Materials Research Bulletin 45 (2010) 17921795

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Materials Research Bulletin

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Preparation of cobaltzinc ferrite (Co0.8Zn0.2Fe2O4) nanopowder via combustion

method and investigation of its magnetic properties
M.H. Youse a, S. Manouchehri a,b,*, A. Arab a, M. Mozaffari b,c, Gh. R. Amiri a,d, J. Amighian e
a
Department of Physics, Malek-Ashtar University of Technology, Shahinshahr, 83145-34177, Iran
b
Department of Physics, Faculty of Science, The University of Isfahan, Esfahan 81746-73441, Iran
c
Physics Department, Razi University, Taghbostah, Kermanshah, Iran
d
Department of Plasma Physics, Science and Research Branch, Islamic Azad University, Tehran, Iran
e
Islamic Azad University, Najafabad Branch, Najafabad, Iran

A R T I C L E I N F O A B S T R A C T

Article history: Cobaltzinc ferrite (Co0.8Zn0.2Fe2O4) was prepared by combustion method, using cobalt, zinc and iron
Received 13 June 2009 nitrates. The crystallinity of the as-burnt powder was developed by annealing at 700 8C. Crystalline
Received in revised form 30 August 2010 phase was investigated by XRD. Using WilliamsonHall method, the average crystallite sizes for
Accepted 15 September 2010
nanoparticles were determined to be about 27 nm before and 37 nm after annealing, and residual
Available online 24 September 2010
stresses for annealed particles were omitted. The morphology of the annealed sample was investigated
by TEM and the mean particle size was determined to be about 30 nm. The nal stoichiometry of the
Keyword:
sample after annealing showed good agreement with the initial stoichiometry using atomic absorption
A. Nanostructures
A. Combustion
spectrometry. Magnetic properties of the annealed sample such as saturation magnetization, remanence
B. Magnetic properties magnetization, and coercivity measured at room temperature were 70 emu/g, 14 emu/g, and 270 Oe,
respectively. The Curie temperature of the sample was determined to be 350 8C using AC-susceptibility
technique.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
Magnetic nanoparticles continue to be a fascinating subject both
from fundamental and applicable point of view. All properties of the
ferrites are sensitive to their composition, microstructure and
processing conditions [1]. The spinel ferrites have remarkable
magnetic and electrical properties; especially CoFe2O4 is interesting
because of its cubic magnetocrystalline anisotropy, high coercivity,
moderate saturation magnetization, and high chemical stability
magnetic and electrical conductivity [24]. Nanosized particles are
also used for magnetic resonance imaging (MRI) and magnetic uid
hyperthermia (MFH) [5]. It is of further interest to replace a magnetic
Co2+ ion by a non-magnetic Zn2+ one in Co-ferrite to understand the
difference in the properties of the new system. The general formula
of the spinel ferrite is AB2O4 in that the cations reside on tetrahedral
(A site) and octahedral (B site) interstices. It has a face-centered
cubic structure with a large unit cell containing eight formula units.
From the resulting 64 A and 32 B sites, only 8 and 16 are occupied,
respectively, by cations in a stoichiometric spinel [6]. The variation
* Corresponding author at: Department of Physics, Malek-Ashtar University of
Technology, Shahinshahr, 83145-34177, Iran. Tel.: +98 9132119565;
fax: +98 3125220605.
E-mail address: dez283@yahoo.com (S. Manouchehri).
of cation distribution over the A and B sites in the spinel ferrite leads
to different magnetic properties [7].
In spinel oxide AB2O4, magnetic order depends on the
competition between various kinds of superexchange interactions
among A and B site cations, i.e., JAB (AOB), JBB (BOB), and JAA
(AOA). Certain amount of site exchange of cations is sufcient to
change JAB and JBB interactions and has shown drastically different
magnetic behavior in nanoparticle spinel in comparison with the
bulk one [8]. In these spinels, the strong surface spin canting effect
occurs when the particle size reduces to nanometer range. The
competition between disordered (canted) surface spins and
ordered core spins determines the magnetic ground state and
usually exhibits the decreasing of magnetization and ordering
temperature in nanoparticle spinel [8].
Curie temperature is one of the important parameters of every
ferrite. It is an intrinsic property of the spinel ferrites that can be
controlled by preparation conditions and substitution of different
metal elements. Bulk CoFe2O4 is a ferrimagnetic material with a
Curie temperature TC of 530 8C [6].
Nanosized ferrites can be prepared by various methods such as
solgel, reverse micelle, co-precipitation, microemulsion, and
mechanical milling [914]. However, most of these methods
cannot be applied on a large scale and economic production
because they require expensive and often toxic reagents,
complicated synthetic steps, high reaction temperature, and long

