high aspect ratio when compared to the spherical nanoparticles.
Owing to the low aspect ratio, nanoparticles may not have an equally strong
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Chapter 2
Particle
Platelet
Fibre
5
= 1100 nm
Aspect ratio 1
= 1001000 nm
Thickness = 1 nm
Aspect ratio 1001000
= 1100 nm
Length = 11000 m
Aspect ratio 103106
10
Figure 2.2
Various nanoller shapes and typical aspect ratios.
impact on mechanical property enhancement, but, on the other hand, they may
provide surface softness, surface shine, etc. Nanollers often possess high
surface energies and are usually surface-modied to reduce the surface energy
and prevent aggregation. Moreover, surface modication of the ller enhances
the compatibility with the polymer matrix, which helps to achieve a good
dispersion of the llers. Table 2.1 gives a summary of dierent nanollers used
in chitosan matrices.
At present, the most intensive research is focused on layered silicates, due to
their availability, versatility, and respectability towards the environment and
health. Of the dierent groups of clay minerals such as kaolinite, smectite, illite,
chlorite, and sepiolite, the most widely studied is the smectite group, because of
its structural uniqueness (expansion and absorption properties). The most
familiar species of the smectite group is MMT clay because of its large surface
area, higher exchange capacity, abundance, and cost-eectiveness. Hence this
chapter presents an overview of the recent progress in the eld of chitosan
nanocomposites based on MMT nanoclays.
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2.3 Structure and Properties of Montmorillonite

MMT clay belongs to the same general family of 2:1 layered or phyllosilicates.
MMT is the name given to the layered silicate found near Montmorillon in
France, where it was rst identied by Knight in 1696. Although MMT is
found in vast deposits around the world, it is always found with impurities such
as gravel, shale, limestone, quartz, and feldspar, among others. This mixture of
materials is known as bentonite, and the MMT is separated from the raw ore
primarily through aqueous separation processes. It consists of platelets with an
inner octahedral layer sandwiched between two silicate tetrahedral layers,91 as
illustrated in Figure 2.3. The octahedral layer may be thought of as an aluminium oxide sheet where some of the aluminium atoms have been replaced
with magnesium; the dierence in valences of Al and Mg creates negative
charges distributed within the plane of the platelets that are balanced by
positive counter ions, typically alkali or alkaline earth cations, located between
the platelets or in the galleries (see Figure 2.3). This type of layered silicate is
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Biosensors for nucleic acid, drug

delivery, enzyme immobilization,
photocatalysis, water purication,
tissue engineering, UV protection
of fabrics, water treatment
Cell stimulation, antibacterial
coatings, biosensors, catalysts, etc.
Thermo-responsive injectable
scaolds, tissue engineering, latent
nger mark detection
pH, electrical actuators, bone tissue
engineering, biological probes,
electrochemical biosensors, paper
coating
Fuel cells, gas separation, drug
delivery, water treatment, catalysis
Biosensing and electrochemical
sensing
Electrophoretic deposition,
ultrasonication, electrochemical deposition, solution
mixing, freeze drying
Solution mixing, spin coating,
dip coating, co-precipitation,
electrochemical deposition
Solution mixing, freeze drying
Solution spinning, freeze

drying, solution mixing,
sonication
Solution mixing, freeze drying,
micro-emulsion process
Solution casting and mixing
Thin lms,
hydrogels,
powders
Thin lms,
hydrogels
Hydrogels,
powders
Composite
bres,
powders,
lms
Film, scaolds,
powders
Films, powders
Other
Bioactive glass, CdS,
quantum dots
SWCNTs, MWCNTs,
Fe nanowires, ZnO
nanowires, Au nanowires,
nanorods, cellulose bres
Graphene, graphene oxide
Layered silicates
Metals
Ag, Au, Pt, Pd, Co, Ni
Metal oxides
ZrO2, Fe3O4, SiO2, Cu2O,
TiO2, ZnO, Al2O3
Application
Preparation method for

chitosan nanocomposite
Nanocomposite
type
Nano material used a
62, 8890
45, 8487
15, 7783
75, 76
7174
7177
Ref.
Summary of various nanollers used in chitosan matrices, the nanocomposite types, their preparation methods, and
targeted applications.
SWCNTs single-walled carbon nanotubes; MWCNTs multi-walled carbon nanotubes.
Platelets
Fibres
Particles
Nanoller
type
Table 2.1
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Chapter 2
1
Tetrahedral sheet
Octahedral sheet
Tetrahedral sheet
Interlayer
or
gallery
Hydrogen
Na+
Oxygen
Silicon
Aluminium
2:1 Layer
10
Magnesium
15
Figure 2.3
Structure of sodium montmorillonite.

(Reproduced with permission from Paul and Robeson.1)
characterized by a moderate surface charge known as the cation exchange

capacity (CEC), which is generally expressed as mequiv per 100 g. This charge is
not locally constant, but varies from layer to layer, and must be considered as
an average value over the whole crystal.1,92
The chemical formula of MMT is Mx(Al4xMgx)Si8O20(OH)4. MMTs CEC
(generally 90110 mequiv per 100 g) and particle length (100150 nm) depends
on the source. The specic surface area of MMT is equal to 750800 m2 g1 and
the modulus of each MMT sheet is around 170 GPa. In its natural state, this
clay exists as stacks of many platelets. Hydration of the sodium ions causes
the galleries to expand and the clay to swell; indeed, these platelets can be
fully dispersed in water. The interlayer thickness of hydrated MMT is equal
to 1.45 nm, and the average density is r 2.385 g mL1. Drying MMT at 150 1C
reduces the gallery height to 0.28 nm, which corresponds to a water monolayer,
and hence the interlayer spacing decreases to 0.94 nm and the average density
increases to 3.138 g mL1.40
Pristine MMT usually contains hydrated Na1 or K1 ions.93 Obviously, in
this pristine state, MMT particles are only miscible with hydrophilic polymers,
such as poly(ethylene oxide) (PEO), poly(vinyl alcohol) (PVA), etc.94,95 To
render MMT particles miscible with chitosan polymer matrices, one must
convert the normally hydrophilic silicate surface to an organophilic one,
making the intercalation of chitosan chains possible. A chemical modication
of the clay surface, with the aim to match the polymer polarity, is often
achieved.39,92 Cationic exchange is the most common technique, but other
original techniques such as organosilane grafting,96,97 the use of ionomers,98,99
or block copolymer adsorption100 are also used. Generally, cation exchange
consists of the substitution of inorganic cations by organic ones. These
are often primary, secondary, tertiary, or quaternary alkylammonium or
alkylphosphonium cations. Alkylammonium or alkylphosphonium cations
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Table 2.2
Commercially available MMT clays and their characteristics.
Commercial
Supplier/clays Designation Modier
Modier
concentration
(mequiv per
100 g)
Weight
loss on
ignition, d-spacing
Dw (%) (A)
Southern Clay
Products
(USA)
Cloisite Na
Cloisite 15A
Cloisite 20A
Cloisite 25A
Cloisite 93A
Cloisite 30B
CNa
C15A
C20A
C25A
C93A
C30B
None
NMe2(tallow)2
1
NMe2(tallow)2
1
NMe2(C8)(tallow)
1
NHMe(tallow)2
1
NMe(EtOH)2(tallow)
125
95
95
90
90
7
43
38
34
37.5
30
11.7
31.5
24.2
16.6
23.6
16.5
Sud-Chemie
(Germany)
Nanol 804
N804
NMe(EtOH)2(tallow)
105
21
16
Laviosa
Chimica
Mineraria
(Italy)
Dellite LVF
Dellite 43B
LVF
D43B
None
1
NMe2(CH2Ph)(tallow)
95
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3235
9.8
16.6
10
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(known as surfactants) in the organosilicates lower the surface energy of the

