Ceramics International 47 (2021) 26511–26518

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Ceramics International
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Microstructural, mechanical and electrical properties of BT, BZT-BCT, and

BNT-BT-BKT ferroelectrics synthesized by mechanochemical route
Sujata Swain a, P. Kumar a, *, Sonia b
a
Department of Physics and Astronomy, National Institute of Technology Rourkela, 769008, Odisha, India
b
Department of Chemistry, Govt. Autonomous College Rourkela, Odisha, 769004, India

A R T I C L E I N F O A B S T R A C T

Keywords: BaTiO3 (BT), 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 (BZT-BCT), 85.4(Bi0.5Na0.5)TiO3-2.6(BaTiO3)-12(Bi0.5K0.5)

Mechanochemical TiO3 (BNT-BT-BKT) lead free ferroelectric ceramics were synthesized by high energy ball milling (HEBM)
BT assisted solid-state reaction route. The Crystallite size of the HEBM powders was found to be in the nano-range.
BZT-BCT
XRD, SEM, dielectric, polarization vs. electric field (P-E) loop and mechanical characterizations and analysis of
BNT-BT-BKT
these sintered ceramics were carried out. Lower calcination and sintering temperatures along with better
densification with the lower average grain size of these ceramics were optimized and obtained compared to the
same systems synthesized by the solid-state reaction route. Enhanced values at room temperature (RT) of
εr~2875, 5133, and 1701 and lower values of tanδ~0.013, 0.015, and 0.058 were obtained for BT, BZT-BCT, and
BNT-BT-BKT sintered ceramics, respectively. Well saturated P-E loops were obtained for all the ceramics, which
confirmed their ferroelectric behaviour. Hardness value ~7.23 GPa, 5.53 GPa, and 5.16 GPa were found for BT,
BZT-BCT, and BNT-BT-BKT sintered ceramics, respectively. The temperature coefficient of capacitance, TCC, was
obtained within ±15% in the temperature range from RT tõ135 ◦ C for BT ceramics with high εr and low value of
tanδ, which suggested its usefulness for multilayer ceramic capacitor (MLCC) applications.

1. Introduction
Lead-free ferroelectrics have a wide range of applications in various
fields such as multilayer ceramic capacitors (MLCC), sensors, resistive
switching, biomedical etc. [1–4]. BaTiO3 (BT), 0.5Ba(Zr0.2Ti0.8)O3-0.5
(Ba0.7Ca0.3)TiO3 (BZT-BCT), 85.4(Bi0.5Na0.5)TiO3-2.6(BaTiO3)-12
(Bi0.5K0.5)TiO3 (BNT-BT-BKT) are the promising lead free ferroelectric
materials, showing excellent dielectric, ferroelectric and piezoelectric
properties [2,5,6]. For multilayer ceramic capacitors, value of dielectric
loss (tanδ) should be as low as possible, because it is directly propor­
tional to the heat dissipation of materials under the application of the
electric field. Maximum allowed dielectric losses of ceramic capacitors,
used in capacitor industries are normally around 5–10% [7]. Properties
of any functional ceramic are greatly influenced by different parameters
such as starting precursors particle size, processing temperatures and
morphology of the sintered product [1]. Mechanical properties of
ferroelectric ceramics are important for determining their reliability in
actuators, MLCC and for biomedical device applications [8,9]. In the
solid-state reaction route, the reaction between the precursors takes
place at the surfaces of the reactants by diffusion of thermally activated
atoms, moving through interfaces. The diffusion of atoms across the
interface depends on the particle size of the starting precursors. The
smaller particle size of the starting precursors results in a higher diffu­
sion rate. This hints that the particle size of the starting precursors af­
fects the processing time and temperatures. Presently, various synthesis
methods like sol-gel, hydrothermal, and wet chemical precipitation
routes have been used to obtain nanoparticles of the starting precursors
[10–12]. Recently, the mechanochemical method has been used to
produce nanoparticles of the starting precursors [13,14]. This process
involves mechanical activation of starting precursors, placed in a
vial/ball mill, and subjected to high energy collisions, induced by stiff
balls. This technique is quite simple, cheap and can be scaled up to yield
tonnage quantities of materials [15]. In mechanochemical milling,
reduced particle size results in more area of contact between the reac­
tant particles, which favour the diffusion process during sintering [16].
Consequently, mechanochemical synthesis requires low processing
temperatures and time compared to normal ball-milled synthesis [13].
In the present study, starting precursors of lead-free BT, BZT-BCT,
BNT-BT-BKT systems were obtained in nano-size order by HEBM.
Structural, microstructural, dielectric, P-E hysteresis loop and various

