Applied Physics A (2018) 124:31

https://doi.org/10.1007/s00339-017-1444-x

Preparation, electronic structure, and chemical bonding of lead-free

(1 − x)(K0.5Bi0.5)TiO3-xBaTiO3 solid solution
S. Sasikumar1 · R. Saravanan1 · S. Saravanakumar2 · M. Charles Robert3

Received: 14 August 2017 / Accepted: 1 December 2017

© Springer-Verlag GmbH Germany, part of Springer Nature 2017

Abstract
Polycrystalline lead-free (1 − x)(K0.5Bi0.5)TiO3-xBaTiO3, ((1 − x)KBT-xBT) (x = 0.00, 0.08, 0.12) ceramics were synthesized
via solid-state reaction method. The powder X-ray diffraction (PXRD) and structural refinement results confirm that a single-
phase tetragonal structure with space group P4mm. Charge density distribution inside the unit cell of (1 − x)KBT-xBT was
investigated by the maximum entropy method. Charge density analysis reveals the reduction in ionic nature along K/Bi–O
bond and enhancement of covalent nature along Ti–O bond with the addition of B ­ aTiO3. The charge density distribution
studies done using maximum entropy method for (1 − x)KBT-xBT have not been done so far. The surface morphology study
was done using scanning electron microscopy (SEM). Energy dispersive X-rays spectra (EDS) were used to investigate the
elemental compositions present in the system. The dielectric constant and loss tangent were studied as a function of frequency.
The dielectric constant and loss were decreased with increase of frequency. Room temperature dielectric constant (ɛ) and
loss (tan δ) were measured for x = 0.00 about 511 and 0.51, respectively, at a frequency of 10 kHz.

1 Introduction c = 4.013 Å at room temperature. From a synthetic per-

In the past several decades, lead zirconate titanate (PZT)
ceramics have dominated the electronic industries because
of their excellent properties and superior technological
applications in actuators, sensors, and other electronic
devices. Most of them are lead containing materials which
cause serious technological and environmental problems
in the production of ceramic samples [1–3]. Recently,
much attention on perovskite bismuth titanate compounds
have been paid to the development of lead-free ceramics,
which is considered as alternative to toxic PZT ceramics
[4]. Potassium bismuth titanate belongs to lead-free ­ABO3
perovskites. The ­K0.5Bi0.5TiO3 (KBT) has tetragonal struc-
ture at room temperature, and it has high Curie tempera-
ture (TC = 380 °C) [5]. From the structural point of view,
KBT has a tetragonal symmetry with a = b = 3.918 Å and
* S. Sasikumar
sasikuhan@gmail.com
1
Research Centre and Post Graduate Department of Physics,
The Madura College, Madurai, Tamil Nadu 625 011, India
2
Department of Physics, Kalasalingam University,
Krishnankoil, Viruthunagar, Tamil Nadu 626 126, India
3
Department of Physics, HKRH College, Uthamapalayam,
Tamil Nadu 625 533, India
spective, piezoelectric ceramics are usually prepared by
solid-state reaction method, which consists of a calcination
process below 1000 °C, where the raw materials such as
­K2CO3, ­Bi2O3, and T­ iO2 react with each other to form the
KBT, in a sintering process above 1000 °C [6–9]. Himura
et al. [10] and Wada et al. [11] reported that the high-density
­K0.5Bi0.5TiO3 samples are difficult to fabricate due to the
high volatility of the bismuth component at sintering tem-
perature. This situation can be improved by forming solid
solutions of KBT with other ferroelectrics such as B ­ aTiO3
[12], ­K0.5Na0.5NbO3 [13], and B­ i0.5Na0TiO3 [14], as well as
the use of sintering aids such as ­Bi2O3, ­La2O3, and ­MnCO3
[15].
This work is specifically concerned with investigating
the electronic structure and chemical bonding of (1 − x)
KBT-xBT ceramics. The solid solutions has been pre-
pared by solid-state reaction method with different com-
positions, x = 0.00, 0.08 and 0.12. The effects of B ­ aTiO3
on the crystal structure, microstructure, and dielectric
properties have been analyzed. The crystal structure and
charge density of (1 − x)KBT-xBT ceramics have been
analyzed to investigate the effect of atomic substitution on
the chemical bonding by means of XRD data. The exper-
imental investigation on electron density distribution

13
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 31   Page 2 of 10 S. Sasikumar et al.

between the constituent atoms has not yet been reported

in (1 − x)KBT-xBT, (x = 0.00, 0.08 and 0.12) ceramics.