inorganic host and improve the wetting characteristics of the polymer matrix,
resulting in a larger interlayer spacing. Additionally, the surfactants can provide functional groups that can react with the polymer matrix, or in some cases
initiate the polymerization of monomers to improve the adhesion between the
inorganic salt and the polymer matrix.101 Dierent types of organically modied MMTs, which dier in the nature of their counter cation and CEC, are
commercially available, for example Cloisite 15A (C15A), Cloisite 20A (C20A),
Cloisite 30B (C30B), Nanol, etc. Table 2.2 presents the characteristics of some
of the commercially available organically modied MMTs.
2.4 Nanocomposites: Preparation, Structure,

and Characterization
Intercalation of polymers with the layered silicate has proven to be a successful
approach to synthesize nanocomposites. Nanocomposites can, in principle, be
formed from clays (pristine and organically modied) by three main methods:40
(i) in situ polymerization, (ii) solvent intercalation, and (iii) the melt intercalation process. The solvent intercalation route consists of swelling the layered
silicates in a polymer solvent to promote diusion of the macromolecules in the
clay interlayer spacing. The in situ intercalation method causes the layered
silicates to swell in the monomer or monomer solution before polymerization.
The melt intercalation process is based on polymer processing in the molten
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Chapter 2
state, such as extrusion. Obviously, the last method is highly preferred in the
context of sustainable and eco-friendly development since it avoids the use of
organic solvents.102
For most purposes, complete exfoliation of the clay platelets, i.e. separation
of the platelets from one another and dispersal individually in the polymer
matrix, is the desired goal of the formation process. However, this ideal morphology is frequently not achieved and varying degrees of dispersion are more
common. The literature often refers to three main types of morphology:
immiscible (conventional or microcomposite), intercalated, and exfoliated. For
microcomposites, the polymer chains have not penetrated into the interlayer
spacing and the clay particles are aggregated. In the intercalated structures, the
polymer chains have diused between the platelets, leading to an increase in
intergallery spacing. In the exfoliated state, the clay layers are individually
delaminated and homogeneously dispersed into the polymer matrix. Intermediate dispersion states are often observed, such as intercalated exfoliated
structures. This classication does not take into account the dispersion multiscale structure, such as the percolation phenomenon, preferential orientation of
the clay layers, etc.39,40,103
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Figure 2.4
Illustration of dierent morphologies of polymer/MMT nanocomposites.

(Reproduced with permission from Paul and Robeson.1)
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The degree of intercalation and exfoliation of layered silicates in polymer

nanocomposites can be quantied using X-ray diraction (XRD) and transmission electron microscopy (TEM). For microcomposites, the wide-angle
X-ray scan of the polymer composite is expected to look essentially the same
as that obtained for the organoclay powder; there is no change of the X-ray
d-spacing. The intercalated layered silicate has a dened interlayer spacing
basal reection corresponding to an increase in the gallery spacing calculated
from XRD peak positions. For completely exfoliated organoclay, no wideangle X-ray diraction peak is expected for the nanocomposite since there is no
regular spacing of the platelets and the distances between platelets would, in
any case, be larger than what wide-angle X-ray scattering can detect.104106
TEM is a complementary technique to XRD wherein an image of the dispersion of the silicate within a polymer matrix can be quantied and analyzed.
These are illustrated schematically in Figure 2.4, along with example TEM
images and the expected XRD spectra.
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2.5 Chitosan/MMT Nanocomposites

Chitin with a deacetylation degree of 75% or above is generally known as
chitosan, which can be considered as a copolymer composed of glucosamine
and N-acetylglucosamine units; it dissolves readily in dilute organic acids,
providing a clear, homogeneous, and viscous solution.107 Thus, the chemically
active groups in the chitosan structure are the free amine groups, located in the
C-2 position of the glucose residue in the polysaccharide chain, and the hydroxyl
groups, with both being susceptible to modication. As a primary aliphatic
polyamine, chitosan is involved in all of the reactions typical of amines. Most of
the applications of chitosan are based on the polyelectrolytic nature and chelating ability of the amine group of the macromolecules, and such properties are
mainly governed by the acidity of the NH31 group.108 The weak-base anionexchange ability of pure chitosan has been applied in the development of chitosan-based lms for chemical and biosensing applications.25,109
However, these materials have poor performance because of the lack of longterm stability due to alteration of the characteristics of chitosan with time.
Recent research has indicated that incorporation of pristine or organically
modied MMT shows much promise for chitosan-based polymer nanocomposites in terms of improvements in their mechanical properties and stability over
those of the unlled formulations.110 Because of the polycationic nature of
chitosan in acidic media, this biopolymer appears as an excellent candidate for
intercalation in MMT silicate layers by means of a cationic exchange process.
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2.5.1 Preparation Methods and Characterization

In the case of natural polymers, the choice of a suitable method for the preparation of nanocomposites is limited by the processing possibilities of the
natural materials. Since nature itself produces the possible matrix polymers,
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Chapter 2
only blending/compounding with suitable inorganic particles, either in the melt

or in solution, is an accessible manufacturing possibility.111 Recently, a new
alternative method for the preparation of nanocomposites, which involves
solid-state mixing at room temperature (ball milling),112 was proposed.
Darder et al.113,114 prepared chitosan/MMT nanocomposite by a conventional method whereby the chitosan solution in acetic acid with a pH of 4.9 was
added to 2 wt% Cloisite Na (CNa) suspension and magnetically stirred for
2 days. The nal mixture was ltered, washed, and air dried at 50 1C to obtain
the composite powder. Nanocomposites with dierent chitosan/CNa ratios
(0.25:1, 0.5:1, 1:1, 2:1, 5:1, and 10:1) were prepared and compared. The XRD
spectra for the 1:1 chitosan/MMT ratio showed an increase of the basal
spacing, which is an indication of intercalation of chitosan with the silicate
layers. The scanning transmission electron microscopy (STEM) images
(Figure 2.5) of composites with a lower chitosan content showed the characteristic platelets of the montmorillonite tactoids, whereas the composites with
chitosan/CNa ratios of 5:1 consisted essentially of well-intercalated phases.
Yu et al.115 prepared a new nanocomposite consisting of poly(butyl acrylate),
chitosan, and methyltrioctadecylammonium bromide-modied MMT by g-ray
irradiation polymerization in aqueous acetic acid solution. XRD results
showed that the layers of MMT are intercalated and orderly dispersed in this
nanocomposite. Lin et al.116 reported on a novel method for the preparation of
chitosan/MMT nanocomposite lms using a solvent casting method. The
MMT was incorporated with potassium persulfate (KPS) in aqueous solution
through cationic exchange rst and then mixed with the acidied aqueous
solution of chitosan, and the composites were cast to form lms. The shifting of
the characteristic MMT peak in the XRD patterns of the composite lms
suggested that the MMT had been almost fully exfoliated, which was supported
by the TEM results. The higher the quantity of the KPS incorporated into the
MMT, the more the MMT exfoliated. As the KPS-incorporated MMT was
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1 m
Figure 2.5
(a)
0.2 m
(b)
STEM images of nanocomposites prepared from chitosan/CNa ratios of

