Chemical Engineering and Processing 85 (2014) 86–107

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Review

Ultrasound assisted in situ emulsion polymerization for polymer

nanocomposite: A review
B.A. Bhanvase a,∗ , S.H. Sonawane b,∗∗
a
Chemical Engineering Department, Laxminarayan Institute of Technology, Nagpur 440033, MS, India
b
Chemical Engineering Department, National Institute of Technology, Warangal 506004, AP, India

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

Article history: This review covers an ultrasound assisted synthesis of polymer nanocomposites using in situ emulsion
Received 24 January 2014 polymerization. First of all, surface modification of core nanoparticles with a coupling agent and surfactant
Received in revised form 16 April 2014 has been employed for the synthesis of core–shell polymer nanocomposites. In addition to application
Accepted 18 August 2014
of ultrasound for the synthesis of core–shell polymer nanocomposites, due to its influential efficiency,
Available online 26 August 2014
sonochemistry has been extensively used not only as an aid of dispersion for inorganic nanoparticles
and organo-clay, but also acts as an initiator to enhance polymerization rate for synthesis of polymer
Keywords:
nanocomposites. In situ emulsion polymerization of hydrophobic monomers, such as methyl methacry-
Sonochemistry
Nanoparticles late, butyl acrylate, aniline, vinyl monomers and styrene, using surfactant and water soluble initiator
Core–shell were carried out for a synthesis of core–shell polymer nanocomposite. This technique assists in prepa-
Polymer nanocomposite ration of stable and finely dispersed polymer nanocomposite with the loading of inorganic particles up
In situ emulsion polymerization to 5 wt.%. Recent developments in the preparation of core–shell polymer nanocomposites using an ultra-
sound assisted method with their physical characteristics such as morphology, thermal, and rheological
properties and their potential engineering applications have been discussed in this review.
© 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2. Ultrasound assisted emulsion polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3. Polymer nanocomposites synthesis techniques and role of ultrasound in polymer nanocomposites preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.1. Solution processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.2. Melt mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.3. In situ polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.3.1. Conventional in situ emulsion polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.3.2. Sonochemical in situ emulsion polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
4. Types of polymer nanocomposites synthesized by ultrasound assisted in situ emulsion polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
4.1. Polymer-oxide particle nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.2. Polymer-metal nanocomposite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.3. Polymer-magnetic particle nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.4. Conducting polymer based nanocomposite particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.5. Polymer-layered silicate (clay) nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
4.6. Polymer-carbon nanotube nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104

∗ Corresponding author. Tel.: +91 712 2531659; fax: +91 712 2561107.
∗∗ Corresponding author. Tel.: +91 870 2462626.
E-mail addresses: bharatbhanvase@gmail.com, bharatbhanvase@yahoo.com (B.A. Bhanvase), shirishsonawane09@gmail.com (S.H. Sonawane).

http://dx.doi.org/10.1016/j.cep.2014.08.007
0255-2701/© 2014 Elsevier B.V. All rights reserved.
 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
1. Introduction
The first attempt to use of the ultrasound in enhancement
of chemical reaction rates was reported by Richards, A.L. Loomis
in 1927 [1]. Since then the use of ultrasound in the synthe-
sis has attracted a lot of interest, in various fields of chemistry,
materials science and chemical engineering [2–4]. Cavitation as a
phenomenon was first identified and reported by Thornycroft and
Barnaby in 1895 [5]. When more powerful ultrasound at a lower fre-
quency is applied to a system, it is possible to produce the chemical
changes as a result of acoustically generated cavitation. The genera-
tion of radicals takes place due to the extreme environment created
by acoustic cavitation [6,7]. In addition, the physical effect of the
medium on the wave is referred to low power or high frequency
ultrasound. The physical effect in the fields of nanomaterials like
thermal heating, mass transfer, emulsification, and surface cleaning
are induced by cavitation [8].
Application of sonochemistry in materials science and nano-
technology has been covered and reviewed by a several authors
[2,8–12]. Early reviews on nanostructured materials prepared using
ultrasound radiation and applications of ultrasound to materials
chemistry were carried out by Suslick and Price [2,9]. Then the
review on “Ultrasound assisted chemical processes” was carried
out by Ashokkumar and Grieser [10]. This review highlighted the
area of synthesis of the nanomaterials using ultrasound assisted
technique. They have reviewed the use of ultrasound in homo-
geneous (radical and pyrolytic) and heterogeneous (synthesis of
metal and semiconductor particles, complex molecules such as pro-
tein and polymers) reaction systems. Further, they have described
the effect of ultrasound on leather processing, drug delivery, intra-
particle collisions, precipitation stripping of rare earth oxalates and
water treatment. The review on sonochemistry for the fabrication
of nanomaterials has been carried out by Gedanken [8]. He has
reviewed the work related to materials science and nanotechnol-
ogy, in which it has been concluded that the sonochemical method
of synthesis is superior over all other existing techniques. The top-
ics reviewed were preparation of amorphous products, insertion of
nanomaterials into mesoporous materials, deposition of nanopar-
ticles on ceramic and polymeric surfaces and the formation of
proteinaceous micro- and nanospheres using cavitation technique.
The recent reviews [11,12] reported the sonochemical fabrication
of polymer nanocomposites and sonochemical synthesis of nano-
structured materials such as carbon nanotubes (CNT), organophillic
clay, and metal nanoparticles.
In the area of polymer science, due to the intense conditions
generated by acoustic cavitation, ultrasound acts as an initiator
by breaking chemical bonds of molecules and thus enhances the
rate of polymerization. Cao et al. [13] have studied the radical
generation mechanism in ultrasonically irradiated emulsion copo-
lymerization of styrene in the presence of a cationic surfactant
(methacryloxyethyl dodecydimethyl ammonium bromide, C12 N+ )
without adding any chemical initiators. Under ultrasonic irradia-
tion condition, C12 N+ undergoes bond scission between the two
alkyl and ionic group thus producing much more original radicals to
initiate the emulsion polymerization. Teo et al. [14] have reported
the miniemulsion polymerization of methacrylate monomers in
the presence of ultrasound without the use of external initiator
and at 30 ◦ C (room temperature synthesis using cavitation). They
have observed that these cavitation based polymerization reac-
tions follow pseudo-first-order kinetics and further it has been
reported that a radical enters the monomer droplet containing
a growing radical will lead to pseudo-instantaneous termination.
The mechanism for the preparation of polymer latex particles
involved in sonochemical process is very similar to that of a
conventional miniemulsion polymerization process. Ultrasonically
initiated emulsion polymerization of methyl methacrylate [14–20],
87
styrene [17,18,21–24], n-butyl methacrylate [25], n-butyl acry-
late [19,22,26] were also studied. The rate of polymerization of
methacrylate monomers [14] is strongly dependent on the tem-
perature, vapor pressure and hydrophobicity of monomer and
ultrasonic intensity, which were the important findings reported
by Teo et al. [14].
For the preparation of polymer nanocomposites either organic
molecules or inorganic particles can be encapsulated into inorganic
materials or organic polymer latex, which could be accomplished
by applying cavitation during the polymerization process. There
have been several research articles which describe the prepara-
tion of polymer nanocomposite by conventional in situ emulsion
polymerization, but attempt was not successful in making com-
plete encapsulation [27–33]. Recently, numbers of attempts were
made by the researchers in the preparation of polymer nanocom-
posites latexes using ultrasonically initiated in situ emulsion
polymerization [34–46]. This ultrasound assisted in situ emulsion
polymerization technique provides an effective way of synthe-
sizing finely dispersed inorganic particles in polymer latex along
with many advantages such as higher polymerization rate, narrow
molecular weight and particle size distribution, higher monomer
conversion and no or small amount of external initiator require-
ment compared to convention in situ emulsion polymerization
[34–46]. Fillers, such as titanium dioxide, calcium carbonate, clays,
several oxides and metal particles were encapsulated by means
of ultrasound assisted in situ emulsion polymerization [34–46].
Addition of untreated inorganic particles during emulsion poly-
merization makes system unstable and leads to agglomeration
of particles. Hence, functionalization of inorganic fillers plays an
important role during the encapsulation process. Surface modifi-
cation of an inorganic particle with an organic molecule is one of
the ways to reduce its surface energy and to increase its compatibil-
ity with the organic polymer matrix. The surface modification has
been extensively carried out using different organic modifiers and
surfactants, e.g. silane coupling agents, titanate coupling agents, or
stearic acid, myristic acid, etc. [47–51].
2. Ultrasound assisted emulsion polymerization
It is well known that for emulsion polymerization, hydrophobic
monomer, emulsifier and hydrophilic initiator are the main con-
stituents could be used in the water phase (continuous phase).
Polymers such as acrylonitrile butadiene styrene, polystyrene,
poly-methyl methacrylate, etc. can be easily prepared via emulsion
polymerization processes. These conventional emulsion poly-
merization processes have different disadvantages, e.g. high
polydispersity of particles, and instability of colloidal particles [19].
Further, separation of the initiator constituents is difficult, which
may affect the purity of the final product. This problem can be
eliminated by avoiding the use of chemical initiator in the reac-
tion medium. Hence, the use of ultrasound for an initiation of
emulsion polymerization has the advantage to synthesis the poly-
mer products with high purity [19,52]. Ultrasound is found to be
one of the most efficient methods for the preparation of stable
monomer droplets without any aggregation during the emulsion
polymerization process [6,53]. Ultrasound assisted emulsion poly-
merization has several advantages over the conventional emulsion
polymerization process such as (1) improved polymerization rate,
(2) narrow molecular weight and particles size distribution, (3)
higher monomer conversion, (4) degassing of oxygen from reaction
mass, which acts as an inhibiting agent, (5) generation of radicals
through the degradation of water, surfactant or polymer chains
which helps in initiating the polymerization, (6) rapid dissocia-
tion of initiator therefore increased production rate of radical, (7)
reduction in polymerization reaction time, and (8) a requirement
88 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
of small amount or no initiator [14,18,19]. Bradley and Grieser [19],
Teo et al. [14], Nie et al. [54] and Yin et al. [22] have reported an
eco-friendliness of an ultrasound assisted emulsion polymeriza-
tion method as there is no use of chemical initiators or costabilizers
during polymerization. The factors contributing to the rates of poly-
merization in ultrasonic initiated miniemulsion polymerization of
different methylacrylate monomers at 30 ◦ C have been investigated
by Teo et al. [14]. The results reported by Teo et al. [14] indicate the
pseudo-first-order kinetics of the reaction. The reported molecular
weights of the polymer formed by ultrasound initiation are con-
siderably larger than those prepared by the conventional method,
which can be attributed to the large number of individual particles
polymerizing independently. The observed trend in the monomer
conversion rates for the reported monomer systems is attributed
to the differences in the surface activities (hydrophobicities) of
the monomers. Parra et al. [15] have studied the effect of sur-
factant nature, and concentration, and monomer concentration on
the synthesis of poly(methyl methacrylate) using high-frequency
ultrasound. In this case also the polymerization was initiated by
the free radicals generated in aqueous solution for the different
concentrations of an anionic or a cationic surfactant and insolu-
ble monomer methyl methacrylate as the dispersed phase [15].
The maximum conversion has been reported in this article, when
the anionic surfactant was employed with average particle size of
poly(methyl methacrylate) latex spheres from 65 to 100 nm. It may
be because of formation of large amount of radicals in the reaction
medium by the dissociation of anionic surfactant in the presence
of ultrasound. Kruus and Patraboy [16] have also proved the initi-
ation of methyl methacrylate polymerization in a vinyl monomer
with the use of an intense ultrasound. Further, Cheung and Gad-
dam [17] have discussed the effect of ultrasound during emulsion
polymerization of methyl methacrylate and styrene in the pres-
ence of azo-bisisobutyronitrile and potassium persulfate initiators
at different temperatures. The rate of polymerization and the final
conversion was reported higher when ultrasound was used for the
polymerization system at lower temperatures (50 ◦ C). However, at
higher temperatures (70 ◦ C) the polymerization rate is seemingly
unaffected by the use of ultrasound. The temperature of the reaction
medium plays an important role during ultrasound assisted poly-
merization. At high temperature the vapor pressure of the reaction
medium is higher that results into less intense cavity collapse. Less
intense cavity collapse leads to formation of less number of radi-
cals which are required for initiation of polymerization. Therefore
ultrasound assisted emulsion polymerization can be performed
at lower temperature which can save the substantial amount of
energy. Wang and Cheung [18] have also shown that the use of
ultrasonic irradiation can induce the polymerization of MMA or
styrene in liquid carbon dioxide in the absence of any form of sta-
bilizer. The reported results demonstrate that the irradiation period
and CO2 :MMA ratio have a significant effect on both the molecular
weight and molecular weight distribution of the resulting polymer.
The overall mechanism of the preparation of polymer latex
particles by ultrasound assisted min-emulsion polymerization is
reported by Bradley and Grieser [19]. There are two types of effects
during ultrasound assisted polymerization reaction (1) physical
effects and (2) chemical effects. In physical effects, due to acoustic
cavitation intense mixing and the strong dispersion of reaction mix-
ture takes place. The high shearing effect also controls the growth of
polymer particle by reducing Ostwald ripening process. Whereas, in
chemical effects, the acoustic cavitation helps in generation of radi-
cal, this will initiate the polymerization process. Recently, Bhanvase
et al. [55] have carried out semibatch miniemulsion polymeriza-
tion for the preparation of PMMA nanoparticles. In their report,
the effect of free radicals produced by ultrasound and an external
addition of initiator on polymerization rate and polymer particle
size has been investigated. The reported particle size of PMMA
nanoparticles is 50 nm with a narrow size distribution. It can be
concluded from the Bhanvase et al. [55] report that the polymer par-
ticle size is significantly get reduced due to the high shearing effect
by reducing Ostwald ripening process. Study of the ultrasound
assisted emulsion polymerization of number of monomers such as
methyl methacrylate, styrene, n-butyl methacrylate, n-butyl acry-
late were carried out by Price et al. [20,52], Ooi and Biggs [21],
Yin et al. [22], Kojima et al. [23], Biggs and Grieser [24], Teo et al.
[25,56,57], Kobayashi et al. [53] and Xia et al. [26]. Some representa-
tive examples of ultrasound assisted emulsion polymerization have
been reported in Table 1.
3. Polymer nanocomposites synthesis techniques and role
of ultrasound in polymer nanocomposites preparation
Preparation of polymer nanocomposite from nano-inorganic
additives and polymers has been accomplished by the means of
surface encapsulation or surface grafting. Several methods have
been implemented to synthesize polymer nanocomposites. Some
of them are, suspension polymerization [58,59] emulsion poly-
merization [60], intercalative polymerization [61], solution casting
method [62], hybrid latex polymerization [63]. Improper dispersion
of inorganic nanoparticles and weak bonding between polymer and
inorganic particles leads to phase separation. There have been sev-
eral studies on the preparation of polymer nanocomposites that
can be divided into two major categories: physical and chemi-
cal methods. Physical methods comprised of solvent processing,
melt-processing, and polymer melt intercalation whereas chemical
methods are in situ polymerization [64].
3.1. Solution processing
In solvent processing method, the nanoparticles were added to
the base polymer or pre-polymer solution, which is prepared in a
suitable solvent. The obtained mixture was agitated to prepare a
uniform mixture. The nanocomposites were prepared by remov-
ing the solvent. This method is being utilized for the preparation
of polymer/layered silicate nanocomposite in which the polymer
or pre-polymer is soluble in a solvent and the silicate layers are
swellable. The layered silicate is first swollen in a solvent, such as
water, chloroform, or toluene. When the polymer or pre-polymer
and layered silicate solutions are mixed thoroughly, the polymer
chains intercalate and displace the solvent within the interlayer
of the silicate. Intercalated structured polymer/layered silicate
nanocomposite was obtained upon solvent removal. The thermo-
dynamics of the solution processing method are explained in the
accompanying text. In this process, the polymer is exchanged with
the previously intercalated solvent in the silicate gallery, where the
necessary Gibbs energy change is negative. The driving force for
the polymer intercalation into layered silicate from solution is the
entropy gained by desorption of solvent molecules, which com-
pensates for the decreased entropy of the restricted, intercalated
chains [65]. By means of this method, intercalation only occurs for
certain polymer/solvent pairs. This method is good for the interca-
lation of polymers with small or no polarity into layered structures,
and assists the production of thin films with polymer-oriented clay
intercalated layers. However, from a commercial standpoint, this
method involves the use of large quantities of organic solvents,
which is typically environmentally unfriendly and economically
very expensive.
Currently an ultrasound assisted solution processing technique
is used for the better dispersion of the nanofillers in the poly-
mer. It has been seen that intense sharing due to ultrasound helps
in the dispersion of nanofillers such as graphite sheets in poly-
mer matrix. This uniform dispersion of nanofiller due to sonication
 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107 89

