Progress in Polymer Science 51 (2015) 127–187

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Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Polymer nanocomposites from modified clays: Recent

advances and challenges
Moumita Kotal, Anil K. Bhowmick ∗,1
Department of Chemistry, School of Basic Sciences, Indian Institute of Technology Patna, Patna 800013, India

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

Article history: Since the end of the last century, the discovery of polymer nanocomposites and their
Available online 20 October 2015 ever-expanding use in various applications has been the result of continuous develop-
ments in polymer science and nanotechnology. In that regard, progress in developments
Keywords: on the use of modified natural and synthetic clays for designing polymer nanocompos-
Nanocomposites ites is presented herein. The modified clays used in composite preparation include natural
Polymer clays such as montmorrilonite, hectorite, sepiolite, laponite, saponite, rectorite, bentonite,
Clays
vermiculite, biedellite, kaolinite, and chlorite, as well as synthetic clays including vari-
Nanoparticles
ous layered double hydroxides, synthetic montmorrilonite, hectorite, etc. The preparation,
Modification
structure and properties of polymer nanocomposites using the modified clays are discussed.
Even at a low loading, these composites are endowed with remarkably enhanced mechan-
ical, thermal, dynamic mechanical, adhesion and barrier properties, flame retardancy, etc.
The properties of the nanocomposites depend significantly on the chemistry of polymer
matrices, nature of clays, their modification and the preparation methods. The uniform
dispersion of clays in polymer matrices is a general prerequisite for achieving improved
mechanical and physical characteristics. Various theories and models used to design poly-
mer/clay nanocomposites have also been highlighted. A synopsis of the applications of these
advanced, high-performance polymer nanocomposites is presented, pointing out gaps to
motivate potential research in this field.
© 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
2. Classification of clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
3. Polymer nanocomposites using modified natural clays, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
3.1. Polymer nanocomposites using modified smectite clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
3.1.1. Polymer nanocomposites using modified montmorillonite, their structure and properties . . . . . . . . . . . . . . . . . . . . . . 130
3.1.2. Polymer nanocomposites using modified saponite, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
3.1.3. Polymer nanocomposites using modified laponite, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3.1.4. Polymer nanocomposites using modified sepiolite, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3.1.5. Polymer nanocomposites using modified hectorite, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

∗ Corresponding author.
E-mail addresses: anilbhowmick@gmail.com, anilkb@rtc.iitkgp.ernet.in (A.K. Bhowmick).
1
Current address: Rubber Technology Centre, Indian Institute of Technology Kharagpur, Kharagpur 721302, India.

http://dx.doi.org/10.1016/j.progpolymsci.2015.10.001
0079-6700/© 2015 Elsevier Ltd. All rights reserved.
128 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187

3.1.6. Polymer nanocomposites using modified rectorite, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.1.7. Polymer nanocomposites using modified bentonite, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
3.1.8. Polymer nanocomposites using modified vermiculite, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
3.2. Polymer nanocomposites using modified kaolinite, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
3.3. Polymer nanocomposites using modified chlorite, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
4. Polymer nanocomposites using modified synthetic clays, their structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
4.1. Polymer nanocomposites using modified synthetic montmorillonite and hectorite: their structure and properties . . . . . . 163
4.2. Polymer nanocomposites using modified layered double hydroxide, their structure and properties . . . . . . . . . . . . . . . . . . . . . . 166
5. Theory and modeling to design polymer/clay nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
6. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180

1. Introduction organic cations or anions [4,6]. The first one, controlled

by thermodynamic criteria, improves their physical and
Since the end of the last century the discovery of var- chemical properties for composite and the structure of the
ious clays and their ever expanding use in a variety of clays remains unaltered. However, the weak force between
applications resulted in continuous developments in poly- the adsorbed molecules and the clay is a significant dis-
mer science and nanotechnology. The term “clay” refers advantage. On the contrary, the second method improves
to a class of materials generally made up of layered sil- the interaction force between clays and modifiers, con-
icates or clay minerals with traces of metal oxides and trolling and tuning their properties. Modification of clay
organic matter. Clay minerals, normally crystalline, are may also lead to improve dispersion of these materials in a
hydrous aluminum phyllosilicates, sometimes with vari- solvent via intercalation with polymer, providing enhance-
able amounts of iron, magnesium, alkali metals, alkaline ment of physico-mechanical and thermal properties of the
earths, and other cations. As a low cost inorganic mate- nanocomposites, as shown in Fig. 1.
rial, clays are used in industrial, engineering and scientific The nanometer size, its features and the extraordinary
fields. In science, these are commonly also used as catalysts, high surface area of the dispersed clay are all related to
decoloration agents and adsorbents and in industrial and the improvements in physical properties, such as tensile
engineering fields, these are used in oil drilling, ceramics strength and modulus, gas permeability, lower coefficient
and the paper industry [1,2]. Generally, clay particles have of thermal expansion, and without changing the opti-
lateral dimension in centimeters, micron sized in-plane cal homogeneity of the material. In order to incorporate
dimension of the individual clay layers and the thickness clay into a polymer matrix, different methods can be
of single clay platelets in the order of nanometers. These applied, such as solution intercalation, melt mixing and
layered clays are characterized by strong intralayer cova- in situ polymerization techniques. In these nanocompos-
lent bonds within the individual sheets comprising the clay ites, not only significant improvement in properties, but
[3]. This is the reason clays pose difficulty in dispersion in a also enhancement in material processing, as well as reduc-
polymer matrix during preparation of polymer nanocom- tion of component weight can be achieved. The more the
posites, generally requiring modification of the clay. polar groups in the polymer may enhance the ionic interac-
The change in the interlayer spacing of clay by interca- tion between the polymer chains and the clays, leading to
lating long chains or by grafting with different functional exhibit greater enhancement in physico-mechanical prop-
groups results in a change from hydrophilic to hydrophobic erties of the nanocomposites. The immiscibility of clays
character, and a wide range of new and fascinating prop- with non-polar polymers, namely PS, PE, PP, etc., may be
erties. Hence, the modification of clay is now of immense overcome by treating clays with surfactant without adding
interest in the preparation of polymer-clay nanocompos- compatibilizer, also discussed in this review. In addition,
ites [4–9]. However, the nanolayers of the clay tend to stack for in situ polymerized nanocomposites, the increased d
face to face leading to agglomerated tactoids in nanocom- spacing created a using larger surfactant as clay modi-
posites, which may negate the properties of the individual fier enables the monomer to penetrate into the gallery
components. The dispersion of the tactoids into discrete space and polymerize, resulting in improved reinforce-
monolayers is further hindered by the intrinsic incom- ment of the polymer matrix, as well as improvement of
patibility of hydrophilic clay and hydrophobic engineering properties of the corresponding nanocomposites. Such fea-
polymers. Since proper dispersion of these nanostructures tures make the nanocomposites as ideal candidates for
in a polymer matrix is essential for the improvement a broad range of applications ranging from strong, heat
of material properties compared with pristine polymer resistant automotive components to high-barrier packag-
or conventional micro- and macro-composites [10–14]. ing materials, aerospace, optical, electronic and medical
Several methods have been developed to improve the dis- devices.
persion of different clays, based on two principal methods Research on the modification of clays essential in the
of modification: (1) physical adsorption and (2) chemical advancement of scientific and technological progress of
modifications, such as grafting functional polymers or func- nanocomposites has been motivated by the inventive and
tional groups on to the surface of clay or ion exchange with pioneering discoveries of polymer-clay nanocomposites by
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 129

Fig. 1. Schematic diagram showing clay modification and intercalation of polymer to form polymer nanocomposites.

Toyota in the early 1990s [15,16]. Since that time, inno-
vative research in this field has exploded. This review
highlights modifications of various clays and their exten-
sive use in polymer nanocomposites during the last decade.
This study presents chemistry of modification of vari-
ous clays and their recent scientific and technological
advances in the field of polymer nanocomposites, including
clays extending from one-dimensional boehmite, sepiolite,
halloysite to two-dimensional montmorillonite, hectorite,
laponite, layered double hydroxides, etc. Various theories
and models to design polymer nanocomposites are pre-
sented to develop better understanding of the formation of
high-performance polymer nanocomposites. This review
describes also how different clays have been applied in
polymer nanocomposite technology.
the phyllosilicates. Modification of clay minerals such as
organoclay and organo-modified clay is a new avenue of
clay mineral research. Therefore, in this review, a general
picture will be provided on the modified clay materials
and the intercalation of polymer within modified clays will
play a significant role in improving properties of polymer
nanocomposites. Note that some of the clays shown in Fig. 2
have not been studied as not all of the clays are useful in
polymeric composites.
3. Polymer nanocomposites using modified natural
clays, their structure and properties
3.1. Polymer nanocomposites using modified smectite
clay

2. Classification of clay Smectite groups belong to the family of 2:1 phyl-

Generally, clay may be broadly classified into two cat-
egories: natural and synthetic clays. Fig. 2 shows the
classification of natural clays. They are basically composed
of alternating sheets of “SiO2 ” and “AlO6 ” units in ratios
of 1:1 (kaolinite), 2:1 (montmorillonite and vermiculite)
and 2:2 (chlorite) [1]. Chlorites are not always considered a
clay, sometimes being classified as a separate group within
losilicates. Their crystal structure consists of stacked
layered made of two silica tetrahedrons fused to an
edge-shared octahedral sheet of alumina to give a
silicate–gibbsite–silicate (s–g–s) stacking sequence. The
layer thickness is about 1 nm and the lateral dimension
may vary from 300 Å to several microns depending upon
the type of smectites used leading to an aspect ratio >1000.
As a result, smectite clays have a higher cation exchange

Fig. 2. Classification of natural clay.

130 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 3. The structure of smectites.
Reproduced from http://pubs.usgs.gov/of/2001/of01-041/htmldocs/
images/monstru.jpg.
capacity of 80–150 mequiv./100 g. There is a van der Waals
gap between the stacking of the layers called the interlayer
or gallery. Negative charges generated by the isomorphic
substitution of the layers are counterbalanced by alkali or
alkaline earth cations placed inside the galleries. Variable
amount of water molecules are also situated in the interlay-
ers. Accordingly, its structure is shown in Fig. 3 displaying
two layers of stacked sheets.
Montmorillonite (MMT), hectorite, saponite, vermi-
culite, laponite, sepiolite, and bentonite are the most
commonly used smectite clays. They differ mostly in
chemical content. The general formula is (Ca, Na,
H) (Al,Mg,Fe,Zn)2 (Si,Al)4 O10 (OH)2−x H2 O, where x repre-
sents the variable amount of water [17]. As they are
hydrophilic in nature, it is miscible with hydrophilic poly-
mers, such as poly(ethylene oxide) [18] or poly(vinyl
alcohol) [19]. In order to be compatible with various engi-
neering polymers, the hydrophilic smectite clay must be
converted into organophilic. This can be done by exchang-
ing the cations with various cationic surfactant including
primary, secondary, tertiary, and quaternary alkylammo-
nium or alkylphosphonium cations, etc. As a result, the
surface energy of the inorganic host is lowered and the
wetting characteristics of the polymer matrix are improved
[9]. Furthermore, the long aliphatic tails attached to their
cationic head result in larger interlayer spacing. However,
among different clays, montmorillonite (MMT) has the
widest acceptability for use in polymer nanocomposites
because of its easy availability, well known intercala-
tion/exfoliation chemistry, high surface area and high
surface reactivity. Their modifications and the respective
polymer nanocomposites are discussed in turn.
3.1.1. Polymer nanocomposites using modified
montmorillonite, their structure and properties
Montmorillonite (MMT) is a very soft layered silicate
named after Montmorillon in France. It comprises
plate-shaped particles with an average diameter
of approximately 1 ␮m. The chemical formula is
(Na,Ca)0.33 (Al,Mg)2 (Si4 O10 )(OH)2 ·nH2 O. The cation
exchange capacity of MMT is about 80–150 mequiv./100 g.
Different types of Cloisites are used in polymer matri-
ces for preparing polymer nanocomposite. Cloisites are
natural MMTs modified with quaternary ammonium
salts. In Cloisite®30B, the quaternary ammonium salt is
methyl tallow bis-2-hydroxyethyl quaternary ammonium
chloride:
where T is tallow (∼65% C18; ∼30% C16; ∼5% C14).
Because of the presence of long alkyl chains, the
interlayer spacing of MMT is enhanced resulting in
hydrophobic MMT, compatible with a polymer matrix.
Bharadwaj et al. [20] prepared crosslinked polyester-
clay nanocomposites by dispersing different wt% of
Cloisite®30B in polyester resin using a methyl ethyl ketone
peroxide catalyst. Cloisite®30B was selected because
of its polar hydroxyl group providing a good wetting
surface for the unsaturated polyester. Li et al. [21]
also used different types of organo MMT-Cloisite®6A,
Cloisite®10A and Cloisite®30B for the preparation of
poly(butylene terepthalate) (PBT)/organoclay nanocom-
posites. In Cloisite®6A and Cloisite®10A, the ammonium
cations are (CH3 )2 (HT)2 N+ and (CH3 )2 (HT)(CH2 C6 H5 )N+ ,
where T is tallow and HT is hydrogenated tallow.
They showed that polybutylene terephthalate/Cloisite®6A
formed conventional composites due to high hydropho-
bicity and lack of compatibility between the polymer
and the organoclay. However, Cloisite®30B can only form
intercalated nanocomposites due to the strong inter-
action between ammonium cations and silicate layers.
Cloisite®30B and Cloisite®10A are also used in the prepa-
ration of biodegradable polymer nanocomposites showing
better improvement in tensile properties and lower
biodegradability in the former case. Sadhu and Bhowmick
[22] studied the influence of organomodifier (octadecyl
amine) and copolymer composition on the properties of
styrene-butadiene rubber (SBR) and nitrile rubber. The
modified organoclays showed complete exfoliation of the
clay in the case of SBR, resulting in improved mechan-
ical properties (Fig. 4a). Nitrile rubber with 19%, 34%
and 50% acrylonitrile contents exhibited similar enhance-
ment when 4 parts of octadecyl amine modified clay was
used (Table 1). Bhowmick and coworkers [23] investigated
the effect of Cloisite30B loading and the functionality of
hyperbranched polyurethane (HBP) on the structure and
properties of in situ polymerized polyurethane nanocom-
posites. The exfoliated structure was obtained in all the
PU nanocomposites even up to 8 phr Cloisite30B load-
ing. 8 phr clay based PU nanocomposites showed 100%
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 131

Fig. 4. (a) Effect of modification of clay on morphology and properties of SBR, where SBRN4 represents 4 parts unmodified MMT/SBR and SBROC4 represents
4 parts of modified MMT/SBR nanocomposites. [22], Copyright 2004. Reproduced with permission from John Wiley & Sons Inc; Variation of the (b) tensile
strength of the different PUs and (c) lap shear strength between aluminum and aluminum with PU adhesive having different clay (Cloisite30B) loadings.
[23], Copyright 2009. Reproduced with permission from the American Chemical Society.

improvement in tensile strength, 120% increment in stor- functionality based HBP showed higher enhancement in
age modulus, 200% enhancement in peel strength, ∼2-fold properties. Fig. 4b and c shows the variation of tensile
increase in lap shear strength and dramatic improvement strength and lap shear strength of different PUs. They fur-
in thermal stability over neat PU. However, the higher ther studied the effect of Cloisite Na+ and Cloisite30B on

Table 1
Mechanical properties of nitrile rubber with unmodified and modified clays.

Sample Tensile Elongation at Work done at Modulus at 50% Young’s modulus × 103 Volume
designation strength (MPa) break (%) break (J/m2 ) elongation (MPa) (kPa) fraction (Vt)

19NBR 3.00 362 2531 0.66 14.6 0.332

19NBRN4a 2.73 147 915 1.00 20.5 0.359
19NBROC4a 3.60 154 1301 1.23 25.0 0.436
34NBR 2.10 399 2138 0.53 11.1 0.215
34NBRN4 2.00 279 1778 0.68 14.6 0.219
34NBROC4 4.85 923 8268 0.52 12.5 0.150
50NBR 2.75 553 3337 0.55 12.4 0.178
50NBRN4 2.10 414 2161 0.57 12.7 0.224
50NBROC4 5.60 679 7567 0.65 15.1 0.264

[22], Copyright 2004, Reprinted with permission from Wiley Inter Science.
a
19NBROC4 = nitrile rubber with 19% acrylonitrile + 4 phr octadecyl amine modified MMT, 19NBRN4 = nitrile rubber with 19% acrylonitrile + 4 phr MMT.
132 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 5. TEM photographs of different polyurethanes with varying clay loadings: (a) PUC2, (b) PUC4, (c) PUC8, (d) PUC16, (e) PU-Gy8 and (f) PU-TMP8.
[25], Copyright 2012. Reproduced with permission from John Wiley & Sons Inc.
physico-mechanical and adhesive properties of polyester-
polyurethane rubber nanocomposites [24]. It was noted
that 3 wt% Cloisite30B reinforced nanocomposites exhib-
ited remarkable improvement in tensile strength, thermal
stability, storage modulus and adhesive properties over
pristine PU.
They further [25] studied the physico-mechanical
properties of new PU nanocomposites derived from
toluene diisocyanate, poly(propylene glycol) and cured
either by third generation hyperbranched (HB3) polyester
polyol (HBP), trimethylolpropane (TMP) or glycerol (Gy).
PU nanocomposites cured by HB3 containing 8 wt%
Cloisite30 B exhibited the highest exfoliated morphol-
ogy, as shown from TEM micrographs in Fig. 5. An HB3
cured polyurethane (PU) nanocomposite containing 8 wt%
Cloisite30B was shown to exhibit ∼140% increase in ten-
sile strength, 23% improvement in storage modulus at 25 ◦ C
along with improvement in onset degradation tempera-
ture (5 ◦ C), temperature at which maximum degradation
occurred (9 ◦ C) compared to the control hyperbranched
polyurethane. The physico-mechanical and thermal prop-
erties for nanocomposites of HB3 cured polyurethanes
were found to be superior to those of the conventionally
cured polyurethanes (cured by HBP and TMP) and their
nanocomposites. This is because of the higher number of
end hydroxyl functional groups that take part in cross-
linking reactions leading to more ionic interaction between
the polymer chains of HBP with Cloisite30B.
Manitiu et al. [26] investigated the viscoelastic
response for supercritical processed polyvinylmethylether
(PVME)/Cloisite®30B (Cloisite®Na+ ) nanocomposites.
They reported that low-frequency moduli were signifi-
cantly more enhanced, accompanied by a plateau, and a
cross-over frequency shift signifying that rheology may
be sensitive to strong interaction between the modi-
fier and the polymer. Plasticized poly(l-lactide)/organo
modified MMT nanocomposites were prepared using
Cloisite®25A (ammonium cations are dimethyl 2-
ethylhexyl (hydrogenated tallowalkyl)), Cloisite®20A
(ammonium cations are dimethyl di(hydrogenated tal-
lowalkyl)) and Cloisite®30B. Of them, the last one showed
higher improvement in thermal stability because of
the stronger interaction between the filler and matrix.
Bhattacharya et al. [27] prepared tailor made SBR
nanocomposites using various fillers, such as Cloisite15A
(montmorillonite modified by dimethyl dihydrogenated
tallow quaternary ammonium salt), quaternary ammo-
nium salt modified sepiolite, hectorite, carbon nanofiber
and graphite. All SBR nanocomposite showed remarkable
improvement in mechanical and dynamic mechanical
properties of the polymer nanocomposites, although
Cloisite15A loaded nanocomposites resulted maximum
improvement in mechanical properties – 146% improve-
ment in modulus, 303% in tensile strength. They used
Cloisite®15A and Na-MMT for the preparation of melt
compounded natural rubber (NR) composites [28]. The
organomodified nanosilicates prepared not only showed
the higher improvement in mechanical properties, but
also promoted the vulcanizing reaction enabling easier
distribution of heat within the NR matrix and thereby
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 133

Fig. 6. Relative permeabilities (to oxygen gas) of Cloisite15A, sepiolite

(SP) and carbon nanofiber (F) filled SBR nanocomposites at 30 ◦ C.
[29], Copyright 2011. Reproduced with permission from Elsevier Ltd.

