Journal of Magnetism and Magnetic Materials 371 (2014) 4348

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Journal of Magnetism and Magnetic Materials

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

Synthesis of cobalt ferrite (CoFe2O4) nanoparticles using combustion,

coprecipitation, and precipitation methods: A comparison study
of size, structural, and magnetic properties
Mahboubeh Houshiar a,n, Fatemeh Zebhi b, Zahra Jafari Razi a, Ali Alidoust a, Zohreh Askari a
a
b

Department of Physics, Shahid Beheshti University, Tehran, Iran

Department of Physics, Semnan University, Semnan, Iran

art ic l e i nf o

a b s t r a c t

Article history:
Received 21 October 2013
Received in revised form
19 May 2014
Available online 21 July 2014

In this work the cobalt ferrite (CoFe2O4) nanoparticles are synthesized using three different methods;
combustion, coprecipitation, and precipitation. Size, structural, and magnetic properties were determined and compared using X-ray diffraction (XRD), scanning electron microscopy (SEM), and vibrating
sample magnetometer (VSM). XRD data analysis showed an average size of 69.5 nm for combustion,
49.5 nm for coprecipitation, and 34.7 nm for precipitation samples which concorded with SEM images.
XRD data further revealed a reverse cubic spinel structure with the space group Fd-3m in all three
samples. VSM data of samples showed a saturation point in the magnetic eld of less than 15 kOe.
Magnetization saturation (Ms) was 56.7 emu/g for combustion synthestized samples, 55.8 emu/g for
coprecipitation samples, and 47.2 emu/g for precipitation samples. Coercivity (Hc) was 2002 Oe for
combustion synthestized samples, 850 Oe for coprecipitation samples, and 233 Oe for precipitation
samples. These results show that various methods of nanoparticle synthesis can lead to different particle
sizes and magnetic properties. Hc and Ms are greatest in the combustion method and least in
precipitation method.
& 2014 Elsevier B.V. All rights reserved.

Keywords:
Cobalt ferrite
Nanoparticles
Combustion
Coprecipitation
Precipitation

1. Introduction
Investigating the effect of decreased size on magnetic properties of nanoparticles has recently gained a great deal of attention.
In this regard, it is usually not possible to maintain magnetic
properties upon decreasing particle size within nanoscale.
The vast application of nano ferrites in; permanent magnets,
ferrouids, storage devices, targeted drug delivery and other uses,
has attracted much attention in their way of synthesizing these
nano materials. Cobalt ferrite (CoFe2O4) is a well-known hard
magnetic material with high coercivity (Hc) and moderate magnetization (Ms). These properties, along with their great physical and
chemical stability, make CoFe2O4 nanoparticles suitable for magnetic recording applications such as audio and videotape, highdensity digital recording disks, etc [1].
The ferrite spinel structure is based on a closed-packed oxygen
lattice, in which tetrahedral (called A sites) and octahedral (called
B sites) interstices are occupied by the cations. Spinels with only

n
Correspondence to:Department of Physics, Shahid Beheshti University, Tehran
1983969411, Iran.Tel.: +982129902769; fax: +982122431775
E-mail address: m-houshiar@sbu.ac.ir (M. Houshiar).

http://dx.doi.org/10.1016/j.jmmm.2014.06.059
0304-8853/& 2014 Elsevier B.V. All rights reserved.

divalent ions in tetrahedral sites are called normal, while compounds with the divalent ions in the octahedral sites are called
inverse. In the inverse spinel structure, all the Co2 ions occupy
the octahedral sites of lattice structure, half of the Fe3 ions also
occupy the same sites and the rest of the Fe3 ions stay in
tetrahedral sites [2].
Large-scale applications of ferrites with small particles and
tailoring of specic properties have prompted the development of
widely used chemical methods, including combustion, coprecipitation, sol-gel, mechanical alloying and precipitation for the
fabrication of stoichiometric and chemically pure spinel ferrite
nanoparticles.
Combustion method is a simple and quick way of synthesizing
nanoparticles which leads to high quality products. Varying the
rate of fuel to nitrates can highly effect the size, magnetization and
magnetic coercivity in this method [36].
Coprecipitation route is a cheap and simple method, in which
the control of size and size distribution is obtained by controlling
the relative rates of nucleation and growth during the synthesis
process. To protect the oxidation and also to stop their agglomeration, the particles are usually coated with some surfactant like
oleic acid, etc. and then dispersed in some medium like ethanol,
methanol or ammonia.