Table 1
Representative examples of ultrasound assisted polymerization.

Reference System Effect of ultrasound (comparison with conventional method)

Cao et al. [13] Copolymerization of styrene and a cationic polymerizable • Rate of copolymerization was high.
surfactant C12 N+ • No external Initiator used.
• Diameter of latex particles is about 26 nm, which is smaller conventional
emulsion polymerization.

Teo et al. [14] Miniemulsion polymerization of methacrylate monomers • No external Initiator used.
• Polymerization at low temperature (30 ◦ C)
• Reactions follow pseudo-first-order kinetics
• Molecular weights of the polymer are larger than prepared by the
conventional method.

Parra et al. [15] Synthesis of poly(methyl methacrylate) using • Polymerization initiated by the free radicals generated due to ultrasonication.
high-frequency ultrasound emulsion polymerization • Radical generation rate is dependent on concentrations of surfactant.
• Maximum conversion for anionic surfactant.
• Average particle size of PMMA latex spheres is in between 65 and 100 nm.

Kruus and Patraboy Methyl methacrylate polymerization • Initiation of MMA polymerization with intense ultrasound.
[16]

[5pt] Cheung and Emulsion polymerization of methyl methacrylate and • Rate of polymerization and final conversion is higher when ultrasound is
Gaddam [17] styrene introduced.
• At higher temperatures the polymerization rate is unaffected by the use of
ultrasound.

Bradley and Grieser Ultrasound assisted min-emulsion polymerization of MMA • Latex size is in the range of 30–100 nm.
[19] and BA • High shearing effect controls the growth of polymer particle.
Power: 7 and 9 W/cm2 • Acoustic cavitation helps in generation of radical.

Price et al. [20] Ultrasound initiated polymerization of MMA • Synthesis of polymers with controlled molecular weight, polydispersity and
tacticity.

Ooi and Biggs [21] Ultrasound initiated emulsion polymerization of styrene • Small latex particle sizes ranges from 40 to 50 nm, No chemical initiators
used.
• Particle size distributions are invariant with acoustic intensity
• Polymerization rate affected by change in acoustic intensity.

Yin et al. [22] Preparation of BA/styrene/acrylamide nanoparticles by • Emulsifier-free emulsion polymerization (environmental friendly).
ultrasonic emulsifier-free emulsion polymerization • No volatile organic solvent and initiator used.
• Particles size is about 80 nm, which was less than particles size (about
140 nm) by conventional emulsifier-free emulsion polymerization method.

Kojima et al. [23] Effect of ultrasonic frequency on polymerization of styrene • Polymerization at the frequencies of 23.4, 45.7, 92, 518 kHz and 1 MHz.
• Polymerization rate and molecular weight increases as frequency decreases
from 92 to 23.4 kHz.
• At the high frequencies no polymerization was occurred.

Biggs and Grieser Polystyrene latex with ultrasound initiated emulsion • Polymerization at low temperature in absence of initiator.
[24] polymerization • No region of steady state was observed (which different than conventional
emulsion polymerization).
• Smaller particle size around 50 nm.

Teo et al. [25] Nano-sized polymer latex particles using high-frequency
ultrasound assisted micro-emulsion polymerization.
• Use of ionic surfactants as stabilizers leads to the formation of transparent
latex particles
• Molecular weights decreases with increasing amount of SDS.
• Polymerization rates were significantly fast and reached near-completion
within 15 min.

Price [52] Effect of ultrasound on (1) the polymerization of cyclic • Rates of reaction in step growth reactions are accelerated by the use of high
lactones to give aliphatic polyesters and (2) the formation intensity ultrasound.
of polyurethanes

Kobayashi et al. Indirect ultrasonic intensified emulsion polymerization of • Ultrasonic generators used as emulsifiers.
[53] styrene • No chemical initiator used.
• Emulsion polymerization under indirect ultrasonic irradiation.

Nie et al. [54] Ultrasonically initiated emulsion polymerization of styrene • Ecofriendly method as there is no use of chemical initiators or costabilizers.
• Emulsion polymerization in the presence of aliphatic alcohols.
• Due to aliphatic alcohols, the polymerization rate gets improved.

Bhanvase et al. [55] Ultrasound assisted semibatch emulsion polymerization in • PMMA particles are in nanosize and spherical in nature of size 50 nm.
the presence of initiator • Syndiotactic phase of PMMA is significant at lower MMA concentration,
increase in surfactant concentration and lower reaction temperature

Teo et al. [56] Sonochemical miniemulsion polymerization of n-butyl • Miniemulsion polymerization at ambient conditions.
methacrylate • Polymerization rate and molecular weight are dependent on the amount and
type of the organic liquid present in the emulsion.
• The size of polymer significantly decreased in the presence of an organic
liquid.

