Journal of Magnetism and Magnetic Materials 324 (2012) 4147–4150

Contents lists available at SciVerse ScienceDirect

Journal of Magnetism and Magnetic Materials

journal homepage: www.elsevier.com/locate/jmmm

Synthesis of Fe3O4 nanocrystals using hydrothermal approach

Shideh Ahmadi a,n, Chin-Hua Chia a, Sarani Zakaria a, Kasra Saeedfar b,d, Nilofar Asim c
a
School of Applied Physics, Faculty of Science and Technology, National University of Malaysia (UKM), 43600 Bangi, Selangor, Malaysia
b
School of Chemical Science and Food Technology, Faculty of Science and Technology, National University of Malaysia (UKM), 43600 Bangi, Selangor, Malaysia
c
Solar Energy Research Institute, National University of Malaysia (UKM), 43600 Bangi, Selangor, Malaysia
d
Departement of Chemistry, Faculty Science, K. N. Toosi University of Technology, 15875-4416 Tehran, Iran

a r t i c l e i n f o abstract

Article history: Magnetite (Fe3O4) nanocrystals were synthesized using a facile hydrothermal method. FeCl2, FeCl3 and
Received 16 November 2011 NaOH with a molar ratio of 1:2:8 were added into an autoclave and this was followed by heat treatment
Received in revised form at elevated temperature (100, 150 and 200 1C). The produced results show that the average crystallite
28 June 2012
and the physical size of the resulting Fe3O4 nanocrystals increased with the hydrothermal temperature.
Available online 27 July 2012
The Fe3O4 nanocrystals exhibited superparamagnetic behavior. The saturation magnetization and
Keywords: coercivity of the produced nanocrystals also increased with the hydrothermal temperature.
Hydrothermal & 2012 Elsevier B.V. All rights reserved.
Magnetite
Nanocrystals
Superparamagnetic

1. Introduction In this study, we have synthesized Fe3O4 nanocrystals using

Magnetic nanocrystals such as magnetite (Fe3O4), maghemite
(g-Fe2O3), and hematite (a-Fe2O3) have attracted a large number
of investigations in recent years due to their excellent magnetic
properties, chemical stability, non toxicity, and low magnetocrys-
talline anisotropy [1]. These nanomaterials have been widely used
in bio-medical applications such as drug delivery [2], biosensor
[3], clinical diagnosis and therapy [4–8].
Magnetic nanocrystals possess controllable size that ranges
from a few nanometers up to 10 nm, which places them at
dimensions that are smaller than or comparable to those of a cell
(10–100 mm), virus (20–450 nm), protein (5–50 nm) or gene
(2 nm wide and 10–100 nm long). Therefore, they can ‘get close’
to a biological entity of interest [9].
Fe3O4 nanocrystals possess an inverse spinel structure with
the Fe3 þ ions distributed randomly between octahedral and
tetrahedral sites, while the Fe2 þ ions solely occupy the octahedral
sites [10]. They are ferromagnetic materials, which have sponta-
neous magnetization. Saturation magnetization is an intrinsic
property, independent of particle size but dependent of tempera-
ture [11]. There are several methods which have been used to
prepare Fe3O4 nanocrystals, including gas phase [12], liquid phase
[13], two-phase such as microemulsion [14], sol–gel [15], chemi-
cal coprecipitation [16] and high pressure hydrothermal [17].
n
Corresponding author. Tel.: þ60 173479487.
E-mail address: shideh.ahmadi@gmail.com (Sh. Ahmadi).
the hydrothermal method. The effects of hydrothermal tempera-
ture on the degree of crystalline, average particle size and
magnetic properties have been investigated.
2. Materials and methods
Ferrous chloride tetrahydrate (FeCl2  4H2O), ferric chloride (FeCl3)
and sodium hydroxide (NaOH) were purchased from Aldrich. Distilled
water was deoxygenated by bubbling it with N2 gas for 15 min prior
to use. All the chemicals used were of reagent grade.
FeCl2  4H2O, FeCl3 at 1:2 M ratio and NaOH were added into an
autoclave which contained 35 ml deoxygenated distilled water. The
autoclave was sealed and nitrogen gas was purged into the autoclave
for at least 10 min to prevent the oxidation of Fe2 þ in the system in
order to maintain the stoichiometry ratio between Fe2þ and Fe3þ .
The autoclave was then heated to the desired temperatures (100, 150
and 200 1C) while stirring continuously throughout the reaction. After
30 min, the autoclave was left to cool to room temperature naturally.
The resulting black precipitate was separated by centrifugation
(4500 rpm for 15 min) and washed with methanol and distilled
water several times before being dried in an oven at 70 1C for 24 h.
X-ray diffraction (XRD) analyses of the resulting Fe3O4 nano-
crystals were carried out in a X-ray diffractometer (Siemens,
D5000) using Cu Ka radiation (l ¼1.5418 Å). Transmission electron
microscope (TEM, Philips CM12) was employed to examine the size
and dispersibility of the nanocrystals. The crystal morphology of
the resulting Fe3O4 nanocrystals was examined using a scanning
electron microscope (SEM, Leo-1450VP). The magnetization