* Corresponding author.
E-mail address: pvn772004@yahoo.co.in (P. Kumar).

https://doi.org/10.1016/j.ceramint.2021.06.064
Received 4 April 2021; Received in revised form 19 May 2021; Accepted 8 June 2021
Available online 17 June 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
S. Swain et al.
Fig. 1. X-ray diffraction patterns of BT, BZT-BCT, BNT-BT-BKT ceramics processed at optimized calcination and sintering temperatures.
mechanical properties of these HEBM assisted solid-state reaction route
synthesized ceramics are studied and discussed in detail.
2. Experimental details
For BT: BaCO3, TiO2 for BZT-BCT: BaCO3, ZrO2, TiO2, CaCO3 and
forBNT-BT-BKT: Bi2O3, Na2CO3, TiO2, BaCO3, K2CO3 were taken as
starting precursors. Stochiometric proportions of these starting pre­
cursors were placed in a vial with zirconia balls in a 1:3 wt ratio and dry
milled for 5 h with a rotation speed of 300 rpm as per the optimized steps
given in our previous study [17]. In high energy ball milling, the vials
were rotating about their axis to and fro. Centrifugal force acts on the
grinding balls in the direction of vial rotation, and the difference be­
tween the speed of the vial and balls results in strong frictional force. On
the other hand, Coriolis forces act on the grinding balls, which make
them get displaced from the vial and fly them to the interior wall of the
vial and impact the samples placed on the opposite wall of the vial. With
the repetition of this process, the particles size of the starting powders
became finer and finer. These HEBM powders were calcined for
single-phase formation in a conventional furnace at different optimized
temperatures (for each system) raised with a heating rate of 5◦ /min.
PVA binder was added into the calcined powder to give proper shape to
the green pellets. These green pellets were pressed uniaxially in a die by
using a hydraulic press. The resulting green pellets were sintered in a
conventional furnace. For dielectric and P-E hysteresis loop measure­
ments, sintered pellets were electrode by using silver paint. X-ray
diffraction (Rigaku Ultima IV X-ray diffractometer) study was carried
out for confirmation of single-phase formation. Bulk density of the sin­
tered samples was measured by using Archimedes’ principle. Micro­
structure of the samples was analysed by scanning electron
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microscope/SEM (JEOL JSM-6480 L V). For dielectric measurements, a
computer interfaced LCR meter (Hioki 3532–50) was used. P-E loop
measurements were carried by using Radiant precision premier II.
Hardness of the sintered samples was measured by using Vicker’s
hardness tester by putting a load of 1 kgf for a 10 s dwell time. Diameter
tensile strength (DTS) of the sintered samples was measured by using a
universal testing machine (UTM).
3. Results and discussion
3.1. XRD study
X-ray diffraction patterns of BT, BZT-BCT, and BNT-BT-BKT samples,
synthesized by HEBM assisted solid-state reaction route, are shown in
Fig. 1. XRD peaks of all the ceramics are found to be very sharp and
distinct, confirming a single perovskite phase, without any trace of
secondary phase peaks. Calcination and sintering temperatures of BT,
BZT-BCT, and BNT-BT-BKT systems have reduced compared to the same
samples synthesized by the solid-state reaction route [6,18]. Calcination
and sintering temperatures of BT samples were optimized at 1000 ◦ C and
1250 ◦ C for 4 h, respectively. Pure phase of the BT system was estab­
lished by matching it with JCPDS card no. 05–0626 and tetragonal
structure of BT system was confirmed from the splitting of XRD peaks at
2θ–45◦ . Similarly, 1100 ◦ C and 1300 ◦ C for 4 h were optimized as
calcined and sintered temperatures of the BZT-BCT system. Pure phase
of BZT-BCT samples was identified by JCPDS card no. 05–0626. Calci­
nation and sintering temperatures of BNT-BT-BKT samples were opti­
mized at 1000 ◦ C and 1150 ◦ C for 4 h, respectively. Reduction of
synthesis temperatures of these effective lead-free ferroelectrics by
HEBM assisted solid-state reaction route is important from application
S. Swain et al. Ceramics International 47 (2021) 26511–26518

