Ferroelectrics

ISSN: 0015-0193 (Print) 1563-5112 (Online) Journal homepage: https://www.tandfonline.com/loi/gfer20

Effect of pore former sucrose on microstructure

and electrical properties of porous BZT-0.5BCT
ceramics

S. Abhinay, P. Dixit & R. Mazumder

To cite this article: S. Abhinay, P. Dixit & R. Mazumder (2020) Effect of pore former sucrose on
microstructure and electrical properties of porous BZT-0.5BCT ceramics, Ferroelectrics, 557:1,
18-27

To link to this article: https://doi.org/10.1080/00150193.2020.1713359

Published online: 07 Apr 2020.

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FERROELECTRICS
2020, VOL. 557, 18–27
https://doi.org/10.1080/00150193.2020.1713359

Effect of pore former sucrose on microstructure and

electrical properties of porous BZT-0.5BCT ceramics
S. Abhinay, P. Dixit, and R. Mazumder
Department of Ceramic Engineering, National Institute of Technology, Rourkela, India

ABSTRACT ARTICLE HISTORY

The present paper aims to study the effect of different pore forming Received 14 July 2019
agent on the density, porosity, pore morphology and electrical prop- Accepted 24 December 2019
erties of porous BZT-0.5BCT ceramics. The electrical property evalu-
KEYWORDS
ation is focused on dielectric constant, ferroelectric properties (P-E
BZT-0.5BCT; polyvinyl
loop) and piezoelectric constant (d33 and g33) of the porous BZT- alcohol; sucrose; dielectric
0.5BCT ceramics. BZT-0.5BCT powder was prepared by solid-state properties; piezoelec-
route. The porous ceramic was prepared by mixing BZT-0.5BCT with tric property
different percentage (10, 20, 30, 40 and 50 vol%) of polyvinyl alcohol
(PVA) and sucrose as pore-forming agents (PFA). As a result, density,
relative permittivity, remanent polarization and piezoelectric constant
decreased linearly with increase in pore former addition. The pores
derived from PVA and sucrose as pore former were spherical to
irregular in shape. Isolated pores are observed up to 30 vol% of PFA
addition and pore interconnectivity is observed at 40 vol% of PVA
and sucrose addition. The decrease in electrical properties is much
higher in sucrose when compared with PVA as a pore former.

1. Introduction
The porous piezoelectric ceramics are of interest for applications like low-frequency
hydrophones because of their high hydrostatic figure of merit and low sound velocity,
which reduces acoustic impedance and enhances coupling with water or biological tissue
[1]. The closer the impedance of piezoelectric material with ambient medium (such as
air or water), the lesser sound energy is reflected at the interface. This ‘impedance
matching’ is achieved by incorporating porosity into the piezo-ceramic that leads to
reduction in the sound velocity and in effect acoustic impedance values becomes closer
to that of water or air. The hydrostatic conditions arise in hydrophones when it
attempts to detect low-frequency signals. The reduction in permittivity (e33) of the por-
ous material as air replaces the piezoelectric ceramic increases the piezoelectric voltage
coefficients, “g” (which is equal to the electric field generated per unit hydrostatic
stress). Since piezoelectric voltage coefficient, g33 ¼ de3333 , the improved d33 (which is
hydrostatic strain coefficient), and reduced e33 of porous piezo-ceramics lead to signifi-
cant improvements in the figure of merit when compared to dense monolithic material
[2]. The increase in g33 implies an increase in the sensitivity of a hydrophone [3].

CONTACT S. Abhinay abhinaysrrm94@gmail.com

Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gfer.
ß 2020 Taylor & Francis Group, LLC
 FERROELECTRICS 19/[115]

