Received: 21 June 2023 Revised: 29 October 2023
DOI: 10.1111/jace.19622
RESEARCH ARTICLE
Porosity effect on the functional properties and energy
harvesting performance of Ba0.85Ca0.15Ti0.90Zr0.10O3
ceramics
Nadejda Horchidan1 Lavinia P. Curecheriu2 Vlad A. Lukacs2
Radu S. Stirbu2 Florin M. Tufescu1 Ioan Dumitru2
Cristina E. Ciomaga1
1 Department of Exact and Natural
Sciences, Institute of Interdisciplinary
Research, Al. I. Cuza University of Iasi,
Iasi, Romania
2 Dielectrics, Ferroelectrics &
Multiferroics Group, Faculty of Physics,
Al. I. Cuza University Iasi, Iasi, Romania
3 National Institute of Research and
Development for Technical Physics, Iasi,
Romania
Correspondence
Nadejda Horchidan and Cristina E.
Ciomaga, Department of Exact and
Natural Sciences, Institute of
Interdisciplinary Research, Al. I. Cuza
University of Iasi, Carol I, 700506 Iasi,
Romania.
Email: nadejda.horchidan@uaic.ro and
cristina.ciomaga@uaic.ro
Funding information
Romanian Ministry of Education and
Research, CNCS—UEFISCDI,
Grant/Award Number:
PN-III-P4-ID-PCE-2020-1988
1 INTRODUCTION
Together with the recent development of low-powered
electronics and wireless sensor technologies, piezoelectric
materials have attracted growing attention for energy har-
vesting devices due to their excellent electromechanical
conversion properties.1–5 Since 2002, when the European
Union adopted legislation to restrict or eliminate the use
J Am Ceram Soc. 2023;1–13.
Accepted: 19 November 2023
George Stoian3
Abstract
In this study, the effect of porosity on the structural and functional (dielectric, fer-
roelectric, nonlinear, and piezoelectric) properties in Ba0.85 Ca0.15 Ti0.90 Zr0.10 O3
ceramics was investigated. Various levels of microporosity in the range of 3%
to 31 vol.% have been produced using poly(methyl methacrylate) microspheres
as sacrificial templates. The structural investigation indicates a phase coexis-
tence, as expected for this composition at room temperature. The maximum
permittivity decreases with increasing porosity, from around 7000 (ceramic with
3 vol.% porosity) down to 3500 (ceramic with 31 vol.% porosity), and the Curie
temperature shifts from 47 to 67◦ C when increasing porosity, related to the pos-
sible porosity-induced structural and internal stress modifications. An enhanced
piezoelectric response was found in the Ba0.85 Ca0.15 Ti0.90 Zr0.10 O3 ceramic with
intermediate porosity around 18 vol.%, with the highest value of piezoelectric
response of 470 pC/N and a figure of merit of 7.3 pm2 /N. The optimum piezoelec-
tric properties at the intermediate porosity level are related to the microstructural
changes (pore shape and connectivity) and possible field-induced structural
modifications. The piezoelectric energy harvesting measurement results have
shown the possibility of using Pb-free porous ferroelectric materials in devices
for energy harvesting applications.
KEYWORDS
BCTZ, dc-tunability, energy harvesting, piezoelectric response, porous ceramics
of Pb in technological applications, viable alternatives to
replace Pb-based piezoelectrics are continuously searched.
The first approach to achieve high piezoelectricity in Pb-
free ferroelectrics was to place the compositions near the
morphotropic phase boundary (MPB) to enhance their
functional responses. About a decade ago, a pseudo-binary
(Ba,Ca)TiO3 –Ba(Zr,Ti)O3 (BCT–BZT solid solution)
