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Dielectric and Polarization Studies of Ca

Substituted in Bi4SrTi4O15 Ceramics
a

Gagan Anand , A. R. James & P. Sarah

Vignan Istitute of Technology and Science, Vignan Hills, Nalgonda,

A.P, India
b

Defence Metallurgical Research Laboratory, Kanchanbagh,

Hyderabad, A.P, India
c

Vardhaman College of Engineering, Shamshabad, Hyderabad, A.P,

India
Published online: 01 Dec 2010.

To cite this article: Gagan Anand , A. R. James & P. Sarah (2010): Dielectric and Polarization Studies
of Ca Substituted in Bi4SrTi4O15 Ceramics, Integrated Ferroelectrics: An International Journal, 116:1,
137-144
To link to this article: http://dx.doi.org/10.1080/10584587.2010.489411

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Integrated Ferroelectrics, 116:137144, 2010

Copyright Taylor & Francis Group, LLC
ISSN: 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584587.2010.489411

Dielectric and Polarization Studies

of Ca Substituted in Bi4 SrTi4 O15 Ceramics
GAGAN ANAND,1 A. R. JAMES,2 AND P. SARAH3
1

Vignan Istitute of Technology and Science, Vignan Hills, Nalgonda, A.P, India
Defence Metallurgical Research Laboratory, Kanchanbagh, Hyderabad, A.P,
India
3
Vardhaman College of Engineering, Shamshabad, Hyderabad, A.P, India

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The processing conditions, microstructure and dielectric properties of strontium bismuth

titanate (SBT) were studied by means of Ca substitution in the strontium site referred to
hereinafter as SCBT. The mechano-chemical activation method permits one to reduce
the particle size of the initial products, so the surface area of the powder is increased,
improving in most cases its reactivity.
X-ray diffraction analysis showed the formation of a single-phase layered perovskite structure of SCBT. Morphological studies were carried out by SEM analysis.
Dielectric measurements in the frequency 100 Hz1 MHz were made using an Impedance
Analyzer (HP4192A) interfaced to a computer and the measurements were carried out
from room temperature to 600 C. a variation in the dielectric constant was observed
by the incorporation of calcium into the layered perovskite structure. The hysteresis
loop revealed a variation in remnant polarization with the substitution of calcium in
strontium. Resonance studies were made on poled sample using an Impedance Analyzer.
Elastic compliance [s33 , s11 ] and coupling factor [k33 , k31 ] were also obtained.

1. Introduction
Bismuth layer-structured ferroelectrics are excellent candidate materials for piezoelectric
and pyroelectric sensors requiring a high stability and high operation temperature. This
is owing to their high Curie temperatures, low ageing rate and strong anisotropic electromechanical coupling factors. Due to their promising fatigue-free nature, bismuth layerstructured ferroelectrics (BLSFs) have attracted considerable attention [1]. The BLSFs
have a crystal structure containing interleaved bismuth oxide (Bi2 O2 )2+ layers and pseudoperovskite blocks which contain BO6 octahedron and generally formulated as (Bi2 O2 )2+
(An-1 Bn O3n+1 )2. In this notation A represents a mono-, bi- or trivalent ion, B denotes a
tetra, penta or hexavalent ion and n is the number of BO6 octahedron in each pseudoperovskite block (n = 1, 2, 3 . . . ) [2]. Among the protype BLSFs, SrBi2 Ta2 O9 is now
studied extensively for its application in FeRAMs. It has been reported that Sr-deficient
and Bi excess SrBi2 Ta2 O9 shows an increase in Curie temperature TC with increasing compositional deviation and a marked increase in remnant polarization [3, 4]. Generally, the
displacive ferroelectrics with a higher TC have a large remnant polarization. Since the TC
of Bi4 SrTi4 O15 (520 C) [5] is higher than that of SrBi2 Ta2 O9 (335 C) [5], a high remnant
Received December 13, 2009; in final form February 5, 2009.