Teo et al. [57] Ultrasound initiated polymerization of butyl methacrylate • No chemical initiator used.
in mini- and microemulsions • Polymerization rate notably enhanced at surfactant concentration greater
than 0.5 wt.%.
• Stable latex dispersions containing nanoparticles of size 40–85 nm.
90 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
significantly improves the mechanical and electrical properties of
polymer nanocomposite, which are always better than conven-
tional methods.
Wang et al. [66] have prepared silicone rubber/montmorillonite
hybrids from solution and melt. In their study, the comparisons
between the tensile properties of aerosilica–polydimethylsiloxane
and clay–polydimethylsiloxane hybrids synthesized from melting
and solution intercalation have been implemented. The reported
result shows that montmorillonite could be dispersed in the sil-
icone rubber matrix more uniformly from solution than from
melt. Yu et al. [67] have also used one step soft solution-
processing route called the solvothermal-copolymerization for
polystyrene/CdS nanocomposites embedded with CdS nanowires
in ethylenediamine media at temperatures 80–140 ◦ C. As per their
report, the polymerization of the monomers and the formation
of the CdS nanocrystallites were carried out simultaneously. It
has been reported that both temperature and solvent were the
important parameters during the preparation of the nanocom-
posites. Yasmin et al. [68] have carried out the preparation of
the nanocomposites consisting of anhydride cured epoxy resin
matrix reinforced with expanded graphite with concentrations
of 1–2 wt.%. The purpose of the processing techniques such as
direct, sonication, shear, and combined sonication and shear mix-
ing techniques during the fabrication of nanocomposites has been
reported. Further, it has been reported that both sonication and
shear mixing helps in the formation of nanosize graphite sheets
from expanded graphite during polymerization. The fine disper-
sion of the said nanofiller in the expanded graphite reinforced
nanocomposites showed higher elastic modulus than neat epoxy. It
has been also stated that sonication time has a strong influence on
the mechanical properties of the resultant nanocomposites. Chen
et al. [69] have reported the new process for the dispersion of
graphite nanosheets in a polymer matrix by in situ polymerization
of monomer in the presence of sonicated expanded graphite during
sonication. Sonicated expanded graphite nanosheets of thickness
of 30–80 nm are dispersed in a polystyrene matrix via in situ
polymerization. The excellent conducting property of resulting
polystyrene/graphite nanosheet nanocomposite films attributed
to the use of sonication during in situ polymerization than those
of composites made by conventional methods has been reported.
This enhancement in the conducting property achieved by Chen
et al. [69] is attributed to the use of ultrasonication which dis-
perses the graphite nanosheets finely in polymer matrix. For
better exfoliation, Cho et al. [70] pulverized expanded graphite
nanoplatelets after heat treatment (900 ◦ C) using ultrasonication,
ball-milling, and vibratory ball-milling techniques to fabricate the
phenylethynyl-terminated polyimide/expanded graphite compos-
ites. The storage modulus dynamic mechanical properties and
glass transition temperature significantly increased with increasing
concentration of expanded graphite nanoreinforcements regard-
less of size. This improvement in the properties is because of the
use of ultrasonication which improves the dispersion as well as
loading of expanded graphite in polymer matrix. Li et al. [71]
have proposed UV/ozone treatment on expanded graphite at room
temperature and atmospheric pressure. Ultrasonication, (Ultrason-
icator at 70 W, 42 kHz), was used for the preparation of uniform
dispersion and interfacial adhesion of expanded graphite with the
epoxy matrix. Improved mechanical and electrical properties were
achieved using this reported technique. This improvement in the
properties may be attributed to the intensity of cavity implosion
which can easily be altered by many factors such as acoustic fre-
quency, acoustic intensity, ambient temperature, static pressure,
choice of liquid and choice of ambient gas. However, authors have
not studied the effect of the mentioned parameter on the disper-
sion of expanded graphite. Safadi et al. [72] and Qian et al. [73] have
explained the basic relationships between processing conditions
and the mechanical and electrical properties of multiwalled carbon
nanotube reinforced polymer composites. Conventional methods
of dispersion of carbon nanotubes use an aggressive chemical mod-
ification of the nanotubes or by the use of a surfactant prior to
dispersion. However, the ultrasonic energy can be used to disperse
multiwalled nanotubes uniformly in solutions and to incorporate
them into composites without chemical pretreatment. Safadi et al.
[72] have dispersed multiwalled nanotubes in polystyrene solu-
tions with aid of ultrasound. This uniform dispersion improves the
tensile modulus and strain to failure of samples significantly.
3.2. Melt mixing
Physical methods for the preparation of polymer inorganic
nanocomposites are based on liquid particle dispersions, but dif-
fer in the case of the continuous phase. In melt process, particles
are dispersed into a polymer at melt condition and then polymer
inorganic nanocomposites are obtained by extrusion. Melt mixing
has been employed for the dispersion of a wide range of materi-
als such as clays, oxides, and carbon nanotubes in polymer melt.
The significant strength of this process is that the large amount
of material can be made by extrusion of injectors. For example,
CaCO3 or nanoscale silica incorporated Nylon composites have suc-
cessfully been synthesized using high velocity oxy-fuel combustion
spray process [74]. Hong and colleagues [74] have also covered the
preparation of nanocomposite by incorporating nano-ZnO in low-
density polyethylene melt in a high-shear mixer, which improves
the thermal stability of resulted nanocomposite [74]. In addition,
Nylon 6/nanosilica [75], polypropylene/nanosilica [76] compos-
ites were successfully processed in a twin-screw extruder. Further,
when the nanofiller such as clays are to be dispersed in a polymer
matrix, they are either intercalated by macromolecules or exfoli-
ated. The best performances are generally observed when complete
exfoliation of clay is achieved in the polymer nanocomposites.
However, complete exfoliation is extremely difficult to achieve by
simple mixing method. Therefore, high intensity ultrasound with
melt processing can be used to overcome this limitation of exist-
ing methods. Ultrasonic assisted melt processing was anticipated
to achieve effective breakup of the clay agglomerates and exfo-
liation of the silicate layers to yield useful various polymer–clay
nanocomposites. Swain and Isayev [77] have prepared high density
polyethylene/organoclay nanocomposites of varying concentra-
tions of clay using a single screw compounding extruder with
the attached ultrasound die operating at amplitude of 10 ␮m. An
ultrasonic treatment enhances the intercalation of high density
polyethylene into lattice layers of clay by increasing d-spacing up to
50%. This leads to an improvement in the rheological and mechan-
ical properties of the nanocomposites after ultrasonic treatment
in comparison with the untreated nanocomposites. However, a
reduction in oxygen permeability of nanocomposites was reported
after ultrasonic treatment. Ryu et al. [78] have also used ultrason-
ically assisted polymerization and melt-mixing processes for the
preparation of polymer-clay nanocomposites. Ultrasonic irradia-
tion has been employed to enhance nano-scale dispersion during
melt-mixing of polymer blends and organically modified clay. The
ultrasound-assisted process has been successfully employed for the
preparation of exfoliated nanocomposites, which results in supe-
rior thermal stability and elastic modulus compared to the base
polymer [78]. Further, Lee et al. [79] have used ultrasonic irradia-
tion (60 W sonicator with 1.5 in. horn, operating at a frequency of
20 kHz) to enhance exfoliation and dispersion of clay platelets in
polypropylene-based nanocomposites. The results stated by them
indicates that ultrasonic processing of polymer nanocomposites
in the melt state is an effective method for improving exfoliation
and the dispersion of nanoclays. From these studies it can con-
cluded that the use of ultrasound in melt mixing process for the
 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
preparation of polymer nanocomposite help in fine dispersion of
clay filler in polymer matrix thereby improving the properties of
the resultant polymer nanocomposite.
Although physical methods being successful in the preparation
of polymer nanocomposites, melt mixing method has several draw-
backs, e.g. (1) this process only builds up relatively weak bonding
between the polymer and the nanoparticles, (2) nanoparticles have
a very strong tendency to aggregate because of their high surface
energy, and (3) for some polymers, this processing method may
be limited due to rapid increase of the viscosity with the addi-
tion of a few volume fractions of nanoparticles. The dispersion of
nanoparticles can be successfully accomplished only after surface
modification of inorganic nanoparticles [74–76,80]. The limitation
of agglomeration and dispersion of nanofiller during melt mixing
has been overcome up to some extent, if the polymer melt and
the nanoparticles are dispersed in solution. The presence of solu-
tion allows surface modification of nanoparticle without drying,
which in turn reduces particle agglomeration [81]. After the dis-
persion, the polymer nanoparticle solution can then be sonicated
by high intensity ultrasound for fine dispersion of nanoparticles or
exfoliation of clay platelets into polymer melt [77–79].
3.3. In situ polymerization
The successful preparation of polymer-inorganic nanocom-
posite is being carried out using chemical methods like in situ
polymerization. In situ polymerization is an effective way for the
synthesis of polymer nanocomposite material. In this method the
nanoparticle are impregnated with a monomer and then polymer-
ization was carried out using different methods. There are several
methods, which are used for the preparation of nanocomposite
with fine dispersion of the inorganic particles by surface encap-
sulation. Out of these techniques, emulsion polymerization has
the significant advantage of generating monodispersed polymer
nanoparticles with controlled molecular weight and employment
of water as a dispersion medium. Further, in situ emulsion polymer-
ization is a convenient way for the encapsulation and preparation
of polymer/inorganic composite particles onto large scale [82–84].
In emulsion polymerization dispersed monomer droplet acts as
nanoreactor for growth of polymer and prevents agglomeration.
These droplets are stabilized by amphiphilic surfactant in continu-
ous phase with reduction or elimination of Oswald ripening process
by encapsulating insoluble core [45].
3.3.1. Conventional in situ emulsion polymerization
Preparation of polymer nanocomposite by in situ emulsion poly-
merization is another technique that has been extensively used
in order to increase interfacial adhesion between the polymers
and the nanoparticles, and to make an encapsulated inorganic
nanoparticle/polymer nanocomposite [85–90]. In this method
nanoparticles are dispersed first in the monomer, aqueous surfac-
tant solution and then the mixture is polymerized by the addition
of initiator. Mahdavian et al. [91] have prepared latex containing
hybrid of copolymer (styrene, methyl methacrylate, acrylic acid)
and inorganic nanoparticles (silica) with core/shell structure using
semibatch in situ emulsion polymerization. During the provision
of (styrene–methyl methacrylate)/SiO2 composite, initially silica
nanoparticles were dispersed in the water phase with the help
of ultrasound to prevent the accumulation of nanoparticles. Then
an emulsion polymerization was performed in the presence of
functionalized silica nanoparticles. The presence of 25–35 nm sil-
ica nanoparticles in the polymer latex with core/shell morphology
of nanocomposite has been confirmed. Mahdavian et al. [91] have
also attempted copolymerization of styrene–methyl methacrylate
in the presence of modified silica particles in order to investigate
the effect of compatiblization. There are several research articles
91
in the literature, which reports successful preparation of core/shell
structured polymer-silica nanocomposite by conventional in situ
emulsion polymerization [85–90].
Poly(methyl methacrylate), PMMA, is an important commer-
cial polymer which has found applications in aircraft glazing,
lighting, dentures, food-handling equipment, contact lenses and
so on [92]. There are several reports about the encapsulation
of CaCO3 into the PMMA by emulsion polymerization [92–95].
Ma et al. [96] have attempted the preparation of CaCO3 /PMMA
composite microspheres by soapless emulsion polymerization pro-
cess. It has been observed that surface modification of CaCO3
with oleic acid improves the compatibility between CaCO3
and the monomer methyl methacrylate, which in turn effec-
tively improves encapsulation of CaCO3 in the nanocomposite.
CaCO3 nanoparticles are in cubic shape with the mean size
around 40 nm and the CaCO3 /PMMA composite microspheres
with the size about 350 nm with CaCO3 nanoparticles are well
encapsulated in the polymeric matrix. Zhang et al. [97] have
also attempted synthesis of Mg(OH)2 /polystyrene nanocompos-
ite by using soapless in situ emulsion polymerization. Also an
attempts were made for the preparation of polystyrene/CaCO3
[98,99], nano-Al2 O3 /poly(styrene–methyl methacrylate) [100],
PMMA/Al2 O3 [101], nano-ZnO/PMMA [102], poly(MMA-M12-
BPMA)/TiO2 [103], PMMA/TiO2 [104], PMMA/flaky aluminum
composite[105], PS/MMT [106,107], polystyrene–laponite [108],
PANI/Zn0.5 Cu0.5 Fe2 O4 [109] and magnetic hollow PMMA [110]
composite nanoparticles by in situ conventional emulsion polymer-
ization.
3.3.2. Sonochemical in situ emulsion polymerization
Polymer nanocomposite prepared by conventional in situ emul-
sion polymerization may find improper dispersion of inorganic
nanoparticles. This in turn leads to an inferior property profile of
polymer nanocomposite. However, to obtain fine and uniform dis-
persion of inorganic nanoparticles in polymer, ultrasound assisted
in situ emulsion polymerization can find potential application in
the preparation of polymer nanocomposite. Recently, ultrasound
assisted in situ emulsion polymerization is a well accepted technol-
ogy for synthesis of finely dispersed inorganic particles in polymer
nanocomposites. Fillers, such as titanium dioxide, calcium carbon-
ate, clays, several oxides and metal particles were encapsulated
by means of ultrasound assisted in situ emulsion polymerization
[34–46]. Preparation of different types of polymer nanocomposites
of various inorganic, inorganic oxides, clay and magnetic particles
by using ultrasound assisted in situ emulsion has been paying more
attention because it not only allows short reaction times, but also
it is easy to handle.
4. Types of polymer nanocomposites synthesized by
ultrasound assisted in situ emulsion polymerization
Encapsulated polymer nanocomposites are intended to combine
the best features of the organic and the inorganic compound. These
hybrid particles can be defined as colloidal particles that include
both organic and inorganic compounds. These polymer nanocom-
posites can be prepared by (a) combining organic and inorganic
components, (b) reacting organic and inorganic precursors, or (c)
polymerizing in situ organic and/or inorganic precursors in the
presence of their corresponding compound. An establishment of
specific interactions at the interface of the organic and inorganic
components is a key issue. This can be accomplished by the incorpo-
ration of inorganic particles in well-defined polymers that provides
required properties to the resulting hybrid polymer nanocompos-
ite through their functionality, composition, and dimensions. Those
92 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107

