Journal of Alloys and Compounds 465 (2008) 227–231

Review

Structural, magnetic and electrical properties of cobalt ferrites prepared by

the sol–gel route
I.H. Gul, A. Maqsood ∗
Thermal Physics Laboratory, Department of Physics, Quaid-i-Azam University, Islamabad 45320, Pakistan
Received 18 August 2007; received in revised form 28 October 2007; accepted 1 November 2007
Available online 19 December 2007

Abstract
Nanosized cobalt ferrites having the general formula CoFe2−x Alx O4 (for x = 0.00, 0.25, 0.50) have been synthesized by the sol–gel route. The
effect of Al3+ ions on structural, Curie temperature, DC electrical resistivity and dielecltric properties are presented in this paper. From the analysis
of powder X-ray diffraction patterns, the nanocrystallite size was calculated by the most intense peak (3 1 1) using Scherrer formula. The crystallite
size decreases with increase in aluminium concentartion. The lattice parameter ‘a’ also decreased with increase in aluminum concentration. The
magnetic and electrical properties have been studied as a function of temperature. The Curie temperature was determined from AC magnetic
susceptibility measurement. It is observed that Curie temperature decreases and DC electrical resistivity increases with increasing concentration
of Al3+ ions. The observed variations in DC electrical resistivity have been explained by Verwey’s hopping mechanism. The activation energy was
found to increase with increasing Al3+ ions. The variations of dielectric constant for all the samples have been studied as a function of frequency
in the range 500 Hz to 1 MHz at room temperature. The room temperature dielectric constant decreases with increase of trivalent Al3+ ions. The
observed variation in dielectric constant has been explained on the basis of space charge polarization.
© 2007 Elsevier B.V. All rights reserved.

PACS: 75.30.Cr; 82.80.Jp; 84.37.+q; 78.20.Ci; 75.50.Gg; 61.46.Df; 61.10.Nz

Keywords: AC magnetic susceptibility; Electrical resistivity; Dielectric constant; Ferrite; Nanoparticles; X-ray diffraction

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
2. Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231

1. Introduction ferrite nanoparticles because of their broad applications in

Cobalt ferrite, a ferrimagnetic ceramic, emerged as one of
the important material due to high electrical resistance with low
eddy current losses. There is an increasing interest in magnetic
∗ Corresponding author. Tel.: +92 51 2601014; fax: +92 51 90642240.
E-mail addresses: iftikhar qau@yahoo.com (I.H. Gul), tpl.qau@usa.net
(A. Maqsood).
permanent magnets, drug delivery, microwave devices and high-
density information storage [1–4]. The interesting and useful
magnetic and electrical properties of the spinel ferrites are gov-
erned by the choice of the cations along with Fe2+ , Fe3+ ions
and their distribution between tetrahedral (A) and octahedral (B)
sites of the spinel lattice as well as preparation conditions, chem-
ical composition, sintering temperature, sintering time, doping
additives and the method of preparation [5–8]. It is very impor-
tant in many applications to control the electrical resistivity of

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228 I.H. Gul, A. Maqsood / Journal of Alloys and Compounds 465 (2008) 227–231