Corresponding author. E-mail: gagan4567@rediffmail.com

[463]/137

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138/[464]

G. Anand et al.

Figure 1. Lattice structure of (a) SBT and (b) SCBT ceramics.

polarization can be expected. Substitution of calcium in strontium sites should further increase the TC . The compound is tetragonal with slight orthorhombic distortion. The a- and
b- axes lie along (110) c where the suffix denotes the cubic perovskite sub cell so that a b
2ac 0.54 nm. The c- axis is inherently long. The pseudo-structure of BLSF compounds
can be seen in Fig 1. These layered perovskite compounds are ferroelectric with high Curie
temperatures [6].
The ionic polarization makes an important contribution to the permanent dipole in the
ferroelectric state. The structural consequence of this polarization is to distort the octahedral
coordination, and thereby to lower the crystal symmetry. Chen Da Ren and Guo Yan Yi
[7] reported piezoelectric properties of a number of compounds by replacing the cations
having similar structural configurations. According to them the Bi3+ ion has an important
effect on the bond strength of Ti4+-O2 (along a- axis) in the compound Bi4 SrTi4 O15 .
Figure 1 is the lattice structure of SBT and SCBT ceramics. The Bi ion in (Bi2 O2 ) 2+ can
only be substituted by a few metal cations which have a sterochemically active lone pair of
electrons, such as Pb2+, Sn2+, Sb2+, or Te4+, because Bi has a stable lone electron pair the
Ca2+, Sr2+, and Bi3+ cat ions disperse in the A sites, and Ti4+ cations occupy the B sites in
the pseudo perovskite layers. The ratio of (Ca, Sr)/Bi in the A site is 1:2 and there are 14 of
A sites vacant in the SCBT lattice [8] as shown in Fig. 1.
The low crystal symmetry and high coercive fields observed in these compounds result
in the high stability of the piezoelectric properties for ceramic materials of Bi4 SrTi4 O15
either under high temperature or under one-dimensional stress. Such compounds are important for many applications involving piezoelectric properties of ceramics. Different methods

Ca Substituted in Bi4 SrTi4 O15 Ceramics

[465]/139

of preparation of the compounds have been suggested viz. hot forging, hot rolling, hot extrusion and super plastic deformation. These methods give ceramics with grain orientations
and different densities [9]. Ferroelectric and dielectric properties of SCBT are investigated,
prepared via high-energy mechano-chemical process.

2. Experimental Details

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2.1 Sample Preparation

The initial compounds SrCO3 , Bi2 O3 , CaCO3 , TiO2 (Sigma Aldrich, 99.9% pure, AR
grade) were mixed in appropriate ratios for the synthesis of the desired compound. The
polycrystalline samples of Bi4 SrTi4 O15 [SBT] and Bi4 Sr0.9 Ca0.1 Ti4 O15 [SCBT] were prepared by the method of reactive sintering. The standard ceramic fabrication procedure has
been followed for the preparation. The oxide mixture, weighing 50 g, was subjected to high
energy milling in a planetary ball mill (Fritsch Pulverisette 6) at a speed of 150 rpm for 5 hr.
A cylindrical tungsten carbide (WC) milling jar, with a usable volume of 250 ml, filled with
50 WC balls, each of 10 mm diameter, was used for the purpose of milling. Both vial and
balls were from Fritsch GmbH. A total of 50 g of powder was placed in the vial using water
as the milling medium. The milling was stopped for 5 min after every 30 min of milling to
cool down the system. Figure 2 illustrates that during each collision the powder particles get
trapped between the colliding balls, between the ball and the inner surface of the vial and
lead to smaller particle size. The particle size of the initial materials ranged from 12 m.
The mixture was stacked in a crucible and calcined in air at 800 C for 4 hr and then cooled.
The calcined powders were milled for a few minutes to crush any lumps that were formed
during the calcinations. The calcined powders were cold isostatically compressed into the
form of a cylindrical rod at a pressure of 3000 Mpa and sintered at 1200 C for 2 hr and then
allowed to furnace cool. Pellets having a diameter of 1 cm and thickness of 1 mm were cut
from the sintered samples using a low speed isomet saw. The entire sintering was done in a
microprocessor-controlled furnace. The densified pellets were used for all measurements.

Figure 2. Milling by crushing of particle between the vial surface and balls.