are primarily related to surface modification of silica, inorganic, the use of surfactant and chemical initiator. It is also reported that
metallic oxides, inorganic oxides, magnetic particles, clays, etc. with an increase in the content of nano-silica, the conversion of
monomer first increases up to 17%, and then decreases. This fact
4.1. Polymer-oxide particle nanocomposites indicates that in the absence of surfactant, instead of micelle, inor-
ganic nanoparticles can become the nuclei and captures the radicals
Liu et al. [34] have developed core–shell magnesium hydrox- to further initiate the encapsulating polymerization.
ide/polystyrene hybrid nanoparticles synthesized by ultrasound Bhanvase and Sonawane [111] have reported the synthesis
assisted in situ copolymerization. Vinylation of magnesium PANI/CaCO3 nanocomposite by in situ semi-batch emulsion poly-
hydroxide nanosheets was carried with 3-(trimethoxysilyl) propyl merization in the presence of indirect ultrasonic (ultrasound bath,
methacrylate and pristine nanosheets in the presence of toluene, 20 kHz, 600 W) irradiation. In situ emulsion polymerization was
aniline and deionized water in an ultrasonic bath (40 kHz). The carried out using distilled aniline as a monomer, ammonium per-
magnesium hydroxide/polystyrene hybrid nanoparticles has been sulfate as an initiator and sodium lauryl sulfate as a surfactant
reported to be prepared by ultrasound assisted in situ copo- for 90 min at 4 ◦ C. It is reported that due to ultrasonic irra-
lymerization of vinylated magnesium hydroxide nanosheets and diation, reaction rate and micro-mixing of reaction mass gets
styrene at 80 ◦ C. The hydroxyl groups present on magnesium enhanced, which resulted in fine dispersion of CaCO3 nanopar-
hydroxide surface react with the silanol groups generated by ticles in the PANI matrix. Also, hydrophobic nature of CaCO3
hydrolysis of an alkyloxyl group of ␥-MPS through dehydration and intense environment created by ultrasonic irradiations plays
and condensation to form Si O Si bonds, thus the vinyl groups important role in producing fine emulsion droplets containing
are covalently attached on magnesium hydroxide surface. Then CaCO3 , which leads to the formation of finely dispersed PANI/CaCO3
the vinylated magnesium hydroxide was further encapsulated by nanocomposite (TEM and EDAX analysis, Fig. 1). Further Bhanvase
in situ copolymerization with styrene lead to core–shell structure of and Sonawane [111] have reported the electrochemical corrosion
magnesium hydroxide/polystyrene hybrid nanoparticles. The pris- tests at room temperature (25 ◦ C). Fig. 2 shows the Tafel plot
tine magnesium hydroxide particles are irregular thin sheets in for neat alkyd resin, PANI/alkyd and PANI-CaCO3 /alkyd coating.
nanometer size with many gaps and empty space leads to the weak It is noted that the electrochemical current (Icorr. ) was decreased
force between the sheets and can be easily separated in a solvent. from 0.89 to 0.03 ␮A/cm2 , when neat alkyd resin and PANI/CaCO3
Copolymerization of styrene and vinylated magnesium hydrox- nanocomposite was tested in NaCl electrolyte solution. Observed
ide occurs in the empty space between the primary nanosheets corrosion current for neat alkyd coating was 0.89 ␮A/cm2 , while
under ultrasonic irradiation. This leads to a breakdown of the for PANI/alkyd and PANI–CaCO3 nanocomposite/alkyd coating
agglomerated magnesium hydroxide nanosheets and formation shows 0.50 and 0.03 ␮A/cm2 respectively. Additionally Ecorr value
of magnesium hydroxide/polystyrene hybrid core–shell structure
with particle size in the range of 20–300 nm. Also the uniformly dis-
persed core–shell structure of magnesium hydroxide/polystyrene
hybrid nanoparticles is attributed to that the ultrasonic irradiation
enhances the dispersion magnesium hydroxide nanosheets in the
formed emulsion particles. This enhances the dispersion of magne-
sium hydroxide nanosheets in the formed latex particles due to the
ultrasonic cavitation effect thereby increasing the thermal stability.
Jiang [35] have prepared PMMA/Ni0.5 Zn0.5 Fe2 O4 nanocomposite
by ultrasound assisted in situ emulsion polymerization of MMA
monomer in the presence of Ni0.5 Zn0.5 Fe2 O4 colloidal suspension.
The reported ultrasonic apparatus (Model KQ-250DB; Kunshan
Ultrasonic Instrument Co. Ltd.) was operated at 50 kHz and using
power 100 W. The reported TEM image of Ni0.5 Zn0.5 Fe2 O4 parti-
cles shows the spherical nature with agglomeration to some extent
because of magnetic dipole interaction between particles. Further
the TEM image of PMMA/Ni0.5 Zn0.5 Fe2 O4 nanocomposite shows
that Ni0.5 Zn0.5 Fe2 O4 nanoparticles with the particle sizes of around
12 nm are well dispersed in the polymer matrix. Further the effect of
power used and frequency of ultrasonication can be used for effec-
tive dispersion of nanoparticles in PMMA matrix. Xia et al. [36] have
also studied the ultrasonic assisted (probe of ultrasonic horn) in situ
emulsion polymerization for the preparation of polymer/inorganic
nanoparticle composites. It has been stated that the pH value,
type of monomers, type of nanoparticle content, surface proper-
ties of nanoparticles, type and concentration of surfactant have
a great influence on the ultrasonic induced encapsulating emul-
sion polymerization and the obtained latex stability. The successful
preparation of polymer/inorganic nanocomposite using cationic
emulsifier (cetyl trimethylammonium bromide), low water soluble
monomer (n-butyl acrylate and styrene), and hydrophobic nano-
silica was carried out in the presence of ultrasonic irradiation under
alkalescent condition. The conversion of butyl acrylate monomer
is reported to be affected by the loading of nanoparticles during
the ultrasonically induced emulsion polymerization [36]. Ultrason- Fig. 1. Transmission electron microscopic images and EDAX Analysis of PANI/CaCO3
ically initiated polymerization of butyl acrylate can also occur in nanocomposite.
the presence of only nanoparticles, monomer and water, without Reprinted from [111]. Copyright (2010), with permission from Elsevier.
 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
Fig. 2. Tafel plots of (1) alkyd resin, (2) PANI dispersed in alkyd resin and (3) PANI-
CaCO3 (PAC) nanocomposite dispersed in alkyd resin coatings recorded in 5% NaCl
solution.
Reprinted from [111]. Copyright (2010), with permission from Elsevier.
shows shifts toward positive side from −1.74 to −1.47 V when
the addition of PANI-CaCO3 nanocomposite in alkyd coating was
accomplished. An overall result reported by Bhanvase and Son-
awane [111] indicates that PANI–CaCO3 nanocomposite shows
an improvement in the anticorrosive properties. It has been also
reported that the physico-mechanical properties of the PANI/alkyd
coatings are found to be significantly enhanced with the load-
ing of the PANI/CaCO3 nanocomposite in alkyd resin coatings.
This improvement in the anticorrosion and mechanical properties
may be attributed to the fine dispersion of CaCO3 nanoparticles in
PANI matrix due to ultrasonic irradiations. Also ultrasound probe
type sonicator can be used for the more fine dispersion of CaCO3
Fig. 3. Mechanism of the formation process of PMMA/CaCO3 nanocomposite by ultrasonically induced encapsulating emulsion polymerization.
Reprinted from [112]. Copyright (2011), with permission from Elsevier.
93
nanoparticles in PANI matrix that may improve the properties sig-
nificantly.
Bhanvase et al. [112] has used intensified processes based on
the ultrasonic irradiations (Ultrasonic stainless steel horn = 13 mm,
22 kHz, 375 W) for the improvement of the process of encapsulation
of inorganic nanoparticles in polymer during the nanocompos-
ite synthesis process. It has been noted that the cavitational
effects produced by ultrasonic irradiations have shown enhance-
ment in the dispersion of functional nano-inorganic particles into
the monomer droplets during the polymerization process. The
model system selected for the study is based on PMMA/CaCO3
nanocomposite which was prepared by ultrasound assisted semi-
batch in situ emulsion polymerization. Pre-treatment of CaCO3
nanoparticles with myristic acid show significant improvement
in the compatibility of the monomer with the inorganic particles.
TEM images of PMMA/CaCO3 nanocomposite particles with well-
defined core–shell structure give direct indication of encapsulation.
Effect of encapsulation of CaCO3 particles on thermal properties
using thermo-gravimetric methods has been also reported and it
has been observed that the PMMA/CaCO3 nanocomposites have
better thermal stability as compared to the PMMA. The mechanism
of ultrasonically induced encapsulating emulsion polymerization
is proposed in Fig. 3. In the initiation stage, radicals are gener-
ated by the dissociation of initiator and water molecules due to
the cavitational effects generated by acoustic cavitation. Subse-
quently, in the nucleation stage micelles formation around MMA
droplet takes place. The size of monomer droplet is expected to
cut down significantly due to the turbulence effects of the cavita-
tion during emulsion polymerization. The free radicals enter the
monomer droplet resulting in the polymerization process. Thus
the presence of cavitating effects leads to an improvement in the
encapsulation of nanoparticles. The formation of nanocomposite
is attributed to both the chemical effects of the formation of free
radicals and the physical effects of intense turbulence and liquid
circulation currents.
94 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
Haldorai et al. [43] have prepared electrically conducting
copolymer poly(aniline-co-p-phenylenediamine)-SiO2 nancom-
posites by ultrasonically assisted in situ emulsion polymerization.
As per their claims, the ultrasound assisted approach can resolve
the problems of the dispersion and stabilization of SiO2 nanoparti-
cles in the copolymer matrix and there is a significant reduction of
the aggregation of SiO2 nanoparticles under ultrasonic irradiation
resulting in spherical nanocomposite particles with well dispersed
SiO2 nanoparticles. The formation of core–shell nanocomposite
was accomplished by the adsorption of comonomer molecules
and polymerization on the surface of SiO2 particles. Zhang
et al. [37] have also used high intensity ultrasonic irradiation
(20 kHz, Ti horn, 100 W cm−2 ) technique for the preparation of
SiO2 /poly(3-aminophenylboronic acid) nanocomposites. As per
their report, polymerization of 3-aminophenylboronic acid was
carried out in the presence of sodium fluoride and d-fructose
to anchor 3-aminophenylboronic acid groups on to SiO2 sur-
face. It has been reported that the nanocomposite prepared in
the presence of sodium fluoride and d-fructose in the poly-
merization medium leads to different morphologies, electrical
properties, thermal behaviors and structural characterizations.
The composite prepared under ultrasonication contributes to
the increase in conductivity in comparison with the composite
prepared with conventional stirring. The higher conductivity of
ultrasonically prepared composite over conventionally prepared
composite is attributed to (i) well dispersed SiO2 nanoparticles
(core) in the polymer (shell) due ultrasonic irradiations favors
electronic transport, (ii) enhancement of thermal stability, (iii)
better morphological structure, and (iv) self doped nature of poly-
mer in the composite. Zhang et al. [37] have further addressed
the issue of the aggregation of nanosilica which reduces sig-
nificantly in the presence ultrasonic irradiation and promotes
finely dispersed SiO2 /poly(3-aminophenylboronic acid) nanocom-
posites. The thermal and crystalline properties of core–shell
SiO2 /poly(3-aminophenylboronic acid) nanocomposite prepared
via ultrasonication method shows a significant enhancement in
the properties in comparison with nanocomposite prepared via
conventional methods. Zhang et al. [113] have also used ultra-
sonic irradiation (4710 series ultrasonic homogenizer, model
CP600, Cole-Palmer Instruments, at a powder level of 8 and
a duty cycle of 70%) for the dispersion of silica powder in a
mixture of styrene and hexadecane and then into a mixture of
sodium lauryl sulfate, sodium bicarbonate, and water to prepare
fine miniemulsion containing SiO2 nanoparticles. Core–shell mor-
phology of SiO2 /polystyrene nanocomposite particles was then
Fig. 4. (A) Cryo-TEM image of nano-PBMA-ZnO latex particles synthesized using sonochemical emulsion polymerization. (B) TEM image of a ZnO nanoparticle synthesized
using ultrasound assisted hydrothermal technique.
Reprinted from [114]. Copyright (2010), with permission from American Chemical Society.
obtained through miniemulsion polymerization by conventional
mechanical mixing. The use of ultrasonication in the first stage for
the dispersion of silica helps in the formation of core–shell mor-
phology of SiO2 /polystyrene nanocomposite particles.
Xia and Wang [38] have used ultrasonic irradiation (tita-
nium horn 22 mm, adjustable power out) to prepare polyani-
line/nanocrystalline TiO2 nanocomposite particles. As per their
report, emulsion polymerization of aniline under ultrasonic irra-
diation in the presence of nanocrystalline TiO2 nanoparticles
was carried out. Xia and Wang [38] have again addressed the
aggregation issue of nanoparticles. It has been reported that the
aggregation of nano-TiO2 can be reduced drastically under ultra-
sonic irradiation, and the nanoparticles can be dispersed finely
in the aqueous solution. During in situ emulsion polymerization
polyaniline gets deposited on the surface of the nanoparticle, which
further leads to a core–shell structured spherical nanocompos-
ite. The polyaniline/nano-TiO2 nanocomposite particles prepared
by the conventional stirring method have a “raspberry” aggre-
gate structure, which is different from that obtained through
ultrasonic irradiation. This suggests that the use of ultrasonic
irradiation leads to formation of fine nanocomposite particles,
which can increase the conductivity of nanocomposite com-
pared with conventional stirring. Sonawane et al. [114] have
studied anticorrosive properties of ZnO encapsulated functional
poly(butyl methacrylate) and polyaniline nanolatex of 50 nm
(Fig. 4) size synthesized by a hydrothermal-sonochemical (Branson
450, ultrasound probe = 19 mm tip, operating at 20 kHz) emul-
sion polymerization technique. The anticorrosive performance
of the synthesized latex on a steel substrate for acid/salt/alkali
induced corrosion is also reported. It has been observed that
the performance of the ZnO-poly(butyl methacrylate) nanocom-
posite coating for acid corrosion was superior to that of the
ZnO-poly(butyl methacrylate)-polyaniline matrix. Sonawane et al.
[42] have also prepared metal oxide loaded poly(butyl methacry-
late) films with the use of ultrasound irradiation (Branson 450,
ultrasound probe = 19 mm tip, operating at 20 kHz) and prepared
composite material was used as photoanodes in photoelectroche-
mical cells. The semiconductor metal oxides used in their study
were ZnO, TiO2 , and Bi2 O3 /ZrTiO4 . It has been reported that pho-
tocurrents generated were directly proportional to the quantity
of metal oxide loading, whereas a decrease in photocurrent was
observed with an increase in the thickness of the latex film. The
fine incorporation of photocatalysts in polymer latex with the use of
ultrasonic irradiation makes photoelectrodes stable that may find
applications in solar cells.
 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
Raspberry-like composite microspheres with polystyrene as
cores and nanosilica particles as the shell has been made
by Zhang et al. [115] through miniemulsion polymerization
using the anionic sodium dodecyl sulfate as surfactants and
2-(methacryloyl)ethyltrimethylammonium chloride as an aux-
iliary monomer. As per their report, during the synthesis of
polystyrene/SiO2 nanocomposite, ultrasonication of an aqueous
solution of initiator, surfactant and monomer was carried out at
0 ◦ C in ice bath to form miniemulsion and then in situ miniemulsion
polymerization was carried by conventional mechanical mixing. It
is reported from TEM analysis that the stable colloidal compos-
ite microspheres have the typical raspberry-like morphology. The
average particle sizes and the final silica contents of the composite
microspheres could range from 150 to 250 nm. Use of ultrasonic
irradiation in the initial stage for the preparation of fine emul-
sion may lead to the formation of finely dispersed nanocomposite.
This approach promises the formation of organic-inorganic hybrid
materials with core–shell structure which has desired properties.
Liu [116], Mahdavian et al. [91] and Zhang et al. [117] have used
ultrasound irradiation to prevent the aggregation of nanoparticles
and to prepare fine emulsion during conventional in situ emulsion
polymerization and use of ultrasonic irradiation in the initial stage
for the preparation of fine emulsion leads to the formation of finely
dispersed nanocomposite. Chowdhury et al. [118] have prepared
poly(N-isopropyl acrylamide)-silica (inorganic/organic) core–shell
nanocomposite sonochemically in an aqueous medium. Feng et al.
[119] have prepared a novel photochromic nanocomposite thin
film containing phosphotungstic acid entrapped in polyacrylamide
using an ultrasound technique. They have reported that the use of
ultrasound shows fine dispersion of polyoxometalates nanoparti-
cles in a polymer matrix.
4.2. Polymer-metal nanocomposite
Usually, nanometal-polymer composites were prepared in two
types in situ methods: (1) the metal ions were reduced to nano-
clusters within the polymer solution or prepolymer solution that
could translate to polymer subsequently; in this case, nanometal
particles would assemble in the polymer matrix because polymer-
ization and reduction occurred separately. (2) The congregational
phenomenon could be avoided effectively by bi-in situ synthesis
technique, when monomer and metallic ions existed and translated
simultaneously into polymer as continuous phase and nanoclusters
as dispersing phase, respectively. Synthesis of Ag/PMMA nanocom-
posites has successfully attempted by Xu et al. [120] using in situ
ultrasonic (50 kHz, 200–1200 W) irradiation of the emulsion con-
taining MMA monomer and silver nitrate without the addition of
an initiator. A simple one-step synthetic route for nanocomposites
with nanosilver as core and PMMA as shell has been studied. As
per the report of Xu et al. [120], silver clusters were prepared ultra-
sonically by silver nitrate within an emulsion containing monomer
without initiator or reductant, while polymerization of monomer
occurred on the surface of the silver clusters. This contributes
to the establishment of the nanocomposites with nanosilver par-
ticles as dispersing phase and acrylate polymers as continuous
phase. The reported results revealed that nanosilver as core within
the composites particles were uniformly dispersed due to use
of ultrasonic irradiations during emulsion polymerization. Bar-
ros et al. [121] have successfully prepared PANI and PANI/silver
nanocomposites using sonochemical (commercial ultrasonic bath,
Branson model 2210, 47 kHz, 35 W cm−2 ) and ionizing radiation
technique. Further, it has been reported that ultrasonic irradiations
are responsible for the formation of • OH and • H radicals, which
acts as an oxidizing agent during the polymerization process of
aniline monomer and as reducing agent for silver ions, respec-
tively. Also the use of ultrasound showed significant reduction