0025-5408/$ see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2010.09.018
 M.H. Youse et al. / Materials Research Bulletin 45 (2010) 17921795
reaction time. Among the current methods for synthesis of
cobalt ferrite, the combustion reaction stands out as an
alternative and highly promising method for the synthesis of
these ferrites [5,15]. The combustion method is quite simple,
fast, and inexpensive, as it does not involve intermediate
decomposition or calcinations steps [16]. The basis of the
combustion synthesis technique comes from the thermochemi-
cal concepts used in propellant chemistry and explosives [17].
This method exploits an exothermic, usually very rapid and self-
sustaining, chemical reaction between the desired metal salts
and a suitable organic fuel [18], usually urea [15,19], glycine
[5,20,21], citric acid [22], hydrazine [22] and carbohydrazide
[23]. In addition, depending on the kind of fuel, for a determined
composition, the molar ratio of the oxidizer to fuel is calculated
based on the total oxidizing and reducing valences of the
oxidizer and fuel, therefore the ratio of numerical coefcients for
stoichiometric balance equals unity and the release energy is
maximum for the reaction [15,17,24]. Powder characteristics
like crystallite size, surface area, extent and nature of
agglomeration are governed by enthalpy or ame temperature
generated during combustion, which itself depends on nature of
the fuel and fuel-to-oxidant ratio [25]. A key feature of this
method is that the heat required to sustain the chemical
reaction is provided by the reaction itself and not by an external
source [17,24].
In this research work, zinc-substituted cobalt ferrite (Co0.8Zn0.2-
Fe2O4) was synthesised by combustion method and consequent
changes on its structural and magnetic properties as well as
comparison of the magnetic properties of cobaltzinc ferrite
nanoparticles with the bulk one. The preparation used in this study
is almost similar to the preparation method for cobalt ferrite [5,15],
while the results are different in physical and magnetic properties.
2. Experimental
2.1. Sample preparation
Nanoparticles of CoZn ferrite were synthesized by combustion
reaction using analytical grade iron, cobalt, and zinc nitrates, and
urea as fuel (all from Merck Co.). Manipulations and reactions were
carried out in air. The stoichiometric composition of mixture was
calculated based on the total oxidizing and reducing valences of
the oxidizer and fuel, which serve as numerical coefcients for
stoichiometric balance, so that, the equivalent ratio is unity, and
the release energy is maximum for each reaction. Solutions of 2M
Fe(NO3)39H2O, 0.5 M Co(NO3)26H2O, 0.5 M Zn(NO3)26H2O, and
6.67 M CO(NH2)2 were dissolved in deionized water. These
solutions were mixed in the volume ratio 5:8:2:5, respectively.
The light red mixed solution was evaporated to dryness by heating
at 100 8C on a hot plate until it became viscous and nally formed
very viscous dark gel. The bubbles of the dark gel came up by
increasing the temperature. Increasing the temperature up to
around 440 8C led to gray smoke and the ignition of the gel was
observed, while the temperature of the sample increased around
900 8C. The dried gel burnt completely in a self-propagating
combustion manner to form a loose powder that responded to a
magnet. Finally, the as-burnt powders were annealed in air at a
temperature of 700 8C for 3 h. The sample before and after
annealing was named S1 and S2, respectively.
2.2. Measurements
XRD patterns of the powders were obtained using a diffrac-
tometer (BRUKER, D8 ADVANCED model), with Cu-Ka radiation
(l = 0.15405 nm). The average crystallite sizes of the samples were