2 Synthesis and characterizations

Polycrystalline powders of (1 − x)(K 0.5Bi 0.5)TiO 3-xBa-

TiO3, (x = 0.0, 0.08 and 0.12) were prepared by solid-state
reaction method. The stoichiometric amounts of K ­ 2CO3
(99.99% purity), ­Bi2O3 (99.99% purity), ­BaCO3 (99.99%
purity), and T­ iO2 (99.99% purity) were used as starting
materials. Before the solid-state reaction, the raw powders
were taken, which satisfies the following reaction:
{ }
(0.5) (0.5)
(1 − x) K2 CO3 + Bi2 O3 + xBaCO3 + xTiO2
2 2
→ (1 − x)K0.5 Bi0.5 TiO3 − xBaTiO3 + CO2 ↑ . (1)

High-purity powders of starting chemicals were ball-

milled for 2 h using agate balls to synthesize solid solu-
tions. The mixed powders were dried and calcined at
800 °C for 2 h. The calcined powders were pressed uni-
axially at a pressure of 200 MPa with 2 wt% polyvinyl
alcohol as a binder. Then, the pellets were sintered using
the conventional sintering method in air at 1050 °C for
3 h.
The synthesized ceramics were structurally character-
ized by powder X-ray diffraction (PXRD) using Bruker
AXS D8 advance diffractometer. The XRD patterns were
obtained using CuKα (λ = 1.54056 Å) radiation in the 2θ
range from 20° to 80°, with the scanning step of 0.02°.
The surface morphology and chemical composition were
investigated by scanning electron microscopy (SEM)
(Carl Zeiss EVO 18, 20 kV) and energy dispersive X-ray
spectroscopy (EDS) (Carl Zeiss EVO 18) respectively.
The dielectric properties were measured at room tempera-
ture using an impedance analyzer (PSM 1735, N4L) in the
wide range of frequency from 10 Hz to 1 MHz.
3 Results and discussion
3.1 Structural analysis and Rietveld refinement
analysis
Figure 1a shows the powder XRD profiles of (1 − x)KBT-
xBT, (x = 0.00, 0.08, 0.12) ceramic samples sintered at
1050 °C for 3 h. The XRD patterns reveal the tetragonal
structure with space group P4mm (#99) (JCPDS PDF #
36-0339) [16]. Figure 1b shows that the enlarged diffraction
peaks shift towards lower angle side of 2θ. The ­Ba2+ substi-
tutions in K
­ 0.5Bi0.5TiO3 are also confirmed by peak shifting
Fig. 1  a XRD patterns of (1  −  x)KBT-xBT, x = 0.00, 0.08, and 0.12
ceramics at room temperature. b Enlarged (101), (111), and (200)
peaks
to lower angle side of 2θ indicating increase of cell param-
eters (Table 1). This is attributed to the fact that the ionic
radius of ­Ba2+ (1.61 Å) cations is substituted for the smaller
ionic radii of ­K+ (1.35 Å) and ­Bi3+ (0.96 Å) [17], which
are expected to be primarily responsible for the increase of
the unit cell dimensions. From cell parameter, tetragonality
(c/a) was obtained by XRD measurement in the range from
1.001 to 1.006, which indicates that the crystal structure is
tetragonal at room temperature.
The XRD data of all the compositions x = 0.00, 0.08,
0.12 were refined by the Rietveld method [18] using JANA
2006 software [19]. The structural refinements were car-
ried out by taking the positional parameter of tetragonal
­BaTiO3 structure. The initial atomic position coordinates
(x, y, z) were taken as (0, 0, 0) for potassium/bismuth, (0.5,
0.5, 0.512) for titanium, (0.5, 0.5, 0.023) for O1, and (0.5,
0, 0.486) for O2 from standard Wyckoff [20] position tables
with space group P4mm. The fitted profiles of XRD data sets
of (1 − x)KBT-xBT with x = 0.00, 0.08, 0.12 are shown in
Fig. 2 (a)–(c). The fitting of observed and calculated profiles
is quite good confirming the tetragonal structure of (1 − x)