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M. Houshiar et al. / Journal of Magnetism and Magnetic Materials 371 (2014) 4348

In this work the size is controlled by quick addition of the

precipitating agent (sodium hydroxide) with the salt solution and
performing vigorous stirring during the reaction [35].
The precipitation method (stober synthesis), same as coprecipitation is simple and does not need any mechanical apparatus.
This method is usually used to synthesize coreshell nanoparticles
and its only difference with coprecipitation method is in the
length of time which is needed to put shell and nally dialyzing
the particles [7,8].
Among nanomaterials, magnetic nanoparticles have received
signicant attentions in different elds of engineering and biomedicine. This is due to the fact that their magnetic behavior provide
a wide variety of applications such as magnetic sensors, magnetic
resonance imaging and magnetic drug delivery [9]. In general,
magnetic nanoparticles includes the class of metallic, bimetallic
and superparamagnetic iron oxide nanoparticles.
The synthesis of magnetic nanoparticles has been intensively
studied in the recent years and the principal role of the preparation conditions on the morphological and structural features of
these magnetic ferrites is also discussed. In this study, magnetic
nanoparticles CoFe2O4 have been prepared by three different
methods; combustion, coprecipitation, and precipitation and their
sizes have been compared. As these nanoparticles show magnetic
behaviors, their magnetizations have also been measured and
compared. The intrinsic magnetic properties of these particles
are mainly affected by their shape, size, surface defects, surface
ligands and temperature to name few [10]. Hence it is imperative
to mention that the design of magnetic nanoparticles for different
applications requires careful evaluation of size modication, on its
magnetic properties. Although it is not possible to consider all
these effects in details for this article, in the next section we have
tried to outline the striking effects of the size factor on the
magnetic properties of these nano particles. Furthermore, we have
explained the basic of magnetism such as ferromagnetism (soft
and hard magnets), and superparamagnetism for their applications in different elds.

2. Soft and hard magnets

Magnetic materials encompass a variety of materials which are
used in a diverse range of applications. They can be classied in
terms of their magnetic behavior. Most common types of magnetic
behaviors are diamagnetism and paramagnetism which account
for the magnetic properties of elements at room temperature.
Consequently, most elements in the periodic table are usually
referred as non-magnetic, whereas, those which are cited as
magnetic are classied as ferromagnetic [10]. Most of magnetic
materials of industrial interests are ferromagenetic materials.
We are aware that a spinning electric charged particle creates a
magnetic dipole, called magneton which are associated in groups
in a ferromagnetic material [10]. Furthermore, the bulk of ferromagnetic material consists of a number of small regions of
magnetons which are called domains. The boundaries between
domains are called domain walls. These domain walls are not thin
surfaces but should be visualized as zones of transition of nite
thickness in which the magnetization gradually changes the
direction from one side to another [10].
Thus, a magnetic domain in a ferromagnetic material refers to the
volume of the material in which all magnetons are aligned in the
same direction by the exchange forces. This concept of domains
distinguishes ferromagnetism from paramagnetism. The ferromagnetic materials in a demagnetized state does not show any magnetization as the total magnetization is cancelled because of the
random orientation of the magnetizations in magnetic domains.
However, on the application of an external magnetic eld, the