ferroelectric similar to the classical PbZrO3 –PbTiO3
wileyonlinelibrary.com/journal/jace © 2023 The American Ceramic Society. 1
2 HORCHIDAN et al.
piezoelectric showing a high piezoelectric response
(d33 ∼620 pC/N) was reported.6 At that time, this discovery
once again returned extensive attention to the BaTiO3 -
based solid solutions. Among them, (Ba,Ca)(Ti,Zr)O3
solid solutions started to be, in the last years, the most
studied Pb-free piezoelectric systems, together with other
Pb-free piezoelectrics with valuable properties.7, 8
Dense electroceramics present superior dielectric, ferro-
, piezo-, and pyroelectric responses, but recent studies
demonstrated that introducing a certain porosity level is
beneficial for improving a few types of properties.1 For
example, a permittivity reduction while preserving a high
tunability induced by a small porosity in ferroelectric
ceramics is useful in tunability applications.9,10 The reduc-
tion of permittivity is also necessary for increasing the
piezoelectric sensing and energy harvesting performances,
but a reasonably high piezoelectric coefficient should be
maintained by considering that the piezoelectric figure of
merit (FOM) is inversely proportional to the material per-
mittivity at constant stress (ε33 T ).1,11,12 The piezoelectric
FOMs (FOMij ) is defined as
2 𝑇
𝐹𝑂𝑀𝑖𝑗 = 𝑑𝑖𝑗 ∕𝜀33 (1)
where dij represents the piezoelectric strain coefficient (the
subscripts denote the direction of applied stress (j) con-
cerning the poling direction (i)), and ε33 T represents the
permittivity at constant stress. Because ferroelectrics are
usually characterized by a high relative permittivity (e.g.,
dense (Ba,Ca)(Ti,Zr)O3 has εr ∼2000 at room tempera-
ture), one approach to obtain an increased piezoelectric
FOM is to reduce permittivity by the addition of pores
(εr ∼1). Another advantage of using porosity in ferroelectric
ceramics instead of forming composites using cheap pre-
cursors and simple processing methods, like partial sinter-
ing, replica template, the use of pore-forming agents, and
freeze casting.13–15 Such porous ceramics are of increas-
ing interest nowadays, driven by the effort to enhance
functionality and performances in various piezoelectric-
based applications, such as pressure and motion sensors,
hydrophones, actuators in robotics, ultrasound generation,
and energy harvesters.1
There are studies that explore the correlation among
porosity levels, piezoelectric properties, and energy stor-
age applications. However, the impact of microstructure
and internal stress modifications caused by different types
of porosity is still unclear. Many studies do not establish
a direct correlation between structural changes caused by
porosity and their impact on piezoelectric properties,12,16
especially for compositions near MPB where structural
modifications can have important effects.
The purpose of this study is to investigate the impact
of varying porosity levels on the functional properties of
Pb-free ceramics, specifically the Ba0.85 Ca0.15 Zr0.10 Ti0.90 O3
system, which is situated at the MPB.17,18 The study aims
to elucidate the relationship between structural changes
induced by porosity and their subsequent effects on piezo-
electric properties. This is particularly relevant for compo-
sitions near MPB, where such structural modifications can
have significant implications.
The research will explore how different levels of poros-
ity influence the microstructure and internal stress of the
ceramics and how these changes affect their piezoelectric
properties and energy storage applications. The ultimate
goal is to enhance the piezoelectric responses and piezo-
electric FOM (FOM33 ) of these ceramics for potential use
in piezoelectric-based energy harvesting applications. To
achieve this, the study will employ polymethyl methacry-
late (PMMA) microspheres as sacrificial templates to gen-
erate varying levels of porosity. The effects of these porosity
levels on the structural, microstructural, and functional
(dielectric, ferroelectric, and piezoelectric) properties of
the ceramics will be reported and comparatively discussed.
2 EXPERIMENTAL PROCEDURES
Ba0.85 Ca0.15 Zr0.10 Ti0.90 O3 (BCTZ) powders have been pre-
pared using precursors of BaCO3 , CaCO3 , ZrO2 , and TiO2
(Sigma-Aldrich, 99.9% purity) in stoichiometric propor-
tions. The raw materials were weighed and ball-milled
with distilled water for 24 h, then the mixture powder
was freeze-dried, lyophilized, sieved, and calcinated at
1000◦ C for 4 h to promote the solid-state reaction. After
calcination, the BCTZ powder was mixed and manually
re-milled by using ethyl alcohol with variable amounts of
(0%–40 wt%) PMMA (microsphere particles with a diam-
eter of around 10 μm) as a pore-forming agent in order to
prepare porous ceramics. The mixed powders have been
isostatically pressed at 1400 bar in disks of 10 mm diame-
ter. All green ceramics were subject to a thermal treatment
consisting of the following steps: increasing temperature
to 240◦ C (with 2◦ C/min) followed by slower heating up to
420◦ C (with 1◦ C/min rate) in order to allow the combus-
tion of PMMA particles and gas elimination before closing
the ceramic pores and then heating up to 850◦ C with a
rate of 2◦ C/min. These thermal processes should allow
the complete burning of the PMMA template, the gases
being eliminated and templated porosity being formed.
Further, the ceramics were heated with a rate of 5◦ C/min
up to the temperature of 1500◦ C and maintained for 2 h
in order to allow the sintering of the ferroelectric ceramic
matrix, according to the burnt-out polymer technique used
in literature.19–21 From this temperature, the ceramic was
slowly cooled down to room temperature in order to allow
full re-oxidation.
HORCHIDAN et al.