(a) 1:1 and (b) 5:1.
(Reproduced with permission from Darder et al.113)
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dispersed in the acidied aqueous solution of chitosan, the KPS instantly

reacted with the chitosan, resulting in cleavage of the polymer chains which
triggered the exfoliation of MMT. Wang et al.117 used a similar method
for the preparation of chitosan/MMT composites with 2.5, 5, and 10 wt%
MMT content. The XRD patterns and TEM images clearly illustrated that the
MMT keeps intercalated and exfoliated structures at the lower MMT content
of 2.5 wt%, while on increasing the MMT content the MMT layers assemble
to form intercalated and occulated structures due to a hydroxylated edge
interaction of the silicate layers.
Xu et al.46 prepared chitosan-based nanocomposite lms with CNa and
C30B using a solvent casting method. Structural characterization using XRD
and TEM indicated that the silicate layers were exfoliated in the chitosan
matrix with small amounts of Na-MMT, and that the intercalation with some
exfoliation occurred with up to 5 wt% Na-MMT. However, microcomposites
(tactoids) formed when C30B was added to the chitosan matrix. For C30B the
clay became organic and its hydrophobicity increased. Hence it is very dicult
to disperse C30B in the chitosan aqueous solution and to form an intermolecular reaction between clay and chitosan in spite of the presence of
hydroxyl groups in the gallery of the C30B.
Rhim et al.118 developed an antimicrobial chitosan lm containing CNa and
C30B and found that the lm incorporated with C30B had signicantly higher
antimicrobial activity than the CNa-containing system. This may be ascribed to
the antimicrobial activity of the quaternary ammonium group in the silicate
layer of the C30B incorporated lm.
On the other hand, Han et al.119 recently reported enhanced antimicrobial
activity of chitosan/Na-MMT composite lms. Formation of exfoliated
nanocomposites of chitosan upon incorporation of small amounts of C10A was
reported by Oguzlu and Tihminlioglu.120 For such nanocomposites the intercalated structure becomes dominant when the clay content is higher than 2 wt%.
In another recent study, Sahoo et al.121 prepared a blend of chitosan, polycaprolactone (80:20 ratio), and C30B by solution mixing. The results indicated
that interaction of C30B occurs together with exfoliation and the extent of
interaction increases with an increase in clay concentration from 1 to 5 wt%.
According to the authors, during the mixing process the external platelets of
C30B are subjected to dynamic high shear forces that ultimately cause their
delamination from the stack of layers building the C30B particles, and then an
onion-like delamination process continues to disperse the platelets of silicate
into the polymer matrix. Blends of chitosan, poly(lactic acid), and C30B were
prepared by Nanda et al.122 by a similar procedure.
Wang et al.123 used two kinds of chitosan derivatives, namely N,O-carboxymethyl chitosan and N,N,N-trimethyl chitosan chloride, to prepare nanocomposite lms with MMT clay by a solution casting method. The XRD and
TEM results indicated that introduction of the carboxymethyl functional
groups into chitosan chains causes a strong reaction with the silicate hydroxylated edge groups through hydrogen bonding, leading to the assembly of
MMT in the polymer matrix to form a strong occulated structure. On the
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Chapter 2
other hand, a quaternized amino group in chitosan improved its aqueous

solubility, made the polymer cationic, and exfoliation of MMT layers is
therefore favoured. Intercalation of quaternized chitosan chains into the NaMMT silicate layers was also reported by Choudhari and Kariduraganavar.124
Depan and co-workers48,84 synthesized nanocomposites of lactic acid-grafted
chitosan and layered silicates by dissolving chitosan and dispersing CNa in an
aqueous solution of L-lactic acid, with subsequent heating and lm casting. A
decrease in the 2y value and an increase in d-spacing in the XRD spectra of the
samples conrmed the intercalation of biopolymer in the clay galleries. This
result was supported by TEM and EDX analyses.
Zhang et al.125 prepared a novel chitosan-g-poly(acrylic acid)/MMT superabsorbent nanocomposite by in situ intercalative polymerization among
chitosan, acrylic acid, and MMT in aqueous solution, using N,N 0 - methylenebisacrylamide as a cross-linker and ammonium persulfate as an initiator.
XRD, IR, and TEM analyses showed that in situ graft polymerization resulted
in exfoliation of MMT and the chitosan chains could intercalate into layers of
MMT to form nanocomposites. From the SEM images shown in Figure 2.6,
the surface of the MMT-containing nanocomposite seemed to be more porous
compared to that of its counterpart without the clay ller, which is ideal for
water penetration. The authors claim that this one-step method is more convenient and the corresponding nanocomposites have higher swelling ability and
pH responsivity compared to the two-step method.
Wang and co-workers126,127 prepared and compared the properties of chitosan/MMT and chitosan/cetyltrimethylammonium bromide (CTAB)-modied
MMT nanocomposites. The TEM and XRD results showed that a better dispersion of clay nanoplatelets was achieved by the modication of the clay with
CTAB, which indicated the formation of an exfoliated nanostructure in the
nanocomposite.
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40
(a)
Figure 2.6
(b)
SEM micrographs of (a) chitosan-g-poly(acrylic acid) and (b) chitosan-gpoly(acrylic acid)/MMT nanocomposite prepared using the one-step
method. Weight ratio of acrylic acid to chitosan is 7.2; MMT content in
the feed is 10 wt %.
(Reproduced with permission from Zhang et al.125)
45
47
A novel method of synthesis of chitosan/MMT nanocomposites in the presence of hydroxyaluminium cations was reported by Tan et al.128 In this procedure, the chitosan solution, the MMT suspension, and the pillaring solution
of hydroxyaluminium oligomeric cations {aluminium Keggin ions
[Al13O4(OH)24(H2O)12]71} with a ratio of 10 mmol Al per g of MMT were
solution mixed and stirred for 2 days at 60 1C. The mixture was nally ltered,
washed, and air dried. The intercalation of the biopolymer and hydroxyaluminium cation in the clay interlayer was conrmed by the decrease of 2y
values from 4.7 to 4.624.38, corresponding to a d001 value of 1.912.02 nm
(Figure 2.7). In this study, the nanocomposites with bilayer chitosan were
obtained at a chitosan/clay ratio of about 3:1 (against a ratio of 5:1 reported by
Darder et al.113), which indicates that the presence of the hydroxyaluminium
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40
Figure 2.7
XRD patterns of (a) Na-MMT, (b) Al-pillared MMT, and nanocomposites prepared from chitosan-CEC at MMT ratios of (c) 1:1, (d) 2:1, (e) 3:1,
(f) 4:1, and (g) 6:1.
(Reproduced with permission from Tan et al.128)
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Chapter 2
cations can accelerate the intercalation procedure and decrease the dosage of
chitosan.
Zhang and Wang129 developed chitosan/Na-MMT/multi-walled carbon
nanotube (MWCNT) nanocomposite lms by a simple solutionevaporation
method. In a typical procedure, the required amount of MMT and MWCNTs
were suspended in distilled water and sonicated. An acetic acid solution of
chitosan was then added to the mixture and mechanically stirred for 20 min.
This solution was then used to form uniform nanocomposite lms by solvent
casting. The XRD results indicated the exfoliation of MMT layers in the
polymer matrix. The introduction of MWCNTs increased the mechanical
properties of the nanocomposite without aecting the interfacial interaction of
the chitosan and MMT layers.
Yao and co-workers130 introduced a novel approach to fabricate articial
nacre-like chitosan/MMT bionanocomposite lms by self-assembly of chitosan/MMT hybrid building blocks, as illustrated in Figure 2.8. The fabrication
process was simple, fast, time-saving, and could be easily scaled up. In this
method, milky white colloidal chitosan/MMT hybrid building blocks were rst
prepared by mixing an aqueous suspension of exfoliated MMT nanosheets and
an aqueous solution of chitosan and stirring to guarantee full adsorption of
chitosan on the MMT nanosheets. The chitosan/MMT hybrid building blocks
were then aligned into the nacre-like structured composite by self-assembly
induced by vacuum ltration or water evaporation.
Lavorgna et al.131 studied the eect of the presence of glycerol as a plasticizer
in chitosan/MMT lms prepared by the solution casting method. The XRD
results suggested that in lms without glycerol the Na-MMT stacks lay with
their platelets parallel to the casting surface, forming a occulated structure
which is attributed to the hydrogen-bonding interactions between the hydroxylated edgeedge of the silicate layers and the amino or hydroxyl functional
groups of chitosan. The addition of the glycerol plasticizer, on the other hand,
reduces the extent of hydrogen-bonding interactions between chitosan and the
MMT edges by favouring preferential interactions between glycerol molecules
and edge-MMT. This hinders the occulation process and facilitates the
intercalation, leaving the MMT stacks randomly orientated in the lm.
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35
Stirring
Adsorption
MTM suspension Chitosan solution
Figure 2.8
Vacuum filtration
self-assembly
Evaporation
self-assembly
Chitosan-MTM suspension
40
Chitosan-MTM film
Fabrication of articial nacre-like chitosan/MMT bionanocomposite

lms.
(Reproduced with permission from Yao et al.130)
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49
132,133
Recently, Shameli et al.