0304-8853/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jmmm.2012.07.023
4148 Sh. Ahmadi et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 4147–4150
measurements were carried out using a vibrating sample magnet-
ometer (VSM, Lakeshore 736) with a maximum magnetic field of
10 kOe at room temperature.
3. Results and discussion
3.1. XRD patterns
The resulting black precipitate, which can be attracted by a
permanent magnet, proved the formation of Fe3O4 crystals. It is
Fig. 1. XRD patterns of the Fe3O4 nanocrystals produced at 100 1C, 150 1C and
200 1C.
Fig. 2. TEM and SEM images of Fe3O4 nanocrystals produced at (a) 100 1C and (b) 200 1C.
also evident from the XRD results shown in Fig. 1, that all the
samples possess inverse spinel structure with face-centered cubic
phase according to the standard JCPDS File No. 85-1436. It can be
clearly seen from Fig. 1 that the diffraction peaks are greater in
intensity and sharper for the Fe3O4 nanocrystals produced at
higher temperature. This has revealed the improvement of the
crystallinity of the resulting Fe3O4 nanocrystals produced at
greater hydrothermal temperature. The estimated average crys-
tallite size is 13.4, 20.8 and 22.8 nm for the Fe3O4 nanocrystals
produced at 100, 150 and 200 1C, respectively. This is consistent
with our previous results [16], reporting that higher temperature
is favorable for the formation of bigger Fe3O4 nanoparticles.
3.2. TEM and SEM micrographs
The SEM and TEM micrographs of the resulting Fe3O4 nano-
crystals produced at 100 and 200 1C are shown in Fig. 2a and b,
respectively. The SEM micrographs show that both samples
consist of finite crystals, which tend to form aggregates due to
high surface energy of the nanocrystals. The morphology of the
crystals could not be easily defined from the micrographs. TEM
micrographs, shown in Fig. 2a and b, reveal the spherical shape of
the crystals. It is also noted that the produced Fe3O4 nanocrystals
possess well-defined and homogenous shape.
The average physical size of the nanocrystals was estimated from
at least 50 crystals in the electron micrograph of each sample. The
result shows that the average physical size of the Fe3O4 crystals
produced at 100, 150 and 200 1C is 19.7, 24.0 and 27.0 nm, respec-
tively. These readings fit well with the average crystallite size
calculated from the XRD patterns, suggesting that the resulting
Fe3O4 nanocrystals possess single crystal structure (Table 1).
3.3. VSM
Fig. 3 shows the M–H curves of the resulting Fe3O4 nanocrys-
tals produced at 100, 150 and 200 1C. The very thin hysteresis
 Sh. Ahmadi et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 4147–4150 4149