The phase composition of the calcinated BCTZ powders
and the sintered porous ceramics was determined with a
SHIMADZU X-ray diffraction (XRD) 6000 diffractometer,
using Ni-filtered CuKα radiation (λ = 1.5418 Å), with a
scan step of 0.02◦ and a counting time of 1 s/step, for 2θ
ranged between 20◦ and 80◦ . The microstructures of the
resulting sintered ceramics with different porosity degrees
have been investigated using high-resolution scanning
electron microscopy with a Carl Zeiss System NEON40EsB
(MicroImaging GmbH). The porosity of the sintered BCTZ
ceramics was determined through Archimedes’ method
and evaluated using the theoretical density of 5.687 g/cm3
for BCTZ.22 For the electric measurements, Ag electrodes
were deposited on the plane–parallel polished surfaces
of the ceramics, followed by annealing in an open-air
atmosphere at 200◦ C for 2 h. The low-field dielectric mea-
surements were carried out in a temperature range of
20–150◦ C by using LCR bridge Hameg HM8118 (Rohde &
Schwarz GmbH & Co. KG). The ferroelectric P(E) loops of
unpoled ceramics were measured using Radiant Precision
Multiferroic II Ferroelectric Test System (Radiant Tech-
nologies, Inc.) under double bipolar input with a frequency
of 1 Hz as the electric driving force. The dc-tunability
was measured at room temperature on the electroded
ceramic disks immersed in transformer oil under high
voltages produced by a function generator coupled with
a high-voltage amplifier (TREK 30/20A-H-CE, Trek Inc.);
at each applied dc field, permittivity 𝜀(𝐸) was determined
by a small voltage testing circuit (1 V amplitude, 18 kHz
sine wave).23 Before the piezoelectric measurements, the
samples were polarized in a silicone oil bath at room tem-
perature at different applied electric fields 3–40 kV/cm
for 10 min. The piezoelectric coefficient (d33 ) was deter-
mined at 24 h after poling by a quasi-static d33 meter
(Piezometer 320) (Piezotest Pte. Ltd.) using a Berlincourt-
type quasi-static meter. The piezoelectric performances
of the porous BCTZ ceramics have been measured after
room temperature poling of samples at different applied
electric fields of 3, 10, 20, 30, and 40 kV/cm, respec-
tively, followed by aging the poled ceramics for 24 h. After
every applied electric field and measurement of the piezo-
electric coefficient (d33 ), the samples were refreshed by
heating at 200◦ C for 2 h. The piezoelectric energy harvest-
ing performance was measured by using an experimental
set-up device based on the vibrational system LDS V201,
LPA100–230 V amplifier (Brüel & Kjær), signal generator
Tektronix AFG3051C, Oscilloscop Teledyne LeCroy high-
definition (2 × 200 MHz), a circuit for rectification and
energy collection, and a computer with LabVIEW pro-
gram for data acquisition. The ceramics were subjected to
a mechanical vibration under a constant applicable clamp-
ing force of approximately 3.5 N. The sinusoidal signal was
of 0.5 mV amplitude, with a variable frequency in a range
3
of 200–1200 Hz. The voltage generated by a ceramic sample
was measured after being passed through a full rectifying
bridge circuit and energy collection. This circuit contains
four BAT43 CD0000766 diodes (STMicroelectronics) and
a capacitor C of 1.5 μF. The high-definition digital oscillo-
scope records the collected signal (voltage on the capacitor
C). For these measurements, all the ceramics were poled at
room temperature for 10 min under an applied 10 kV/cm
electric field (for which the highest values of d33 were
registered).
3 RESULTS AND DISCUSSION
3.1 Phase characterization
Figure 1A,B presents the structural investigations for
the calcinated powder and BCTZ ceramics with various
degrees of porosity. The X-ray diffractogram of BCTZ pow-
ders shows a predominant BaTiO3 -based solid solution
with an orthorhombic phase structure (reference PDF
card no. 01-081-2197). The presence of small amounts of
secondary phases identified as BaZrO3 (reference PDF
card no. 01-074-1299) and CaTiO3 (reference PDF card
no. 01-078-1013) revealed that the formation of the final
perovskite composition was not completed. The sintering
treatment at 1500◦ C for 2 h promotes the formation of
the Ba0.85 Ca0.15 Zr0.10 Ti0.90 O3 perovskite phase in ceramics
without any detectable secondary phases. Previous works
indicated an influence of porosity in inducing structural
modifications in BaTiO3 ceramics19,24,25 and in its solid
solutions.8, 26 In particular, BCTZ with nominal composi-
tion around MPB is expected to show phase coexistence,
and the phase compositions are influenced by microstruc-
tural factors such as grain size and porosity level. The
observed XRD patterns of the investigated BCTZ porous
ceramics indeed show the coexistence of Orthorhombic
(O, space group Amm2) and Tetragonal (T, space group
P4mm) phases, but the presence of other polymorphs is
not excluded (Figure 1A). It is worth mentioning that the
presence of an orthorhombic phase among the BCTZ poly-
morphs is controversial. Some papers indicate that the
different temperatures of phase transitions also involve
the presence of the rhombohedral phase.27 The enlarged
view of the peak from 2θ = 45◦ shows a diffuse split-
ting of the (200) peak and the coexistence of phases with
modifications induced by increasing porosity (Figure 1B).
