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Journal of the European Ceramic Society 32 (2012) 3325–3337

Preparation and magnetoelectric properties of NiFe2O4–PZT composites

obtained in-situ by gel-combustion method
Cristina Elena Ciomaga a,∗ , Mirela Airimioaei b , Valentin Nica a , Luminita M. Hrib a ,
Ovidiu F. Caltun a , Alexandra R. Iordan b , Carmen Galassi c , Liliana Mitoseriu a,∗ ,
Mircea N. Palamaru b
aFaculty of Physics, Al. I. Cuza University, Iasi 700506, Romania
b Faculty of Chemistry, Al. I. Cuza University, Iasi 700506, Romania
c CNR-ISTEC, Via Granarolo no. 64, I-48018, Faenza, Italy

Received 20 September 2011; received in revised form 30 March 2012; accepted 30 March 2012
Available online 8 May 2012

Abstract
Magnetoelectric composites of xNiFe2 O4 –(1 − x)Pb(Zr,Ti)O3 with x = 2, 5, 10, 20, 30% were prepared by citrate–nitrate combustion using PZT-
based template powders. In order to ensure a better connectivity of dissimilar phases, we have used chemical methods for preparation in situ
composites, followed by adequate sintering procedure. The structural, microstructural and functional properties of di-phase magnetoelectric
composites of NiFe2 O4 –PZT are reported. The XRD analysis is demonstrating the synthesis of pure ferrite phase directly on the ferroelectric
templates. An excellent mixing was obtained in the composite powders, as proved by a detailed SEM analysis.
The magnetic and dielectric behaviors of the ceramic composites vary with the ratio of the two phases. The dielectric behavior is greatly
influenced by the magnetic phase. The magnetoelectric (ME) coefficient was measured as a function of applied DC magnetic field. The maximum
ME coefficient (dE/dH) varies from 0.0011 mV/(cm Oe) to 0.5 mV/(cm Oe) with increasing of NF addition.
© 2012 Elsevier Ltd. All rights reserved.

Keywords: Sol–gel processing; Ferrites; PZT; Dielectric properties; Magnetic properties

1. Introduction properties, not existing in individual components are envisaged,

The composites are artificial systems containing at least two
phases with different physical and chemical properties separated
at mesoscopic level in the final product, which are attracting an
increasing interest in view of various applications. Their proper-
ties are determined by the number, type and volume ratio of the
phases, as well as by the individual properties, degree of inter-
connectivity and interface properties. The composite is formed
by the filler embedded into a matrix (ceramic, polymer, metallic,
etc.).1–3 While the structural composites were largely used since
long time ago in applications using their superior performances
(mainly mechanic ones)3 , the “electronic composites” are smart
materials in which better electromagnetic performance and new
∗ Corresponding authors. Tel.: +40 232201102x2406; fax: +40 232201205.
E-mail addresses: cristina.ciomaga@uaic.ro, CRISFEDOR@yahoo.com
(C.E. Ciomaga), lmtsr@uaic.ro (L. Mitoseriu).
make them to be used in the microelectronic industry.4 The
design and preparation of composite materials are realized also
in the view of increasing the degree of multifunctionality, the
final aim being a higher degree of miniaturization in devices for
microelectronics and micromechanics.
The functional properties of composites are derived both
from the constituents’ properties as from their reciprocal inter-
actions that might be: (i) sum property, in which a function is
the weighted sum of the individual contributions, (ii) combina-
torial property, when for specific circumstances, the amplitude
of the property is higher in the composite than for individual
components; (iii) product property, indicating effects absent
in the individual components and present in the composite,
as result of a kind of coupling between the components.1–3
The last ones are the most interesting because by acting on
the microstructures and interfaces, radically new properties can
be induced. Combination of two phases, such as a combina-
tion of magnetostrictive and ferroelectric (thus, piezoelectric)

