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Magnetic properties of γ‐Fe2O3 nanoparticles

made by coprecipitation method

Article in physica status solidi (b) · June 2004

Impact Factor: 1.49 · DOI: 10.1002/pssb.200304549

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phys. stat. sol. (b) 241, No. 7, 1593 – 1596 (2004) / DOI 10.1002/pssb.200304549

Magnetic properties of g-Fe2O3 nanoparticles made

by coprecipitation method
Jong-Ryul Jeong*, 1, Seung-Jun Lee2, Jong-Duk Kim2, and Sung-Chul Shin1
1
Department of Physics and Center for Nanospinics of Spintronic Materials,
Korea Advanced Institute of Science and Technology, Daejeon 305-701, Korea
2
Department of Chemical & Biomolecular Engineering,
Korea Advanced Institute of Science and Technology, Daejeon 305-701, Korea

Received 13 November 2003, accepted 1 March 2004

Published online 6 May 2004

PACS 61.46.+w, 75.50.Mm, 75.75.+a, 87.61.–c

We have synthesized maghemite (γ-Fe2O3) nanoparticles using chemical coprecipitation technique
through a typical pipette drop method (pipette diameter: 2000 µm) and a piezoelectric nozzle method
(nozzle size: 50 µm). The size distribution of the maghemite nanoparticles prepared by the pipette drop
method is from 5 nm to 8 nm. However, the nanoparticles made by the piezoelectric nozzle method show
smaller size and very narrow size distribution from 3 nm to 5 nm. Zero-Field-Cooled (ZFC)/Field-Cooled
(FC) magnetization and magnetic hysteresis measurement were performed using a superconducting quan-
tum interference device (SQUID) magnetometer from 5 K to 300 K to investigate the magnetic properties
of nanoparticles. The SQUID measurements revealed superparamagnetism of nanoparticles with the
blocking temperature of 119.5 K and 94.3 K for the nanoparticles made by the pipette drop method and
the piezoelectric nozzle method, respectively.
© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction Nanoparticles of magnetic metals and oxides have attracted great interest in recent
years because of their unique physical and chemical properties [1 – 3]. Especially, maghemite (γ-Fe2O3)
nanoparticles attracts great deal of interest due to their technological and fundamental importance, such
as information storage, magnetic resonance imaging contrast agent, superparamagnetism, and macro-
scopic quantum tunnelling associated with size quantization and electronic quantum confinement effects
[4 –7]. The maghemite, (γ-Fe2O3), is a red-brown magnetic material and isostructural with magnetite, but
with cation deficient sites. Various methods have been reported for the synthesis of iron oxide nanoparti-
cles, such as sonochemical synthesis, sol-gel reactions, and chemical solution. In this study, we have
investigated the magnetic properties of maghemite (γ-Fe2O3) nanoparticles synthesized by a chemical
coprecipitation technique of ferric and ferrous ions in alkali solution through a typical pipette drop
method (pipette diameter: 2000 µm) and a piezoelectric nozzle method (nozzle size: 50 µm).

2 Experiments The maghemite (γ-Fe2O3) nanoparticle was synthesized by a chemical coprecipitation

technique of ferric and ferrous ions in alkali solution through the pipette drop method and the piezoelec-
tric nozzle method. The ferrous chloride tetrahydrate and ferric chloride hexahydrate were dissolved in
D.D.I water. This solution was poured with drop-wise (pipette diameter: 2000 µm, 0.04 ml/drop) method
and piezoelectric nozzle (nozzle size: 50 µm, 0.01 ml/drop) method into alkali solution. The resulting
black precipitate was collected with a magnet and the supernatant was removed from the precipitate by
decantation. Deoxygenated Milli-Q water was added to wash the powder and the solution was decant-

*
Corresponding author: e-mail: midpath@kaist.ac.kr, Phone: +82 42 869 8167, Fax: +82 42869 8162

© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1594 J.-R. Jeong et al.: Magnetic properties of γ-Fe2O3 nanoparticles made by coprecipitation method

(311)
400
Intensity (Arb. unit)