More than that, from Figure 1B, the XRD pattern of
Ba0.85 Ca0.15 Ti0.90 Zr0.10 O3 (BCTZ) ceramics with various
levels of porosity could demonstrate a shift of the diffrac-
tion peaks with increasing porosity, which could be related
to the presence of pores that can act to decrease in the
volume of the average unit cell, which contributes to the
4 HORCHIDAN et al.
F I G U R E 1 (A) X-ray diffraction (XRD) patterns of BCTZ calcinated powder and of the dense and porous BCTZ ceramics; (B) the
enlarged views of the peaks at 2θ ∼ 5◦ .
lattice strain and internal stress. The internal stresses are
established in the ceramic’s volume due to spontaneous
strain produced in the ferroelectric state illustrated by
the changes (shift and broadening) of relevant diffraction
peaks, such as the (200) diffraction profile at 2θ ≈ 45.5◦ .
Such modifications are reported in Refs. [19, 24–26, 28–30],
in which authors demonstrated experimentally and by
theoretical simulations that the internal stress is propor-
tional with the material Young modulus and presents a
decrease with the increasing porosity level. This shift could
also be associated with possible chemical inhomogene-
ity due to issues during the synthesis process, resulting
in a nonuniform distribution of cations within the crys-
tal lattice. The substitution of Ca2+ into the Ba-site can
be modified to the Ti-site. Because the ionic radius Ca2+
(1.06 Å) is between those of the Ba-site (1.43 Å) and Ti-
site (0.64 Å),31, 32 it is possible that Ca2+ is forced into the
Ti-site, thus the volume of the average unit cell changes.
These modifications directly impact the BCTZ material’s
properties and performance and will be discussed in
the following sections. The resolution of the standard
XRD experiment does not allow a relevant quantitative
analysis to discriminate the amounts of polymorph and
to detect possible inhomogeneity in BaTiO3 -based solid
solution (BCTZ) or porosity-induced structural changes.
However, other reported XRD investigations on similar
BCTZ composition performed by in situ analysis with
high-resolution synchrotron XRD indicated the phase
coexistence of orthorhombic and tetragonal phases and
modifications induced by microstructural parameters and
external driving forces as electric or strain–stress fields.
17, 33, 34
3.2 Microstructural analysis
Figure 2A–E shows the scanning electron micrographs
of the investigated BCTZ ceramics with 3, 8, 12, 18, and
31 vol.% of porosity, realized in cross-sections. The denser
ceramic presents a natural 3 vol.% porosity, which is inher-
ent to the densification process, whereas the increased
porosity level in the other ceramics is a result of burn-
ing out the progressively increasing polymeric content.
Using different amounts of PMMA, porosity from 8% up to
31% was produced. The dependence of porosity versus the
pore-forming PMMA amount is illustrated in Figure 2F.
The dense BCTZ ceramic realized without the addition
of PMMA (Figure 2A) presents a well-sintered homoge-
nous microstructure with an average grain size of about
10 μm, with faceted grains and perfect triple points, and
with a naturally resulting intragrain porosity uniformly
distributed inside the ceramic body. The addition of grad-
ual amounts of PMMA resulted in the formation of porous
ceramics, with different types of pore interconnectivity
([0–3] and [3–3]) when increasing the porosity level from
8 vol.% (for 5 wt% addition of PMMA) to 31 vol.% (for
40 wt% addition of PMMA), and a decrease of the BCTZ
ceramic grain size from about 10 to 4–6 μm. For low PMMA
additions (Figure 2B), the resulting pores are mostly spher-
ical, but when increasing the amount of pore-forming
HORCHIDAN et al. 5

F I G U R E 2 Scanning electron micrographs (SEMs) of fresh fractured surfaces of porous BCTZ ceramics produced by the addition of
various amounts of PMMA: (A) dense (3% natural porosity) and porous BCTZ ceramics with porosity of (B) 8%, (C) 12%, (d) 18%, and (E) 31%;
(F) porosity versus the amount of pore-forming PMMA polymer.