95
of particle size of PANI and silver nanoparticles. The formation
of • OH and • H radicals generated due to cavity collapse caused
by ultrasonic irradiations may initial the polymerization reaction
in the absence of initiator. Barkade et al. [122] have attempted
ultrasound assisted (20 kHz, 600 W) in situ miniemulsion polymer-
ization of aniline along with different loading of silver nanoparticles
and studied its application for ethanol vapor sensing. It has been
reported that ethanol vapor sensing ability of the nanocomposite
increases with the addition of silver nanoparticles in the poly-
mer matrix. The encapsulation of Ag nanoparticles into polyaniline
matrix nanocomposite (50 nm) without any aggregation is also
reported. This uniform dispersion is attributed to ultrasonic irradi-
ation and strong affinity of silver for nitrogen. The average particle
size of Ag nanoparticles reported is in the range of 5–10 nm. There-
fore it can be predicted that the use of ultrasound for the uniform
and higher loading of metal nanoparticles like Ag in conducting
polymers like PANI may improve the gas sensing properties and
will have great application in sensing research area.
An innovative and a novel sonochemical (20 kHz, 600 W)
method for the preparation of polyaniline-Au composite have been
employed by Sivakumar and Gedanken [39]. This method utilizes
ultrasound radiation as an energy source to facilitate the reaction by
reducing the reaction time with considerable increase in the yield.
The average particle sizes of both the composite and PANI, pre-
pared by using ultrasound, are about 30 nm. While nanoparticles of
the composite and PANI particles obtained through conventional
stirring are in irregular aggregates and the size is in the sub-
micrometer range. It is also reported that the sonochemical method
reduces the reaction time by 1/48 times during synthesis of con-
ductive PANI as well as an Au–PANI composite therefore it can save
a substantial amount of energy. Park et al. [123] have also used a
sonochemical in situ emulsion polymerization method for prepara-
tion of conducting hybrid nanocomposite composed of polypyrrole
and gold or platinum nanoparticles. It has been concluded that
uniformly dispersed Au or Pt/polypyrrole nanocomposites with
narrow size distribution is obtained by means of ultrasonic irra-
diation in the aqueous solution in the presence of sodium dodecyl
sulfate as a stabilizer.
4.3. Polymer-magnetic particle nanocomposites
Magnetic nanoparticles without polymer coatings can be used
in magnetic drug targeting, tissue engineering, magnetic reso-
nance imaging, hyperthermia, detoxification of biological fluids
and magnetic guidance of particle systems for specific drug deliv-
ery processes [124]. There are several applications for mechanical
and electrical devices, which take advantage of the magneto-
rheological properties of ferrofluids, e.g. in loudspeakers, seals,
sensors, dampers [125]. Their advantages of biocompatibility and
availability in a size range below 300 nm [126] are accompanied
by an irregular particle shape and a soft particle matrix that causes
them to be sensitive to mechanical stress. In order to encapsulate
such magnetite particles in the monomeric phase and obtain a good
dispersion, reaction conditions must be maintained such that all
the magnetite particles must transfer uniformly into the result-
ing nanocomposite particles. Surface modification of magnetite
nanoparticles would be implemented to make them dispersible
in hydrophobic monomers in order to become a successful encap-
sulation. Ultrasound assisted in situ emulsion polymerization can
also be used for better dispersion of magnetite nanoparticles in the
polymer latex. Ultrasonic treatment also facilitates the formation
of mini-droplet of monomer containing magnetite nanoparticles
resulting in stability of the miniemulsion. Lu et al. [127] have
used ultrasonic irradiation (40 kHz, 50 W) in the aqueous solu-
tion of aniline, ammonium peroxydisulfate, phosphoric acid, and
the quantitative amount of Fe3 O4 for the preparation of PANI
96 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
nanotubes containing Fe3 O4 nanoparticles at room temperature.
The PANI/Fe3 O4 nanotubes with outer diameter about 100 nm and
the inter diameter between 10 and 20 nm could be synthesized
successfully. Typical magnetization curves of the PANI nanotubes
with Fe3 O4 nanoparticles reported by Lu et al. [127] does no show
any pronounced hysteresis loop, which indicates that both the
retentivity and the coercivity of the composite nanotubes are zero.
This observation is consistent with superparamagnetic behavior.
It has also been stated that the PANI/Fe3 O4 composite nano-
tubes have a saturated magnetization of Ms = 8 emu/g for 10 wt.%
Fe3 O4 nanoparticles and Ms = 12 emu/g for 20 wt.% Fe3 O4 nanopar-
ticles. The magnetic properties of the PANI nanotubes containing
Fe3 O4 nanoparticles showed that the samples have a superpa-
ramagnetic behavior. These superparamagnetic properties of the
prepared PANI/Fe3 O4 nanotubes composite may be attributed to
the fine dispersion of Fe3 O4 nanoparticles in PANI matrix. Jiang
[35] have attempted synthesis of PMMA/Ni0.5 Zn0.5 Fe2 O4 nanocom-
posite with superparamagnetic behavior by using ultrasound
(power = 100 W, operated at 50 kHz) assisted in situ emulsion poly-
merization of MMA in the presence of Ni0.5 Zn0.5 Fe2 O4 colloidal
suspension. Further, the morphological analysis clearly shows that
Ni0.5 Zn0.5 Fe2 O4 nanoparticles with the particle sizes of around
12 nm are well dispersed in the PMMA matrix. It has been
also reported that the magnetization of PMMA/Ni0.5 Zn0.5 Fe2 O4
nanocomposite exhibits a clear, super paramagnetic behavior,
which indicates that the size of Ni0.5 Zn0.5 Fe2 O4 particles of PMMA
matrix is smaller than super paramagnetic critical size. Uniform
dispersion plays very important in improvement in magnetization
which is attributed to the use of ultrasonic irradiation during the
preparation of polymer nanocomposite.
Qiu et al. [40] have prepared polystyrene/Fe3 O4 magnetic emul-
sion and nanocomposite using ultrasonically initiated (titanium
probe = 25 mm, 20 kHz) miniemulsion polymerization of styrene in
the presence of Fe3 O4 nanoparticles at room temperature without
the addition of initiator. The room temperature ultrasound assisted
synthesis is very effective due to intense cavity collapse at low tem-
perature (i.e. at low vapor pressure) which leads to formation of
large amount of radicals that initiate the polymerization reaction.
It is found that with an increase in the amount of Fe3 O4 nanopar-
ticles there is a drastic increase in the reported polymerization
rate. The possible reasons reported for increasing the polymer-
ization rate with an increase in Fe3 O4 nanoparticles quantity are
as follows. (1) Fe2+ from the dissociation of Fe3 O4 nanoparticles
reacts with H2 O2 from formed through the sonolysis of water
to produce the hydroxyl radicals, which in turn greatly increases
the number of radicals to initiate the miniemulsion polymeriza-
tion. (2) The addition of a small amount of Fe3 O4 nanoparticles
increases the cavitation bubbles, resulting in the increase of the
number of monomer droplets in the miniemulsion and the rate of
radical production, leading to a larger amount of the nucleation
locus and higher polymerization rate. Polystyrene latex particles
prepared in the presence of Fe3 O4 nanoparticles are spherical in
nature with particle size ranges from 20 to 80 nm. This narrow
size distribution is due to cavitational effects generated by ultra-
sonic irradiation, which generates fine emulsion and also assists
for fine dispersion of Fe3 O4 nanoparticles in polystyrene latex. It
is reported that polystyrene/Fe3 O4 nanocomposites can be sepa-
rated from the emulsion under an external magnetic field indicating
successful formation nanocomposites. The fine dispersion of Fe3 O4
nanoparticles due to ultrasonic irradiation may lead to formation
of finely dispersed polymer nanocomposite which has enhanced
property profile. Mahdavian et al. [128] have also used ultrasonic
irradiation for the surface modification of nano-Fe3 O4 by oleic acid
and dispersion of modified Fe3 O4 in the monomer phase containing
hexadecane, styrene and butylacrylate, SDS and Span 80. The mag-
netite dispersion was reported to be prepared in ultrasonic bath
with frequency of 35 kHz and preparation of polymer nanocompos-
ite was performed using direct ultrasonication, i.e. 3 mm titanium
probe immersed in the samples operating at 20 kHz frequency.
The obtained Fe3 O4 -poly(butyl acrylate–styrene) nanocomposite
shows the core–shell morphology of the particles with well-
dispersed hydrophobic nano-magnetite particles as the core in the
polymeric shell. The magnetization properties were observed to
be decrease with oleic acid modification of Fe3 O4 nanoparticles
and it is 82.6% of pure Fe3 O4 . Two reasons could be designated
for such observation: (i) addition of oleic acid for surface modifica-
tion of magnetite (about 9 wt.%), this will cause a reduction in the
magnetization per gram of magnetite, (ii) in the presence of ultra-
sound irradiation, oxidation of Fe3 O4 to ␣-Fe2 O3 is also possible.
Therefore, it is also expectable to have some loss in magnetiza-
tion due to the formation of ␣-Fe2 O3 and that is the disadvantage
and limitation of ultrasound. Therefore by adjustment and opti-
mization of the conditions need to study for the minimization
of loss of magnetization was obtained in the final product. The
amounts of magnetization for nanocomposite films containing dif-
ferent quantities of Fe3 O4 have the capability of estimation of
magnetite content. It is important to note that approximately 33%
decrease in magnetization would be discovered through the over-
all process of encapsulation reaction and preparation of magnetic
nanocomposite particles. This is a good achievement in preserva-
tion of overall magnetization in the final product using cavitation
technique. Two reasons could be attributed for obtaining higher
magnetization relative to the previously reported ones: (i) applying
lower power for direct ultrasonication and (ii) providing conditions
for less conversion of H2 O to H2 O2 (as an oxidizing agent) during
sonication process in the procedure. Recently Gyergyek et al. [129]
have prepared nanocomposite particles containing high concen-
trations of superparamagnetic ␥-Fe2 O3 nanoparticles dispersed in
PMMA using the mini-emulsion polymerization. In their experi-
mentation, ultrasound irradiation (500 W Power) was used for the
preparation of miniemulsion in first stage and then polymerization
was carried out in 100 mL glass reactor equipped with a glass stir-
rer, and submerged in an oil bath, preheated to 60 ◦ C for 16 h at
constant stirring speed of 500 rpm. The high resolution TEM image
shows a high content of the iron oxide nanoparticles in their cores
and a polymer shell without the nanoparticles. In such nanocom-
posite particles the iron-oxide nanoparticles are well protected by
the surface layer of polymer. It is also reported that superparamag-
netic nanocomposite particles with a large content of dispersed
magnetic iron-oxide nanoparticles, which reached approximately
39 wt.%, were prepared using mini-emulsion polymerization. It is
due to the application ultrasound irradiation in the initial stage of
emulsion polymerization for preparation of miniemulsion.
4.4. Conducting polymer based nanocomposite particles
Conducting polymer/inorganic nanoparticle composites with
the combinations of the two different components have been
attracted more attention, since they have interesting physical prop-
erties and many potential applications [130]. However, conducting
polymer is not dissolved in nature and usually is insoluble in
common solvents, so it is difficult to synthesize conducting poly-
mer/inorganic nanocomposites by conventional blending or mixing
in solution or melt form. Doped PANIs are conducting materials of
interest for its use in electrochemical application that have been
also satisfactorily combined with inorganic redox oxides [131].
Xia and Wang [38] have used a novel approach, i.e. ultrasound
(titanium horn 22 mm diameter) assisted in situ emulsion poly-
merization of aniline in the presence of nanocrystalline TiO2 for
the preparation of PANI/nanocrystalline TiO2 composite particles.
In their study, ultrasound assisted in situ emulsion polymeriza-
tion of aniline was reported in the presence of nanocrystalline
 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
TiO2 as a nanofiller, (NH4 )2 S2 O8 as an initiator and sodium lau-
ryl sulfate as a surfactant in aqueous solution. Further, ultrasonic
irradiation has been carried out with the probe (ultrasonic horn)
directly immersed into the mixture emulsion system for 1 h. It has
been concluded that the aggregation of nano-TiO2 in the aqueous
solution can be broken down under ultrasonic irradiation, and the
formed PANI deposits on the surface of the nanoparticle, which con-
tributes to the establishment of a core–shell structure. The reported
conductivity of the composites obtained through ultrasonic irra-
diation is found decreased with increasing TiO2 content. Further,
ultrasonic irradiation contributes to the increase in the conductivity
of prepared nanocomposite compared with conventional stirring.
Wang et al. [41] have used high intensity ultrasonic irradiation for
the preparation of PANI and gamma-zirconium phosphate (␥-ZrP)
nanocomposite by intercalation of aniline into ␥-ZrP. A weighed
amount of ␥-ZrP was added into a sonication reactor (28 mm outer
diameter) and the sonication was carried out by a titanium horn
(20 kHz, 100 W cm−2 ), which was inserted 1 cm below the solu-
tion. It is noted that the intercalation rate of aniline into ␥-ZrP was
improved significantly in the presence of power ultrasound irradi-
ation, particularly in the acid environment. The polymerization and
cross-linking of aniline occurred in low pH initiated by (NH4 )2 S2 O8
and exfoliation of ␥-ZrP in PANI bulk takes place with the aid
of ultrasound irradiation. Ultrasound assisted (Ultrasound probe,
600 W, 240 kHz) in situ polymerization of aniline have been car-
ried out by Mosqueda et al. [132] in the presence of LiNi0.8 Co0.2 O2 .
It has been reported that the ultrasound treatment emerges to be
more effective than conventional methods, such as magnetic stir-
ring, to produce more homogeneous materials containing a large
amount of the metal oxide particles of small size. The proper disper-
sion and good contact between polymer and oxide particles leads to
increase in the electrical conductivity of the composite compared
to the pristine oxide. Park et al. [123] have attempted colloidal
dispersions of hybrid nanocomposite composed of polypyrrole
and gold nanoparticles or platinum nanoparticles by a sonoche-
mical method (13 mm titanium horn, Input power 30 W, 20 kHz)
in the presence of sodium dodecyl sulfate. The uniform disper-
sion has been reported with the use of ultrasonic irradiation. Lu
et al. [127] have synthesized PANI/Fe3 O4 nanotubes under ultra-
sonic irradiation (40 kHz, 50 W) of the aqueous solutions of aniline,
ammonium peroxydisulfate, phosphoric acid, and the quantitative
amount of Fe3 O4 . The mechanism of the formation of PANI/Fe3 O4
nanotubes may be attributed to the ultrasonic irradiation. Zhang
et al. [37] have used high intensity ultrasonic irradiation (ultrasonic
probe, 20 kHz, Ti horn, 100 W cm−2 ) method in the preparation
of core–shell SiO2 nanoparticles/poly(3-aminophenylboronic acid)
composites. Kowsari and Faraghi [133] have used sonochemi-
cal (ultrasonic titanium horn, 40 kHz, 100 W) method for the
preparation of polyaniline-Y2 O3 nanocomposite with controlled
conductivity with the assistance of an ionic liquid. This method
may open a new pathway for the preparation of nanoscale con-
ducting polymer nanocomposites with the aid of ionic liquids. The
effect of different parameters such as ultrasonic irritation time and
frequency on the morphology, conductivity and yield has been also
reported. The conductivity is found to be increased with an increase
in frequency.
A novel ultrasound (ultrasonic bath, 40 kHz) assisted Pickering
emulsion (solids-stabilized emulsion) polymerization route was
used first time by Xiao et al. [134] for the preparation of PANI/nano-
Fe3 O4 composites. Sphere-like morphology and sub-micrometer
fibers of PANI/nano-Fe3 O4 composites have been synthesized in
a toluene/water emulsion stabilized by Fe3 O4 nanoparticles. It
has been told that the morphology of the resulting PANI/nano-
Fe3 O4 composites is dependent on the amount of Fe3 O4 in the
reaction scheme. When the Fe3 O4 /aniline mass ratio was 0.14,
the sub-micrometer PANI fibers and the core–shell structure of
97
PANI/nano-Fe3 O4 composites was obtained simultaneously. How-
ever, only core–shell structure of PANI/nano-Fe3 O4 composites
has been obtained with the increase of the Fe3 O4 /aniline mass
ratio in the reaction system. It has been also reported that the
conductivity of PANI/nano-Fe3 O4 composites at room tempera-
ture increases up to 3.21 × 10−3 S/cm with an increase in the
mass ratio of Fe3 O4 /aniline from 0 to 0.14. Conversely, when the
Fe3 O4 /aniline mass ratio was 0.28, the conductivity of composites
was 1.7 × 10−3 S/cm. Contreras et al. [135] have also used similar
method, i.e. ultrasound assisted Pickering emulsion polymerization
for the synthesis of carbon black/polystyrene conductive nanocom-
posite.
Sonawane et al. [42] have synthesized metal oxide-
encapsulated poly-butyl methacrylate (PBMA) latex by ultrasound
assisted (Branson 450, ultrasound probe = 19 mm tip diameter,
operating at 20 kHz) in situ miniemulsion polymerization for
the preparation of stable photo-electrodes. It has been reported
that the particle size, determined by TEM analysis of TiO2 , ZnO,
and Bi2 O3 /ZrTiO4 embedded into PBMA latex was found to be
21, 15, and 7 nm, respectively. Fringes are also noted on the
particles in the case of Bi2 O3 /ZrTiO4 nanoparticles indicating
that the semiconductor nanocomposite oxides synthesized using
ultrasound-assisted methods are crystalline in nature. The gen-
eration of photocurrent is an also reported to increase with an
increase in the semiconductor oxide loading, whereas a reverse
effect was observed with an increase in the thickness of the
latex. The order of photocurrent generation efficiency with the
different catalysts was Bi2 O3 /ZrTiO4 > ZnO > TiO2 . Haldorai et al.
[43] and Barkade et al. [122] have also used ultrasound assisted
in situ emulsion polymerization for the preparation of electrically
conducting copolymer poly(aniline-co-p-phenylenediamine) and
SiO2 nancomposites and PANI/silver nanocomposite respectively.
It has been reported that this approach can solve problems in the
dispersion and stabilization of nanoparticles in the polymer latex.
Recently, Barkade et al. [136] have used ultrasound assisted
in situ emulsion polymerization of pyrrole in the presence of ZnO
for the preparation of polypyrrole-zinc oxide nanocomposites. The
reported approach gives particles size of nanocomposite of around
100 nm with uniformly dispersed ZnO nanoparticles in polypyr-
role matrix (Fig. 5). This controlled size and uniform dispersion
Fig. 5. TEM image of polypyrrole functionalized ZnO prepared by ultrasound
assisted miniemulsion polymerization.
Reprinted from [136]. Copyright (2013), with permission from American Chemical
Society.
98 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107

