Journal of Physics and Chemistry of Solids 68 (2007) 15221526

Dielectric properties and magnetoelectric effect of

(x)NiFe
2
O
4
+(1x)Ba
0.8
Sr
0.2
TiO
3
composites
D.R. Patil, S.A. Lokare, R.S. Devan, S.S. Chougule, Y.D. Kolekar, B.K. Chougule

Composites Materials Laboratory, Department of Physics, Shivaji University, Kolhapur 416004, India
Received 17 March 2006; received in revised form 14 March 2007; accepted 15 March 2007
Abstract
Magnetoelectric composites of NiFe
2
O
4
and Ba
0.8
Sr
0.2
TiO
3
were prepared using conventional double-sintering ceramic method. The
phase formation of magnetoelectric composites was conrmed by XRD technique. Variation of dielectric constant and loss tangent at
room temperature with frequency in the range 100 Hz1 MHz has been studied. Also the variation of dielectric constant and loss tangent
with temperature and composition at xed frequencies of 1 kHz, 10 kHz, 100 kHz and 1 MHz is reported. The static value of the
magnetoelectric conversion factor was measured as a function of intensity of the magnetic eld. The ME voltage coefcient of about
430 mV/cmOe was observed for 15% NiFe
2
O
4
+85% Ba
0.8
Sr
0.2
TiO
3
composite. All the samples show linear variation of magnetoelectric
conversion in the presence of static magnetic eld.
r 2007 Published by Elsevier Ltd.
Keywords: C. X-ray diffraction
1. Introduction
Magnetoelectric materials prepared by combining to-
gether the ferroelectric and ferrite materials in which the
coupling interaction between ferroelectric and ferrite
substances could produce an interesting effect have drawn
signicant interest in recent years due to their multi-
functionality [1]. These materials provide opportunities for
potential applications as transducers, actuators and sensors
[2]. These magnetoelectric composites exhibit an extrinsic
magnetoelectric effect characterized by the appearance of
an electric polarization (ME output) on applying a
magnetic eld. The ME effect occurs as a product
property resulting from interactions between the ferrite
and ferroelectric phases and is not available in the
individual component phases [3]. When a magnetic eld
is applied to the composites, the ferrite particles change
their shape along the piezoelectric phase, resulting in an
electric polarization [4]. The ME effect obtained in
composites is more than hundred times that of single
phase ME materials, such as Cr
2
O
3
.
To realize higher output of ME conversion in compo-
site materials, the following guidelines are to be kept in
mind [5]:
1. The two phases must be in equilibrium.
2. Mechanical contact between grains must be perfect.
3. The value of magnetostriction coefcient of piezo-
magnetic phase must be high.
4. The value of piezoelectric coefcient of the piezoelectric
phase must be high.
5. Proper poling strategy is to be adopted for the material
to show higher ME conversion.
6. The accumulated charges must not leak through the
piezomagnetic phase. Hence this phase should have
resistivity greater than 10
8
ohmcm.
In the present work, the principle motivation is to
investigate the overall dielectric properties and magneto-
electric effect of (x)NiFe
2
O
4
+(1x)Ba
0.8
Sr
0.2
TiO
3
ME
composites to understand the conduction mechanism and
magnetoelectric interactions. Nickel ferrite (NiFe
2
O
4
) is a
ARTICLE IN PRESS
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0022-3697/$ - see front matter r 2007 Published by Elsevier Ltd.
doi:10.1016/j.jpcs.2007.03.029

Corresponding author. Tel.: +91 0231 2609223;

fax: +91 0231 2691533.
E-mail addresses: bkchougule@yahoo.com,
sucomposites@yahoo.co.in (B.K. Chougule).
well-known spinel magnetic material having high resistivity
and magnetostriction coefcient that gives rise to a strong
pseudo-piezomagnetic effect in a magnetic eld [6]. Also
BaSrTiO
3
has been considered to be an important material
for tunable microwave devices because of its high dielectric
constant, large electric eld tunability, relatively low
dielectric loss and variable Curie temperature (from 400
to 30 K) depending on the content of strontium [7].
A detailed study of variation of dielectric constant with
temperature, composition and frequency of the composites
is reported. This study offers valuable information about
the mechanism of electrical conduction and dielectric
polarization in the present composites, which in turn helps
to explain the result on magnetoelectric effect.
2. Experimental
The composite samples in the present case were prepared
by standard double-sintering ceramic method. The ferrite
phase was prepared through solid-state reaction using NiO
(99.9% purity) and Fe
2
O
3
(99.9% purity) in appropriate
molar proportions. The basic oxides were mixed and
ground in agate mortar for couple of hours and presintered
at 900 1C for 9 h. The ferroelectric phase was prepared
using the same route by mixing BaCO
3
, SrCO
3
and TiO
2
in
their appropriate molar proportions and presintered at
1000 1C for 10 h. The ME composites were prepared by
mixing 15, 30 and 45 mol% of NiFe
2
O
4
phase with 85, 70
and 55 mol% of Ba
0.8
Sr
0.2
TiO
3
phase, respectively. The
composite mixtures were presintered again at 1100 1C for
11 h. The pellets having 34 mm thickness and 10 mm
diameter were prepared using the hydraulic press. The
pellets were nal sintered at 1200 1C for 12 h to yield the
nal products.
The samples were characterized by using X-ray diffract-
ometer (Philips Model PW 3710) using Cu Ka radiation
(l 1.5418 A