prepared Ag/MMT/chitosan composites
using a green UV irradiation method. In a typical procedure, 500 mL of AgNO3
(0.02 M) was added to the chitosan solution in acetic acid under constant
stirring. This solution was then added to the clay suspension and stirred vigorously at room temperature. The mixture was then irradiated with UV light
for dierent time intervals at l 365 nm while it was stirred at a speed of
195 rpm. The TEM results showed successful incorporation of Ag nanoparticles in the chitosan/MMT matrix. It was found that the increase in
UV irradiation time caused a decrease in particle size and size distribution.
The XRD conrmed a face-centred cubic lattice for the Ag crystals and
intercalation of chitosan in the MMT structure.
In conventional processing techniques, such as extrusion, compression, and
injection moulding, the specic mechanical energy, shear impact, pressure,
plasticizer, time, and temperature are important parameters to determine the
clay dispersion and chemical cross-linking which ultimately dene the composite properties. In wet processing, the extent of the interaction of clay with
the chitosan depends mainly on the surface modication of the clay and
functional groups on the polymer and the lm-forming conditions such as the
drying temperature and drying rate, the moisture content, the solvent type, the
plasticizer concentration, and the pH.
The organic modier plays an important role in producing the nanocomposite. It may either enhance the interaction between the clay and the
polymer, making it more suitably mixed, or it may favour the intercalation of
the polymer chain by dictating the gallery spacing. Most of the studies on the
preparation of chitosan/MMT clays given in this section indicate that, irrespective of whether the clays are organically modied or not, a lower concentration of MMT clay (mostly 15 wt%) favours the formation of exfoliated
or intercalated structures, whereas at a higher clay content the clay layers
interact to form occulated structures.
Full exfoliation (individual platelet dispersion) of nanoclay in a chitosan
matrix by using conventional preparation techniques is still very dicult owing
to the large lateral dimensions of the layers and a strong inclination of clay
platelets to aggregate. However, the degree of exfoliation can be improved to
some extent by optimizing the processing conditions such as shear forces or
mixing rates when using extruders, mixers, ultrasonicators, ball milling, etc.
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35
2.5.2 Properties
Bionanocomposites consisting of chitosan and MMT (organically modied or
not) frequently exhibit moderate enhancement in mechanical and various other
properties when compared to neat chitosan. Improvements generally include a
higher modulus, both in the solid and melt states, increased strength and
thermal stability, reduced gas permeability, and better biodegradability. The
main reason for these improved properties in nanocomposites is the stronger
interfacial interaction between the matrix and layered silicate with nanoscale
dimensions, against the conventional microller-reinforced systems.
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50
2.5.2.1
Chapter 2
Mechanical Properties
A general reason for adding llers to polymers is to increase the modulus or

stiness via reinforcement mechanisms described by theories for composites.134,135 Properly dispersed and aligned clay platelets have proven to be very
eective for increasing the stiness of polymer matrices. The level of adhesion
of the clay platelets to the polymer matrix is also crucial in deciding the
mechanical properties of the resultant nanocomposites. Dynamic mechanical
analysis (DMA) is one of the methods by which we can measure viscoelastic
properties of a material when subjected to oscillatory deformation through
controlled stress or strain. Under the applied stress, most polymeric materials
show a combination of elastic and viscous types of behaviour, i.e. they react
elastically, ow to some extent at the same time, and are termed viscoelastic.
The stress and strain curves will be therefore out of phase. DMA measures the
amplitudes of the stress and strain as well as the phase angle between them.
This is used to resolve the modulus into an in-phase component, i.e. the storage
modulus (G 0 or E 0 ), and an out-of-phase component, i.e. the loss modulus (G 0 0
or E 0 0 ). The ratio of the loss to the storage moduli (G 0 0 /G 0 ) is tan delta (tan d)
and is often called the damping factor. It is a measure of the energy dissipation
of a material, which is useful in measuring the glass transition temperature (Tg).
Another procedure to understand the mechanical properties of a polymer
nanocomposite is tensile testing. It predicts the behaviour of the material under
dierent types of forces. Tensile tests produce a stressstrain diagram, which is
used to determine the tensile modulus. Properties that are directly measured via
a tensile test are ultimate tensile strength and maximum elongation (elongation
at break). From these measurements, properties like Youngs modulus and
yield strength can also be determined.
Nanoindentation is another means of testing the mechanical properties
of small volumes of material where small loads and tip sizes are used to
measure the load-displacement properties and extract parameters like Youngs
modulus.
Xu et al.46 studied the tensile properties of chitosan nanocomposite lms
containing CNa and C30B, and the results are summarized in Table 2.3. With
the introduction of 1 and 3 wt% of CNa, the tensile strength of the composite
lms increased by 35 and 62%, which was suggested to be due to the exfoliated
Table 2.3
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35
Mechanical properties of chitosan/nanoclay composites.
Materials
Tensile strength (MPa)
Elongation at break (%)
Chitosan
1% CNa
3% CNa
5% CNa
1% C30B
3% C30B
5% C30B
40.62 0.84
54.98 4.83
65.67 2.20
44.51 3.91
45.01 0.16
47.97 4.91
47.29 3.10
13.14 3.85
8.72 0.97
10.81 0.52
8.98 1.21
14.40 1.47
5.71 1.72
4.42 0.19
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51
state and the uniform dispersion of MMT in the chitosan matrix. Aggregation
of MMT nanoparticles with high surface energy resulted in a decrease of
tensile strength at higher clay content. When C30B was added to the
chitosan matrix, the tensile strength did not increase signicantly, although
it improved the load bearing capacity of the composites initially. This was
attributed to the formation of microcomposites.
The eect of tricetadecylmethylammonium bromide (TRIAB)-modied
MMT on the mechanical properties of hybrid composites of poly(butyl acrylate) and chitosan has been reported by Yu et al.136 The nanocomposites
exhibited an enhancement of the E 0 and tensile properties at relatively small
amounts of TRIAB-modied MMT (r3 wt%) loadings, whereas higher
TRIAB-modied MMT loadings decreased the mechanical properties due to
cluster formation. On the other hand, the Tg of the nanocomposite increased
with the introduction of TRIAB-modied MMT. This is due to inhibition of
the rearrangement of the bond structure of chitosan.
Lin et al.137 investigated the tensile properties of chitosan/KPS-MMT
nanocomposites with MMT incorporating various cation exchange capacities
(CEC) of KPS. It was found that when 0.5 CEC KPS was used to incorporate
with the MMT, the resulting nanocomposite had higher tensile strength but
lower Youngs modulus than the pristine chitosan. With increasing the amount
of KPS incorporated in the MMT, more MMT exfoliated along with the
degradation of chitosan so that the Youngs modulus increased but the tensile
strength decreased. Nevertheless, both of them were still much greater than
those of the chitosan-containing KPS only.
The synergistic eect of MWCNTs and Na-MMT on the mechanical properties of chitosan was reported by Zhang and Wang.129 The results given in
Figure 2.9 indicate that MMT and MWCNTs simultaneously introduced into
chitosan lm can greatly improve the mechanical properties. The Youngs
modulus of the chitosan lm is increased about 50% as 1.0 wt% MMT and
1.0 wt% MWCNTs are introduced. A very similar trend was observed in the
case of tensile strength after the introduction of MWCNTs. Although the
elongation at break decreased gradually with increasing MWCNT content,
the MMT could compensate for the negative eect of the MWCNTs. The highest
elongation at break is obtained when the contents of MMT and MWCNTs are
0.5 and 0.5 wt%, respectively. The NH31 groups on the chains of chitosan
adsorbed on the surface of MWCNTs could interact with the negatively charged
MMT sheets and form a third MMT chitosan MWCNTs subassembly,
which may be responsible for the synergistic eect of MMT and MWCNTs on
the mechanical properties of the neat chitosan lm.
Yao et al.130 compared the tensile properties of hybrid nanocomposites of
chitosan and MMT prepared by three dierent techniques, namely conventional, evaporation, and self-assembly by vacuum ltration. The mechanical
performance of the well-aligned articial nacre-like lm is better than that of
the lm made by conventionally simply mixing the constituents. The Youngs
modulus and ultimate tensile strength of the well-aligned articial nacre-like
lms are respectively 35-fold and 23-fold higher than that of conventional
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Chapter 2
1
90
4500
4000
3500
CTS/MMT
CTS/MWCVTs
CTE/MMT/MWCNTs
3000
2500
(a)
Tensile strength [MPa]
Young's modulus [MPa]
5000
1
2
3
4
5
Content of functional additives [wt%]
Elongation at break [%]
12
80
60
50
40
(b)
70
CTS/MMT
CTS/MWCVTs
CTE/MMT/MWCNTs
0
1
2
3
4
5
CTS/MMT
CTS/MWCVTs
CTE/MMT/MWCNTs
10
15
8
6
4
20
(c)
Figure 2.9
10
0
1
2
3
4
5
Variation of (a) Youngs modulus, (b) tensile strength, and (c) elongation
at break for chitosan/MMT, chitosan/MWCNTs, and chitosan/MMT/
MWCNTs nanocomposite lms with dierent additive contents.
(Reproduced with permission from Zhang and Wang.129)
lm. The electrostatic attraction between the OH and NH31 groups of chitosan
and the MMT surface could contribute to the improvement in the mechanical
properties of the nanocomposite.
An increase of approximately 80% in tensile strength and 50% in strain at
break with the addition of 10 wt% of C10A to chitosan was reported by Oguzlu
and Tihminlioglu.120 The improvement in tensile strength can be described
as the formation of an exfoliated/intercalated state and the uniform dispersion
of clay in the chitosan matrix or the strong interaction between chitosan and
clay.
Lavorgna et al.131 studied the mechanical properties in tensile mode of
chitosan/MMT nanocomposite lms in the presence of glycerol as a plasticizer
using a nanoindentation technique. In the case of lms containing glycerol, the
tensile strength is considerably higher than that of neat chitosan with only
glycerol. The presence of glycerol changes the hydrogen-bonding network
within the material and allows both a better interaction between the nanoller
and matrix and a higher extent of chitosan intercalation in Na-MMT clay. An
increase in storage modulus and glass transition temperature was also observed
for the nanocomposite lms, from DMA analysis.
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53
2.5.2.2
Thermal Properties
In general, it has been reported that the polymer/clay nanocomposites are

