Available online at www.sciencedirect.

com

APCBEE Procedia 3 (2012) 140 146

ICCCP 2012: 5-6 May 2012, Kuala Lumpur, Malaysia

New Finding on Magnetite Particle Size Reduction by Changing

Temperature and Alkaline Media Concentration
Maryam Tajabadi a,*, Mohammad E. Khosroshahi a,b
a

Amirkabir University of Technology, Faculty of Biomedical Eng., Biomaterial Group, Laser and Nanobiophotonics Lab.,Tehran, Iran
b
Amirkabir University of Technology, Laser, Optic Reaserch Center, Tehran, Iran

Abstract
By controlling of two significant parameters mainly alkaline media concentration and temperature, magnetite
nanoparticles were produced via coprecipitation method. Effect of named parameters on the particle size, size distribution
and magnetic behaviour of particles were analyzed by means of X-ray diffraction spectroscopy (XRD), transmission
electron microscopy (TEM), and vibrating sample magnetometry (VSM). To the best of our knowledge, there is no report
on evaluation of sample preparation at room temperature and then post stirring at higher temperature on particle size and
its magnetic properties. Results show the particles synthesized at elevated temperature (70C) and lower alkaline
concentration (0.9 M) have highest saturation magnetization , about 68 emu/gr at 70C, compared with 63 emu/gr at 25C
and smallest particle size.

2012
2012Published
PublishedbybyElsevier
ElsevierB.V.
B.V.
Selection
and/or
review
under
responsibility
of Asia-Pacific

Selection
and/or
peerpeer
review
under
responsibility
of Asia-Pacifi
c Chemical,
Chemical,&Biological
& Environmental
Engineering
Society
Biological
Environmental
Engineering Society
Open access
under CC BY-NC-ND license.
Keywords: Magnetite, Alkaline media concentration, Temperature, Particle size reduction

1. Introduction
High variety of iron chemistry arisen from the occurrence of two stable oxidation states begets the key role
for iron oxides in the field of science[1-2]. As magnetite nanoparticles have high magnetization saturation,
can easily load with biomolecules and are biocompatible, this kind of material has extraordinary position
among iron oxides[3]. Magnetite has inverse spinel structure and its unite cell structure represents with

* Corresponding author. Tel.: +98(21)77370334; fax: +98(21)76263876.

E-mail address: m.tajabadi@aut.ac.ir.

2212-6708 2012 Published by Elsevier B.V. Selection and/or peer review under responsibility of Asia-Pacific Chemical,
Biological & Environmental Engineering Society Open access under CC BY-NC-ND license.
doi:10.1016/j.apcbee.2012.06.060

Maryam Tajabadi and Mohammad E. Khosroshahi / APCBEE Procedia 3 (2012) 140 146

(Fe3+)A(Fe3+Fe2+)BO4 where A and B respectively stand for tetrahedral and octahedral sites coordinated with
oxygen ions at face centred cubic array[2, 4-5].
Magnetite nanoparticles find a conceivable application in scientific fields such as magnetic memories,
optics, production of pigment, electronics, activators, ferrofluids, and biomedical [3, 6]. The most significant
aspect of synthesising such materials for biomedical applications is to have high saturation magnetization (Ms)
as well as small particle size [3].
Various synthetic methods have been used to produce these kinds of nanoparticles including
coprecipitation, microemulsion, laser pyrolysis, and hydrothermal synthesis [5-8]. In an alkaline medium such
as ammonium or NaOH aqueous solution, coprecipitation of Fe2+ and Fe3+ ions which is one of the most
important chemical synthesis methods is done. As this method is one of the most efficient ones and isnt used
any surfactant, many researcher attempt to optimize this magnetite production strategy [3, 9].
Some problems regarding coprecipitation method are its uncontrollability of particle size and size
distribution and sometimes simultaneous presence of different iron oxide phases such as magnetite and
maghemite [10-12]. There are some articles on investigation of parameters affecting the production of
magnetic nanoparticles including pH, alkaline species [12-13], reaction temperature [3, 10, 14], kind of iron
salts [15] and concentration of ingredients. Based on this background, we studied the effect of alkaline
medium concentration and temperature on magnetite particle size and magnetic properties. As far as the
authors are concerned no report in the literature was recorded regarding the effect of extra stirring time (30
minute in our case) at elevated temperature on the synthesis method.
2. Experimental
2.1. Synthesis of Magnetite Nanoparticles
Solutions of 0.012 M ferrous chloride hexahydrate (FeCl3.6H2O, 99%, Merck) and 0.006 M ferric sulphate
heptahydrate (FeSO4.7H2O, 99%, Merck) used as iron source, were prepared by dissolution of proper amount
of material in double distilled water. After the ferric and ferrous solution were mixed together, the mixture
was then deoxygenated by bubbling N2 gas and sonicated for 30 minutes to prevent from oxygenation.
Ammonia solutions with 0.9-2.1 M concentration was used as alkaline source and vigorously stirred under N2
bubbling at room temperature. The mixture of ferric and ferrous solution was dropwisely added to the stirring
ammonia solution, the colour of reaction mixture immediately turned to black. In this experiment, group 1 and
2 are defined as the groups containing the different alkaline concentration at two different temperatures ie.
25 C and 70C respectively. The reaction temperature of group 1 was kept constant at 25C for 1 hour then
all the mixtures were purified. After an hour, the group 2 was transferred to 70C water bath where the
mixture was strongly stirred for 30 minutes. The next step was to purify the black mixture of both groups
using a magnetic separation five times and then it was sedimented by centrifugation. The resultant material
was finally dried by freeze dryer for 24 hours.
2.2. Characterization
Crystalline phase of magnetite nanoparticles was studied using x ray diffraction using Cu K radiation
(XRD, = 1.5406 , FK60-40 X-ray diffractometer). Saturation magnetization of samples was measured by
means of vibrating sample magnetometer (VSM-PAR 155) at 300 K under magnetic field up to 8 kOe.
Particle size and morphology of these nanoparticles were determined by transmission electron microscopy
(TEM, Philips CM-200-FEG microscope, 120 KV).

