Journal of the European Ceramic Society 41 (2021) 4826–4834

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Journal of the European Ceramic Society

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Sonochemically activated solid-state synthesis of BaTiO3 powders

Seung Hyun Jin a, Hae Won Lee a, Na Won Kim a, Byung-Woo Lee b, Gil-Geun Lee b,
Youn-Woo Hong c, Woo Hyun Nam d, Young Soo Lim a, b, *
a
Dept. Smart Green Technology Engineering, Pukyong National University, Busan, 48513, Republic of Korea
b
Dept. Materials System Engineering, Pukyong National University, Busan, 48513, Republic of Korea
c
Technology Convergence Division, Korea Institute of Ceramic Engineering and Technology, Jinju, 52851, Republic of Korea
d
Energy and Environmental Division, Korea Institute of Ceramic Engineering and Technology, Jinju, 52851, Republic of Korea

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

Keywords: We report the sonochemically activated solid-state synthesis of BaTiO3 powders. Unlike conventional ball-mill
Sonochemical activation mixing, coarse BaCO3 and fine TiO2 powders were sonochemically mixed in ethanol, requiring only 5 min for
Solid-state reaction full mixing and activation. Significantly accelerated phase conversion to BaTiO3 via a solid-state reaction was
BaTiO3
achieved by the sonochemical mixing, and the process exhibited almost Arrhenius-type activation behavior
Dielectric property
depending on the ultrasonic power. The sonochemical activation was attributed to the preferential fragmentation
of BaCO3 by the ultrasonic irradiation, which led to the particle size reduction and homogeneous mixing in the
sonochemical mixtures. Based on the structural, dielectric, and ferroelectric characterizations, we suggest that
the sonochemical mixing can replace the time-consuming ball-mill mixing for the solid-state synthesis of BaTiO3
powders and can also be applied to develop a time-saving, contamination-free, and cost-effective process for
various ceramic industries.

1. Introduction for homogeneous incorporation of dopants and additives into the

BaTiO3 and related ferroelectric perovskite oxides are key materials
for multi-layer ceramic capacitors (MLCCs), one of the most important
passive electronic components in a variety of industries [1–5]. As the
dielectric layer thickness decreases to accommodate the miniaturization
of MLCCs, the synthesis of BaTiO3 powders with a fine and uniform size
and low defect density has become necessary to ensure the
high-performance and reliability of the MLCCs with a high volume ef­
ficiency [3–6]. Well-dispersed, fine, and uniform BaTiO3 powders have
been prepared using a hydrothermal method [3,7,8]. However, hy­
droxyl groups inevitably incorporated in the hydrothermal process
result in the formation of intragranular pores [3,7–10], and the porosity
leads to the reduction of tetragonality and relative permittivity of the
BaTiO3 powder [6]. Furthermore, this type of intragranular pore can
accelerate the degradation in the breakdown strength of BaTiO3
dielectric layers in MLCCs [11].
Highly dense BaTiO3 powders have been conventionally prepared
based on the solid-state reaction of BaCO3 and TiO2 starting powders at
high temperatures [12–14]. Compared to the hydrothermal process, the
solid-state synthesis is cost-competitive and is an advantageous process
perovskite lattice [1,3,15]. However, under conventional solid-state
synthesis conditions using coarse starting powders (> 1 μm) at high
calcination temperatures (~ 1200 ◦ C), coarse particle sizes, strong
agglomeration, and a broad size distribution are typically observed in
the solid-state synthesized BaTiO3 powders, which are incompatible
with the processing of thin dielectric layers in MLCCs [3,12]. Mean­
while, recent studies have shown that the solid-state synthesis of BaTiO3
can be completed at relatively low temperatures (≤ 1100 ◦ C) when
using ultrafine raw powders or high-energy ball milling, which me­
chanically downsizes and activates the raw powders [15–22].
As the solid-state reaction is primarily controlled by the coupled
diffusion of Ba2+ and O2− ions into the TiO2 lattice, downsizing the raw
powders of BaCO3 and TiO2 and their homogeneous and intimate mixing
are crucial in the solid-state synthesis of BaTiO3 [15–22]. In this regard,
ball milling is a key process for the homogeneous and intimate mixing of
BaCO3 and TiO2 and downsizing the raw materials to maximize the
contact surface between them, which facilitates the diffusion-controlled
phase transition [1]. Nonetheless, this ball milling generally requires a
long processing time to achieve the necessary degree of downsizing and
mixing. In addition, unfavorable contaminations from the milling media