thermally more stable than neat polymers. The eect of clay layers has usually
been attributed to superior insulation and a mass transport barrier against the
volatile compounds generated during the decomposition of polymer chains
under thermal conditions. Clay minerals are inorganic materials and are largely
stable in the temperature ranges when organic polymers are degraded into
volatile compounds.40,138,139 Compositional analysis is often made using themogravimetric analysis (TGA), which can separate llers, polymer resin, and
other additives. TGA can also give an indication of thermal stability and the
eects of additives. TGA measures the amount and rate (velocity) of change in
the mass of a sample as a function of temperature or time in a controlled
atmosphere. Dierential scanning calorimetry (DSC) is another widely used
technique for examining polymers to check their composition, melting point,
and polymer degradation. In this method, the dierence in the amount of heat
required to increase the temperature of a sample and reference is measured as a
function of temperature. Thermal properties of chitosan/MMT nanocomposites have been analyzed and compared with that of neat chitosan under various
oxidative (air) or non-oxidative (inert gases) environments.
Wang et al.140 reported a systematic improvement in the thermal stability
of a chitosan matrix by the incorporation of nanodispersed MMT clay, studied
by TGA and dierential thermogravimetry (DTG) under both nitrogen and
air ows. The degradation patterns for neat chitosan or derivatives of chitosan
and their nanocomposites with pristine MMT were dierent, indicating
two dierent mechanisms for the composite degradation (Figure 2.10). Under
a nitrogen atmosphere there are two steps of degradation. The rst range
(50200 1C) is associated with the loss of water by about 58 wt%, whereas the
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30
100
100
MMT
90
80
CS-2.5
CS-10
70
60
CS-5
CS-2.5
50
40
Wt (%)
Wt (%)
80
60
CS-10
CS
CS-5
40
20
CS
Air
N2
40
(a)
100 200 300 400 500 600 700 800

Temperature (C)
Figure 2.10
35
(b)
100 200 300 400 500 600 700 800

Temperature (C)
TGA curves of MMT, chitosan (CS), and various nanocomposites (wt%

MMT): (a) CS, CS-2.5, CS-5, and CS-10 in a nitrogen ow; (b) MMT,
CS, CS-2.5, CS-5, and CS-10 in an air ow.
(Reproduced with permission from Wang et al.140)
45
54
Chapter 2
second range (200450 1C) corresponds to the degradation and deacetylation of