magnetic domain walls are washed away and magnetic moments

become aligned to the direction of the magnetic eld and saturate
the magnetization. This magnetization is called saturation magnetization (Ms). On removal of the applied magnetic eld, instead of
retracing its original path, ferromagnets retain some memory of the
applied eld called as remanence. To reduce the magnetization of
that material to zero, a coercive force must be applied to a
ferromagnetic material so as to close the loop. Thus coercivity
measures the resistance of a ferromagnetic material to become
demagnetized. This behavior of the ferromagnetic material is known
as the hysteresis and the path which it follows is known as the
hysteresis loop. The hysteresis depicts the behavior of ferromagnets
under the inuence of the magnetic eld and differentiates them
from paramagnets.
Due to its varied dependence on the magnetic eld the
ferromagnetic materials can be categorized into soft and hard
magnetic materials. Soft magnetic materials are those which can
be demagnetized at low magnetic elds and hence the coercivity
(Hc) is low. On the other hand, soft magnetic materials can be
easily magnetized and hence the permeability is high. Consequently, for a ferromagnetic material to be soft, their magnetocrystalline anisotropy must be low which can be responsible for
the easy migration of the magnetic domains [10]. Anisotropy can
be dened as a difference in a materials physical or mechanical
properties such as magnetic, absorbance, refractive index, conductivity, tensile strength, etc. when measured along different
axes. However, when the domain wall is difcult to migrate a
higher magnetic eld is required for the alignment of the magnetic
moments of the ferromagnetic material [10]. These types of
ferromagnetic materials are referred to as hard magnets [10]. In
other words, these types of ferromagnetic materials are difcult to
magnetize, but once magnetized, they are difcult to demagnetize.
Hence, it is an obvious fact that in contrast to the soft magnetic
materials the hard magnetic materials have high magnetocrystalline anisotropy and coercivity (Hc).
Normally, hard ferromagnetic materials have memory because
they remain magnetized after the external magnetic eld has been
removed. Whereas, soft ferromagnetic materials such as iron or
silicon steel have very narrow magnetic hysteresis loops resulting
in very small amounts of residual magnetism making them ideal
for a variety of biological applications. Additionally, since a
coercive force must be applied to overcome this residual magnetism, work must be done in closing the hysteresis loop. This
magnetic hysteresis results in the dissipation of energy in the
form of heat with the energy wasted being in proportion to the
area of the magnetic hysteresis loop. Thus the amount of loss
depends on the materials value of coercive force. Since the heat
loss is determined by the hysteresis loop which is in turn
determined by the magnetic material, the type of magnetic
material plays an important role in any desired engineering
application. Thus the coercivity (Hc) of the material usually denes
the application of a particular magnet. In a broader sense, the
magnetic properties of any ferromagnets depend on various
factors such as particle size, shape, defects, surface effects, and
temperature to name but a few. In the following section we have
tried to discuss the dependence of coercivity on the particle size,
shape, and surface coatings of the magnetic materials as these are
the controlling factors in the engineering of nanoparticles
applications.

3. Coercivity dependence on the nanoparticle size

The domain structure of a ferromagnetic material determines the
size dependence of its magnetic behavior. In fact, the two most
studied nite-size effects in nanoparticles are the single domain limit

M. Houshiar et al. / Journal of Magnetism and Magnetic Materials 371 (2014) 4348

and the superparamagnetic limit [11]. A large magnetic particle is

well known for its multidomain structure with regions of uniform
magnetization which are separated by domain walls. This formation
of the domain walls is energetically favorable if the energy consumption for the formation of the domain walls is lower than the
difference between the magnetostatic energy of the single domain
and the multidomain states [10]. As the dimensions of the particles
are reduced, the relative contribution of the various energy terms to
the total energy of the ferromagnetic material is changed. Thus, the
surface energy of the domain walls becomes more important than
the magnetostatic energy. Below the critical diameter it costs more
energy to create a domain wall than to support the magnetostatic
energy of the single-domain state [11]. Hence, when the size of a
ferromagnetic material is reduced below the critical diameter, it
becomes a single domain. The conguration of the magnetization
inside a single domain particle then depends strongly on the
magnetic anisotropy and the particles shape [10]. As stated previously, the effect of ferromagnetic materials in an applied eld is
well described by the hysteresis loop, which is characterized by two
main parameters viz remanence and coercivity. The latter is related to
the thickness of the curve. Dealing with ne particles, the coercivity
is the single property of most interest and it is strongly sizedependent. It has been found that as the particle size is reduced,
the coercivity increases to a maximum, and then decreases towards
zero. With a further decrease in particle size below the critical
diameter, the coercivity becomes zero and such particles become
superparamagnetic.
When considering only the dipolar interactions between magnetic particles, for smaller particles the simple magnetization
reversal energy becomes equal to the energy at room temperature
[10,12]. Thus when typical ferromagnets obtain a critical diameter
of o 30 nm, the thermal uctuations at room temperature are
strong enough to spontaneously demagnetize a previously saturated assembly and hence these particles have zero coercivity and
have no hysteresis. Therefore, superparamagnetic nanoparticles
become magnetic in the presence of an external magnet, but
revert to a non-magnetic state when the external magnet is
removed. This avoids any active behavior of the particles when
there is no applied eld.
Kim et al. synthesized various nanocubes in the range of 20
160 nm and measured their coercivity at 300 K. When the sizes of
the nanoparticles were plotted against coercivity, the resulting
single domain curve conrmed that a superparamagnetic character would be observed for the particle size of 20 nm [13]. Thus
the magnetic properties of the nanoparticles depend to a great
extent on its size. In the following different methods for synthesis
of nanomagnetic cobalt ferrites are used and their size and
magnetic properties are compared.

