ME effect studies of ferrite-ferroelectric
Magnetoelectric Composite
R. A. Kunale1, R. H. Kadam1*, D. R. Mane2, G. B. Todkar3
1
2
Department of Physics, Shrikrishna College Gunjoti, Tq. Omerga, Dist. Osmanabad, India.
Registrar of Dr. Babasaheb Ambedker Marathwada University Aurangabad,Aurangabad, India.
3
Dayananad Science College Latur, Dist. Latur, India.
*
Corresponding author’s e-mail:rkunale@yahoomail.com, Tel.: +91-8600656959
Abstract
The magnetoelectric (ME) composites with
composition (1-x) Ni0.5Cu0.3Mg0.2Fe2O4 + (x) BaTiO3 in
which x = 0, 0.20, 0.40, 0.60,0.8 and 1 mol were prepared
by conventional solid state reaction. The phase purity of
ferrite and ferroelectric in composites is confirmed by xray diffraction studies. ME voltage coefficient was
measured as function of applied dc magnetic field and
variation in ME response has been explained in terms of
the content of piezoelectric phase and the intensity of
applied magnetic field. The magnetoelectric properties of
these composites depend on the ferrite content,
ferroelectric content and resistivity of constituent
component of composites. The ME Voltage coefficient
increases with increase in ferroelectric content in
composites. The maximum ME voltage coefficient of
257mV/cm-Oe was observed for composite with x=0.8.
Keywords:Magnetoelectric effect, Resistivity, Composites,
X-ray diffaraction, ferrite, ferroelectric.
Introduction
Magnetoelectric composites prepared by
combining together ferrite i.e. magnetic materials and
ferroelectric i.e. electric materials, in which the
mechanical coupling between ferrite and ferroelectric
substances can produce magnetoelectric effect, have
drawn significant attention in recent years. The
materials which exhibit magnetoelectric effect are
termed as magnetoelectric ceramics and they are
considered to be promising candidates for sensors,
processors, actuators and memory systems. These
composites possess ME effect which is absent in their
individual ferrite and ferroelectric phases [1]. ME effec
couples two field effect in which 1)electric polarization
on application of AC or DC magnetic field and 2) the
magnetic polarization on application of AC or DC
electric field[2,3]. The magnetoelectric effect is due to
the mechanical coupling between piezomagnetic-ferrite
and piezoelectric-ferroelectric phases [4]. The ME
effect is a result of the product of inherent properties
like magnetostriction and piezoelectric effect of the
constituent phases present in the composite. Van
Suchtelen [1] proposed the “product property” for ME
composites. ME composites are prepared by sintering
mixtures of piezoelectric and magnetostrictive
materials. ME effect in these composites entails the
combined deformation of the matrix of the
piezoelectric and magnetostrictive components [4, 5].A
primary deformation of the magnetostrictive phase
causes polarization of the piezoelectric particles of
composite; on the other hand, electric polarization of
piezoelectric materials causes change in magnetization
of the ferrite phase due to mechanical coupling of
piezomagnetic (ferrite) and piezoelectric (ferroelectric)
phases. In the last few decades, extensive work has
been conducted in the era of magnetoelectricity. The
composite of ferrite-ferroelectric phase can be
synthesized by ceramic method [6-9] and wet chemical
method [10]. From literature it is clear that the work on
these magnetoelectric composites is limited to
measurement of ME effect only. V.L. Mathe have
studied the ME effect in CoFe2O4–BaTiO3. The value
of magnetoelectric voltage coefficient observed was
140 μV/cm/Oe [11]. Gelyasin [12] have measured the
ME coefficient with ac magnetic field for NiFe2O4–
BaTiO3 composites. All researcher are trying to obtain
maximum ME voltage coefficient by using different
elements and their composition in ferrite and
ferroelectric phase. Small amount of change in
composition causes large change in ME effect. This
effect would make the conversion between electric
energy and magnetic energy possible. This provides
Opportunities for potential applications of these as ME
memories, wave-guides, transducers, radioelectronics,
optoelectronics, microwave electronics and as
transducers in instrumentation [13, 14].