chitosan and leaves about 50 wt% solid residue.
In the air ow, there exists another degradation step (450700 1C) with a
maximum decomposition rate around 600 1C, which may be assigned to the
oxidative degradation of the carbonaceous residue formed during the former
step. The chitosan/MMT composites containing residual acetic acid showed
lower thermal stability than the composites free from acetic acid.
At 50% weight loss, the decomposition temperature of CS/MMT nanocomposites with 2.5 to 10 wt% MMT are 25100 1C higher than that of pure
CS. The clay acts as a heat barrier as well as assisting in the formation of char
after thermal decomposition. The nano-dispersed lamellae of clay in the
polymer matrix will result qualitatively in a spatially more uniform and thicker
char during decomposition. The nano-dispersed clay enhances the formation of
char on the surface of the polymer matrix and, as a consequence, reduces the
rate of decomposition.
In another study, Wang et al.123 compared the thermal stability of two different chitosan derivatives (N,O-carboxymethyl chitosan and N,N,N-trimethyl
chitosan chloride) and their MMT-containing nanocomposites. For the
carboxymethyl chitosan/MMT system, with respect to neat chitosan/MMT the
thermal stability was higher. However, fast degradation in the early thermal
stage of the nanocomposites was observed in the case of the trimethyl chitosan/
MMT nanocomposites.
The thermal properties of chitosan/MMT nanocomposites containing CNa
and C30B were analyzed by DSC and TGA by Xu et al.46 DSC plots of
chitosan and the corresponding CNa-containing nanocomposites are presented in Figure 2.11. Two endothermic peaks, one at 102 1C (attributed to
the solvent evaporation) and another one in the range of 168196 1C, showed
that the crystallization of the chitosan was not inhibited by the nanoclays. Pure
chitosan lm had a melting temperature (Tm) of 193.6 1C and a melting
enthalpy (DHm) of 6.05 J g1.
Addition of 1 and 3 wt% of CNa increased the Tm to 196 1C and the DHm
to 11 J g1, respectively. However, the Tm of the composite lm decreased to
194.5 1C when the amount of CNa was increased to 5 wt%. On the other hand,
both Tm and DHm decreased with the addition of C30B, suggesting that the
degree of crystallinity of chitosan was reduced. The well dispersed C30B acted
as a physical barrier to hinder the growth of crystals and their perfect
ordering.141 An increase in thermal stability of chitosan/MMT lms was also
observed when CNa was used as a nanoller. This was reected by the fact that
the onset temperatures for thermal degradation increased by 12 and 7 1C with
the incorporation of 1 and 3 wt% CNa, respectively, into the chitosan matrix,
owing to the formation of nanoscale composites. On the other hand, the onset
degradation temperature of chitosan lms did not increase signicantly with
the addition of C30B because of tactoid formation. Gunister and co-workers142
and Han et al.119 also reported higher thermal stability for chitosan/pristine
MMT composites. Because inorganic species have good thermal stabilities, it is
generally believed that the introduction of inorganic components into organic
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55
10
15
Figure 2.11
DSC thermographs of chitosan and its MMT (CNa) nanocomposites

with dierent MMT contents.
(Reproduced with permission from Xu et al.46)
materials can improve their thermal stability. This increase in the thermal
stability can be attributed to the high thermal stability of clay and to the
interaction between the clay particles and the chitosan.
Depan et al.143 investigated the eect of Na-MMT on the thermal properties
of chitosan-g-lactic acid lms prepared by solvent casting. The thermal
decomposition prole showed that the maximum decomposition temperature
was for nanocomposites with a clay loading of 5 and 10%. With further
increase in clay content, the thermal stability decreased. The addition of clay
enhanced the thermal properties by acting as a superior insulator and mass
transport barrier to the volatile products generated during decomposition.
Enhancement in the thermal stability of hybrid nanocomposites of poly(butyl
acrylate) and chitosan with the introduction of TRIAB-modied MMT was
reported by Yu and co-workers.115 Because of its inherent high thermal and
barrier properties the organoclay can prevent the heat from transmitting
quickly and can limit the continuous decomposition of the nanocomposites.
2.5.2.3
Barrier Properties
The barrier properties of chitosan can be signicantly altered by inclusion of

inorganic platelets with sucient aspect ratio to alter the diusion path of
penetrant molecules. Clay sheets are naturally impermeable. Clays increase the
barrier properties of polymers by creating a maze or complex path that retards
the diusion of gas molecules through the polymer matrix. The degree of
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56
Chapter 2
enhancement in the barrier properties depends on the degree of tortuosity

created by the clay layers in the diusion path of molecules through the
polymer lm, which in turn depends on the aspect ratio of the clay. Increasing
the side length of the clay sheet, as well as increasing the exfoliation or degree of
dispersion, results in barrier enhancement in the polymer matrix. Many studies
have reported the barrier properties of chitosan/MMT nanocomposites against
the diusion of gases and water vapour.141,144,145
Assuming silicate layers as crystalline lamellae in the matrix in a semi-crystalline polymer based on Klutes theory,146 the permeability P of composites is
P P0(1 Fs) z(Fs), where P0, Fs, and z are the permeability of the matrix in
the composite, the clay layers volume fraction, and a function for the reduction
of the permeability due to the clay layers in the polymer matrix, respectively.
Thus, the relative permeability for composites can be obtained as the following
equation: Rp (1 Fs) z(Fs). Nielsen147 formulated a detour model for
the rectangular ller particles, with length and width l and thickness d.148 For
the clay platelets dispersed parallel in a polymer matrix, the tortuosity factor
can be formulated as: t 1 (l/2d)fclay, where fclay is the volume fraction of
the dispersed clay particles.
A typical test method provides the determination of gas transmission rate
(GTR), the permeance of the lm to gas (P), the permeation coecient of the
lm to its thickness, and permeability coecient in the case of homogeneous
materials at given temperature and relative humidity (%RH) level.
Rhim et al.116 studied the water vapour permeability (WVP) for chitosanbased nanocomposite lms containing dierent types of nanollers and the
results are summarized in Table 2.4. The WVP value of the chitosan lm was
(1.31 0.07) 1012 kg m1 s1 Pa1. The WVP of the nanocomposite lms
decreased signicantly (Po0.05) by 2530%, depending on the nanoparticles
used. Among the nanocomposite lms tested, the chitosan/C30B lm had the
lowest WVP, showing improvement in barrier properties which may be due to
the development of a complex composite structure of chitosan with organoclay
nanoparticles. However, this particular nanocomposite showed the highest
hydrophilicity (lowest contact angle), against expectations (usually, the more
Table 2.4
AQ1
Water vapour barrier and water resistance properties of chitosanbased nanocomposite lms.a
Film type
MC (wt%)
WVP (1012 kg m1

s1 Pa1)
RH (%)
CA (1)
WS (%)
Neat chitosan
Na-MMT
Cloisite 30B
Nano-silver
Ag-ion
27.1 0.8a
26.4 0.4a
24.3 0.2b
24.5 0.0b
22.3 0.3c
1.31 0.07
0.98 0.15
0.92 0.03
0.95 0.12
0.96 0.05
76.2 1.4
78.8 0.6
78.2 0.2
78.1 0.2
77.3 0.4
45.6 0.2
47.4 0.2
43.4 1.3
48.5 1.1
50.4 1.0
13.6 1.1
12.5 0.8
13.2 1.0
14.1 0.8
15.4 0.6
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25
30
35
40
MC, moisture content; WVP, water vapour permeability; RH, actual relative humidity value
underneath the lm covering the WVP measuring cup; CA, contact angle of water drop; WS, water
solubility.
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57
hydrophilic a material is, the lower the contact angle value it has; the organoclay by nature is hydrophobic).
Oguzlu and Tihminlioglu120 investigated the water vapour and oxygen permeabilities of pure chitosan and chitosan/C10A nanocomposite lms at a
constant temperature (23 1C) and relative humidity (0% RH) conditions with
510 cm3 min1 gas ow. The WVP of the chitosan nanocomposite lms was
signicantly reduced even in the 2 wt% clay-containing chitosan lm. Moreover, the WVP decreased as the clay content increased in the polymer matrix.
The WVP of pure chitosan was found to be 3.4 g mm m2 d1 mmHg1,
whereas for the composite lms the value decreased to as low as 2.4 g mm
m2 d1 mmHg1, i.e. by 2027% depending on the clay loading.
For all clay loadings the nanocomposite lms were better oxygen barriers
than the pure chitosan lm, exhibiting 8392% reduction in oxygen permeability with the addition of 210 wt% clay in the chitosan. The decrease in
permeabilities of the nanocomposite lms is believed to be due to the presence
of ordered dispersed particle layers with large aspect ratios in the polymer
matrix. As a consequence of the decrease in permeability, the barrier properties
of chitosan for use in food packaging, protective coating, and other applications can be improved with the addition of clay to the polymer matrix.
The eect of shear rate on the barrier properties during homogenization of
Na-MMT into the chitosan matrix was reported by Hong et al.149 Oxygen and
water vapour permeabilities decreased dramatically as the amount of Na-MMT
increased up to 5 wt%, and it did not change signicantly with only a little
increase above 5 wt%. The lowest values for oxygen and water vapour permeabilties were 4.2 1019 kg m1 s1 Pa1 and 1240 g m1 s1 Pa1, respectively, at a shear rate of 16 000 rpm. Therefore, homogenization at an optimal
shear rate of 16 000 rpm is an eective method for dispersing Na-MMT in a
chitosan polymer matrix to improve the barrier properties.
2.5.2.4.
Water Swelling Properties
The water absorption property of chitosan-based nanocomposites is very

