220 Int. J. Nanoparticles, Vol. 3, No.

3, 2010

Synthesis, crystal structure and magnetic properties

of iron oxides nanoparticles for biomedical
applications

S. Rashdan*
Department of Chemistry, University of Bahrain,
P.O. Box 32038, Kingdom of Bahrain
E-mail: [email protected]
*Corresponding author

M. Bououdina and A. Al-Saie

Nanotechnology Centre,
University of Bahrain,
Sakhir Campus, P.O. Box 32038, Kingdom of Bahrain
and
Department of Physics, College of Science,
University of Bahrain,
Sakhir Campus, P.O. Box 32038, Kingdom of Bahrain
E-mail: [email protected]
E-mail: [email protected]

E. Ghanem, A. Bin-Thani and S. Althawadi

Department of Biology, University of Bahrain,
P.O. Box 32038, Kingdom of Bahrain
E-mail: [email protected]
E-mail: [email protected]
E-mail: [email protected]

Abstract: Magnetic Fe3O4 nanoparticles have been synthesised by two

methods: co-precipitation using a range of Fe3+ and Fe2+ raw materials;
oxidative hydrolysis using various Fe2+ salts. X-ray diffraction analysis shows
that most of the samples prepared by the co-precipitation method resulted in a
mixture of two iron oxide phases (Fe2O3 and Fe3O4) with the presence of
impurities (unreacted precursors) while using the oxidative hydrolysis method,
Fe3O4 was found to be a major product. Magnetic measurements confirm the
results obtained by X-ray diffraction. The sample prepared using FeSO4 as
precursor in urea and PEG 200 at 40–50°C for 3 hours (nominated as E2)
gives an average crystallites size around 70 nm, a saturation magnetisation
Ms = 75 emu/g, a remanence of Mr = 12 emu/g and a coercivity of
Hc = 110 kOe, which can be a good candidate for biomedical applications.

Keywords: magnetic nanoparticles; co-precipitation method; oxidative

hydrolysis method; X-ray diffraction; magnetic properties.

Copyright © 2010 Inderscience Enterprises Ltd.

 Synthesis, crystal structure and magnetic properties 221

Reference to this paper should be made as follows: Rashdan, S.,

Bououdina, M., Al-Saie, A., Ghanem, E., Bin-Thani, A. and Althawadi, S.
(2010) ‘Synthesis, crystal structure and magnetic properties of iron oxides
nanoparticles for biomedical applications’, Int. J. Nanoparticles, Vol. 3, No. 3,
pp.220–228.
Biographical notes: Suad Rashdan is an Assistant Professor of Chemistry in
the College of Science at University of Bahrain, Kingdom of Bahrain. She
received her PhD in Organic Chemistry from University of Southampton
(Southampton, UK) in October 2007. Her research interests are in the field of
supramolecular and host-guest chemistry.
Mohamed Bououdina is the Director of Nanotechnology Centre at the
University of Bahrain, Kingdom of Bahrain. He received his PhD in Physics
from the Universite Joseph Fourier (Grenoble, France). His research interests
are in the field of nanoscience and nanotechnology, renewable energy such as
hydrogen storage, materials science, biomaterials and neutron diffraction.
Ahmad Al-Saie is an Associate Professor in the College of Science at the
University of Bahrain, Kingdom of Bahrain. He received his PhD from the
University of Edinburgh (Scotland, UK). His current research interests include
nanomaterials and thin films.
Essam H. Ghanem is a Professor in Microbiology and Biotechnology
Department of Biology, College of Science, University of Bahrain. He received
his PhD from Al-Azhar University in Microbiology 1983. His research interests
are in the fields of environmental biotechnology, antibiotics production from
actinomycetes, biofuel, and more recently biotechnological applications of
nanotechnology.
Ali Bin-Thani is an Assistant Professor of Molecular Microbiology in the
College of Science at the University of Bahrain, Kingdom of Bahrain. He
received his PhD in Microbiology from the University of Leicester, UK. His
research interests include the use of magnetic nanoparticles conjugated with
biological molecules in nano-medicine.
Salwa Al-Thawadi is an Assistant Professor in Biology Department,
College of Science, Kingdom of Bahrain. She received her PhD from Murdoch
University, Western Australia. Her current interests are in biotechnology,
bio-nanotechnology and bioinformatics.