0955-2219/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
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3326 C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337
phases, can yield a desirable magnetoelectric (ME) property,
in spite the individual components do not show it. An electric
field will induce in the ferro-piezoelectric phase a deformation
that will be transmitted to the magnetostrictive component giv-
ing rise to a change of its magnetic properties, so that finally
an electric field causes a change in the magnetic state, i.e. ME
coupling. The ME effect is realized in composites based on
the concept of product property.5 In order to realize compos-
ites with radically new properties (for example the transition
dielectric-conductor) and exceptional characteristics in compar-
ison to those of the individual components, the investigation
of functional properties and the understanding of the intrin-
sic/extrinsic contribution to the properties are presently of high
interest.
In spite of a large number of recent publications referring to
composite systems, there are many problems of chemical, struc-
tural and thermodynamic compatibility of the components. In
order to get diphase composites with high spatial homogeneity,
with a specific type of interconnectivity, clean interfaces, high
density in the view of a good interphase mechanical coupling
and superior electrical properties the preparation routes must
be carefully controlled; for example, in the case of MEs, the
coupling between the magnetic and ferroelectric phases are real-
ized by piezoelectric-magnetostriction effects, which imposes
structural compatibility of the components to reduce internal
stresses and the absence of porosity at the interfaces between
the phases. Consequently, the complex problems of the multi-
functional diphase composites with ME coupling is far to be
solved and their investigation is still of high interest.
Lead zirconate titanate Pb(Zr1−x Tix )O3 solid solution
belongs to the ferroelectric perovskites family with formula
ABO3 with Ti4+ and Zr4+ ions randomly occupying the B
positions, with excellent electromechanical, dielectric and pyro-
electric characteristics that are strongly dependent on the
stoichiometry. The NiFe2 O4 (NF) has an invers spinel struc-
ture and was chosen in order to introduce large resistivity, high
piezomagnetic coefficient, low anisotropy and high initial per-
meability, which are very important and one of the prerequisites
to increase the efficiency of ME effect.
Different methods have been used to synthesize the
ME di-phase ceramic composites formed of ferrites such
as MnFe1.8 Cr0.2 O4 , CuFe2 O4 , CoFe2 O4 , NiFe2 O4 or
Ni0.5 Co0.5 Fe2 O4 and BaTiO3 , Pb(Zr,Ti)O3 ferroelectric
or Ba0.8 Pb0.2 TiO3 relaxor.
In the large majority of publications reporting data on com-
posite ceramics the conventional sintering technique was using
for producing the composite because of cost effectiveness, ease
of fabrication and better control of the process parameters. The
powders of magnetic oxides (e.g. ferrites) and piezoelectric
ceramics are mixed firstly together, and then the mixed pow-
ders are pressed into green bulks followed by sintering at high
temperature.6–8 The maximum values of the ME output for the
compositions prepared by mixing oxides route was found to be
around 200–300 ␮V cm−1 Oe−1 . The reported dielectric con-
stant and losses present a frequency-dispersion characterized
by a strong decrease of permittivity from thousands to ∼300
when frequency is ranging from Hz to MHz, with tangent losses
>1 for f < 10 kHz and tangent losses >10 at f < 1 kHz at room
temperature.6,7
Recently, in order to obtaining the ME ceramic composites
with high density and purity, hot pressing and spark plasma
sintering SPS techniques have been employed to replace the
conventional sintering. Hot-pressed and SPS samples exhibited
a large improvement in the ME voltage coefficient, as compared
to the conventionally sintered samples.9
Several wet chemical methods, such as the hydrothermal
method, co-precipitation process, and sol–gel technique, have
been developed for the synthesis of oxide ceramic powders to
improve their properties. Auto-combustion synthesis method
attracted considerable attention in fabricating homogeneous
and de-agglomerated fine ceramic powder. Availability of inex-
pensive precursors, simple calculations, eases optimization
of process parameters proved to be advantageous in auto-
combustion synthesis.
Di-phase ceramic composites as
0.50BaTiO3 –0.50Ni0.5 Zn0.5 Fe2 O4 with limited reaction at
interfaces, higher density and better dielectric properties
(tan δ < 5% and εr ∼300–800 for f > 104 Hz at room tempera-
ture) were obtained by co-precipitation of Fe, Ni, Zn salts in
solutions containing BaTiO3 powders, than that obtained by
mixing BaTiO3 and Ni0.5 Zn0.5 Fe2 O4 powders.10
The in situ sol–gel method followed by a conventional sinter-
ing, used for obtaining the ME ceramic composites, have gained
attention because ensures a better mixing and much more dense,
well-developed and homogeneous microstructures, leading to
serious reduction of the dielectric losses. The composition and
purity of the two constituent phases is maintained after sintering
at low temperature.
In the present work, we have studied the struc-
tural, microstructural and functional properties of the
xNiFe2 O4 –(1 − x)PZT with x = 2, 5, 10, 20, 30 wt% and Z/T ratio
47/53 magnetoelectric composites prepared in situ by sol–gel
method. In the following the original results are presented and
discussed in detail.
2. Sample preparation and experimental details
The powder precursors of xNiFe2 O4 and
(1 − x)Pb(Zr0.47 Ti0.53 )O3 with various x concentration were
synthesized by in situ processing based on sol–gel method. We
have started with Pb(Zr0.47 Ti0.53 )O3 (PZT) (ρth = 7.952 g/cm3 )
template powders which were firstly prepared by a conventional
solid state reaction method by using reagent grade PbO
(Aldrich 211907, purity 99.9%), ZrO2 (MEL SC101), and TiO2
(Degussa P25). The precursors were ball milled with zirconia
milling media in water for 48 h, freeze dried, sieved to 250 ␮m
and calcined at 800 ◦ C/4 h. The calcined powder was wet milled
in ethanol (100 h), then dried and sieved. The mean diameter
(d50 ) of the PZT calcined powder was 0.71 ␮m and the specific
surface area was 2.67 m2 /g.
NiFe2 O4 nanoparticles (NF) and xNF–(1 − x)PZT (x = 2, 5,
