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

nanoparticles by ion exchanging sulfonated polystyrene
Magnetic nanoparticles have potential applications resin matrix with iron (II) chloride. This method also
ranging from contrast enhancement in magnetic reso- allows for recycling, with each successive cycle produ-
nance imaging to expanded memory storage [1,2]. The cing higher concentrations and larger particles. It
past decade has seen a surge in the development of follows that this process can be used to control particle
different methods to synthesize magnetic nanoparticles size and magnetic properties.
[3]. Though these methods are able to produce such The method of ion exchange [4] has the potential to
particles, they are limited by two drawbacks—the produce nanoparticles of ferrites and other structures.
tendency for the synthesized particles to aggregate, and Spinel ferrite-based nanoparticles represent sizeable
the conversion of g-Fe2O3 phase to a-Fe2O3 phase at a progress toward engineering specific magnetic carriers.
relatively low temperature of 300
C. Methods that In particular, the capability of producing size control
60
incorporate nanoparticles into a polymer, glass, or Co-ferrite-based nanoparticles offers exciting possibi-
ceramic matrix are not restricted by these drawbacks. lities for targeting neoplastic cells with antibody-coated
nanoparticles [5,6]. In this paper, we report the synthesis
*Corresponding author. Tel.: +1-313-577-2104; fax: +1- and characterization of magnetic nanoparticles of iron
313-577-3932. oxide and (iron, cobalt) oxide in a polystyrene resin
E-mail address: naik@physics.wayne.edu (R. Naik). 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
a
16

(emu/gram of sample)
Magnetic nanoparticles were synthesized by treating

Magnetic Moment
sulfonated divinyl benzene polystyrene resin matrix with b
aqueous solutions of (1) FeCl2, (2) FeCl3, (3) 2FeCl2:- (a) - FCW for Sample 1
FeCl3, (4) 9FeCl2:CoCl2, and (5) 4FeCl2:CoCl2. These (b) - ZFC for Sample 1
five samples have been characterized by XRD, 57Fe 8 (c) - FCW for Sample 3
c
Mossbauer spectroscopy, XPS, TEM and SQUID (d) - ZFC for Sample 3
magnetometry. d

0
3. Results and discussion 0 100 200 300
Temperature [K]
The X-ray powder diffraction results on the samples
show that the synthesized magnetic nanoparticles are Fig. 2. Field-cooled and zero-field cooled magnetization vs.
single phase with average particle sizes of 9, 3, 4, 10, temperature plots for samples 1 (d ¼ 9 nm) and 3 (d ¼ 4 nm).
10 nm for samples 1–5, respectively, as determined by
XRD peak broadening. These results agree with those
obtained using TEM. Magnetization vs. temperature results performed after
57
Fe Mossbauer spectra were recorded at 300, 78 and zero-field-cooling (ZFC) and field-cooling (FC)
4 K. The room-temperature Mossbauer spectrum of the (H ¼ 0:05 T) samples 1 and 3 are shown in Fig. 2. The
first sample prepared by FeCl2 solution shows a six-line ZFC curve for sample 3 shows a narrow, low-
pattern superimposed with a quadrupole doublet (figure temperature maximum, while that for sample 1 is
not shown), implying a broad distribution of both broader and occurs at a higher temperature. For an
particle size and blocking temperatures. In contrast, the assembly of magnetic nanoparticles, the temperature
spectrum of the sample prepared using 2FeCl2: FeCl3 and width of these maxima are typically related to a
solution consists only of a quadruple doublet from room distribution of relaxation times t, and correspondingly
temperature down to 78 K, indicating a much narrower the particle size (volume) distribution. The temperature
superparamagnetic particle size distribution with a TB of the maximum in the ZFC curve is called the blocking
below 78 K (see Fig. 1). At 4 K, the spectrum exhibits two temperature TB ; below which the magnetic moment of
superimposed six-line patterns, suggesting the presence of the particles is frozen or blocked. Above TB ; the
g-Fe2O3 and Fe3O4. The results of the sample prepared by particles behave superparamagnetically. From the mag-
FeCl3 solution are similar to the sample with 2FeCl2: netic data, blocking temperatures of 215, 20, 20, 300,
FeCl3. The Mossbauer results for samples 4 and 5 (figures and 300 K are obtained for the five samples. Thus,
not shown) synthesized by using FeCl2 and CoCl2 samples 2 and 3 would have the smaller particle sizes, in
solutions are characteristic of the presence of a CoFe2O4 agreement with the X-ray diffraction and TEM analyses.
spinel phase and Fe3O4. All the Mossbauer assignments Likewise, the relatively narrower ZFC maximum for
are based upon the values of the hyperfine fields, sample 3 indicates a narrower distribution of relaxation
quadrupole splitting, and isomer shift of the peaks. 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.
Fig. 1. 57Fe Mossbauer spectra of sample 3 (d ¼ 4 nm) at (a) In summary, we have shown that the chemical
300 K (b) 78 K and (c) at 4.2 K. 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 e1241

resin matrix offers a method to control particle size and [2] S. Sun, C.B. Murray, D. Weller, L. Folks, A. Moser,
distribution, and hence the magnetic properties. Science 287 (2000) 1989.
[3] J. Weissmuller, Nanomaterials: Synthesis, Properties and
Applications, Institute of Physics Publishing, Philadelphia,
Acknowledgements 1996.
[4] R.F. Ziolo, E.P. Giannelis, B.A. Weinstein, M.P. O’Horo,
B.N. Ganguly, V. Mehrotra, M.W. Russell, D.R. Huffman,
This work is supported by the National Science
Science 257 (1992) 5067.
Foundation DGE-9870720. [5] U.O. Hafeli, G.J. Pauer, J. Magn. Magn. Mater. 194 (1999)
76.
[6] U.O. Hafeli, S.M. Sweeney, B.A. Beresford, Nucl. Med.
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