There are numerous methods for increasing porosity of ceramics such as (1) By par-
tial sintering or selection of a granular composition for initial molding mixture [4, 5],
(2) Introduction of additives (PMMA, PVA, starch, etc.) and their subsequent removal
by evaporation, dissolution, burning-out or decomposition [6–9], (3) Involvement of air
into ceramic suspension or gas bubbles arising from chemical reaction or decomposition
of pore-former [10], (4) Extrusion of plasticized ceramic mixtures [11]. The porous cer-
amic materials are usually prepared by several shape-forming processes such as dry-
pressing, iso-pressing, slip-casting, and freeze-casting. Each preparation technique
results in the distinct microstructure, such as pore size, pore morphology, pores con-
nectivity, and pore alignment. The simple uniaxial pressing method was used in the pre-
sent work to study how the additive affects the properties of porous BZT-0.5BCT
ceramics. Zhang et al. [12] fabricated porous PZT ceramics with porosity ranging from 3%
to 40 and 3% to 43% using PMMA and stearic acid as pore formers, respectively. The
author also reported that dielectric constant and acoustic impedance decreases linearly with
increase in bulk porosity. The breakthrough made by Liu and Ren et al. in BaTiO3-based
ceramics with co-doping of Zr, and Ca has offered a significant impact on the development
of lead-free piezo ceramics. The high saturation polarization (17mC/cm2) and piezoelectric
properties (d33 > 500pC/N) of 0.5Ba(Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)TiO3 [BZT-BCT] makes it
a potential material for piezoelectric materials [13]. Abhinay et al. [14] studied the effect of
PVA & PVP as pore formers on electrical properties of BZT-0.5BCT ceramics. Porosity
ranging from 2% to 6% and 8–12% was produced by sintering at 1500  C/4h by using
PVA & PVP as pore formers, respectively. However, their study was limited to 40 vol.% of
pore former addition and did not mention the effect of porosity or pore morphology on
acoustic impedance. There are few reports where sucrose has been used as a pore former
as well as binder [15–17]. Mohanta et al. [16] fabricated porous alumina ceramics using
sucrose as a pore former with porosity ranging from 20 to 66 vol% having isolated and
inter connected porosity. Guo et al. [15] fabricated micro porous carbon materials by using
sulfuric acid pretreated sucrose. Wang et al. [17] fabricated 3D-inter connected calcium
phosphate glass ceramics using sucrose as pore formers. Sucrose which has a lower molecu-
lar weight and a shorter chain length compared to PVA. So, it is expected that it may cre-
ate different pore morphologies and connectivity in the ceramics when used as a pore
former. So, in the present work sucrose which is cheaply available has been selected as a
pore former and systematic work has been done to study the effect of pore former
(sucrose) variation (10–50 vol%) on electrical properties and compared with that of porous
BZT-0.5BCT fabricated by using PVA as a pore former. The evaluation of electrical proper-
ties is mainly focused on dielectric constant, acoustic impedance, ferroelectric, and piezo-
electric properties.

2. Experimental procedure
The BZT-0.5BCT ceramics were synthesized by solid state route. Barium carbonate
[BaCO3 (Sigma-Aldrich, 99%)], calcium carbonate [CaCO3 (Sigma-Aldrich, 99%)], zir-
conium dioxide [ZrO2 (Sigma-Aldrich, 99.9%)] and TiO2 (Sigma-Aldrich, 99.0%) were
used as the precursor materials. A stoichiometric amount of powders was pot milled for
6 h with zirconia balls using isopropyl alcohol as the media. The mixture was dried at
20/[116] S. ABHINAY ET AL.

Figure 1. (a) XRD pattern of BZT-0.5BCT with variation in calcination temperature, (b) FESEM micro-
graph of BZT-0.5BCT calcined at 1300  C/4h.

100  C overnight in an oven. The mixture was placed in an alumina crucible, which was
subsequently inserted into the furnace and heated at 1200  C and 1300  C/4hr. For the
bulk sample preparations, the calcined powder was mixed with PVA (Mol. wt 
1,15,000) and sucrose (Mol. wt  342) in different vol%. (10, 20, 30, 40, and 50 vol%)
in a mortar pestle followed by drying. The pellets from the synthesized powders were
prepared using uniaxial pressing at a pressure of 350 MPa. The sintering was done at
1400  C and 1500  C/4h. The phase identification of all the samples were characterized
using an XRD analysis [RIGAKU/ULTIMA-IV] with a Cu Ka radiation (1.54178 Å).
The powder morphology and microstructure of the sintered samples were characterized
using field emission scanning electron microscope (FESEM) [NOVA NANOSEM 450].
The density and porosity of the sintered sample were measured by Archimedes prin-
ciple. For dielectric measurement, the surfaces of the sintered pellets were polished fol-
lowed by the application of a silver conducting paste on the two opposite surfaces of
the sample. The silver paste was then cured at 550  C for 30 min. The dielectric constant
(er), dissipation factor (tand) were measured using HIOKI 3532-50 LCR Hitester. The
ferroelectric hysteresis loops were obtained for unpoled samples at room temperature
using a modified Sawyer Tower circuit. The piezoelectric strain constant (d33) was
measured on a d33 meter (YE2730A d33 tester) after poling the samples in silicone oil at
room temperature at 2 kV/mm field for 20 min. The impedance with frequency was
measured on the poled samples.

3. Results and discussion

Figure 1a depicts the XRD pattern of BZT-0.5BCT calcined at 1200 and 1300  C/4h. At
1200  C impure phases like BaTi2O5 (JCPDS No 70-1188) and BaTi4O9 (JCPDS No 34-
0070) are observed. With increasing the calcination temperature to 1300  C, the complete
phase purity can be observed. Figure 1b shows the FESEM micrograph of BZT-0.5BCT cal-
cined at 1300  C/4h. It can be observed that the particles are agglomerated with a spherical
to irregular in shape with particles size is in the range of 270–500 nm.
 FERROELECTRICS 21/[117]

Figure 2. Variation of bulk porosity as a function of PFA at (a) 1400 C/4h and (b) 1500 C/4h.