). The dielectric constant and loss tangent

were determined at room temperature from the measure-
ment of capacitance and tan d-value as a function of
frequency in the range 100 Hz1 MHz and as a function of
temperature at xed frequencies of 1 kHz, 10 kHz, 100 kHz
and 1 MHz using LCR meter bridge (Model HP 4284 A).
The magnetoelectric coefcient of the composites was
measured as a function of dc magnetic eld. The
composites had to be poled electrically and magnetically
before measuring the ME effect. The magnetic poling
enhances the magnetostriction coefcient of the ferrite
phase, whereas the electric poling enhances the piezo-
electric coefcient of the ferroelectric phase, being helpful
for observing ME effect in the composites [8]. The electric
poling was carried out in a DC eld of 1.5 kV/cm during
constant cooling of samples from 130 1C to room
temperature. The samples were magnetically poled by
applying dc magnetic eld of 5 KOe at room temperature.
The static magnetoelectric voltage coefcient (dE/dH)
H
was measured using Keithley Electrometer (Model 2000) in
dc magnetic eld using the same setup.
3. Results and discussion
The X-ray diffraction (XRD) patterns for the composites
with x 0.15, 0.30 and 0.45 are shown in Fig. 1. The peaks
in the XRD patterns are identied to be characteristics of
both Ba
0.8
Sr
0.2
TiO
3
and NiFe
2
O
4
phases. A comparison
between the XRD patterns of composites reveals that the
intensity of ferrite peaks increases with increasing percen-
tage of ferrite phase in the composites. The number of
peaks of ferrite phase also increases with increasing ferrite
content. The lattice parameters for the ferrite and ferro-
electric phases were calculated. The NiFe
2
O
4
ferrite phase
has a cubic spinel structure with a 8.33 A

. The ferro-
electric phase Ba
0.8
Sr
0.2
TiO
3
has a tetragonal perovskite
structure with lattice parameters a 3.98 A

and
c 3.99 A

. The lattice parameters of the ferrite and

ferroelectric phases in composites match fairly well with
the lattice parameters of the individual constituent phases.
ARTICLE IN PRESS
0
200
400
600
800
1000
1200
1400
1600
20 30 40 50 60 70 80 90 100
100
300
500
700
900
1100
1300
2(degree)
100
300
500
700
900
1100
*
(
2
2
1
)
*
(
1
0
0
)

(
2
2
0
)
*
(
1
1
0
)

(
3
1
1
)

(
5
1
1
)
*
(
1
1
1
)
*
(
2
0
0
)
*
(
2
1
0
)
*
(
2
2
0
)
*
(
2
2
2
)
*
(
3
2
1
) *
(
2
1
1
)
*
(
3
0
1
)

(
4
2
2
)

(
7
3
1
)

(
4
0
0
)

(
3
1
1
)
*
(
1
0
3
)

(
4
4
0
)

(
2
2
2
)
x=0.45
x=0.30
x=0.15
*-Ferroelectric Phase
-Ferrite Phase
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)