polymeric phase amounts, more elongated pores form due
to the plastic deformation of merged PMMA particles dur-
ing the pressing step (Figure 2C–E). Besides the increase
of porosity level, the addition of PMMA sacrificial tem-
plate also strongly impacts the ceramic morphology, giving
rise to a modification of pore shape, size, and connec-
tivity (0–3 connectivity for a low addition of PMMA to
almost 3–3 connectivity for a higher addition of 40 wt% of
PMMA).
3.3 Dielectric properties
The room temperature dielectric constant as a function of
frequency is presented in Figure 3A,B. From the frequency
dependence of the real part of permittivity (Figure 3A), it
can be noticed at 10 kHz a gradual reduction of permittivity
from 8900 (for 3% porosity) to 3070 (for 31% porosity) val-
ues, which takes place because of the “dilution effect” due
to the presence of low permittivity air pores (Figure 3A—
6 HORCHIDAN et al.

F I G U R E 3 Frequency dependence for porous BCTZ ceramics of (A) real part of permittivity (inset: dependence of permittivity vs.
porosity for the frequency of 10 kHz), and (B) dielectric loss (tanδ) versus frequency. The dependences were recorded at room temperature.

F I G U R E 4 The temperature-dependent of (A) real part of permittivity and (B) dielectric loss (tanδ) of BCTZ ceramics with different
degrees of porosity.

inset). The dielectric loss versus frequency dependences
show that in the low-frequency range (<100 Hz), the
dielectric loss of all the BCTZ ceramics increases. This
behavior is related to a small conductivity level assigned
to the interfacial polarization, local charge inhomogeneity
at the grain boundary interfaces, and the interfaces among
air pore–ceramic inside the sample volume. All the BCTZ
ceramics investigated have a dielectric loss of less than 2.5%
across the entire frequency range, even for the ceramic
with a high porosity of 31% (tanδ < 2%). Therefore, all
porous ceramics possess proper dielectric properties and
can be employed for poling and testing their piezoelectric
character (Figure 3B).
Therefore, by taking into account the porosity value of
BCTZ, the role of microstructures (pore size, shape, dis-
tribution, and connectivity) plays an essential factor in
determining the functional properties, including the low-
field dielectric properties, as the theoretical predictions are
explained in detail in Refs. [9, 35].
The temperature dependence of permittivity and dielec-
tric loss at 10 kHz frequency for the BCTZ ceramics
with different degrees of porosity are represented in
Figure 4A,B. As porosity increases, the dielectric permit-
tivity presents a decrease (Figure 4A) and a shift of the
Curie temperature from 47◦ C, in the dense BCTZ samples
to higher temperatures of around 65–70◦ C for the BCTZ
sample with 31% porosity. The maximum of the real part
of permittivity and the dielectric loss peaks correspond
to the ferroelectric-to-paraelectric transition point. There-
fore, the presence of pores in BCTZ ceramic materials
induces a shift of the Curie temperature to higher values
in dense ceramics. The same effect was reported in the
literature36, 37 and was explained by the release of internal
stresses inside the ceramic body induced by the presence
of pores. As the phase transition from the paraelectric to
the ferroelectric phase takes place during cooling when the
free energy of the ferroelectric phase is smaller than the
free energy of the paraelectric phase, the crystal surfaces
perpendicular to the c-axis of the paraelectric phase move
outward and those parallel to the c-axis move inward. The
phase transition takes place at the normal Curie point in
the absence of internal stresses. However, when the grain
HORCHIDAN et al.
F I G U R E 5 (A) Ferroelectric hysteresis loops for different porosity levels in BCTZ ceramics; (B) Remanent polarization (Pr ) and
hysteresis rectangularity factor Pr /Ps versus porosity (%) for the porous BCTZ ceramics with indicated porosity levels.