1 Introduction

Fe3O4 NPs are extensively studied because they exhibit unique electric and magnetic
properties due to the transfer of electrons between Fe2+ and Fe3+ ions and they magnetise
strongly under an external applied field without leaving any permanent magnetism once
the field is removed. The morphology of these particles plays an important role in
determining their magnetic and electronic properties. Experimentally, it is difficult to
obtain nanoparticles with variable morphology in a controllable manner, as the crystal
growth is extremely difficult to control in the complicated reaction system (Hyeon,
2003). Recently, there is an extensive search have been devoted toward the development
of new methods for the synthesis of Fe3O4 nanoparticles that afford a high degree of
reproducibility in terms of nonmaterial size, structure and morphology and also allow
222 S. Rashdan et al.

process scale-up without affecting the quality of the products. There are several different
reported methods for synthesising of Fe3O4 NPs such as sol-gel method (Xu et al., 2007),
co-precipitation from a solution of Fe3+/ Fe2+ mixed salt in alkaline media (Hong et al.,
2007) and thermal hydrolysis of Fe2+ salt (Ozkaya et al., 2009).
The range size of iron oxide NPs play an important role in their applications. It has
been reported that the particles size can be controlled by using protective such as
polyethylene glycol (PEG) (Yangde et al., 2008) and sodium dodecyl sulphate (SDS)
(Yan et al., 2008). For example, the addition of PEG, which replaces the water molecules
on the surface of the nanoparticles, prevents agglomeration.
This paper represents the synthesis of Fe3O4 nanoparticles by co-precipitation and
oxidative hydrolysis methods under atmospheric air using a range of raw iron materials
and different protective agents to investigate the effect of raw material and the surfactants
on the formation of Fe3O4 nanoparticles, purity, crystallites size and the magnetic
properties. The synthesised Fe3O4 have been characterised by X-ray diffraction and
magnetic measurements were carried out.

2 Experimental

2.1 The general procedure for oxidative hydrolysis method

FeSO4. 7H2O (0.540 g) was added to distilled water (100 ml) containing PEG (200)
(1.00 g). The mixture was allowed to stir at room temperature for 30 min, then urea
(1.55 g) was added and the mixture was refluxed at 50°C for 3 hours. During refluxing
the mixture colour changed from red-dark brown to black. After completion, the black
solid was washed by decantation with ethanol (three times), water (three times) and then
dried in the oven at 60°C for 48 hours to give a black solid of Fe3O4.

2.2 The general procedure for co-precipitation method

FeCl3.6 H2O (0.541 g, mol) and FeSO4. 7H2O (0.277 g, mol) were dissolved in distilled
water (100 ml) containing PEG 200 (1.01 g). The mixture was stirred for 30 min then
urea (3.00 g) was added and then refluxed at 50°C for 3 hours. After 2 hours refluxing a
NaOH (1 M, 5 ml) was added, the solution was immediately turned black and continued
to reflux for 1 hour. The product was washed with ethanol (three times), water (three
times) by decantation and dried in the oven at 60ºC for 48 hours to give Fe3O4 as black
solid.

2.3 Samples characterisations

The procedure for the preparation of iron oxide nanomaterials are shown in Table 1. The
prepared powders were analysed with powder X-ray diffraction using Philips
diffractometer equipped with Cu α-radiation and the magnetic measurements were
carried out at room temperature using PMC MicroMag 3900 model vibrating sample
magnetometer (VSM) having a 1 Telsa magnet. The results of these measurements are
summarised in Table 1.
 Synthesis, crystal structure and magnetic properties 223

Table 1 The preparation procedures for the synthesised iron oxide nanomaterials and their
magnetic properties: the crystallites size (Cs, nm), saturation magnetisation (Ms),
remanence (Mr) and coercivity (Hc)