10, 20, 30%, w/w) nanocomposite were synthesized by auto-
combustion method.11,12 All chemicals are analytical grade
and used without further purification. Ni(NO3 )2 ·6H2 O and
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C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337
Fe(NO3 )3 ·9H2 O solutions were mixed and after the nitrate solu-
tion obtained was mixed with aqueous citric acid (C6 H8 O7 )
under magnetic stirring.
Citric acid was used with two important roles: as fuel for the
combustion reaction and as a chelating agent to form complexes
with metal ions, preventing the precipitation of hydroxylated
compounds.13
The Ni:Fe mole ratio was 1:2 and the molar ratio
NiFe2 O4 :citric acid was 1:3. The as-prepared PZT powder was
dispersed in the nitrate/citric acid solution by magnetic stirring.
The suspension of PZT–(nitrate/citric acid solution) was
heated at 80 ◦ C under constant stirring until the water evap-
oration was completed and a viscous gel was obtained. After
formation of gel, the temperature was increased gradually to
∼350 ◦ C. A large amount of gases (CO2 , H2 O, N2 ) was released
and the auto-combustion occurred. The combustion reaction was
completed within a few seconds and it was formed a fine powder.
This was completely crushed and powdered. The as-combusted
brown powders were calcined at 500 ◦ C for 8 h resulting in fine
composite powders of xNF–(1 − x)PZT (x = 2, 5, 10, 20, 30%,
w/w).
The composite powders were ground, and then cold iso-
statically pressed at 300 MPa into discs of 30 mm diameter
(green bodies). The samples were sintered at 1200 ◦ C/1 h, in Pb
atmosphere maintained by a PbZrO3 source in a closed Al2 O3
crucible. After sintering the ceramic pellets were polished to
remove the surface layers. In order to measure the dielectric
properties selected sintered and ground samples were screen
printed with silver electrodes, fired at 750 ◦ C and finally poled
into silicon oil at 120 ◦ C, under a DC field of 3 kV/mm for
40 min.
XRD patterns of the powders and ceramic composites were
recorded using Shimadzu LabX 6000 diffractometer (CuK␣
radiation, λ = 0.15406 nm). The samples mounted in reflection
mode were analyzed in ambient atmosphere with scanning rate
of 0.02◦ and counting time of 1 s/step over the 2θ = 20–80◦ range.
The average crystallite size of the particles for each sample
was calculated from the full width at half maximum (FWHM)
of the XRD peak profile using a Lorentzian convolution. The
error for the determination of crystallite size affects approx-
imately by 2% the calculated values. The lattice parameters
were determined using the linear multiple regressions based
on the Least Squares procedure with a Si standard powder
correction.
The phase formation of the NiFe2 O4 ferrite onto the PZT
ferroelectric templates was checked by using a Fourier transform
infrared spectra (FT-IR), recorded in the range 4000–400 cm−1
with 2 cm−1 resolution using a Bruker FTIR spectrophotometer
TENSORTM 27-type with an anvil ATR cell.
Scanning electron microscopy (SEM) (Hitachi Instrument)
was used to obtain the microstructure and phase compositions
of the ceramic composites.
The electrical characterization was performed on the disk
shaped samples following the standard IEEE 176-1987. The
elasto-piezo-dielectric constants were calculated from the val-
ues of resonance and antiresonance frequencies of the planar
mode.
3327
The dielectric properties vs. frequency at the
20 Hz–2 × 106 Hz frequency domain in the range temper-
ature of 25–250 ◦ C were determined by performing complex
impedance measurements with an impedance bridge type
Agilent E4980A Precision LCR Meter.
In order to determine the M(H) hysteresis loops in the
range 0–1.4 T (14,000 Oe), a MicroMagTM magnetometer VSM
(Vibrating Sample Magnetometer) model 3900 system from
Princeton Measurements Co. was used. The magnetoelectric
properties were studied by measuring the induced electric poten-
tial (Vin ) at a small AC magnetic field superimposed (Hac ) onto
a DC magnetic bias (Hdc ), both of which were parallel to the
thickness direction of the pellets. The AC field was produced by
a Helmholtz coil (470 turns with a diameter of 80 mm), which
was driven by the reference signal from lock-in. The amplitude
of the AC and DC field was measured by means of a gaussmeter
(Model 455 DSP Gaussmeter). The ME signals was measured
with a lock-in amplifier (Model SR830 DSP Lock-In Amplifier).
Data acquisition was performed by computer using a LabView
interference program.
3. Results and discussions
3.1. Phase identification
The X-ray diffraction measurements for xNF–(1 − x)PZT
ceramics composites with x = 2, 5, 10, 20, 30%, at room temper-
ature are shown in Fig. 1a and b. The Bragg reflections match
the reported values of tetragonal PZT and face-centered cubic
nickel ferrite systems with the space group P4mm and Fd3m,
respectively (Powder Diffraction Files, cards no 50-0346 and
74-2081, respectively). Pure diphase powder composites with
a good crystallinity were obtained after the calcination steps
(Fig. 1a).
Fig. 1b indicates the presence of NiFe2 O4 spinel phase and
maintenance of Pb(Zr,Ti)O3 ferroelectric phase. It confirms
the formation of diphase ceramic composites after sintering at
1200 ◦ C/1 h and the lack of secondary phases at interfaces. The
tiny peak around 2θ ∼ 28◦ (Fig. 1b) existing in the samples with
low concentration of Ni ferrite, (for x = 2 and 5%), could corre-
spond to ZrO2 and may come from the starting material ZrO2−x .
The (3 1 1) peak intensity of the nickel ferrite phase increases
with increasing the NF content in composites.
From Fig. 1a we can observe that the peak (1 1 0) belonging
to the PZT does not change even in composites, while the posi-
tion of the peaks (1 1 1), (2 0 0), (2 1 1) is slightly splitted. This
indicates tetragonal structure of the PZT ferroelectric phase.
The lattice parameters of the ceramic composites are detailed
in Table 1. The XRD patterns reveal that there is no chemical
reaction between PZT and NF. Thus, the in situ processing gives
a feasible method in order to obtain highly crystalline ceramic
composites which leads to multifunctional properties.
3.2. FTIR
The IR absorption spectroscopy was used to monitor the syn-
thesis of these samples. For this purpose, spectra were recorded
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3328 C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337