important, depending on the application for which they are envisaged. For
packaging applications, materials need good water resistance to maintain their
physical strength. On the other hand, for superabsorbent materials for drug
delivery and waste water treatment, a higher water or pH swelling capacity is
required. So the water swelling property becomes an important characteristic of
chitosan/MMT nanocomposites. In a typical procedure, a specic amount of
chitosan/MMT composite was immersed in an excess of distilled water at room
temperature for 8 h to reach the swelling equilibrium. Swollen samples were
then separated from unabsorbed water either by ltering or using blotting
paper. Water absorbency of the material was then calculated gravimetrically.
Yu et al.115 also carried out a similar study on chitosan-g-poly(butyl acrylate)
hybrid nanocomposites containing TRIAB-modied MMT. The results
showed a decreasing trend of water absorption percentage with the increase of
organoclay concentration (Table 2.5). This could be attributed to the large
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Table 2.5
Chapter 2
Water absorption of chitosan-g-poly(butyl acrylate)/MMT nanocomposites as a function of MMT content.
MMT conc. (wt%)

Water absorption (%) at 24 h
0
133.2
3
82.2
5
80.5
7
75.6
5
numbers of cross-linking points created by organo-MMT in the polymer
matrix, which prevents water absorption. However, Zhang et al.125 reported
higher water absorption capacity for chitosan-g-poly(acrylic acid)/MMT
nanocomposites prepared by in situ intercalative polymerization when compared to the absorption property of similar nanocomposites prepared by a twostep method. The MMT during the in situ polymerization could form a loose
and porous surface, with improved water absorbency of the chitosan-g-poly(acrylic acid) superabsorbent.
Depan and co-workers48 studied the water swelling properties of chitosan-glactic acid/MMT nanocomposite scaolds. The swelling behaviour and water
retention properties of the nanocomposites were found to be signicantly
higher than pure chitosan lm. The MMT acts as a physical barrier and prevents moisture from exuding out of the lms. In tissue engineering applications,
during the course of cell proliferation the retained hydrophilicity of the scaold
would enhance cell attachment and proliferation on its surface.
2.5.2.5
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20
Other Properties
The higher adsorption property of chitosan/MMT composites when compared

to pure chitosan for Congo red dye was reported by Wang and Wang.126 The
dye adsorption process was also found to be dependent on the molar ratio of
chitosan to MMT (adsorption increased from 1:10 to 1:1) and the initial pH
value of the dye solution and temperature. In another study,127 they compared
the adsorption capacity of CTAB-modied MMT with that of chitosan/
organo-MMT nanocomposites. The nanocomposite exhibited higher adsorption capacities for Congo red when the molar ratio of chitosan to organo-MMT
was less than 10:1. The same group reported the adsorption characteristics of
methylene blue on chitosan-g-poly(lactic acid)/MMT hybrid composites.150
According to the results, composites containing 2 wt% MMT clay showed the
highest adsorption property when compared to the other samples. The interaction of the OH groups of MMT during graft polymerization and MMT
exfoliation in the polymer matrix helps to create a loose and porous structure
with improved adsorption capacity. At higher clay loadings the interaction
among MMT, chitosan, and monomer becomes intensive, leading to more
chemical and physical cross-linkages whereby the elasticity of the polymer
chains decreases, which decreases the adsorption capacity of the nanocomposite. Improved adsorption properties of chitosan/MMT nanocomposites for
tannic acid were also reported by An and Dultz.151
Rhim and co-workers152 investigated the antimicrobial properties of
chitosan lms containing CNa and C30B. The analyses showed that the
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59
C30B-incorporated lm showed signicantly higher antimicrobial activity

against food pathogenic bacteria (S. aureus and L. monocytogenes) than
Na-MMT-incorporated lm, even though the basic structure of MMT is the
same for both. This may be attributed to the antimicrobial activity of the
quaternary ammonium group in the silicate layer of the C30B-incorporated
lm. The eectiveness of such groups bearing alkyl substituents is more eective in disrupting bacterial cell membranes and causing cell lyses. Han et al.119
also reported increased antibacterial properties for chitosan/MMT nanocomposites against pure chitosan and MMT. Shameli et al.132 recently studied
the antimicrobial property of chitosan/MMT composites containing Ag
nanoparticles. According to the results, introduction of Ag nanoparticles
improves the antibacterial property of chitosan/MMT nanocomposites. Ag
nanoparticles, because of their size and greater surface area, can easily reach the
nuclear content of bacteria.
Gunister et al.142 studied the rheological properties of chitosan/MMT colloidal dispersions. The rheological parameters such as viscosity, yield value,
and apparent and plastic viscosity were reduced by the addition of MMT to the
chitosan dispersions, which indicated that the clay particles caused the decrease
in the resistance of the polymer against the ow. The negatively charged clay
particles interacted with the positively charged polymer electrostatically by
attaching them to its surface, allowing the ow to proceed more easily.
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15
20
2.6 Applications of Chitosan/MMT Nanocomposites

Chitosan is one of the most abundant naturally occurring macromolecules and
the new class of composites based on chitosan and MMT clay dispersed at a
nanometric level can result in low cost, highly competitive, and environmentally friendly materials for a variety of applications. The incorporation of
MMT nanoclay into the chitosan matrix is suitable for the improvement of
physical, barrier, and antimicrobial properties of the neat chitosan. These
improved properties brought by the nanoller could present a wide range of
possibilities, such as packaging, electrochemical devices, super adsorbent, or
biomedical applications.
One of the widely researched applications of chitosan/MMT nanocomposites
is as biodegradable active packaging materials. Incorporation of nanostructured MMT (either pristine or organically modied) into the chitosan
matrix results in improved mechanical properties, water vapour and oxygen
barrier properties, and thermal stability of the resulting nanocomposites
without sacricing biodegradability. Such property improvements are generally
attained at low nanoclay content (less than 5 wt%) compared to that of conventional llers (in the range of 1050 wt%). For these reasons, nanocomposites are far lighter in weight than conventional composite materials, making
them competitive with other materials for packaging.40,104 Moreover, the
application of these materials can be expanded by adding multiple functionalities like antimicrobial and antioxidation properties. Dierent types of
nanoparticles can be used as additives in this case.
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60
Chapter 2
Chitosan/MMT nanocomposites have gained great attention as eective