Table 1 4. Conclusion
Consequence of temperature on the average crystallites size, average particles
size, and magnetic properties of the Fe3O4 crystals.
Highly crystallite Fe3O4 nanocrystals have been successfully
Temperature Average Average dm (nm) Ms (emu/g) Hc (Oe) synthesized using a facile hydrothermal method in this study. The
(oC) crystallite particles average crystallite and the physical size of the produced nano-
size (nm) size (nm) crystals were found to have increased with the increase of the
hydrothermal temperature from 100 to 200 1C. Both average
100 13.4 19.7 3.46 27.2 58.4
150 20.8 24.0 3.79 30.7 60.6
particle and crystallite size of the Fe3O4 nanocrystals are well-
200 22.8 27.0 4.43 33.9 85.9 fitted, revealing the single crystal structure of the nanocrystals.
The produced Fe3O4 nanocrystals possess superparamagnetic
behavior while the Ms and Hc increase with the increase of the
hydrothermal temperature.

Acknowledgments

The authors acknowledge the financial support given by the

Ministry of Science, Technology and Innovation of Malaysia (MOSTI)
for e-Science Fund (0301-02-SF0030) and Universiti Kebangsaan
Malaysia for the Research University Operation Grant (UKM-OUP-
NBT-28-124-2010), and ExxonMobil University Research Grant
(STGL-012-2008).

References

Fig. 3. M–H curves of the Fe3O4 nanocrystals produced at different hydrothermal
temperatures.
reveals the superparamagnetic behavior of the produced
Fe3O4 nanocrystals. The saturation magnetization (Ms) of the
Fe3O4 nanocrystals increased from 27.4 to 33.9 emu/g when the
hydrothermal temperature increases from 100 to 200 1C. The
coercivity (Hc) of the Fe3O4 nanocrystals is also increased from
58.4 to 85.9 Oe as the temperature increases from 100 to 200 1C.
The increment of both the Ms and Hc of the Fe3O4 nanocrystals
can be attributed to the decrease of the surface-to-volume ratio
of the nanocrystals and the spin canting effect (Table 1)
[18,19].
The magnetic size (dm) of the Fe3O4 nanocrystals was inves-
tigated from the hysteresis loops, which calculated using the
equation below:
" #1=3
18kB T ðdM=dHÞH-0
dm ¼
p rM2 S
where dm is the magnetic diameter, kB is the Boltzmann’s
constant, T is the temperature (100, 150, and 200 1C), dM/dH is
the slope of curve near zero field, and r which is the density of
Fe3O4 (5.1 g/cm3). The dm of nanocrystals was enhanced, when
the hydrothermal temperature increased (Table 1). One layer on
the surface is due to the magnetically ‘dead’, which comes from
the disordered surface spins on the iron core [20]. The nanocrys-
tals, which have no coating layer on the particle surface, has
magnetic size that is smaller than their physical size [21]. The
obtained dm is less than the average crystallite size due to the
existence of surface anisotropy [22].
[1] L. Fu, V.P. Dravid, K. Klug, X. Liu, C.A. Mirkin, Synthesis and patterning
of magnetic nanostructures, European Cells and Materials 3 (2002)
156–157.
[2] V.P. Torchilin, Drug targeting, European Journal of Pharmaceutical Science 11
(2000) S81–S91.
[3] G.K. Kouassi, J. Irudayaraj, Magnetic and gold-coated magnetic nanoparticles
as a dna sensor, Analytical Chemistry 78 (2006) 3234–3241.
[4] C.F.D. Chan, D.B. Kirpotin, A.B.J. Paul, Synthesis and evaluation of colloidal
magnetic iron oxides for the site-specific radiofrequency-induced hyperther-
mia of cancer, Journal of Magnetism and Magnetic Materials 122 (1993)
374–378.
[5] A.S. Lübbe, C. Bergemann, H. Riess, F. Schriever, P. Reichardt, K. Possinger,
et al., Clinical experiences with magnetic drug targeting: a phase I study with
4’-epidoxorubicin in 14 patients with advanced solid tumors, Cancer
Research 56 (1996) 4686–4693.
[6] S. Mornet, S. Vasseur, F. Grasset, E. Duguet, Magnetic nanoparticle design for
medical diagnosis and therapy, Journal of Materials Chemistry 14 (2004)
2161–2175.
[7] C.H. Reynolds, N. Annan, K. Beshah, J.H. Huber, S.H. Shaber, R.E. Lenkinski,
et al., Gadolinium-loaded nanoparticles: andnbsp; new contrast agents for
magnetic resonance imaging, Journal of the American Chemical Society 122
(2000) 8940–8945.
[8] A. Dyal, K. Loos, M. Noto, S.W. Chang, C. Spagnoli, K.V.P.M. Shafi, et al.,
Activity of Candida rugosa lipase immobilized on g-Fe2O3 magnetic nano-
particles, Journal of the American Chemical Society 125 (2003)
1684–1685.
[9] Q.A. Pankhurst, J. Connolly, S.K. Jones, J. Dobson, Applications of magnetic
nanoparticles in biomedicine, Journal of Physics D: Applied Physics 36 (2003)
R167–R181.
[10] S. Klotz, G. Steinle-Neumann, Th. Strässle, J. Philippe, Th. Hansen,
M.J. Wenzel, Magnetism and the Verwey transition in Fe3O4 under pressure,
Physical Review B 77 (2008) 012411–012414.
[11] R.M. Cornell, U. Schwertmann, The Iron Oxides: Structure, Properties, Reac-
ð1Þ tions, Occurrences and Uses, Weinheim ed: Wiley-VCH, 2003.
[12] H.O. Pierson, Handbook of Chemical Vapor Deposition: Principles, Technol-
ogy, and Application, 1999.
[13] P. Majewski, B. Thierry, Functionalized magnetite nanoparticles-synthesis,
properties, and bio-applications, Critical Reviews in Solid State and Materials
Sciences 32 (2007) 203–215.
[14] J. Zhi, Y. Wang, Y. Lu, J. Ma, G. Luo, Reactive and Functional Polymers 66
(2006) 1552–1558.
[15] U.T. Lam, R. Mammucari, K. Suzuki, N.R. Foster, Processing of iron oxide
nanoparticles by supercritical fluids, Industrial and Engineering Chemistry
Research 47 (2008) 599–614.
[16] C.H. Chia, S. Zakaria, R. Farahiyan, LT. K., K.L. Nguyen, M.H. Abdullah, et al.,
Size-controlled synthesis and characterization of Fe3O4 nanoparticles
by chemical coprecipitation method, Sains Malaysiana 37 (2008)
389–394.
[17] A. Tavakoli, M. Sohrabi, A. Kargari, A review of methods for synthesis of
nanostructured metals with emphasis on iron compounds, Chemical Papers
61 (2007) 151–170.
4150 Sh. Ahmadi et al. / Journal of Magnetism and Magnetic Materials 324 (2012) 4147–4150