the spinel ferrite. For this purpose two major possibilities are The tangent of dielectric loss angle can be calculated using the relation
available, controlling the sintering temperature and substitu-
1
tions. Ferrites are also very good dielectric materials and have tan δ = , (3)
2πfRs Cs
many applications in technology ranging from microwave to
radio frequency. They are also used as microwave absorbers. where δ is the loss angle, f is the frequency, Rs is the equivalent series resistance
Some ferrites absorb microwave by losing interaction of the and Cs is the equivalent series capacitance.
electric and magnetic field vector of incident wave and in the The dielectric loss factor (ε ) is also measured in terms of tangent loss factor
process transfer microwave energy into thermal energy. Radar (tanδ) defined by the relation [14]
absorbing paint made from ferrite can be used to coat military
ε = ε tan δ, (4)
aircraft for stealth operation. The order of magnitude of the elec-
trical conductivity greatly influences the dielectric and magnetic
behaviour of ferrites. Cobalt ferrite possesses an inverse spinel 3. Results and discussion
structure and the degree of inversion depends upon heat treat-
ment [9–11]. In this paper an attempt is made to present the The X-ray patterns of the synthesized samples CoFe2−x
behaviour of structural, magnetic and electrical properties such Alx O4 (for x = 0.00, 0.25, 0.50) are shown in Fig. 1. All the
as dielectric constant (ε ), tangent of dielectric loss angle (tanδ) samples can be indexed as the single-phase cubic spinel struc-
and dielectric loss factor (ε ) of the system CoFe2−x Alx O4 (for ture. No additional phase was detected. The borad peaks signifies
x = 0.00, 0.25, 0.50) as a function of frequency. lower crystallite size of the synthesized samples. The average
crystallite size for each composition was calculated using the
2. Experimental Scherrer formula [12] from the line broadining of the XRD peak
corresponding to the (3 1 1) plane of the spinel structure. The
The starting materials were iron nitrate, aluminum nitrate, cobalt nitrate, cit- crystallite size remains with in the range 18–23 nm. The lattice
ric acid and ammonia, all of analytical grade. The solutions of CoCl2 ·6H2 O,
Fe(NO3 )3 ·9H2 O and Al(NO3 )3 ·9H2 O in their stoichiometry (200 ml of
0.1 M Co(NO3 )2 ·6H2 O, 200 ml of 0.15 M Fe(NO3 )3 ·9H2 O, 200 ml of 0.05 M
Al(NO3 )2 ·9H2 O in the case of CoFe1.5 Al0.5 O4 and similarly for the other val-
ues of x) were dissolved in a deionized water. Citric acid was then added to the
prepared aqueous solution to chelate Co2+ , Fe3+ and Al3+ , in the solution. The
molar ratio of citric acid to total moles of nitrate ions was adjusted at 1:1. The
mixed solution was neutralized to pH 7 by adding 2 M solution of ammonia.
The neutralized solution was evaporated to dryness by heating at 100 ◦ C on a
hot plate with continuous stirring, until it becomes viscous and finally formed a
very viscous gel. Increasing the temperature up to 200 ◦ C led to the ignition of
the gel. The dried gel burnt completely in a self-propagating combustion man-
ner to form a loose powder. Finally, the as-burnt powders were calcined in air
at temperatures of 800 ◦ C for 6 h with a heating rate of 5 ◦ C/min to obtain the
spinel phase.
The structural characterization of all the samples was carried out by the
X-ray diffraction (XRD) and confirmed the formation of well-defined single-
phase spinel structures. XRD data were taken at room temperature using Cu
K␣ (λ = 1.5406 Å) radiation. The crystallite size, t311, was calculated using the
Scherrer formula [12].
DC electrical resistivity for all these samples was measured by two-probe
method. A low value of constant voltage was applied across the sample and
the current through the sample was measured as a function of temperature. The
sample was heated with microfurnace fitted to the sample holder assembly. Tem-
perature of the pellets was measured with Chromel–Alumel thermocouple. The
DC electrical resistivity of all the samples decreases with increasing temperature
according to Arrhenius equation [13]
 E 
ρ = ρ0 exp , (1)
kB T

where kB is Boltzmann constant, T is temperature and E is the activation

energy.
The dielectric constant (ε ) measurements were carried out in the frequency
range from 500 Hz to 1 MHz at room temperature using LCR meter bridge (WK
LCR 4275). The dielectric constant was determined from the formula

Cd
ε = , (2)
εo A

where C is the capacitance of the pellet in farad, d the thickness of the pellet
in meter, A the cross-sectional area of the flat surface of the pellet and εo the
constant of permittivity of free space. Fig. 1. Indexed X-ray pattern of CoFe2−x Alx O4 ferrite nanoparticles.
 I.H. Gul, A. Maqsood / Journal of Alloys and Compounds 465 (2008) 227–231 229