Figure 2 depicts the effect of bulk porosity with addition of PVA and sucrose as pore
former (PFA) sintered at different temperatures. The bulk porosity of porous BZT-
0.5BCT ceramics was calculated by the following equation [14]:
q  qBD
P ¼ TD  100 (1)
qTD
(true density of BZT-0.5BCT is 5.72 g/cc)
where P is the bulk porosity, qTD is the true density of the porous BZT-0.5BCT and
qBD is the measured bulk density of the porous BZT-0.5BCT. From the figure, it can be
observed that the bulk porosity increases with an increase in PFA content at a fixed
temperature and at a fixed PFA content, it decreases with an increase in sintering tem-
perature. Identification of the samples name with different percentage of PVA and
sucrose are given in Table 1. The dashed line indicates that the sites of added PFA can
be completely inherited by the resultant pores with the same volume fraction. As shown
in Figure 2, the resultant porosities were significantly lower than the corresponding vol-
ume fraction of added PFA, when sintered at high temperature. This result could be
explained by considering the sintering of a polymer-dispersed powder compact. The
added dispersed polymers may have various size and shapes. When the powder compact
was heated at high temperature (<700  C), the added PVA and sucrose pyrolyzed, leaving
the pores with the same volume fraction, as indicated by the dashed line. In the following
sintering stage, the pores and the surrounding ceramic matrix shrank. However, small pores
and tiny channels connecting the large pores disappeared due to the sintering. In effect, the
volume fraction of the pores contributing to bulk porosity was less than the volume frac-
tion of PVA and sucrose [1, 14]. It is interesting to note that the samples prepared using
sucrose and PVA have similar porosity up to 40 vol% of pore former addition when fired
at 1400  C. Further, in case of 1500  C sintered sample, sucrose-added samples shows
higher porosity compared with PVA-added samples. However, in our case significant differ-
ence between PFA content and total porosity may be attributed to the high binding prop-
erty of the PVA and sucrose and high sintering temperature [1, 14].
Figure 3 depicts the FESEM micrograph of a BZT-0.5BCT samples sintered at
1500  C/4h by using PVA as a PFA. From figure, it can be observed that the isolated
pores which were spherical to irregular in shape can be observed at low PFA content.
We can also observe that the porosity increased with an increase in PFA and size of the
22/[118] S. ABHINAY ET AL.

Table 1. Identification of samples.

Sample Index PFA
S1-10 10 vol.% PVA
S1-20 20 vol.% PVA
S1-30 30 vol.% PVA
S1-40 40 vol.% PVA
S1-50 50 vol.% PVA
S2-10 10 vol.% Sucrose
S2-20 20 vol.% Sucrose
S2 30 30 vol.% Sucrose
S2-40 40 vol.% Sucrose
S2-50 50 vol.% Sucrose

Figure 3. FESEM micrographs of S1 derived BZT-0.5BCT ceramics sintered at 1500  C/4h.

pore also increased at 30 vol% PFA. Some pore interconnectivity can be observed at 40
vol% PFA. The interconnectivity between the pores highly increased at 50 vol% PFA.
Figure 4 depicts the FESEM micrograph of sucrose-derived porous BZT-0.5BCT sam-
ples that were sintered for 4 h at 1500  C. Likewise, in PVA derived porous BZT-
0.5BCT ceramics, the isolated pores which were spherical to irregular in shape can be
observed at 10 vol% PFA content. In sucrose derived porous BZT-0.5BCT some pores
began to interconnect at 40 vol% sucrose addition and the interconnectivity gradually
increased with an increase in PFA. High pore interconnections can be observed at 50
vol% PFA content.
Figures 5a,b and 6a,b show the frequency dependence of dielectric constant (er ) and
dielectric loss (tan d) for BZT-0.5BCT with PFA sintered at 1400  C/4h and 1500  C/4h
respectively. It was observed that for a particular PFA content er value increases with an
increase in sintering temperature and tan d decreases with an increase in sintering tem-
perature. It is obvious that the density increases with an increase in sintering tempera-
ture. In comparison with sucrose derived BZT-0.5BCT ceramics, PVA derived ceramics
 FERROELECTRICS 23/[119]

Figure 4. FESEM micrographs of S2 derived BZT-0.5BCT ceramics sintered at 1500  C/4h.