[18] S. Linderoth, P.V. Hendriksen, F. Bodker, S. Wells, K. Davies, S.W. Charles,
et al., On spin-canting in maghemite particles, Journal of Applied Physics 75
(1994) 6583–6585.
[19] A.G. Roca, M.P. Morales, K. O’Grady, C.J. Serna, Structural and magnetic
properties of uniform magnetite nanoparticles prepared by high temperature
decomposition of organic precursors, Nanotechnology 17 (2006) 2783–2788.
[20] F. Bødker, S. Mørup, S. Linderoth, Surface effects in metallic iron nanoparti-
cles, Physical Review Letters 72 (1994) 282–285.
[21] J. Popplewell, L. Sakhnini, The dependence of the physical and magnetic
properties of magnetic fluids on particle size, Journal of Magnetism and
Magnetic Materials 149 (1995) 72–78.
[22] M. Ghominezhad, A. Sebt, M., Akhavan Charaterization of magnetic nano-
crystalline systems. In: M. Akhavan (Sharif University of Technology), I), J.
Jensen (Niels Bohr Institute, Denmark), K. Kitazawa (University of Tokyo,
Japan) (Eds.), Magnetic and Superconducting Materials (Proceedings of the
First Regional Conference), Tehran, Iran, 1999, p. 1099–106.