(440)
300 (220) (511) 10 nm
(400)
(a) (b)
(b) (111) (422)
200 5 nm

100
(a)
0
10 20 30 40 50 60 70
2 θ (Deg.)
(I) (II)
Fig. 1 (I) X-ray diffraction patterns of maghemite (γ-Fe2O3) nanoparticles prepared by (a) the pipette drop method
and (b) the piezoelectric nozzle method. (II) TEM images of maghemite (γ-Fe2O3) nanoparticles prepared by (a) the
pipette drop method and (b) the piezoelectric nozzle method.

ed after centrifugation at 4000 rpm. After washing the powder at least five times, 0.01 M HCl solution
was added to the precipitate to neutralize the anionic charges on the nanoparticles surface. The resulting
magnetite (Fe3O4) black powder was isolated using an external magnetic field. These magnetites were
transformed into maghemite nanocrystallites by oxidizing them at 300 oC by aeration.
The microstructure of nanoparticles was investigated by transmission electron microscope (TEM) and
scanning electron microscope (SEM). X-ray diffraction (XRD) measurement using Cu Kα radiation was
performed to identify the crystal structure of iron oxide nanoparticles. Magnetization measurements were
performed using a SQUID magnetometer from 5 K to 300 K.

3 Results and discussion The crystal structure of synthesized nanoparticles was investigated using
XRD measurement using Cu Kα radiation. Figure 1(I) illustrate the XRD patterns obtained from
nanoparticles prepared by the pipette drop and piezoelectric nozzle methods. The XRD patterns match
well that of γ-Fe2O3 (Powder Diffraction file, JCPOS card no. 25-1402). Elemental analysis by energy
dispersive X-ray spectroscopy (EDX) showed that the resulting brown powder contains only Fe, O and
trace of C (estimated <4%). It is worthwhile to note that these are different from the nano-amorphous
products that are made by sonochemical synthesis is used [8]. The size of maghemite nanoparticles were
measured using TEM. Figure 1(II) shows the TEM pictures of maghemite nanoparticles. It is found that
the size distribution of the maghemite nanoparticles prepared by the typical pipette drop method is from
5 nm to 8 nm. However, the nanoparticles made by the piezoelectric nozzle method shows smaller size
and very narrow size distribution from 3 nm to 5 nm.
To investigate the magnetic properties of γ-Fe2O3 magnetic nanoparticles, FC/ZFC measurements
have been made using a SQUID magnetometer. Figure 2 shows the FC and ZFC curves for the
maghemite (γ-Fe2O3) nanoparticles made by (a) the pipette drop method and (b) the piezoelectric nozzle
Mangetization (10 emu/g)

24
Magnetization (10 emu/g)

24
22 FC
22
FC 20
-3

20
-3

18
18
16
16
H=500 Oe 14 H=500 Oe
ZFC
14
ZFC 12
12
10
10
0 50 100 150 200 250 300
0 50 100 150 200 250 300
(a) Temperature (K) (b)
( )
Fig. 2 ZFC and FC magnetization (H = 500 Oe) for the maghemite prepared by (a) the typical pipette
drop method and (b) the piezoelectric nozzle method.

© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

phys. stat. sol. (b) 241, No. 7 (2004) / www.pss-b.com 1595

Fig. 3 Field dependence of

5K 5K magnetization for (a) the typical
pipette drop method and (b) the

Mangetization (10 emu/g)

Mangetization (10 emu/g)

15 K 25 K piezoelectric nozzle method

with varying the temperature.