140/[466]

G. Anand et al.

The density of the pellets was determined by Archimedes principle. For electrical measurements, samples were polished and coated with Au electrodes on the larger faces. Typical
sample dimensions were 10 mm diameter and 1 mm thickness. In order to make electrical
measurements, it is necessary to make the samples piezoelectrically active. Therefore,
electrical poling was done at a field of 5 kV cm1 for 30 min at 100 C immersing the
R
). The field was retained while cooling
samples in a silicon oil bath (Dow Corning 704
as well. The dielectric measurements were made on electrically poled samples with an
Impedance Analyzer (HP4192A) at different frequencies from room temperature to 600 C.
These measurements were carried out on silver coated pellets by placing them in between
two electrodes, which in turn were connected to the leads of the impedance analyzer.
The resonance measurements were carried out in the frequency range 100 Hz1 MHz at
room temperature using HP-4294A interfaced to computer. The ferroelectric hysteresis
loop measurements were done placing the silver coated samples in a silicon oil bath in
between two electrodes using a ferroelectric hysteresis loop analyzer based on a modified
Swayer-Tower circuit interfaced to computer. Samples used for PE measurements were
not poled. Resonance data was used to calculate elastic compliance [s33 , s11 ] and coupling
factor [k33 , k31 ] for SBT and SCBT [10] respectively.

3. Results and Discussions

3.1 Dielectric Measurements
The SBT, SCBT phase evolution was studied by X-ray analysis. Figure 3 contains the XRD
patterns of SBT and SCBT ceramics. It can be observed that the substitution of Ca ions for
Sr ions didnt have much impact on the change of the phase. The density of the samples
was found to be > 90% of the XRD density.
Figures 4(a) and 4(b) show the SEM scan for SBT and SCBT ceramics. Figures 5(a)
and 5(b) show the relative dielectric constants and dielectric losses at different frequencies

. .
.

(a )

..
2 5

30

3 5

40

(0210)

..

(028)

. .

(0016)
(0013)

(117)

(111)

(0010)

..

(020)

(b )

20

S B T

(119)

.
RELATIVE INTENSITY

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2.2 Characterization and Measurements

4 5

2
Figure 3. XRD trace of (a) SBT and (b) SCBT ceramics. (See Color Plate XI)

[467]/141

Figure 4. SEM trace of (a) SBT and (b) SCBT ceramics.

as a function of temperature for SBT. An increase in the dielectric constant can be seen
with the substitution of calcium ions in strontium site. An increase in the Curie temperature
can be observed from the Figs. 5(a) and 5(c) as a result of calcium substitution. When the
temperature rises, the thermal vibration leads to increase in Ca mobility. Therefore, the
contribution from the ionic polarization and the dielectric permittivity are enhanced [11].

2000

(b)

1000

50Hz
100Hz
500Hz
1kHz

500
0

Dielectric loss

1500

2000

200
400
0
Temperature ( C)

600

400

600

(d)

200

50Hz
100Hz
500Hz
1kHz

500

(c)

1000

50Hz
100Hz
500Hz
1kHz

Temperature ( C)

1500

Dielectric loss

Dielectric constant

(a)

Dielectric constant

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Ca Substituted in Bi4 SrTi4 O15 Ceramics

200

400
0

Temperature ( C)

600

50Hz
100Hz
500Hz
1kHz

200

400

600

Temeperature ( C)

Figure 5. Temperature dependence of (a) dielectric constant and (b) loss tangent of SBT measured
at different frequencies. Temperature dependence of (c) dielectric constant and (d) loss tangent of
SCBT at different frequencies. (See Color Plate XII)

142/[468]

G. Anand et al.
Table 1
The values of TC and Dielectric constant for SBT and SCBT samples

Sample

Dielectric Constant

TC ( C)