Fig. 1. XRD patterns of xNF–(1 − x)PZT with x = 2, 5, 10, 20, 30%: (a) calcined
powders at 500 ◦ C for 8 h; (b) sintered ceramics at 1200 ◦ C for 1 h with various
compositions.

for samples thermally treated at 200 ◦ C and 1200 ◦ C (Fig. 2a

and b).
The absorption band at ∼3284 cm−1 in the spectra of samples
thermally treated at 200 ◦ C (Fig. 2a) was associated to O H
vibration. Peaks localized at 1567 cm−1 and 1390 cm−1 can be
assigned to the stretching vibration of carboxylate and nitrate
groups, indicating that the self-propagating high temperature
synthesis process is incomplete.14
We can also see that the spectra of these compounds present
two absorption bands at ∼756 cm−1 and ∼528 cm−1 that can
be attributed to the stretching vibration of the M O bonds,
characteristic for the parent PZT and ferrite phases.
Fig. 2. IR spectra of the xNF–(1 − x)PZT composites after thermal treatment at:
(a) 200 ◦ C and (b) 1200 ◦ C/1 h.
For the samples sintered at 1200 ◦ C/1 h (Fig. 2b) only the
absorption bands characteristic for the stretching vibrations of
the M O bonds from two parent phases – NF and PZT are
present in the spectra. Thus the shoulders from ∼583 cm−1 to
∼670 cm−1 may be associated with the stretching vibrations of
Ti O bonds belonging to PZT phase.15,16 The broader absorp-
tion band from 487 cm−1 and the shoulder at ∼751 cm−1 are

Table 1
Average crystallite size and lattice parameters of the ferroelectric phase from composite systems.
xNF–(1 − x)PZT ceramic x = 2% x = 5% x = 10% x = 20% x = 30%
samples

Crystallite size (nm) 22 23 21 20 17

Lattice parameters a (Å) 4.0173 ± 0.0020 4.0221 ± 0.0024 4.0313 ± 0.0063 4.0303 ± 0.0031 4.0577 ± 0.0050
ferroelectric phase
Lattice parameters c (Å) 4.1279 ± 0.0024 4.1244 ± 0.0029 4.1284 ± 0.0021 4.1287 ± 0.0023 4.1054 ± 0.0049
ferroelectric phase
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C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337 3329

Fig. 3. SEM micrograph of xNF–(1 − x)PZT ceramic composites for x = 30%
NiFe2 O4 .
associated with stretching modes (Zr O stretch) in the ZrO6
octahedron of the PZT structure.17
The nickel ferrite has an inverse spinel structure, the Fe3+
ions being positioned on the tetrahedral sites and also on the
octahedral ones, while the Ni2+ ions are placed only in octahe-
dral sites. In the absorption spectra of the NF ferrite with cubic
spinel structure and in the spectra of xNF–(1 − x)PZT composite
materials thermally treated at 1200 ◦ C/1 h, an absorption band
at ∼529 cm−1 , characteristic of intrinsic stretching vibrations
of the (Mtetra ↔ O) bonds from tetrahedral units, is found. Usu-
ally the IR spectra of the ferrites present a smaller adsorption
band attributed to the stretching vibrations of the (Mocta ↔ O)
from the octahedral units, situated at wave numbers smaller than
400 cm−1 .
3.3. SEM analysis
The SEM micrograph of the xNF–(1 − x)PZT ceramic com-
posites with x = 30% magnetic phase, sintered at 1200 ◦ C/1 h
are shown in Fig. 3. The SEM image of the polished surface
demonstrate that dense and homogeneous magnetoelectric com-
posites were obtained with a good dispersion of the Ni ferrite
spinel phase (black color for NF) in PZT ferroelectric phase
matrix (grey color for PZT). The average grain size of the NF
grains becomes larger at increasing content of NF. Thus, the
sol–gel method influences the degree of connectivity of the two
phases and this can yield to some differences in the functional
properties.
Fig. 4. Variation of the piezoelectric properties of composites with NF content.
composition with low concentration of Ni ferrite of 2% is
52 × 10−12 m/V, but with increasing the NF addition, the d33
of the composites drops rapidly to 18 × 10−12 m/V for the com-
position with 30% NF content. The increasing ferrite content
leads to the reduction of the piezoelectric coefficient as a result
of the much smaller resistance of the ferrite in comparison to
the PZT. The piezoelectric voltage constant, g33 , presents also a
decrease at increasing content of Ni ferrites in the composite.
3.5. Magnetic properties
The magnetic properties of the xNF–(1 − x)PZT ceramic
composites with x = 2, 5, 10, 20, 30% are presented in Fig. 5 and
proved the ferromagnetic nature of the materials. These prop-
erties are a consequence of the “sum property” and interface
effects.
If in case of NiFe2 O4 the saturation magnetization was found
to be ∼45 emu/g, for the xNF–(1 − x)PZT magnetoelectric com-
posites, the saturation magnetization decrease from 13.63 emu/g
for x = 30% to 0.33 emu/g for x = 2% Ni ferrite phase. The coerci-
tive field (Hc ) for all the composite samples is larger than
that for the pure NiFe2 O4 phase, Hc ∼ 200 Oe for x = 2% and
Hc ∼ 11.5 Oe for NF, as the results of mixing of ferrimagnetic