Fig. 7. Schematic representation for the (a) attachment of ATRP initiator

resulting in higher torque value. The gas permeability of onto clay surface via esterification and (b) the subsequent formation of
Cloisite®15A, sepiolite and carbon nanofiber filled SBR polyacrylate chains by surface-initiated ATRP using a sacrificial initiator.
[30], Copyright 2008. Reproduced with permission from John Wiley & Sons
nanocomposites was investigated using O2 as the perme-
Inc.
ant [29]. The Cloisite®15A filled nanocomposite exhibited
the best barrier properties (Fig. 6) due to high aspect ratio and distearyl dimethyl ammonium chloride (Praepagen).
and exquisite dispersion as evident from morphological Distearyl dimethylammonium chloride has also been used
studies. The improvement reflects the increase in tortuos- for the modification of MMT and the preparation of cor-
ity and reduction in free volume. Relative permeabilities responding electron-beam modified atactic polypropylene
were compared from the existing permeation models nanocomposites [34]. Electron beam modified atactic PP
and a novel function was introduced to represent the used as a compatibilizer in non-polar atactic PP along with
deviations. modified MMT was shown to exhibit improved disper-
Tailor-made hybrid exfoliated nanostructure of sion of clay as well as improved thermal stability. Moraes
poly(ethyl acrylate)/Cloisite30B was prepared by surface- et al. [35] investigated the influence of these modified
initiated atom transfer radical polymerization by tethering MMT on the material properties of poly(styrene-co-butyl-
ATRP initiator on active hydroxyl groups lying in the acrylate) nanocomposites and reported that CTAC modified
surface as well in the organomodifier of MMT, as shown in MMT containing nanocomposites showed the largest
Fig. 7 [30]. The polymer chain attached on the clay surface increment in mechanical properties. N,N-dimethyl-N-(4-
may have the ability to provide enhanced compatibility vinylbenzyl)stearyl ammonium (VSA) has been used as a
with common polymers in composites.
Datta et al. [31] established a one pot synthesis of the
tailor-made poly(ethyl acrylate)/organo MMT exfoliated
nanocomposites. It was reported that the rate of poly-
merization was remarkably increased in the presence
of organo MMT (Cloisite30B and Cloisite20A) because of
the interaction of the nanoclay with the carbonyl group
of the monomer reducing the electron density of the
conjugated C C bond leading to increase the reactivity of
the monomer. Such an in situ polymerized nanocomposite
showed significant 17 ◦ C shift of the glass transition tem-
perature when compared to neat polymer as presented in
Fig. 8.
Cloisite®93A is another organically modified MMT
(montmorillonite modified by methyl dihydrogenated tal-
low ammonium salt) that has also been used in the prepa-
ration of polymer nanocomposites showing a relatively
better effect on the improvement in properties compared
to the neat polymer [32,33]. In addition to these examples,
different ammonium salts are used for the modification of Fig. 8. tan ı vs. temperature plot of neat polymer and its in situ prepared
MMTs, such as cetyl trimethyl ammonium chloride (CTAC), hybrid composite.
[31], Copyright 2008. Reproduced with permission from the American
alkyl dimethyl benzyl ammonium chloride (Dodigen), Chemical Society.
134 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
modifier of MMT, employed in the preparation of resin-clay
nanocomposites [36] with inclusion of VSA-MMT into vinyl
ester resin giving enhanced hardness and thermal stability.
Lopez et al. [37] used octadecylamine modified MMT
for the improvement in dispersion of filler in polyamide
matrix and thereby enhancing the enhancement in
mechanical and thermal properties of the correspond-
ing nanocomposites. Gilman et al. [38] compared the
clays modified with dioctadecyl-substituted ammonium
to those modified with monooctadecyl-substituted ammo-
nium through melt-blending with polystyrene; the former
gave nanocomposite with an intercalated structure, while
the latter formed only a microcomposite. In the case of
in situ polymerization, the increased d spacing by larger
surfactant enables the monomer to penetrate into the
gallery space and polymerize providing an advantage for
the polymerization process. Sadhu and Bhowmick [39]
prepared styrene butadiene rubber (SBR)/MMT nanocom-
posites using organic amines of varying chain lengths. The
amines used were stearyl amine, hexadecyl amine, dodecyl
amine and decyl amine. The improvement in mechanical
and thermal properties of the nanocomposites is remark-
ably higher for longer chain length based amine modified
MMT compared to shorter chain length based amine mod-
ified MMT. Octadecyl amine modified MMT has also been
used in low density polyethylene (LDPE), for which maleic
anhydride grafted polyethylene acts as a compatibilizer
leading to the exfoliation of silicate layers [40]. In this
nanocomposite, a remarkable improvement in mechani-
cal properties was observed. Stearyl amine modified MMT,
octadecylamine modified MMT and Na+ -MMT were used
in the preparation of poly(styrene-(ethylene-co-butylene)-
styrene] (SEBS) and fluoroelastomer nanocomposites [41].
It was found that Na+ -MMT showed enhanced proper-
ties in resulting fluoroelastomer nanocomposites, while
hydrophobic organo-MMT showed best results in SEBS
nanocomposites. Maiti et al. [42] also used octadecyl
amine as organomodifier for the preparation of exfoliated
ethylene-octene copolymer (Engage)/MMT nanocompos-
ites by solution blending technique. Such nanocomposites
showed improvement of 44% tensile strength, 63% modu-
lus, 14% storage modulus and 10 ◦ C shift in glass transition
temperature compared to the neat copolymer. Sadhu and
Bhowmick further used octadecyl amine modified MMT
and unmodified MMT for the preparation of SBR and
acrylonitrile butadiene rubber nanocomposites and stud-
ied their viscoelastic behavior [43]. The modified MMT
showed better influence on the dynamic mechanical prop-
erties of rubbers even at smaller loading. Xidas and
Triantafyllidis [44] used four different alkyl ammonium
modifiers-primary octadecyl ammonium ion (Nanomer
1.30E), quaternary octadecyl ammonium ions (nanomer
1.28E), quaternary dihydrogenated tallow ammonium
ions (C15A and C20A) and quaternary benzyl-substituted
hydrogenated tallow ammonium ions (C10A) for the
modification of MMT and investigated their effect on
thermal and mechanical properties of epoxy nanocom-
posites. They reported that the primary alkylammonium
ion modifiers with reactive/acidic hydrogen atoms, com-
pared to the other modifiers were the most effective for
the formation of exfoliated epoxy nanocomposites which
Fig. 9. Comparative plots of the mechanical properties achieved for CL20A
(4 parts of Cloisite20A)–SEBS systems in the melt and solution processes.
[46], Copyright 2006. Reproduced with permission from John Wiley & Sons
Inc.
exhibited improved properties compared to the pristine
epoxy polymers. Another organic modifier of MMT is
dimethyl-hexadecyl-imidazolium used for the preparation
of acrylonitrile-butadiene-styrene (ABS) nanocomposites
which is compared with the corresponding nanocompos-
ites containing alkyl-ammonium modified MMT [45]. It
was inferred that imidazolium-treated MMT was stable
at the processing temperature of 200 ◦ C, whereas alkyl
ammonium modified MMT showed significant degradation
leading to superior performance of imidazolium-treated
MMT/ABS nanocomposites in enhancement in mechani-
cal properties and thermal stability. Ganguly et al. [46]
compared the effect of different organomodified MMTs,
such as octadecyl amine modified MMT, Cloisite20A and
Cloisite10A on the mechanical and dynamic mechanical
properties of solution blended and melt blended ther-
moplastic elastomeric nanocomposites from poly(styrene-
(ethylene-co-butylene)-styrene]triblock copolymer. The
best improvement in mechanical and dynamic mechan-
ical properties was observed in Cloisite20A based SEBS
nanocomposites. A 4 phr Cloisites 20A loaded melt pro-
cessed SEBS nanocomposite and a solution blended SEBS
nanocomposite showed similar shifts of the tan ı peak as
that of solution blended SEBS nanocomposite. On the other
hand, solution processed nanocomposite rendered better
improvement in the 50 and 300% moduli compared to the
former, although melt based nanocomposites showed bet-
ter results in tensile strength and toughness compared
to the solution process. Fig. 9 provides the comparative
plots of the mechanical properties of Cloisite20A-SEBS
nanocomposites prepared by solution and melt process.
Ganguly and Bhowmick [47] also quantified the surface
forces of SEBS/Cloisite20A solution blended nanocompos-
ites by atomic force microscopy in the blocks and clay
regions. The roughness and power spectral density analy-
ses of surface topography results showed the improvement
in random roughness of the nanocomposite surface com-
pared to neat SEBS surface.
They also studied the effect of Na+ -MMT and Cloisite20A
loadings on morphology and properties of sulfonated
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 10. Lowering in AC electrical resistance properties of (a) sulfonated SEBS nanocomposites and on (b) immersion in water–MeOH (80:20) mixture for
7 days.
[48], Copyright 2008. Reproduced with permission from Springer.
SEBS nanocomposites and demonstrated its application as
proton transfer membrane for fuel cells [48]. The Na+ -
MMT did not provide any improvement in properties
of SEBS nanocomposites, while Na+ -MMT showed excel-
lent improvement in mechanical, dynamic mechanical and
thermal properties and also controlled water–methanol
mixture uptake, permeation and AC resistance of the sul-
fonated SEBS nanocomposites. This is due to the better
dispersion of Na+ -MMT in sulfonated SEBS matrix and
stronger interaction with sulfonated SEBS. Fig. 10 showed
the AC electrical resistance of the nanocomposites in dry
along with water–methanol uptake condition. The AC resis-
tance decreased on water–MeOH wet samples compared
to dry samples due to the formation of the hydrophilic
ion channels leading to easy movement of protons in sul-
fonated SEBS.
They further studied the quantification and corre-
lation drawn on the effect of MMT in the lamellar
ordered nanocomposites of poly[styrene-b-(ethylene-co-
butylene)-b-styrene] triblock copolymer (SEBS) and polar-
modified SEBSs using small angle X-ray scattering and
modulated DSC analysis [49]. 2–4 wt% Cloisite20A loading
resulted in a positive shift in Tg by DSC, thereby assist-
ing increment in the lamellar orders of the neat SEBS.
Polar-modified SEBS showed deviation of the correspond-
ing ordering length and patterns, while a nanocomposite
based on unmodified MMT exhibited structural regener-
ation of ordering pattern due to the nucleating effect of
MMT, as shown in Fig. 11.
Mitra et al. [50] prepared nanocomposite gels of nat-
ural rubber and styrene butadiene rubber with Na+ MMT
by a special latex blending technique. In either case, 54%
improvement in tensile strength or 200% improvement in
Young’s modulus was noted compared to the correspond-
ing neat polymer gel. The nanocomposite gels also showed
marked improvement in storage modulus, glass transition
temperature and thermal stability compared to the unfilled
gels. They also prepared SBR and NR based MMT nanocom-
posite gels by suspending clay with NR and SBR lattices,
135
followed by prevulcanization [51]. Such nanocomposite
gels showed excellent improvement of tensile strength,
modulus along with noticeable changes in rheological and
dynamic mechanical properties.
A few representative modification of Cloisites and the
representative polymer nanocomposites are presented in
Table 2 along with relevant properties and applications.
Someya et al. [75] prepared poly(glycidylmethacrylate-
co-methyl acrylate)/MMT nanocomposites using four
surfactants – octadecylamine (ODA), 12-aminolauric
acid (ALA), N-lauryldiethanolamine (LEA) and hexadecyl-
tributylphosphonium bromide (HBP) and showed higher
improvement in mechanical and thermal decomposition
temperature of the nanocomposites compared to neat
polymer. A gas barrier properties of in situ polymerized
poly(n-butyl methacrylate)/surface modified natural MMT
nanocomposites by a two-stage process have been stud-
ied using (acryloyloxy) ethyl alkylammonium cations as
organomodifier [76]. The first stage process consisted of the
modification of MMT via ion exchange with (acryloyloxy)
ethyl alkylammonium cations, with the second process
associated with in situ polymerization of n-butyl methacry-
late and the unsaturated acryloxy ethyl groups anchored
on the surface of MMT. The total reaction scheme of both
processes is presented in Fig. 12. The second stage material
shows higher improvement in barrier properties than that
from the first stage.
Pramanik et al. [77] prepared ethylene vinyl acetate-
45 (rubber)/clay nanocomposites using dodecyl amine
modified MMT showing remarkable enhancement in
tensile properties, storage moduli and glass transi-
tion temperature. Poly(methyl methacrylate) (PMMA)
and polystyrene (PS) nanocomposites have been
prepared by an in situ polymerization using a 2-
methacryloyloxyethylhexadecyldimethylammonium
bromide (MHAB) modified MMT [78]. Naveau et al. [79]
used two different MMT modifiers and studied their effect
on structure and mechanical properties of polyamide-
6 nanocomposites: a new phosphonium organoclay
136 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187

Fig. 11. Tapping mode AFM phase images of (a) lamellar spaghetti-like morphology for neat SEBS, (b) oriented morphology of MA4SEBS, (c) lamellar
with spherical PEB patchy domains morphology of AA6SEBS, (d) distorted (from lamellar) with near spherical morphology of S6SEBS (all insets show
corresponding 2-D FFT). Bright-field TEM morphology of (e) neat SEBS (stained), (f) agglomerated SEBS-MT4 (stained), (g) exfoliated SEBS-OMT2, (h)
intercalated-exfoliated SEMS-OMT4, (i) thick stacks of SEBS-OMT8, (j) near-exfoliated MASEBS-MT4, (k) exfoliatedSSEBS-MT4, and (l) AA6SEBS-MT4
nanocomposites after selective staining.
[49], Copyright 2008. Reproduced with permission from the American Chemical Society.

(trihexyltetradecylphosphonium) obtained at pilot scale
in supercritical carbon dioxide (scCO2 ) and a commercially
available ammonium modified-silicate. They established
that the new phosphonium organoclay is more effec-
tive for the exfoliation of MMT in the matrix than the
ammonium modified-silicate. Rama and Swaminathan
[80] prepared polycarbonate (PC)/clay nanocomposites
using MMT modified with quaternary phosphonium and
imidazoilium cation based modifiers with and without
reactive functionalities. They reported that exfoliated
PC/MMT nanocomposites were obtained using an organo
MMT containing reactive bisphenol group in the modifier,
whereas intercalated or phase separated morphology were
obtained from organo MMT modified with compounds
having no reactive functionality.
Tyan et al. [81] prepared reactive organomodified clay
using p-phenylenediamine as a swelling agent for silicate
layers of MMT and further used this for the preparation of
orderly exfoliated polyimide nanocomposites. The swelling
process was carried out through ion exchange between the
onium of one amine end group of p-phenylenediamine and
the sodium ion in MMT and the other end group reacted
with dianhydride end group of poly(amic acid), as shown
in Fig. 13. As a result glass transition temperature, thermal
decomposition temperature, maximum stress, elongation
at break, tensile modulus and coefficient of thermal expan-
sion increase in the case of modified MMT loaded polyimide
nanocomposites compared to the neat polymer.
They also modified MMT by mono, di and trifunctional
swelling agents and reacted them with poly(amic acid)
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 137

Table 2
Examples of modified clays and their polymer nanocomposites.

Modified clay Preparation Products Properties References

method

Phosphonium salt Emulsion Polystyrene Molecular weight were slightly [10]

(APP) and polymerization (PS)/APP-Cloisite®Na+ lowered and coefficient of thermal
ammonium 4-(4- and PS/APB-Cloisite®Na+ expansion exhibited
adamantylphenoxy)- nanocomposites approximately a 44–55% decrease
1-butanamine (APB) for APB- and APP-intercalated clay
salts modified nanocomposites relative to the
Cloisite®Na+ neat PS, while Tg and thermal
decomposition temperature were
improved for those exfoliated
nanocomposites
Cloisite®20A Solution Specialty polymer Improvement in Mechanical [41]
blending fluoroelastomer and properties
poly(styrene-b-ethylene-
co-butylene-b-styrene
(SEBS)]/Cloisite®20A
Cloisite®Na+ Solution Fluoroelastomer/Cloisite®Na+ Improvement in thermal [52]
Cloisite®20A blending and stability-however such an
fluoroelastomer/Cloisite®20A improvement is poorer in O2
atmosphere than that in N2
atmosphere, decrease in intrinsic
viscosity and improvement in
activation energy with
Cloisite®20A
Cloisite Na+ , Solution Hydrogenated nitrile Remarkable improvement in [53]
Cloisite®30B, blending butadiene thermal stability with Cloisite®30B
Cloisite®15A and rubber/Cloisite®30B and
sepiolite Hydrogenated nitrile
butadiene
rubber/Cloisite®15A
Cloisite Na+ and Melt mixing Natural rubber Cloisite15A based NR [54]
Cloisite15A (NR)/Cloisite Na+ and nanocomposites exhibited
Natural rubber substantial increment in tensile
(NR)/Cloisite15A properties
Closite®15A and In situ Hyperbranched Dramatic improvement in gas [55]
Closite® 30B polymerization polyurethane barrier properties with
(PU)/Cloisite®15A and Cloisite®30B
hyperbranched
PU/Cloisite®30B
Closite®20A Solution Poly[styrene-b- Change in area of the endothermic [49]
blending (ethylene-co-butylene)- transition and change in
b-styrene]/Cloisite®20A morphology
Octaammonium In situ Epoxy/MMT Random dispersion of [56]
chloride salt of polymerization nanocomposites intercalated/exfoliated aggregates
octaaminopropyl throughout the matrix, thermal
polyhedral stability and char residue were also
oligomeric improved, however Tg remain
silsesquioxane invariant up to 10 wt% POSS-MMT
(OapPOSS) modified and showing decrease in Tg at
MMT 15 wt% POSS-MMT
(OapPOSS-modified
MMT)
Cloisite®10A, Melt blending Cloisite®10A/natural Determined the specific surface [57]
Cloisite®15A, and rubber (styrene area of each nanocomposite by
Cloisite®20A butadiene rubber), small angle X-ray scattering
cloisite®15A/natural
rubber (styrene
butadiene rubber), and
cloisite®20A/natural
rubber (styrene
butadiene rubber)
Cloisite®30B, In situ free PMMA/Cloisite®30B,PMMA/ Improvement in thermal stability [58]
Cloisite®25A, and radical bulk Cloisite®25A and and Young’s modulus with
Cloisite®15A polymerization PMMA/Cloisite®15A Cloisite®30B
Cloisite®30B Melt blending PEO/Cloisite®30B and Improvement in thermal stability [59]
And Cloisite Na+ PEO/Cloisite Na+ and mechanical properties with
Cloisite®30B
138 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187

Table 2 (Continued)

Modified clay Preparation Products Properties References

method

Cloisite30B Solution Polysulfide Improvement in adhesive, mechanical [60]

blending rubber/Cloisite30B and dynamic mechanical properties of
the nanocomposites compared to neat
elastomer
Cloisite®15A Melt blending Isotactic Improvement in storage modulus was [61]
polypropylene/Cloisite®15A less affected in reprocessing cycles;
nanocomposites however, thermal and mechanical
properties almost unchanged during
recycling
Cloisite®30B Melt blending Polycarbonate/Cloisite®30B Increase in dynamic moduli with [62]
content of Cloisite®30B
+
Closite Na and Solution Fluoroelastomer/Closite Better enhancement in [63]
Cloisite20A blending Na+ and Fluoroelas- solvent-resistance property like
tomer/Cloisite20A sorption, diffusion and permeation for
Cloisite Na+ /fluoroelastomer
composite compared to the later
Closite Na+ and Solution Fluoroelastomer/Closite The unmodified clay filled composite [64]
Cloisite20A blending Na+ and Fluoroelas- showed better improvement in
tomer/Cloisite20A viscoelastic properties than that of
modified MMT based nanocomposite.
Cloisite30BTM Melt blending Polyamide-6/LDPE-g- Increase in Tg , enhancement in impact [65]
MA/Cloisite30BTM strength and decrease in tensile
strength
Na-MMT and Melt mixing Poly(hydroxybutyrate) Higher degree of exfoliation of 30B in [66]
Cloisite30B (PHB)/Na-MMT and PHB matrix, increase in crystallization
Poly(hydroxybutyrate)/ temperature and decrease in
Cloisite30B spherullite size, increase in moduli of
the nanocomposites
Octadecyl Melt blending Poly(butylene succinate)/ Intercalated nanocomposites with [67]
trimethylammonium octadecyltrimethylam- improved storage modulus, tensile
ion modified MMT monium ion modified stiffness, O2 gas barrier property
MMT compared to neat PBS
Dimethyl- Melt Poly(␧-caprolactone)/all Exfoliated nanocomposites, Young’s [68]
distearylammonium intercalation organomodifiied MMT modulus increased significantly and
modified MMT, onset degradation temperature
dimethyl-stearyl- decreased significantly
benzyl ammonium
modified MMT and
Cloisite30B
Cloisite®Na+ , In situ Furan resin/Cloisite®Na+ , Significant differences in cure [69]
Cloisite®30B and polymerization Furan resin/Cloisite®30B mechanisms compared with neat furan
Cloisite®10A and Furan resin
resin/Cloisite®10A
nanocomposites
Cloisite15A and Melt blending Natural rubber Cloisite15A based NR nanocomposite [70]
sepiolite (NR)/Cloisite15A and exhibited the best barrier properties.
NR/sepiolite However, 60% decrement in O2
nanocomposites permeability of carbon black filled
sepiolite based NR nanocomposites
were shown to observe more stronger
and durable multifunctional materials
Cloisite®30B Solution Chitosan/polylactide/ Control release of the anticancer drug [71]
blending Cloisite®30B paclitaxel, however, drug release was
nanocomposites more pronounced in basic medium
than acidic medium
Cloisite®Na+ , Solution Chlorinated Significant improvement in tensile [72]
Cloisite®30B and intercalation polyethylene/Cloisite®Na+ , strength, Young’s modulus, storage
Cloisite®15A Chlorinated modulus and thermal stability were
polyethylene/Cloisite®30B found for Cloisite®15A loaded
and Chlorinated nanocomposite
polyethylene/Cloisite®15A
Cloisite Na+ Two roll Prevulcanized Improvement in peel strength, tensile [73]
mixing EPDM/Cloisite Na+ and strength, monomer friction coefficient
Unvulcanized of the nanocomposites compared to
EPDM/Cloisite Na+ neat EPDM
Hexadecylamine Solution EPDM/EVA/16Me-MMT Significant increase in storage [74]
modified MMT blending modulus, glass-transition temperature,
(16Me-MMT) tensile modulus, thermal stability for
blend nanocomposites compared to
neat EPDM/EVA blend
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 139

Fig. 12. Reaction Scheme 1: surface modification of natural montmoril-

lonite Cloisite® Na+ via ion exchange reaction. Reaction Scheme 2: free
radical in situ polymerization of n-butyl methacrylate with surface mod-
ified Cloisite® Na+ .
[76], Copyright 2010. Reproduced with permission from Elsevier Ltd.

to give MMT/polyamide nanocomposites [82]. The total

scheme for the reaction is shown in Fig. 14.
They used trifunctional swelling agent since with a
difunctional swelling agent, one functional group formed
an ionic bond with negatively charged silicates and
the other with poly(amic acid) containing dianhydride
end groups, whereas for a trifunctional swelling agent,
two functional groups reacted with two poly(amic acid)
molecules resulting in structures where modified silicates
situated at the end of the polymer chain with the difunc-
tional agent, but situated in the middle of the newly
coupled polymer chain using the trifunctional agent. As
a result, 5% trifunctional swelling agent-modified MMT
showed 70% increase in Young’s modulus, 50% increase in
maximum stress and 30% reduction in coefficient of ther-
Fig. 13. Schematic drawing of montmorillonite intercalated by poly(amic
mal expansion in polyamide matrix. Similarly, Ma et al. [83] acid) and (a) nonreactive swelling agent containing one functional group
used three types of surfactant-triisopropanol amine, m- NH3 + (reversible) and (b) reactive swelling agent having double functional
xylenediamine and allyl amine to modify MMT and further groups NH3 + and NH2 (irreversible).
[81], Copyright 1999. Reproduced with permission from the American
used for the preparation of corresponding SBR nanocom-
Chemical Society.
posites. As a result exfoliation was achieved for allyl amine
modified MMT based SBR nanocomposites and enhance-
ment of mechanical properties was more prominent than these were compared with corresponding nanocomposites
that of carbon black based SBR composites. of Cloisite®10A [85]. Exfoliation occurred if the ammonium
Ditallow dimethylammonium chloride (DDAC) was ion contained a double bond participated in the poly-
used for the modification of fractionated MMT and its merization reaction. However, the particular preparative
corresponding polystyrene (PS) nanocomposites com- technique used has a large effect on the type of material
pared with commercial Cloisite15A/PS nanocomposites obtained.
[84]. Fractionated MMT (F-MMT) was prepared by collect- 3-Aminopropyltriethoxysilane has also been used for
ing the supernatant from the centrifugation of dispersed the modification of Cloisite Na+ and further been used
MMT in water. The preparation procedure of F-MMT and for the preparation of polymer nanocomposites. Silane
DDAC modified MMT is shown in Fig. 15. The trans- modified MMT/epoxy composites exhibit lower friction
parency and rheological properties of DDAC modified coefficient and specific wear rate compared to unmodified
fractionated MMT based PS nanocomposites were better MMT/epoxy composites indicating improved dispersion of
compared to PS/cloisite®15A nanocomposites, as evident the modified MMT in epoxy and increased adhesion with
from Figs. 16 and 17. epoxy [86]. The specific wear rate of epoxy, unmodified and
Styryldimethylhexadecylammonium chloride was also surface-modified clay/epoxy nanocomposites at different
used as a modifier of MMT for the preparation of PS and sliding speed is shown in Fig. 18.
PMMA nanocomposites by bulk, solution, suspension and Silane-functionalized MMT also has been used in
emulsion polymerization and melt blending methods and the preparation of epoxy nanocomposites [87] using
140 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187

Fig. 14. Schematic drawings of (a) difunctional group ( NH2 ) swelling agent and (b) trifunctional group swelling agent for intercalating layered silicates
and reacting with poly(amic acid) molecules.
[82], Copyright 2001. Reproduced with permission from the American Chemical Society.

N-(2-aminoethyl)-3-aminopropyltrimethoxysilane as the incorporated in the polymer backbone. In the grafting from

modifier. Silane modified clay is effective in the exfoliation
of MMT in an epoxy matrix. Many of the nanocomposites
based on this clay exhibit increased storage modulus and
glass transition temperature Tg .
Polymer grafting technique by either of two methods
– grafting to and grafting from methods provides another
approach for modification of MMT. In the grafting to
method, the organic salt to be exchanged in the clay
interlayer bears a double bond able to polymerize and be
or surface initiated method, an initiator is attached to the
clay and the polymerization occurs by addition of monomer
units to the attached initiator fragment. Mansoori et al.
[88] prepared polyacrylamide/MMT nanocomposites by
the free-radical grafting through approach. Cloisite®20A
was reacted with vinyltricholorosilane to exchange the
edge hydroxyl groups of the MMT with a vinyl moiety,
maintaining the same basal spacing as the precursor.
The modified MMT followed radical polymerization with

Fig. 15. Extraction and synthesis of FMT and DDAC modified FMT particles. The original MMT dispersion in water is centrifuged to separate out the large
aggregates. The supernatant was centrifuged again, and the pellet was FMT. These particles were then functionalized with the cationic surfactant DDAC to
yield the o-FMT particles.
[84], Copyright 2009. Reproduced with permission from the American Chemical Society.
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 16. Transmission of visible light through 200-␮m-thick nanocom-
posite films containing either o-FMT (dashed lines) or 15A solid lines) at
different concentrations.
[84], Copyright 2009. Reproduced with permission from the American
Chemical Society.
Fig. 17. Dynamic rheology of PS nanocomposites based on DDAC modified
FMT and Cloisite®15A. (a) Data for the elastic modulus G . (b) Data for the
complex viscosity *.
[84], Copyright 2009. Reproduced with permission from the American
Chemical Society.
141
Fig. 18. Specific wear rate of neat epoxy, unmodified and surface-
modified clay/epoxy nanocomposites at different sliding speed.
[86], Copyright 2008. Reproduced with permission from Elsevier Ltd.
acrylamide leading to dramatic improvement of glass
transition temperature (61 ◦ C) for the nanocomposites.
The total reaction is shown schematically in Fig. 19.
An ammonium cation terminated polymeric surfactant
was first used as the modifier of MMT by Hoffman et al. [89].
Allyl amine was added to an anionic polystyrene capped
by dimethylcholorosilane to form an amine-terminated
PS, followed by interaction with MMT. Individual sili-
cate platelets of 1 nm diameter and 600 nm length were
obtained when shear force was applied during melt com-
pounding of organoclay modified with high molar mass
PS. It was found that dispersion of such in situ formed
nanoparticles with aspect ratio of 600 accounted for
unusual elastic properties in the low frequency range of
the dynamic modulus, while organoclay modified with
low molecular mass PS did not exfoliate, and exhibited
rheological behavior almost similar to that of conven-
tional fillers. A macroinitiator may also be used for the
modification of MMT by the grafting from method on the
corresponding waterborne acrylic nanocomposites [90].
The macroinitiator may be synthesized by the nitroxide
mediated polymerization of vinylbenzyl trimethylammo-
nium chloride, methylmethacrylate and styrene at 90 ◦ C
using BlocBuilder® . It is then followed by exchanging
with Na+ -MMT, resulting in a surface modified MMT. The
bulk polymerization of the polymer from the clay sur-
face resulting in exfoliation of clay in the matrix and the
nanocomposites used as masterbatch further dispersed
in monomers to provide miniemulsion polymerization
resulting in improved the adhesion strength. An innova-
tive organo MMT containing polybutadiene chains was
prepared to make exfoliated NR and styrene butadiene
rubber (SBR) nanocomposites by melt blending [91]. The
schematic reaction of polybutadiene with MMT is dis-
played in Fig. 20. The tensile and dynamic mechanical
properties were improved compared to neat NR or SBR.
Therefore, this modification technique is a powerful tool
to steer the material properties of rubber nanocomposites.
Novel biobased nanocomposites from soybean oil
and (4-vinylbenzyl)triethylammonium chloride modified
MMT have been prepared by Lu and Larock [92]. A
142 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 19. Free radical polymerization of vinyl modified Cloisite®20A with acrylamide.
[88], Copyright 2010. Reproduced with permission from Elsevier Ltd.
Fig. 20. Exemplified reaction between polybutadiene and organo-
modifier of Cloisite®30B.
[91], Copyright 2012. Reproduced with permission from Elsevier Ltd.
significant improvement in thermal stability, dynamic
storage modulus, compressive modulus, compressive
strength, compressive strain at failure and the vapor
barrier performance was observed in the correspond-
ing nanocomposites containing 1–2 wt% modified MMT.
2-(Acryloxyethyl)trimethylammonium chloride (AETMC)
and vinyl acetate (VAc) were also used as the organic
modifier of MMT and further used in preparing correspond-
ing exfoliated poly(vinyl acetate) (PVAc) nanocomposites,
even at 20 wt% loaded modified MMT [93]. These PVAc
nanocomposites further served as masterbatches for
preparing their ethylene vinyl acetate (EVA) nanocompos-
ites. Improvement in thermal stability and storage moduli
was observed for the cationic PVAc modified MMT/EVA
nanocomposites due to the exfoliated morphology (as
shown in Fig. 21) and a synergistic effect of the PVAc and
silicates.
Wang et al. [94] used a novel hydrophilic nanocom-
posite additive, coupling the hydrophilic modifier by
surface modifying MMT with N-vinyl pyrrolidone (NVP)
via a “grafting from” polymerization in the presence of
H2 O2 NH3 ·H2 O as the initiator. Then the nanocomposites
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 143

Fig. 21. (a) Exfoliated morphology of cationic PVAc modified MMT and (b) its corresponding EVA nanocomposites.
[93], Copyright 2007. Reproduced with permission from the American Chemical Society.