Figure 5. Variation of (a) er (b) tand as a function of PFA at 1400  C/4h.

exhibited higher dielectric constants, this can be attributed to higher density in PVA
derived ceramics. Further, it was also observed that er decreases linearly with increase in
PFA. The rapid decrease in er values after 30 vol% sucrose addition may be due to the
presence of high interconnectivity in pores than PVA derived ceramics which correlates
with FESEM micrographs shown in Figure 4. Every sample shows stable frequency
response of dielectric constant and dielectric loss. However, it is to be noted that lower
dielectric constant was observed for sucrose derived samples due to its higher porosity
compared with PVA derived samples. Data given in parenthesis (Figures 5 and 6) shows
the porosity of the samples.
Figure 7 shows the polarization (Pr) vs electric field (Ec) (P–E) loops of the samples
sintered at 1500  C/4h. It can be observed from the figure that the remanent polariza-
tion decreases with increase in PFA. Hysteresis loops (P–E loops) are not considerably
saturated for the sintered samples at 1400  C/4h, as the sintering temperature is
24/[120] S. ABHINAY ET AL.

Figure 6. Variation of (a) er (b) tand as a function of PFA at 1500  C/4h.

Figure 7. Polarization vs. electric field (PE) loops of BZT-0.5BCT ceramics sintered at 1500  C/4h a) S1 b) S2.

increased to 1500  C/4h, substantially saturated hysteresis loops are observed which
might attributed to the better densification of the sintered samples at high temperature.
The samples prepared using PVA has better saturation and remanent polarization com-
pared to samples prepared using sucrose. Table 2 shows the variation in d33 and g33 of
S1 and S2 derived samples sintered at 1500  C/4h. The value of d33 is much higher in
case of PVA as compared to sucrose. The value of d33 is much higher for S1-10 sam-
ples, this may be due to the less porosity and the values of d33 has much degraded in
case of S1-40, 50 and S2-40, 50 samples, this may be due to the presence of intercon-
nected pores leading to inefficient poling of the samples.
Figure 8 shows the impedance vs. frequency curves for porous BZT-0.5BCT ceramics
produced by using PVA and sucrose as pore formers, respectively. From the diagram, it
can be observed that both resonance and antiresonance frequency decreases with an
increase in PFA. Further, it can also be observed that the difference in resonance and
antiresonance frequency is much less for sucrose added sample. The relation between
acoustic impedance and bulk porosity is given by the formula given below [1]
Acoustic impedance ¼ qBD Dofr (2)
where qBD ¼ bulk density of porous BZT-0.5BCT, Do ¼ Diameter of the sample, and
fr ¼ Resonance frequency
 FERROELECTRICS 25/[121]

Table 2. Variation of piezoelectric properties with PFA concentration at 1500  C/4hrs (a) d33 and
(b) g33.
d33 (pc/N)
(a) S1 S2
10 428 346
20 360 279
30 280 235
40 220 190
50 158 112
g33 (V-m/N)103
(b) S1 S2
10 12.5 10.6
20 11.6 9.53
30 9.67 8.93
40 8.12 8.36
50 6.13 6.01

Figure 8. Impedance vs frequency for BZT-0.5BCT ceramics sintered at 1500  C/4h (a) S1 and (b) S2.

Figure 9. Acoustic impedance of porous BZT-0.5BCT ceramics as a function of bulk porosity.

From Figure 9, it is clear that the acoustic impedance decreases linearly with increase
in bulk porosity from 17.5 to 10.7 MRayls (106 kg/m2s) and 12.8 to 10.8 MRayls (106
kg/m2s) for PVA and sucrose-derived porous BZT-0.5BCT ceramics, respectively. The
26/[122] S. ABHINAY ET AL.

decrease in acoustic impedance with an increase in bulk porosity is much less for
sucrose added sample [1].

4. Conclusions
Porous BZT-0.5BCT ceramics with porosity were prepared using sucrose and PVA as
pore former. In case of sucrose, 5–18% porosity was obtained and 3–10% porosity was
obtained fro PVA when fired at 1500  C/4h. Pores derived from PVA and sucrose as a
pore-former are spherical to irregular in shape. Pore began to interconnect at 40 vol%
sucrose pore former addition. Higher pore interconnectivity can be observed at 50 vol%
PFA in both the cases. At a given pore former content, the sucrose-derived porous
BZT-0.5BCT ceramics had higher porosity than PVA derived ceramics. With an
increase in sintering temperature, the dielectric and piezoelectric properties were
improved. The density, relative permittivity, remanent polarization and piezoelectric
constant were decreased with an increase in pore former addition. Degradation of d33
was much higher in sucrose when compared with PVA as a pore former. A higher
amount of interconnected porosity may lead to inefficient poling of the samples and
poor piezoelectric property. The acoustic impedance decreased sharply with an increase
in bulk porosity for PVA, whereas for sucrose the decrease is gradual. Thus, it can be
concluded that the porous BZT-0.5BCT ceramics may be promising for low-frequency
SONAR applications.

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