using the reported innovative preparation method minimizes the
response time to sense the liquefied petroleum gas significantly
(2.2 min for polypyrrole-zinc oxide nanocomposites). The forma-
tion mechanism of polypyrrole-zinc oxide nanocomposites using
ultrasound assisted miniemulsion method reported by Barkade
et al. [136] is shown in Fig. 6. As reported by Barkade et al. [136],
the presence of ultrasonic irradiation generates cavitation condi-
tions that ensure the formation of miniemulsion. The generation
of high temperature and pressure within the bubbles and strong
shear forces in the solution due to the collapse of cavitation bubbles
provide conditions suitable for the uniform and quick dissocia-
tion of initiator ferric chloride into iron (ferric) and chloride ions.
The physical effects caused by the ultrasonically induced cavita-
tion play an important role in the generation of uniform nano-sized
droplets. The shock-waves that are created by acoustic cavitation
also results in strong shear and fragmentation of the particles, dis-
rupting the particle aggregation and has better control over the
mean size and size distribution and this results into the formation
of core–shell structured polypyrrole-zinc oxide nanocomposites
hybrid nanocomposite. Barkade et al. [137] have also prepared
polythiophene-SnO2 nanocomposite particles with the use of an
ultrasound assisted in situ polymerization. In their report, it has
been told that the usage of ultrasound leads to fine dispersion of
SnO2 nanoparticles in polythiophene matrix which significantly
improves the liquefied petroleum gas sensing properties of the
prepared nanocomposite material.
4.5. Polymer-layered silicate (clay) nanocomposites
Because of many advantages such as good mechanical property,
gas permeabilities, ionic conductivities, thermal stability, flame
retardation, etc. [138–140] polymer/clay nanocomposites have
been deeply investigated. Among the all polymerization methods
in situ emulsion polymerization is one of the important methods