3.4. Piezoelectric characterization

The piezoelectric constants of PZT and the magnetostriction

of NF are essential parameters that determine the mag-
netoelectric effect. The piezoelectric constant (d33 ) of the
xNF–(1 − x)PZT composites decreases with the decrease of
concentration of pure PZT ferroelectric phase, similar to the
dielectric constant.
Fig. 4 shows the piezoelectric constant d33 of the compos-
ites with various NF contents. The d33 value of the ceramic Fig. 5. Magnetic hysteresis loops of the xNF–(1 − x)PZT ceramic composites.
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3330 C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337

Fig. 6. Dielectric dispersion at various temperatures in the xNF–(1 − x)PZT ceramic composite with x = 2, 5, 10, 20, 30% of NF: (a–e) real and (f–j) imaginary part
of the dielectric constant.
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C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337
Table 2
Piezoelectric characteristics of xNF–(1 − x)PZT ceramic composites.
xNF–(1 − x)PZT ρ (g/cm3 ) ρ (%) d31 (10−12 m/V)
x = 2% 7.58 95.9 19.8
x = 5% 7.61 97.3 18.6
x = 10% 7.40 96.7 22.8
x = 20% 7.13 95.7 8.6
x = 30% 6.81 95.0 7.4
phase with PZT phase. As in the pure Ni ferrite, the sponta-
neous magnetization in xNF–(1 − x)PZT ceramic composites
originates from the unbalanced antiparallel spins (ferrimagnetic
character), which can give rise to the mentioned small coerciv-
ities and saturation fields.
3.6. Dielectric properties
3.6.1. Dielectric constant characterization
The dielectric constant of xNF–(1 − x)PZT ceramic com-
posites with x = 2, 5, 10, 20, 30% were checked at different
temperatures 25–250 ◦ C as a function of frequency, in the range
of 100 Hz to 2 MHz, and are presented in Fig. 6. As expected,
the dielectric constant of the xNF–(1 − x)PZT system compos-
ites decreases with increasing the ferrite phase addition as a
consequence of the sum property, similar to the piezoelectric
properties (Table 2). From Fig. 6a–e can be observed that the
real parts of dielectric permittivity (ε (f)) are strongly frequency-
dependent and their values dramatically increase with reducing
frequency, arriving to ε ≈ 4 × 104 , at f = 100 Hz for x = 2% and
ε ≈ 1 × 106 , at f = 100 Hz for x = 30% of Ni ferrite at T = 250 ◦ C
(Fig. 6a–e). The increasing of dielectric constant with increas-
ing of temperature is a thermally activated process, which results
in an increase of dielectric polarization. The dielectric constant
is a combined effect of dipolar, electronic, ionic and interfacial
polarizations. At lower frequency, the dipolar and interfacial
polarizations contribute significantly to the dielectric constant
and at higher frequency only the electronic polarization became
significant. Hence, it increases at a higher value for 100 Hz
as compared to 10 kHz or 2 MHz. The dielectric behavior in
composites can also be explained on the basis of the polariza-
tion mechanism in ferrites because conduction beyond phase
percolation limits is due to ferrite.18 In ferrites, the rotational
dispalcement of Fe3+ ↔ Fe2+ dipoles results in orientation polar-
ization that may be visualized as an exchange of electrons
between the ions, the dipoles align themselves with the alternat-
ing field. The transport properties such as electrical conductivity
and dielectric dispersion of ferrite are mainly due to the exchange
mechanism of charges among the ions situated at crystallograph-
ically equivalent sites.19
The frequency dependence of the imaginary part of per-
mittivity (ε (f)) presents a few characteristic of dielectric and
conductivity relaxations in the investigated frequency range
100 Hz–2 MHz: (i) an increasing of the imaginary part with
increasing temperature at low frequency, mainly due to the
interfacial polarization (Maxwell–Wagner relaxation phenom-
ena) and also to the heterogeneity in the samples20 and (ii) a
3331
d33 (10−12 m/V) g31 (10−3 m/N) g33 (10−3 m/N)
52 2.89 7.63
37 2.79 5.61
49 3.87 8.36
23 2.13 5.61
18 1.89 4.65
frequency dispersion in the frequency range 103 –106 Hz, for
all the compositions, which are manifests in a broad Debye-
type maximum with a shift to higher frequency (Fig. 6f–j).26
The Maxwell–Wagner relaxation mechanism is associated with
uncompensated surface charges at interfaces inside the com-
posite ceramics. Such phenomenon is determined by the local
inhomogeneity of sample caused by a high number of charged
defects located inside the ceramic grains and at the grain bound-
aries, which produce local charge unbalance in the sample
volume. These charges are created by external (contacts) or inter-
nal (grain boundaries, domain walls, inhomogeneities) boundary
layers and induce local conductivity variation. Due to the local
compositional inhomogeneity and enhanced fluctuations of the
local electrical properties in the ferroelectric-magnetic compos-
ite systems, the barriers for the thermally activated dielectric
relaxations and conductivity are much lowered, so that they
give unavoidable contributions even at room temperature. As