The product was then cooled to room temperature. To get free

particles from sodium and chlorine compounds, the precipitate
was then washed twice with distilled water and then with ethanol,
to remove the excess surfactant from the solution. To isolate the
supernatant liquid, the beaker contents were then centrifuged for
15 min at 3000 rpm. The precipitate was then dried at 100 1C for
10 h. The dried sample was subsequently annealed at 600 1C for
10 h to get the desired nanoparticles [1517,3].
In precipitation method, 50.4 g FeCl3  6H2O was dissolved in
40 ml of distilled water and the obtained orange color solution was
heated to 50 1C. At the same time 37.2 g of CoCl2  4H2O was
dissolved in 1 ml of chloride acid together with 4 ml of distilled
water and then was heated to the temperature of 50 1C. Then at
this temperature both solutions were mixed and the temperature
was raised to 100 1C. At this temperature 99.7 g NaOH which was
added to 200 ml of distilled water, was mixed with the solution. As
a result a black precipitate appeared quickly. This step ended with
another half an hour of stirring. The product was then cooled to
room temperature and was washed a few times with double
distilled de-ionized water. After that 24.4 g of Fe(NO3)3  9H2O
was added to 30 ml of distilled water and mixed with the solution.
The solution was then heated to the temperature of 100 1C and
stirred for 30 min at this temperature. Then the solution was
washed with nitric acid. Then 10 ml of double distilled de-ionized
water was added. The suspension was dialysed for two weeks [7].

5. Results and discussion

Fig. 1 shows the XRD patterns of CoFe2O4 samples, prepared by
combustion, coprecipitation and precipitation methods. The structural analysis of the samples were made with the aid of Xpert
software and the crystal structure of the samples was found to be
inverse cubic spinel type. Using Sherrers equation, the average
sizes of the crystals were estimated to be 69.5, 49.5 and 34.7 nm
for combustion, coprecipitation, and precipitation methods,
respectively.
The presence of (1 1 1), (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1)
and (4 4 0) in XRD pattern is in accordance with inverse cubic
spinel structure with space group fd-3m (Fig. 2) which is in
agreement with JCPDS standard cards no. 01-077-0426 with no
extra phases. To determine the lattice constant, the equation a d
(h2 k2 l2)1/2 is used where d is the bragg plane distance. The
average size of particles and the lattice constants are shown in
Table 1.

4. Synthesis
To obtain CoFe2O4 by combustion method, two water solutions
of, Co(NO3)2  6H2O and Fe(NO3)3  9H2O, were blended by stoichiometric amounts and then glycine was added to the solution [8]. The
solution was heated untill combustion occurred. Then the sample
was annealed to a temperature of 200 1C for 1/2 h [14].
In coprecipitation method the amount of salt solutions of 0.4 M
iron chloride and 0.2 M cobalt were choosen according to Maaz
et al. [15] and nickel chloride was prepared in double distilled
de-ionized water and then they were all mixed together. Sodium
hydroxide of 3.0 M was added to the salt solution drop-wise. The
reactants were constantly stirred using a magnetic stirrer until a
pH level of 12 was reached. A specied few drops of oleic acid
were used as the surfactant. The liquid precipitate was then
brought to a reaction temperature of 80 1C and stirred for 1 h.

45

Fig. 1. XRD pattern of the samples.

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M. Houshiar et al. / Journal of Magnetism and Magnetic Materials 371 (2014) 4348

As seen in (Table 1) lattice constants in three methods are

almost equal. The values obtained for lattice constants are in
agreement with that reported in literatures for cobalt ferrite
(a 8.39 ) compounds.

Fig. 2. Inverse cubic spinel structure.