Fig. 2. Surface microstructure of (a) BT, (b) BZT-BCT, and (c) BNT-BT-BKT ceramics.

were obtained [22]. Table .1 shows the microstructure and mechanical

Table 1
properties of BT, BZT-BCT, and BNT-BT-BKT ceramics. Mechanical
Microstructure and mechanical properties of BT, BZT-BCT, and BNT-BT-BKT
properties like Vicker’s hardness, diameter tensile strength/DTS, and
ceramics.
yield strength were investigated for all three systems. Mechanical
Sample Density Average Crystallite Hv Y Σ properties depend on the density and microhardness of the sintered
Name (g/cc) Grain Size size (nm) (GPa) (GPa) (MPa)
(μm)
samples. In the present study, the hardness value of BT ceramics, sin­
tered at 1250 ◦ C/4 h was found to be ~7.23 GPa Whereas, B. Ertuget
BT 6 3.92 19.24 7.23 2.41 15.42
et al. measured hardness value as ~7.1 GPa for BT samples sintered by a
BZT-BCT 5.54 5.46 14.49 5.53 1.84 16.17
BNT-BT- 5.59 0.54 33.97 5.16 1.72 30.93 two-step sintering process and a value of ~5.73 GPa for the one-step
BKT sintering process [23]. Better hardness value of BT ceramics, synthe­
sized by HEBM assisted solid-state reaction route, can be related to its
having better density and smaller average grain size. In the present
points of view. BT, BZT-BCT, and BNT-BT-BKT systems, synthesized by study, Vicker’s hardness value of ~5.53 GPa was obtained for BZT-BCT
solid-state reaction route, require high temperature, which in turn samples. Yield strength (Y) of all the sintered ceramics was obtained by
produce coarse grains ceramics and makes them unsuitable for different the formula
applications [16]. The Crystallite size of calcined powders was obtained
by using the Debye-Scherer formula [19]. Bulk density of the sintered Y=Hv/3 (1)
samples was measured by applying Archimedes’ principle [20] and for
BT, BZT-BCT, and BNT-BT-BKT systems it is found to be ~99%, ~96%,
and ~93% of theoretical density, respectively.
Table 2
εr, tanδ, and diffusivity value of BT, BZT-BCT and BNT-BT-BKT ceramics at 1 kHz
3.2. Microstructure and mechanical study frequency.
Sample RT εr RT Tc/oC εr at Tc tanδ at Diffusivity
Fig. 2 shows SEM micrographs of sintered BT, BZT-BCT, and BNT-BT- Name (100 Hz) tanδ (1 (1 kHz) Tc (1 (1 kHz)
(100 kHz) kHz)
BKT samples. It was observed that micrographs of all samples, synthe­
Hz)
sized by HEBM assisted solid-state reaction route, are dense and well
compacted with microstructures having regular shaped grains. Average BT 2875.02 0.013 147 9691 0.0074 1.05
BZT- 5132.54 0.015 94 11,956 0.0225 1.89
grain size of BT, BZT-BCT, and BNT-BT-BKT samples is found to be BCT
smaller compared to the same systems synthesized by the solid-state BNT-BT- 1700.87 0.058 326 3926 0.0304 1.94
reaction route [6,18,21]. For BNT-BT-BKT ceramics, inhibited grain BKT
growth with rectangular shape grains having average grain size 0.54 μm

Fig. 3. Variation of εrand tanδ at (a) RT with frequency and with (b) temperature at different frequencies of BT system.

