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Procedia Materials Science 10 (2015) 168 – 175

2nd International Conference on Nanomaterials and Technologies (CNT 2014)

Microstructural and Electrical Properties of Barium Strontium

Titanate and Nickel Zinc Ferrite Composites
Rutvi J. Pandyaa* , U. S. Joshia and O. F. Caltunb
a
Department of physics, School of science, Gujarat University, Ahmedabad-380009, India
b
Faculty of Physics, Laboratory of Magnetic Materials for Technological Applications (LMAT), Alexandru Ioan Cuza University, Iasi, Romania

Abstract

Structural and electrical properties of oxide composite of two ferroic ternary Ba0.6Sr0.4TiO3 and Ni0.5Zn0.5Fe2O4 were investigated.
Powder x-ray diffraction studies show that the end products, BST possess cubic perovskite structure and NZF possess cubic
spinel structure. A very systematic phase transition between these two phases has been achieved for intermediate doping ranges.
Surface morphology revealed a uniform grain distribution with very low porosity for entire composite series. Real and imaginary
permittivity and loss tangents for all the composites up to 1 MHz frequency range show high dielectric constants and low losses,
respectively. Exceptionally, high dielectric permittivity values were obtained for composite samples as compared to pristine end
products. At lower frequencies, the values of dielectric permittivity were high, because the excitation of bound electrons, lattice
vibration, dipole orientation and space charge polarization are active. At high frequencies, the dielectric permittivity exhibited
frequency independence behavior for entire series. AC conductivities determined from the dielectric data exhibited strong
frequency dependence with a non linear increase with increasing frequencies. The electrical conduction in the system may be
modeled by hopping model.
© 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2015 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review underresponsibility
Peer-review under responsibility of the
of the International
International Conference
Conference on Nanomaterials
on Nanomaterials and Technologies
and Technologies (CNT 2014).
(CNT 2014)

Keywords:Multiferroics, Barium Strontium Titanate,Nickel Zinc Ferrite, Dielectric properties, AC conductivity

* Corresponding author. Tel.: +91-79-26303041; fax: +91-79-26308545.

E-mail address: rutvi.pandya@yahoo.com

2211-8128 © 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the International Conference on Nanomaterials and Technologies (CNT 2014)
doi:10.1016/j.mspro.2015.06.038
 Rutvi J. Pandya et al. / Procedia Materials Science 10 (2015) 168 – 175 169

1. Introduction

Magnetoelectric Multiferroics, defined as simultaneous coexistence of two or more ferroic orders such as
ferroelectricity, ferromagnetism and ferroelasticity is an interesting subject for researcher due to their vast
applications in transducers, actuators, sensors and memory devices [Eerenstein et al. (2006), Gupta et al. (2014),
Lawes and Srinivasan (2011)]. Also the coupling between spin and charge (i.e. magnetoelectric coupling) has made
this subject fascinating and adds the additional degree of freedom in device designing. Limitations of single phase
materials such as weak coupling and their less availability in nature have led the researchers for synthesis of new
composites multiferroics [Hill (2005) and Ce-Wan et al. (2008)]. In order to achieve multiferroicity or
magnetoelectric (ME) coupling in the composites, their electrical properties are as important as their magnetic
properties. Here, two distinct materials exhibiting large ferroelectric and ferromagnetic properties are taken and can
be tuned to achieve the maximum FE and FM properties simultaneously. Here, Ba0.6Sr0.4TiO3 (BST) is a cubic
perovskite selected as a ferroelectric phase and Ni0.5Zn0.5Fe2O4 (NZF) is a spinel ferrite selected as ferromagnetic
phase. BST is well-known for its excellent dielectric properties, large electric field tunability and comparatively low
dielectric loss [Wang et al. (2012) and Ostapchuk (2009)]. Also its Curie temperature is compositional dependent
hence above mentioned properties can be tuned [Bao et al. (2008)]. Ba0.6Sr0.4TiO3 is a best system for room
temperature applications as its Curie temperature remains below the room temperature hence BST remains in the
paraelectric state. Nickel ferrites doped with Zn+2 Jahn–Teller ion have ability to show high ME coupling and
possess compositional dependent high electrical resistivity, strong magnetostriction coefficient and high curie
temperature [Adhlakha et al. (2011)]. In many reports available in the literature on all oxide composite multiferroics,
ME coupling were tried to establish in phase separated composites with poor crystallite qualities. However, it is very
important to synthesis the phase pure composites with high crystalline qualities and then investigating the possible
ME coupling. Moreover, electrical properties of the composites are also need to be investigated in order to
understand the mechanism governing the electrical transport in such systems. In present work, our main objective is
to study the microstructural properties and to enhance the electrical properties of the composites. Here, the
systematic study about the composite (1-x) Ba0.6Sr0.4TiO3+x (Ni0.5Zn0.5Fe2O4) (x=0.0, 0.4, 0.6, 1.0) is carried out and
its microstructural, dielectric properties and AC conductivity are studied.

