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Materials Letters 62 (2008) 37 – 40

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Preparation and characterization of TiO2/polystyrene core–shell nanospheres

via microwave-assisted emulsion polymerization
H.L. Luo, J. Sheng, Y.Z. Wan ⁎
School of Materials Science and Engineering, Tianjin University, Tianjin 300072, PR China
Received 30 January 2007; accepted 19 April 2007
Available online 22 May 2007

Abstract

A combined procedure of sol–gel and microwave-assisted emulsion polymerization has been developed to prepare TiO2/polystyrene core–shell
nanospheres with nano-scale TiO2 core and smooth and well-defined polystyrene shell. The core–shell structure and morphology were examined by
TEM. The diameter and its distribution of the nanospheres were measured by dynamic light scattering. The nanospheres were characterized with Fourier
transform infrared spectroscopy (FTIR). It is found that the diameter and its distribution of the TiO2/polystyrene core–shell nanospheres can be regulated
by the concentration of styrene monomer in the emulsion solution.
© 2007 Elsevier B.V. All rights reserved.

Keywords: TiO2; Polystyrene; Nanomaterials; Sol–gel preparation; Emulsion polymerization

1. Introduction nism of microwave heating involves agitation of polar molecules

Inorganic–organic nanocomposites in which inorganic fillers
are uniformly dispersed in a polymer matrix possess improved
strength, toughness, processability, dimensional stability, wear
properties, and so forth when compared to conventional
composites. Undoubtedly, uniform dispersion of nano-scale
fillers in polymeric matrices is of paramount importance.
Unfortunately, particle agglomeration is a great problem for
many inorganic–organic systems [1] such as TiO2/polystyrene
due to the hydrophilicity of TiO2. To ensure uniform dispersion of
inorganic particles in polymeric matrices and to improve particle–
polymer adhesion inorganic particles are often modified with
surfactants or coupling agents by physical adsorption or chemical
reaction in solution [2–4] or coated with polymeric materials by
various processes [5–8]. Microwave-assisted polymerization is
an effective way of preparing clean and superfine polymer
particles and has been used by various research groups in light of
its advantageous features like rapid reactions, high conversions,
and low energy consumption [9–11]. The fundamental mecha-
⁎ Corresponding author. Tel./fax: +86 22 2740 5056.
E-mail address: yzwantju@yahoo.com (Y.Z. Wan).
0167-577X/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2007.04.108
or ions that oscillate under the effect of an oscillating electric field.
In the presence of an oscillating field, particles try to orient
themselves. This constant reorientation creates friction and
collisions between molecules, thus producing heat [12]. On the
other hand, emulsion polymerization has been used to prepare not
only polymeric particles but also nanocomposite particles with
inorganic cores [13–15]. This kind of nanoparticles may find
applications in electron paper display [16,17]. In this paper, we
report, for the first time to our knowledge, a novel combination of
sol–gel and microwave-assisted emulsion polymerization to
prepare TiO2/polystyrene core–shell nanospheres. The objective
of this preliminary study is to present our successful synthesis and
characterization of the TiO2/polystyrene nanospheres.
2. Experimental
2.1. Experimental set-up
The equipment used was a microwave irradiation apparatus
(XH100B, Beijing Xianghu Science and Development Co. Ltd.,
Beijing, China) operating at 2450 MHz with a maximum output
power of 800 W. Inside this microwave oven, a flask equipped
with a magnetic stirrer and a reflux condenser was installed.
38 H.L. Luo et al. / Materials Letters 62 (2008) 37–40

2.2. Preparation of TiO2/polystyrene core–shell nanospheres

Typically, 3 ml tetra-n-butyl titanate (Ti(OC4H9)4) liquid

(purchased from No. 1 Tianjin Chemicals Company, Tianjin,
China) was added into a flask containing 50 ml ethanol and
rigorously stirred to obtain a solution (solution A). Solution B was
a mixture of 100 ml deionized water and 30 ml ethanol with a pH