Fig. 6. Mechanism of functionalization of ZnO nanoparticles using polypyrrole in presence of ultrasound during miniemulsion polymerization.
Reprinted from [136]. Copyright (2013), with permission from American Chemical Society.
 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
because of the use of water as a dispersion medium. Water makes
the galleries of layered silicates widen, which in turn leads to
the intercalation of monomer and/or micelles into the galleries
of layered silicates. However, sodium montmorillonite forms gels
containing isolated silicate layers and aggregate of several lay-
ers in the presence of limited quantities of water. Therefore, the
size of aggregated montmorillonite during polymerization should
be reduced to improve the exfoliation and homogenous disper-
sion of clay platelets in aqueous medium of emulsion system and
form the final exfoliated polymer/clay nanocomposites. Ultrasonic
irradiation can be used for the dispersion of clay platelets in the
emulsion. It is likewise well known that an ultrasound treatment
of aqueous clay suspensions stabilizes the colloidal system. Wang
et al. [44] have attempted ultrasonically initiated in situ emulsion
polymerization for the synthesis of intercalated polystyrene/Na+ -
MMT nanocomposites. They were used following steps for the
preparation of polystyrene/Na+ -MMT nanocomposite: (1) Aqueous
solution of dispersed Na+ -MMT in a surfactant solution by ultra-
sonic irradiation was added in the reactor into the reaction vessel,
(2) Then, the desired amount of styrene monomer was added in
the dispersion at temperature of 30 ◦ C, and (3) The polymeriza-
tion was then initiated by subjecting this emulsion to ultrasonic
irradiation for 90 min. Virgin polystyrene does not exhibit any
diffraction peak. The diffraction patterns of the (0 0 1) plane of sil-
icate occurring at 4.338 and 5.628, corresponding to 20.37 and
15.72 Å, respectively, shifted to lower angles compared to that of
pristine Na+ -MMT (6.738). This indicates that styrene or monomer-
swollen micelles are infused into the sheets of silicate, and then
polymerized between clay sheets via ultrasonic initiation to widen
the space of the silicate layers. It has been reported that due to
high intensity ultrasound, the hydrophobic polystyrene is forced
to intercalate into the hydrophilic clay galleries. At the same time
intense cavitations at the interfaces of solid and liquid phase results
into radical generation which helps to initiate the polymerization
of styrene in or near the silicate layers, thus widen the d-spacing of
nanocomposites. Likewise, during polymerization, monomers will
be reacted competitively in two regions: one is the hydrophilic
gallery of clay layers and the other is the hydrophobic exterior
of clay particles. Due to the negative charge of sodium dodecyl
sulfate (SDS), SDS micelles have a tendency to exist outside of
clay particles rather than between the interlayer of clay, which
is helpless to widen the d-spacing of MMT, unless there is an
outfield, high intensity ultrasound to force monomer-containing
micelles intercalate into the hydrophobic clay galleries. It is also
reported that due to the strong hydrophobic polystyrene intercala-
tion into the galleries of hydrophilic montmorillonite via ultrasonic
initiated in situ emulsion polymerization, the improvement of
the thermal properties of nanocomposite takes place. Further-
more, ultrasonic irradiation can not only initiate polymerization
of styrene at room temperature while clay layers were dispersed
at the nanoscale, but can also shorten the polymerization time and
save the energy. Thus, the ultrasonically initiated in situ emulsion
polymerization is a novel, simple, and fast approach to prepare
polymer/layered inorganic nanocomposites. Formation of core and
shell poly(styrene-co-methyl acrylate)-bentonite nanocomposite
using miniemulsion process was studied by Borthakuar et al. [45]
and the reported the application of ultrasound only in the stage
one, i.e. during emulsion formation. It has been reported that ben-
tonite was dispersed within the monomer mixture with the help of
ultrasonic irradiation, which leads to the monomers absorption by
the pore/layers of bentonite and the monomers form a layer over
the clay. Subsequently the monomer covered clay particles were
dispersed in water, which were stabilized by the non-ionic–ionic
(Span-60–SDBS) surfactant mixture. This dispersion was subjected
to sonication to initiate polymerization. Meanwhile, the presence
of the surfactant mixture causes the exfoliation of the clay layers.
99
Then polymerization was carried out in the presence of AIBN initia-
tor at 70 ◦ C. The polymer phase forms a nearly uniform layer over
the exfoliated layers of the bentonite particles. Since the nano-clay
has a sheet like structure, its presence in the core phase distorts
the spherical structure of the nanocomposite particles. This con-
firms the formation of nanocomposite particles with core–shell
morphology. TEM and XRD analysis reports complete exfoliation
of clay in polymer latex leads to spherical shape nanocomposite
particles with an average diameter of 700 nm.
The mechanism of synthesis of exfoliated p(methyl
methacrylate-co-Styrene)/O-MMT nanocomposite has been
depicted in Fig. 7. Initially, O-MMT was mixed with monomer in
the presence of ultrasonic irradiations which help in obtaining
the exfoliated structure. High shear levels associated with intense
turbulence due to the cavitational effects result in clay exfoliation
into single platelets, which can be then easily dispersed into the
monomer phase [45]. Further, OH group of SDS adsorbs at the
edges of the O-MMT clay platelets, which will interact with the
polar carboxyl groups of the methyl acrylate and styrene [141].
During emulsion polymerization, primary radicals generated
in the aqueous phase by the dissociation of initiator at higher
temperature and by the adiabatic implosion of cavities due to the
ultrasonic irradiations [13] react with the monomer molecules
at the cavitation bubble/solution interface. The generation of
enhanced quantum of radicals along with the reduced diffusion
resistance due to turbulent conditions generated due to cavi-
tational effects results in initiation and faster progress of the
polymerization reaction [12,14]. Further, it has been reported
by Bhanvase et al. [142] that the polymerization of MMA with a
styrene monomer takes place around the O-MMT clay platelets
lead to the exfoliated structure of the p(methyl methacrylate-co-
Styrene)/O-MMT nanocomposite. Ianchis et al. [143] have also
used ultrasound irradiation in the initial stage of polymerization
for the preparation of new nanocomposites based on polyacrylates
and five types of montmorillonites modified by edge covalent
bonding. Wang et al. [144] used ultrasound assisted emulsion
polymerization for one-pot preparing montmorillonite–exfoliated
polystyrene nanocomposite. Interestingly, they found that the
nanocomposite grew in one direction to become a bundle during
the ultrasonic irradiation. It is well known that the ultrasonic
wave propagation is a good technique for nondestructive analysis.
Further, polymer-clay nanocomposites based on the PMMA and
organically modified montmorillonite via a two-stage ultrason-
ically assisted polymerization was also prepared by Ryu and Lee
[145] and Ryu et al. [146]. It has been reported that ultrasonic
irradiation successfully generates exfoliated nanocomposite pro-
vided sufficient interaction between monomer and organic chains
of the interlayer. Also, the clay aggregates in the ultrasonically
processed nanocomposites are more finely dispersed than in the
simple mixing methods.
Sonawane et al. [147] have prepared polyacrylic acid-nanoclay
nanocomposite in an aqueous medium and ultrasound environ-
ment. They have investigated its application in dye removal.
Heidarian et al. [148] have prepared polyurethane/organically
modified montmorillonite clay nanocomposite by effective dis-
persing of organically modified montmorillonite nano-layers in
the polyurethane matrix through an ultrasound assisted pro-
cess. Use of ultrasonic irradiation de-agglomerates the clay stacks
effectively. Shirsath et al. [149] have used ultrasound assisted
in situ emulsion polymerization for synthesis of poly(acrylic
acid)-bentonite-FeCo hydrogel nanocomposite and evaluated the
response of the nanocomposite hydrogel using a cationic dye,
crystal violet under different temperatures, pH, and cavitation
environment. Recently, Mallakpour and Dinari [150] have pre-
pared poly(vinyl alcohol) (PVA)/organoclay/surface modified Al2 O3
nanocomposites of different compositions via ultrasound-assisted
100 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
Fig. 7. Schematic mechanism for exfoliation of MMT and the formation process of P(MMA-co-St)/O-MMT nanocomposite.
Reprinted from [142]. Copyright (2012), with permission from Elsevier.
technique. The improvement in the thermal properties of the
hybrid materials is reported due to the strong hydrogen bond-
ing between OH groups of PVA, free acid functionalized groups
of organoclay and the oxygen atoms of Al2 O3 nanoparticles. It
has been further reported that the use of ultrasonic irradiations
improves the dispersion of organoclay and Al2 O3 homogeneously
in PVA matrix.
4.6. Polymer-carbon nanotube nanocomposites
Carbon nanotubes (CNTs) are ideal reinforcing fibers for com-
posites because of their high aspect ratio, high mechanical strength,
and high electrical and thermal conductivity. As compared to con-
ventional carbon fiber or glass fiber with a large size, carbon
nanotubes/polymer composite are easily formed. The approaches
used for the preparation of polymer/CNT nanocomposites include
in situ bulk and condensed polymerization, solution mixing and
casting, and melt blending. The big challenges encountered dur-
ing the preparation of polymer/CNT composites are (1) to break
the entanglement of CNTs and overcome the van der Waals force
between CNTs; (2) to improve the dispersion and orientation of
CNTs in polymer matrix; and (3) to raise the interfacial interac-
tion between polymer and CNTs. In situ emulsion polymerization
has many advantages over other method as many properties of
the materials, including mechanical properties, adhesion strength,
aging resistance, UV resistance, weather resistance, and surface
appearance can be improved. However, it is very difficult to dis-
perse CNTs in the polymer emulsion at the nanoscale through
simple mixing because of their high surface energy, strong van der
Waals interaction and its low interface affinity toward polymer.
To overcome these issues, ultrasonically assisted in situ emulsion
polymerization can be used to prepare polymer/CNTs compos-
ite. Xia et al. [46] have used a novel ultrasonically (titanium
horn 22 mm, adjustable power output) initiated in situ emul-
sion polymerization approach for modification of multi-walled
carbon nanotubes (MWCNTs). Ultrasonically initiated emulsion
polymerization of monomer n-butyl acrylate and MMA was car-
ried into the presence of MWCNTs for 30 min. It has been reported
that by using the multiple effects of ultrasound, i.e. dispersion,
pulverizing, activation, and initiation, the aggregation and entan-
glement of CNTs in aqueous solution can be broken down. Further,
in situ polymerization of monomer n-butyl acrylate or MMA on
the surface of MWCNTs takes place without any addition of chem-
ical initiator leading to finely disperse CNTs in polymer latex
and strong interaction between the polymer and CNTs. Also the
polymer-encapsulated CNTs can be well dispersed in Nylon 6
matrix. The interfacial adhesion between polymer-encapsulated
carbon nanotubes and Nylon 6 has been improved. The yield
strength is reported to improve ∼30% and the Young’s modu-
lus ∼35% at only 1 wt.% content of polymer-encapsulated CNTs.
Xia et al. [151] have also attempted similar type of work with
different polymers, i.e. poly(methyl methacrylate-co-n-butyl acry-
late). As per their report, during the preparation of poly(methyl
methacrylate-co-n-butyl acrylate)/CNTs nanocomposite, they have
adopted two staged emulsion polymerization method. Stage I
includes ultrasonic (titanium horn 22 mm, adjustable power out-
put) dispersion, surface activation of CNTs, surfactant adsorption on
CNTs, monomer adsorption, and adsorption of micelle on the sur-
face of CNTs, as well as in situ polymerization of monomer on CNTs.
In this step, the polymerization of monomer was initiated by ultra-
sonic cavitation. As polymerization proceeds, ultrasonic dispersion
and encapsulation of CNTs in polymer has been taking place. To
obtain high concentrated polymer/CNTs composite emulsion with
high monomer conversion, they have used conventional emulsion
polymerization (Stage II) in the presence of polymer-coated CNTs.
The reported value of Young’s modulus has been raised from 124
to 289 MPa and the yield strength is improved by ∼14% of com-
posite film with an increase in CNTs content. Li et al. [152], Cheng
et al. [153] and Lahelin et al. [154] have used two staged ultrasound
assisted in situ emulsion polymerization method for the synthesis
of carbon nanotubes/poly(methyl methacrylate), multiwall carbon
nanotubes/polyacrylonitrile and polystyrene/CNT and poly(methyl
methacrylate)/CNT nanocomposites respectively with slightly var-
ied conditions.
Further, Markovic et al. [155] have been used ultrasonically
(titanium horn 13 mm, Power 300 W) initiated in situ emulsion
polymerization for the preparation of multiwalled carbon nano-
tube/polyaniline composites (MWNTs/PANI). For the preparation of
Table 2
Representative examples of polymer nanocomposites synthesized by ultrasound assisted in situ emulsion polymerization.
Reference
Liu et al. [34]
Jiang [35]
Xia et al. [36]
Zhang et al. [37]
Haldorai et al. [43]
Xia and Wang [38]
Sonawane et al. [114]
Sonawane et al. [42]
Zhang et al. [115]
Liu [116]
Mahdavian et al. [91]
Zhang et al. [117]
Xu et al. [120]
Stage in which ultrasound used
Ultrasound assisted in situ
copolymerization at 80 ◦ C
Ultrasound assisted in situ emulsion
polymerization of methyl methacrylate
at 80 ◦ C.
Ultrasonic assisted encapsulation of
SiO2 , Al2 O3 , and TiO2 by in situ
emulsion polymerization
Ultrasound assisted polymerization
Ultrasonically assisted in situ emulsion
polymerization
Ultrasound assisted emulsion
polymerization of aniline
Hydrothermal-sonochemical emulsion
polymerization
Sonochemical polymerization method
• Ultrasonication to form miniemulsion
• Conventional in situ miniemulsion
polymerization
• Ultrasonication to prepare fine
emulsion without aggregation of
nanoparticles
• Conventional in situ emulsion
polymerization
• Ultrasonication to prepare fine
emulsion without aggregation of
nanoparticles
• Conventional emulsion
polymerization
• Ultrasonication to prepare fine
emulsion without aggregation of
nanoparticles
• Conventional emulsion
polymerization
Ultrasound initiated bi-in situ
emulsion polymerization
System
Magnesium hydroxide/polystyrene
nanocomposite
PMMA/Ni0.5 Zn0.5 Fe2 O4
Nanocomposite
Monomers: n-butyl acrylate, methyl
methacrylate and styrene
Nanofillers: SiO2 , Al2 O3 , and TiO2
SiO2 /Poly(3-aminophenylboronic acid)
composites
Poly(aniline-co-p-phenylenediamine)
and SiO2 nanocomposites
Polyaniline/nanocrystalline TiO2
composite
ZnO-PBA and ZnO-PBA-PANI
nanocomposite
Poly(butylmethacrylate)/TiO2 , ZnO,
and Bi2 O3 /ZrTiO4 nanocomposite
Polystyrene/SiO2 composite
Zinc oxide/polystyrene nanocomposite
Poly(styrene-methyl
methacrylate)/SiO2 composite
nanoparticles
ZnO/polystyrene nanocomposite
Ag/PMMA nanocomposite
Effect of ultrasound on shape, size, etc.,
of polymer nanocomposite
• Particle size in the range of
20–300 nm
• Spherical nature of Ni0.5 Zn0.5 Fe2 O4
particles
• Nanoparticles with size 12 nm
dispersed in polymer.
• Stability of nano-silica is the best
among the three different
nanocomposite latexes
• Average size of composite particle is
∼20 nm
• Core–shell morphology
• Spherical nanocomposite particles
with the average size of 70–95 nm
• Core–shell morphology
• Composite particles are spherical,
Particle sizes ranges between 30 and
200 nm.
• Average size: 50 nm
• Spherical nanocomposite particles
• Particle sizes of TiO2 , ZnO, and
Bi2 O3 /ZrTiO4 embedded into PBMA
latex were 21, 15, and 7 nm.
• Raspberry-like morphology
• Average particle sizes of composite
microspheres in the range of
150–250 nm
• Core/shell morphology
• Average particle sizes of the
composite is in the range of 64–199 nm
• Core/shell morphology
• Core/shell morphology
• Average particle size of the
composite is around 100 nm
• Core–shell structure
• Nanocomposite particles with
nanosiliver as core with size 10–20 nm
Enhancement in properties of polymer
nanocomposite due to ultrasound
• Core–shell structure.
• Enhanced dispersion.
• Improved thermal stability.
• Superparamagnetic behavior.
• Fine dispersion of Ni0.5 Zn0.5 Fe2 O4 in PMMA
polymer matrix.
• Polymerization of butyl acrylate takes place
in presence of only nanoparticles.
• No use of surfactant and chemical initiator.
B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
• Enhanced electronic, crystalline and thermal
properties.
• Ultrasonication improves the conductivity.
• Core–shell morphology.
• Reduced aggregation of SiO2 nanoparticles.
• Improved thermal stability and
room-temperature conductivity
• Increase the electrical conductivity of
nanocomposite compared with conventional
stirring
• Functionalized latex coatings are superior in
corrosion performance.
• Photocurrent generation increases with an
increase in the semiconductor oxide loading.
• Photocatalysts in polymer makes stable
electrodes.
• Final silica contents improved from 10 to
40 wt.% due to ultrasonication in initial stage.
• Polymerization in absence of surfactant
• Improved dispersion of nanoparticles due to
ultrasonication
• Ultrasonication to prevent aggregation of
nanoparticles
• Ultrasonication to prevent aggregation of
nanoparticles
• Improved thermal stability
• Monomer conversion improved with silver
nitrate concentration
101
 102
Table 2 (Continued)