surface’s motion is constrained by the surrounding ceramic
grains, the internal stress level will increase, leading to an
increase in the free energy of the ferroelectric phase and
decreasing the Curie point because the ferroelectric phase
is less stable. Alternatively, if the movement of the crystal
surface is enhanced by the presence of pores, cracks, and
grain boundaries, the Curie point could increase. There-
fore, the investigated BCTZ ceramics with a high porosity
fraction present higher Curie points than the dense BCTZ
ceramic because porosity can reduce the material’s inter-
nal stress.13 Another explanation proposed as a possible
reason for the shift of Curie temperature could be related
to the cation ordering in the (Ba,Ca)(Ti,Zr)O3 system.38
The Ca2+ ions with larger polarization than Ba2+ ions
might strengthen the interaction between A- and B-site
ions, leading to the effective Ca2+ ions occupying both A-
and B-sites in the ABO3 perovskite structure and inducing
the long-range-order array of the lattice.8, 18, 38 In Figure 4B
(the dielectric loss vs. temperature), a more sensitive phase
transition character of porous BCTZ ceramics could be
observed. For the investigated samples, the dielectric loss
versus temperature reveals two peaks of the phase tran-
sition at about 55◦ C and about room temperature around
27◦ C, which are related to two structural phase transitions:
Tetragonal to Cubic (TT–C ) and Orthogonal to Tetragonal
(TO–T ), respectively.33
3.4 Ferroelectric properties
The modifications induced by increasing porosity on the
ferroelectric P(E) loops of BCTZ ceramics are shown in
Figure 5A,B. The samples present saturated and symmet-
rically shaped hysteresis loops, demonstrating a proper
ferroelectric response of all the investigated porous BCTZ
ceramics (Figure 5A). The remnant polarization and loop
7
squareness gradually decrease with increasing the poros-
ity fraction of BCTZ ceramics. The remnant polarization
is reduced to a half, from Pr = 7 μC/cm2 (BCTZ ceram-
ics with 3%–8% porosity) to Pr = 3.5 μC/cm2 (BCTZ
ceramic with 31% porosity), whereas the coercive field
(Ec ) is around 2.2 kV/cm and saturation polarization is
decrease from Psat ≅ 18 μC/cm2 for the denser BCTZ sam-
ple to Psat ≅ 12 μC/cm2 for the porous ones (Figure 5B).
First, it is simple to propose the decrease in polariza-
tion as only related to the presence of the air pores,
which are areas with zero ferroelectric polarization. How-
ever, the polarization reduction does not scale to the
loss in material density, and, therefore, other effects also
contribute to this dependence. Additionally, a tilting of
the P(E) hysteresis loops combined with the reduction
of rectangularity factor Pr /Ps when increasing porosity
are caused by the local electric field distribution inside
the porous material and indicate that domain switch-
ing occurs over a wider range of electric fields in the
higher porosity materials, compared to the denser mate-
rials. These two findings suggest that pores play a more
significant function in the switching process than would
be expected from a simple “dilution effect.” The experi-
mentally P(E) determined for the porous BCTZ samples
are in accordance with ones resulted from previous sim-
ulations concerning the ferroelectric switching behavior
of porous ferroelectrics,9, 35 in which it was discussed the
role of inhomogeneous field distribution determined by
the presence of porosity, the shape, and connectivity of
pores inside the ceramic body on the switching properties.
Therefore, by increasing the porosity in BCTZ ceramics, a
progressively reduced amount of ferroelectric contribution
plus the additional depolarization factor determined by the
shape of the pores and the associated electric field distribu-
tion around the pores contribute to the total polarization
response.39
8 HORCHIDAN et al.

FIGURE 6 (A) Field dependence permittivity and (B) dc-tunability versus electric field for porous BCTZ ceramics.

3.5 Nonlinear dielectric properties in tunability hysteresis area decreases with increasing poros-
porous BCTZ ceramics ity. Only for the ceramic with 31% porosity, the hysteresis
area tends to reaper.
The nonlinear dielectric character was checked for the The relative dc-tunability is represented in Figure 6B
porous BCTZ samples by measuring the variation of per- and is described with Equation (1):
mittivity under a complete increase/decrease dc field cycle
(dc-tunability), with a field amplitude of ±10 kV/cm, start- 𝜀 (0) − 𝜀 (𝐸)
𝑛𝑟 = (2)
ing from a depolarized state (Figure 6A,B). The relative 𝜀 (0)
permittivity versus the applied electric field, 𝜀(𝐸), indi-
The relative dc-tunability presents a maximum value of
cates that these ceramics present a tendency to saturation
𝑛𝑟 = 0.67 for Edc = 10 kV/cm for 12% and 18% porosi-
for dc fields above 8 kV/cm, and a reduction of permittiv-
ties, respectively (Figure 6B), followed by a reduction for
ity with increasing porosity while preserving a strong 𝜀(𝐸)
the samples with higher porosity. Therefore, with a proper
variation. From Figure 6A, it can be seen that the samples
level of porosity (10%–20%), improved tunable properties
with a porosity between 8% and 22% show peculiar depen-
can be obtained compared with dense ceramic (𝑛𝑟 = 0.59).
dencies at intermediate electric fields around 3–5 kV/cm.