Fig. 22. Schematic Representation of Two-Step Synthesis of the Hydrophilic Nanocomposite Additive, NVP-g-MMT.
[94], Copyright 2012. Reproduced with permission from the American Chemical Society.

membranes of poly(vinylidene fluoride) (PVDF) and NVP-
g-MMT were prepared by a wet phase inversion method.
They showed better separation performance of the
prepared PVDF/NVP-g-MMT nanocomposite membranes
compared to the control PVDF membrane, indicating the
synthesis of hydrophilic nanocomposite additive is favor-
able for water treatment. Fig. 22 shows a schematic
diagram for the preparation of NVP-g-MMT.
Triethylaluminum (TEA) used in the preparation of
modified MMT-k10 was the modifier in the preparation
of exfoliated PMMA nanocomposites by an in situ poly-
merization in the presence of Ni(acac)2 /methyl alumino
oxane (MAO) catalyst [95]. The total reaction procedure
is shown schematically in Fig. 23. The storage modulus,
glass transition temperature, tensile strength and tensile
modulus were remarkably improved for PMMA/PEA-MMT
nanocomposites compared to neat PMMA.
Oligomerically modified MMT has also been used as a
filler in the preparation of polymer nanocomposites. Zhang
Fig. 23. Schematic illustration of reaction process for formation of TEA-
modified clay and the PMMA/clay nanocomposites.
[95], Copyright 2008. Reproduced with permission from the American
Chemical Society.
et al. [96] modified MMT with an oligomeric surfactant
containing styrene and lauryl acrylate units, along with
a small amount of vinylbenzyl chloride to permit the
formation of an ammonium salt. This modified MMT
was melt blended with polystyrene (PS), high-impact
polystyrene (HIPS), styrene acrylonitrile copolymer
(SAN) and acrylonitrile-butadiene-styrene (ABS) to pre-
pare the corresponding polymer nanocomposites. They
showed that PS and HIPS have an immiscible morphology,
while SAN and ABS nanocomposites exhibited interca-
lated/delaminated morphology. Further, the plasticization
from the oligomeric surfactant was suppressed in compar-
ison with similar modified clay of lower organic content,
giving better tensile properties. Difunctional l-isoleucine
amino acid used as modifier for Cloisite®Na+ MMT [97],
with one of the amine groups of the modifier forming an
ionic bond with the negatively charged silicates, while the
remaining acid functional groups of the modifier further
interacted with polyimide chains. Nanocomposites with
varying amounts of modified MMT were prepared by
in situ polymerization through thermal imdization. These
nanocomposites exhibited good optical transparencies
and mechanical properties. Choudhury et al. studied the
effect of Cloisite®30B on accelerated aging resistance
of hydrogenated nitrile rubber (HNBR) nanocomposites
and their life-time prediction [98]. For this purpose, the
materials were subjected to accelerated heat aging at 70,
100 and 135 ◦ C over varying time periods. The nanocom-
posites improved the retention of physicochemical
properties by disrupting the oxidative process, while neat
HNBR showed a decrease in properties. This is because that
Cloisite®30B protected the elastomer from surface rupture
during oxidation, as evident from AFM (Fig. 24). As a result,
144 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 24. AFM phase images of (a) HNBR, (b) HNBR/Cloisite®30B (before aging), (c) HNBR and (d) HNBR/Cloisite® 30B (after aging).
[98], Copyright 2010. Reproduced with permission from Elsevier Ltd.
Cloisite®30B protected the HNBR from oxidative crosslink-
ing that lead to embrittlement and ultimately to failure,
thereby providing excellent aging resistance to the matrix.
Therefore, it can be concluded ionic interaction between
the polymer chains and the silicate layers will usually
increase with increasing polar groups in the polymer,
leading to enhanced physico-mechanical properties of the
nanocomposites. However, different polymer nanocom-
posites based on the same clay exhibited different extents
of improvement of properties, which may be due to the
different methods followed for preparing nanocomposites
and also different structure of the polymers. Apart from
these, among different modifiers, primary alkylammonium
ion modifiers with reactive/acidic hydrogen atoms were
the most effective for the formation of exfoliated polymer
nanocomposites with improved properties.
3.1.2. Polymer nanocomposites using modified saponite,
their structure and properties
Saponite is a trioctahedral mineral of the smectite group
that possesses negatively charged layers neutralized by
positively charged counter ions (Na+ and Mg2+ ). Its chem-
ical formula is Ca0.25 (Mg,Fe)3 ((Si,Al)4 O10 )(OH)2 ·n(H2 O).
It is also in the 2:1 smectite family, i.e., silicate lay-
ers sandwiching a gibbsite (or brucite) layer in a
silicate–gibbsite–silicate (s–g–s) stacking sequence. The
cation exchange capacity of saponite is 100 mequiv./100 g.
Vuillaume et al. [99] used a synthetic saponite clay,
Sumecton, that self-assembled with 12-phospho-tungstic
acid (PTA) heteropolyacid in the preparation of new hybrid
styrene/ethylene-co-butylene/styrene block copolymer
(SEBS) nanocomposites. For comparison, they used two
types of SEBS-poly(oxyethylene/oxypropylene)-grafted-
SEBS and maleic anhydride grafted SEBS. It is observed
that the former was more effective for the dispersion
of PTA-saponite complexes. Cetyl trimethylammonium
bromide was treated with saponite for the preparation
of exfoliated acrylic nanocomposites [100]. However, as
acrylic resins are hydrophobic in nature, they have strong
affinity with CTAB exchanged saponite. Therefore, mechan-
ical shearing, i.e., ultrasonication, was applied for the
exfoliation of saponite in acrylic matrix. In addition to
CTAB, meristyltrimethylammonium bromide (MTAB) and
octadecyltrimethylammonium bromide (OTAB) were also
used as the modifiers of saponite [101,102]. Stable water-
based polystyrene/saponite exfoliated nanocomposites
were also synthesized by miniemulsion polymerization
[103]. For this purpose, saponite was modified by octade-
cyltrimethyl ammonium bromide (OTAB). The addition of
modified saponite slightly reduced both the reaction rate
and the conversion. One pot synthesis of cetyltrimethylam-
monium (CTA) modified saponite by hydrothermal method
has been compared with classical post synthesis interca-
lation root of the CTA-saponite [104]. The former process
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 25. Schematic view of the organization of CTA+ in (a) CTA-saponite-
one pot synthesis and (b) CTA-saponite in post synthesis method.
[104], Copyright 2011. Reproduced with permission from the American
Chemical Society.
did not significantly affect the structure and morphology of
saponite. Inorganic layers of saponite played an important
role in stabilizing and protecting the surfactant molecules
by increasing their thermal stability. Fig. 25 is a schematic
of the organization of CTA+ in CTA modified saponite in one
pot synthesis and that in classical post synthesis method.
Hrobarikova et al. [105,106] used four different
modifiers in saponite: hexadecyltrimethylammonium
(HDTA), (2-hydroxyethyl)dimethylhexadecylammonium
(HEDMHA), di(2-hydroxyethyl)methylhexadecylammo-
nium (DHEMHA) hexadecyltrimethylammonium (HDTA),
tetradecyltrimethylammonium (TEDTA), and dode-
cyltrimethylammonium (DDTA) and hexadecyltrimethyl-
phosphonium (HDTP) cations. Poly(␧-caprolactone)
nanocomposites were prepared by in situ polymerization
using these modified saponites. The highest polymer
insertion was found for the saponite with the highest
charge, although the chain mobility of the nanocom-
posites was not significantly influenced by the charge
of the modified saponite. Quaternary ammonium and
phosphonium ions were also used as the organomodifier
of saponite which was further treated in poly (ethylene
oxide) by supercritical CO2 method [107]. Supercritical
CO2 treatment caused an increase in cationic mobility
leading to decreased activation energy.
Sinha Ray et al. [108] modified saponite with quater-
nary hexadecyl tri-n-butylphosphonium bromide for the
preparation of poly(butylenes succinate) (PBS) nanocom-
posites by melt intercalation technique. They reported the
structure–property relationship of these nanocomposites
145
by studying the rheological properties in detail, reporting
that a flocculated structure has a strong effect on material
properties. They also observed concurrent improvement of
the tensile, dynamic mechanical properties and decrease
in O2 gas permeability of the nanocomposites compared
to neat PBS [109]. The biodegradability of the nanocom-
posite was also studied and the degradation rate of the
nanocomposites was high (Fig. 26) because of the presence
of alkyl phosphonium surfactant. Many cracks appeared in
nanocomposite samples as compared to that of neat PBS
indicating improved degradability of nanocomposites.
Polymer modified saponite nanocomposites were pre-
pared by electrostatic layer by layer assembly of exfoliated
saponites and substituted ionic polyacetylenes [110].
Substituted polyacetylenes were prepared using poly(N-
octadecyl-2-ethylpyridinium bromide). These nanocom-
posites exhibited high conductivity as well as gas barrier
properties due to the synergistic combination of both sub-
stituted polyacetylene and smectites. Jaber et al. [111]
prepared novel bionanocomposites using saponite with an
amino acid, l-DOPA (l-3,4-dihydroxyphenylalanine). They
concluded that l-DOPA zwitterions were accommodated
vertically in the interlayer regions of saponite as a mono-
layer of partially superimposed species.
In general, insertion of polymer chains inside saponite
is favored by increasing charge on the clay, resulting in bet-
ter exfoliation of the polymer nanocomposites and thereby
enhancing the increment in physico-mechanical properties
of the corresponding nanocomposites.
3.1.3. Polymer nanocomposites using modified laponite,
their structure and properties
Laponite belongs to synthetic layered silicates under
2:1 smectite groups. It has a relatively small particle
size compared to MMT, with a basic unit consisting of
a layered hydrous magnesium silicate platelet of diam-
eter 25–30 nm with a thickness of approximately 1 nm.
Laponite and MMT have similar structures, but with an
interstitial charge deficiency created by the replacement
of Mg2+ with Li+ . The cation exchange capacity of laponite
is 0.55 mequiv. per gram. The chemical formula of laponite
is Si8 (Mg5.45 Li0.4 )H4 O24 Na0.75 .
Laponite can be covalently functionalized with mono-
and tri-alkoxy silanes carrying terminal reactive mathacry-
loyl group through a condensation reaction of the silanol
groups of laponites [112]. The modification of silylating
agents on laponite is shown schematically in Fig. 27.
Wheeler et al. [113] also used mono- and trifunctional
alkoxy silane for the modification of laponite. They used
various 3-aminopropyltrimethoxy silane and amino
propyldimethylethoxysilane as the silylating agent for
the covalent functionalization of laponite. It was reported
that trialkoxy silanes linked the clay sheets together,
increasing the clay basal spacing and surface area making
them nondispersible in water, while monoalkoxy silane
formed a flat monolayer on the edge of the clay plates
[114] leading to less effect on the basal spacing and surface
area of laponites. Therefore, monoalkoxysilane modified
laponite is recommended for nanocomposite applications.
Dimethyl-octylmethoxysilane was also used as silylating
agent on laponite [115].
146 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 26. Biodegradability of neat PBS and various nanocomposites sheets (a) under compost and (b) under soil field.
[109], Copyright 2003. Reproduced with permission from John Wiley & Sons Inc.
Ionic modification may be carried out on laponite using
dodecyl ammonium chloride and cetyltrimethyl ammo-
nium bromide (CTAB) [116,117]. Wheeler et al. [117]
prepared poly(methyl methacrylate) (PMMA) nanocom-
posites using CTAB modified laponoite in two ways:
reaction of methacrylate monomer with CTAB modified
laponite followed by in situ free radical polymerization
of methyl methacrylate or attachment of an ATRP initia-
tor followed by brush polymerization. The reaction with
CTAB yielded laponites with ca. 75 wt% of PMMA bound,
whereas the use of the ATRP initiator one yielded 68 wt%
of PMMA bound to laponite. The PMMA modified laponite
Fig. 27. Schematic representation of the coupling reaction of the mono-
functional and trifunctional silane molecules on the clay edges.
[112], Copyright 2004. Reproduced with permission from the American
Chemical Society.
was used for the formation of intercalated and exfoli-
ated, optically transparent PMMA nanocomposites using
a commercial PMMA. The room temperature storage mod-
ulus increased by 50% at 5 wt% laponite with no surfactant
and PMMA free-radical attachment (Fig. 28), whereas the
combined surfactant and polymer-treated clays showed
a modulus increase of 25% at 3 wt% concentration, indi-
cating that this particular surfactant treatment of clay
might be unnecessary and even detrimental to mechanical
properties.
Dual modifications using ionic and covalent techniques
were also applied on laponite to promote uniform dis-
persion of laponites in a polymer matrix. Following the
earlier work done on modification of clays and their use
in polymers by Bhowmick et al. [6], Mishra et al. used
CTAB as ionic modifier and octyl trimethoxy silane and 3-
aminopropyl triethoxy silane as covalent modifier for the
dual modification of laponite for the preparation of ther-
moplastic polyurethane (TPU) nanocomposites by both ex
situ and in situ methods [118]. They reported improve-
ment in tensile strength and elongation at break of the ex
situ prepared nanocomposites with the modified clay, with
less tethering compared to the in situ prepared nanocom-
posites. The dual modification of laponite is shown in
Fig. 29.
Mondal et al. [119] used dual modified laponite using
previous modifiers in the preparation of TPU nanocom-
posites. They reported that dual modified laponite is
more effective; equivalent to commercial MMT with ref-
erence to viscoelastic properties and thermo-dimensional
stabilities of nanocomposites. Laponite may also be
modified by cation exchange and edge modification
by alkoxysilanes grafting. Borsacchi et al. [120] used
double-chain surfactant dimethyldioctadecylammonium
chloride (2 C18 ) as cation exchange and alkoxysilane
employed 3-(trimethoxysilyl)propyl methacrylate, TSPM)
as edge modifier. The total schematic representation
of the arrangement of laponite platelets is shown in
Fig. 30.
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 147

Fig. 28. (a) Storage modulus (23 ◦ C) of PMMA blends at various concentrations of clays: () sodium laponite, () methacrylate/PMMA, and () ATRP/PMMA.
Error bars represent ±1 standard deviation for three measurements and (b) Storage modulus (23 ◦ C) of PMMA blends at various concentrations of clays:
() CTAB laponite, () methacrylate/CTAB/PMMA, and () ATRP/CTAB/PMMA. Error bars represent ±1 standard deviation of three measurements.
[117], Copyright 2006. Reproduced with permission from the American Chemical Society.

Fig. 29. Proposed structure of the dual modified laponite platelets (a) octyltrimethoxysilane as covalent modifier and (b) 3-aminopropyl triethoxysilane
as covalent modifier.
[118], Copyright 2011. Reproduced with permission from Elsevier Ltd.

Fig. 30. Schematic representation of the platelets arrangement in laponite RD (left) and after treatments with 2C18 (middle) and TSPM (right), R indicates
further TSPM units in the oligomeric chain.
[120], Copyright 2007. Reproduced with permission from the American Chemical Society.
148 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
By this technique, the adjacent plates are twisted,
resulting in increased disorder of the platelets and the con-
formational structure of the intercalated organic cation
chains, as well as reduction in the clay inter-platelet
distances. The double treatment facilitates the uniform
dispersion of laponites in nonpolar polymer matrices
[117,121].
Laponite clays may also be functionalized by ion
exchange with a free radical initiator – 2,2-azobis(2-
methylpropionamidine) hydrochloride (AIBA). This func-
tionalized laponite was used for the preparation of a series
of nanocomposites by seeded emulsion (co)polymerization
of styrene and butyl acrylate [121]. Polystyrene/laponite
nanocomposites may be prepared by an improved emul-
sion method, in which laponite surface was modified by 5%
macromonomer poly(ethylene oxide) 1000 monomethyl
ether methacrylate [122]. By this method, significant
increase in storage and tensile moduli was noted in both
glassy and rubbery state. The extent of exfoliation of
laponite increased as well.
Laponite can also be modified by l-DOPA (3,4-
dihydroxyphenylalanine). Jaber and Lambert [123]
used laponite and Melanin for the preparation of
l-DOPA/laponite nanocomposites. The aqueous poly-
merization of l-DOPA was considerably accelerated in the
presence of suspended laponite. Laponite clays were also
modified by short-chain aliphatic amines (diethylamine,
DEA or triethylamine, TEA) [124]. At high Laponite content,
extremely stable suspension was formed due to the gel
structure of the suspension and the particle shell of the
droplet.
It was concluded that dual functionalized laponite was
more effective, equivalent to commercial MMT, than their
singly modified counterparts in exfoliation of laponite in
polymer matrices. Larger improvement in properties of
the corresponding polymer nanocomposites was observed,
even in nonpolar polymer matrices.
3.1.4. Polymer nanocomposites using modified sepiolite,
their structure and properties
Sepiolite is a fibrous hydrated magnesium sil-
icate with the theoretical half unit-cell formula
Si12 O30 Mg8 (OH)4 (OH2 )4 ·8H2 O. Its structure is similar
to the 2:1 layered structure of MMT containing octahe-
dral sheets of magnesium oxide/hydroxide sandwiched
between two tetrahedral silica layers, except that the
layers lack continuous octahedral sheets [125,126]. The
structure of sepiolite is shown in Fig. 31. These tetrahedral
sheets are extended to a considerable distance in the “a”
and “b” directions, although at regular intervals along
the b axis, there is an inversion of tetrahedral sheets.
Hence, sepiolite is also known as an “inverted ribbon”. The
discontinuity gives rise to the presence of silanol groups
at the edges of the tunnels, resulting in the opening to
the external surface of the sepiolite particles. Its particle
length is about 4–8 mm. Sepiolite has a surface area of
about 300 m2 /g, with a very high density of silanol groups
and possesses a micropore channel of the dimension
0.36 nm × 1.1 nm along the length of the fiber. Because
of its high surface area, it has remarkable absorptive and
adsorptive properties and therefore it has been used in
preparation of polymer nanocomposites with improving
processability, dimensional stability, mechanical strength
and thermal resistance.
In our laboratory, Bhattacharya et al. [27] studied the
influence of different nanofillers, namely sepiolite, MMT,
etc., on the properties of natural rubber nanocompos-
ites. Of the clay-based NR nanocomposites investigated,
sepiolite based NR nanocomposite showed the maximum
improvement in modulus, due to the high surface energy
of sepiolite (38 mJ/m2 ) compared with the rubber. They
also analyzed the wear characteristics of natural rubber
nanocomposites containing sepiolite and carbon nanofiber
[127]. By analyzing the micrographs of the abraded sur-
face and the corresponding debris, it was revealed that the
specific wear rate of both the nanocomposites increased
beyond a critical fractal dimension, i.e., with increasing
structural complexity of the debris formed, although the
rate of wear decreased sharply for carbon nanofiber loaded
NR composite (Fig. 32a). They also studied the synergis-
tic effect of sepiolite and carbon nanofiber on morphology,
mechanical and dynamic mechanical properties of car-
bon black filled NR ternary nanocomposites [128]. These
ternary nanocomposites exhibited better improvement
in mechanical and dynamic mechanical properties com-
pared to individual NR/clay, NR/CNF and NR/carbon black
nanocomposites. These ternary nanocomposites showed
remarkable improvement in tear strength (18%), modulus
at 300% elongation (40%) and room temperature storage
modulus (326%) over the control nanocomposite. This is
due to the formation of the nanochannels through small CB
aggregates in the space between the clay/fiber, as shown
in Fig. 32b. They also addressed the wear behavior along
with dynamic mechanical characteristics of those ternary
nanocomposites [129]. Tribological characteristics showed
that wear loss decreased by 33% under low load and 75%
under severe wear conditions for the dual filler based
nanocomposites. Wear characteristics of NR sepiolite and
CNF nanocomposites in the presence of CB are presented
in Table 3. Viscoelastic measurements showed that the
ternary nanocomposite exhibited a high performance win-
dow for good wet skid and low rolling resistance.
Choudhury et al. [11] studied the difference in the
interaction parameter of hydrogenated nitrile butadiene
rubber (HNBR)-sepiolite nanocomposites with various sol-
vents. Dimethylbenzylalkylammonium chloride was used
to make the sepiolite more organophilic. The improve-
ment in mechanical, thermal and optical properties was
found to be best with a chloroform/methyl ethyl ketone
solvent, for which the difference in interaction parame-
ter of rubber-solvent and clay-solvent was lowest. Roy
et al. [130] reported the structure–property relationship of
in situ polydimethylsiloxane (PDMS)-sepiolite nanocom-
posites prepared by anionic ring opening polymeriza-
tion of octamethylcyclotetrasiloxane. This nanocomposite
showed improvement in tensile strength by 210%, modulus
by 460% and degradation temperature by 167 ◦ C compared
to neat PDMS rubber, attributed to the strong polymer-
filler interaction and greater degree of filler dispersion.
Comparison of stress–strain curves and TGA curves of neat
PDMS and PDMS/sepiolite nanocomposites is shown in
Fig. 33.
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 149

Fig. 31. Structure of sepiolite.

[11], Copyright 2009. Reproduced with permission from Elsevier Ltd.

Fig. 32. (a) Variation of specific wear rate with fractal dimension of the debris formed. [127], Copyright 2010. Reproduced with Permission from Elsevier
Ltd; (b) Microstructural development in nanoclay and nanofiber based nanocomposites in the presence of CB. [128], Copyright 2010. Reproduced with
permission from Springer.

Fig. 33. Comparison of (a) stress–strain curves and (b) TGA curves of the unfilled, filled PDMS and sepiolite.
[130], Copyright 2010. Reproduced with permission from Elsevier Ltd.
150 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187

Table 3
Wear characteristics of NR-nanoclay and -CNF nanocomposites in the presence of CB.

Sample Vol. loss × COF Temp. diff. Aggregate particle Intrinsic particle
designation 106 (m3 ) (◦ C)
FeretDmtr. Area Perim FeretDmtr. Area Perim
(mm) (mm2 ) (mm) (mm) (mm2 ) (mm)

High wear
NR 10.66 1.16 10 3.0 2.1 11.2 1.0 0.4 3.4
R-0/N3-50 5.04 1.18 11 2.8 2.1 11.0 1.1 0.4 4.7
NC-4/N3-30 2.59 0.96 3 1.9 0.9 8.4 1.2 0.4 3.9
NC-4/N3-40 2.51 0.95 5 1.5 0.8 7.4 1.1 0.3 3.7
NC-4/N3-50 2.22 0.93 7 1.5 0.6 5.3 0.9 0.3 3.0
NF-6/N3-30 2.19 0.93 3 2.2 0.9 8.0 1.2 0.4 3.6
NF-6/N3-40 1.76 0.91 4 1.5 0.7 6.4 0.9 0.3 3.3
NF-6/N3-50 1.26 0.90 5 1.4 0.5 5.0 0.8 0.3 2.8

Low wear
NR 0.58 1.26 1 2.8 2.6 11.0 1.3 0.9 4.3
R-0/N3-50 0.15 1.19 1 1.8 1.4 8.1 0.8 0.7 3.8
NC-4/N3-30 0.25 1.25 1 1.9 0.9 9.9 1.4 0.6 4.1
NC-4/N3-40 0.21 1.24 1 1.6 0.8 9.6 1.4 0.6 4.0
NC-4/N3-50 0.14 1.19 2 2.1 0.7 7.1 1.1 0.5 3.9
NF-6/N3-30 0.15 1.19 1 1.7 0.7 8.6 0.8 0.5 4.1
NF-6/N3-40 0.14 1.16 1 1.6 0.6 7.8 0.7 0.4 3.8
NF-6/N3-50 0.11 1.11 1 1.5 0.5 6.2 0.9 0.3 3.0

[129], Copyright 2010, Reprinted with permission from Springer).

NC-4 represents 4 organooclay loading in NR, NF-6 represents 6phr carbon nanofiber loaded NR and N3-30, 40 and 50 represent 30, 40 and 50 phr of CB.