Cs Ms Mr Hc
Sample Method of preparation Results
(nm) (emu/g) (emu/g) (Oe)
E2 Oxidative hydrolysis of 70 74.7 11.6 110 • Gave Fe3O4 as a
FeSO4 in urea and PEG 200 major and some
at 40–50°C for 3 hours Fe2O3
• Strong magnetism
properties
E4a Co-precipitation of FeCl3 24 11.6 0.93 39 • Gave Fe2O3 as a
and FeSO4 salts in urea major product
(PEG 200) at 40–50°C for • VSM shows weak
3 hours with addition of magnetism properties
NaOH (1M, 5 ml)
E4b Co-precipitation of FeCl3 23 31.0 2.14 40
and FeSO4 salts in urea
(PEG 3000) at 40–50°C for
3 hours with the addition of
NaOH (1M, 5 ml)
E1 Co-precipitation of FeCl3 27 14.3 0.84 83 • Gave a mixture of
and FeSO4 salts in urea Fe2O3 and Fe3O4 and
(PEG 200) at 40–50°C for some impurities
3 hours without the addition • Weak magnetism
of NaOH solution properties
E3 Similarly to E1. Using PEG 26 0.66 0.07 109
(3000) without the addition
of NaOH (1 M, 5 ml) was
added to the reaction mixture
after 2 hours refluxing
E5 A mixture of FeCl2 and 47 - - - • Gave a mixture of
FeCl3 in NaOH was refluxed phases (FeCl2, FeCl3)
at 80°C for 30 min then • No magnetic
collected and PEG 3000 was properties were
added and the mixture was obtained
stirred at room temperature
for 24 hours. The precipitate
(ppt) was washed with
water, collected by
centrifuging, dried in an
oven at 60°C for 48 hours
E6 Co-precipitation of FeCl3 100 1.5 0.16 128 • Gave Fe2O3 as a
and FeSO4 salts in urea and major product
PEG (200) at 40–50°C for • VM shows weak
3 hours magnetism properties
E7 Similarly to E1. Using PEG 11 42.3 1.41 14 • Gave mainly Fe3O4
(200) and after 1 hour of as major product
refluxing NaOH (1 M, 10 • Strong magnetic
ml) was added. Black ppt properties
was immediately formed.
The refluxing resumed for
2 hours and the ppt was
washed and collected
similarly to E1
224 S. Rashdan et al.

3 Results and discussion

Co-precipitation method is a chemical process which involves a simultaneous

precipitation of more than one substance. The formation of spinel oxide nanoparticles is
accomplished by co-precipitation of various salts (chloride, sulphate, nitrate, etc.) under a
fine control of pH by using NaOH, NH4OH or urea solutions. The formation mechanism
of Fe3O4 nanoparticles is shown in equation (1) (Gupta and Gupta, 2005).

Fe 2 + + 2Fe3+ + 8OH − → Fe3O 4 + 4H 2 O (1)

Lian et al. (2004) have suggested the formation mechanism of Fe3O4 from Ferric chloride
and ferrous sulphate salts in the presence of urea as a base; see equations (2) to (6). Note
that at the beginning of the reaction, urea is thermally hydrolysed giving ammonium
hydroxide, which will react with ferric ion to give a yellow precipitate of ferric
hydroxide. Ferric hydroxide then decomposes to give ferricoxyhydroxide (FeOOH),
which reacts with ferrous hydroxide to form Fe3O4.

(NH 2 ) 2 CO + H 2 O → 2NH3 + CO 2 (2)

Fe3+ + 3OH − → Fe(OH)3 (3)

Fe(OH)3 → FeOOH + H 2 O (4)

Fe 2 + 2OH − → Fe(OH) 2 (5)

Fe(OH) 2 + 2FeOOH → Fe3O 4 + 2H 2 O (6)