Fig. 1. XRD patterns of (x)NiFe
2
O
4
+(1x)Ba
0.8
Sr
0.2
TiO
3
composites.
D.R. Patil et al. / Journal of Physics and Chemistry of Solids 68 (2007) 15221526 1523
Fig. 2 shows the variation of dielectric constant as a
function of frequency for the composites at room
temperature. The dielectric constant decreases rapidly with
increase in frequency showing dispersion in the lower
frequency region and attains a saturation limit at higher
frequencies. The samples show dispersion due to Maxwell
Wagner type interfacial polarization in agreement with
Koops phenomenological theory [9]. The pattern at lower
frequencies may be attributed to different types of
polarizations (electronic, atomic, interfacial and ionic,
etc.). The high value of dielectric constant observed at
lower frequencies is explained on the basis of space charge
polarization due to inhomogeneous dielectric structure.
The inhomogeneities in the ferrite and ferroelectric
composites are impurities, porosity and grain structure,
and at higher frequencies it arises due to the contribution
from electronic polarization. However, in case of compo-
sites, the high value of dielectric constant is ascribed to the
fact that ferroelectric regions are surrounded by non-
ferroelectric (ferrite) regions [10]. The dielectric constant is
found to decrease with increasing ferrite content. Fig. 3
shows the variation of tan d with frequency for the
composites. At lower frequencies, tan d is large and it
decreases with increasing frequency. The tan d is the energy
dissipation in the dielectric system, which is proportional to
the imaginary part of dielectric constant e
00
. At higher
frequencies, the losses are reduced and the dipoles
contribute to the polarization. This shows a similar
dispersion as that of dielectric constant with frequency.
The dielectric loss is found to be maximum for x 0.15
and minimum for x 0.45. The dielectric loss is increased
in proportion to the increase in dielectric constant.
The variation of dielectric constant with temperature at
different frequencies viz. 1 kHz, 10 kHz, 100 kHz and
1 MHz for composites with x 0.15, 0.30 and 0.45 is
shown in Figs. 46, respectively. The dielectric constant
increases with rise in temperature and attains a maximum
ARTICLE IN PRESS
0
200
400
600
800
1000
1200
1400
1600
1800
2 2.5 3 3.5 4 4.5 5 5.5 6
log f
x=0
x=0.15
x=0.30
x=0.45
x=1
Fig. 2. Variation of dielectric constant with frequency for (x)NiFe
2
O
4
+
(1x)Ba
0.8
Sr
0.2
TiO
3
composite.
0
1
2
3
4
5
6
7
8
9
2 2.5 3 3.5 4 4.5 5 5.5 6
log f
x=0
x=0.15
x=0.30
x=0.45
x=1
Fig. 3. Variation of dielectric loss with frequency for (x)NiFe
2
O
4
+(1x)
Ba
0.8
Sr
0.2
TiO
3
composite.
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
0 100 200 300 400 500 600
Temperature (C)
1 kHz
10kHz
100kHz
1 MHz
Fig. 4. Variation of dielectric constant with temperature for 15%
NiFe
2
O
4
+85% Ba
0.8
Sr
0.2
TiO
3
composite.
0
1000
2000
3000
4000
5000
6000
7000
0 100 200 300 400 500 600
Temperature (C)
1 kHz
10 kHz
100 kHz
1 MHz
Fig. 5. Variation of dielectric constant with temperature for 30%
NiFe
2
O
4
+70% Ba
0.8
Sr
0.2
TiO
3
composite.
D.R. Patil et al. / Journal of Physics and Chemistry of Solids 68 (2007) 15221526 1524
value at Curie temperature followed by a decreasing trend
indicating phase transition. The transition temperature in
the present case shifts toward lower temperature side as the
ferrite content increases. The dielectric constant is found to
decrease with increase in ferrite content in the composites.
The decrease in dielectric constant is attributed to the
doping effect of ferrite addition in these composites. It is
reported that different behavior of permittivity as a
function composition is a result of superposition of two
effects, modication of the piezoelectric material with
ferrite components and change in grain size of piezoelectric
materials. Also, the increase in ferrite content results in
decrease in polarization efciency as a result of increased
conductivity [11].
Conduction in ferrite, which is due to electron hopping,
also causes local displacement in the direction of the
external eld, inuencing dielectric polarization in ferrites.
In case of ferrites, it is well known that electron hopping
between Fe
2+
and Fe
3+
and hole hopping between Ni
3+
and Ni
2+
ions in B sites in the spinel structure are
responsible for electrical conduction in bulk NiFe
2
O
4
ferrite. As the temperature increases, ac electrical con-
ductivity increases due to increase in drift mobility of
thermally activated electrons [8]. As a result, dielectric
polarization increases causing an increase in dielectric
constant and loss tangent. In addition, as ferrites are
basically ionic solids, there is an inherent ionic polariza-
tion. Hence there is a net increase in dielectric constant
with temperature. A further increase in temperature
however adds to the relative vibrational motion of ions
and electrons, which becomes less susceptible to orienta-
tion in the eld direction. Hence the dielectric constant
decreases after passing through the transition temperature
(T
c
605, 595 and 590 1C, respectively) [12,13], which is
closer to ferrite transition temperature, rather than ferro-
electric transition temperature, which is 45 1C [Fig. 7]. One
of the manipulation of ME interaction in composite is shift
in magnetic transition temperature due to an electric eld.
The dielectric constants are observed to be 8345, 6625 and
5205 for x 0.15, 0.30 and 0.45, respectively at Curie
temperatures (for 1 kHz frequency).
Fig. 8 shows the variation of magnetoelectric conversion
factor with applied magnetic eld for composites with
x 0.15, 0.30 and 0.45 composites. It is well known that
the magnetoelectric effect in composite is determined by
the magnetostrictional deformation of ferrite phase and
piezoelectric effect of the ferroelectric phase. For this, the
magnitude of magnetoelectric sensitivity dE/dH should
depend in a complicated way on the compositions of the
composite materials [14]. It is clear that (dE/dH)
H
increases
gradually with increasing magnetic eld up to 1.2 KOe and
thereafter decreases and attains saturation at higher elds.
This is because in the spinel ferrite, the magnetostrictive
coefcient reaches saturation at a certain value of magnetic
eld. Beyond saturation, the magnetostriction and the
strain thus produced would also produce a constant electric
eld in the piezoelectric phase forcing (dE/dH)
H
to
ARTICLE IN PRESS
0
1000
2000
3000
4000
5000
6000
0 100 200 300 400 500 600
Temperature (C)
1 kHz
10 kHz
100 kHz
1 MHz
Fig. 6. Variation of dielectric constant with temperature for 45%
NiFe
2
O
4
+55% Ba
0.8
Sr
0.2
TiO
3
composite.
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
25 125 225 325 425 525 625
Temperature (C)
x=0.15
x=0.30
x=0.45
Fig. 7. Variation of dielectric constant with temperature at 1 kHz
frequency for (x)NiFe
2
O
4
+(1x)Ba
0.8
Sr
0.2
TiO
3
composites.
0
50
100
150
200
250
300
350
400
450
500
400 1200 2000 2800 3600 4400 5200
magnetic field H (Oe)
d
E
/
d
H