* Corresponding author at: Dept. Smart Green Technology Engineering, Pukyong National University, Busan, 48513, Republic of Korea.
E-mail address: yslim@pknu.ac.kr (Y.S. Lim).

https://doi.org/10.1016/j.jeurceramsoc.2021.03.043
Received 26 January 2021; Received in revised form 19 March 2021; Accepted 20 March 2021
Available online 24 March 2021
0955-2219/© 2021 Elsevier Ltd. All rights reserved.
S.H. Jin et al. Journal of the European Ceramic Society 41 (2021) 4826–4834

may occur, which can be more problematic when high-energy ball

milling is used [1,20,16–22].
To overcome the inherent disadvantages of the ball milling process, a
sonochemical mixing process, which uses ultrasonic irradiation for the
mixing of raw materials, has been developed for the solid-state synthesis
of BaTiO3 powder [23,24]. Although this is a very promising process,
only few studies have been reported thus far. Rotaru et al. reported that
the solid-state synthesis of BaTiO3 powder could be considerably
accelerated by the sonochemical mixing in aqueous solutions [23].
Akbas et al. also reported on the sonochemical activation effect on the
solid-state synthesis of BaTiO3 powders [24]. Furthermore, they
described a comparative study of BaTiO3 ceramics produced from
powders synthesized through sonochemical and conventional ball-mill
mixing. They claimed that the sintering behavior and dielectric prop­
erties of BaTiO3 ceramics could be improved by the sonochemical
mixing; however, they did not provide a detailed mechanism for the
improvement. Since the structural and dielectric properties of BaTiO3
ceramics are strongly determined by the powders used for the sintering
[3–5], their result suggests that the properties of the BaTiO3 powder
(size, nonstoichiometry, defect, etc.) could be considerably modified just
by the mixing method, although the raw materials and the calcination
conditions for the solid-state synthesis were all the same. Nonetheless,
they compared the properties of a limited number of samples, and a
systematic assessment of the detailed effect of sonochemical mixing on
these properties has not been reported yet.
Here, we describe and evaluate the sonochemically activated solid- Fig. 1. Schematic of the sonochemical mixing process.
state reaction for synthesizing BaTiO3. The solid-state reaction to
BaTiO3 was considerably accelerated by the sonochemical mixing con­ 2.2. Characterization
ducted for only 5 min, and the detail mechanism of the sonochemical
activation in the solid-state synthesis of BaTiO3 was discussed on the Crystal structures were investigated using an X-ray diffractometer
basis of microstructural, crystal-structural, thermogravimetric charac­ (XRD, Ultima IV, Rigaku Corp, Tokyo, Japan) with a step size of 0.02◦
terizations. Furthermore, we demonstrate that the dielectric and ferro­ and scan speed of 1 s/step. The conversion rate of the sonochemical
electric properties of BaTiO3 ceramic prepared through sonochemical mixtures to BaTiO3 phase through the solid-state reaction and detailed
mixing are comparable to those of ceramic prepared through conven­ crystal structure of the resulting BaTiO3 powders were characterized by
tional ball-mill mixing. Our results pave the way for the development of Rietveld refinements using Profex software (version. 3.14.3) [25]. The
a time-saving, cost-effective, and contamination-free process in the particle size distributions were characterized by using a particle size
solid-state synthesis of ceramic powders. analyzer (PSA, LA-950, Horiba Ltd., Kyoto, Japan). Thermogravimetric
analysis (TG, DTG-60H, Shimadzu, Kyoto, Japan) under a 0.1 L/min
2. Material and methods flow of dry air at 1 atm pressure was performed to evaluate the weight
loss of the starting powders between room temperature and 1300 ◦ C at a
2.1. Sample preparation constant heating rate of 5 ◦ C/min. Microstructural characterizations
were performed by using a scanning electron microscope (SEM, Mira 3,
Reagent-grade BaCO3 (≥ 99 %; Sigma-Aldrich, St. Louis, Missouri, Tescan, Brno, Czech) and a spherical aberration-corrected transmission
USA) and TiO2 (≥ 99 %; Sigma-Aldrich, St. Louis, Missouri, USA) were electron microscope (TEM, Titan Themis Z, FEI Company, Hillsboro,
used as starting materials. The equimolar mixtures (total 20 g, Oregon, USA) using an energy dispersive spectrometer (EDS, Super-X,
14.2378 g of BaCO3 and 5.7622 g of TiO2) of the starting materials were FEI Company, Hillsboro, Oregon, USA). The Ba/Ti ratio in the
dispersed in ethanol (150 mL) in 250 mL beakers, and then they were calcined powder was characterized by X-ray Fluorescence (XRF,
sonochemically mixed using an ultrasonic homogenizer (Boshi Elec­ XRF-1800, Shimadzu, Kyoto, Japan). Dielectric measurements were
tronic Instrument, Hangzhou, China) with the ultrasonic power levels of performed from − 120 to 170 ◦ C in a custom-designed furnace by using
300, 400, 600, and 900 W at 20 kHz for 5 min. The diameter of the ul­ an LCR meter (HP 4194A, Hewlett-Packard, Palo Alto, California, USA)
trasonic probe was 16 mm, and the gap between the probe and the with an oscillating voltage of 1.0 V. Ferroelectric measurements were
bottom of the beaker was maintained at 15 mm (Fig. 1). For a performed at room temperature using a ferroelectric tester (TF Analyzer
comparative study, a conventional ball-mill mixing of the same raw 2000, AixAcct, Aachen, Germany) with a 1 Hz frequency.
materials was also performed with stabilized zirconia balls (diameter:
5 mm) in alcohol for 24 h. These mixtures were dried in an oven at 3. Result and discussion
120 ◦ C and then calcined at 900–1200 ◦ C in air for 3 h with a heating
rate of 3 ◦ C/min. The calcined powders were mixed with 1–2 wt% 3.1. Effect of sonochemical mixing on the particle size distribution of raw
polyvinyl alcohol binder (PVA, Mw 85,000–124,000, Sigma-Aldrich, St. materials
Louis, MO), and then uniaxially pressed at 100 MPa. The binder was
burned out at 500 ◦ C for 60 min and subsequently sintered at 1300 ◦ C in Because the solid-state synthesis of BaTiO3 is strongly dependent on
air for 4 h. For dielectric and ferroelectric measurements, silver paste the particle size distribution of raw materials, we first investigated the
was deposited on the polished surfaces by screen-printing and a heat effect of sonochemical mixing on the particle size distribution of the
treatment was conducted at 600 ◦ C for 1 h. starting powders. Fig. 2(a) shows the particle size distributions in the
mixtures of BaCO3 and TiO2 powders, which were sonochemically
mixed in ethanol for 5 min. All the mixtures exhibited a bimodal size
distribution due to the coexistence of submicron-sized TiO2 and micron-