Choudhury et al. [131] also studied the effect of different
nanofillers, such as Cloisite Na+ , Cloisite30B, Cloisite15A,
sepiolite and nanosilica on thermal, mechanical and
dynamic mechanical properties of HNBR nanocompos-
ites. The nanosilica based nanocomposite rendered highest
improvement in thermal stability, while the increment of
storage modulus was highest for sepiolite and Cloisite30B
based HNBR nanocomposite. They also studied the effect
of acrylonitrile content in HNBR and the effect of different
nanofillers, such as Cloisite30B, sepiolite and nanosilica on
mechanical and thermal properties of the corresponding
nanocomposites [132]. It was noted that the mechanical
and thermal properties gradually increased with increasing
acrylonitrile content, whereas a reverse trend on thermal
properties was found for the nanocomposites containing
different acrylonitrile content due to better level of dis-
persion of the fillers. However, mechanical and dynamic
mechanical properties of the nanocomposites exhibited
similar trend due to the stronger polymer-filler inter-
action through the formation of H-bonds. Variations in
mechanical and thermal properties of different fillers and
acrylonitrile contents of HNBR nanocomposites are shown
in Table 4. These were further investigated by varying the
diene content in the elastomer and it was found that 5.5%
diene content HNBR composites exhibit better improve-
ment in thermal, mechanical and dynamic mechanical
properties because of better dispersion of the fillers in the
matrix.
The influence of sepiolite nanoclay on the adhesive tack
strength of brominated isobutylene-co-p-methylstyrene

Table 4
Thermal, mechanical and dynamic mechanical properties of HNBR nanocomposites where S1 and S3 are the elastomer having acrylonitrile content 34%
and 43% respectively.

Properties S1-Filler nanocomposite S3-Filler nanocomposite

S1-B20-8 S1-30B-8 S1-A300-8 S3-B20-8 S3-30B-8 S3-A300-8

Thermal
Ti , ◦ C 460 (21) 455 (16) 455 (16) 446 (5) 452 (11) 454 (13)
Tmax , ◦ C 484 (24) 481 (21) 481 (21) 467 (1) 480 (14) 481 (15)

Mechanical
Mod. at 100% elong., MPa 2.2 (340%) 1.0 (100%) 0.6 (20%) 2.3 (155%) 0.9 (0%) 0.8 (0%)
Tensile strength, MPa 7.3 (265%) 11.5 (475%) 5.7 (185%) 10 (233%) 8.0 (167%) 8.0 (167%)

Dynamic mechanical
Storage modulus, MPa 1.0 (900%) 1.1 (1000%) 0.8 (700%) 0.6 (400%) 0.7 (480%) 0.2 (67%)
(log E )
at 25 ◦ C
Tg , ◦ C −13 (7) −14 (6) −14 (6) −12 (1) −12 (1) −11 (2)

[132], Copyright 2010, Reprinted with permission from John Wiley & Sons Inc.
The value within the parentheses represent the extent of improvement of properties in the case of nanocomposites over unfilled rubber. B20-8 indicates
sepiolite at 8 parts loading and A300-8 indicates nanosilica at 8 parts loading.
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 34. Effect of loading of sepiolite on adhesive tack strength of BIMS
rubber.
[133], Copyright 2010. Reproduced with permission from the American
Chemical Society.
rubber was also investigated in our laboratory [133]. It
was found that tack strength increased by about 300%
over the tack strength of neat BIMS rubber. Fig. 34 reveals
the variation of tack strength on loading of sepiolite in
BIMS rubber. The self-diffusion coefficient of BIMS rubber
decreased upon addition of sepiolite because of its rein-
forcing effect, although the average penetration depth of
the BIMS chains across the interface in the composites was
sufficient to establish the entanglement at either side of
the interfaces causing the more resistance of the entangled
chains to separate during stressing, leading to increase in
tack strength of the corresponding nanocomposites.
Lu et al. [134] modified sepiolite nanofibers with vinyl-
triethoxysilane (VTS) as a polymerizable silyl group and
further treated it with unsaturated polyester in forming the
nanocomposites. They reported that the reaction between
sepiolite nanofibers and unsaturated polyesters led to
increase in crosslinking density and thereby improved
the interfacial interaction between them, resulting in an
increase in thermal and flame retardant properties of the
nanocomposites.
Sepiolite was also modified with three different
organomodifiers-dimethyl benzyl hydrogenated tallow
quaternary ammonium (B2MTH), trimethyl hydro-
genated tallow quaternary ammonium (3MTH) and
N-hydrogenated tallow-1,3-diaminopropane (DIAMINT)
[135]. These modified sepiolites were used in the prepa-
ration of polyamide 6 (PA6) nanocomposites by melt
extrusion. The smaller organomodifier provided better
dispersion of sepiolite in a PA6 matrix and the higher
nanofiller content exhibited better interaction between
them resulting in improvement of 180% in elastic modulus
and 190% in heat deflection temperature respectively.
Sepiolite was also modified with trimethyl hydrogenated
tallow quaternary ammonium using different contents
of the modifier with respect to sepiolite and was further
used in the preparation of PA6 nanocomposites by melt
extrusion [136]. The catalytic effect of sepiolite was found
to decrease with increase in the amount of the modifier.
151
The elastic modulus and heat deflection temperature
of the nanocomposites increased about 2.5 times com-
pared to neat PA6 suggesting reinforcement efficiency
of organosepiolite on PA6. Nohales et al. [137] prepared
bisphenol A-based epoxy nanocomposites using pristine
sepiolite (Pangel S9) and the organophillic sepiolite (Pan-
gel B5). The initial thermal decomposition temperature
was unaffected by the addition of sepiolite, while flexural
strength was reduced due to the stress concentrations
by the sepiolite modifiers. Miltner et al. [138] prepared
modified sepiolite using amino functionalization on sepi-
olite by ␥-aminopropyltriethoxysilane. They applied an
innovative thermal analysis methodology for the prepa-
ration of poly(␧-caprolactum)/sepiolite nanocomposites
by grafting the polymer on modified sepiolite. As a result,
the dispersion quality of sepiolite into the polymer matrix
was strongly enhanced.
Sepiolite was also modified with 12-amino lauric
acid (ALA) and hexadecyltrimethylammonium bromide
(CTAB) and these modified sepiolites were further used
in the synthesis of polylactide nanocomposites by solu-
tion blending [139]. The random distribution of sepiolite
formed the exfoliated polylactide nanocomposites in either
case, although the improvement in thermal stability
is more in unmodified sepiolite nanocomposites than
that with modified sepiolites. This is attributed to the
prevention of the interaction between sepiolite surface
and polylactides by hydrophobic parts of the organic
modifiers.
Chen et al. modified sepiolite with ␥-
aminopropyltriethoxylsilane (KH550-Sp) and further
studied the effect of modification of sepiolite on thermal
properties of polyurethane (PU) nanocomposites [140].
They observed an improvement in glass transition tem-
perature of the hard segment and thermal stability of PU
nanocomposites with increase of modified sepiolites, as
shown in Fig. 35. However, the tensile properties before
and after aging showed decreased percentage loss in
tensile strength upon addition of the modified sepiolites
in PU.
Franchini et al. [141] used both unmodified and mod-
ified sepiolite based epoxy nanocomposites. They used
amino silane and glycidylsilane surface modified sepiolite
and investigated their influence and process development
to prepare epoxy nanocomposites. The best dispersion of
sepiolite was achieved using either emulsion process or
glycidyl functionalized sepiolite. A shear thinning behavior
was observed in sepiolite/epoxy nanocomposites exclud-
ing low content of filler. Sepiolite surface was also modified
with polyethylene glycol and d-˛-tocophenol polyethylene
glycol succinate and finally composites were prepared by
melt blending with poly(ethylene oxide) (PEO) [142]. It was
found that the modulation of interfacial (nucleation) and
confinement phenomena depended on the nature of the
sepiolite surface and its ratio in the composites, although
both had an opposing effect on the polymer’s crystalline
phase. This modulation tuned the final morphology, struc-
ture, elastic modulus and gas permeability of PEO.
Darder et al. [143] prepared biopolymer/sepiolite
nanocomposites by adsorbing chitosan on sepiolite in
acidic medium, as shown in Fig. 36. The adsorption
152 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 35. (i) DSC curves and (ii) TGA curves of: (a) PU, (b) PU/KH550-Sp (1%), (c) PU/KH550-Sp (3%) and (d) PU/KH550-Sp (5%) nanocomposites.
[140], Copyright 2012. Reproduced with permission from Elsevier Ltd.
isotherm showed significant coverage of chitosan on
sepiolite indicating a multilayer adsorption. This bio-
nanocomposites incorporated in carbon paste electrodes in
aqueous salt solution was an effective technique for rapid
assessment of ion exchange behaviors. It is also used as
membrane for different processes, such as separation of
ions and gases, as well as component in electrochemical
devices, such as fuel-cells and potentiometric sensors.
Recently, sepiolite was modified by alkyl benzyl
dimethyl ammonium chloride enhancing the compati-
bility between sepiolite and [poly(p-dioxanone), PPDO]
Fig. 36. Idealized representation of chitosan adsorption on the sepiolite
surface.
[143], Copyright 2006. Reproduced with permission from the American
Chemical Society.
and thereby facilitating dispersion of organo sepiolite in
PPDO matrix [144]. For ring opening polymerization of
p-dioxanone, triethylaluminum was used as catalyst. The
presence of Si OH on the surface of sepiolite facilitat-
ing the surface-initiated reaction to form organosepiolite
grafted poly(p-dioxanone). It was found that the incor-
poration of organosepiolite in PPDO matrix significantly
enhanced the crystallization rate, modulus and viscos-
ity of nanocomposites, although the nanocomposites still
displayed the liquid-like behavior as neat PPDO. Sepi-
olite was also modified by two different processes of
functionalization: adsorption of quaternary ammonium
salts or of amines on the sepiolite surface or grafting of
silane reagents by covalent bonding on surface silanols
[145]. The grafted sepiolite based polymer nanocomposites
of polypropylene (PP) and poly(butylene terephthalate)
(PBT) exhibited higher thermal stability compared to
that of adsorbed sepiolite. Thermal behavior of PBT was
not affected by sepiolite, whereas the PP nanocom-
posites revealed a polymer crystalline structure. Vargas
et al. [146] modified sepiolite by ion exchange with
cetyltrimethyl ammonium bromide (CTAB) use in the
preparation of polypropylene and polypropylene grafted
maleic anhydride nanocomposites by melt extrusion, com-
paring these with the corresponding unmodified sepiolite
based nanocomposites. The best interaction was found
for polyprolylene/polypropylene grafted maleic anhy-
dride/CTAB modified sepiolite nanocomposite, leading to
increased elastic modulus and thermal resistance. Also, this
composite decreased the maximum heat release rate com-
pared to neat polymer.
A cationic starch was used as a sepiolite modifier,
where the cationic functions were quaternary ammo-
nium ion with chloride as counter-anion [147]. This
cationic starch modified sepiolite was incorporated into
the plasticized starch matrix to prepare starch/sepiolite
nano-biocomposites. The well-nanodispersed morphology
provided a method to tune the plasticized starch proper-
ties, even with respect to the more common MMT-based
nano-biocomposites. This modified sepiolite also increased
the material stiffness.
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 37. Structure of hectorite.
Reproduced from nature.com/pj//journal/v43/n3/fig tab/pj2010141f2.
html.
Consideration of the preceding shows that compared
with layered montmorillonite, polymer chains have a bet-
ter chance not only of interacting with the external surface
of the sepiolite, but also of penetrating into the structure.
Those features facilitate dispersion of the clays in the poly-
mer matrix, and maintaining a well-entangled network.
Sepiolite also provides a pseudoplastic and thixotropic fea-
ture, making it a valuable material in multiple applications
to improve the processability, application or handling of
the final product.
3.1.5. Polymer nanocomposites using modified hectorite,
their structure and properties
Hectorite is a magnesium-lithium trioctahedral smec-
tite that occurs in the Mojave Desert near Hector, California.
It is a rare, soft, greasy, white clay mineral with a chemical
formula of Na0.3 (Mg,Li)3 Si4 O10 (OH)2 . Therefore, it con-
tains only silicates, while MMT is an aluminosilicate.
These materials comprise individual platelets containing
a metal oxide center sandwiched between two silicon
dioxide outer layers, as shown in Fig. 37. Alternatively,
It can be delineated as layers of negatively charged two-
dimensional silicate sheets detained together by cationic
species in the inter laminar space, which are susceptible
to ion exchange. The interlayer of hectorite is the most
expandable among all smectite clays and it is an excellent
adsorbing agent for polar organic molecules. It is an expen-
sive clay due to its unique thixotropic properties. The cation
exchange capacity of hectorite is 55 mequiv./100 g.
Hectorite is mostly used in cosmetics, as well as in
chemical and industrial material production. As with MMT,
it is also most commonly used in the preparation of poly-
mer/layered silicates nanocomposites because of its high
153
ion exchange capacity, surface area, aspect ratio com-
parable to MMT, thermally stable and rich intercalation
allowing them to be chemically modified and compatible
with polymer matrix.
Dubois et al. [148] prepared polyolefin nanocompos-
ites of varying polymers ranging from thermoplastics
to elastomers using hectortrimethylaluminum-depleted
methylaluminoxane modified hectorite. As hectorite has
high ion exchange capacity, lithium ion modified hec-
torite may be prepared, as used by Sandi et al. [149]
for the preparation of corresponding poly(ethylene oxide)
nanocomposites applied in Li ion cells. Hectorite was
also modified with cetyltrimethylammonium ion and
used in the synthesis of PS and PMMA nanocom-
posites by solution blending [150]. Hectorite may be
modified with two different quaternary ammonium
salts-styryldimethylhexadecylammonium chloride (VB 16,
denoted VB) and dimethylbenzyl hydrogenated tallow
chloride (10A) for the preparation of flame retardant PS
nanocomposites [151]. Such modifications significantly
enhanced the mechanical properties of PS nanocompos-
ites. PVC/hectorite nanocomposites were prepared using
tallow-triethanol-ammonium ion [152]. Upon incorporat-
ing such an organomodified hectorite in PVC matrix led
to increase in mechanical, thermal, dynamic mechanical
properties as well decrease in peak heat release rate of
the corresponding nanocomposites. Crystal polymorphism
in electrospun composite nanofibers of poly(vinylidene
fluoride) (PVDF) with both modified and unmodified hec-
torite was studied [153]. LucentiteTM STN and SWN were
used as modified and unmodified hectorite in PVDF matrix
by solution blending. Trioctyl methyl ammonium ion was
used as ionic organic modifier in hectorite. The nonpo-
lar ␣ crystal conformer was totally eliminated even with
a small amount of STN. Therefore, ionic organic modi-
fier made STN much more effective than SWN in causing
crystallization of the polar beta and gamma phases of
PVDF. Recently, Osman et al. [154] prepared biomedical
TPU/hectorite nanocomposites using octadecyltrimethy-
lammonium ion as the organomodifier in hectorite and
siloxane based TPU by a solvent casting technique. A
hydrophobic organohectorite with a low aspect ratio at
2 wt % was effectively delaminated in TPU matrix, pro-
viding additional hard domain connectivity and thereby
enhancements in tensile, tear strength and remarkably
improved creep resistance. However, at higher loading
(4 wt%), the morphology was changed in the microdomain
texture of TPU, resulting in poor effect on mechanical prop-
erties of TPU nanocomposites and dramatic increase in soft
microphase transition temperature and stiffening. There-
fore, it can be said that such an organohectorite acted as
a very potent interfacial compatibilizer. Onium salt was
used as the organomodifier for hectorite for the synthe-
sis of in situ polymerized PMMA nanocomposites [155]. A
minimum of 6% fluorohectorite concentration was found
to achieve reduction in peak heat release rate. Dimethyl
dehydrogenated tallow ammonium chloride was used to
modify hectorite and further treated with LDPE foam by
melt blending [156]. The nanocomposite foams exhibited
differences in the crosslinking degree, showing lower gel
content values (from 35% of the neat LDPE to as low as
154 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 38. The synthetic route for the formation of the terpolymer MAST.
[160], Copyright 2006. Reproduced with permission from Elsevier Ltd.
28% for the 7 wt.% hectorite foam), expansion behavior,
cell aspect ratio, with the foamed nanocomposites show-
ing more isometric type of cells, and cell wall texture with
regard to the neat LDPE foams. Timmaraju et al. [157] pre-
pared organo hectorite/polyamide 66 nanocomposites for
structural applications due to their high modulus and good
corrosive resistance. High hysteretic energy dissipation per
cycle and high induced stress in mist were found to cause
significant drop in fatigue life in mist compared with that
in air. Dimethyl dehydrogenated tallow ammonium chlo-
ride modified hectorite/LDPE exfoliated nanocomposites
were prepared by melt blending, which showed improved
thermal stability and mechanical properties compared to
neat LDPE foams [158]. Hectorite has also been modi-
fied with dimethyldioctadecylammonium chloride, which
acted as an emulsifier for the immiscible polystyrene
(PS)/poly(ethyl methacrylate) (PEMA) mixtures [159]. As a
result, PEMA was selectively adsorbed by organohectorite
which simultaneously decreased the domain size of PS
chains within PEMA/organo hectorite, facilitating efficient
mixing of polymers and thereby resulting in intercalated
structure and only one Tg in DSC thermograms. Zheng et al.
[160] used oligomerically modified hectorite in order to
prepare corresponding PS nanocomposites by melt blend-
ing. They prepared the modified hectorite designated as
MAST from maleic anhydride (MA), styrene (ST) and vinyl-
benzyltrimethylammonium chloride (VBTACl) terpolymer,
as shown in Fig. 38. They observed that the compatibility
between hectorite and PS increased through such a mod-
ification. The thermal stability of PS nanocomposites also
improved compared to neat PS. The peak heat release rate
decreased considerably upon addition of MAST-hectorite
in PS, as shown in Fig. 39.
Polyamide 66 (PA 66)/organomodified hectorite was
prepared by twin screw extruder and their mechani-
cal properties studied with different amounts of imbibed
moisture and organohectorite [161]. The moisture content
was found to decrease with increasing loading of organo
hectorite in PA 66,. It was also reported that the imbibed
moisture greatly improved the ductility of the nanocom-
posites and simultaneously reduced the tensile strength
and modulus.
A trialkoxysilane such as phenyltriethoxysilane has also
been used as organomodifier in hectorite. Hansen et al.
[162] studied the effect of unmodified and modified hec-
torite in water soluble polymers, such as PVA. However,
it was noted that the influence of unmodified hectorite
in PVA was higher in gas barrier properties than that of
modified hectorite. In addition, different types of alkoxy
silane have also been used for the modification of hec-
torite, such as ((methacryloxy)propyl)trimethoxysilane,
(3-acryloxypropyl)trimethoxysilane and tetraethoxysilane
[163]. Okada et al. [164] conducted ion exchange reaction
of 1,1 -dimethyl-4,4 -bipyridinium chloride (methylvio-
logen) with different layer charged hectorite for the
adsorption of organic compounds (N,N-dimethylaniline
and 2,4-dichlorophenol). They investigated that the
nanospace was different in each case because of the larger
adsorption capacity of 2,4-dichlorophenol than that of N,N-
dimethylaniline.
Hectorite/fluoroelastomer nanocomposites were pre-
pared by Maiti et al. [165] using laboratory synthesized
hectorite and natural hectorite, comparing their effects
on mechanical, dynamic mechanical, swelling and ther-
mal properties of the nanocomposites. Synthetic clay was
found to provide better improvement in the properties
than the natural hectorite filled nanocomposites. Alkyl
phosphonium ion modified hectorite was prepared in
supercritical CO2 and used in the preparation of polyamide
6 nanocomposites by melt blending and compared with
ammonium modified hectorite/polyamide 6 nanocompos-
ites [166]. The phosphonium ion modified hectorite was
found to be more thermally stable than the conventional
alkylammonium modified hectorite. However, the time
of ignition of the nanocomposites decreased more in the
case of ammonium-based compounds than for phospho-
nium based hectorite due to the presence of larger amount
Fig. 39. Heat release rate curves for PS MAST clay nanocomposites.
[160], Copyright 2006. Reproduced with permission from Elsevier Ltd.
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 40. (Left) synthetic pathway of O-hect; and (right) chemical structure
of the polycationic modifier.
[168], Copyright 2012. Reproduced with permission from Elsevier Ltd.
of degradation product in ammonium modified hectorite
originated from the more prominent Hofmann degradation
of the materials during melt blending.
Fluorohectorite is another type of hectorite containing
mixed silicates, oxides, fluorides of lithium and magne-
sium. It is also an effective candidate for the preparation
of polymer nanocomposites due to its high aspect ratio,
surface area and good ion exchange chemistry.
Zanetti et al. [167] prepared EVA/fluorohectorite
nanocomposites using octadecylammonium or aminodo-
decanoic acid as organomodifier of fluorohectorite. They
investigated that the former, i.e., octadecylammonium
modified hectorite formed exfoliated EVA nanocomposites
compared to later. The former showed delayed heat
release during combustion due to the barrier effect of
the dispersed nanolayers, whereas the later accelerated
the heat release rate due to its immiscible character.
PMMA/organofluorohectorite (o-hect) nanocomposites
by melt blending were prepared using polycationic qua-
ternary copolymer poly(2-(2-bromoisobutyryloxy)ethyl
methacrylate)-stat-(2-dimethyl-aminoethyl methacry-
late) (PBD) as organomodifier for fluorohectorite [168].
The total procedure is shown schematically in Fig. 40.
Such modified nanoplatelets offered significantly
improved toughness and stiffness of PMMA nanocompos-
ites compared to neat PMMA without reducing strength.
An enhancement in fracture toughness of about 66% was
observed due to the effective dispersion of organofluoro-
hectorite, as well as crack deflection, crack pinning and
debonding effects with platelets pull-out.
Octodecyl trimethyl ammonium-modified fluorohec-
torite/polymer nanocomposites were prepared in order
to study the shear-induced orientation by in situ X-
ray scattering [169]. It was found that a more highly
concentrated fluorohectoite dispersion showed less rate
dependence in orientation state. On the contrary, a mod-
erately lower concentration of fluorohectorite showed
shear rate dependent anisotropy factor, orientation angle
and partial relaxation of orientation upon flow cessa-
tion, although the effect of lower concentration of MMT
was more responsive to shear flow. It was concluded
155
that the rheological phenomena arose from a combina-
tion of flow-induced particle orientation and rate- and
time-dependent destruction or reformation of particle net-
works. N-(cocoalkyl)-N,N-[bis(2-hydroxyethyl)]-N-methyl
ammonium cations modified fluorohectorite was melt
blended with poly(l-lactide) (PLLA) to study the isothermal
melt crystallization behavior by time dependent infrared
and TEM [170]. The crystalline lamellae of the PLLA
nanocomposite grew up along the layered silicate, while
the orientation of the neat PLLA resulted in more disordered
orientation because of the absence of the organomodified
hectorite.
It may be assumed that as the cation exchange capacity
of hectorite is small, the intercalation of polymer within the
hectorite layers even after organomodification is compara-
tively low compared to other clays, namely MMT, laponite,
etc. However, hectorite has a distinct advantage over ben-
tonite/MMT in heat stability because its crystal structure
contains no catalytic (acidic) sites that can cause poly-
mer degradation at elevated temperatures. Fluorohectorite
showed higher reinforcement in polymer nanocomposites
due to its larger surface area and higher ion exchange
capacity.
3.1.6. Polymer nanocomposites using modified rectorite,
their structure and properties
Rectorite is also a smectite layered silicates. It is a type
of regularly interstratified clay mineral with alternating
pairs of dioctahedral mica-like layer (nonexpansible) and a
dioctahedral smectite-like layer (expansible) in a 1:1 ratio.
The width and length of single rectorite layer is of one
or several microns and the thickness is about 2 nm. The
organic or inorganic cations may be easily exchanged with
interlayer cations of rectorite. Importantly, pure rectorite
is hydrophobic leading to poor affinity with hydrophilic
polymer. Therefore, research on organically modified rec-
torite based polymer nanocomposites has been extensively
carried out.
Wang et al. [171] modified rectorite by cetyltrimethyl
ammonium bromide (CTAB) for the preparation of chi-
tosan/organic rectorite nanocomposite film by solution
mixing method. They investigated that in vitro drug
controlled release is slower for nanocomposite films com-
pared to neat chitosan films; the drug-delivery cumulative
release was shown to be proportional to the amount
and the interlayer distance of organorectorite. Therefore,
chitosan/organorectorite nanocomposite films provided
applications as antimicrobial agents, water-barrier com-
pounds, anti-ultraviolet compounds, and drug-controlled
release carriers in antimicrobial food packaging and
drug-delivery system. A natural rubber (NR)/rectorite
nanocomposite was prepared by Wang et al. [172] using
co-coagulating NR latex and rectorite aqueous suspen-
sion. They reported that the nanocomposite exhibited
lower tan ı peak value, slightly higher glass transition tem-
perature and little broader glass transition region than
neat NR. Most importantly, the gas barrier properties of
the nanocomposites were remarkably improved compared
to pristine NR, as shown in Fig. 41. Such a remarkable
improvement in barrier properties is attributed to the
increase of tortuosity of the diffusion path for penetrant
156 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 41. Correlation of experimental values of NR/rectorite nanocompos-
ites and Nielsen model (solid lines are Nielsen model).
[172], Copyright 2005. Reproduced with permission from Elsevier Ltd.
molecules and reduction of permeable amorphous rubber
content in the nanocomposites. They analyzed the perme-
ability results with Nielsen model [173] showing better
fitting of the permeability of the nanocomposites when the
aspect ratio of rectorite is 20–30. The nanocomposites also
exhibited unique stress–strain behavior and higher modu-
lus at the same stress compared to neat NR originated from
the reinforcement and the hindrance of rectorite layers to
the tensile crystallization of NR, as shown in Fig. 42.
The influence of rectorite and carbon black on free
volume and gas barrier properties in styrene-butadiene
rubber (SBR) has also been analyzed by positron annihila-
tion lifetime spectroscopy (PALS) [174]. However, layered
rectorite showed more promising effect on restraining
polymer chain mobility leading to decrease of free vol-
ume and gas permeation than carbon black. The decrease
in gas permeation is attributed to the effective dispersion
of rectorite clay in SBR resulting in increase in tortu-
osity of diffusion path by the platelet morphology of
rectorite and decrease of fractional free volume of the SBR
Fig. 42. Stress–strain curves for (a) pure NR; (b) NR/rectorite (100/5); (c)
NR/rectorite (100/10); and (d) NR/rectorite (100/20).
[172], Copyright 2005. Reproduced with permission from Elsevier Ltd.
Fig. 43. Effect of H+ -REC (CHCl = 2 mol/L) and CTA+ -REC (OD = 9.67 wt%)
content on the water absorbency.
[175], Copyright 2009. Reproduced with permission from Elsevier Ltd.
nanocomposites. Recently, rectorite showed superadsor-
bent properties in the polymer nanocomposites. Guar gum
grafted poly(sodium acrylate)/rectorite (GG-g-PNaA/REC)
superabsorbent nanocomposites were synthesized in
aqueous solution using acidified rectorite (H+ -REC), organ-
ified rectorite (CTA+ -REC) by cetyltrimethylammonium
bromide (CTAB) as organomodifier, ammonium persul-
fate as initiator and N,N -methylenebisacrylamide (MBA)
as crosslinker [175]. Water absorbency of acidified rectorite
and organomodified rectorite in GG-g-PNaA is presented in
Fig. 43. Effects of HCl concentration of H+ -REC, organomod-
ification degree of CTA+ -REC and content of REC on swelling
capabilities of the nanocomposites were reported. GG-g-
PNaA/CTA+ -REC nanocomposite exhibited higher swelling
capability and swelling rate constant with respect to GG-
g-PNaA/H+ -REC. Such an improved swelling capability of
the superadsorbent nanocomposites based on modified
rectorite and natural and biodegradable GG has provided
promising applications as water-manageable materials.
Four different chitosans (two fully deacetylated, with
low and high molecular weight) and their glycosylated
analogs based rectorite nanocomposites were prepared
[176]. The largest interlayer distance of rectorite of 3.35 nm
was achieved for the 2:1 mass ratio of low molecular weight
non-substituted chitosan to rectorite. The colloidal stabil-
ity of the nanocomposites loaded with DNA showed higher
colloidal stability and retention of DNA for the nanocom-
posites prepared from high molecular weight chitosans
than those from low molecular weight counterpart. On the
contrary, gene delivery efficacy in human cells was high-
est for the polyplexes and the nanocomposites containing
low molecular weight and trimer-substituted chitosans.
The effect of epoxide equivalent ranging from 188 to
1110 on microstructure of epoxy/rectorite nanocomposites
was studied by positron annihilation lifetime spectro-
scope (PALS) along with XRD [177]. XRD pattern showed
that exfoliated nanocomposite was formed at epoxide
equivalent >263. More importantly, PALS measurement
revealed that the free-volume concentration was remark-
ably decreased with increasing epoxide equivalent from
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 157