2. Experimental Details :

Standard solid state reaction route was employed for the synthesis of powdered composites
(1-x) Ba0.6Sr0.4TiO3+x (Ni0.5Zn0.5Fe2O4) (x=0.0, 0.4, 0.6, 1.0). Ba0.6Sr0.4TiO3 was prepared using stoichiometric
amounts of BaCO3, SrCO3 and TiO2 (purity > 99.9%) powders. Ni0.5Zn0.5Fe2O4 was prepared using stoichiometric
amounts of NiO, ZnO and Fe2O3 powders with equivalent purity. These powders were weighted in required
proportions and ground using pestle mortar in a semi wet medium of highly pure acetone. The mixtures with its
constituent phases, x=0.0, 0.4, 0.6, 1.0 were then prepared by grinding the appropriate proportions of BST and NZF
using above mentioned generic formula. Finely ground white to gray and black powders with different compositions
were pressed into cylindrical pellets using polyvinyl alcohol (PVA) as a binder. Finally the pellets were sintered at
1200°C for 24 hours with intermediate grindings. Structural studies were done using powder X-ray diffraction
(XRD, PANalytical Expert Pro) with Cu Kα wavelength. Surface microstructure was studies using scanning electron
microscope (SEM, MIRA II LMH, TESCAN) with Energy Dispersive analysis of X-rays (EDX). Dielectric
measurements were carried out using precision LCR meter (Agilent Model 4981A) in the frequency range of 20 HZ
to 1MHz.
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3. Results and discussions

3.1. Phase analyses

Fig: 1 X-ray diffraction patterns for (1-x) BST+(x) NZF composites.

Typical XRD patterns of (1-x) BST+ x (NZF) with x=0.0, 0.4, 0.6 and 1.0 composite are shown in fig.1. x = 0.0
is indentified as pure ferroelectric BST phase having cubic perovskite structure (JCPDs card no. 34-0411), while x =
1.0 possesses cubic spinel structure (JCPDs card no. 08-0234).
Table: 1 Calculated lattice parameters and crystallite sizes for composite (1-x) BST+(x) NZF

Composition(x) Lattice parameter (A°) Crystallite size(nm)

X=0.0 3.961 24.9
X=0.4 3.955 27.1
X=0.6 8.413 28.3
X=1.0 8.411 28.9

The calculated lattice parameters of the composites are almost equal to their constituent phases. No other phase
except pure BST and pure NZF is observed. With increasing NZF composition, x, the intensity of characteristic
(311) peak of spinel phase found to systematically increase and on the other hand the intensity of perovskite BST
peak, (110) decreases in equal proportions (fig. 1). This indicates the good dispersion of ferrite content in the
composite with very good homogeneity [Bammannavar et al. (2009) and Adhlakha et al. (2011)]. The crystallite size
and lattice parameters were determined for each composition. Crystallite sizes for each composition are calculated
using Scherrer’s formula.

0.94O
t (1)
B cos T

Where λ=X-ray wavelength (1.54 A0), θ=Bragg’s angle and B=FWHM. Crystallite sizes estimated from the
Scherrer’s formula found to increase upon NZF doping for BST.
 Rutvi J. Pandya et al. / Procedia Materials Science 10 (2015) 168 – 175 171

X-ray densities were estimated using equation (2) and found to be 5.82 g/cm3, 5.86 g/cm3 and 5.95 g/cm3 for X=0.4,
0.6 and 1.0 compositions respectively which show that density of the composites increase with increase in NZF for
the BST.
ZM
U xray (2)
N aV
Where Z= number of molecules per unit cell, M= molecular weight, Na= Avogadro number, V= unit cell volume.
[Cullity (1956)]
Table: 1 summarizes the results obtained from the XRD.

3.2. Morphological studies and Elemental analyses

SEM images shown in Fig. 2 (a) and (b) depict the surface morphology of the samples X=0.4 and 0.6
respectively. It is seen that all the samples are well sintered and dense with few pores.

Fig. 2: SEM micrographs and EDX for (1-x)BST+ (x)NZF for the samples (a) SEM for x=0.4; (b) EDX for x=0.4; (c) SEM for x=0.6 and (d)
EDX for x=0.6.
172 Rutvi J. Pandya et al. / Procedia Materials Science 10 (2015) 168 – 175

Further, the crystallite facets are also clearly visible in fig. 2 (a, c). It is observed that with increase in the NZFO
concentration, the density of the composites increases slightly and grain size decreases, which is also in agreement
with values of calculated x-ray densities of the composites. To confirm the elemental distribution of the sintered
composites, Energy Dispersive analysis (EDX) is studied for X=0.4 and 0.6 which is shown in Fig. 2(c) and (d).