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S.H. Jin et al.
Fig. 2. (a) Particle size distributions of the physical and sonochemical mixtures
of micron-sized BaCO3 and submicron-sized TiO2 starting powders. A TEM
micrograph of TiO2 is shown in the inset. (b) and (c) are SEM micrographs of
pristine and 900 W-sonicated BaCO3 in ethanol for 5 min.
sized BaCO3. The mean particle size of TiO2 (d50 ~ 80 nm) was not
affected by the sonochemical mixing, and the value was in reasonable
agreement with the TEM result in the inset.
However, as the ultrasonic power increased, the mean particle size of
BaCO3 decreased monotonically from ~3.8 μm (pristine) to ~2.7 μm
(900 W). Furthermore, as compared to the physical mixture (pristine),
sonochemical mixtures exhibited a slightly increased frequency in the
submicron region (~0.1 μm) as indicated by the arrow in Fig. 2(a). This
can be attributed to the fragmentation of BaCO3 particles during the
sonochemical mixing. Sonochemical irradiation induces pressure waves
in the liquid, leading to the formation of cavities, which will collapse
implosively when the internal pressure is sufficiently high [26,27]. The
collapse of the cavity releases energy in the surrounding liquid through
microjet impact and shockwave damage. This cavitation process can
lead to the sudden and extreme increases in local pressure and tem­
perature. The cavitation energy transferred to the particles dispersed in
the vicinity of the collapsing cavity can give rise to the deagglomeration
and/or fragmentation of the particles [28–30], and this sonochemical
fragmentation renders the particle size distribution bimodal, as reported
by Kusters et al. [30]. Therefore, the reduced particle size in the
micron-sized region and the increased frequency in the submicron-sized
region suggest together the preferential fragmentation effect of BaCO3
particles during the sonochemical mixing process.
To obtain more direct evidence of the sonochemical fragmentation,
we compared the microstructure of BaCO3 powder before and after
sonochemical irradiation at 900 W for 5 min in ethanol. As shown in
Fig. 2(b), the pristine BaCO3 powder mostly comprises micron-sized
particles with typical needle-like shapes [15], and submicron-sized
fragments were hardly observed in the SEM measurements. Mean­
while, in the sonochemically irradiated powder, fragments with a size of
~ 100 nm could be easily observed as indicated by the arrows in Fig. 2
(c). However, this kind of fragmentation was not observed at all in the
TiO2 powders. Therefore, these results revealed that the preferential
fragmentation of BaCO3 particles occurred by the sonochemical mixing,
and similar preferential crystallographic degradation of BaCO3 has been
reported in mechanically activated mixtures [22].
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Journal of the European Ceramic Society 41 (2021) 4826–4834
Furthermore, we performed the TEM-EDS measurements of a 900 W-
sonochemical mixture of BaCO3 and TiO2. Fig. 3(a) shows a high-angle
annular dark-field (HAADF) TEM micrograph of the mixture, and Fig. 3
(b) and (c) show the EDS spectra obtained from points 1 and 2 in the
HAADF image, respectively. From the HAADF image and EDS spectra, it
was clearly observed that TiO2 nanoparticles (point 1) were surrounded
by ultrafine BaCO3 fragments (point 2) tens of nanometers in size that
can increase the contact surface between the powders. This result con­
firms that the sonochemical mixing not only leads to size reduction of
the BaCO3 raw materials, but it also promotes the intimate mixing be­
tween the raw materials in the mixture.
3.2. Enhanced solid-state synthesis of BaTiO3 powders by sonochemical
mixing
The sonochemically mixed powders at each ultrasonic power (300,
400, 600 and 900 W) were calcined at 900–1200 ◦ C in air for 3 h, and
the resulting crystal structures were investigated by XRD. In this calci­
nation temperature range, only two phases, tetragonal BaTiO3 and
Ba2TiO4, were identified for all calcined powders and unreacted TiO2
was not detected by XRD [15]. Fig. 4 shows the XRD patterns of the
powders calcined at 1000 ◦ C as an example, exhibiting the decrease in
the intensity of the Ba2TiO4 secondary phase with the increase in the
ultrasonic power (highlighted by the dotted box in the figure). To
determine the details of the effect of the ultrasonic power on the con­
version ratio, we performed Rietveld refinements of the XRD patterns
using Profex software.
Fig. 5 shows the Arrhenius-type ultrasonic power-dependence of the
BaTiO3 conversion ratio at each calcination temperature, which was
determined through Rietveld refinements. It is noteworthy that the
phase conversion to BaTiO3 increased almost exponentially by
increasing the ultrasonic power. In particular, 900 W-sonochemical
mixtures were almost fully transformed to single-phase perovskite (≥ 99
%), as highlighted by the dotted box, which correlates to the calcination
temperature higher than 1000 ◦ C. Therefore, it was confirmed that the