The selection of ferrite and ferroelectric
materials depends on the various factors like high
magnetostriction
coefficient
and
piezoelectric
coefficient, high dielectric permeability and poling
strength. As reported earlier the Ni containing ferrite
were high resistive and magetostrictive. In the present
work Ni0.5Cu0.3Mg0.2Fe2O4 is used as ferrite phase. The
Ni ferrite shows better magnetic properties. The Ni
ferrite is substituted with Mg and Cu. Ni2+ and Cu2+
are Jahn–Teller ions. The Ni–Cu ferrite have high
mechanical coupling leading to high magnetostriction
and high saturation magnetization. BaTiO3 (BTO) is
selected as the ferroelectric phase. It was well known
that BaTiO3 exhibits a better piezoelectric properties
and a high dielectric constant. The two compounds can
be successfully incorporated into a composite, it is
expected that the composites might have interesting
0.00
0.20
0.40
0.60
0.80
1.00
Lattice constant
for ferroelectric
(Ao)
a
c
c/a
rati
o
3.784
3.983
3.986
4.009
4.020
1.010
1.011
1.011
1.011
1.010
3.822
4.026
4.029
4.052
4.060
The values of lattice constant ‘a’ for ferrite
phase, ‘a’ and ‘c’ for ferroelectric phase are given in
Table1. The variation of lattice constant ‘a’ for ferrite
phase and ‘a’ and ‘c’ for ferroelectric phase with
composition ‘x’ is shown in Fig.2. It is clear from Fig.
2, that the values of lattice constant ‘a’ for ferrite phase
decreases as the percentage of ferroelectric material in
composite increases and the values of lattice constants
‘a’ and ‘c’ for ferroelectric phase increases as the
percentage of ferrite material decreases in composite.
1800
x=0.80
# Ferrite phase
* Ferroelectric Phase
1600
1400
1200
1000
*(220)
400
*(210)
600
*(211)
800
*(200)
The crystal structures of composites and
their constituent phases were determined by XRD
technique using Philips X-ray diffractometer using Cu
Kα radiation. The magnetoelectric (ME) effect
measurements of the samples were carried out under
induced electric polarization by an applied magnetic
field and induced magnetization by an applied electric
field. Electric and magnetic poling of the composites
was made to increase the magnetostriction coefficient
of the ferrite phase and the piezoelectric coefficient of
the ferroelectric phase. The electric poling was carried
out by heating the samples at about 30oC above the
ferroelectric Curie temperature in an external electric
field. The magnetic poling was carried out by
applying DC magnetic field at room temperature and
in the same setup the static ME voltage coefficient
(dE/dH)H measured. The magnetic field applied
normal to the flat and polished surfaces of the
composite pellets with good electric contacts induces
the electric voltage as a function of magnetic field and
was measured with high impedance kiethley electrometer.
Lattice
Consta
nt for
ferrite
(Ao)
8.316
8.281
8.260
8.255
8.250
-
*(111)
property
Com
posit
in
*(110)
and
Lattice parameters of Ferrite, Ferroelectric phases with
their c/a ratios of (1-x) Ni0.5Cu0.3 Zn0.2 Fe2O4+(x)
BaTiO3 for (x = 0.0-1.0)
#(311)
2. Characterization
measurement:
Table: 1
#(220)
The components of present composites
are
BaTiO3 as
ferroelectric
phase and
Ni0.5Cu0.3Mg0.2Fe2O4 as a ferrite phase with general
formula (1-x)Ni0.5Cu0.3Mg0.2Fe2O4+ (x) BaTiO3 in
which x = 0, 0.20, 0.40, 0.60, 0.80,1 mol were
prepared by conventional solid state reaction. The
ferrite phase was prepared by NiO, CuO, MgO, and
Fe2O3 in required molar proportions. These oxides
were mixed and grind in agate mortar for couple of
hours. The ferroelectric phase was prepared by using
BaO and TiO2 as starting materials. These oxides are
also mixed and grind in agate mortar. The ME
composites were prepared by mixing 0.8,0.6,0.4 and
0.2 mol of ferrite phase with 0.2,0.4,0.6,and 0.8 mol
of ferroelectric phase respectively. The required
molar proportions were mixed and grind for 3 hour.
The grind powder mixture was pressed into pellets
using hydraulic press. The pelletized sample was
final sintered in programmable furnace and slow
cooled to room temperature to yield the final
product.
*(100)
1. Experimental:
Fig.1 shows the XRD pattern of composites
with x=0.80. The peaks are characteristics of both
ferrite and ferroelectric phases. The intensity as well
as number of ferroelectric peaks increases with
increase in ferroelectric content in composites. It may
be due to increase of molar percentage of
ferroelectric. The Ni0.5Cu0.3Zn0.2Fe2O4 ferrite phase
has cubic spinel structure. The ferroelectric phase has
tetragonal pervoskite structure. The lattice parameters
are shown in the following table 1.
Intensity(arb.unit)
electrical as well as magnetoelectric properties. Hence
we have chosen Ni0.5Cu0.3Mg0.2Fe2O4 as a ferrite phase
and BaTiO3 as a ferroelectric phase to form the
composites. We report here magnetoelectric effect of
these ME composites.