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where, Fmax, D, and t are maximum breaking force, diameter, thickness

of sintered samples respectively [24]. Among studied ceramics, the
highest DTS (σ) value of ~30.93 MPa was obtained in BNT-BT-BKT
samples, which can be attributed to its having a lower grain size [24].

Fig. 4. Variation of log (ε1r − 1

εr(max) ) vs. log (T-Tc) of BT system at 1
kHz frequency.

Fig. 7. Variation of log (ε1r − 1

εr(max) ) vs. log (T-Tc) of BZT-BCT at 1 kHz frequency.

Fig. 5. Variation of TCC(%) with the temperature of BT system at 1

kHz frequency.

where Hv is the Vicker’s hardness value of sintered samples. DTS (σ)

value was calculated by using the formula
Fig. 8. Variation of TCC(%) with the temperature of BZT-BCT system at 1
σ = (2 × Fmax)/(π × D × t) (2) kHz frequency.

Fig. 6. Variation of εrand tanδ at (a) RT with frequency and with (b) temperature at different frequencies of BZT-BCT system.

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Fig. 9. Variation of εrand tanδ at (a) RT with frequency and with (b) temperature at different frequencies of BNT-BT-BKT system.

3.3. Dielectric study

3.3.1. Dielectric study of BT system

Variation of εr and tanδ with frequency in 100 Hz to 1 MHz range at
room temperature (RT) for BT samples is shown in Fig. 3(a). A gradual
decrease of εr with the increase of frequency was observed. This can be
related to filtration of polarization with the increase of frequency [25].
An increase in tanδ with the increase in frequency suggests dissipation of
electric energy and approaching dielectric relaxation [6]. At higher
frequency, dielectric loss is caused by the dipole polarization relaxation
process as this process can not keep up with the change in frequency
resulting increase in tanδ with an increase in frequency [26]. εr~2875
with tanδ~0.015 were obtained at 100 Hz frequency for BT samples,
which are better than the earlier reports on the same system [16]. The
appearance of a high value of εr with a low value of tanδ highlights the
advantage of using the HEBM assisted solid-state processing technique
as shown in Table 2. With this synthesis method, density ~99% of the
theoretical density of BT was obtained. Moreover, the dense and uniform
grain morphology also accounts for the better dielectric properties of the
Fig. 10. Variation of log (ε1r − 1 BT system. Dielectric properties of BT system depends on processing
εr(max) ) vs. log (T-Tc) at 1 kHz frequency of BNT-BT-
BKT system. techniques as it is well reported that grain size effect plays an important
role on dielectric properties of BT system [16,27]. A higher value of εr of
BT system suggests a change in domain structure and internal stress,
which may be caused by a decrease in grain size [28]. The formation of a
smaller average grain size (~3.92 μm) in the final sintered body can
cause an increase in internal stress, which can result in the alignment of
dipoles in the same direction and an increase in polarization and εr
values, respectively. Additionally, an increase of εr suggests the increase
of 90◦ domain wall density [29]. For BT system having grain size<10
μm, domain width decreases which increases the area of 90◦ domain
walls [30].
Variation of εr and tanδ at different frequencies (1 kHz to 1 MHz)
with temperature is shown in Fig. 3(b). From RT to up to temperature
~135 ◦ C, εr, at different frequencies, was almost independent of tem­
perature. Beyond 135 ◦ C, εr increases with the increase of temperature
and reaches a maximum value ~9691 at 1 kHz frequency near ~150 ◦ C,
called Curie temperature (Tc). This high value of Tc than the earlier
reports may be due to an increase of tetragonal distortion [31]. After Tc,
εr decreases because of the transition of ferroelectric phase to para­
electric phase. Value of tanδ increases with an increase in temperature
due to mobility of ions and defects. A higher value of εr and a lower value
of tanδ was achieved in this study compared to previous literature re­
Fig. 11. Variation of TCC(%) with the temperature of BNT-BT-BKT system at 1
ports on the BT system [32,33]. Diffusivity parameter of ferroelectric
kHz frequency.
systems is calculated by using modified Curie Weiss [34]law given by