It is noted that the obtained tunability values are compa-
The dielectric activity is conducted by intrinsic and
rable to or even higher than the literature-reported data
extrinsic contributions. When external electric fields are
of other porous BaTiO3 -based materials.19,45 These exper-
applied, the intrinsic contribution is expressed in dielectric
imental features support the results obtained by previous
response due to lattice distortion and domain wall propa-
finite element method simulations,46,47 which showed that
gation, and for the extrinsic contribution, a reversible or
the permittivity decreases while preserving a high degree
irreversible displacement of the domain walls or phase
of tunability for relatively low porosity levels. This behav-
boundaries motion may be responsible.40–42 Therefore, in
ior also demonstrated that the field concentration in the
the case of investigated BCTZ ceramics, which is present-
ferroelectric matrix close to the pores determines the high-
ing phase superposition around room temperature, the
field dielectric response. Therefore, the local field increase
nonlinear dielectric response at low and high applied elec-
generated in the porous structures is beneficial and leads
tric field most probably relates to domain wall mobility,
to higher values of tunability for porosity levels far below
domain switching, or domain clamping effect and may
the percolation values.
modify the weights of possible coexisting polymorphs or
even induce new phases in a reversible or irreversible way,
as, for example, in the case of dense BaTiO3 ceramics.
Additionally, introducing pores into dense ceramics will
3.6 Piezoelectric properties and energy
cause stress concentrations concentrated around the pores;
harvesting performance
moreover, the air pore interfaces can act as pinning centers
The variation of piezoelectric response and permittivity for
for domain walls, which evolve under an inhomogeneous
different levels of porosity in BCTZ ceramics is presented
electric field, thus reducing their mobility, and this could
in Figure 7A. It could be noticed that the samples present
lead to a modification in the nonlinear property of the bulk
a non-monotonous porosity dependence of piezoelectric
ceramics.19,25,26,43,44 In addition, it can be noticed that the
HORCHIDAN et al.
F I G U R E 7 Piezoelectric coefficient d33 versus porosity on (A) BCTZ ceramics poled at 10 kV/cm and (B) after poling at different electric
fields at room temperature.
coefficient d33 with an enhanced value in the range of
porosity between 7% and 18% (d33 = 470 pC/N), followed
by a slow decrease occurred above 20% porosity. As shown
in Figure 7B, the piezoelectric coefficient exhibits its
highest value when subjected to a poling electric field in
the range of 3–10 kV/cm. This result confirms the presence
of the field-induced polymorph modifications observed in
tunability measurements below 10 kV/cm.
The investigated BCTZ sample exhibits improved piezo-
electric properties when its porosity ranges from 5% to 18%.
This can be attributed to the field inhomogeneity as well
as changes in the pore geometry and connectivity of the
ceramic material. Specifically, we noticed that elongated
pores began forming in the intermediate porosity range,
leading to a change from a (0–3) connectivity to a more pre-
dominant (3–3) connectivity with some percolated pores at
higher porosity levels.
Other contributions may come from the possible field-
induced modifications of the phase composition during
poling by considering the compositional range around
MPB, where multiple polymorphs may potentially coexist.
The stability and relative quantities of these polymorphs
may be subject to change under the influence of applied
fields, and their stability and relative amounts under the
applied fields may change.17,48,49
When comparing the highest d33 obtained in the present
work for 18% porosity with values corresponding to other
lead-free porous ceramics obtained by different synthe-
sis techniques (Figure 8A), one could notice that it is
among the largest reported values. Therefore, using iso-
static pressing of BCTZ powders simply mixed with PMMA
polymer as a sacrificial template for generating porosity
was demonstrated to be a simple and effective method to
generate high piezoelectric responses with respect to other
lead-free porous piezoelectrics.8,50–55
9
Since in the intermediate porosity range, the d33
coefficient increases, while permittivity monotonically
decreases in all the porosity ranges, the requirements
for enhancing the piezoelectric FOM (FOM33 ) may be
fulfilled at the intermediate porosity level. In order to
explore the capability of these porous BCTZ ceramics to
be used for mechanical energy harvesting applications,
the calculated piezoelectric FOM, according to relation
(1) versus porosity (Figure 8B), reveals that the piezo-
electric energy harvesting FOM33 increases with increas-
ing porosity until reaching the highest value of 18%.
Therefore, peculiar BCTZ ceramics with porosity around
20% characterized by lower permittivity than the dense
one and high piezoelectric response d33 are character-
ized by enhanced piezoelectric FOMs, which make them
promising for sensing and piezoelectric energy harvesting
applications.
The piezoelectric energy harvesting performance
was measured by using an experimental setup device
(Figure S1a,b) based on the vibrational system, amplifier,
signal generator, oscilloscope, a circuit for rectification
and energy collection, and a computer with a LabVIEW
program for data acquisition. The method for measuring
the output voltage generated by converting mechanical
vibrations is similar to the one described by Roscow
et al.16
The piezoelectric energy harvesting performance was
tested for the densest BCTZ (3% porosity) (as shown in
Figure S2a) and porous ceramics with 12% (Figure S2b)
and 18% (Figure S2c) porosity, which present the highest
piezoelectric response. Figure S2a–c presents the capac-
itor load dependencies after rectifications for a selection
of frequencies in the range where the highest voltage val-
ues on the capacitor were recorded (around resonance
system frequency). It is noted that the very fast charging
10
F I G U R E 8 (A) Comparison of d33 of the porous BCZT ceramics with ones obtained for other lead-free porous piezoelectrics produced by
other methods (refs. BT freeze casting50 ; BCTZ (BURPS)51 ; BCTZ (Freeze casting)8 ; NKNS (Freeze casting)52 ; BCZT (Freeze casting), BCZT
(BURPS_PMMA), and BCZT (CNT)53 ; (B) piezoelectric energy harvesting figure of merit versus porosity level in porous BCTZ ceramics.