-3
-3

55 K 48 K

95 K 100 K

135 K 126 K

40 30
0 300 K 0 300 K
-40 -30
-4000 -2000 0 2000 4000 -4000 -2000 0 2000 4000
Field (Oe) (a) Field (Oe) (b)

method from 5 K to 300 K at 500 Oe. As shown in Fig. 3, the FC/ZFC magnetization measurements
show a typical superparamagnetic behaviour. For the maghemite nanoparticles prepared by the typical
drop method, the ZFC and FC curves are coincided with each other above 175 K and separated below
175 K. The ZFC curve shows a broad peak at Tmax ~ 120 K indicative of a characteristic blocking tem-
perature for superparamagnetic particles [3, 9, 10]. However, for the maghemite nanoparticles prepared
by the piezoelectric nozzle method, Tmax is detected at about 100 K with relatively sharp ZFC cusp. The
lower blocking temperature of the maghemite nanoparticles prepared by the piezoelectric nozzle method
could be ascribed to smaller nanoparticle size as shown in Fig. 1(II).
Magnetic hysteresis measurements at different temperatures from 5 K to 300 K were performed in
order to get more information about magnetic properties of nanoparticles. Figure 3 shows the evolution
of magnetic hysteresis loops with varying the temperature for the maghemite nanoparticles made by (a)
the pipette drop method and (b) the piezoelectric nozzle method with varying the temperature. As shown
in Fig. 3, ferromagnetic hysteresis loop could not be observed at room temperature but observed below
100 K. It is well known that superparamagnetism is dependent with the critical size for the single domain
structure. The typical values of the critical size are about 15 nm for Fe and 25 nm for Co [11]. Since the
size of the nanoparticle is less than 10 nm as shown in Fig. 1(II), it is considered that the nanoparticles
used in this study have single domain structure. In the theory of superparamagnetism, the coercivity (HC)
of the sample has the temperature (T) dependence below the blocking temperature as follows [3, 12]:
1/ 2
HC T 
= 1−   , (1)
H C0  TB 
where HC0 is the coercivity at 0 K and TB is the blocking temperature. In Fig. 4, we plot the coercivity
with respect to the T1/2. From the least square fitting for temperature-dependent coercivity of Fig. 3, it is
found that TB = 119.5 K with HC0 = 337 Oe and TB = 94.3 K with HC0 = 330 Oe for the nanoparticles
made by the pipette drop method and the piezoelectric nozzle method, respectively. It is worthwhile to
note that the blocking temperature obtained from the magnetic hysteresis measurements with varying the
temperature are in good agreement with the above FC/ZFC measurements results. The size of nanoparti-
cle is estimated using the simple relationship [12]
KV
TB = , (2)
25kB

where K is the anisotropy constant, kB is the Boltzmann’s constant, and V is the volume of the nanoparti-
cle. We could estimate the size of nanoparticles using the TB obtained from Eq. (1) and anisotropy con-

© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1596 J.-R. Jeong et al.: Magnetic properties of γ-Fe2O3 nanoparticles made by coprecipitation method

300 250
250
200

Coercivity ( Oe )
200
Coercivity (Oe)

150 150

100
100
50
50
0

-50 0

1 2 3 4 5 6 7 8 9 10 2 3 4 5 6 7 8 9 10 11
1/2 1/2 1/2 1/2
Temperature (K ) (a) Temperature (K ) (b)
1/2
Fig. 4 Coercivity (HC) plot with respect to T for the nanoparticles made by (a) the typical pipette drop
method and (b) the piezoelectric nozzle method.

stant of 1.2 × 106 erg/cm3 [13]. It is found that the estimated particle size is 4.3 nm and consistent with
the TEM measurement.

4 Conclusions The maghemite (γ-Fe2O3) nanoparticles have been obtained by a chemical coprecipita-
tion technique of ferric and ferrous ions in alkali solution through the pipette drop method and the piezo-
electric nozzle method. The size distribution of the maghemite nanoparticles prepared by typical pipette
drop method is from 5 nm to 8 nm. However, the nanoparticles made by piezoelectric nozzle method
show smaller size and very narrow size distribution from 3 nm to 5 nm. The SQUID measurements show
superparamagnetism of nanoparticles with a blocking temperature of TB = 119.5 K and 94.3 K for the
nanoparticles made by the pipette drop method and the piezoelectric nozzle method, respectively.

Acknowledgements This work was supported by the Korean Ministry of Science & Technology through the
Creative Research Initiatives Project and Strategic National R&D Program. The authors would like to express sin-
cere thanks to Dr. Sang-Jun Oh for helping in SQUID measurements.

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