Table 1
Crystallite size (t), lattice parameter (a), lattice volume (V), X-ray density (ρx ),
measured density (ρm ), Curie temperature (Tc ), activation energy (E), correla-
tion coefficient (R), DC electrical resistivity (ρ), dielectric constant (ε ), tangent
of dielectric loss angle (tanδ) and the dielectric loss factor (ε of CoFe2−x Alx O4
ferrite nanoparticles
Parameter x = 0.00 x = 0.25 x = 0.50

t(3 1 1) (nm) 23 20
a (Å) 8.474(5) 8.455(6)
V (Å3 ) 609 604
ρx (g cm−3 ) 5.129 5.010
ρm (g cm−3 ) 3.138 2.995
Tc (±5K) 667 594
E ± 0.001 0.557 0.590
R 0.999 0.999
ρ ( cm) at 373 ± 0.01 K 2.59 × 106 4.49 × 108
ε at 1 MHz 13 11
tanδ at 1 MHz 0.41 0.36
ε at 1 MHz 5.26 4.03
constant a, was calculated using the relation
 with an increasing Al3+ concentration has been explained by a
a = d h k l h2 + k 2 + l 2 ,
where the values of lattice constant a, for each composition
are calculated and tabulated in Table 1. The lattice parameter
decreases from 8.474–8.414 Å with Al3+ concentration (x). The
decrease in lattice parameter may be due to the substitution of
smaller Al3+ ions (0.51 Å) for large Fe3+ ions (0.64 Å) in the
system CoFe2−x Alx O4 . Since smaller ions are replacing larger
ones, a decrease in the lattice parameter is expected. Hence the
observed behaviour of the lattice parameter can be understood.
Measured density was calculated from the weight and dimen-
sions of the sintered samples according to the following relation:
(ρm = m/V) [12], where m is the mass of the sample and V its
volume and the values are tabulated in Table 1. From the table,
it is seen that the measured density decreases from 3.138 to
2.402 g cm−3 with Al3+ concentration. This may be due to the
fact that Al has smaller atomic weight (26.98 amu) than the Fe
(55.85 amu) atoms. The X-ray density was calculated using the
relation: (ρx = 8M/Na3 ) [12], where N is the Avogadro’s num-
ber, ‘a’ is the lattice parameter and M is the atomic weight. The
X-ray density decreases from 5.129 to 4.957 g cm−3 with Al3+
concentration for all the compositions, because the decrease in
mass over takes the decrease in volume of the unit cell.
The AC magnetic susceptibility (χ) measurements for all the
samples were carried out in the temperature range from 300 to
800 K. Fig. 2 shows the AC magnetic susceptibility spectra for
CoFe2−x Alx O4 ferrites. The inverse susceptibility rise sharply
when the magnetic state of the ferrite nanoparticles changes
from ferromagnetic to paramagnetic states. It is observed from
the figure that the Curie temperature is lower when Al3+ con-
centration is high. This is expected because of the insulation of
non-magnetic Al3+ ions preferentially occupy the B sites [15] of
the spinel lattice. According to Neel model, the A–B interaction
is most dominant in ferrites, therefore, Curie temperature of fer-
rites are determined from the overall strength of A–B interaction
[16]. The value of Curie temperature with Al3+ concentration is
also tabulated in Table 1 The decrease of Curie temperature
18
8.414(3)
596
4.957
2.402
528
0.660
0.999
1.06 × 109
5
0.24
1.21
Fig. 2. Inverse AC magnetic susceptibility vs. temperature of CoFe2−x Alx O4
ferrite nanoparticles.
(5)
modification of the A–B interaction strength due to the change
of Fe3+ concentration between A and B sites, reducing thereby
the A–B exchange interaction. This could be attributed to the
decrease in distance between the moment of A and B sites,
which is confirmed by the decrease in lattice parameter with
Al3+ concentration.
Temperature variation of DC electrical resistivity has been
measured by two-probe method as a function of temperature in
Fig. 3. It is evident from the figure that as the concentration
of Al3+ increases, the DC electrical resistivity increases. It is
well known that Al3+ occupy octahedral site B, while Co2+ and
Fe3+ ions occupy A and B sites [15,2]. The observed variation in
DC electrical resistivity may be explained by Vervey’s hopping
mechanism [17]. According to Vervey, the conduction mech-
anism in ferrite occurs mainly through the hopping between
