ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 272–276 (2004) e1239–e1241

Magnetic properties of iron-oxide and (iron, cobalt)-oxide

nanoparticles synthesized in polystyrene resin matrix
R. Naika,*, E. Krolla, D. Rodaka, G.M. Tsoia, E. McCullena, L.E. Wengera,
R. Suryanarayananb, V.M. Naikc, P.P. Vaishnavad, Qu Taoe, P. Boolchande
a
Department of Physics, Wayne State University, Detroit, MI 48201,USA
b
LPCES, University of Paris-Sud, Orsay, France
c
Deapartment of Natural Sciences, University of Michigan- Dearborn, Dearborn, MI 48128, USA
d
Kettering University, Flint, MI 48504,USA
e
Department of ECECS, University of Cincinnati, Cincinnati, OH 45221, USA

Abstract

A sulfonated polystyrene resin matrix was ion exchanged with aqueous solutions of (1) FeCl2, (2) FeCl3, (3)
2FeCl2:FeCl3, (4) 9FeCl2:CoCl2, and (5) 4FeCl2:CoCl2 to prepare magnetic nanoparticles of varying size. The samples
were characterized by X-ray diffraction (XRD), 57Fe Mossbauer spectroscopy, X-ray photoelectron spectroscopy
(XPS), and transmission electron microscopy (TEM), and identify two major phases: g-Fe2O3, CoFe2O4, and perhaps a
minor Fe3O4 phase. SQUID magnetometry measurements indicate superparamagnetic particles with blocking
temperatures (TB ) ranging from 20 K to room temperature.
r 2003 Elsevier B.V. All rights reserved.

PACS: 75.50.Kj

57
Keywords: Magnetic iron oxide nanoparticles; Superparamagnetism; Fe Mossbauer spectroscopy; Blocking temperature

1. Introduction Ziolo et al. [4], for example, synthesized g-Fe2O3

Magnetic nanoparticles have potential applications
ranging from contrast enhancement in magnetic reso-
nance imaging to expanded memory storage [1,2]. The
past decade has seen a surge in the development of
different methods to synthesize magnetic nanoparticles
[3]. Though these methods are able to produce such
particles, they are limited by two drawbacks—the
tendency for the synthesized particles to aggregate, and
the conversion of g-Fe2O3 phase to a-Fe2O3 phase at a
relatively low temperature of 300
C. Methods that
incorporate nanoparticles into a polymer, glass, or
ceramic matrix are not restricted by these drawbacks.
*Corresponding author. Tel.: +1-313-577-2104; fax: +1-
313-577-3932.
E-mail address: naik@physics.wayne.edu (R. Naik).
nanoparticles by ion exchanging sulfonated polystyrene
resin matrix with iron (II) chloride. This method also
allows for recycling, with each successive cycle produ-
cing higher concentrations and larger particles. It
follows that this process can be used to control particle
size and magnetic properties.
The method of ion exchange [4] has the potential to
produce nanoparticles of ferrites and other structures.
Spinel ferrite-based nanoparticles represent sizeable
progress toward engineering specific magnetic carriers.
In particular, the capability of producing size control
60
Co-ferrite-based nanoparticles offers exciting possibi-
lities for targeting neoplastic cells with antibody-coated
nanoparticles [5,6]. In this paper, we report the synthesis
and characterization of magnetic nanoparticles of iron
oxide and (iron, cobalt) oxide in a polystyrene resin
matrix.