141

142

Maryam Tajabadi and Mohammad E. Khosroshahi / APCBEE Procedia 3 (2012) 140 146

3. Results and Discussion

3.1. XRD Analysis
XRD Results obviously confirmed the formation of magnetite phase of iron oxide with inverse spinel
structure (JCPDS file no.19-0629). Thermodynamic modelling represents in oxygen free environment, pH
7.5-14 and Fe2+:Fe3+ ratio equal to 1:2, precipitation of magnetite is completed as follow:
(1)
Fe2+ + Fe3+ + 8OH- Fe3O4 (black precipitation) + 4H2O
If this reaction takes place in oxygen containing media, the reaction condition will be ready to oxidation of
Fe3O4. Oxidization of Fe2+ to Fe3+ ions (Fe2++O2Fe3+) declines the effective ratio to less than 0.5 and if Fe3+
ions is kept on elevated pH, goethite can be produced[16-17]:
(2)
Fe3O4 + 0.25 O2 + 4.5 H2O 3 Fe(OH)3
As usage of strong alkaline medium (such as NaOH, KOH, and LiOH) as a hydrolyzing agent can cause
formation of nonmagnetic iron components [3, 9] in order to avoid this matter, NH4OH was used as alkaline
media in present study. Also, since in this study coprecipitation reaction was performed under N2 atmosphere,
the single magnetite phase without any interference of other iron oxide phase was obtained. The particle size
of nanoparticles could be determined using Debay-Sherrers equation (eq. 3) which measures the size of
particles according to broadening of the most intense peak (311) in XRD graph (Fig. 1) of prepared materials
[18].
K
(3)
cos
where D is mean diameter of particles, is full width at half maximum (FWHM), is wavelength of incident
X-ray and constant K is equal to 0.9. Based on this equation, particle size of samples synthesized at 25C and
70C were determined 10.10nm and 9.98 nm, respectively.
D=

Fig. 1. XRD pattern of synthesized magnetite nanoparticles under A) 25C B) 70C

Maryam Tajabadi and Mohammad E. Khosroshahi / APCBEE Procedia 3 (2012) 140 146

3.2. TEM Analysis

Morphology and mean particle size of prepared nanoparticles at 25C and 70C were determined by TEM
(Fig. 2). Particles are quasi sphere and have sizes ranging from 9.5 to 16 nm respect to different synthesis
conditions. Polydispersity and surface aggregation of samples prepared at room temperature could be figured
out from Fig. 2, this regards to small size, increased surface-to-volume ratio and thus augmented magnetic
dipole-dipole interactions [19] (at synthesising conditions of prolonged time and elevated temperature, surface
aggregation and polydispersity were reduced).

Fig.. 2. TEM micrograph of samples prepared at A) 25C B) 70C

As some separate articles mentioned, in order to produce tiny nuclei, the initial temperature of this study
set to 25C and after 1 hour group 1 was purified which resulted in particles with larger size (about 11 nm).
Depending on reaction time, the diffusion and growth process of samples could be completed. At elevated
temperature and prolonged time, the reaction condition set to be completed and samples with less crystal
defects and smaller particle size (about 9.5 nm) were produced [20-21]. With increase of ingredient (alkaline
media) concentration more material is available on the growth phase and thus particles with higher diameter
could be obtained (Fig. 3).