Reference Stage in which ultrasound used System Effect of ultrasound on shape, size, etc., Enhancement in properties of polymer
of polymer nanocomposite nanocomposite due to ultrasound

Barkade et al. [122] Ultrasound assisted in situ Ag/PANI nanocomposite • Size of polyaniline/Ag nanocomposite • Improved ethanol vapor sensing ability and
miniemulsion polymerization of is 50 nm dispersion of Ag.
aniline

Sivakumar and Ultrasound assisted in situ emulsion Polyaniline-Au composite • An average particle size is about • Reduction in the reaction time by 1/48 times
Gedanken [39] polymerization of aniline 30 nm which is less than that of by • Enhanced dispersion of Au without
conventional method. aggregation.

Park et al. [123] Sonochemical in situ emulsion Polypyrrole/gold or platinum • Polypyrrole with uniform size • Uniform dispersed Au or Pt/polypyrrole
polymerization method composite nanoparticles distribution: 40 nm nanocomposites
• Spherical particles

B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
Lu et al. [127] Ultrasound assisted in situ emulsion PANI/Fe3 O4 nanotubes • PANI/Fe3 O4 nanotubes with diameter • Superparamagnetic behavior
polymerization method about 100 nm

Qiu et al. [40] Ultrasound initiated miniemulsion Plystyrene/Fe3 O4 magnetic emulsion • Spherical in nature with particle size • Reaction at low temperature without
polymerization and nanocomposite ranges from 20 to 80 nm initiator, Enhanced polymerization rate with
loading of Fe3 O4 and Improved magnetic
behavior

Mahdavian et al. [128] Ultrasound initiated miniemulsion Fe3 O4 -poly(butyl acrylate-styrene) • Composite particle size: 150–200 nm. • Loss in magnetization due to the formation of
polymerization particles • Composite nanospheres. ␣-Fe2 O3 in ultrasound irradiation.

Gyergyek et al. [129] • Ultrasound for preparation of Superparamagnetic ␥-Fe2 O3 /PMMA • Core–shell structure • Loading of iron-oxide nanoparticles reached
mini-emulsion nanocomposite • Average size of the nanocomposite in to 39 wt.% due ultrasound.
• Polymerization by conventional range from 25 to 49 nm. • Superparamagnetic behavior
method.

Wang et al. [41] Ultrasound assisted preparation of PANI/␥-ZrP nanocomposite • Average particles size is around • Superior thermal stability than PANI
PANI/␥-ZrP 500 nm.

Mosqueda et al. [132] Ultrasound assisted in situ PANI/LiNi0.8 Co0.2 O2 composite • Core–shell structure of spherical • Improved electrical conductivity compared
polymerization of aniline nanocomposite to the pristine oxide

Kowsari and Faraghi Ultrasound and ionic-liquid-assisted Polyaniline/Y2 O3 nanocomposite • Fiber type morphology. • Ultrasound and ionic liquids replaces
[133] synthesis of polyaniline/Y2 O3 • With an increase in a frequency from conventional oxidants and metal complexes.
nanocomposite 20 to 40 kHz, the morphology evolves • Improved thermal stability and electrical
as sphere shapes. conductivity.

Xiao et al. [134] Ultrasound assisted pickering PANI/nano-Fe3 O4 composites • Sphere-like morphology • Improved conductivity at room temperature.
emulsion polymerization • Core–shell structure

Contreras et al. [135] Ultrasound assisted pickering Carbon black/polystyrene • Composite particle size in the range • Reduction in polymer resistivity.
emulsion polymerization nanocomposite 50–90 nm • Sonication improves the dispersion of
• Spherical morphology. nanofillers.

Barkade et al. [136] Ultrasonically assisted in situ emulsion Polypyrrole-zinc oxide nanocomposite • Uniform particle size of around • Improved liquefied petroleum gas sensing
polymerization 100 nm properties.
• Spherical morphology • % response is found enhanced

Barkade et al. [137] Ultrasonically assisted in situ Polythiophene-SnO2 nanocomposite • Spherical morphology • High sensitivity of formed nanocomposite for
polymerization sensing liquefied petroleum gas.

Wang et al. [44] Ultrasonically initiated in situ Polystyrene/Na+ -MMT • Intercalated polymer/clay structure • Improved in thermal properties
emulsion polymerization nanocomposites

Borthakuar et al. [45] • Ultrasound assisted dispersion of Poly(styrene-co-methyl • Exfoliated structure and spherical • Improved barrier properties and thermal
bentonite clay and fine mini-emulsion acrylate)-bentonite nanocomposite shape of nanocomposite with average stability.
• Polymerization by conventional diameter of 700 nm • Transparency of the polymer is retained in
method. the nanocomposite.
 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
Wang et al. [144] Ultrasound assisted emulsion MMT/polystyrene nanocomposite • Exfoliated structure of polymer • Reduced aggregation of nanoparticles due to
polymerization nanocomposite ultrasound.

Ryu and Lee [145] Ultrasound assisted polymerization PMMA-clay nanocomposites • Exfoliated nanocomposite • Superior thermal stability and mechanical
performance.

Xia et al. [46] Ultrasound initiated in situ emulsion PBA/MWCNTs, PMMA/MWCNTs and • Encapsulated structure of carbon • Improved yield strength and Young’s
polymerization PA6/CNT nanocomposite nanotubes in the polymer latex. Modulus, improved the dispersion of CNTs.

Xia et al. [151] Stage I: ultrasonic dispersion of CNTs. Poly(MMA-co-n-BA)/CNTs • Encapsulated structure of carbon • Improved yield strength, Young’s Modulus
Stage II: conventional emulsion nanocomposite nanotubes in the polymer latex. and encapsulation of CNTs.
polymerization

Cheng et al. [153] Stage I: ultrasonic dispersion of CNTs. MWCNTs/polyacrylonitrile • MWCNTs are coated with • No emulsifier
Stage II: conventional polymerization polyacrylonitrile chains • Improved thermal stability.

Markovic et al. [155] Ultrasonically initiated in situ MWNTs/PANI composites • Encapsulated structure with size in • Reaction at low temperature.
emulsion polymerization 300 W energy output between 38 and 50 nm. • Reduced amount of initiator.
• No agglomeration and coagulation of • Enhanced electric conductivity and thermal
CNTs. stability

Li et al. [156] Ultrasonically initiated in situ PANI/SWNTs nanocomposite • Ultrasound enhances the dispersion • Improvements in the electrical and
emulsion polymerization of CNTs electrochemical properties
• Encapsulated polyaniline
nanocomposite

Zelikman et al. [157] Ultrasound assisted in situ dynamic PANI/SWNT nanofibers • Single SWNT is coated uniformly • Improvements in the mechanical and
inverse emulsion polymerization with PANI electrical properties

Suckeveriene et al. Ultrasound assisted in situ dynamic PANI/CNT nanocomposites • Encapsulated polyaniline • Improvements in the mechanical properties
[158] inverse emulsion polymerization nanocomposite and electrical conductivity

103
104 B.A. Bhanvase, S.H. Sonawane / Chemical Engineering and Processing 85 (2014) 86–107
MWNTs/PANI composite, they have used the ultrasonic irradiation
device equipped with a standard titanium horn of 13 mm diameter
set at 300 W energy output. In the first step, the use of sonication
to remove aggregations in the thermally treated CNTs in aqueous
solution of the SDS solution at low temperature has been reported,
which leads to adsorption of the surfactant to wet the surface of the
CNT creating a stable aqueous solution. Further, ultrasound assisted
emulsion polymerization of aniline was reported in the presence
of CNTs, which contribute to the formation of CNT encapsulated
polyaniline nanocomposite. Also a reduced amount of initiator was
added as high-powered ultrasonic radiation alone cannot generate
a sufficient amount of free radicals for the reaction. The reported
size of MWNTs/PANI composite prepared by ultrasonication is in
between 38 and 50 nm. Further, it can be concluded that the use of
ultrasonic irradiation ensures both dispersion of the CNTs in aque-
ous solution without agglomeration and prevention of coagulation
of CNTs during emulsion polymerization. MWNT/PANI nanocom-
posites shows enhanced electric conductivity and thermal stability
in comparison with pure PANI. Li et al. [156] have also used a simi-
lar method for the synthesis of PANI/SWNTs nanocomposite. It has
been also reported that the use of ultrasound enhances the dis-
persion of CNTs which in turn leads to great improvements in the
electrical and electrochemical properties of the resulting nanocom-
posites.
Zelikman et al. [157] and Suckeveriene et al. [158] have used
ultrasonically assisted in situ dynamic inverse emulsion polymer-
ization of aniline in the presence of MWNT in toluene. It has been
observed that in situ preparation of PANI/SWNT composite shows
single SWNT is coated uniformly with PANI, whereas ex situ prepa-
ration shows the improper dispersion of SWNT in PANI. It has
been also reported that the PANI coated MWNT shows remark-
able improvement in separation and dispersion in toluene, which
otherwise would have rapidly coagulated and settled. Further,
the addition of CNT by ultrasound irradiation method enhances
both the mechanical properties and electrical conductivity of PANI.
Some representative examples of polymer nanocomposites synthe-
sized by ultrasound assisted emulsion polymerization have been
reported in Table 2.
5. Conclusions
The current development of polymer nanocomposites prepared
by ultrasound assisted in situ emulsion polymerization with inor-
ganic particles such as inorganic oxides, metal, magnetic particle,
CNT and clay have been reviewed. In this ultrasonic irradia-
tion not only initiate polymerization of monomers such as MMA,
nBA, styrene, etc. at room temperature while inorganic nanopar-
ticles/clay layers were dispersed at the nanoscale, but can also
shorten the polymerization time and save the energy. Thus, the
ultrasonically initiated in situ emulsion polymerization is a novel,
simple, and fast approach to prepare polymer/layered inorganic
nanocomposites. Furthermore, ultrasonic irradiation enhances the
polymerization rates, reduces reaction conditions and achieves bet-
ter dispersion of the nanoparticles in the polymer latex which may
not be accomplished by conventional in situ emulsion polymer-
ization methods. Further, ultrasound assisted in situ semibatch
emulsion polymerization can improve the controlled polymeriza-
tion rate with better dispersion of nanoparticles in polymer latex,
which leads to the improvement in the property profile of form-
ing polymer nanocomposite. Also under the monomer starved
conditions, the particles did not undergo an appreciable growth
during polymerization and as a result a large number of smaller
and uniform size polymer particles could be obtained. Further
use of ultrasound assisted semibatch in situ emulsion polymer-
ization for the preparation of polymer nanocomposite for different
applications can be extended without use of initiator and emulsifier
at room temperature. Use of this method at room temperature can
save substantial amount of energy and the synthesis process with-
out use of initiator and emulsifier may becomes environmentally
friendly.
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