discussed in detail in Refs. 21–23, such extrinsic phenomena
cause the peculiar dielectric properties observed in all the mag-
netoelectric composites reported in the literature.
Analyzing the frequency dependence of permittivity at vari-
ous temperatures in the range 25–250 ◦ C (Figs. 6a–j), it can be
clearly seen that a typical thermally activated dispersion domi-
nates the dielectric response of the xNF–(1 − x)PZT system.
Similar dielectric properties were reported for PZT-Ni fer-
rite prepared by spark plasma sintering,24 in PZT-(Ni,Zn) ferrite
ceramics prepared by powder-in-sol precursor hybrid processing
route25 and other composite systems.26,27
Dielectric losses are proportional to the dielectric imaginary
part of the permittivity (ε ) in the studied system. Thus, the
dielectric losses (tan δ) are below 0.16 for all the ceramic com-
positions and increase with NF amount.
The impedance spectroscopy plots at room temperature are
shown in Fig. 7. It can be seen that impedance spectra for the
compositions x = 2, 5, 10% exhibit a single semicircular arcs,
demonstrating a good homogeneity of the dielectric and con-
ductive properties. For the compositions with low concentration
of magnetic phase, x = 2, 5, 10%, the influence of ferrite phase
is weak, and the NF phase in small quantity is only discontinu-
ously imbedded in the PZT ferroelectric matrix. The presence of
the single semicircular arcs, whose pattern changes with compo-
sition, indicate a modification of the resistance/reactance ratio
when increasing the ferrite addition x. The composition with
x = 20, 30% addition of Ni ferrite show more than one component
in the complex impedance plot demonstrating that the ceramic
samples present some degree of local electrical heterogeneity
even if they are homogeneous from structural and compositional
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3332 C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337
Fig. 7. Complex impedance spectroscopy for xNF–(1 − x)PZT composites with
x = 2, 5, 10, 20, 30% at room temperature.
point of view. Similar phenomenon was reported on ferroelectric
BaTiO3 and ferrite (Ni0.3 Zn0.7 )Fe2.1 O4 , synthesized via solid
state reaction route.20
3.6.2. Dielectric modulus characterization
A better representation for understanding if more than one
relaxation process is involved in the dielectric response of the
composite ceramics is given by the formalism of the dielectric
modulus (M*), defined as28,29 :
M ∗ (f ) = M  (f ) + iM  (f ),
where:
ε (f ) ε (f )
M  (f ) = and M  (f ) =
ε 2 (f ) + ε 2 (f ) ε 2 (f ) + ε 2 (f )
The frequency dependence of the complex modulus has been
investigated, taking into account the complex dielectric constant
(ε*(f) = 1/M*(f)) (Fig. 8a–j). Figs. 8a–e and f–j show the varia-
tion of the real and imaginary part of the complex modulus with
frequency of xNF–(1 − x)PZT ceramic composites.
From Fig. 8a–e, it is observed that M (f) increases with fre-
quency up to 10 kHz and reaches a rather constant value at higher
frequency, while ε , as expected, decreases quickly to an almost
constant value.
The variation of M (f) as a function of frequency pro-
vides, also, useful information concerning the charge transport
mechanism such as electrical transport and conductivity relax-
ation and has been successfully used to distinguish localized
dielectric relaxation processes from long-range conductivity
and short/long range polaron hoping in composite materials
(Fig. 8f–j). A conductivity relaxation is indicated by the pres-
ence of a peak in M (f) spectra and no peak would appear in
corresponding plot ε (f), while the dielectric relaxation gives
maxima both in the ε (f) and M (f). In the studied frequency
range M present maximum as in the frequency dependence of
ε (f), for all compositions, indicating the dielectric relaxation
processes.
Two types of dispersion phenomena are determined for the
composite samples: (i) one at frequencies below 10 kHz, a
pronounced maximum of M which shifts toward higher fre-
quencies with increasing temperatures, and (ii) a rather constant
values of M up to 1 kHz with a decreasing with increasing
of frequency range. The fact that only at low frequency both
the imaginary part of permittivity and dielectric modulus show
maxima indicates a Maxwell–Wagner dispersion in this fre-
quency range, while at higher frequencies both in the range of
102 –104 Hz and above 105 Hz, combined dielectric relaxation
and AC-conductivity relaxations are most probably responsi-
ble with the observed dielectric response. In case of the sample
composite with x = 30% the frequency dependence of imaginary
part of dielectric modulus, M , presents two well defined con-
voluted components. Both of them are thermally activated: the
maxima are shifted toward higher frequencies as the temperature
is increasing.
Both low and high-frequency observed relaxations in
xNF–(1 − x)PZT ceramic composites are thermally activated
phenomena, for which the characteristic activation energy can
be deduced from the maximum of the imaginary part of the
dielectric modulus by the Arrhenius law:
 
