Advanced Materials Research Vol.

627 (2013) pp 869-872

Online available since 2012/Dec/27 at www.scientific.net
© (2013) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.627.869

Design and Synthesis of Novel Hematite Core-Shell Polymeric

Composites
Hong Wang a, Xuefei Lib Ying Wangc and Jiao Rend
Key Laboratory of Material Corrosion & Protection of Sichuan Province, Department of Materials &
Chemical Engineering, Sichuan University of Science & Engineering, Zigong, 643000, P.R. China
a
[email protected], [email protected], [email protected] [email protected]

Keywords: Poly(styrene-co-methyl methacrylate), Nanocomposite, Thermal property, α-Fe2O3

Abstract. A novel synthetic method was developed for the preparation of core-shell composites
consisting of α-Fe2O3 cores with poly(styrene-co-methyl methacrylate) (P(St-co-MMA)) shells via
emulsion copolymerization of styrene and methyl methacrylate monomer with surfactant of PVP.
The structure, morphology and thermal properties of the composites were been characterized by
scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared
spectroscopy (FTIR), and differential scanning calorimetry (DSC). The results confirmed that there
was no chemical interaction between α-Fe2O3 and copolymer, and the onset of thermal
decomposition for nanocomposites shifted to a higher temperature than that for neat copolymer.

Introduction
Incorporation of inorganic nanoparticles in a polymer matrix can significantly affect the thermal,
mechanical, optical, electrical, magnetic and flammability properties [1]. Iron oxide nanoparticles are
of special significance because of their application in catalysis, gas sensors, magnetic storage,
magnetic refrigeration and colour imaging. The influence of ferric oxide nanoparticles on the thermal
properties of polymer nanocomposites has been widely studied, such as α-Fe2O3 /polystyrene
nanocomposites and α-Fe2O3/poly(methyl methacrylate) nanocomposites[2-4]. To the best of our
knowledge, preparation of α-Fe2O3/P(St-co-MMA)composites and investigation of their thermal
properties has not been described.
In this work, α-Fe2O3/P(St-co-MMA) nanocomposites were prepared by in emulsion copolymeri-
zation of styrene and methyl methacrylate monomer in the presence of α-Fe2O3 nanoparticles. The
effect of α-Fe2O3 contents on the morphology and structure of the composites were characterized by
XRD, SEM and FTIR. Thermal properties of the composites were also investigated with DSC.

Experiment
Freshly distilled the styrene (St) and methyl methacrylate(MMA) monomers were used for the
synthesis of copolymer. All reagents were analytically pure and used without further purification.
Synthesis of α-Fe2O3 nanoparticles. Monodisperse α-Fe2O3 nanoparticles were synthesized via a
hydrothermal route [5]. 1.5g of polyvinylpyrrolidone(PVP) was dissolved in 20ml distilled water,
then 5.0×10-3mol of NH4HCO3 was added under vigorous magnetic stirring, followed by the addition
of 10ml of 0.4mol/L of FeCl3·6H2O aqueous solution. After the mixture was stirred and transferred
into a Teflon-sealed autoclave, and heated at 160℃ for 20 h. Then the product was washed several
times with deionized water and ethanol to remove byproducts, and then dried at 60 ℃.
Preparation of α-Fe2O3/P(St-co-MMA) composite particles. The composites were prepared
by in emulsion copolymerization with a methanol-water mixture in the presence of α-Fe2O3 nano-
particles. The α-Fe2O3 nanoparticles, PVP (0.15g) and methanol (30ml) were introduced into the
beaker, impetuously stirred. The reaction was carried out in a 250 ml flask equipped with a
mechanical stirrer. The flask was charged with 40 ml methanol 9g St, 1 g MMA, and 0.980 g
NaHCO3. Then α-Fe2O3 was added to the reaction flask under impetuously stirring. The flask was