sonochemical mixing conducted for only 5 min activates the starting
materials and enhances the solid-state reaction similar to mechanical
activation using high-energy ball milling [20–22]. It is noteworthy that
this process leaves no intrinsic contaminations in the mixture, which
differs from the high-energy ball milling.
The solid-state synthesis of BaTiO3 can be divided into three stages
[12–17]. In the initial stage, BaTiO3 nucleates at the contact surface
between BaCO3 and TiO2 by rapid surface diffusion as presented in re­
action (1), and further growth of the BaTiO3 shell proceeds with the
diminishing TiO2 core [14,13–17]. Using TEM and XRD, Lee et al. re­
ported that the surface diffusion appeared at ~400 ◦ C and the nucle­
ation began to be observed at ~500 ◦ C when ultrafine BaCO3 and TiO2
powders were used [19]. Furthermore, based on TG analysis, many
authors have observed that this direct reaction (1) occurs at relatively
low temperatures (500–700 ◦ C) when raw materials are ultrafine and/or
mechanically activated [15–21].
BaCO3 (s) + TiO2 (s) → BaTiO3 (s) + CO2 (g) (1)
As the formation of BaTiO3 proceeds, the solid-state reaction tends to
be retarded by the slow lattice diffusion through the BaTiO3 shell. Thus,
it gives rise to the formation of Ba-rich secondary phase of Ba2TiO4
between the BaCO3 raw powder and the BaTiO3 shell through the re­
action (2), leading to the spatial separation between the secondary phase
and unreacted core by the BaTiO3 shell [14]. Because the lattice diffu­
sion process across the BaTiO3 layer can be effectively operative at high
temperatures, especially above the decomposition temperature of
BaCO3 (~ 830 ◦ C in air), the formation of BaTiO3 involves the decom­
position process of BaCO3 and proceeds through the reactions (3) and
(4) [15–17].
BaCO3 (s) + BaTiO3 (s) → Ba2TiO4 (s) + CO2 (g) (2)
S.H. Jin et al.
Fig. 3. (a) A HAADF image of 900W-sonochemical mixture. (b) and (c) are EDS spectra obtained from points 1 and 2 in.(a), respectively. The EDS spectra in (b) and
(c) indicate that the particles in points 1 and 2 are TiO2 and BaCO3 fragment, respectively.
Fig. 4. XRD patterns of 1000 ◦ C-calcined sonochemical mixtures.
Fig. 5. Arrhenius-type ultrasonic power-dependence of the conversion ratio at
each calcination temperature (900–1200 ◦ C).
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Journal of the European Ceramic Society 41 (2021) 4826–4834
BaCO3 (s) → BaO (s) + CO2 (g) (3)
BaO (s) + TiO2 (s) → BaTiO3 (s) (4)
For the completion of the solid-state synthesis of BaTiO3, the Ba2TiO4
secondary phase should disappear by the reaction with remaining TiO2,
as described in reaction (5) [14]. This reaction is quite slow as compared
to the other reactions and proceeds gradually. Beauger et al. proposed
the spatial separation of Ba2TiO4 and TiO2 as an origin of the slow rate,
and they proved this model using diffusion couple experiments [14].
Ba2TiO4 (s) + TiO2 (s) → 2BaTiO3 (s) (5)
In terms of the diminishing core model discussed above, the particle
size of TiO2 is of paramount importance because the phase conversion
occurs through the inward diffusion of Ba2+ and O2− into the TiO2 core.
The smaller the TiO2 particle size, the larger the contact surface and the
shorter the diffusion length. However, the size of BaCO3 is also impor­
tant. Hennings et al. reported that submicron-sized BaCO3 (~170 nm)
strongly inhibits the formation of the Ba2TiO4 secondary phase and re­
duces the temperature for the complete conversion into BaTiO3 to
900 ◦ C [15]. Buscaglia et al. reported that, when ultrafine BaCO3 and
TiO2 powders or BaCO3-TiO2 core-shell powders with maximized con­
tact surfaces are introduced, complete conversion to BaTiO3 can be
achieved even through the reaction (1) alone at temperatures below
700 ◦ C [17,31]. On the other hand, when BaCO3 particles are
micrometer-sized or poorly mixed with TiO2, the reaction (1) barely
occurs and the phase conversion to the perovskite phase proceeds only
through the high-temperature reactions of (2)–(5) instead, leading to the
agglomeration and coarsening of the resulting powders [3].
In this experiment, only two phases, BaTiO3 and Ba2TiO4, were
observed by XRD in all powders calcined in the temperature range of
900–1200 ◦ C. At a given calcination temperature, the degree of the
phase conversion to BaTiO3 was almost exponentially proportional to
the ultrasonic power. If the reaction was mostly dominated by the high-
temperature reactions, the phase conversion ratio should be almost in­
dependent of the ultrasonic power for two reasons. First, the decom­
position temperature of BaCO3 is constant regardless of the BaCO3
particle size [15]. Second, diffusivity of any diffusing species into the
TiO2 core, a deterministic factor of the high-temperature reactions,
should be the same at a given temperature. Therefore, we can assume
that the difference made by the ultrasonic power reflects the degree of
S.H. Jin et al. Journal of the European Ceramic Society 41 (2021) 4826–4834