Particle diameter (nm)

20

15

10

5
25 C
70 C

0
0.012-0.9

0.012-1.5

0.012-2.1

Sample

Fig. 3. Variation of particle size with alkaline media concentration and temperature measured by TEM
3.3. Magnetic Measurements
Magnetic properties of nanoparticles were determined by VSM at room temperature, results show that
these materials have strong magnetic properties of 63.1 emu/gr and 67.8 emu/gr for samples synthesized at
25C and 70C, respectively.

143

Maryam Tajabadi and Mohammad E. Khosroshahi / APCBEE Procedia 3 (2012) 140 146

80
60

Ms (emu/gr)

40
20
-10000

-5000

0
-20 0

5000

10000

-40
-60

25 C
70 C

-80
H (Oe)

Fig.. 4. VSM result of samples prepared at A) 25C B) 70C

Bulk material of magnetite has higher saturation magnetization , the small particle size and breaking of a
large number of exchange bonds for surface atoms (pinning effect) cause this reduction [6, 22]. As figure 4
shows, complete reversibility of magnetization process confirms the superparamagnetic behaviour of prepared
nanoparticles. Because of higher amount of alkali media, with increase of alkaline media concentration, the
probability of non-magnetite layer production (magnetically dead layer) increased which decrease the amount
of saturation magnetization (see the Fig. 5.) revealing that the positive effect of alkaline media on saturation
magnetization has a limit.

70
60

Ms (emu/g)

144

50
40

25 C

30

70 C

20
10

70 C

0
0.012-0.9

25 C
0.012-1.5

0.012-2.1

Sample

Fig. 5. Change of Ms as change of alkaline media concentration and temperature

Using Langevins equation and magnetic experimental data, the average magnetic particle diameter were
calculated[2]:
18K B T dM
(4)
a M3 =
(
) H 0
0 M b M s dH
where aM is the magnetic particle diameter, kB is Boltzmanns constant, 0 is the vacuum magnetic
permeability, and Mb is magnetization of bulk magnetite. Figures 5 and 6 represent increase of magnetic
properties and slight decrease of particle size with respect to elevated temperature. Owing to prolonged
reaction time and elevated temperature, synthesis reaction could be completed [18] thus particle size was
reduced and because of loss of surface defects, magnetic saturation was increased.

Maryam Tajabadi and Mohammad E. Khosroshahi / APCBEE Procedia 3 (2012) 140 146

Particle diameter (nm)

16
12
8
4
25 C
70 C

0
0.012-0.9

0.012-1.5

Sample

0.012-2.1

Fig. 6. Variation of particle size with alkaline media concentration and temperature measured by VSM

4. Conclusion
This work, present the effect of changing of alkaline media concentration and temperature on
copercipitation method by which the particle size could be optimized and higher magnetic properties could be
obtained. The results indicate that concentration and temperature have significant effects on magnetic
properties, particle size and size distribution. Increasing the alkaline concentration increased the particle size
from about 9nm to 16nm and elevated temperature and prolonged synthesis time resulted in decline of surface
defects and thus reduction of particle size. The saturation magnetization increased from about 63 emu/gr at
25C to 68 emu/gr at 70C (in the condition of lowest alkaline concentration). In this study the smallest
particle size with highest saturation magnetization was obtained at alkaline media concentration of 0.9 M and
prolonged synthesis time at 70C.
References
[1] J.P. Jolivet, C. Chaneac, E. Tronc, Iron oxide chemistry. From molecular clusters to extended solid networks. chem. commun.,
2004: p. 481-487.
[2] Racuciu, M., Synthesis protocol influence on aqueous magnetic fluid properties. Curr. Appl. Phys. , 2009. 9: p. 1062-1066.
[3] G. Gnanaprakash, S. Mahadevan, T. Jayakumar, P. Kalyanasundaram, J. Philip, B. Raj, Effect of initial pH and temperature of
iron salt solutions on formation of magnetite nanoparticles. Mater. Chem. Phys., 2007. 103: p. 168-175.
[4] E. Tronc, J.P. Jolivet, R. Massart Defect spinel structure in iron oxide colloids. Mater. Res. Bull., 1982. 17: p. 1365-1369.
[5] B. J. Tabares, A. A. Zuleta Gil, F. J. Isaza, Effects of the synthetic method on the particle size and purity of magnetite. Rev. Fac.
Ing. Univ. Antioquia 2009. 50: p. 9-16.
[6] Y. W. Guang, Z. T. Lai, Q. X. Jing, Z. J. Guo, Y. Li, Effects of synthetical conditions on octahedral magnetite nanoparticles.
Mater. Sci. Eng., B 2007. 136: p. 101-105.
[7] R. Hong, J. Li, J. Wang, H. Li, Comparison of schemes for preparing magnetic Fe3O4 nanoparticles. China Particuology 2007.
5: p. 186-191.
[8] T. Iwasaki, K. Kosaka, S. Watano, T. Yanagida, T. Kawai, Novel environmentally friendly synthesis of superparamagnetic
magnetite nanoparticles using mechanochemical effect. Mater. Res. Bull. , 2010. 45 p. 481-485.
[9] H. Iida, K. Takayanagi, T. Nakanishi, T. Osaka, Synthesis of Fe3O4 nanoparticles with various sizes and magnetic properties by
controlled hydrolysis. J. Colloid Interface Sci. , 2007. 314: p. 274-280.
[10] K. Tao, H. Dou, K. Sun, Interfacial coprecipitation to prepare magnetite nanoparticles: Concentration and temperature
dependence. Colloids Surf., A, 2008. 320: p. 115-122.