SBT
SCBT

1765
1949

527
556

= C/(T Tc ),
Where is the dielectric constant, C is the Curie constant and Tc is the transition temperature.
Figures 5(b) and 5(d) depict the variation of tan as a function of both temperature and
frequency for SBT and SCBT respectively. The value of tan increases appreciably before
the dielectric transition. It decreases with increasing frequency at higher temperatures and
the peak in tan becomes broader. From Figs. 5(b) and 5(d) it is observed that the tan
value decreases considerably by the incorporation of Ca in SBT.
Figure 6 shows the polarization Vs electric field (P Vs E) Hysteresis loop for the
sintered SBT and SCBT samples. The values of Pr and Ec are shown in Table 2. Previous
studies on similar compounds have shown relatively lower values of Pr . In the current case
we have found significant enhancement of Pr which is noteworthy. The enhancement of
Pr could be due to any or all of the following reasons: absence of a significant number
of domain wall pinning centers, uniform distribution of grain size in the milled samples,
uniform distribution of composition, low defect density etc. In the present case samples
of SCBT were prepared so as to obtain a grain size distribution, which was in a narrow
window. Thereby clamping of domain wall grain boundary from neighbours due to very
small size could be avoided.

SBT
SCBT

Polarization (C/cm )

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The transition is considered to be the Curie point and is of second-order [12]. The dielectric
constant and transition temperature for SBT and SCBT samples are shown in Table 1.
The dielectric constant vs. temperature curve obeyed a Curie-Weiss law.

-4

-80

-40

40

80

Electric field (kV/cm)

Figure 6. Polarization vs. Electric field Hysteresis loop for SBT & SCBT. (See Color Plate XIII)

Ca Substituted in Bi4 SrTi4 O15 Ceramics

[469]/143

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Table 2
The values of Pr and Ec for SBT and SCBT samples
Sample

Coercive field
(kV/cm)

Remnant Polarization
(C/cm2)

SBT
SCBT

11.011
34.451

0.773
3.220

It is possible that conditions used during synthesis of SCBT viz high-energy milling
provided an environment conducive for formation of a significant number of 180 domain
walls thereby, resulting in significant enhancement in remnant polarization. The 2Pr reaches
a maximum value of 6.23 [C/cm2]. On the other hand the tolerance factor, t, for the
perovskite structure is given by
(r + r0 )
t= A
2(rB + r0 )
Where rA, rB and ro are ionic sites of an A-site cation, a B-site cation and oxygen ion
respectively. In SCBT, rA is 0.117 nm (Bi3+) or 0.132 nm (Sr2+) or 0.099 nm (Ca), rB is
0.0559 nm (Ti4+) and ro is 0.14 [13].
Obviously the tolerance factor of SCBT is less than 1.0 and the substitution of Ca for
Sr should lead to the increase in t. The maximum field applicable was limited on account
of the power supply limitations.

3.2 Piezo-Electric Electromechanical Coupling

Ceramic samples as per IEEE standards were used to determine piezoelectric and electromechanical coefficients. The resonance and anti-resonance frequencies were determined
from the first minimum and maximum impedance peaks respectively, from the impedance
Vs frequency scan. Table 3 shows the Elastic compliance [s33 , s11 ] and electromechanical
coupling factor [k33 , k31 ] for SBT and SCBT.

Table 3
The Measured Electromechanical Coefficients
Constant
k33
k31
kp
s33 D
s33 E
s11 E
s11 D
c33 D

SBT

SCBT

0.38
0.39
0.41
1.62 1012m2/N
1.90 1012m2/N
1.84 1012m2/N
1.56 1012m2/N
1.139 1011N/m2

0.23
0.23
0.23
1.34 1012m2/N
1.42 1012m2/N
1.41 1012m2/N
1.33 1012m2/N
1.055 1011N/m2

144/[470]

G. Anand et al.

4. Conclusions
The electric properties of SBT are notably improved by Ca substitution. The TC of SBT
shows a slight shift to higher temperature upon Ca substitution. This implies that Casubstitution enhances the TC of the un-doped material SBT thereby increasing the operating
range of the material. Further Ca substitution also results in a significant enhancement of
Pr of SCBT. The sample SCBT has a large remnant polarization and a high TC near 556 C.
It is believed that SCBT is potentially an attractive candidate for piezoelectric sensor
applications.

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Acknowledgments
The authors thank the Director DMRL for providing experimental facilities, Dr KC James
Raju, School of Physics, HCU, for resonance data, Department of Physics, MRL, Osmania
University, for dielectric measurements. One of the authors (GA) thanks Principal and
Management of Vignan Isntitute of Technology and Science, Nalgonda for their constant
encouragement.

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