biosorbents due to their low cost and the high content of amino and hydroxyl
functional groups, which show signicant adsorption potential for the removal
of various aquatic pollutants. The improved adsorption of tannic acid on
chitosan beads made of a hybrid of chitosan ake and clay was reported by
Chang and Juang.50 Similar results were obtained on freeze-dried chitosan/
MMT composites by An and co-workers.151 Wang et al.126,127,150 successfully
prepared chitosan/MMT nanocomposites and hybrid composites (with pristine
and organically modied MMT) and used them eciently for the removal of
organic dyes such as Congo red and methylene blue from aqueous euents.
Another interesting application of chitosan/MMT nanocomposites is as
electrochemical sensors. The intercalation of the cationic biopolymer chitosan
in MMT provides a robust nanocomposite with anionic exchange properties.113
These materials have been successfully used in the development of bulk-modied electrodes applied to the potentiometric determination of several anions
with a high selectivity towards monovalent anions, such as NO3, CH3COO,
and Cl. Although the resulting sensors are used in the determination of several
anions, the remarkable selectivity towards monovalent anions may be attributed to the special conformation of the biopolymer in the clay interlayer space.
The high anity between the chitosan and the MMT substrate is the basis of
the high stability of the intercalated biopolymer against desorption or degradation, and, consequently, of the long-term stability of the developed
sensors.114
The potential use of novel hybrid composites of chitosan/MMT in controlled
drug delivery and tissue engineering applications is also widely investigated. In
such drug delivery systems, the drug is stored in the interlayer region of the
lamellar host, and the drug is released as a consequence of diusion and/or a
de-intercalation process by controlling the interaction between the host and the
drug. In chitosan/MMT nano-hydrogels, the incorporation of negatively
charged delaminated MMT electrostatically interacts with the positively
charged NH31 group of chitosan to generate a strong cross-linked structure,
which greatly aects the macroscopic property of the nano-hydrogel and the
drug diusion through the bulk entity.48,153
Liu et al.153 prepared nano-hydrogels composed of chitosan and MMT for
the controlled release of vitamin B12 under electrostimulation. Under an
applied voltage, the drug release behaviour was strongly inuenced by the
concentration of MMT, which aected the cross-linking density of the nanohydrogels. The electro-responsiveness of the nano-hydrogel with higher MMT
concentrations was reduced, but its anti-fatigue behaviour was considerably
improved. The nano-hydrogel with 2 wt% MMT achieved a mechanically
reliable and practically desirable pulsatile release prole and excellent antifatigue behaviour, compared with that of pure chitosan. Depan et al.48 reported
the use of a chitosan-g-lactic acid/MMT porous scaold for the controlled
release of an anticancer drug. According to the results, clay reinforcement to
the chitosan matrix contributes signicantly to the mechanical, swelling, and
controlled drug release properties of the resultant nanocomposite materials.
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Controlled release of ooxacin using chitosan/MMT nanocomposite hydrogels

was investigated by Hua and co-workers.154 Compared to pure chitosan beads,
the incorporation of MMT enhanced the drug entrapment, improved the
swelling behaviour, and reduced the drug release. The observations suggested
that the electrostatic interaction between chitosan and MMT enhanced the
stability of the beads and showed good potential for the use as drug carriers for
sustained release. Recently, Nanda et al.122 reported the improved drug
releasing properties of a blend containing chitosan, poly(lactic acid), and C30B
for the anticancer drug paclitaxel.
10
2.7 Current Research Status and Future Scope

This chapter summarizes the preparation, characterization, properties, and
applications of chitosan/MMT nanocomposites. Solvent casting and solution
mixing have been shown as feasible methods of preparation for various chitosan/MMT nanocomposites. Chitosans with varying degrees of deacetylation
and dierent types of MMTs (Na-MMT and organically modied MMT with
dierent surfactants) have been used for the preparation of nanocomposites.
Hybrid polymer matrices containing chitosan and other biodegradable polymers, such as poly(lactic acid), poly(butyl acrylate), etc., are suggested to be
advantageous in improving the nanocomposite properties. It has been clearly
demonstrated that dierent parameters, such as MMT dispersion (tactoid,
intercalated, or exfoliated), chitosan/MMT anity, and clay content, can aect
the structure and the bionanocomposite properties. It has to be noted that the
higher reinforcing eect is generally limited to small clay amounts (o5 wt%)
and is reached for exfoliated states. In the case of good exfoliation and dispersion of MMT clays, the mechanical properties, thermal stability, biodegradability, and barrier properties were generally improved. These new
materials open up a range of applications in which chitosan can be moulded
into a variety of structures such as hydrogels, lms, powders, or even colloids.
The development of novel polymeric materials based on chitosan presents a
very interesting and promising approach in the context of concerns about
environmental waste problems. On the basis of the current literature on chitosan/MMT nanocomposites, exceptionally strong future prospects can be
predicted for these materials, which will broaden the scope of applications. In
spite of improvements in mechanical, thermal, and barrier properties that have
been reported, these are not sucient for petroleum-based plastics to be
replaced. The development of optimum formulations and processing methods
to obtain the desired properties to meet a spectrum of applications, as well as
cost reduction of the bionanocomposites, still needs serious attention. The
possibility of chitosan modication to make it more compatible with MMT
nanostructures, the development of melt intercalation techniques, blending
chitosan with one or more natural biopolymers or other biodegradable polymers, changing the chemistry of MMT nanoclays, etc., are expected to make an
impact in chitosan nanocomposite research in the future.
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Chapter 2
Acknowledgments
The authors wish to acknowledge the nancial support from the Department of
Science and Technology and the Council for Scientic and Industrial Research,
Pretoria, Republic of South Africa.
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1

SREEJARANI K. PILLAI* AND SUPRAKAS S. RAY

DST/CSIR Nanotechnology Innovation Centre, National Centre for

RSC Green Chemistry No. 17

2.2 Structure and Properties of Chitosan

Chemical structures of (a) chitin and (b) chitosan.

obtained by (partial) deacetylation of chitin in the solid state under alkaline

2.2.1 Importance of Chitosan

mechanical properties. Hydrophobic materials, such as neutral lipids, fatty

2.2.2 Chitosan-based Nanocomposites

2.2.3 Importance of Chitosan-based Nanocomposites

chitosan can be improved by the addition of nano-hydroxyapatite, bioactive

2.2.4 Types of Chitosan-based Nanocomposites

Various nanoller shapes and typical aspect ratios.

2.3 Structure and Properties of Montmorillonite

Biosensors for nucleic acid, drug

Solution spinning, freeze

Graphene, graphene oxide

Preparation method for

Nano material used a

SWCNTs single-walled carbon nanotubes; MWCNTs multi-walled carbon nanotubes.

Structure of sodium montmorillonite.

characterized by a moderate surface charge known as the cation exchange

Commercially available MMT clays and their characteristics.

(known as surfactants) in the organosilicates lower the surface energy of the

2.4 Nanocomposites: Preparation, Structure,

Illustration of dierent morphologies of polymer/MMT nanocomposites.

The degree of intercalation and exfoliation of layered silicates in polymer

2.5 Chitosan/MMT Nanocomposites

2.5.1 Preparation Methods and Characterization

only blending/compounding with suitable inorganic particles, either in the melt

STEM images of nanocomposites prepared from chitosan/CNa ratios of

dispersed in the acidied aqueous solution of chitosan, the KPS instantly

other hand, a quaternized amino group in chitosan improved its aqueous

MTM suspension Chitosan solution

Fabrication of articial nacre-like chitosan/MMT bionanocomposite

Recently, Shameli et al.

A general reason for adding llers to polymers is to increase the modulus or

Mechanical properties of chitosan/nanoclay composites.

Tensile strength (MPa)

Elongation at break (%)

Tensile strength [MPa]

Young's modulus [MPa]

Elongation at break [%]

In general, it has been reported that the polymer/clay nanocomposites are

100 200 300 400 500 600 700 800

100 200 300 400 500 600 700 800

TGA curves of MMT, chitosan (CS), and various nanocomposites (wt%

second range (200450 1C) corresponds to the degradation and deacetylation of

DSC thermographs of chitosan and its MMT (CNa) nanocomposites

The barrier properties of chitosan can be signicantly altered by inclusion of

enhancement in the barrier properties depends on the degree of tortuosity

WVP (1012 kg m1

Water Swelling Properties

The water absorption property of chitosan-based nanocomposites is very

Water absorption of chitosan-g-poly(butyl acrylate)/MMT nanocomposites as a function of MMT content.

MMT conc. (wt%)

The higher adsorption property of chitosan/MMT composites when compared