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Table 1  Refined parameters of (1  −  x)KBT-xBT ceramics through obtained from Rietveld refinement [18]. MEM is used to
refinement of PXRD data reconstruct the electronic charge density structures. The
Parameters x = 0.00 x = 0.08 x = 0.12 MEM computations were carried out on (1 − x)KBT-xBT‚
(x = 0.00, 0.08, 0.12) unit cells, which were divided into
Space group P4mm P4mm P4mm
64 × 64 × 64 pixels along a, b, and c axes of the tetragonal
a = b (Å) 3.9760 (6) 4.0139 (3) 4.0287 (2)
lattice. Then, each pixel was assigned with a prior charge
c (Å) 4.0018 (6) 4.0201 (3) 4.0541 (2)
density of F000/V, where F000 is the total number of elec-
α = β = γ (°) 90 90 90
trons in the unit cell and V is the volume of the unit cell.
Volume (Å3) 63.23 (9) 64.79 (6) 65.35 (4)
The resultant charge density is plotted using visualization
Density (gm/cc) 5.77 (1) 5.63 (1) 5.58 (3)
software VESTA [22].
Rp (%) 5.90 5.88 6.06
The 3D charge density distributions in the unit cell with
Robs (%) 2.83 5.66 4.80
an iso-surface level of 1.0 e/Å3 for (1 − x)KBT-xBT ceram-
GOF 1.14 1.68 1.44
ics show the model of the structure as presented in Fig. 3a–c.
F(000) 97 97 97
Figures 4 and 5 show the 2D electron density contour in the
c/a 1.006 1.001 1.006
contour range of 0–1 e/Å3 with an interval of 0.04 e/Å3.
Position parameters
Figure 4a shows the shaded (001) plane in the 3D unit cell.
 K/Bi
Figure 4b, c demonstrates the 2D charge density contour
 x 0 0 0
maps corresponding to the (001) plane, which shows the K/
 y 0 0 0
Bi-O bonds. It can be observed that the charge accumula-
 z 0 0 0
tion between K/Bi and O ions in the undoped ­K0.5Bi0.5TiO3
Ti
ceramic reveals covalent nature due to the lone pair effect
 x 0.5 0.5 0.5
of ­Bi3+ ions. The charge density contours are further faded
 y 0.5 0.5 0.5
away at the middle portion of the K/Bi-O bond path for
 z 0.5455 0.4952 0.4855
increasing Ba doping levels at x = 0.08 and 0.12. This indi-
O1
cates that the K/Bi-O bond becomes more ionic for x = 0.08
 x 0.5 0 0.5
and 0.12 with B ­ a2+ substitution in the host lattice. Therefore,
 y 0.5 0.5 0.5
the contours of the 2D electron density distribution on (001)
 z 0.0533 0.0 0.0288
plane are faded away at the middle portion of the K/Bi-O
O2
bond for x = 0.12 (Fig. 4d) with respect to the x = 0.00, 0.08.
 x 0 0 0
Figure 5a shows the 3D unit cell with (002) plane shaded.
 y 0 0 0
Figure 5b, c illustrates the 2D contour maps corresponding
 z 0.4575 0.4632 0.4586
to the (002) plane, which also show the Ti-O bonds. 2D con-
Rp profile reliability factor, Robs observed profile reliability factor, tour maps on (002) plane show the charge overlap between
GOF goodness of fit, F(000) number of electrons in the unit cell Ti and O ions along the bonding region, which confirms
the covalent nature of bonding between the Ti and O ions.
Similar results have been reported in the previous studies
KBT-xBT (x = 0.00, 0.08, 0.12). In Fig. 2a–c, the cross sym- [23, 24].
bol represents the observed XRD profile; the continuous line An analysis can be done on the 1D electron density pro-
represents the calculated XRD profile, along with the error files of (1 − x)KBT-xBT‚ (x = 0.00, 0.08 and 0.12) along K/
bar (difference (Ic − Io)) and respective Bragg’s positions. Bi–O and Ti–O bonding directions and the valence contribu-
The room temperature lattice constants of K ­ 0.5Bi0.5TiO3 are tion for the three systems is shown in Fig. 6a, b. The bond
determined using Rietveld refinement [18] and found to length variation and charge density values at mid-bond of K/
be a = b = 3.9760 Å, c = 4.0018 Å and volume = 63.23 Å3 Bi–O and Ti–O bonds are obtained from the MEM analysis
(Table  1). The fractional atomic coordinates, reliability and are given in Table 2. The bond length of Ba-O bond
factors, and goodness of fit were calculated from Rietveld for x = 0.00 is 2.7880 Å. The bond length is increased from
refinement [18], and the results are listed in Table 1. 2.8261 to 2.8265 Å with the increasing of Ba content for
x = 0.8 and x = 0.12 respectively. In addition, the bond length
3.2 Charge density by maximum entropy method for Ti-O bond for x = 1.9730 Å, which increases with the
addition of Ba doping in the host lattice. The expansion of
The electronic structure and bonding nature of (1 − x)KBT- bond length with the incorporation of Ba is consistent with
xBT, (x = 0.00, 0.08, 0.12) ceramics were estimated by maxi- XRD data. The variation in bond length values with Ba dop-
mum entropy method (MEM) [21]. Charge distribution in ing indicates distortion in the ­K0.5Bi0.5TiO3 structure. From
the unit cell was carried out using the structural parameter Table 2, for the concentration x = 0.00, the electron density