calculated from the widths of the peaks using the WilliamsonHall
1793
method for uniform deformation [26,27]
0:9l
B cos u 4h sin u (1)
D
where u is the Bragg angle, h the strain, D the mean crystallite
diameter in nm, and B is the full width at half maximum (FWHM) of
the diffraction lines. The value of B was determined from the
experimental peak width by applying standard correction for the
instrumental broadening. The lattice constants of the samples
were determined using tune cell program of EVA software
(supplied by BRUKER).
The particle morphology of the annealed sample was studied
using TEM (LEO-906E).
The concentrations of Co, Fe, and Zn ions in the prepared
samples were obtained using an atomic absorption spectropho-
tometer (AAS) (Shimadzu, AA-680).
Room temperature magnetization measurements up to a
maximum eld of 10 kOe were carried out using a vibrating
sample magnetometer (PAR EG&G 4500).
The Curie temperature of the sample S2 was determined from
the temperature dependence of the real part of the AC-
susceptibility, x0 . Measurements of x0 were carried out at
temperatures between room temperature and 450 8C in an AC-
magnetic eld of 100 A/m at a frequency of 100 kHz, using an LCR-
meter (Fluke, PM6306).
3. Results and discussion
The combustion reaction was done very quickly, due to
decomposition of urea that is highly exothermic, and then the
consumption energy is low through the preparation process.
Nitrate salts were decomposed by the thermal energy of the
reaction and the nal products were obtained.
X-ray patterns of the synthesized samples of Co0.8Zn0.2Fe2O4 as-
burnt powders (S1) and annealed one (S2) are shown in Fig. 1. The
XRD result for sample S1 indicates the existence of CoZn ferrite as
a major phase and ZnO as a minor phase. In fact, some of the zinc
ions do not react in the formation of the ferrite. However, for
sample S2, no additional phase was detected and the sample can be
indexed as the single-phase spinel structure. The lattice constants
using tune cell program of EVA software were obtained to be
8.385  0.002 A and 8.393  0.002 A for the samples S1 and S2,
respectively. The diffusion of zinc ions in to the tetrahedral sites are
cause of an increase in lattice parameter of sample S2, due to
annealing S1. The broad peaks in Fig. 1 show that crystallite sizes of
the samples are small. Furthermore, the XRD pattern of S1 contains
strain (Fig. 1a) that may be due to residual stress through chemical
reaction process. The origin of the strain is the present of some crystal
imperfections that can be high through the process of combustion
reaction. The strain has disappeared after annealing sample S1
(Fig. 1b). Also as can be seen after annealing, the average crystallite
size is larger due to grain growth of the particles. Fig. 2 shows the
variation of B cos u vs. sin u for the samples. According to the
WilliamsonHall equation, this curve must be linear and the average
crystallite size and strain for each sample can be calculated from
these curves. The average crystallite sizes were calculated as
27  4 nm and 37  2 nm for the samples S1 and S2, respectively.
The slopes of lines in Fig. 2 show the strains and a decrease from
(4.0  0.5)  103 for the sample S1 to (1.1  0.1)  103 for the
sample S2, which suggests that grain growth is present and the strain
developed in the particles reduces on annealing the material. The
characteristics of the sample S2 are listed in Table 1 and have been
compared with the same nanosized sample synthesized by copre-
cipitation method and the bulk CoFe2O4 and Co0.8Zn0.2Fe2O4.
[()TD$FIG]
1794 [()TD$FIG]
M.H. Youse et al. / Materials Research Bulletin 45 (2010) 17921795