188 to 263 and the high sensitivity of positron annihila-

tion detected that the structure of rectorite was changed
by entering rectorite an epoxy.
Unmodified rectorite based PU nanocomposites with
mixed exfoliated and unexfoliated morphology were pre-
pared by a one-pot in situ PU synthesis [178]. PU
nanocomposite of 2 wt % rectorite showed maximum elon-
gation (1449%) and strength (32.66 MPa), i.e., 2.7 and
1.4 fold over those of neat PU, respectively. The inter-
facial interaction of rectorite lamella is responsible for
enhancing the strength and the inter-twisting of PU chains
with rectorite and the gliding over the reactorite lamellae
resulted in enhanced strain. Therefore, high performance
PU nanocomposites were prepared without modifying rec-
torite or using any complicated treatment for exfoliation
of rectorite in PU. Rectorite/thermoplastic polyurethane
rubber (TPUR) nanocomposites were prepared by melt
processing intercalation using two different quaternary
ammonium salts and benzidine as organo modifiers for
rectorite [179]. The two quaternary ammonium salts used
for organomodification were dodecyl benzyl dimethyl
ammonium bromide and hexadecyl trimethyl ammonium
bromide. Most of the modified clays formed exfoliated
nanocomposites and showed substantial enhancement
in mechanical properties of the TPU nanocomposites.
The maximum tensile strength was obtained for 2 wt %
organo rectorite (OREC) content of all TPU nanocompos-
ite, while tear strength increased gradually with increasing
loading of OREC. This work was further followed by a
study of dynamic mechanical properties, thermal and oil
resistant properties [180]. It was found that the storage
modulus, loss modulus and glass transition tempera-
ture increased gradually with increasing organo rectorite
loading from 1 to 8 wt%, as shown in Fig. 44. The ther-
mal stability of the nanocomposites increased by about
10 ◦ C at 10% weight loss compared to neat TPUR and
oil uptake of the nanocomposites was also remarkably
reduced compared to neat TPUR. Wang et al. [181] stud-
ied the effect of epoxidized natural rubber (ENR) on
the properties of rectorite/carbon black/natural rubber
nanocomposites by preparing the nanocomposites in two
ways – one was the direct incorporation of ENR and
the other was the incorporation of spray-dried REC/ENR
compound. They reported that REC formed more exfo-
liated structure in the spray-dried REC/ENR compound.
ENR increased both the crosslinking density as well as Fig. 44. The curves of dynamic mechanical properties for TPUR and its
the interfacial interaction between the REC layers and nanocomposites.
[180], Copyright 2005. Reproduced with permission from John Wiley &
the matrix for the composite filled with REC/ENR com- Sons Inc.
pound. Therefore, the mechanical properties, cutting and
chipping resistance and abrasion resistance of the com-
posites were greatly improved by the addition of REC/ENR tensile strength and water vapor barrier of PS/REC compos-
compound. ites were higher than those of PS/CREC composites as CREC
Rectorite was also modified by cationic guar gum (CGG) agglomerated more in PS/CREC than REC did in PS/REC
using a cation exchange reaction to obtain CGG modi- composites. Such composites are very useful in food pack-
fied rectorite (CREC) [182]. Both rectorite and CREC were aging application.
used as filler in plasticized starch matrix to form corre- It is assumed that as rectorite has a higher aspect ratio
sponding nanocomposites by casting process. The CREC and longer interlayer distance than MMT, it may form
formed stronger interaction with starch than REC leading promising intercalated or exfoliated polymer nanocompos-
to increase in relative viscosity for PS/CREC compared to ites with improved properties. One of the advantages of
PS/REC and increase in thermal stability of PS/CERC com- rectorite is that it showed superadsorbent properties in the
posite with increasing loading of CREC in PS. However, the polymer nanocomposites.
158 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 45. Structure of bentonite.
Reproduced from http://elements.geoscienceworld.org/content/5/2/99/
F2.large.jpg.
3.1.7. Polymer nanocomposites using modified bentonite,
their structure and properties
Bentonite is an absorbent aluminum phyllosilicates,
consisting mostly of MMT (montmorillonite). It is sedi-
mentary rock consisting of large proportion of clays with a
typical 2:1 layered structure (smectites) and a high content
of sodium and calcium ions situated between the layers, as
shown in Fig. 45. The quantity of smectites (major min-
erals for bentonite) is vital to improve the superiority of
bentonite. The presence of common impurities are-calcite,
feldspar, quartz, mica, organic matter provided adverse
effect on the thermal stability and cation exchange capacity
of bentonites [183,184]. However, in order to obtain higher
physical properties, such as mechanical, thermal properties
as well as to find optimum clarity in packaging applications,
purification of bentonite is essential. Therefore bentonite
clays were purified by sedimentation before surface mod-
ification step [185].
In recent years, preparation of organic-inorganic super-
absorbent composites has attracted considerable interest
owing to their natural abundance, low production cost,
high water absorbency and their wide range of applica-
tions in agriculture and horticulture. A wide variety of
polymers, including thermoplastics, namely polyolefins,
styrenics, etc., and thermosetting materials, such as epoxy
resins and phenolics have been used in the preparation of
polymer/bentonite nanocomposites.
Santiago et al. [186] prepared a series of superadsorbent
composite and nanocomposite hydrogels by copolymeriza-
tion of partially neutralized acrylic acid (SA) on bentonite
(BT) clay using potassium persulfate as an initiator and
N,N -methylenebisacrylamide as a crosslinker. They used
octadecylammonium chloride as an organomodifier for
sodium bentonite. They studied the effect of sodium ben-
tonite, organo bentonite and the content of bentonite in
Table 5
Absorption characteristics for the poly(SA)/BT.
Series A1 A2
BT (wt %) W∞ (g/g) t∞ (s) W∞ (g/g)
0.0 885 20 154
3.0 852 20 151
5.0 741 20 89
10.0 819 20 136
14.0 955 20 215
[186], Copyright 2007, Reprinted with permission from Elsevier.
copolymer gels on the swelling behavior and found that
equilibrium swelling (W∞ ) decreased in the case of small
amount of BT, while (W∞ ) increased with higher amount
of BT. However, best absorption (955 g/g) was obtained for
14 wt % sodium BT. Table 5 showed the absorption char-
acteristics of poly(SA)/BT superadsorbent composite and
nanocomposite. The time required for reaching equilib-
rium swelling (T∞ ) was independent of type of clay and
the amount of BT. The thermal stability of the composite
was higher than that of the nanocomposite due to the early
degradation of octadecylammonium ions of organo BT.
A BT clay was also modified with polymeric quaternary
ammonium salts – using p-xylenedichloride and diamine
[187]:
The use of polymeric quaternary ammonium salts as
organomodifier is very effective compared to ordinary
ammonium salts because of its higher thermal stabil-
ity and the faster ion exchange process. Melt blended
polymer nanocomposites were prepared using organo BT
and three linear polymers (polyamide, polystyrene and
polypropylene). Polyamide based 2 wt % of organo-BT
showed the maximum improvement in tensile strength
by 53% and Charpy impact by 140%, whereas the tensile
strength of polystyrene mixed with 2 wt% organoben-
tonite increased to 28% and Charpy impact enhanced to
25%, as shown in Table 6. Thermal stability of polyamide
and polystyrene based nanocomposites was higher com-
pared to their corresponding pristine polymer. However,
polypropylene/organobentonite composites did not show
any improvement in mechanical and thermal properties.
On the contrary, Filho et al. [188] modified polyca-
tionic BT clay with cetyl trimethylammonium bromide and
prepared melt mixing isotactic PP nanocomposites. They
reported that during thermal aging, PP based organomod-
ified BT showed higher thermal stability compared to that
of unmodified BT due to the formation of nanostructure.
However, the thermal degradation of PP with modified BT
was higher than the neat PP due to the acidic nature of
BT acting as catalyst to the PP oxidation, decomposition
of organic salts and interaction of BT with PP stabilizers.
Polyamide 6/bentonite/ammonium polyphosphate (APP)
melt mixing composites have been prepared in order to
achieve acceptable level of flame retardancy of polyamide
B1 B2
t∞ (s) W∞ (g/g) t∞ (s) W∞ (g/g) t∞ (s)
10 885 20 154 10
10 526 20 120 10
10 649 20 127 10
10 762 20 136 10
10 899 20 177 10
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 159

Table 6
Physical–mechanical properties of polymer nanocomposites.

Polymer Properties Content of pure bentonite (wt %) Content of organo-bentonite (wt %)

0 1 2 5 1 2 5

Tensile strength (MPa) 30.86 39.84 36.76 32.71 46.17 47.12 34.61
Polyamide 6 Charpy impact (kJ/m2 ) 31.78 28.15 24.12 21.71 68.13 76.12 51.20
Elongation at break (%) 28.75 22.15 18.31 10.81 35.00 34.61 17.22

Tensile strength (MPa) 17.50 18.80 18.41 16.50 21.15 22.34 17.72
Polystyrene Charpy impact (kJ/m2 ) 15.50 10.42 12.50 9.12 17.31 19.62 11.98
Elongation at break (%) 13.53 25.00 19.75 8.17 39.51 42.15 12.34

Tensile strength (MPa) 14.78 12.77 15.50 6.73 19.36 21.08 20.27
Poly-propylene Charpy impact (kJ/m2 ) 53.35 25.40 21.55 21.82 43.37 47.73 36.65
Elongation at break (%) 61.33 80.00 90.67 40.00 133.0 157.21 26.67

[187], Copyright 2005, Reprinted with permission from Elsevier.

6 [189]. The nanocomposites showed improvement in ther-

mal stability by 18 ◦ C as compared to neat polyamide
6 during degradation after 425 ◦ C; however, the decom-
position temperature decreased by 100 ◦ C on inclusion
of APP in PA6/BT nanocomposites. The char yield was
increased by 20% in PA6/Org-BT/APP while no significant
char was formed in PA6/Org-BT nanocomposites. Char yield
increased by 16% in the case of PA6/APP composite, and
Org-BT/APP was a combined system for flame retarding of
PA6. However, no significant effect of thermal stability and
char yield was noted by reducing the particle size of APP.
Oil-removal effectiveness of polymer/BT nanocomposites
was studied using ionenes (cationic polyelectrolytes) and
sodium BT and organo bentonite (Viscogel B8-S8), where
18 carbon chain hydrocarbon was used as a modifier [190].
The sodium BT based composite showed 70% oil removal,
while organo BT based polymer nanocomposite showed
90% oil removal. Generally, oil removal depends on several
factors, such as concentration of oil in the contaminated
water, mass of material and the contact time.
BT was also modified by dimethyldioctadecyl ammo-
nium (DMDA) chloride (Cl), tetrakisdecyl ammonium (TKA)
bromide (Br), and tributylhexadecyl phosphonium (TBHP)
bromide (Br) [191]. Using three different modified BT,
Seyidoglu and Yilmazer [191] prepared ternary nanocom-
posites of linear low-density polyethylene (LLDPE)/organo
BT/LOT and binary composites of organo BT/LOT by melt
mixing. A random terpolymer of ethylene, butyl acrylate,
and maleic anhydride with the trade name Lotader3210
(LOT) was used as compatibilizer. The BT modified by
DMDA and TBHP formed partially intercalated and exfo-
Fig. 46. Frequency (ω) dependence of G (ω)/G m (ω) and */*m of the
liated ternary nanocomposites, while BT modified by TKA
nanocomposites with DMDA organoclay.
was not intercalated during compounding with compati- [191], Copyright 2012. Reproduced with permission from John Wiley &
bilizer, as the crowded environment limited the diffusion Sons Inc.
of LOT chains through BT layers. Low frequency rheolog-
ical analysis the nanocomposites of 5 wt% TBHP modified LDPE, large surface area of organo BT, nano-level disper-
showed remarkable improvement in storage modulus (G ) sion and clay-matrix tethering, although the improvement
by 1393% and dynamic viscosity (*) by 339% compared in properties was higher for TBHP modified BT based
to neat LDPE, while that of 5 wt% DMDA modified BT nanocomposites because of its higher degree of exfolia-
showed 807% and 196% enhancement in G and *, as tion in LDPE compared to the DMDA modified BT based
shown in Figs. 46 and 47. Tensile strength, Young’s modulus nanocomposites.
and elongation at break increased by 16–9%, 33–41% and Organo BT based polyamide 66 nanocomposites were
75–144% for the nanocomposites of DMDA and TBHP mod- prepared by melt compounding with and without a
ified BT, respectively. Such an improvement in properties compatibilizer (LOT) [192]. Alkyl and aryl phosphonium
might be due to the strong interaction of organo BT with surfactant cations (tetraoctyl phosphonium bromide
160 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 47. Frequency (ω) dependence of G (ω)/G m (ω) and */*m of the
nanocomposites with TBHP organoclay.
[191], Copyright 2012. Reproduced with permission from John Wiley &
Sons Inc.
(TO-P Br) and benzyltriphenyl phosphonium chloride
(BZLTP-P Cl) were used for the modification of BT after
its purification by sedimentation to avoid problem of low
temperature decomposition of quaternary ammonium
organoclays usually used in polymer nanocomposite.
However, the aliphatic group modified BT showed
more compatibility with PA66 compared to aromatic
group modified BT. Therefore, TO-P modified BT/PA66
nanocomposites showed higher tensile strength, modulus,
elongation at break and impact strength compared to
the nanocomposites of BZLTP-P-modified BT. Ouaad et al.
[193] prepared partially exfoliated PMMA/organo BT
nanocomposites by in situ intercalative polymerization
initiated by a neutral Ni(II) ␣-benzoinoxime complex
(NBO) as a single component initiator in dioxane at room
temperature. Significant improvement in thermal stability
and glass transition temperature (Tg ) by 45 ◦ C and 10 ◦ C of
the nanocomposites respectively were noted compared to
neat PMMA. They further prepared copolymer based poly-
mer nanocomposites using organo BT. They modified BT by
hexadecylammonium chloride and used as a filler for the
preparation of 32 mol% 4-vinyl pyridine (4VP) and methyl
methacrylate (MMA) containing copolymer (PMMA4VP32)
based exfoliated nanocomposite via solution intercalation
method. The copolymer was prepared radically in the
presence of a neutral Ni(II) ␣-benzoinoxime complex as
initiator. A significant improvement in thermal stability
(28 ◦ C onset degradation temperatures) and glass transi-
tion temperature Tg (12–18 ◦ C) of the nanocomposites was
observed as compared to the neat copolymer.
Stearyldimethylammonium chloride salt was also used
for the modification of BT and the preparation of cor-
responding flame retardant high-density polyethylene
(HDPE) nanocomposites [194] by injection molding using
polar compatibilizer, maleic anhydride grafted polyethy-
lene (polybond-3009). BT was modified by different
percentages of quaternary ammonium salt, 100, 125, and
150% based on cation exchange capacity of BT. It was
reported that with increase in organo salt content in
BT improved the dispersion of BT in HDPE matrix and
thereby enhanced the thermal stability as well as the
flame retardancy of the corresponding nanocomposite. The
peak heat release rate gradually decreased with increase
in the percentage of ammonium salt in BT. This is due to
increase in catalytic effect of the corresponding organo BT
in HDPE with increasing percentage of ammonium salt in
BT, thereby forming more protective layer as a barrier to
combustion.
The economic advantages as well as the identical
structure to MMT make bentonite a logical choice for an
alternative nanofiller for the reinforcement of low cost
nanocomposites. In addition, the aliphatic group modified
BT showed more compatibility with polar polymers com-
pared to aromatic group modified BT. Nonpolar polymer
based BT nanocomposites displayed much weaker proper-
ties compared to polar polymer based BT nanocomposites,
perhaps due to the reduced interaction between BT and
nonpolar polymer chains.
3.1.8. Polymer nanocomposites using modified
vermiculite, their structure and properties
Vermiculite (VMT) is a mica-type silicate with a 2:1
structure, meaning it has 2 tetrahedral sheets for every one
octahedral sheet. Vermiculite has a large internal surface,
high cation exchange capacity at 100–150 mequiv./100 g
and higher negative charge on the silicate layers compared
to other 2:1 phyllosilicates. Importantly, organomodifi-
cation of VMT is difficult by ion exchange process with
other organic molecules owing to its high interlayer charge
density. It is generally used as a packaging material for anti-
shock and is abundant and lesser expensive than MMT,
hectorite or saponite. Vermiculite clays are weathered
micas in which the potassium ions between the molecular
sheets are replaced by magnesium and iron ions, as shown
in Fig. 48.
VMT was modified by (oleyl bis(2-hydroxyethyl) methyl
ammonium) chloride, silane grafting (␥-glycidoxypropyl
trimethoxysilane) and combining silane grafting and alky-
lammonium cation intercalation followed by melt com-
pounding with poly(l-lactic acid) (PLLA) [195]. The type
of modification and the effect of modified VMT concentra-
tion on nanostructure and properties of PLLA/organo-VMT
(OVMT) nanocomposites were investigated. The double
modification of VMT resulted in a high level of exfoliation
compared to individually modified VMT due to the strong
interaction between the end groups of PLLA and VMT
containing epoxy groups, as shown in Fig. 49. Cold crys-
tallization temperature and glass transition temperature
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 48. Structure of vermiculite.
Reproduced from http://pubs.usgs.gov/of/2001/of01-041/htmldocs/
images/verstru.jpg.
were slightly lower, while crystallization enthalpies and
thermal stability increased in the nanocomposites com-
pared to pristine PLLA. However, the crystallinity and the
reduction of fire hazards were unaffected by the presence
of OVMTs.
Zhang et al. [196] prepared biopolymer chitosan/VMT
nanocomposites by solution intercalation process using
three different modified VMT-hydrochloride modified VMT
(HVMT) nanocomposites, sodium modified VMT (NVMT)
and cetyl trimethyl ammonium bromide (OVMT). In all
cases, silicate layers were randomly dispersed in the
matrix in nano-dimension level. However, the dramatic
improvement in thermal stability was observed for chi-
tosan/HVMT nanocomposites compared to the other two
chitosan nanocomposites because of the better dispersion
Fig. 49. TEM images of (a) PLLA/OVMT2, (b) PLLA/OVMT5, (c) PLLA/OVMT10, (d) PLLA/OVMTS2, (e) PLLA/OVMTS5 and (f) PLLA/OVMTS10 nanocomposites
prepared by melt blending at 50 rpm for 5 min.
[195], Copyright 2013. Reproduced with permission from Elsevier Ltd.
161
of HVMT and interaction of HVMT with chitosan. Qian
et al. [197] synthesized quaternary ammonium salts with
tertiary amine groups for the modification of VMT as
catalytically active modifiers for PU. By this technique,
they explored the efficacy of interlayer tertiary amines as
novel catalytic modifiers to enhance the VMT exfoliation
in bulk polymerized thermoset elastomers through dis-
persing polyol with catalyst modified VMT. This method
resulted in a high degree of intercalation/exfoliation of
modified VMT in PU matrix. However, the micro phase
separated structure of PU matrix remained almost unaf-
fected after the addition of VMT. PU nanocomposites
having 5.3 wt% of Q-50 VMT showed 390% improvement
in tensile modulus and 40% reduction in CO2 perme-
ability. Such an improvement in properties makes them
promising materials for coating and adhesive applications.
They further prepared VMT-reinforced PU nanocomposites
using cetyltrimethylammonium bromide and octade-
cyl bis(hydroxyethyl)methylammonium chloride as the
organomodifier for VMT [198]. Hexadecyltrimethylammo-
nium bromide (HDTMAB) modified VMT was used as the
filler for the preparation of ternary blend composites of
PLLA/PMMA/PEO [199]. It was found that OVMT showed
good interaction and acceptable dispersion in the ternary
polymer matrix without altering the crystal structures
of the PLLA/PEO constituents. The overall crystallization
kinetic rates were increased while the activation energy
was lowered by the addition of OVMT in the ternary blend.
Cation exchanged VMT (Mn+ -VMT), where M is Li+ ,
Na , K+ , Mg2+ , Ca2+ or Al3+ , has been used for the prepa-
+
ration of superadsorbent exfoliated nanocomposites by
the solution radical polymerization of natural guar gum,
partially neutralized acrylic acid with ammonium persul-
fate as the initiator and N,N -methylene-bis-acrylamide as
the crosslinker [200]. All Mn+ -VMTs showed remarkable
enhancement of water absorption of the nanocompos-
ites compared to neat GG-g-poly(sodium acrylate) matrix,
although the enhancement was maximum for Al3+- VMT
based nanocomposite. These nanocomposites were found
to exhibit intriguing overshoot swelling characteristics in
a multivalent saline solution and acidic pH solution, and
162 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 50. Structure of kaolinite.
Reproduced from http://matsec.ustb.edu.cn/uploadFiles/natural/
Structure/gaolingshi.gif.
showed switching pH-responsive behaviors in buffer solu-
tions between pH 2 and pH 7.2.
Comparison of MMT and VMT shows that VMT has
higher charge on silicate layer over that of MMT that
may lead to higher stability of VMT. Moreover, the cation
exchange capacity and aspect ratio of VMT are relatively
higher than MMT. It is noted that the double modification
of VMT resulted in the higher level of exfoliation compared
to individually modified VMT due to the strong interac-
tion between the end groups of polymer chains and two
organomodifiers of VMT.
3.2. Polymer nanocomposites using modified kaolinite,
their structure and properties
Kaolinite belongs to the 1:1 layer silicates category. The
general structure of the kaolinite group is composed of sili-
cate (s) sheets bonded to aluminum oxide/hydroxide layers
called gibbsite (g) layers. The silicate and gibbsite lay-
ers are tightly bonded together. Water molecules situated
in between the sheets holds them together by hydrogen
bonding. Different cations present, such as K+ , Ca2+ and
Mg2+ in kaolinite neutralizes the negative charges of the
oxide ions. The structure of kaolinite is shown in Fig. 50
displaying two layers of stacked sheets. It is layered
Fig. 51. Schematic representation of the proposed structure models for silane-modified kaolin/silica core–shell nanoparticle procedures.
[207], Copyright 2009. Reproduced with permission from Elsevier Ltd.
silicates with chemical composition Al2 Si2 O5 (OH)4 . Kaoli-
nite has a low shrink-swell capacity and a low cation
exchange capacity (1–15 mequiv./100 g). Its name proba-
bly derived from the Chinese word kauling, meaning high
ridge, the name of a hill near Jauchau Fu, China, where the
material was mined centuries ago.
The modification of kaolinite hydroxyl surfaces has been
studied over a range of intercalating agents. The hydroxyl
groups at the particle edges are considered to be the
most reactive sites of kaolinite surface, engaging approx-
imately 10% of the whole surface [201]. Frost et al. [202]
reported the intercalation of potassium acetate in kaolinite
causing disorder. Recently, Methods of silylation of kaoli-
nite have been established by intercalating urea, dimethyl
sulfoxide, hydrazine and so on with kaolinite to expand
its interlayer space, facilitating further chemical graft-
ing of organic molecules with interlayer hydroxyl groups
[203]. However, as the organic modifiers electrostatically
bind with kaolinite, the adhesion is not strong. Therefore,
acid hydrolysis and various plasma treatments have been
attempted, resulting in additional reactive hydroxyl groups
on kaolinite surface to make it more reactive [204,205].
Such a modified kaoline has been used as the reinforc-
ing filler in polymer matrix to improve the mechanical
properties of the nanocomposites and reduce the effective
cost of the products [206,207]. Zhang et al. [207] estab-
lished a new method for the modification of kaolin by
preparing silylated kaolin/silica core–shell nanoparticles
and further used the modified silica to fabricate biodegrad-
able nanocomposites, showing remarkable improvement
in mechanical properties. The proposed model for the
silane-modified kaolin/silica core–shell nanoparticle pro-
cedures is schematically shown in Fig. 51. The weak
interaction force between filler and polymer matrix also
can be overcome using a modification with urea, then
with an ammonium salt and a surface treatment with
a silane coupling agent [208]. Such a surface treatment
of kaolin leads to improved mechanical properties and
the thermal stability of the nanocomposites compared to
neat polypropylene. Kaolin can also be modified thermally,
leading to a change in the mineralogical and chemical
composition. Kaolin was heated to >1000 ◦ C for a long
time followed by addition in polyethylene (PE) agricultural
films to improve their infra red barrier properties [209].
Another procedure for the modification of kaolinite is acid
treatment leading to improve the catalytic properties of
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 163