13
 31   Page 4 of 10 S. Sasikumar et al.

Fig. 2  a Refined powder XRD

profile for ­(K0.5Bi0.5)TiO3. b
Refined powder XRD pro-
file for 0.92(K0.5Bi0.5)TiO3-
0.08BaTiO3. c Refined powder
XRD profile for 0.88(K0.5Bi0.5)
TiO3-0.12BaTiO3

13
Preparation, electronic structure, and chemical bonding of lead-free (1 −… Page 5 of 10  31

Fig. 3  3D electron density dis-

tribution for (1 − x)KBT-xBT,
a x = 0.00, b x = 0.08, c x = 0.12
with iso-surface level of 1 e/Å3

Fig. 4  a 3D unit cell of (1 − x)

KBT-xBT with (001) plane
shaded. 2D electron density
distribution on (001) plane for
(1 − x)KBT-xBT, b x = 0.00, c
x = 0.08, d x = 0.12

13
 31   Page 6 of 10
Fig. 5  a 3D unit cell of (1 − x)
KBT-xBT with (002) plane
shaded. 2D electron density
distribution on (002) plane for
(1 − x)KBT-xBT, b x = 0.00, c
x = 0.08, d x = 0.12
at the bond critical point is found to be 0.4212 e/Å3. This is
due to the lone pair effect of B ­ i3+ ions as discussed above
and the electron density values are decreased with increase
of ­Ba2+ concentration. This confirms that the K/Bi–O bond
is ionic in nature for x = 0.08 and 0.12. Again, from Table 2,
the mid-bond electron density values range from 0.7232 e/Å3
to 0.6265 e/Å3, which lead to the covalent behavior between
Ti and O ions.
3.3 Microstructure and EDS analysis
Figure 7a–c shows the SEM micrographs of the (1 − x)KBT-
xBT, (x = 0.00, 0.08, 0.12) ceramics sintered at 1050 °C.
The SEM images were recorded at different magnifications
(× 5000, × 10,000, ×25,000, and × 50,000) and the images
with × 5000 are presented. It can be seen that there is a sig-
nificant change in the surface morphology and particle size
for the undoped and doped samples. Particles of irregular
shape with pores heterogeneously distributed are seen for
x = 0.08 sample. However, for x = 0.12 sample, very fine
particles with agglomeration are noticed. For all the sam-
ples, it is observed that there is no clear grain boundary.
The elemental compositional analysis of the synthesized
samples was done by energy dispersive X-ray spectroscopy
13
S. Sasikumar et al.
(EDS) and the recorded EDS spectra of (1 − x)KBT-xBT‚
(x = 0.00, 0.08 and 0.12) ceramics are shown in Fig. 8a–c.
Each peak in the EDS spectra refers to particular atomic spe-
cies present in the prepared sample. The atomic and weight
percentages of the elements (K, Bi, Ti, Ba, and O) present
in the synthesized sample with the expected proportions and
are given in Table 3. It confirms that there are no impurities
present in the sample.
3.4 Frequency dependence of dielectric constant
measurements
Figure 9a, b shows the variation of dielectric constant and
dielectric loss (tan δ) for all the samples with frequency
range 10 Hz to 1 MHz at room temperature. Figure 9a shows
that dielectric constant of all synthesized samples decreases
with increasing frequency and becomes constant above
1 kHz. The plot at lower frequencies may be attributed to dif-
ferent types of polarization (electronic, atomic, interfacial,
ionic, etc.). At higher frequencies, the dielectric constant
decreases due to the contribution from electronic polariza-
tion [25, 26]. Variation of dielectric loss as a function of fre-
quency at room temperature for all compositions is shown in
Fig. 9b. Figure 9b shows the decreasing trend in loss values
Preparation, electronic structure, and chemical bonding of lead-free (1 −… Page 7 of 10  31