0.016

y = 0.0161x + 0.0052
(a) 2
R = 0.9683
Co-Zn Ferrite 0.012
Intensity (a u.)

ZnO
s1

B cos
s2
0.008

0.004 y = 0.0045x + 0.0037

2
R = 0.9877

20 30 40 50 60 70 80 90 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
2Theta (degree)
sin

Fig. 2. WilliamsonHall curves of the samples S1 and S2.

(311)
[()TD$FIG]
(b)
Co-Zn Ferrite
Intensity (a u.)

(440)
(220)

(511)
(400)
(111)

(222)

(422)

(533)
(622)

(642)

20 30 40 50 60 70 80 90
2Theta (degree)

Fig. 1. XRD patterns of cobaltzinc ferrites (a) before annealing and (b) after
annealing at 700 8C.

The nano crystalline nature of S2 was conrmed by TEM (Fig. 3)

and the mean particle size was determined to be 30 nm, but this
size is smaller than XRD result.
The amount of metal ions present in the nal product was
estimated using AAS and the initial and nal cation concentrations
Fig. 3. The TEM micrograph sample S2. The scale on TEM micrograph is 50 nm.
of the sample S2 are given in Table 2. The nal stoichiometry was in
accordance with the initial stoichiometry.
Fig. 4a shows the magnetization variation of the sample S2 with sample S2 is smaller than the bulk CoFe2O4 [6] and Co0.8Zn0.2Fe2O4
magnetic eld up to 10 kOe at room temperature. The saturation [28]. Also the results are in good agreement with the same
magnetization of the sample S2 was determined from the nanosized counterpart one that produced by coprecipitation
extrapolation of the curve M vs. 1/H as 1/H ! 0. The magnetic method [28]. The reduction of magnetization in nanosized sample
characteristics of the sample are listed in Table 1. From the data in is due to spin canting and size effect. The reduced coordination of
Table 1, it can be observed that the saturation magnetization of the surface spins causes a fundamental change in the magnetic

Table 1
Characteristics of the sample S2 compared with the same sample synthesized by coprecipitation method and bulk of CoFe2O4 and Co0.8Zn0.2Fe2O4.

Sample Lattice constant (A) Average crystallite Saturation magnetization Remanence Coercivity (Oe) Curie temperature (8C)
size (nm) (emu/g) (emu/g)

S2 this work 8.393  0.002 37  2 70  1 14  1 270  5 350  5

Co0.8Zn0.2Fe2O4 nanoa 8.395 3050 74 * * *

Co0.8Zn0.2Fe2O4 bulka 8.404 Bulk 85 * *

450
CoFe2O4 bulkb 8.38 Bulk 80 * *
530
CoFe2O4 bulkc * * *
13 918 *

a
Ref. [28].
b
Ref. [6].
c
Ref. [29].
*
Not reported.
 M.H. Youse et al. / Materials Research Bulletin 45 (2010) 17921795 1795

Table 2 spins determines the net magnetization which leads to a decrease

Initial and nal cation concentrations of the sample S2 (errors on values = 0.01).
in magnetization and ordering temperature in nanoparticle spinels
Cation concentration [8].
Co Zn Fe
4. Conclusion
Initial Final Initial Final Initial Final
0.80 0.8 1 0.20 0.25 2.00 1.94
[()TD$FIG] For the preparation of cobaltzinc ferrite nanopowders,
combustion method is a very simple, fast, and inexpensive
80 method. This method can be applied for a semi-large scale and
even large scale preparation of ferrite nanopowders. The saturation
60
magnetization of the prepared nanosized sample was comparable
40 with the bulk CoFe2O4 and Co0.8Zn0.2Fe2O4. XRD pattern shows a
Magnetization (emu/g)

20 nanostructure single phase Co0.8Zn0.2Fe2O4 with the mean

crystallite size of around 37 nm after annealing. In addition, the
0 strain factor has been reduced by annealing the sample. The mean
-20 particle size of the sample was determined by TEM and was
comparable with the XRD result. The Curie temperature for the
-40
nanosized particle is lower than that of the bulk one and this has
-60 been attributed to the reduction of superexchange interaction.
-80
Acknowledgment
-10000 -5000 0 5000 10000
Field (Oe) This study was carried out at the University of Isfahan and
supported by The Ofce of Graduate Studies. The authors are
grateful to the ofce for their support.
Ac-susceptibility (a u.)

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