kaolnite. As the catalytic behavior is determined by the

nature of the surface, acid treatment leads to the modi-
fication of original active sites [210].
Another important member of the kaolin sub group
of minerals is halloysite clay. Halloysite is also 1:1 lay-
ered silicates combining the geometry of nanotubes and
the chemistry of kaolinite. It has a similar composition
except that it contains additional water molecules between
the layers. It also exhibits a two-layer structure. Gener-
ally, the external surface of the groups has a tetrahedral
sheet composed of siloxane groups whereas the inner sur-
face occupied by octahedral sheets of alumino groups. The
mismatch of the alignment of the two layers results in
cylindrical from. The most significant advantage of hal-
loysites compared to other layered silicates is the ease
with which they dispersed in a polymer matrix because
of weak secondary interaction among the nanotubes. Tang
et al. [211] studied the effect of processing methods on
the fracture toughness of as-received and phenylphos-
phonic acid (PPA) treated halloysite-epoxy composites.
It was demonstrated that composites with added hal-
loysite had a higher fracture toughness than that of neat
epoxy. It was reported that large-sized particle clusters
occurred during mechanical mixing process were signif-
Fig. 52. Structure of chlorite.
icantly decreased by ball milling homogenization and a Reproduced from http://pubs.usgs.gov/of/2001/of01-041/htmldocs/
much more uniform dispersion was obtained in the cured images/chlstru.jpg.
composites. In the case of PPA treated composite, hal-
loysite nanotube changed to nanoplatelets and thereby 2:1 sandwich structure (2:1 sandwich layer = tetrahedral
increasing the total contact area between halloysite and –octahedral–tetrahedral = T–O–T· · ·), as shown in Fig. 52.
epoxy leading to enhance fracture toughness. Zhao et al. As in other 2:1 clay minerals, a chlorite’s interlayer
[212] also used ␥-methacryloxypropyltrimethoxysilane for space (the space between the layers filled by a cation) is
the modification of HNT and used the modified HNT in composed of (Mg2+ , Fe3+ )(OH)6 . This (Mg2+ , Fe3+ )(OH)6
the preparation of polystyrene (PS) nanocomposites by unit is more commonly referred to as the brucite-like
in situ polymerization showing improvement in thermal layer, due to its closer resemblance to the mineral brucite
properties. Improvements in Young’s modulus, impact (Mg(OH)2 ). Therefore, chlorite’s structure appears as
strength and glass transition temperature were observed in follows: –T–O–T–brucite–T–O–T–brucite with the crystal
poly(hydroxybutyrate-co-hydroxyvalerate) using similar unit containing two silica tetrahedral sheets and two
modified technique [213]. Rooj et al. [214] prepared ‘green’ magnesium-dominated trioctahedral sheets, giving rise to
nanocomposites by mechanical mixing natural HNT and 2:1:1 or 2:2-type structure.
natural rubber (NR). Bis(triethoxysilylpropyl)-tetrasulfide An older classification divided the chlorites into two
used as silane coupling agent of HNT for the enhancement subgroups: the orthochlorites and leptochlorites. The
of the properties of the nanocomposites. They observed terms are seldom used and the ortho prefix is somewhat
that the onset thermal decomposition temperature was misleading as the chlorite crystal system is monoclinic and
improved by approximately 64 ◦ C with the addition of 10 not orthorhombic.
parts HNT per hundred of rubber due to the uniform dis- Although chlorite based polymer nanocomposites have
persion of HNT in NR matrix. not been studied to the extent of other clays, Xie et al. [13]
It may be inferred that kaolinite has low shrink-swell reported starch/chlorite nano-biocomposites. They also
capacity, low cation exchange capacity and smaller basal reported the effect of chlorine in Chitosan matrix; however,
spacing compared to smectite clays which may lead to the improvement in properties was not significant.
lower interaction with a polymer. Also, as the organic Chlorite is less abundant than the smectite clays and
modifiers are electrostatically bound with kaolinite, the therefore polymer nanocomposites based on chlorite have
adhesion is not strong. Therefore, the unique structure and been less studied.
properties of kaolinite compared to other clays results in
some difficulties in dispersing the particles in polymeric 4. Polymer nanocomposites using modified
matrices. synthetic clays, their structure and properties

4.1. Polymer nanocomposites using modified synthetic

3.3. Polymer nanocomposites using modified chlorite,
montmorillonite and hectorite: their structure and
their structure and properties
properties

The typical general formula of chlorite is: Along with naturally occurring MMT, laboratory syn-
(Mg,Fe)3 (Si,Al)4 O10 (OH)2 ·(Mg,Fe)3 (OH)6 . Chlorites have a thesized MMT has also used in the preparation of
164 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187

Table 7
Different compositions for montmorillonite-layered silicate synthesis with the elemental analysis of products.

Sample Starting materials Elemental analysis (%) (SEM-EDX) Elemental analysis (%) (XRF)

Na 5.10
Mg 2.26
Commercial sodium Al 20.27
NA –
montmorillonite Si 63.98
Ca 0.87
Fe 7.53

Na 2.32 Na2 O 3.02

0.028 M Mg (II)
Mg 6.76 MgO 5.85
M SiO2
SM-A Al 13.99 Al2 O3 15.45
0.015 M Al(OH)3
Si 76.93 SiO2 71.07
M NaCl
Cl 1.53

0.028 M Mg (II) Na 1.82

M SiO2 Mg 11.0
SM-B –
0.015 M Al(OH)3 AL 6.65
M NaCl Si 80.52

0.028 M Mg (II) Na 3.58

M SiO2 Mg 13.76
SM-C –
0.015 M Al(OH)3 Al 12.08
M NaCl Si 70.58

0.028 M Mg (II) Na 2.80

M SiO2 Mg 9.65
SM-D –
0.028 M Al(OH)3 Al 14.85
M NaCl Si 72.70

Na 5.39 Na2 O 3.86

0.028 M Mg (II)
Mg 13.38 MgO 12.90
M SiO2
SM-E Al 7.68 Al2 O3 10.55
0.01 M Al(OH)3
Si 73.55 SiO2 69.92
M NaCl
Cl 2.16

0.02 M Mg (II) Na 2.38

M SiO2 Mg 8.03
SM-F –
0.015 M Al(OH)3 Al 7.54
M NaCl Si 82.04

0.036 M Mg (II) Na 2.55

M SiO2 Mg 14.27
SM-G –
0.015 M Al(OH)3 Al 9.66
M NaCl Si 73.53

[215], Copyright 2008, Reprinted with permission from Elsevier.

polymer-MMT nanocomposites. Maiti and Bhowmick
[215] synthesized MMT in the laboratory using solution of
Mg(OH)2 , Al(OH)3 and NaCl. To maintain pH 9–10, water
was added to the above slurry followed by hydrother-
mal crystallization at 325 ◦ C for 2 h and vacuum drying
to obtain the synthetic MMT. They prepared different
synthetic MMT by varying the concentration of the start-
ing materials. Table 7 shows the varying composition
for synthetic MMT. It was found that SM-B, SM-C, SM-
F and SM-G combinations did not yield layered silicates
as the characteristic peak for smectite-type layered sili-
cates were not found in the 2–10 degree region. Using this
synthetic MMT, they prepared corresponding fluoroelas-
tomer nanocomposites and their findings were compared
with the fluoroelastomer nanocomposites obtained from
commercial MMT. Synthetic MMT filled nanocomposites
exhibited better properties compared to commercial filled
MMT based nanocomposites (Fig. 53).
However, among all the clays, FSM-A4 showed best
improvement of properties of the corresponding nanocom-
posites due to its better exfoliation in fluoroelastomer,
lower particle size, high surface area and larger gallery-
gaps, leading to provide better polymer-filler interaction
compared to other synthetic as well as natural clays of the
same group.
Laponite is one of the most used synthetic hectorites
in the preparation of polymer nanocomposites. Along
with hexadecyltrimethylammonium bromide modified
laponite, Kunipia-MMT and two commercial organomodi-
fied MMTs-Nanomer I.30E modified with primary octade-
cylammonium ions and Cloisite10A modified with qua-
ternary dimethyl benzyl hydrogenated-tallow ammonium
ions were used in the preparation of corresponding PET
nanocomposites by melt mixing technique [216]. It was
found that among all the clays, organo MMT-I.30E induced
higher crystallization rates, lower activation energy lead-
ing to better effectiveness regarding the PET crystallization
compared to other types of organo clays. This is due to
its better dispersion and exfoliation of clay nanolayers
into the PET matrix. The synthetic hectorite (Lucentite
SPN) modified with poly(oxypropylene) methyl diethyl
ammonium chloride ion [(C2 H5 )2 (CH3 )N+ (O-iPr)25 ]Cl− was
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 165

Fig. 53. (a) Comparison of physico-mechanical properties, (b) log E vs. temperature plot and (c) tan delta vs. temperature plot of different montmorillonite-
like layered silicate based nanocomposites. F, FNA4, FSM-A4, FSM-D4 and FSM-E4 represent neat fluoroelastomer, 4 parts NA, 4 parts SM-A, 4 parts SM-D
and 4 parts SM-E.
[215], Copyright 2008. Reproduced with permission from Elsevier Ltd.

used to study the thermal and thermo-oxidative stability

of vinylidene chloride-co-vinyl chloride copolymer (VDC-
VC) nananocomposites [217]. An exfoliated structure was
formed, showing a single step thermal degradation in
nitrogen atmosphere and a two-step thermo-oxidative
degradation in air atmosphere. The first stage degrada-
tion in air atmosphere was similar to the degradation in
nitrogen atmosphere, in which the thermo-oxidative sta-
bility of VDC-VC/SPN nanocomposites was affected by the Fig. 54. Preparation of K-hectorite from Na-hectorite by ion exchange
ternary ammonium salt and oxygen rather than its mor- method.
[219], Copyright 2010. Reproduced with permission from the American
phology. However, in the second degradation stage in air Chemical Society.
atmosphere, both the enhanced thermo-oxidative stability
and the flame-retardant ability of VDC-VC/SPN nanocom-
posites were related to the morphology of the composites. the interlamellar reactivity of a synthetic fluorohectorite
Polystyrene nanocomposites with novel shear stiffness by simple cation exchange (Fig. 54). Initially, Na+ cation
were synthesized using mica-like nanoplatelets from syn- was exchanged with Mg2+ to yield a solid content of
thetic hectorite [218]. This mica-like material exhibited 10 wt% followed by exchanged with K+ ions to provide
huge aspect ratios (350) and was prepared by a fast and K-hectorite having solid content of 3 wt% according to the
facile process from a synthetic Na fluoro-hectorite. The procedure reported by Möller et al. [219]. The possibility
essence of this procedure is the nonreversible alteration of of switching from highly hydrated to collapsed interlayers
166 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 55. (a) TGA of oligomeric modifier (䊉), surface modified K-hectorite (×), pure PS (), solution blended PS nanocomposite (), and melt blended PS
nanocomposite () and (b) Comparison of heat release rates (HRRs) for pure PS (), solution blended K-hectorite (䊉) nanocomposite and melt blended
K-hectorite () nanocomposite.
[218], Copyright 2011. Reproduced with permission from the Royal Society of Chemistry.
facilitated a highly efficient exfoliation in the swollen
state, while providing shear-stiffness in the collapsed
state. As a result, this method restricts cation exchange in
the mica-like nanoplatelets to the outer surfaces leading
to significant advantage for use in the nanocomposites
since the easy inflammable organic content of the filler
is significantly reduced (40 wt %) as compared to con-
ventional organoclays, such as MMT. The filler was used
in the preparation of PS nanocomposites by solution
blending and melt blending methods. The nanocomposites
exhibited significantly higher mechanical, thermal and
fire retardant properties compared to conventional clay
based nanocomposites. However, the solution blended
nanocomposites showed higher improvement in Young’s
modulus (16%) compared to melt blended PS nanocom-
posites. The onset temperature of the solution blended
nanocomposite was increased by 11 ◦ C, whereas the onset
of the melt blended nanocomposite was shifted by 7 ◦ C
and the PHRR for solution blended nanocomposites was
reduced by 47% (Fig. 55). The higher improvement in
properties for solution blended PS nanocomposites was
due to the better dispersion of the fillers.
The advantages of using synthetic clay over natural
clay are the smaller size (usually less than 50 nm in length)
and also the narrower distribution in size, which facilitate
easier encapsulation of polymer chains to enhance their
interaction with polymer, as well as improve the proper-
ties of polymer nanocomposites. With synthetic clay, the
control over the geometric arrangement of the layered
clays can be achieved so that tunability of the properties
can be accomplished in wider applications of polymer
nanocomposites. On the contrary, the advantages of the
natural clays are their easy availability and low cost.
4.2. Polymer nanocomposites using modified layered
double hydroxide, their structure and properties
Layered double hydroxide is an important synthetic clay
with a structure derived from brucite (Mg(OH)2 ). Brucite
layers are formed by octahedrons in which the center
Mg2+ is octahedrally surrounded by hydroxyl groups. The
isomorphous substitution of some divalent cations by
trivalent cations gives brucite-like layers with the positive
charge, counter balanced by some interlayer anions and
water leading to a neutral LDH structure [220]. The gen-
eral formula of LDH is [MII 1−x MIII x (OH)2 ]x+ (An− )x/n ·mH2 O,
where wherein MII , MIII , and A represent divalent cation
(Mg2+ , Ca2+ , Zn2+ , Cu2+ , Co2+ , Ni2+ , etc.), trivalent cation
and the interlayer anion, respectively. The interlayer anion
An− (Cl− , CO3 2− , NO3 − , etc.) may vary over a wide range
and has a high exchangeable capacity. The value of x lies
in the range of 0.2 ≤ x ≤ 0.33, i.e., MII /MIII ratios are in the
range of 2–4. However, there are many exceptional exam-
ples of LDHs with x values outside the range, e.g., 0.67 for
CoII /AlIII LDH [221], 0.5 for FeII /FeIII LDH [222], 0.07 for
MgII /GaIII CO3 LDH [223], 0.41–0.48 for MII /MIII CO3 LDHs
(MII = Mg, Ni, Co, Cu; MIII = Al,V) [224]. The interlayer anions
in LDH are exchangeable with their order of preference
as: NO3 − < Br− < Cl− < F− < OH− < MoO4 2− < SO4 2− < CrO4 2−
< CO3 2− . Since NO3 − is a weakly held anion, nitrate salts are
preferred in most of cases as a precursor for the prepara-
tion of LDHs. A wide range of cations with radius not higher
than 0.07 nm may be introduced into the brucite-like lay-
ers. Larger ions, such as Mn2+ , Pd2+ , Cd2+ , Ca2+ , Y3+ and
La3+ , may be incorporated into the brucite-like layers by
distorting the close-stacking configuration to some extent,
i.e., puckering or combining with other divalent or trivalent
cations as in Mg/Cd/Al and Mg/Al/La systems. Tetravalent
cations, such as V4+ , Ti4+ , Zr4+ , and Sn4+ have also been
introduced into the brucite-like layers to replace triva-
lent cations. The most commonly known LDH is MgAlLDH:
Mg6 Al2 (OH)16 CO3 ·4H2 O, shown in Fig. 56 [225]. It is com-
posed of close-packed planes of OH ions situated on
triangular lattice and the metal cations place on octahe-
dral holes of OH planes in triangular lattice. The interlayer
gallery space and layer thickness of Mg-Al LDH are ∼0.76
and 0.48 nm respectively, suggesting a gallery height of
∼0.28 nm [12].
Several synthetic methods are available for the prepa-
ration of LDH. The most commonly used methods
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 56. Structure Mg–Al layered double hydroxide.
[225], Copyright 2009. Reproduced with permission from Elsevier Ltd.
are co-precipitation, urea hydrolysis, ion exchange and
hydrothermal crystallization methods [226]. In a co-
precipitation method, precipitation of two or more cations
containing aqueous solutions of MII (or mixtures of MII
species) and MIII (or mixtures) was carried out simulta-
neously under supersaturation condition so that the most
soluble hydroxide is precipitated. By this method, a wide
variety of anions can be directly intercalated between the
hydroxide sheets [227]. In the urea hydrolysis method,
mixed metal nitrate solution along with urea are heated
till precipitation is observed [228,229]. By this method,
a highly crystalline, uniform structure of LDH with high
stability is obtained. During urea hydrolysis, NH3 was gen-
erated which played an important role in the synthetic
process of hydrotalcite pellets. In an ion exchange process,
the guests are exchanged with anions present in the inter-
layer regions of preformed LDHs. This method is useful if
the co-precipitation method is not applicable. There are
several factors which affect the anion exchange process
including affinity of anions, exchange medium, pH value
and chemical composition of layers. In the hydrothermal
crystallization method, aqueous solution of mixed metal
salts and ammonium hydroxide solution are hydrother-
mally heated at high temperature for long time to induce
precipitation.
In the preparation of polymer nanocomposites with a
pristine LDH the polymer chains are unable to intercalate
in the interlayer space of LDH due to its relatively smaller
interlayer spacing compared to the monomer diameter
of polymers. In addition, the high charge density of LDH
also hinders the insertion of hydrophobic polymer chains.
Therefore, LDHs need to be organomodified by treating
it with the anionic surfactants, e.g., sodium carboxylates
[230] sodium dodecyl sulfate [231,232], sodium dode-
cyl benzene sulfonate [233], sodium stearate [234,235],
sodium oleate [236], alkyl phosphonates [237], etc. These
long chain organic anions exist in the interlayer space
of LDHs in the form of simple bilayer, interpenetrating
pseudomonolayer and monolayer surfacial arrangements
depending on the concentration of the anion and the tem-
perature of the reaction [238]. The monolayer packing
is readily formed when the anion/M3+ ratio is close to
unity, while the bilayer packing is favored by the pres-
ence of excess carboxylate, which is incorporated as the
free acid even at high pH. The grafting of hydroxyl groups
on either side of the layer surfaces of organomodified LDH
167
is found to further increase its interlayer spacing [239].
As a result, more polymer chains could be intercalated
between the interlameller spaces of the LDH compared to
the organomodifed LDH.
Among various polymer/LDH nanocomposites system,
Mg-Al LDH has been studied extensively as nanofiller
due to its easy availability, low charge density and high
anion exchange capacity. The interlayer anion of Mg-Al
LDH may be easily replaced by different organic anions,
including sodium dodecyl sulfate (SDS), sodium dodecyl
benzene sulfonate (SDBS), amino benzoate, etc. [231–233].
This facilitates increase of the gallery height and helps
polymer chains intercalate within the interlayer spacing
of organomodified LDH. Hsueh et al. [240] used amino
benzoate modified LDH for the preparation exfoliated
polyimide/LDH nanocomposites. The mechanical as well
as thermal properties of these nanocomposites were
dramatically improved compared to neat polyimide.
Tseng et al. [241] used two different organomodifier –
aminobenzoate and carbonate for LDH and studied their
effect on thermal and mechanical properties of epoxy
nanocomposites. It was found that exfoliated and more
compatible aminobenzoate modified LDH based epoxy
nanocomposites exhibited remarkable performance in
mechanical and thermal properties, while the later showed
little enhancement on their properties due to the weak
compatibility of LDH-carbonate with epoxy polymer and
its poor dispersion. Costa et al. [242] studied the mor-
phology and fracture behavior of polyethylene/Mg-Al LDH
nanocomposites. They modified LDH by sodium dodecyl-
benzene sulfonate (SDBS). They observed that maximum
fracture was developed at 5 wt % loaded SDBS modified
LDH based PE nanocomposite. Therefore, large-scale plas-
tic deformation of the matrix at higher LDH concentration
is effectively arrested favoring small strain failure leading
to the transition. This was a ductile to brittle transition,
supported by the shifting of the shear-thinning behavior
with increasing LDH concentration in rheological analysis.
They further studied the rheological properties of the
corresponding nanocomposites [243]. Due to the stronger
interaction between LDH and maleic anhydride grafted
polyethylene, the shear thinning nature of the composite
melt gradually increased with increasing LDH loading. The
composite showed apparent plateau behavior in low fre-
quency region in a dynamic frequency sweep experiment,
as shown in storage modulus vs. frequency plots (Fig. 57).
168 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187

Fig. 57. Storage modulus (G ) vs. frequency plots of (a) HDPE-g-MA/LDH (PBXLDH ) and (LDPE/LDH (PEXLDH ) nanocomposites. Again trends in the low
frequency region show strong influence of LDH concentration on flow behavior. The plateau region in the flow curve indicates practically no change in
relaxation behaviors of the system. The plateau region in the flow curve indicates practically no change in the relaxation behaviors of the system occurs
with frequency.
[243], Copyright 2006. Reproduced with permission from Elsevier Ltd.