Fe2+ and Fe3+ in the B sites. The hopping probability depends
upon the separation between the ions involved and activation
Fig. 3. Variation of DC electrical resistivity (lnρ) with inverse temperature
(1/kB T) for CoFe2−x Alx O4 ferrite nanoparticles.
230 I.H. Gul, A. Maqsood / Journal of Alloys and Compounds 465 (2008) 227–231
energy. The distance between the two metal ions at B sites are
smaller than the distance between two metal ions one at B site
and another A site. The electron hopping between B and A sites
under normal conditions therefore has a very small probabil-
ity compared with that for B–B hopping. Hopping between A
and B sites does not exit for the simple reason that there are
only Fe3+ ions at A site and only Fe2+ ions formed during pro-
cessing preferentially occupy B sites only. Thus, the deficient
of Fe2+ ions with increasing Al3+ concentration gives further
reason for the increase of the DC electrical resistivity. The mea-
sured values of DC electrical resistivity at 373 K were found to
vary from 2.59 × 106 to 1.06 × 109  cm as the concentration of
Al3+ increases from x = 0.00 to 0.50. High DC electrical resistiv-
ity and relatively easy preparation make CoFe2−x Alx O4 ferrite
nanoparticles widely useable for the cores of intermediate and
high frequency electromagnetic absorbers.
The activation energy of each sample in the measured tem-
perature range can be determined from the slope of the linear
plots (Fig. 3) of DC electrical resistivity. The value of activa-
tion energy ranges from 0.557 to 0.660 eV. In ferrite samples,
the activation energy is often associated with the variation of
mobility of the charge carriers rather than with their concentra-
tion. The charge carriers are considered as localized at the ions
or vacant sites and conduction occurs via a hoping process. The
hopping depends upon the activation energy, which is associated
with the electrical energy barrier experienced by the electrons
during hopping.
The dielectric properties of ferrite nanoparticles are influ-
enced mainly by the method of preparation, cations distribution,
grain size, sintering temperature, oxygen parameter, the ratio of
Fe2+ /Fe3+ ions and oxygen anion vacancies in lattices. Fig. 4
shows the variation of dielectric constant (ε ) as a function of
frequency at room temperature from 500 Hz to 1 MHz. A sample
with high DC electrical resistivity acquires low values of dielec-
tric constant and vice versa [18,19]. The dielectric behaviour can
be explained qualitively by the supposition that the mechanism
of the polarization process in ferrites is similar to that in the con-
duction process. The value of the dielectric constant is very high
Fig. 4. Variation of dielectric constant with lnf (Hz) of CoFe2−x Alx O4 ferrite
nanoparticles at room temperature.
at lower frequencies and decreases with the increase of frquency.
At lower frequencies the grain boundaries are more effective
than grains in electrical conduction. This is in agreement with
ealier observations of other workers on ferrites [20,21]. By the
electronic exchange Fe2+ ⇔ Fe3+ + e−1 , one obtains local dis-
placements of electrons in the direction of the applied electric
field. These displacements determine the polarization in the fer-
rites. It is well known that the effect of polarization is to reduce
the field inside the media. The decrease of polarization of the
dielectric constant with increasing frequency is due to the fact
that beyound certain frequency of the electric field, the elec-
tronic exchange between Fe2+ and Fe3+ ion cannot follow the
alternating field. Since an assembly of space charge carriers in
a dielectric requires finite time to line up their axes parallel to
an alternating electric field, if the frequency of the field reversal
increases, a point will reached when the space charge carriers
cannot keep up with the field and the alternation of their direc-
tion lags behind the field. As the frequency of the field continues
to increase, at some stage the space charge carriers will barely