3.3. Dielectric properties

Dielectric characterization were carried out using precision LCR meter in the frequency range of 20 HZ to
1MHz. Real permittivity is calculated by the relation
cd
H' (3)
AH 0
Where ε0 = 8.85×10-12 F/m, c capacitance, d thickness of the sample, A area of the sample.
Imaginary permittivity is calculated by
H '' H ' tan G (4)
Fig. 3(a) and 3(b) and 3(c) show the variations of real permittivity, imaginary permittivity and loss tangent with
frequency, respectively. The plots of real and imaginary permittivity show dielectric dispersion in composites. It is
seen that values of permittivity decrease promptly from its higher values at lower frequencies. At lower frequency
the values of dielectric permittivity were high, because the excitation of bound electrons, lattice vibration, dipole
orientation and space charge polarization are active. At higher frequencies, both, ε’ and ε’’ become almost constant
i.e. frequency independent region. This can be understood from Maxwell-Wagner type polarization and Koop’s
phenomenological theory of dielectrics [Wagner (1993) and Koops (1951)]. In the low frequency region, electric
dipoles follow the frequency of applied field but in the high frequency region the electric dipoles cannot follow the

Fig.3 Frequency dependent dielectric properties of (1-x)BST+(x)NZF composites (a) Real permittivity; (b) Imaginary permittivity and (c) Loss
tangent.
 Rutvi J. Pandya et al. / Procedia Materials Science 10 (2015) 168 – 175 173

Fig. 4: AC conductivity as a function of frequency for (1-x) BST + (x) NZF

fast variations of the applied field [Chougule et al. (2007)].Thus, the values of ε’ and ε’’ remain constant. It should
be noted that for x=0.4, exceptionally high values of high dielectric constant was observed. Moreover, although the
loss tangent is found to slightly higher for x =0.4, as compared to other compositions, its maximum value below 3.0
fig. 3(c)), offers a great promise for this composite for tuneable frequency filter applications. A similar trend is
observed for ε’’ as shown in fig. 3 (b).

3.4. AC conductivity

AC conductivity was calculated the dielectric data. The AC conductivity was calculated by following relation [R.
Rani et al. (2014)].

V AC ZH ' H 0 tan G (5)

Where ω=angular frequency, ε0=vacuum permittivity, ε’ = Real permittivity

Table 2: Values of real permittivity, imaginary permittivity and AC conductivity @ 1MHz frequency for composite (1-x) BST+(x) NZF

Composition(x) Real Imaginary AC conductivity

permittivity(ε’) permittivity(ε”)
X=0.0 111 1 0.0065
X=0.4 39 7 0.0391
X=0.6 12 2 0.0154
X=1.0 23 8 0.0454

Fig.4 shows variations in AC conductivity as a function of frequency. From the plots, it is seen that AC
conductivity increases almost linearly for x = 0.0. However, with incorporation of ferrite NZF in higher
concentration, i.e. beyond x = 0.4, a non-linear increase in the AC conductivity was observed (fig. 4). Similar type
of behavior in AC conductivity was reported by [Devan et al. (2006)]. The electrical conduction in ferrites can be
understood by hopping model. According to hopping model the conduction takes place due to the hopping of
174 Rutvi J. Pandya et al. / Procedia Materials Science 10 (2015) 168 – 175

electrons between Fe2+ and Fe3+ ions at neighboring octahedral sites and also hole hopping between Ni +2 and Ni+3
may take place [Zaki (2005)]. The linear increment in conductivity is due to small polarons type conduction while a
very small decrement in conductivity is due to mixed polaron type conduction [Devan et al. (2006)]. These results
suggest a competition between small and mixed polaron conductions for composites with x ≥ 0.4 in the BST+NZF
composites. The values of real permittivity, imaginary permittivity and AC conductivity at 1MHz frequency for the
composites are shown in table 2.

4. Conclusions

In summary, oxide composite of two ferroic ternary Ba0.6Sr0.4TiO3 and Ni0.5Zn0.5Fe2O4 were synthesized by solid
state reaction route. A systematic phase transition from cubic perovskite BST to cubic spinel ferrite phase of NZF
has been observed, while the end products crystallize in to single phase cubic perovskite BST and spinel NZF
structures, respectively. Calculated lattice parameters were found to be nearly equal to their constituent phases.
Crystallite sizes estimated from the Scherrer’s formula found to increase upon NZF doping for BST. SEM images
showed dense and homogeneous structure with few pores. Density of composites increases with NZF content.
Dielectric studies for the composites follow Maxwell-Wagner type polarization and Koop’s phenomenological
theory of dielectrics. For intermediate composites, such as x=0.4, exceptionally high values of high dielectric
constant was observed with a reasonably low loss tangent. Such a finding offers a great promise for this composite
for tuneable frequency filter applications. Based on the AC conductivity results, the conduction mechanism in the
composites is due to the hopping of electrons between Fe2+ and Fe3+ ions at neighboring octahedral sites. The
increase in conductivity can be understood by small polarons and mixed polarons type conduction.

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