Table 1
The average size and lattice constant of the crystal.
Method

Size (nm)

Lattice constant ()

Combustion
Coprecipitation
Precipitation

69.5
49.5
34.7

8.36
8.37
8.34

(Fig. 3) shows SEM and TEM images taken for CoFe2O4 samples
prepared by combustion, coprecipitation, and precipitation methods respectively which aggreas with the results calculated by
DebyeSherrers relation used for estimation of average crystal
sizes.
(Fig. 4) shows the magnetization changes versus eld upto
15,000 Oe at room temperature. The values of saturated magnetization
and coercivity of all three samples are given in (Table 2). These curves
are obtained using a VSM instrument. As seen in (Table 2), by
decreasing particle size, saturated magnetization has decreased.
Fig. 5 shows the values of coercivity versus nanoparticle sizes of
all 3 samples (Table 1). As discussed earlier the coercivity
decreases linearly with the decrease of size which shows that
the particles are in single domain area [11]. We can also infer that
the surface spins dominates the magnetization decreases with size
reduction [18].
Also we can see in Table 2 that Hc and Ms are greatest in the
combustion method and least in precipitation method.
The obtained hysteresis data in Fig. 4 makes it possible to
calculate susceptibility of all three nanoparticle samples at room
temperature. Fig. 6 is a plot of susceptibility versus magnetization
of all samples. The magnetization data of x-axis is chosen only
upto 80 emu/g for clarity. The behavior of susceptibility is a sharp
drop by increasing magnetization and the curve attens at higher
values. This behavior has not been reported so far.
To get a better idea of the susceptibility behavior, inverse
susceptibility has been plotted as a function of magnetization in
Fig. 7 and as a function of magnetic eld upto 10k (Oe). The inverse
susceptibility shows linear behavior with external eld H, from
10,000 (Oe) down to about 2000 (Oe) for all the three samples at
room temperature, which then shows an almost exponential
decrease down to zero elds. The result of temperature dependent

Fig. 3. SEM images of (a) combustion, (b) coprecipitation and (c) TEM image of precipitation methods.

M. Houshiar et al. / Journal of Magnetism and Magnetic Materials 371 (2014) 4348

47

50

precipitation
1.6

coprecipitation
combustion

1.2
0.8

-50

0.4

50

M(emu/g)

20

40

60

80

M (emu/g)

Fig. 6. Susceptibility versus magnetization for CoFe2O4 nanoparticles with different

methods.

-50

350
50

precipitation

300

coprecipitation
250

combustion

200
-50

150

-20000

-10000

10000

20000

100

H(Oe)
Fig. 4. Hysteresis loop of nano particles of CoFe2O4 synthesized by (a) combustion,
(b) coprecipitation and (c) precipitation methods.

50
0
0

20

40

60

Table 2
The magnetic characterization of CoFe2O4 samples.
Method

Ms (emu/g)

Hc (Oe)

Combustion
Coprecipitation
Precipitation

56.7
55.8
47.2

2002
850
233

Fig. 7. The inverse suceptibility versus magnetization for CoFe2O4 samples.

350
precipitation
coprecipitation
combustion

300
250

2500

200
150

Coercivity (Oe)

2000

100

1500

50

1000

500
0
20

2000

4000

6000

8000

10000

H(Oe)

30

40

50
Size (nm)

60

70

80

Fig. 5. Coercivity versus nanoparticle size of CoFe2O4 samples.

susceptibility of nanomagnet particles are usually reported in the

literatures, As our susceptibility results only show the room
temperature values, it cannot be compared with those reported
earlier and are presented for visual comparison of different
synthesis only (Fig. 8).

Fig. 8. The susceptibility versus external magetic eld of CoFe2O4 nanoparticles

made with different methods.

6. Conclusions
Cobalt ferrite nanoparticle can be synthesize by combustion,
coprecipitation, and precipitation methods.
The average sizes of the crystals were estimated to be 69.5, 49.5
and 34.7 nm for combustion, coprecipitation, and precipitation
methods. XRD pattern is in accordance with inverse cubic spinel
structure (Mfe2O4) with space group fd-3m.

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M. Houshiar et al. / Journal of Magnetism and Magnetic Materials 371 (2014) 4348

VSM data of samples showed that by decreasing particle size,

saturated magnetization has decreased. Hc and Ms are greatest in
the combustion method and least in precipitation method.
Combustion method is simple and quick. The rate of fuel to
nitrates can highly effect the size and magnetic properties. In
coprecipitation method the size is controlled by quick addition of
the precipitating agent (sodium hydroxide) with the salt solution
and performing vigorous stirring during the reaction.
As seen in (Fig. 3) in precipitation method, we observe less
adhesion, so we can infer that, this method is suitable to
synthesize coreshell nanoparticles.
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