XRD patterns of prepared samples by co-precipitation method are reported in Figure 1,

while the hysteresis loop for magnetic measurements (VSM) is shown in Figure 2.
The diffraction peaks of E1 and E3 samples can be considered as a mixture of Fe2O3
and Fe3O4. Some additional peaks are observed as well which can be attributed to
impurities such as chloride (remaining from incomplete chemical reactions). For both
samples the average crystallites size was identical (Table 1). On the other hand, the XRD
of E7 sample which is prepared by similar procedure as E1 but with the addition of
(NaOH) as a base, gives pure Fe3O4 nanoparticles with a very small crystallites size of 11
nm and it gives strong magnetism compared to E1 (Figure 2). This result shows the
importance of using urea at an early stage of the reaction followed by the addition of a
strong base. The XRD pattern of E5 sample can be identified as mixture of phases (FeCl2,
FeCl3) with an average crystallites size of 47 nm. The magnetic measurement of E5
sample confirmed this result, as no magnetic properties were obtained (Table 1,
Figure 2). The XRD pattern of sample E6 sample shows Fe2O3 as a major product with
crystallites size around 100 nm. This result is also confirmed by VSM measurements as it
gives weak saturation magnetisation (Table 1, Figure 2).
The formation mechanism of Fe3O4 from ferrous ions in the presence of a base is
shown in equations (7) to (9) (Refait and Génin 1993; Olowe and Génin, 1991). In this
reaction, FeOOH is first produced by partial oxidation of ferrous hydroxide by O2,
equation (8). Then, Fe3O4 NPs are formed as a result of the dehydration reaction of
ferrous oxide and FeOOH, equation (9).
 Synthesis, crystal structure and magnetic properties 225

Fe 2 + + 2OH − → Fe(OH)2 (7)

3Fe(OH) 2 + 1/ 2O 2 → Fe(OH) 2 + 2FeOOH + H 2 O (8)

Fe(OH) 2 + 2FeOOH → Fe3O 4 + 2H 2 O (9)

Figure 1 XRD patterns of prepared samples (see online version for colours)

Note: ●: Fe2O3, ■: Fe3O4, ▲: impurities.

226 S. Rashdan et al.

Figure 2 VSM curves of prepared samples (see online version for colours)

The diffraction peaks observed for E2, E4a and E4b samples can be considered as a
mixture of Fe2O3 and Fe3O4. Some additional peaks are observed as well which can be
attributed to impurities such as chloride (remaining from incomplete chemical reaction).
The crystallites size of the Fe3O4 NPs obtained by mixing ferrous sulphate salt with urea
was about 70 nm which is about three times larger than that obtained by mixing ferric and
ferrous ions with urea, 18–26 nm (Table 1). Sample E2 gives strong saturation
magnetisation, 74.7 emu/g compared to 11.6 and 31 for E4a and E4b, respectively. The
coercivity (Hc) is the intensity of the applied magnetic field required to reduce the
magnetisation of that molecule to zero after the magnetisation has been driven to
 Synthesis, crystal structure and magnetic properties 227

saturation. Although samples E4a and E4b give low coercivity, 38.6 and 40.0 Oe,
compared to 110 Oe for E2, the coercivity value for E2 is still in acceptable range for
medical application according to the reported values in the literature (Kim et al., 2008;
Yan et al., 2008). Both methods gave mixture of two phases (Fe3O4 and Fe2O3) which can
be attributed to the reaction time and the temperature are not enough for the completion
of the transformation of a mixture of Fe2+ and Fe3+ ions or Fe2+ into Fe3O4 nanoparticles.
We conclude that relatively higher temperature (>50°C) and shorter time (< 3 h) are
required to obtained high purity Fe3O4 nanoparticles.

4 Conclusions

In this work, we have found that the formation of Fe3O4 nanoparticles can be
accomplished by two methods:
1 co-precipitation of a mixture of ferric and ferrous salt in urea as a base under
atmospheric air conditions
2 thermal oxidative reaction of ferrous salt under the same conditions as the first
method.
Both methods gave mixture of two phases (Fe3O4 and Fe2O3) which can be attributed to
the reaction time and the temperature are not enough for the completion of the
transformation of a mixture of Fe2+ and Fe3+ ions or Fe2+ into Fe3O4 nanoparticles. It is
also important to note that using magnetic measurements is a useful and easy physical
measurement to check the phase formation and purity of iron oxide materials.

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