the phase conversion through the direct reaction (1), which is highly
dependent on the particle size. As the ultrasonic power increases,
submicron-sized BaCO3 fragments increasingly populate in the sono­
chemical mixtures and react directly with TiO2, leading to the acceler­
ated solid-state synthesis of BaTiO3 powders. Micron-sized BaCO3
particles unreacted at this initial stage contribute to the solid-state
synthesis after their decomposition at higher temperatures.
In order to elucidate this mechanism, differential TG (DTG) charac­
terizations of physical and 300, 600, and 900 W-sonochemical mixtures
were performed with a constant heating rate of 5 ◦ C/min, which can
indicate the temperatures when the formation of BaTiO3 occurs inten­
sively. The results are shown in Fig. 6. The physical mixture exhibited
two distinct DTG peaks at ~830, and ~980 with a shoulder peak at
~930 ◦ C. Because all the peaks were observed above the decomposition
temperature of BaCO3 (~ 830 ◦ C), this result shows that the weight loss
proceeded through the high-temperature routes (2)–(5), owing to the
coarse BaCO3 particle size. Meanwhile, the sonochemical mixture
exhibited only two DTG peaks comprising a shoulder peak at
670–700 ◦ C (peak A) and a major peak at ~ 830 ◦ C (peak B). The low-
temperature DTG peak (A) demonstrates that the direct reaction (1)
could appear due to the submicron-sized BaCO3 fragments produced by
the sonochemical mixing [15–21]. As the ultrasonic power increased,
the intensity of the shoulder peak A increased. This result indicates that
the degree of the fragmentation involved in the reaction (1) increased
with the increase in the ultrasonic power. Furthermore, the
high-temperature reaction corresponding to the peak B finished at
relatively low temperatures with increasing ultrasonic power as marked
by the arrow owing to the fragmentation and intimate mixing effect.
Based on these results, we concluded that the sonochemical mixing ac­
celerates the solid-state synthesis of BaTiO3 by reducing the BaCO3
particle size through the sonochemical fragmentation and correspond­
ingly by increasing the degree of mixing.