Fig. 6  1D electron density profiles along a K/Bi-O, b Ti–O bonds in

(1 − x)KBT-xBT‚ (x = 0.00, 0.08 and 0.12)

with increasing frequency. It can also be observed from

Fig. 9b that the dielectric loss (tan δ) decreases with increas-
ing Ba substitution for further doping. The decreasing value
of dielectric loss at higher frequencies is expected to be due
to the grain resistance [27]. The dielectric constant ε and
loss (tan δ) for x = 0.00 are found to be 511 and 0.51, respec- Fig. 7  SEM images of the (1  −  x)KBT-xBT solid solutions with a
tively, at 10 kHz frequency measured at room temperature. x = 0.00, b x = 0.08, c x = 0.12
Dielectric properties of the (1 − x)KBT-xBT‚ (x = 0.00, 0.08,
0.12) ceramics at 10 kHz are given in Table 4.
Table 2  Bond lengths and Samples Bonding
mid-bond electron densities
for K/Bi-O and Ti-O bondings K/Bi–O Ti–O
for (1 − x)KBT-xBT, (x = 0.00,
0.08, 0.12) Bond length (Å) Mid-bond electron Bond length (Å) Mid-bond
density (e/Å3) electron density
(e/Å3)

x = 0.00 2.7880 0.4212 1.9730 0.7232

x = 0.08 2.8261 0.3614 2.0011 0.8683
x = 0.12 2.8265 0.2967 2.0036 0.6265

13
 31   Page 8 of 10 S. Sasikumar et al.

Fig. 8  EDS spectra (1 − x)

KBT-xBT ceramics a x = 0.00, b
x = 0.08, c x = 0.12

13
Preparation, electronic structure, and chemical bonding of lead-free (1 −… Page 9 of 10  31

Table 3  Elemental composition Samples Atomic percent (%) Weight percent (%)

of the (1 − x)KBT-xBT‚
(x = 0.00, 0.08, 0.12) ceramics K Bi Ti Ba O K Bi Ti Ba O
determined by EDS analysis
x = 0.00 9.12 6.32 26.67 - 5.89 9.20 34.02 32.91 - 23.87
x = 0.08 8.76 5.06 21.67 8.39 56.12 7.63 23.57 23.12 25.68 20.00
x = 0.12 9.06 7.43 17.80 12.78 52.92 6.61 28.97 15.89 32.74 15.79

that the (1 − x)KBT-xBT ceramics crystallized in a tetrago-

nal structure. Substitution of ­Ba2+ at ­(K0.5Bi0.5)2+ site leads
to increase of lattice constant and cell volumes as revealed
by profile refinement. The chemical bonding nature and
charge density distributions in the unit cell of (1 − x)KBT-
xBT ceramics were investigated by maximum entropy
method (MEM). The mid-bond electron density values
reveal the covalent nature between Ti-O ions and ionic
nature between K/Bi-O ions. The morphological proper-
ties of the solid solutions were analyzed from SEM images.
Chemical compositions were further confirmed by EDS
spectra. Frequency dependence of dielectric constant and
losses was investigated at room temperature in the frequency
range from 10 Hz to 1 MHz.

Acknowledgements  The authors S. Sasikumar and R. Saravanan thank

the Naval Research Board of DRDO, India, for providing a grant in
research project (No. NRB/DRDO/MAT/269). The authors S. Sasi-
kumar and R. Saravanan would like to express their special thanks,
Dr.T.Mukundan, Material Science Division and Dr.R.Ramesh, Trans-
ducers division, NPOL, Cochin. In addition, the authors thank SAIF
(Sophisticated Analytical Instrument Facility), CUSAT, Cochin for the
PXRD measurements. The authors thank the International Research
Centre, Kalasalingam University for the SEM/EDS measurements. The
authorities of The Madura College, Madurai-625 011, Tamil Nadu,
India are gratefully acknowledged for their constant encouragement of
the research activities of the authors.

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