Chen [244] prepared exfoliated polyamide-6/LDH
nanocomposites via an in situ intercalative polymerization
using stearate modified LDH. Thermal and combus-
tion behaviors of dodecyl sulfate modified LDH/nylon 6
nanocomposites prepared by melt blending were also stud-
ied [245]. Improvement in crystallization temperature by
12 ◦ C, decrease in thermal stability along with consider-
able decrease in heat release rate (HRR) and mass loss rate
(MLR) of the composite to 664 kW/m2 and 0.161 g/m2 s
from 1064 kW/m2 and 0.252 g/m2 s of pristine nylon 6
were found. Fig. 58 displays HRR and MLR for the pure
nylon 6 and nylon 6/MgAl-LDH nanocomposites for which
the nanocomposite showed dramatic decrease in HRR and
MLR.
Chen et al. [246] synthesized exfoliated nanocom-
posites of polyethylene grafted maleic anhydride
(PE-g-MA)/Mg-Al LDH by solution intercalation method.
The nanocomposites exhibited a faster rate of thermal
degradation in the temperature range of 210–360 ◦ C
due to the early degradation of organo LDH and higher
thermal stability above 370 ◦ C compared to pure PE-g-MA.
According to them such a type of weight loss at the
first step of decomposition is highly advantageous to
promote the charring process and enhance the fire safety
of the nanocomposites. At a 50% weight loss selected as
a point of comparison, the nanocomposites with 5 wt%
LDH loading showed about 60 ◦ C higher decomposition
temperatures than that of PE-g-MA. However, in a compar-
ative experiment, Qiu et al. [247] observed that LLDPE/LDH
nanocomposites showed much higher thermal degradation
temperatures than LLDPE/MMT nanocomposites at similar
filler content. From a kinetic study of the polymer degra-
dation of two nanocomposites, they determined that the
mechanism of enhanced thermal stability in LLDPE/MMT
and LLDPE/LDH differed, with the former showing protec-
tive char layer formed by the dehydrogenation of LLDPE
molecules, whereas with the later, the barrier effect of
LDH layers with very high activation energy prevented the
diffusion of oxygen from the gas phase into the polymer
nanocomposites and thereby hindered the dehydrogena-
tion of LLDPE molecules as well as protected C C main
chains from thermal degradation. The non-isothermal

Fig. 58. (a) Heat release rate (HLR) and (b) mass loss rate (MLR) of pristine nylon 6 and nylon6/DS-LDH nanocomposites. NC-5, NC-10 and NC-20 represent
5, 10 and 20 wt% DS-LDH filled nanocomposites.
[245], Copyright 2007. Reproduced with permission from Elsevier Ltd.
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 59. TEM images of PU/DS-LDH nanocomposites containing (a) 3 wt% and (b) 8 wt% DS-LDH.
[231], Copyright 2009. Reproduced with permission from John Wiley & Sons Inc.
crystallization behavior of Mg-Al LDH/Polypropylene
nanocomposites prepared by melt-dispersion was also
compared with that of MMT/PP nanocomposites [248]. The
combined effect of LDH modification by dodecyl sulfate
and blending the PP with maleic anhydride-grafted PP
(PP-g-MAH) and maleic anhydride grafted SEBS (SEBS-g-
MAH) were investigated. Both LDH and MMT are active
substrate for the heterogeneous nucleation of PP, although
PP-g-MAH contributed to enhance the nucleation activ-
ity in PP/LDH nanocomposites but did not provide any
appreciable effect on PP/MMT nanocomposites. Kotal
et al. [231] also used DS-LDH for the preparation solution
blended thermoplastic polyurethane (TPU) intercalated
nanocomposites as evident from TEM analysis (Fig. 59).
It exhibited 67% improvement in tensile strength, 29 ◦ C
improvement in thermal stability and 21% enhancement
in limiting oxygen index at 3 wt% DS-LDH loading.
However, at similar loading of DS-LDH, in situ polymer-
ized PU nanocomposite [249] showed remarkably higher
improvement in tensile strength (TS), about 407%, due to
the formation of partially exfoliated structure enhancing
the interfacial interaction through bridge, loop and tail link-
ages of the PU chains with DS-LDH layers via H-bonding
and polar-polar interaction, as shown in Fig. 60. In addition,
polyol Tg used as a crosslinker of PU also contributed more
linking points with DS-LDH. It also exhibited improvement
in thermal stability, dynamic mechanical properties, adhe-
sion and limiting oxygen index [250]. Partially exfoliated
TPU/NBR nanocomposites using varying DS-LDH by solu-
tion blending were further prepared [232]. These blend
nanocomposites exhibited higher improvement in ten-
sile strength, storage and loss moduli, thermal stability,
glass transition temperature and limiting oxygen index
compared to neat blend or their individual counterparts.
The effect of stearate modified LDH and their content on
mechanical and thermal properties of solution blended
TPU nanocomposites were also investigated [234]. This
nanocomposite exhibited 45% improvement in TS at 1 wt%
169
loading, 20% enhancement in storage and loss moduli, 15 ◦ C
shifting of Tg and 32 ◦ C increase in thermal stability at 8 wt%
loading along with a 6 ◦ C shifting of melting temperature
of soft segment in DSC at 1 wt% loading. The variation of
stress–strain plots and temperature dependence of stor-
age moduli of TPU/ST-LDH nanocomposites are displayed
in Fig. 61. In situ polymerized PU/St-LDH nanocompos-
ite developed exfoliated structure and therefore provided
higher improvement in TS (175%) at 3 wt% St-LDH
loading and lap shear strength (200%), peel strength (130%)
at 5 wt% St-LDH loading and gradual improvement in lim-
iting oxygen index with ST-LDH content [235].
Kotal et al. [239] developed a novel approach for inter-
lamellar surface modification of the hydroxyl groups of
pristine and organomodified LDH by grafting with iso-
cyanate group of methylene diphenylene diisocyanate
(MDI) and isophorone diisocyanate (IPDI) and further
studied the synergistic effect of organomodification and
isocyanate grafting of LDH in reinforcing properties of PU
nanocomposites. Fig. 62 shows the grafting of MDI and IPDI
on pristine LDH and organomodified LDH. Interestingly,
3 wt% loaded MDI-grafted ST-LDH/PU showed maximum
improvement in TS (391%), thermal stability (26 ◦ C) and
glass transition temperature (11 ◦ C) compared to other iso-
cyanate grafted organomodified LDH, individual grafted
and organomodified LDH based PU nanocomposites due to
better exfoliation and interfacial interaction of MDI-g-ST-
LDH with PU. TEM images of all the isocyanate grafted LDH
based PU nanocomposites are shown in Fig. 63.
Decane sulfonate modified Mg-Al LDH was used to
investigate its effect on dispersion, mechanical proper-
ties and interfacial adhesion on two different elastomers
having widely different polarities and functional groups –
ethylene propylene diene terpolymer, i.e., EPDM and car-
boxylated nitrile rubber, i.e., XNBR [251]. Although in either
case LDH forms exfoliated structure along with soft clus-
ters, XNBR/LDH based nanocomposite exhibited prominent
improvement as LDH was crosslinked with carboxylated
170 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187

Fig. 60. Proposed mechanism for interaction between DS-LDH and PU chains.
[249], Copyright 2010. Reproduced with permission from American Scientific Publishers.

elastomers leading to secondary interaction between
LDH and XNBR, as shown in Fig. 64. This conclusion is
supported by the formation of stable polymer-filler inter-
face in XNBR-LDH nanocomposites as observed from
fracture surface analysis.
Kutlu et al. [252] prepared melt-spun LDH/HDPE
nanocomposites using three different organomodifier-
hexadienoic acid (sorbic acid), tetradecanoic acid (myristic
acid) and octadecanoic acid (stearic acid). 1 wt% myris-
tic acid modified LDH based HDPE nanocomposites
exhibited highest exfoliation degree as investigated by
semi-quantitative and quantitative rheological models.
Therefore, this material provided the best processing con-
ditions and best mechanical properties of fiber spun
filaments. Polyvinylalcohol (PVA)/Zn-AL LDH nanocom-
posites were prepared by a one step method based on
coprecipitation of LDH in PVA aqueous solution [253].
Such PVA/LDH nanocomposites exhibited exfoliated mor-
phology with enhanced photostability over PVA, making
this composite efficient for coating applications. Guo et al.

Fig. 61. (A) Stress–strain plots and (B) temperature dependence of logarithmic storage modulus for (a) neat PU and its nanocomposites containing (b)
1 wt%, (c) 3 wt%, (d) 5 wt% and (e) 8 wt% St-LDH.
[234], Copyright 2011. Reproduced with permission from John Wiley & Sons Inc.
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 171

Fig. 62. Schematic illustration of interlammelar grafting of hydroxyl groups of pristine, DS and St-LDH layers with (a) MDI and (b) IPDI.
[239], Copyright 2011. Reproduced with permission from the Royal Society of Chemistry.

[254] prepared exfoliated UV-cured polyester acrylate/LDH
nanocomposites by modifying LDH with N-lauroyl gluta-
mate (LG). The wear resistance of the nanocomposites was
shown to improve significantly with respect to the neat
polymer. The coefficient of static friction, dynamic friction
and gloss of the nanocomposites containing 2 wt % LDH-
G decreased to 0.114◦ , 0.062◦ and 87.5◦ compared with
0.856◦ , 0.758◦ and 94.0◦ of the pure polymer, respectively.
This is due to the uniform dispersion of LDH-LG in the
polymer matrix which played the role of physical crosslink-
ing point to the polymer network leading to improve the
strength and wear resistance property of the polymer film.
However, the addition of LDH-LG resulted in a decrease
in thermal stability since the alkaline LDH sheets in UV-
curable polyester acrylate matrix catalyzed the depolymer-
ization and transesterification reactions of the UV-curable
acrylate resulting in worse degradation stability. Yuan
et al. [255] also prepared exfoliated UV-cured acrylate/

Fig. 63. TEM images of (a) PU/MDI-g-pristine LDH, (b) PU/IPDI-g-pristine LDH, (c) PU/MDI-g-DS-LDH, (d) PU/IPDI-g-DS-LDH, (e) PU/MDI-g-St-LDH and (f)
PU/IPDI-g-St-LDH nanocomposites showing the nature of dispersion of MDI and IPDI grafted pristine, DS and St-LDH layers in PU matrix.
[239], Copyright 2011. Reproduced with permission from the Royal Society of Chemistry.
172 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Fig. 64. Typical stress–strain plots of (a) XNBR/LDH and (b) EPDM/LDH nanocomposites.
[251], Copyright 2008. Reproduced with permission from Elsevier Ltd.
LDH nanocomposites by intercalating a photoinitiator
into LDH interlayers, followed by photopolymerizaion.
For intercalating photoinitiator into LDH, they initially
used fragments photoinitiator – 2-hydroxy-2-methyl-1-
phenylpropane-1-one for reacting with IPDI followed by
reaction with LDH modified by aminoundecanoic acid.
Compared with the neat polymer, these nanocomposites
possessed enhancement in mechanical, dynamic mechan-
ical and thermal properties as well as hardness. Using
a photoinitiator complex-Irgacure 2959 modified LDH,
exfoliated acrylate/LDH nanocomposites were prepared
via UV-initiated photopolymerization of acrylates [256].
LDH-2959 was prepared by the esterification of 2-hydroxy-
4 -(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure
2959) with thioglycolic acid, followed by the reac-
tion with 3-(2,3-epoxypropoxy)propyltrimethoxysilane
(KH-560), finally intercalation into the sodium dode-
cyl sulfate-modified LDH. The nanocomposites exhibited
higher Tg (9 ◦ C), higher tensile strength (149%) and higher
hardness compared to the neat polymer.
Chung and Lai [257] prepared biodegradable starch/LDH
nanocomposites by directly synthesizing LDH in starch
dispersion. They found that LDHs were homogeneously
dispersed in acid-modified corn starch while LDHs were
aggregated in normal corn starch. Therefore, acid modified
starch based LDH nanocomposite exhibited 37% improve-
ment in Young’s modulus. Alginate-LDH nanocomposites
were prepared by dispersing LDH in alginate aqueous solu-
tion [258]. This nanocomposite showed greater thermal
stability and enhanced mechanical properties compared
to neat alginate. Acharya et al. [259] prepared par-
tially exfoliated nanocomposites of ethylene propylene
diene methylene (EPDM) with dodecyl sulfate interca-
lated layered double hydroxide (DS-LDH) nanocomposites
by solution blending methods. The mechanical proper-
ties showed significant improvement in EPDM/DS-LDH
nanocomposites (2–8 wt.%) with respect to neat EPDM.
Thermogravimetric analysis (TGA) showed that the ther-
mal stability of the nanocomposites containing 3 wt.%
DS-LDH improved by ∼40 ◦ C when 10% weight loss
is selected as point of comparison. Wang et al. [260]
prepared disordered exfoliated PMMA nanocomposites
using 10-undecanoated modified LDH (LDH-U). They moni-
tored the formation of exfoliated LDH/PMMA nanocompos-
ites and the dispersion behavior of modified LDH during the
preparation of PMMA nanocomposites. LDH layers were
exfoliated in a disordered fashion in PMMA matrix at 5 wt%
LDH-U loading. Using benzoate modified LDH, the influ-
ence of three different divalent metals – Ca, Mg and Zn
on the dispersion and fire properties of PS and PMMA was
investigated by preparing the corresponding nanocompos-
ites through in situ bulk polymerization in the presence
of benzoate-modified LDHs [261]. The benzoate modified
Ca-Al LDH (Ca-Al-LDH-B) showed excellent dispersion of
exfoliated LDH layers in both the polymers while ben-
zoate modified Zn-Al LDH (Zn-Al-LDH-B) and Mg-AL LDH
(Mg-Al-LDH-B) showed the presence of tactoids in either
polymer matrices. However, all benzoate modified LDHs
based PMMA nanocomposites exhibited higher thermal
stability compared to neat PMMA (Fig. 65) but only Ca-Al-
LDH-B/PS showed higher thermal stability due to its better
dispersion in polymer matrices. The largest reduction (52%)
in PHRR observed in Mg-Al LDH-B/PMMA nanocompos-
ites while that for PS nanocomposite showed only 15%.
However, PS/Zn-Al-LDH-B and PS/Ca-Al-LDH-B nanocom-
posites showed slightly lower PHRR of about 41% and 42%
respectively.
Monomer anions containing (1) reactive vinyl groups,
such as acrylate, methacrylate (MA), 2-acrylamido-2-
methyl-1-propanesulfonate (AMPS), and 4-vinylbenzoate
(VB), (2) polymerization initiator, such as 4,4 -azobis(4-
cyanopentanoate), and (3) hydrophobizing agent, such as
dodecyl sulfate (DS) were used for modification of Mg-
Al-LDH and Zn-Al-LDH and these intercalated LDHs were
further used as co-monomers or initiators for the prepa-
ration of LDH/poly(butyl methacrylate) nanocomposites
by in situ polymerization and solution polymerization
[262]. However, The best dispersion was achieved in the
solution polymerization. In addition to these, porphyrin
intercalated LDHs were also prepared in preparing pho-
toactive LDH/poly(butyl methacrylate) nanocomposites.
However, without modifying LDH by any organomodifier,
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 173

Fig. 65. (a) TGA curves of (a) neat PMMA and PMMA/Ca-Al-LDH-B nanocomposites at 1, 3, 5, 7 and 10% Ca-Al-LDH-B loading (b, c, d, e and f). (b) TGA
curves of (a) neat PMMA and PMMA/Zn-Al-LDH-B nanocomposites at 3, 5 and 10% Zn-Al-LDH-B loading (b, c and d). (c) TGA curves of (a) neat PMMA and
PMMA/Mg-Al-LDH-B nanocomposites at 3, 5 and 10% Mg-Al-LDH-B loading (b, c, and d).
[261], Copyright 2013. Reproduced with permission from Elsevier Ltd.

Zhan et al. [263] prepared biodegradable poly(butylenes
succinate)(PBS)/LDH nanocomposites via melt-blending to
study the nonisothermal crystallization and morphology
behavior of the nanocomposite. They found that after
incorporation of LDH in the polymer matrix, crystal-
lization rate was accelerated due to the heterogeneous
nucleation effect of LDH although the crystal structure
of PBS was almost unchanged. Hu et al. [264] pre-
pared a novel waterborne hyperbranched polyurethane
acrylate (WHPUA)/Mg-AL-LDH nanocomposites by in situ
polymerization approach. For this purpose, LDH was
first modified with dodecyl sulfate, followed by grafting
with isophorone diisocyanate (LDH-DS-NCO]. The residual
hydroxyl groups after modification with succinic anhy-
dride were crosslinked by the semi-adduct of IPDI reacted
with hydroxyethyl acrylate (HEA) and LDH-DS-NCO, fol-
lowed by neutralization reaction with triethylamine and
exposing to a mercury lamp, forming a partially exfoliated
WHPUA/LDH nanocomposites in the presence of a frag-
mental initiator. These nanocomposites exhibited higher
thermal stability and pencil hardness. Bao et al. [265]
developed poly(vinyl chloride)/dodecyl sulfate modified
LDH (DS-LDH) nanocomposites via in situ suspension poly-
merization process. TGA analysis showed that the 5% and
10% weight loss temperatures of PVC resins significantly
increased with filler loading. It was found that the rate
of degradation of PVC was decreased and the tempera-
ture corresponding to a certain weight loss was increased.
According to them, in the composite, resin LDH can absorb
and react with HCl produced. Dynamic mechanical anal-
ysis (DMA) showed that the storage modulus (E ) of the
PVC/DS-LDH nanocomposites was greater than pristine
PVC below the glass transition region. The glass transi-
tion temperature (Tg ) of the PVC phases in pristine PVC
and PVC/DS-LDH nanocomposites with 1 and 3 wt% was
observed at 79.9, 80.9 and 81.6 ◦ C which confirmed that
well dispersed nanocomposites restricted the motion of
PVC segmental chain. Tensile strength and Young’s mod-
ulus of the nanocomposites were also higher compared
to that of neat PVC. Liu et al. [266] prepared poly(vinyl
chloride)/layered double hydroxide (PVC/LDH) nanocom-
posite via solution intercalation process using dodecyl
sulfate (DS) or stearate anion modified LDH. The nanocom-
posites containing Mg-Al LDH-stearate had the maximum
increased dehydrochlorination time, 15 times that of neat
PVC, and more than twice that of PVC/LDH-NO3 compos-
ite and PVC/DS-LDH nanocomposite at 5 wt% loading. It
was also noted that the thermal stability of the PVC/Mg-
Al LDH-stearate (10 wt%) nanocomposites was 20 times
higher compared to neat PVC. The reason may lie with the
absorption of the released HCl during degradation by both
nanoscale dispersed LDH particles and stearate anions.

Fig. 66. Comparison of the fire properties of PE and PMMA of Zn-ALDH and MgAl-LDH. The % reduction in PHRR was plotted vs. the LDH loading (wt.%) and
the cone heat flux was set to 50 kW/m2 . (A) PE systems; (B) PMMA systems.
[268], Copyright 2009. Reproduced with permission from Elsevier Ltd.
174 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Du et al. [267] synthesized exfoliated poly(propylene
carbonate)/Mg-Al LDH nanocomposites via solution inter-
calation process. The thermal degradation temperature of
the exfoliated PPC/Mg-Al LDH nanocomposites with 1 wt%
organomodified Mg-Al LDH loading was ∼10 ◦ C higher than
that of pure PPC resin when 20% weight loss was selected
as a point of comparison. This is because the exfoliated
LDH layers dispersed randomly in the PPC matrix at the
nanoscale level producing hindered effect for the escape
of degraded small gaseous molecules and thus remedies
the negative catalytic degradation of organomodified Mg-
Al LDH on the PPC resin. The data from the mechanical
test showed that the tensile strength of the PPC/Mg-Al
LDH nanocomposites with 5 wt% LDH was 36.9 MPa, which
was 72% and 30% higher than those of neat PPC resin and
the sample mixed with the same content of LDH, and its
Young’s modulus was 1303 MPa, which was 57% and 21%
higher than those of the same two samples, respectively.
Oleate modified Mg-Al-LDH and Zn-Al-LDH were also used
to prepare nanocomposites of PE, poly(ethylene-co-butyl
acrylate) and PMMA [268]. The oleate modified Zn-Al-LDH
was better dispersed in PE, while MgAl-LDH was better dis-
persed in PMMA. These findings are consistent with the fire
properties observed in the composites. Zn-Al-LDH based
composites led to a large reduction in PHRR in PE, while
Mg-Al-LDH based composite led to the enhancement in fire
properties of the more polar PMMA. Fig. 66 shows the com-
parison of fire properties of PE and PMMA nanocomposites
containing Zn-Al-LDH and Mg-Al-LDH. However, neither
of these LDHs showed the efficacy with poly(ethylene-co-
butyl acrylate) indicating a selective interaction between
LDH and the various polymers. Dodecylbenzene sulfonate
modified Zn-Al-LDH based PP nanocomposites were pre-
pared by melt blending for studying their DSC, SAXS, WAXS
and dielectric relaxation spectroscopy behavior [269].
Scanning microfocus SAXS investigations showed that Zn-
Al-LDH was homogeneously distributed in the PP matrix as
stacks of 4–5 layers with an intercalated morphology. From
DSC and WAXS results, the degree of crystallinity decreased
linearly with DBS-LDH content.
In summary, LDHs have been well-known as a
promising new additive class for generating polymer
nanocomposites with enhanced thermal stability and
improved flammability properties without halogen. A few
representative modification of all Mg-Al-LDH, Zn-Al LDH,
Ca-Al-LDH, Fe-Al-LDH, Ni-Al-LDH, Co-Al-LDH, Mg-FE-LDH,
etc., are presented in Table 8 along with relevant prop-
erties and applications. An advantage of these materials
over structurally similar smectite clays is the ability to
tune physical and chemical properties via simple synthetic
strategies that can modify the metal hydroxide layer and/or
the identity of the charge-balancing interlayer anion. More-
over, they have high chemical purity and homogeneous
structure. Since the range of metals and the range of anions
which can be used in LDHs are quite large, one has the
opportunity to select the metals to obtain the desired result
and also study the effect of anion on a particular prop-
erty. However, the disadvantage of LDHs over smectite is
that the anion exchange capacity of these clays is quite
high, typically more than 200 mequiv. per 100 g, while for
MMT, the cation exchange capacity is about 100 mequiv.
per 100 g, and it is quite difficult to fully exchange the anion.
In addition, MMT in its pure state is an inert and electrically
insulating material, showing unique features of marked
cation exchange properties, expandability, water uptake
or organic molecules between their interlayer spaces and
thereby increasing the d-spacing of the material. There-
fore, a small amount of MMT can significantly enhance the
mechanical and physical properties, such as the stiffness,
strength, gas-barrier and dimensional stability of polymer
nanocomposites. However, in clay-polymer nanocompos-
ites, the reinforcing efficiency of the nanoclay depends on
their dispersion in the polymer matrix. A fully exfoliated
nanocomposite based on LDH should contain more exfoli-
ated layers per unit amount of filler added than the layered
silicate-polymer nanocomposites. This is due to the fact
that each platelet layer of clays is composed of single octa-
hedral sheet of mixed metal hydroxide, whereas layered
silicate type clays contain multiple octahedral/tetrahedral
sheets of metal oxide/hydroxide.
5. Theory and modeling to design polymer/clay
nanocomposites
The thermodynamic aspects of nanocomposite forma-
tion have been studied by the mean-field lattice-based
description of polymer melt intercalation, as first reported
by Vaia and Giannelis [297]. The advantage of this model is
the ability to analytically determine the effect on composite
formation from various characteristics of the polymer and
organically modified layered silicates, although this model
considered only layered clays. In brief, the free energy
change per interlayer volume, fv , associated with poly-
mer intercalation, has been expressed as:
fv = ev − TSv (1)
where, ev and sv are the internal energy and entropy
change per interlayer volume, respectively, given as:
polymer
sv = NA KB [svchain + sv ]
  
2 1 2  a1 2 √ u a1
= NA KB ln(c)(Xs − Xs0 ) − + 3√
v2 v1 6 h m1 h
(2)
1
2 2
ev = 1 2 εsp,sa + εap (3)
Q h0 r2
sv is the sum of entropy change associated with the
organically modified layered clays svchain , and the entropy
change related with the confinement of the polymer,
polymer
sv · h0 and h are the initial and final gallery heights
after polymer intercalation, respectively. mi , vi , i , ri and ai
are the number of segments per chain, the molar volume
per segment, the interlayer volume fraction, the radius of
the interaction surface and the segment length of the ith
interlayer species. u is a dimensionless excluded volume
parameter, Q is a constant near unity, and Xs and Xs0 are the
fraction of interlayer volume near the surface at heights h
and h0 , respectively, which influence the potential chain
conformations. εap represents the pair wise interaction
energy per area between the aliphatic chains and the poly-
mer and εsp,sa = εsp − εsa , i.e., the difference between the