200
0
20
30
40
50
60
70
80
2Theta(Degree)
3. Result and Discussion:
3.1 Phase Determination
Fig.1 XRD Patterns of (1-x)Ni0.5Cu0.3Mg0.2Fe2O4+
(x) BaTiO3 (x = 0.80)
8.4
3.3 Magnetoelectric (ME) Effect:
8.36
8.32
8.28
8.24
Lattice constant 'a' (Ferrite phase)
Lattice constant 'a' and 'c' (Ferro. phase)
Ferroelectric
phase 'c'
Ferroelectric
Phase 'a'
Ferrite phase
'a'
8.2
0
0.2 0.4 0.6 0.8
Composition 'x'
1
Fig. 2: Variation of lattice constant ‘a’ and ‘c’ for both
ferrite and ferroelectric phases of the series (1-x)
Ni0.5Cu0.3Mg0.2Fe2O4+(x)BaTiO3
3.2 Scanning Electron Microscopy:
dE/dH (mV/Cm-Oe)
Powder morphology was observed via
scanning electron microscopy. Scanning electron
microscope (SEM) is one of the most versatile
instruments available for the examination and analysis
of the micro structural characteristics of materials. The
reason for using the SEM is the high resolution and
appropriate magnification. The scanning electron
micrographs of the all the samples of series under
investigation are presented in Figs. 2. The scanning
electron micrographs of samples show that the sample
has an agglomerated large grain structure. Heating
results in the well-faceted grains to form solid bodies.
First the ME effect was observed a single
crystal (Cr2O3). The ME effect is due to the local
interaction between the ordered magnetic and
ferroelectric sub-lattices. ME response depends on both
magneto-mechanical resonance in ferrite phase and
electro-mechanical resonance in ferroelectric phase. ME
effect depends on the applied magnetic field, mole
percentage of constituent phases and mechanical
coupling between the two phases . ME coupling can be
achieved by mediating stress in between the two phases.
The variation in magnetoelectric conversion factor with
applied DC magnetic field is shown in Fig.3. From Fig.
3 it is to be noted that there is increase in ME output
[dE/dH]H with applied magnetic field, then reaches a
maximum value and there after decreases. The constant
value of [dE/dH]H indicates the saturation value of
magnetostriction at the time of poling and it produces
constant electric field in the ferroelectric phase. The ME
effect depends on mol% of ferrite and ferroelectric
phases. Initially ME coefficient increases slowly and
after that increase in mole percentage of ferroelectric
phase [dE/dH]H increases. The maximum value of ME
voltage coefficient of 257 mV/come was observed for
x=0.80 of composite and the lower values of ME output
obtained at x=0.20. Due to low resistivity of ferrite
phase, the transfer of the accumulated charges takes
place between ferrite and ferroelectric phases at the time
of poling [15]. The increase in ME output at x=0.80 is
due to the uniform distribution of small grain sizes in
the two phases. The strong compositional dependence
that peaks at low ferrite content is a common feature for
ferrite composites, because the conductivity percolation
between ferrite grains tends to limit the effect of poling
and to shorten the internal electrical field required for
piezoelectricity.
300
x=0.2
x=0.4
x=0.6
x=0.8
250
200
150
100
50
0
0
1
2
3
Magnetic field (KOe)
4
Fig.3 Variation of magneto electric coefficient with
magnetic field for (1-x)Ni0.5Cu0.3Mg0.2Fe2O4+ (x)
BaTiO3
Fig 2: SEM images of (1-x) Ni0.5Cu0.3Mg0.2Fe2O4+
(x)BaTiO3 for x=0.0
Comparing the maximum value of dE/dH, 257
mV/cm-Oe for present composite, with the data in the
literature, we find it is several orders higher than that
of the magnetoelectric compounds and solid solutions
[16, 17] and that of spinel-ferrite/BaTiO3 (16.2
mV/cm-Oe), spinel-ferrite/ PZT (30.2 mV/cm-Oe)
composites [18, 19] and Ni-ferrite/PZT (up to 115
mV/cm/Oe) composites [20].
Conclusion:
The ferrite-ferroelectric ME composites
prepared successfully by standard ceramic method.
The XRD pattern shows presence of both ferrite and
ferroelectric phases. The intensity and number of
ferroelectric peaks are observed to increases with
increase in ferroelectric content in the composites.
SEM image shows the grain formation. The ME
voltage coefficient also increases with increase in
ferroelectric content. The maximum value of the ME
voltage coefficient is 257 mv/cm/Oe observed for
composite with x=0.8
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