Fig. 7. (a) Lattice constants and (b) tetragonality of calcined powders as a

3.3. Structural properties of BaTiO3 powders prepared by sonochemically
activated solid-state reaction
Fig. 7(a) and (b) show the lattice parameters and corresponding
tetragonality of the BaTiO3 phase in each calcined powder, respectively.
Although the calcined powders exhibited different phase conversion
ratios depending on the ultrasonic power and calcination temperature as
shown in Fig. 5, a trend of increasing tetragonality with increase in the
calcination temperature is evident. The average tetragonality of the
BaTiO3 phase in 900, 1000, 1100, and 1200 ◦ C-calcined powders were
0.52, 0.67, 0.85 and 0.96 %, respectively. On the other hand, the ul­
trasonic power, which significantly affected the phase conversion ratio,
seemed not to clearly affect the tetragonality.
Fig. 6. DTG curves for the solid-state reaction of the physical and sonochemical
mixtures with a constant heating rate of 5 ◦ C/min in air.
function of calcination temperature at each ultrasonic power (300–900 W).
Meanwhile, calcination temperature can strongly affect the particle
size of the resulting BaTiO3 particles, consequently determining the
tetragonality. To characterize the effect of the calcination temperature
on the structural properties of BaTiO3 powders prepared via the sono­
chemically activated solid-state reaction, we chose the powders with a
phase conversion ratio of ≥ 99 %. As indicated by the dotted box in
Fig. 5, 900 W-sonochemical mixtures could be almost fully converted to
a single perovskite phase by the calcination at 1000, 1100, and 1200 ◦ C
for 3 h. They are referred to as SC-1000, SC-1100, and SC-1200,
respectively. Fig. 8 shows their microstructures and particle size distri­
butions. The BaTiO3 particle size increased when increasing the calci­
nation temperature; however, the particle size was in submicrometers in
all samples. The average particle sizes in SC-1000, SC-1100, and SC-
1200 measured by SEM were ~254, ~305 and ~355 nm, respectively,
and the BET surface areas (SBET) of the samples were characterized as
~4.8, ~4.6, and ~2.9 m2/g, respectively. Assuming completely dense
particles (density, ρ =6.02 g/cm3) as they were prepared at high tem­
peratures, their equivalent BET diameters (dBET = 6/(ρ⋅SBET)) were
estimated to be ~180, ~292, and ~369 nm, respectively, and these
values were in reasonable agreement with the SEM results. The crys­
tallite size was also increased with the calcination temperature. The
values for SC-1000, 1100 and 1200 were calculated to be ~64, ~77 and
~81 nm from the XRD pattern in Fig. 4, respectively. Therefore, the
increase in the tetragonality with increasing the calcination temperature
(0.70 % for SC-1000, 0.84 % for SC-1100 and 0.94 % for SC-1200) was
caused by the particle coarsening [32].
For comparison, BaTiO3 powders were also prepared by the solid-
state reaction under the same experimental condition, except for the
mixing method. Fig. 9 shows SEM micrographs and particle size distri­
butions of the BaTiO3 powders prepared by the calcination of the ball-