0304-8853/$ - see front matter r 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2003.12.300
 ARTICLE IN PRESS
e1240 R. Naik et al. / Journal of Magnetism and Magnetic Materials 272–276 (2004) e1239–e1241
2. Experimental
Magnetic nanoparticles were synthesized by treating
sulfonated divinyl benzene polystyrene resin matrix with
aqueous solutions of (1) FeCl2, (2) FeCl3, (3) 2FeCl2:-
FeCl3, (4) 9FeCl2:CoCl2, and (5) 4FeCl2:CoCl2. These
five samples have been characterized by XRD, 57Fe
Mossbauer spectroscopy, XPS, TEM and SQUID
magnetometry.
3. Results and discussion
The X-ray powder diffraction results on the samples
show that the synthesized magnetic nanoparticles are
single phase with average particle sizes of 9, 3, 4, 10,
10 nm for samples 1–5, respectively, as determined by
XRD peak broadening. These results agree with those
obtained using TEM.
57
Fe Mossbauer spectra were recorded at 300, 78 and
4 K. The room-temperature Mossbauer spectrum of the
first sample prepared by FeCl2 solution shows a six-line
pattern superimposed with a quadrupole doublet (figure
not shown), implying a broad distribution of both
particle size and blocking temperatures. In contrast, the
spectrum of the sample prepared using 2FeCl2: FeCl3
solution consists only of a quadruple doublet from room
temperature down to 78 K, indicating a much narrower
superparamagnetic particle size distribution with a TB
below 78 K (see Fig. 1). At 4 K, the spectrum exhibits two
superimposed six-line patterns, suggesting the presence of
g-Fe2O3 and Fe3O4. The results of the sample prepared by
FeCl3 solution are similar to the sample with 2FeCl2:
FeCl3. The Mossbauer results for samples 4 and 5 (figures
not shown) synthesized by using FeCl2 and CoCl2
solutions are characteristic of the presence of a CoFe2O4
spinel phase and Fe3O4. All the Mossbauer assignments
are based upon the values of the hyperfine fields,
quadrupole splitting, and isomer shift of the peaks.
Fig. 1. 57Fe Mossbauer spectra of sample 3 (d ¼ 4 nm) at (a)
300 K (b) 78 K and (c) at 4.2 K.
a
16
(emu/gram of sample)
Magnetic Moment
b
(a) - FCW for Sample 1
(b) - ZFC for Sample 1
8 (c) - FCW for Sample 3
c
(d) - ZFC for Sample 3
d
0
0 100 200 300
Temperature [K]
Fig. 2. Field-cooled and zero-field cooled magnetization vs.
temperature plots for samples 1 (d ¼ 9 nm) and 3 (d ¼ 4 nm).
Magnetization vs. temperature results performed after
zero-field-cooling (ZFC) and field-cooling (FC)
(H ¼ 0:05 T) samples 1 and 3 are shown in Fig. 2. The
ZFC curve for sample 3 shows a narrow, low-
temperature maximum, while that for sample 1 is
broader and occurs at a higher temperature. For an
assembly of magnetic nanoparticles, the temperature
and width of these maxima are typically related to a
distribution of relaxation times t, and correspondingly
the particle size (volume) distribution. The temperature
of the maximum in the ZFC curve is called the blocking
temperature TB ; below which the magnetic moment of
the particles is frozen or blocked. Above TB ; the
particles behave superparamagnetically. From the mag-
netic data, blocking temperatures of 215, 20, 20, 300,
and 300 K are obtained for the five samples. Thus,
samples 2 and 3 would have the smaller particle sizes, in
agreement with the X-ray diffraction and TEM analyses.
Likewise, the relatively narrower ZFC maximum for
sample 3 indicates a narrower distribution of relaxation
times and particle sizes than for sample 1. Moreover, the
FC magnetization for sample 1 exhibits a smaller
temperature-dependent behavior, which is consistent
with larger particle sizes and their inability to reach
thermal equilibrium even in the FC process. It should be
noted that FC curves above the blocking temperature
for all of the samples do not follow a Curie–Weiss
behavior, suggesting the presence of strong inter-particle
interactions.
X-ray photoelectron spectroscopy (XPS) spectra of
the five samples show a maximum in photoelectron
intensity at 710.5 eV, which is characteristic of a
trivalent iron [7]. This suggests that the surface of the
nanoparticles consists of g-Fe2O3 and Fe3O4 in the first
three samples and CoFe2O4/Fe3O4 for the last two
samples.
In summary, we have shown that the chemical
synthesis of magnetic oxide nanoparticles in a polystyrene
 ARTICLE IN PRESS
R. Naik et al. / Journal of Magnetism and Magnetic Materials 272–276 (2004) e1239–e1241
resin matrix offers a method to control particle size and
distribution, and hence the magnetic properties.
Acknowledgements
This work is supported by the National Science
Foundation DGE-9870720.
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