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870 Advances in Textile Engineering and Materials

immersed into a water-bath at 80 °C and the aqueous solution containing 0.1 g K2S2O8 was added to
initiate the polymerization. After reaction for 10 h, the resulting products were filtrated, washed with
distilled water and ethanol and then dried at 60°C. Moreover, to study the influences of the α-Fe2O3
contents on the morphology, structure, and properties of the products, the α-Fe2O3/P(St-co-MMA)
composites were prepared by adjusting mass of α-Fe2O3 nanoparticles at 0.10g, 0.15g and 0.20g.
Neat P(St-co-MMA) was prepared under the same conditions without α-Fe2O3 nanoparticles.
Characterization. The morphology of the sample measurements were carried out with a JEOL
JSM-6700F field emission scanning electron microscope (SEM). The X-ray diffraction (XRD)
patterns of the as-prepared products were performed using Bruker AXS D8 diffractometer equipped
with amonochromator, using Cu Kα radiation (λ= 1.5405Å), at 40kV and 40mA. FTIR spectra of KBr
wafers were collected on a Thermo Nicolet 6700 FTIR spectrometer. Thermal properties were
measured on the DSC/TG analyzer (STA 409 PC/PG, Netzsch, Germany) at a rate of 10 ºC/min under
a dynamic atmosphere of N2.

Results and discussion

Fig.1 SEM images of (a) α-Fe2O3, α-Fe2O3/P(St-co-MMA) composites synthesized by adjusting

mass of α-Fe2O3 nanoparticles (b) 0.10g, (c) 0.15g and (d) 0.20g, and (e) P(St-co-MMA)

Fig. 1a showed the SEM image of the as-synthesized α-Fe2O3 nanoparticle, which clearly displayed
that the products were composed of a large amount of monodisperse α-Fe2O3 nanoparticles with
average size of about 110nm. In Fig. 1b-d, by copolymerization of St and MMA monomers while
α-Fe2O3 nanoparticles existing, it was interestingly found that the produced α-Fe2O3/P(St-co-MMA)
composites all possessed sphere-like structures, and was different from the size of α-Fe2O3
nanoparticles. When the composites prepared by adjusting mass of α-Fe2O3 nanoparticles 0.10g,
0.15g and 0.20g, the size of the composites are about 450nm, 400nm and 300nm in average diameter,
respectively. It indicated that the α-Fe2O3 nanoparticles were enwrapped by P(St-co-MMA)
copolymer effectively, and fully core/shell structures were produced for α-Fe2O3/P(St-co-MMA)
nanocomposites. Neat P(St-co-MMA) copolymer microsphere with an average diameter of about 0.6
µm was produced by dispersion copolymerization without α-Fe2O3 nanoparticles(Fig. 1e). As the
increase in the α-Fe2O3 content in α-Fe2O3/P(St-co-MMA) composites, the size in the diameters of
the composites decrease , which were perhaps due to the decreasing thickness of the P(St-co-MMA)
shells.
Fig. 2 showed the XRD patterns for α-Fe2O3 nanoparticles, α-Fe2O3/P(St-co-MMA) composites
and P(St-co-MMA) microspheres. In Fig.2a, all of the sharp diffraction peaks can be indexed to
rhombohedral α-Fe2O3 with lattice constants a=0.50355 and c= 1.3747 nm, which were consistent
 Advanced Materials Research Vol. 627 871

with the values in the literature (JCPDS 33-0664). As for α-Fe2O3/P(St-co-MMA) composites(Fig.
2b-d), the diffraction peaks of α-Fe2O3 crystals could be clearly distinguished for all the samples,
while the diffraction intensities of the peaks decreased with the reduction of the content of α-Fe2O3
nanoparticles. Furthermore, it was observed that a broad amorphous diffraction peak appearing at 2θ
of 14-26° in XRD curves of P(St-co-MMA)(Fig.2e) and α-Fe2O3/P(St-co-MMA) composites, which
was corresponding to the P(St-co-MMA), and this broad diffraction peak of P(St-co-MMA) in the
α-Fe2O3/P(St-co-MMA) composites was slightly weak, indicating that structural disorder of
P(St-co-MMA) in the composites were enhenced by addition of α-Fe2O3 nanoparticles.