1 Ea
τM = = τ0 exp , (3)
2πfM kB T
where fM is maximum peak position for the high frequency
relaxation, kB is the Boltzmann constant, τ 0 is a pre-exponential
factor, and Ea is the activation energy. The values of the pre-
exponential factor and activation energies corresponding to
(1)
ferroelectric region are given in Table 3. These values of the acti-
vation energies obtained by us are in the range of ones reported
in other composite materials.30–32
(2)
3.6.3. AC-conductivity characterization
The variation of the AC conductivity as a function of fre-
quency for a few temperatures is shown in Fig. 9a–e. For all the
compositions the conductivity (σ) increases with the increas-
ing of frequency, indicating also a thermally activated process.
We can identified two distinct frequency regions in the AC-
conductivity dependence (e.g. Fig. 9a–e): (i) a low-frequency
region for which the conductivity corresponding to low tem-
peratures (T < 150 ◦ C) tends to an almost zero conduction (ii) a
region at high frequencies above 103 Hz with a large increase
of conductivity for all temperatures. The increasing in tempera-
ture at low frequency confirms the Maxwell–Wagner relaxation
present in all studied ceramic composites. The linearity of AC
conductivity plots (Fig. 9a–e), at lower temperature, indicates
that the conduction occurs by hopping of small polaron type of
charge carriers among the localized states.
As we have mention before an important contribution to the
conduction mechanism in the ceramic samples is explained on
the basis of hopping of charge carriers between the Fe2+ and
Fe3+ ions on the octahedral site from ferrite phase, and with
addition of this one. The increase in frequency enhances the
hopping frequency of charge carriers, resulting in an increase in
the conduction process, thereby decreasing the resistivity. The
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C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337 3333

Fig. 8. Frequency dependence of the complex dielectric modulus at a few temperatures in the range of 25–250 ◦ C: (a–e) real part (M ) and (f–j) imaginary part (M )
for xNF–(1 − x)PZT ceramic composites with x = 2, 5, 10, 20, 30%.
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3334 C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337

Table 3
Activation energies in ferroelectric region for xNF–(1 − x)PZT ceramic composites with x = 2, 5, 10, 20 and 30%.
xNF–(1 − x)PZT ceramic samples T (◦ C) τ 0 (s) Ea (eV) from M (f)

25–120 3.7 × 10−8 0.024

x = 2%
160––250 8.7 × 10−8 0.168
25–140 1.4 × 10−6 0.026
x = 5%
160–250 2.9 × 10−8 0.15
x = 10% 160–250 3.7 × 10−8 0.147
x = 20% 160–250 3.3 × 10−8 0.13
120–240 3.3 × 10−8 0.047
x = 30%
160–250 2.6 × 10−8 0.12

Fig. 9. Variation of AC conductivity with frequency for xNF–(1 − x)PZT composites at a few temperatures.

results are similar to that observed by other authors for different The ME output of the present xNF–(1 − x)PZT ceramic com-
composites.28,31,33,34 posites is studied as a function of the addition of Ni ferrite and
of DC magnetic field (Hdc ) (Fig. 10). The ME coefficient (α) is
calculated with the following formula35 :
3.7. Magnetoelectric effect

In the ME composites, the static ME voltage coefficient

depends on the mechanical coupling, resistivity and content of V
α= (4)
the constituent phases. Hac × d
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C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337 3335

Table 4
Comparative study of dielectric properties and magnetoelectric coefficient of composite systems.
Reference ME composite Preparation route At room temperature

ε at 1 kHz tan δ Ea (eV) dE/dH

(mV/(cm Oe))

20 BaTiO3 –(Ni0.3 Zn0.7 )Fe2.1 O4 Solid state 10,000 at 100 Hz 0.8

x = 0.3
26 (x)Ni0.9 Zn0.1 Fe2 O4 + (1 − x)PZT Solid state, 512 at 1 kHz 0.3 0.082 0.68
x = 0.30 double-sintering
method
25 Ni0.5 Zn0.5 Fe2 O4 –PbZr0.53 Ti0.47 O3 Solid state 740 0.025
x = 25%
31 NiFe2 O4 + Pb0.93 La0.07 (Zr0.60 Ti0.40 )O3 Solid state 720 0.5 0.035
x = 0.30
40 (y)Ni0.5 Zn0.3 Co0.2 Fe2 O4 +(1 − y)BaTiO3 Solid state 0.54 0.43
x = 0.30
38 (x)Ni0.5Zn0.5Fe2 O4 +(1 − x)BPZT Solid state 700 0.5 0.69
x = 0.30
12 CoFe2 O4 –Pb(Zr,Ti)O3 Sol–gel 187 1.25
x = 0.30
27 Ni0.2 Co0.2 Fe2 O4 –PbZr0.8 Ti0.2 O3 Solid state 680 0.05 0.39 0.76
x = 0.30
30 xNi0.8 Zn0.2 Fe2 O4 + (1 − x)Pb0.93 La0.07 (Zr0.60 Ti0.40 )O3 Solid state 650 0.55 0.05 4.64
x = 0.30
32 Pb(Zr0.53 Ti0.47 )O3 –(Ni0.5 Zn0.5 )Fe2 O4 Modified hybrid 190 at 100 ◦ C 0.7 0.28
process
Present study xNF–(1 − x)PZT Sol–gel 600 0.16 0.0470.12 0.5
x = 0.30