F I G U R E 9 Comparison of the maximum voltage recovered
with ones obtained for BaTiO3 porous ceramics in similar
conditions.
(around 2 s) of the capacitor allows increased efficiency
of the system created for energy collection. This con-
trasts the 40 s necessary to attain peak voltage in barium
titanate with a relative density of ρrel = 0.55.56 Accord-
ing to the results, the maximum voltage recovered was
approximately 0.6 V for 12% and 18% porosities, which
is slightly higher than the voltage for denser investigated
BCTZ sample (Vcap = 0.55 V). The obtained values (0.6 V)
are higher than those obtained in similar experimental
recovery conditions for BaTiO3 (0.234 V) porous ceramics
with relative densities of 55% (Figure 9) at a frequency of
100 Hz.16,56
Based on these results, it has been confirmed that the
harvested energy can be increased by increasing the poros-
ity, as predicted by the piezoelectric energy harvesting
FOMs. This demonstrates that porous ferroelectric mate-
rials can effectively be utilized as piezoelectric energy
harvesters.
HORCHIDAN et al.
4 CONCLUSIONS
This study shows that BCTZ (with porosity in the 3%–31%
range) prepared by using the PMMA polymer and burn-
out method, isostatic pressing, and composition around
MPB are characterized by high functional responses. The
analysis of dielectric, ferroelectric, piezoelectric, and non-
linear properties was done emphasizing the correlation of
microstructural modifications induced by different poros-
ity levels. This approach, rarely found in previous studies
reported in the literature, provides significant insights
related to piezoelectric properties’ study. The structural
investigation at room temperature indicates that the T
and O phases coexist, which seems to play an important
role in inducing a high d33 piezoelectric response in this
composition. The temperature dependence of permittivity
reveals that porosity induces a Curie temperature shift,
which was interpreted as due to the diminishing of the
internal stress created by porosity. Therefore, the porosity
level influences the phase composition and functional
properties. The nonlinear dielectric character has shown
the beneficial role of introducing porosity in BCTZ ceram-
ics: A low porosity level leads to increased dc-tunability
with the applied electric field while reducing permit-
tivity, and this makes such BCTZ ceramics interesting
as potential materials for tunable applications. For a
10 kV/cm poling electric field, the porous BCTZ ceramics
show a maximum piezoelectric response, with the highest
value of d33 = 470 pC/N for 18% relative porosity and
with an enhanced piezoelectric FOM33 . A significant
result obtained in this study is that the harvested energy
can be increased by increasing the porosity in the range
of (12%–18%), as predicted by the piezoelectric energy
harvesting FOMs. The maximum measured voltage across
the charged capacitor was found to be 0.6 V for BCTZ
HORCHIDAN et al.
ceramics with 12%–18% porosity, corresponding to an
improvement of 11% compared with denser ceramic.
AC K N OW L E D G M E N T S
This work was supported by a grant from the Romanian
Ministry of Education and Research, CNCS—UEFISCDI,
project no. PN-III-P4-ID-PCE-2020-1988 “Engineering of
lead-free porous ceramic materials for piezo-, pyroelec-
tric sensors with energy harvesting applications” (acronim:
EnginPOR).
C O N F L I C T O F I N T E R E S T S TAT E M E N T
The authors declare that they have no known conflicts
of interests or personal relationships that could have
appeared to influence the work reported in this paper.
ORCID
Lavinia P. Curecheriu https://orcid.org/0000-0002-1788-
1348
Vlad A. Lukacs https://orcid.org/0000-0002-9209-6649
Cristina E. Ciomaga https://orcid.org/0000-0002-1287-
7702
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S U P P O RT I N G I N F O R M AT I O N
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How to cite this article: Horchidan N,
Curecheriu LP, Lukacs VA, Stirbu RS, Tufescu FM,
Dumitru I, et al. Porosity effect on the functional
properties and energy harvesting performance of
Ba0.85 Ca0.15 Ti0.90 Zr0.10 O3 ceramics. J Am Ceram
Soc. 2023;1–13. https://doi.org/10.1111/jace.19622