have started to move before the field reverses and make virtually
no contribution to the polarization of the dielectric. Therefore,
dielectric constant of a material may decrease substantially as
the frequency is increased.
The tangent of dielectric loss angle (tanδ) was determined
using Eq. (3). Fig. 5 shows the variation of tanδ at room tem-
perature as a function of applied field frequency in the range
500 Hz to 1 MHz for all the samples. It can be seen that a small
abnormal behaviour was observed for all the samples at dif-
ferent frequencies. According to Rezlescu model the relaxation
peak may be due to the collective contribution of both p and n
type of charge carriers [22]. The electronic exchange between
Fe2+ ⇔ Fe3+ and hole transfer between Co2+ ⇔ Co3+ in octa-
hedral sites are responsible for such behaviour. Furthermore,
the jumping frequencies of localized charge carriers are almost
equal to that of the applied AC electric field.
The dielectric loss factor (ε ) was determined using Eq. (4).
Dielectric loss is an important part of the total core loss in fer-
Fig. 5. Variation of tangent of dielectric loss angle with lnf (Hz) of
CoFe2−x Alx O4 ferrite nanoparticles.
 I.H. Gul, A. Maqsood / Journal of Alloys and Compounds 465 (2008) 227–231
Fig. 6. Variation of dielectric loss factor with lnf (Hz) of CoFe2−x Alx O4 ferrite
nanoparticles.
rites [23]. The dielectric loss factor as a function of frequency
for all the compositions is depicted in Fig. 6. The dielectric loss
profiles are similar to those of dielectric constant. The increase
in hoping electrons result in a local displacement in the direction
of the extent electric field causing an increase in electric polar-
ization enhances dielectric loss. Hudson [24] has shown that, the
dielectric losses in ferrite is reflected in the conductivity mea-
surements where the materials of high conductivity exhibiting
high losses and vice versa. Thus, the present ferrite nanoparti-
cles with relatively lower losses could be useful at frequencies
higher than those of the individual ferrites.
4. Conclusions
Single-phase well-crystallized ferrite nanoparticles
CoFe2−x Alx O4 (for x = 0.00, 0.25, 0.50) were successfully syn-
thesised using the sol–gel route. The particle size was calculated
from the most intense peak (3 1 1) using the Scherrer formula.
The crystallite size of all the samples decreases the substitution
of Al3+ in the lattice. The lattice parameter ‘a’ decreases with
increase of Al3+ concentration due to smaller ionic radius of
Al3+ compared to Fe3+ . The Curie temperature decreases from
667 to 528 K with increase of Al3+ concentration. The decrease
of Curie temperature with non-magnetic Al3+ concentration
has been explained by the A–B exchange interaction strength
due to the change of Fe3+ distribution between A and B sites.
Temperature dependent DC electrical resistivity decreases
with increase in temperature ensuring the semiconductor like
behavior of the samples. Activation energy calculated from
the DC electrical resistivity versus temperature for all the
231
samples increases with the increase of Al3+ concentration. The
dielectric constant decreases with increasing frequency for
these all cobalt ferrite nanoparticle compositions. The values
of ε , tanδ and ε decreases from 11 to 5, 0.41 to 0.24 and
5.27 to 1.21, respectively, at 1 MHz. Low dielectric constants
increase the penetration depth of the electromagnetic waves by
decreasing the skin effect. Hence, the much lower dielectric
constants obtained for the ferrites warrant their application at
high frequencies as microwave absorbers.
Acknowledgements
The authors would like to acknowledge Higher Education
Commission (HEC) Islamabad, Pakistan and Quaid-i-Azam
University Research fund (URF) for providing financial sup-
port for this work. The authors are grateful to Mr. Naeem Ashiq,
Department of Chemistry of this university for his kind help in
preparation of ferrite nanoparticles.
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