145

146

Maryam Tajabadi and Mohammad E. Khosroshahi / APCBEE Procedia 3 (2012) 140 146

[11] M.E. Khosroshahi, L. Ghazanfari, M. Tahriri, Characterisation of binary (Fe3O4/SiO2) biocompatible nanocomposites as
magnetic fluid. J. Exp. Nanosci., 2011. 6: p. 580-595.
[12] H. Mohammad-Beigi, S.Yaghmaei, R.Roostaazad, H.Bardania, A.Arpanaei, Effect of pH, citrate treatment and silane-coupling
agent concentration on the magnetic, structural and surface properties of functionalized silica-coated iron oxide nanocomposite particles.
Physica E 2011. 44: p. 618-627.
[13] M. A. Verges, R. Costo, A. G. Roca, J. F. Marco, G. F. Goya, C. J. Serna, M. P. Morales, Uniform and water stable magnetite
nanoparticles with diameters around the monodomainmultidomain limit. J. Phys. D: Appl. Phys. , 2008. 41: p. 1-10.
[14] S. Mahadevan, G. Gnanaprakash, J. Philip, B.P.C. Rao, T. Jayakumar, X-ray diffraction-based characterization of magnetite
nanoparticles in presence of goethite and correlation with magnetic properties. Physica E 2007. 39: p. 20-25.
[15] N. Mizutani, T. Iwasaki, S. Watano, T. Yanagida, T. Kawai Size control of magnetite nanoparticles in hydrothermal synthesis by
coexistence of lactate and sulfate ions. Curr. Appl. Phys., 2010. 10: p. 801-806.
[16] D.K. Kim, Y. Zhang, W. Voit, K.V. Rao, M. Muhammed, Synthesis and characterization of surfactant-coated
superparamagnetic monodispersed iron oxide nanoparticles. J. Magn. Magn. Mater. , 2001. 225: p. 30-36.
[17] S. Beyaz, H. Kockar, T. Tanrisever, Simple synthesis of superparamagnetic magnetite nanoparticles and ion effect on magnetic
fluids. J. Optoelectronics. Adv. Mat. - Symposia 2009. 1(3): p. 447 - 450.
[18] A.P.A.Faiyas, E.M.Vinod, J.Joseph, R.Ganesan, R.K.Pandey Dependence of pH and surfactant effect in the synthesis of
magnetite (Fe3O4) nanoparticles and its properties. J. Magn. Magn. Mater., 2010. 322: p. 400-404.
[19] D.L. Zhao, X.W. Zeng, Q.S. Xi, J.T. Tang, Preparation and coercivity and saturation magnetization dependence of inductive
heating property of Fe3O4 nanoparticles in an alternating current magnetic field for localized hyperthermia. J. Alloys Compd. , 2009.
469: p. 215-218.
[20] T. Hosono, H. Takahashi, A. Fujita, R. Justin Joseyphus, K. Tohji B. Jeyadevan, Synthesis of magnetite nanoparticles for AC
magnetic heating. J. Magn. Magn. Mater., 2009. 321: p. 3019-3023.
[21] I. Nyirokosa, D. Csakberenyi Nagy, M. Posfai, Size and shape control of precipitated magnetite nanoparticles. Eur. J. Mineral.,
2009. 21: p. 293302.
[22] M. E. Khosroshahi, L. Ghazanfari, Preparation and characterization of silica-coated iron-oxide bionanoparticles under N2 gas.
Physica E 2010. 42: p. 1824-1829.