Due to a decrease in grain size, no. Of grain boundaries increases which 1 1 (T − TC )γ

− = (3)
offer more resistance to the dislocation motion and thereby the value of εr εr(max) C
σ increases.

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Fig. 12. P–E hysteresis loop of BT, BZT-BCT, and BNT-BT-BKT system.

Decrease of εr with the increase of frequency can again be related to a

Table 3 decrease in net polarization of the system. In the present study, RT value
Ps, Pr, and Ec values of BT, BZT-BCT, BNT-BT-BKT ceramics.
of εr ~5220at100 Hz frequency was observed, which is highest among
Sample Name Ps(μC/cm2) Pr (μC/cm2) Ec (kV/cm) all the reports on the same system [34,38]. In general, the enhanced
BT 31.9 10.47 4.03 value of εr is related to the MPB nature of the selected composition of
BZT-BCT 25.9 9.66 1.9 this system. There exist mixed phases: tetragonal and orthorhombic in
BNT-BT-BKT 28.5 17.5 22.8 this composition, which increases the no. Of polarization directions and
contributes more polarization and hence high εr [38].
Temperature-dependent εr and tanδ at different frequencies of the
where, εr(max) represents maximum dielectric constant at Tc, γ is the BZT-BCT system are shown in Fig. 6(b). It can be seen that phase tran­
diffusivity parameter, and C is the Curie constant. The graph between sition temperature, corresponding to ferroelectric to paraelectric phase
log (ε1r − εr(max)
1
) and log (T-Tc) of BT system at 1 kHz frequency is shown in transition, occurred at ~94 ◦ C at 1 kHz, which coincides nearly with the
Fig. 4 and diffusivity factor (γ) is calculated by the least-square fitting earlier reports on the same system [39]. Maximum value of εr at Tc was
method. Value of γ ranges from 1 (normal ferroelectrics) to 2 (diffusive found to be ~11,956 at 1 kHz, which is higher than the earlier reports on
phase ferroelectrics). From Fig. 4, γ value at 1 kHz frequency was found the same system, synthesized by other routes [11,40]. Additionally, it is
to be ~1.05, which is a characteristic of normal ferroelectric. Fig. 5 observed that, with the increase of frequency from 1 kHz to 1 MHz, Tc
shows the variation of temperature coefficient of capacitance (TCC) with shifts towards the higher temperature side, which is a signature of
the temperature of the BT system at 1 kHz frequency. Temperature relaxor ferroelectrics. Further, the diffused phase transition of this sys­
stability is defined by the temperature coefficient of capacitance (TCC), tem confirms the relaxor nature. The broad distribution of phase tran­
which describes the change in capacitance over a temperature range sition in the temperature region in a relaxor is associated with the
relative to room temperature, given by Ref. [35], randomly oriented nano polar regions, present in the system. These nano
polar regions, consisting of dipoles, do not interact with each other.
CT − CRT
TCC (%) = ( ) × 100 (4) Diffuse nature of relaxation times for different cluster orientations
CRT originates from the distribution of potential barrier separating the
where CT and CRT are the values of capacitance at any temperature over different orientational states [41]. The graph between log (ε1r − εr(max)
1
) and
the temperature range and at room temperature respectively. TCC of (± log (T-Tc) of BZT-BCT system at 1 kHz frequency is shown in Fig. 7 and
15%) was observed in the temperature range from room temperature to diffusivity factor (γ) is calculated by least-square fitting method. From
~135 ◦ C as shown in Fig. 5 and signifies the usefulness of this system for Fig. 7, γ value at 1 kHz frequency was obtained to be ~1.89, which
MLCC applications [36,37]. confirms its diffusive nature. TCC of (±15%) was observed in the tem­
perature range from room temperature to ~54 ◦ C, as shown in Fig. 8.
3.3.2. Dielectric study of BZT-BCT system
Fig. 6 (a) shows RT variation of εrand tanδas a function of frequency.