Fig. 2. Diameter and its distribution of TiO2/polystyrene nanospheres

Fig. 1. TEM images of TiO2/polystyrene nanoparticles synthesized under varying
synthesized under varying concentrations (by volume) of styrene monomer (a)
concentrations (by volume) of styrene monomer (a) 2.0%, (b) 3.5%, and (c) 5%.
2.0%, (b) 3.5%, and (c) 5%.
 H.L. Luo et al. / Materials Letters 62 (2008) 37–40
Fig. 3. FTIR spectra of (a) pristine polystyrene, (b) bare TiO2, (c) TiO2/
polystyrene at 2.0% styrene, (d) TiO2/polystyrene at 3.5% styrene and (e) TiO2/
polystyrene at 5.0% styrene.
of 9 adjusted by adding 1 mol/l NaOH. Under vigorous stirring,
10 ml solution A was added into 130 ml solution B. The mixed
solution (with a total volume of 140 ml) was then placed in the
microwave to start the hydrolysis reaction under the microwave
irradiation. The reaction was carried out at 40 °C for 40 min,
resulting in light white and transparent TiO2 colloids. The
resulting colloids were heated up to 70 °C under nitrogen
atmosphere. Immediately, 0.2 g sodium dodecyl sulfonate
(purchased from Research Institute of Fine Chemical Engineer-
ing, Tianjin, China), 0.2 g of ammonium persulfate (from No. 3
Chemicals Company, Tianjin, China), and varying amount (3, 5,
and 7 ml) of freshly distilled styrene monomer (purchased from
Kewei Chemicals Co. Ltd., Tianjin, China) were added into the
flask to initiate the emulsion polymerization on the surface of
TiO2 colloids. The microwave-assisted polymerization reaction
continued for 1.5 h and was followed by centrifugation, washing,
and vacuum drying, resulting in the core (TiO2)–shell (polysty-
rene) nanospheres.
All chemicals used in this work were analytical grade and the
styrene monomer was purified by distillation at a reduced
pressure before use. In the present work, the concentration of
styrene monomer (with respect to the emulsion solution) was set
at ca. 2.0, 3.5, and 5.0% by volume respectively.
Table 1
Assignments of typical peaks presented in Fig. 3
Wavenumber (cm− 1) Type of vibration
3410 Stretching motion of the surface hydroxyl or the adsorption water
3082, 3059, 3026 Aromatic C–H stretching
2925, 2850 Methylene C–H stretching
1674–1942 C–H out-of-plane deformation bending of aromatic ring
1640 The bending vibration of the OH bonds of the adsorbed water
1449 Methyl C–H bending; in-plane phenyl ring-bending mode
1330 Stretching of residual organic functional groups
700, 759 Out-of-plane phenyl ring-bending mode
600 Characteristic peak of TiO2
39
2.3. Characterization
The particle size was characterized by dynamic light scattering
using a Brookhaven BI-90 submicron particle size analyzer
(Brookhaven Instruments Corp., Holtsville, NY, USA). Infrared
spectra of various samples pressed into KBr pellets were obtained
on a Bio-Rad FTS 6000 FTIR spectrophotometer. The morphol-
ogy of the particles was examined with a JEOL 2000FX
transmission electron microscope (TEM) with an accelerating
voltage of 200 kV. Samples were prepared on carbon-coated grids.
3. Results and discussion
3.1. Morphologies
Typical TEM pictures of the TiO2/polystyrene nanoparticles are
shown in Fig. 1. The particles show spherical shape and very smooth
surfaces. Fig. 1 reveals a core–shell structure, the core being the
material that is more opaque viz. TiO2 in this case and the shell being
polystyrene. Clearly, the entire surfaces of all TiO2 core are covered by
polystyrene. The thickness of the polystyrene coating varies with the
concentration of styrene monomer in the emulsion solution.
The diameter and its distribution of the core–shell nanoparticles
prepared under different concentrations of styrene monomer were
measured with a Brookhaven BI-90 submicron particle size analyzer.
The result is presented in Fig. 2. It is clearly shown that the nanospheres
show varying diameters depending on the concentration of styrene
monomer, which agrees well with the TEM observation. Note that the
average diameter of the particles increases with the concentration of
styrene monomer in the emulsion solution, which is 123, 161, and
175 nm when a monomer concentration of 2.0, 3.5, and 5.0% by
volume respectively was employed. The increase of the diameter (i.e.,
the thickness of polystyrene coating) with the content of styrene is
simply due to the fact that more styrene monomer is involved to the
polymerization reaction. It is interesting to note that the size
distribution is also controlled by the styrene monomer concentration
in the emulsion solution. At styrene concentrations of 2 and 3.5%
monodisperse nanospheres are obtained while the size distribution of
the nanospheres is relatively wide at a higher styrene concentration of
5%. Unfortunately, how the concentration affects the size distribution is
not fully understood yet.
3.2. FTIR analysis
Typical FTIR spectra of various nanospheres obtained in this work
are given in Fig. 3. For the sake of comparison, the spectra of the
Polystyrene (curve a) TiO2 (curve b) TiO2/polystyrene
(curves c–e)
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40 H.L. Luo et al. / Materials Letters 62 (2008) 37–40

pristine polystyrene spheres (curve a) synthesized separately and TiO2 Acknowledgment

nanoparticles (curve b) are included in this figure. The assignments of
these curves are listed in Table 1. It is noted that the characteristic peaks This study was financially supported by the National Natural
of TiO2 particles are located at around 600 cm− 1 (see curve b). The Science Foundation (Grant No. 50390090).
broad peak at 3410 cm− 1 corresponds to the stretching motion of the
surface hydroxyl or the adsorption water and the peak at 1640 cm− 1
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