(

V
/
c
m
.
O
e
)
x=0.15
x=0.30
x=0.45
Fig. 8. Variation of magnetoelectric conversion factor with dc magnetic
eld for (x)NiFe
2
O
4
+(1x)Ba
0.8
Sr
0.2
TiO
3
composites.
D.R. Patil et al. / Journal of Physics and Chemistry of Solids 68 (2007) 15221526 1525
decrease with increasing magnetic eld [4]. It also decreases
with increasing ferrite content in the composites. The
decrease in (dE/dH)
H
with ferrite content is attributed to
lower resistivity of ferrite phase as compared to ferro-
electric phase resulting in the leakage of charges developed
in the piezoelectric grains through low resistance ferrite
grains [15,16]. When the composite contains too much of
ferrite phase, it cannot be poled using higher voltage for its
low resistance and one cannot get good piezoelectric effect
due to the leakage of charges. The leakage of charges
reduces the ME effect of the composites. Hence, there is a
limit to the addition of ferrite content. It is noted that the
composites having compositions up to 50%50% show the
good ME effect. The maximum value of (dE/dH)
H
was
observed to be maximum (430 mV/cmOe) for x 0.85,
whereas it is minimum (280 mV/cmOe) for x 0.55
composite.
Fig. 9 shows the variation of dielectric constant at Curie
temperature and ME coefcient with ferrite content in the
composites. Both the dielectric constant and ME effect are
observed to decrease with increasing ferrite content.
Similar behavior has been reported earlier by other
workers [1317].
4. Conclusions
The two phase ME particulate composites containing
ferrite and ferroelectric phases were prepared by standard
ceramic method. The coexistence of NiFe
2
O
4
and
Ba
0.8
Sr
0.2
TiO
3
phases in the composites was conrmed by
XRD technique. The intensity of their diffraction peaks
depends on the amount of the corresponding phase. The
intensity and number of peaks of ferrite phase are observed
to increase with increasing ferrite content. The decrease in
dielectric constant with frequency shows dielectric disper-
sion at lower frequencies. The dielectric constant increases
with increasing temperature and starts decreasing after
passing through the transition temperature indicating
phase transition from ferroelectric state to paraelectric
state at Curie temperature (T
c
). The dielectric constant is
found to decrease with increasing ferrite content. The ME
effect vary linearly with applied magnetic eld. The ME
effect of the composites is strongly dependent on the
volume fraction of the ferrite phase. The ME effect is
observed to decrease with increase in ferrite content
because of low resistivity of the ferrite phase. The lower
resistivity of the ferrite phase exerts an important inuence
on the ME effect of the composites, which provides
guideline for proper selection of compositions of the
phases.
Acknowledgment
The work is carried out with nancial assistance from
UGC, New Delhi under UGC-DRS-II Program.
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ARTICLE IN PRESS
Fig. 9. Variation of dielectric constant and ME coefcient with x in
(x)NiFe
2
O
4
+(1x)Ba
0.8
Sr
0.2
TiO
3
composites.
D.R. Patil et al. / Journal of Physics and Chemistry of Solids 68 (2007) 15221526 1526