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3.3.3. Dielectric study of BNT-BT-BKT system
Fig. 9(a)shows the variation of εr and tanδ with frequency (100 Hz to
1 MHz) at room temperature. The decrease of εr with the increase of
frequency can again be related to the filtration of polarization. The in­
crease of tanδwith the increase of frequency suggests that the dielectric
relaxation process sets up near high frequencies [18]. Maximum εr and
low tanδ at RT of ~1700 and ~0.058, respectively, were observed at
100 Hz frequency. Temperature dependence of εrand tanδ as a function
of frequency (1 KHz to 1 MHz) is shown in Fig. 9(b). It can be seen that
εrincreases with the increase of temperature and having two dielectric
anomalies. The first anomaly near temperature ~120 ◦ C, named depo­
larization temperature Td, corresponds to ferroelectric to intermediate
antiferroelectric phase transition temperature [21]. Another anomaly
near ~320 ◦ C, named Tm, corresponds to antiferroelectric to paraelectric
phase transition. It is observed that dielectric peak near Tm is broad,
which is a signature of diffuse type of phase transition [42]. γ value at 1
kHz frequency was obtained to be ~1.94, shown in Fig. 10, confirmed
the diffuse phase transition nature of this system. Maximum εr of ~3926
and low tanδ of 0.0304 were observed at 1 kHz frequency for
BNT-BT-BKT system at Tm which are better than compared to properties
of the same system synthesized by solid-state reaction route [21]. TCC of
(±15%) was observed in the temperature range from room temperature
to ~75 ◦ C and shown in Fig. 11.
3.4. PE loop study
Fig. 12 shows P-E, loops at frequency 10 Hz of BT, BZT-BCT, BNT-BT-
BKT ceramics. Well saturated P-E hysteresis loops were observed for all
the ceramics, confirming their ferroelectric behaviour. Values of
remnant polarization (Pr), coercive field (Ec), and saturation polariza­
tion (Ps) for all ceramics are given in Table .3. P-E loop of BZT-BCT
ceramics was observed to be asymmetric i. e it is shifted to positive
polarization axis, which can be attributed to domain pinning effects,
caused by defects [43]. Obtained slim PE loop for the BZT-BCT system is
the characteristic feature of relaxor ferroelectrics because polar domains
are nano-sized and randomly oriented [44] which can be correlated to
the diffusive nature of the BZT-BCT system in the dielectric study.
Compared to other synthesis routes, Pr value of BT, BZT-BCT ceramics
was found to be more [31,45,46].
4. Conclusions
A decrease in processing temperatures highlighted the usefulness of
HEBM assisted solid-state reaction route. εrmax~9691, ~11,956, ~3926
with low values of tanδ~0.0074, ~0.0225, and ~0.0304 for BT, BZT-
BCT, and BN-BT-BKT ceramics, respectively, are higher than the
earlier reports on the same systems, synthesized by solid-state reaction
route. Better densification with optimum grain size was obtained in all
the sintered ceramics, which accounted for their better dielectric prop­
erties. Higher hardness and DTS values suggested their reliability for
actuator, MLCC, and also for biomedical applications. TCC of (± 15%)
was observed in the temperature range of RT tõ135 ◦ C for BT ceramics,
which highlighted its usefulness for MLCC applications.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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