Fig.2 XRD patterns of (a) α-Fe2O3 nanoparticles, Fig.3 FTIR spectra of (a) neat P(St-co-MMA)
α-Fe2O3/ P(St-co-MMA) composites synthesized copolymer, α-Fe2O3/ P(St-co-MMA)
by (b) 0.10g, (c) 0.15g and (d) 0.20g α-Fe2O3 composites synthesized by (b) 0.10g,
nanoparticles and (e) neat P(St-co-MMA) (c) 0.15g and (d) 0.20g α-Fe2O3 nano-
copolymer particles

FT-IR spectra of the obtained P(St-co-MMA) copolymer and α-Fe2O3/ P(St-co-MMA)

composites were shown in Figure 3. For P(St-co-MMA) copolymer (Fig.3a), Absorption bands at
2923 (C–H stretching), 1728 (C=O stretching), 1149–1200 (C–O stretching), 3028, 3060 (aromatic
C–H stretching), and 753 cm-1 (aromatic C–H bending) were the consequences of the P(St-co-MMA)
copolymer respectively. As can be seen from Fig. 3b-d, the samples exhibited absorption signal at
468 cm-1 were assigned to the lattice vibrations of the FeO6 octahedron were characteristic of
crystalline α-Fe2O3 [6]. After combining with α-Fe2O3, a similar characteristic vibration peaks in the
FT-IR absorption spectra of P(St-co-MMA) was observed and almost have no shifts as compared
with those for copolymer. XRD and FT-IR analyses perhaps indicated that there was no obvious
chemical interaction between α-Fe2O3 cores and P(St-co-MMA) shells in the composites, but that
α-Fe2O3 nanoparticles only served as the nucleation centers for the polymerization of
P(St-co-MMA). These FT-IR spectra provided supportive evidence that copolymers was coated on
the surface of α-Fe2O3 nanoparticles, and α-Fe2O3/ P(St-co-MMA) composites were successfully
prepared.
Figure 4 was the thermogravimetric analysis (TG) curves of P(St-co-MMA) and α-Fe2O3/
P(St-co-MMA) composites. As seen in Fig. 4, a slight weight loss was observed at the first stage from
50°C to 160°C, corresponding to the loss of moisture. The weight loss of the composites at
200-500°C (Fig. 4b) was attributed to decomposition of P(St-co-MMA) chains. According to Fig. 4,
thermal stabilities of all the nanocomposites were higher than the neat copolymer. Also, degradation
temperature of the nanocomposites was raised with the increasing content of the α-Fe2O3. The
P(St-co-MMA) started to decompose at about 270°C, while α-Fe2O3/P(St-co-MMA) composites
(synthesized by 0.10g and 0.20g α-Fe2O3) started to decompose at about 285 and 290°C, about 15 and
20°C higher than that of neat copolymer. The improved thermal stability should be attributed to the
quite strong interactions between α-Fe2O3 and P(St-co-MMA) chains. It indicated the coating
formation and the binding efficiency on the surface of α-Fe2O3 nanoparticles.
872 Advances in Textile Engineering and Materials

Fig. 4 TG curves of (a) neat P(St-co-MMA) Copolymer, α-Fe2O3/P(St-co-MMA) composites

synthesized by (b) 0.10g and (c) 0.20g α-Fe2O3 nanoparticles

Conclusions
In summary, α-Fe2O3/P(St-co-MMA) nanocomposites were prepared by in emulsion copolymeri-
zation of styrene and methyl methacrylate monomer in the presence of α-Fe2O3 nanoparticles. The
structure and morphology of the nanocomposites were characterized by SEM, FTIR, XRD. The
results showed that P(St-co-MMA) was coated on the surface of α-Fe2O3 nanoparticles, and the
contents of α-Fe2O3 greatly affected the structure and morphology of synthesized composites during
the polymerization. Moreover, thermal stabilities of all the nanocomposites were higher than the neat
copolymer, and the degradation temperature of the nanocomposites were raised by the increasing of
the α-Fe2O3 content.

Acknowledgements
This work is supported by Research Sichuan Province Education Commission (12ZA092),
Foundation of Sichuan University of Science & Engineering (2011RC17), and Research Foundation
of Zigong Municipal science and technology Commission (20110041).

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Design and Synthesis of Novel Hematite Core-Shell Polymeric Composites

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