Table 8
Examples of modified LDH based polymer nanocomposites and their properties.
Modified LDH
10-undecanoate modified
Mg-AL LDH
Dodecyl sulfate and
terephthalate intercalated
Mg-AL LDH
Palmitate modified Mg-AL
LDH
Oleate modified Mg-Al LDH
and Zn-AL LDH
Benzoate modified
Ca-Al-LDH (Ca-Al-LDH-B)
Decavanadate
intercalated-␥-
aminopropyltriethoxysilane
modified Zn-Al LDH
(AD-LDH)
Alginate-modified Zn-Al-LDH
Porphyrin intercalated
Mg-Al-LDH and Zn-Al-LDH
3-Sulfopropyl methacrylate
(SPMA)-modified
Zn-Al-LDH
Glycinate modified
Mg-Al-LDH
Dodecyl sufate modified
Mg-Al-LDH
Dodecyl sulfate intercalated
␥-(2,3-epoxypropoxy)
propyl trimethoxysilane
modified Mg-Al-LDH
grafted with
trimethylolpropane
thioglycolic acetate
(LDH-SH)
Dodecyl sulfonate/itaconic
acid intercalated
Mg-Al-LDH (LDH-SI)
Dodecylsulfate intercalated
and dodecyl sulfate
undertaken Ni-Al-LDH
M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187 175
Preparation method Products Morphology and properties References
In situ bulk LDH-U/PMMA Disorderly exfoliated structure and [270]
polymerization significant improvement in Tg ,
decomposition temperature, tensile
modulus of the nanocomposites
In situ polymerization Polyethylene Microwave process improved the [271]
by conventional and terephthalate dispersion and thermal stability of PET
microwave heating (PET)/DS-LDH and nanocomposites although the
PET/Tph-LDH improvement was higher in
nanocomposites PET/DS-LDH nanocomposites.
Melt blending PMMA/palmitate-LDH Improvement in thermal stability and [272]
nanocomposites fire retardant properties-showed best
reduction in PHRR by 51% at 10 wt%
palmitate-LDH loading
Melt blending PP/oleate Zn Mg-Al Both composites were well dispersed [273]
LDH nanocomposites in nanometer level, Mg-containing
by varying ratios of Zn composite showed higher thermal
to Mg stability while Zn-containing
composite exhibited higher reduction
in heat release rate during combustion
In situ bulk PS/Ca-Al-LDH-B In situ polymerized PS nanocomposites [274]
polymerization and nanocomposites showed better dispersion and better
melt blending thermal and fire properties compared
to the melt blended PS
nanocomposites.
In situ polymerization Polyaniline/AD-LDH PANI chains not intercalated in the [275]
nanocomposites interlayer of AD-LDH and the corrosion
resistance property of PANI/AD-LDH
coating better than that of d-LDH and
PANI
Coprecipitation Polyvinylpyrrolidone Exfoliated structure with significant [276]
method (PVP)/ALG-Zn-Al-LDH enhancement in bulk dc conductivity
nanocomposites and capacitive response of PVP
nanocomposites
Solvent casting and Porphyrin-LDH/PU and Good dispersion of porphyrin-LDH in [277]
melt blending porphyrin- polymer matrices and the
LDH/poly(butylenes nanocomposites allowed the
succinate) (PBS) elaboration of photoactive surfaces
nanocomposites with a precise control of singlet O2
concentration leading to effective for
photoactive coatings
Bulk polymerization SPMA-LDH/PS The nanocomposite showed slight [278]
nanocomposites effect on the photooxidation rate
although there was not any
improvement in thermal stability.
Solution blending Epoxy/glycinate-LDH Improvement in mechanical and [279]
nanocomposites flame-retardant properties of the
nanocomposites
In situ Urethane Improvement in mechanical and [280]
photopolymerization acrylate/DS-LDH and thermal properties of the
acrylate/DS-LDH nanocomposites
nanocomposites
Solution blending Acrylic resin/LDH-SH Exfoliated structure with improvement [281]
nanocomposites in storage modulus (27%), tensile
strength (9.4%) and Persoz hardness
(23%) of the nanocomposites
Melt mixing PP/LDH-SI Increasing of crystallinity, thermal [282]
nanocomposites stability and flame retardancy of the
nanocomposites
Melt blending EVA/DDS intercalated EVA/DDS intercalated LDH [283]
Ni-Al-LDH and nanocomposite showed best
EVA/DDS-surface compatibility and significant heat
undertaken LDH release rate, smoke production rate,
nanocomposites average mass loss rate, the production
of CO (COP), best thermal stability,
tensile strength and ductility compared
to both EVA and other nanocomposites
176
Table 8 (Continued )
Modified LDH
Dodecylsulfate modified
Zn-Al-LDH
Dodecylsulfate modified
Mg-Al-LDH
Dodecylsulfate modified
Co-Al-LDH
Dodecylsulfate modified
Co-Al-LDH
Dodecylsulfate modified
Mg-Fe-LDH
Terephthalate intercalated
Mg-Al-LDH
Adipate modified Mg-Al-LDH
Dodecylsulfate modified
Co-Al-LDH
Benzoate modified
Ca-Al-LDH
Dodecylbenzenesulfonate
modified Zn-Al-LDH
Lauryletherphosphate
modified Mg-Al-LDH
Sulfanilic acid salt-modified
layered double hydroxide
(MgAl LDH-SAS)
Unmodified Mg-Al-LDH
(LDH–NO3 ) and
␥-polyglutamate modified
LDH (␥-LDH)
pairwise interaction energy per area between the aliphatic
chain and the surface, εsp , and that between the polymer
and the surface, εap . Xs (h) can be expressed as:
a2
 h Bhowmick and co-workers followed this model and cal-
s (h) = cos2
h 2 h˛
M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
Preparation method Products Morphology and properties References
Melt blending and EVA/DS-Zn-Al-LDH Exfoliated structure with improved [284]
solution intercalation nanocomposites thermal stability (13–35 ◦ C), higher
tensile strength (2.5–4.8 MPa) and
higher ensile modulus of the
nanocomposites
Solution intercalation EVA/LDPE/DS-LDH Complete exfoliation with higher [285]
blend nanocomposites tensile strength, higher thermal
stability, higher limiting oxygen index
and higher solvent resistance
properties of the nanocomposites
In situ polymerization Polyamide 6 Homogeneous dispersion of LDHs in [286]
(PA6)/DS-Co-Al-LDH PA6 matrix and substantial
nanocomposites improvement in tensile modulus
(100%), yield strength (75%) and the
hardness (25%) of the nanocomposites
at 1 wt% LDH
In situ intercalation Polyurethane/DS-Co- Exfoliated nanocomposites with [287]
polymerization Al-LDH excellent improvement in mechanical
nanocomposites properties, faster thermal degradation
and slower thermo-oxidative rate
compared to neat PU due to the barrier
effect of LDH layers.
In situ polymerization PMMA/DS-Mg-Fe-LDH Well dispersed nanocomposites with [288]
nanocomposites improved thermal stability
In situ polymerization PET/TA-Mg-Al-LDH Partially exfoliated nanocomposites [289]
nanocomposites with enhanced thermal stability,
nucleation and crystallization of PET
Solid state Polyamide Partially intercalated and partially [290]
polymerization 6.6/Ad-Mg-Al-LDH exfoliated nanocomposites with
nanocomposites significant improved thermal stability
at 0.1% LDH content.
Solution blending PS/DS-Co-Al-LDH Exfoliated nanocomposites with [291]
nanocomposites greater thermal stability (12 ◦ C) and
higher Tg (14 ◦ C) compared to neat PS.
In situ polymerization Epoxy Intercalated nanocomposites with [292]
resin/B-Ca-Al-LDH decreased thermal stability and glass
nanocomposites transition temperature
Melt-compounding Poly(lactic acid) Nanocomposites exhibited good [293]
(PLA)/DBS-Zn-Al-LDH dispersion of DS-Zn-Al-LDHs and
nanocomposites significant improvement in fire
retardance performance
Solution intercalation PVC/LDH-PK Uniform dispersion of LDH with lower [294]
nanocomposites Tg , higher dehydrochlorination
temperature, lower maximum
degradation rate, higher char
formation and enhanced the stability
of Cl atom on the PVC chains of the
nanocomposites
In situ polymerization Poly(ethylene tereph- Nanocomposites exhibited good [295]
thalate)/sulfanilic acid thermal stability, increased storage
salt-modified layered modulus, gas barrier properties
double hydroxide relative to neat PET
(PET/MgAl LDH-SAS)
exfoliated
nanocomposites
Melt blending Poly(l-lactide) The Young’s modulus, thermal stability [296]
(PLLA)/LDH-NO3 and and barrier properties improvement
PLLA/␥-LDH (water vapor permeability decreased)
nanocomposites were more in PLLA-␥ LDH
nanocomposites than PLLA/LDH–NO3
nanocomposites.
When the free energy change (Gs or fs ) of the sys-
tem is negative, the mixing of two components is favorable.
From the above parameters, ev and Hs have been cal-
culated for different clay based polymer nanocomposites.
(4) culated those values for hydrogenated nitrile butadiene
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
rubber (HNBR) nanocomposites based on modified and
unmodified MMT clays, sepiolite and nanosilica [131]. They
found that Hs and ev for Cloisite30B and sepiolite based
nanocomposites are negative and lowest. Therefore, Gs
or fs is least for these two nanocomposites, although
Hs and ev are zero and +0.84 nm−1 , respectively for
the unmodified MMT, indicating that the mixing of it with
HNBR is not favorable.
For solution intercalated polymer nanocomposites, Vaia
and Giannelis suggested that entropy loss of the interca-
lated polymer is compensated by an entropy gain via the
increased conformational freedom of the surfactant chain
as the clay layers separate. They further proposed that com-
plete layer separation depends on the establishment of
very favorable polymer-organic layered silicates interac-
tion. Choudhury et al. [131] reported that entropy change
for Cloisite30B and sepiolite based HNBR nanocomposites
is +ve, while for unmodified MMT, entropy change is −ve
suggesting further unfavorability of the unmodified MMT
with HNBR. Generally, when the polymer chains enter and
get trapped in the rubber matrix in the initial stage as
in Cloisite30B based nanocomposites, the mobility of the
polymer chains is restricted resulting in SE to be −ve.
However, later on, polymer chains break the layer struc-
ture of clay until complete exfoliation occurs leading to
+ve SC , which compensates the entropy loss in the initial
stage. Therefore, overall entropy change SC is +ve, making
thereby Gs −ve. On the contrary, for fibrous like particles,
sepiolite, SC should be +ve from TEM image and therefore
Gs to be −ve.
Hs can also be calculated from IR spectra using
Fowkes’s equation [298]:
HS = 0.236 × 
, (5) the rubber–filler bond remaining intact, a consequential
where v, the shift in the IR peak for different groups, indi-
cates the level of interaction between the polymer and the
filler. For the composites, if v is highest indicating high-
est level of interaction leading to Gs to be −ve. These
thermodynamic phenomena explain the cause of signif-
icant improvement of physico-mechanical properties of
clay based polymer nanocomposites.
Balazs et al. [299] modeled the phase behavior of
polymer/clay nanocomposites to probe the interactions
between polymers and clay sheets with the help of the
self-consistent field (SCF) theory. They determined the
177
chains. Ginzburg et al. [302] also proposed a simple ‘Kink’
model to describe the dynamics of polymer-melt interca-
lation in the gallery between the adjacent clay sheets in
polymer-clay nanocomposites. Ganeshan and Jayaraman
[303] reviewed various theories and simulation of effective
interactions, phase behavior and morphology in poly-
mer nanocomposites. Most of the studies discussed were
related to the behavior of polymer–nanoparticle (grafted
and ungrafted) mixtures.
Buxton and Balazs [304] predicted mechanical proper-
ties of homopolymers containing either solid spheres, rods,
or platelets using a three-dimensional lattice spring model.
The increased reinforcement efficiency in nanocompos-
ites is explained as a consequence of platelet exfoliation.
Fornes and Paul [305] modeled properties of nylon
6/clay nanocomposites using the composite theories of
Halpin–Tsai and Mori–Tanaka. The theories satisfacto-
rily capture the stiffness behavior for their composites.
Sinsawat et al. [306] performed molecular dynamics
simulations of stacks of two-dimensional platelets in
a polymer melt and predicted the influence of poly-
mer matrix composition and architecture on polymer
nanocomposite formation. Kropka et al. [307] investigated
a relation between glass transition temperature in poly-
mer nanocomposites and polymer thin films by examining
a percolation model. They reported that the thin films
might be used to quantitatively predict the properties of
polymer nanocomposites. Kraus [308] considered a filler
particle of radius R in rubber matrix for determination
of the restriction to swelling offered by adhering filler. It
was assumed that the polymer–filler interaction is strong
enough to withstand the interfacial stresses generated
due to swelling. Therefore, as the rubber swells, with
restriction to swelling is recorded. However, nanoclays,
have different structures and hence the model generated
with spherical filler as the restraining body is not gen-
eral. Thus, the entrapment of a non-expansible elliptical
filler (with eccentricity ε) within the rubber matrix is con-
sidered. However, the shape and the aggregation effects
of the clays have not been duly considered in the Kraus
plot. Therefore, Bhattachrya et al. [309] logically deduced
an Interface Area Function (IAF) which is a correction fac-
tor corresponding to interfacial area, which is very large
for nanoparticles. The interfacial area function, is a
dimensionless quantity to accommodate the shape and
free energy profiles when a polymer melt penetrates the aggregation effects. is a function of  (filler density), 
gap between clay sheets and predicted characteristics of (specific surface area),
(correlation length between the
the surfactants, polymers, and substrate for miscible mix- nanoparticles embedded in the matrix) and ˚ (filler vol-
tures. They generated a phase diagram for a mixture of
·˚. The details are
homopolymers and rigid disks. An increase in length of
the polymer requires a decrease in Flory–Huggins interac-
tion parameter for the mixture to be thermodynamically
stable. Ginzburg et al. [300] used a “compressible” ver-
sion of lattice self-consistent field theory (SCFT) to describe
thermodynamic behavior of organically modified clays in
polymer melt. Ginzburg and Balazs [301] proposed cal-
culations for constructing phase diagrams of a mixture
containing organo modified clay, non-functionalized poly-
mer and a small volume fraction of end functionalized
ume fraction) and is the product = ··
given in [309], with some elaboration in the following. The
function has been introduced to reduce the weight given
to aspect ratio and increase the effect of correlation length
and nanofiller dispersion. IAF reflects the surface energy,
aspect ratio, nanofiller content, and also the dispersion
of the nanofillers in the nanocomposite and successfully
maps the filler characteristics in the nanocomposite. In this
model, the volume fraction of gum rubber in the swollen
gel, Vr0 , volume fraction of filled rubber in the swollen gel,
Vrf and can be related by the following expression:
178 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187

Vr0  molecules into, diffusion through, and desorption from the
=1−m
Vrf 1− 
where m is a constant.
Bhowmick and coworkers [309] also discussed the
superior reinforcing efficiency of rubber nanocomposites
by introducing this new Interface Area Function (IAF)
into the composite theories proposed by Halpin and Tsai
[310,311]. The aspect ratio determination for each parti-
cle in a polymer nanocomposite is impractical. It would
require rigorous sample preparation, followed by trans-
mission electron microscopy imaging and its complicated
image analysis. Halpin–Tsai expressed the elastic modu-
lus of composites reinforced by discontinuous cylindrical
fibers or lamellar shapes as:
(6) film. Among them, the diffusion step plays a significant
role in evaluating the overall rate of the permeation [312].
Nielsen’s model [173] initially has been used to predict
gas permeation properties of polymer/clay nanocompos-
ites. This model was based on the barrier layers consisting
of ribbons contained in the polymer matrix. The ribbons
have a width w, thickness t, and infinite length, wherein
all are assumed to be perfectly dispersed and aligned in
the polymer matrix. Cussler’s initial model [313] assumed
the perpendicular alignment of the ribbons or flakes to the
direction of the permeating molecules as well as an even
distribution of the flake-like platelets. The Lape-Cussler
[314] model considered the polydispersity effects in the
matrix and incorporated the randomness of arrangement
of the flake-like structures in the matrix, at constant flake
1 +

E = Em (7)
1 − 
where,
= 2˛ and  = ((Ef /Em ) − 1)/((Ef /Em ) +
) formulation and finite element calculation. In a recent
They tailored Halpin–Tsai equation into a much simpler
form for PNCs comprising of matrix–filler combinations
having extremely disparate sets of Young’s moduli, which
could be done by addressing the shape, size and aggregate
related factors ˛. For rubber–clay system, Ef Em . There-
fore, (Ef /Em ) − 1 ≈ (Ef /Em ) +
≈ (Ef /Em ) and  ≈ 1 dom platelet orientation (S = 0), the tortuosity reduces with
Hence, the modified Halpin-Tsai equation is:
 1 + 2˛ 
E = Em (8)
1−
As the Halpin–Tsai equation contains a term ˛, raised
to the power of unity to accommodate the filler aspect
ratio. Therefore, they intended to displace the same and
the new equation is expected to have a reduced depen-
dence on the aspect ratio. This understanding is subjected
to test by sequentially diluting the presence of aspect ratio
in the equation. The first modified Halpin–Tsai equation
contains a correction term in the form of a shape reduction
thickness. Gusev and Lusti model [315] accounted for the
second-order approximation from a multiple scattering
amendment of Nielsen model, Bharadwaj [316] incorpo-
rated an orientation parameter, S, in which a range of
relative orientations of the nanofillers with respect to each
other represented by q (the angle between the direction of
permeant flow and the normal) could be applied. For ran-
orientation and diffusion is facilitated as opposed to paral-
lel orientation (S = 1 for Nielsen model). Therefore, these
models relate the effective permeability of the nanocom-
posite, P, to the intrinsic permeability of the polymer, P0 ,
the aspect ratio, ˛1 , and the flake volume fraction, ˚. All the
corresponding equations of these models are represented
as:
P 1−
Nielson’s Model : = (11)
P0 1 + (˛1 /2)
P 1−
Cussler’s Model : = (12)
P0 1 + (˛1 /2)
2

factor (˛0.5 ) Eq. (9), while the second modified Halpin–Tsai

equation, Eq. (10), is devoid of any extra shape related cor- (Regular array)
rections. P 1−
The first modified Halpin–Tsai equation is: Cussler’s Model : = (13)
P0 1 + (˛1 /3)
2


1 + ˛0.5 
E = Em (9) (Random array)
1− 
P 1−
and the 2nd modified Halpin–Tsai equation is: Bharadwaj’s Model : = (14)
P0 1 + ˛1 (2S + 1)/6

1+  where S = (3cos2  − 1)/2
E = Em
1− 
Therefore, it can be concluded that unlike the original
Halpin–Tsai equations, these are able to predict the com-
posite’s Young’s modulus within acceptable limits, which
further underline the necessity of inclusion of IAF and the
justification in choosing its constituents.
Bhattacharya et al. [29] also compared the relative
permeabilities of multifunctional rubber nanocomposites
based on existing permeation models and introduced a
novel function to address deviations. Models describ-
ing steady-state transport of permeants through dense
polymeric films have three-step mechanism (i.e., solu-
tion diffusion mechanism): the sorption of permeating
(10)
P 1−
sev-Lusti Model : = (15)
P0 exp {(˛1 /3.47)}
0.71
Bhattacharya et al. [29] measured the permeability of
Cloisite15A and sepiolite based SBR nanocomposites by
melt blending and compared the relative permeabilities
predicted by the models cited above. The Bharadwaj’s
model exhibited the best fit. Deviations from Lape & Cus-
sler regular array, and Gusev-Lusti’s model are attributed
to the over reliance on the aspect ratios and the difficulty
in their accurate determination from TEM images. Also, the
actual measurement of thickness of the nanofiller (which
is around 1–10 nm) is tedious and erroneous, the sampling
 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
errors can be minimized by introducing the characteris-
tic correlation length instead. Correlation length (which
are at least 100 nm for most nanocomposites) may be also
estimated from statistically analyzing TEM micrographs.
To address this problem, Bhattachrya et al. [309] have
extended the purview of the Interfacial Area Function, to
determine and predict the swelling behavior and Young’s
modulus of the nanocomposites, and introduced them into
two models in the random filler orientation domain which
yielded the poor predictions.
As mentioned in the preceding, the corrective function,
(Interface area function – IAF), has been used to accom-
modate the shape and aggregation effects expressed as:
179
After considering the correlation length, the effect of
dispersion in the overall matrix, a better approximation of
the impermeable phase and the effective tortuosity could
be achieved. Hence, it offered a more comprehensive rep-
resentation of the filler structure and morphology in the
nanocomposites.
Dong et al. [317] established novel computational mod-
els by implementing an innovative-object oriented finite
elemental analysis code (OOF) to predict tensile moduli of
polypropylene/layered silicates nanocomposites with good
agreement with the experimental data and theoretical
models [318–320]. They applied following mathematical
models for evaluating the tensile moduli of the nanocom-
posites:
=··
· (16)
E 1
Hui-Shia Model : =
where,  is filler density,  is specific surface area,
is corre- Em 1 − (f /4)[(1/
) + (3/
+ )]
lation length between the nanoparticles embedded in the (19)
matrix and ˚ is filler volume fraction.
Here, all the functions are dimensionless quantities and where,
may be used to replace the dimensionless aspect ratio

Em (1 − g)˛22 − (g/2)
term. It would be better to characterize the property with-
= f + + 3(1 − f )
Ef − Em ˛2 − 1
out any significant bias arising out of the differences in 2
magnitudes of the constituting components. Actually, the


function has been introduced to reduce the weight given to  3(˛22 + 0.25)g − 2˛22
aspect ratio and increase the effect of correlation length and g = ˛2 ;  = (1 − f ) ;
2 ˛2 − 1 2
nanofiller dispersion. Therefore, the IAF which reflects the
surface area, aspect ratio, nanofiller content and also, the
dispersion of the nanofillers in the nanocomposite, would Voigt upper bound : E = f Ef + (1 − f )Em (20)
successfully record the filler features in the nanocompos- (rule of mixture)
ites.
The two models in the random filler orientation domain 1 f (1 − f )
Reuss lower bound : = + (21)
which yielded the widest differences between predicted E Ef Em
and observed values (Lape-Cussler, random array and
(inverse rule of mixture)
Gusev-Lusti) have been modified by Bhattacharya et al.
[29] with IAF in order to make them applicable in polymer
where, Em is the tensile modulus of the polymer, Ef is
nanocomposites. They have introduced the IAF to reduce
the tensile modulus of the clay,
is the shape-parameter
over reliance on aspect ratio in those models and to account
(2l/t); l and t are the length and thickness of dispersed
for the influence of random distributions of nanofillers,
clays, f is the filler volume-fraction and ˛2 is the inverse
characterized here by their correlation lengths in polymer
aspect ratio of the dispersed clays (˛2 ≤ 0.1). They reported
matrices. Therefore the modified equations representing
that both the experimental data and modeling results
the two models after introducing the IAF can be expressed
fall between the Voigt upper bound and Reuss lower
as:
bound being used as generic principles for the elasticity of
P 1− multiphase composites. They showed that OOF modeling
= (17)
P0 exp {( /3.47)}
0.71 prediction is in good-agreement with the experimental
data. The comparison with Halpin-Tsai model and Hui-
and Shia model in two fixed aspect ratios (l/t = 10 and l/t = 100)
P 1− indicated the experimental data and modeling results
= (18) were much nearer to these model curves with l/t = 10,
P0 (1 + /3)
2
i.e., with Hui-Shia model rather than with Halpin-Tsai
After introducing IAF, those models provided the best Model. Therefore, it could be concluded that intercalated
fits with the experimental values. The introduction of IAF nanocomposites are formed when l/t is approximately
provides definitive change to the predicting ability of the 10 and exfoliation takes place when l/t is in the range of
Gusev-Lusti and Lape-Cussler (random array) models for 100–1000 [321].
barrier properties of polymer nanocomposites. It signifies Qiao et al. [322] also described the mechanics of
the need of a correction factor which is incorporated in polymer-clay nanocomposites. They also reported that the
the form of an interface area function (IAF), which con- modulus enhancement is strongly related to the volume
sists of the specific surface area, correlation length between of added clay as well as volume of constrained polymer.
nanofillers in the composite and the filler volume fraction Actually, modulus enhancement follows a power law with
resulting in better fitment, indicated by higher regression the content of the clay and is modeled well by Mooney’s
coefficients. equation for the soft-polymer-based nanocomposites. This
180 M. Kotal, A.K. Bhowmick / Progress in Polymer Science 51 (2015) 127–187
modeling indicates that the increment of modulus is deter-
mined by the high aspect ratio of the intercalated clay and
the strong interfacial strength, in the form of Einstein coef-
ficient, K, when the modulus of matrix is much lower than
that of clay, Ef /Em > 100. They suggested that the interca-
lated clay phase served as nonmelting crystalline phase,
resulting in enhancement in mechanical and thermal prop-
erties of the nanocomposites.
6. Concluding remarks
The nanocomposite concept has been considered to be
an exciting route for creating new and innovative mate-
rials with improved performance properties to achieve a
continuing demand for the advancing rubber and plastic
manufacturing industries. Both modified natural and syn-
thetic clays including montmorillonite, hectorite, laponite,
sepiolite, saponite, halloysite nanotube, etc., along with
synthetic MMT, hectorite, and layered double hydroxide
are some of the most widely used clays for designing
high-performance polymer nanocomposites. Modification
of each clay has been considered for the preparation of cor-
responding polymer nanocomposites and their effects on
the structure and properties of polymer nanocomposites
have been discussed in this review. Even at a low load-
ing, these nanocomposites exhibited remarkably higher
mechanical, thermal, dynamic mechanical, adhesion and
barrier properties, flame retardancy, etc., compared to
that of conventionally filled system. For these reasons,
nanocomposites are far lighter in weight than conventional
composite materials, making them competitive with other
materials for specific applications. However, the major
topic not thoroughly addressed in most articles is the
impact of modifying clays by extracting the surfactant as
most of the surfactants decompose very early to products
which catalyze the degradation of the polymer matrix and
provoke earlier ignition resulting in deteriorating the fire
retardance properties. The theory and modeling to design
polymer nanocomposites are also presented to develop
better understanding of the formation of high-performance
polymer nanocomposites. Combination of various poly-
mers with clays has been tried. The clays chosen for a
particular polymer by are chosen essentially at random in
any case, rather than by a selection using a relevant sci-
entific principle (at least no such a process was reported).
The results were explained later by invoking some the-
ories or understanding the chemistry of the process or
interaction. Although a variety of polymers covering plas-
tics, rubber, fiber, etc., were taken up for investigation,
the number of clays selected was limited, usually con-
centrated on the smectite group because of their well
documented exfoliation characteristics. All these investi-
gations were mostly solution based and loading of filler
beyond a certain concentration was futile. The properties
investigated were not very broad, excepting those cov-
ered in few patents [323,324]. There is scope of research
in these areas. Application of polymer nanocomposites has
gained momentum and these nanocomposites show excel-
lent promise in future. New applications are coming out
on the horizon. Some clays are found to exhibit excellent
reinforcement characteristics, while others need special
treatment. In view of their natural origin and abundance,
these materials are bound to find a variety of applications
as these are considered to be green applications. Proper
technology needs to be developed for their wide rang-
ing applications. There is no doubt that the characteristics
of a polymer should be combined with the characteris-
tics of fillers, where modification would be important.
Structure–property relationship of various polymer com-
posites should be undertaken in a vigorous way because
of the above promise. Modified clays in combination with
other fillers would be a subject of several future investi-
gations for which the work has been started. The goals for
their use are vast and hence there can be many pathways
for utilization of these clays. In terms of chemistry of modi-
fication of clays, although a few have been attempted, there
are opportunities for new chemistries and exploitation of
these modified clays in polymers is a good research topic.
Along with such esthetic properties which are addressed,
long-term durability, cost-effectiveness should be equally
considered so that ready-to-use products with market
acceptance could be designed. Though an attempt to
address the health and environmental safety issues has
been taken in this review, there is yet lot more to be done
in this field. However, the above described problems are
expected to be resolved in near future by providing con-
tinuous effort on the theoretical as well as applied work
of modified clay based polymer nanocomposites globally
both in academia and industry.
Acknowledgements
The authors would like to acknowledge the Bridgestone
Corporation, Japan for partial support of this work.
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