saturation, the magnetostriction and the mechanical strain thus

Fig. 10. Variation of ME coefficient as a function of static magnetic field for
xNF–(1 − x)PZT ceramic composites.
where V is the voltage generated due to the magnetoelectric
effect, Hac is the amplitude of the sinusoidal magnetic field and
d is the thickness of the sample.
The α values shown in Fig. 10 are obtained after subtraction of
α value at Hdc = 0. From this figure, it is observed that α increases
up to 500 Oe, attains a maximum value and then decreases with
further increase of Hdc . This behavior was observed also by
other researchers who studied magnetoelectric composites with
nickel ferrite.36,37 The explanation given for the variation of ME
coefficient with the applied DC magnetic field was as follow:
at a certain value of Hdc magnetic field, the magnetostriction
coefficient of the ferrite phase reaches to saturation. Beyond
produced would also generate a constant electric field in the
piezoelectric phase which leads to the decrease of the ME coef-
ficient values.
The increase of the magnetoelectric signal with ferrite
amount could be attributed to the increase of the mechanical
deformation in the magnetoestrictive phase. The maximum α of
∼0.5 mV/(cm Oe) observed in the composition with x = 30% of
ferrite, may be originated, also, from more uniform distribution
of ferrite and PZT phase. The same values of ME coeffi-
cient were reported in literature on Ni0.5 Zn0.5 Fe2 O4 –BPZT
composites,38 CoFe2 O4 –BaTiO3 and CoMn0.2 Fe1.8 O4 –BaTiO3
ceramic composites.26,39,40
The synthesis method for obtaining the magnetoelectric com-
posites, the connectivity pattern of the component phases in the
systems are of important for the electrical properties such as
dielectric constant (ε ), tangent losses (tan δ), activation energy
(Ea (eV)), and hence the ME constant (dE/dH). Table 4 presents a
comparative study in a synthetic way of the values obtained over
time on various ME composites, together with their preparation
routes and sintering conditions.
4. Conclusions
In summary, we have studied the xNF–(1 − x)PZT magnetic-
ferroelectric ceramic composites with different compositions
(x = 2, 5, 10, 20, 30%) prepared in situ by sol–gel method
using Pb(Zr,Ti)O3 template powders obtained by mixed
oxide method. The XRD patterns confirmed the successful
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3336 C.E. Ciomaga et al. / Journal of the European Ceramic Society 32 (2012) 3325–3337
formation of a di-phase composite for each composition, formed
by the spinel NiFe2 O4 and Pb(Zr,Ti)O3 perovskite phases in the
nominal proportion. The existence of the two distinct phases
in the xNF–(1 − x)PZT composite systems, the ferrite and the
ferroelectric phase, was confirmed also by SEM analysis.
The magnetic properties measured at room temperature
showed that the saturation magnetization and the remnant mag-
netization of the composites increase with increasing the amount
of Ni ferrite. Dielectric measurements with frequency showed a
decrease of the dielectric constant at increasing ferrite addition
as a consequence of the sum property. The dielectric constant
vs. frequency at room temperature and at a few temperatures
in the range 25–250 ◦ C indicate the dielectric relaxation caus-
ing by space charge effects and Maxwell–Wagner phenomena,
particularly at low frequency and high temperature, and Debye
relaxation in the range of frequency 103 –2 × 106 Hz. Using the
sol–gel method, we have obtained homogeneous microstructure
and a reducing of the dielectric losses.
The complex impedance representation reveals that the com-
positions with x = 2, 5, 10% NF present electrical homogeneity,
while compositions with higher Ni ferrite content show local
electrical inhomogeneity due to the presence of more than one
components. The xNF–(1 − x)PZT ceramic composites are good
candidates for the ME applications, due to the fact that both the
ferroelectric and magnetic phases preserve their basic properties
in the bulk composite form.
The dependence of the ME response of the xNF–(1 − x)PZT
ceramic composites on the applied magnetic fields is dom-
inated by NF addition. The maximum ME coefficient
∼0.5 mV/(cm Oe) is observed for 30% Ni ferrite phase. These
composites have a better sensitivity in the low field range.
Acknowledgements
The financially supported by the Projects: POS-
DRU/89/1.5/S/63663 and by CNCSIS-PCCEID-76 is highly
acknowledged. The authors thank the COST Action MP0904:
“SIMUFER: Single- and Multiphase Ferroics and Multiferroics
with Restricted Geometries” and Mr. C. Capiani (ISTEC) for
the skillful preparation of the samples.
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