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S.H. Jin et al.
Fig. 8. (a)–(c) SEM micrographs of SC-1000, SC-1100, and SC-1200 powders, respectively. (d)–(f) Corresponding particle size distributions measured from (a)–(c),
respectively.
milled mixtures for 24 h. Based on the calcination temperatures, they
are referred to as BM-1000, BM-1100, and BM-1200 for 1000, 1100, and
1200 ◦ C, respectively. The average particle size of BM-1000, BM-1100,
and BM-1200 measured by SEM were ~ 238, ~312, and ~351 nm and
those by BET were ~189, ~245, and ~348 nm, respectively. These
values were quite similar to those of sonochemically prepared powders.
Furthermore, the crystallite sizes of the BM-series were also similar to
those of SC-series (~62, ~72 and ~80 nm for BM-1000, BM-1100 and
BM-1200, respectively). Therefore, it was confirmed that the sono­
chemical mixing conducted for only 5 min can provide the same result
as the time-consuming ball-mill mixing from the viewpoint of the par­
ticle size.
3.4. Dielectric and ferroelectric properties of BaTiO3 ceramics
Fig. 10 shows SEM micrographs of the fractured surfaces of BaTiO3
ceramics sintered at 1300 ◦ C for 4 h using SC-1100 and BM-1100 pow­
ders, respectively. Because the Ba/Ti ratio measured by XRF were 1.003
for SC-1100 and 1.000 for BM-1100, the nonstoichiometric effect on the
sintering behavior was negligible [33,34]. Their density was higher than
98 % in all samples, and their grain size was in the same range within a
few microns of each other. Therefore, unlike the report of Akbas et al.
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Journal of the European Ceramic Society 41 (2021) 4826–4834
[24], no significant difference was observed between the sintering
behavior of the powders. Owing to the similar grain size and density, it
was possible to compare the dielectric and ferroelectric properties of the
ceramics directly and rule out the scaling effect which was caused by
external contributions [5,35–41].
Fig. 11(a) shows the dielectric constant and dielectric loss as a
function of temperature measured at a frequency of 10 kHz for SC-1100
and BM-1100 ceramics. Their dielectric loss was less than 3% over the
entire temperature range; this indicates that the quality of sintering is
appropriate for the dielectric measurements. At similar phase transition
temperatures, both ceramics exhibited three typical dielectric anomalies
corresponding to the phase transitions from rhombohedral to ortho­
rhombic, from orthorhombic to tetragonal, and from tetragonal to cubic
phase [5]. The room temperature dielectric constant was quite similar to
each other (3321 for SC-1100 and 3416 for BM-1100), and no significant
difference was observed in the ceramics over the entire temperature
range. Their Curie constant (1.93 × 105 K for SC-1100 and 1.87 × 105 K
for BM-1100) and Curie-Weiss temperature (92.2 ◦ C for SC-1100 and
91.9 ◦ C for BM-1100) were also quite similar to each other.
Fig. 11(b) shows polarization-electric field (P-E) hysteresis loops of
SC-1100 and BM-1100 ceramics measured at room temperature. Both
ceramics exhibited the saturation polarization (Ps) under an electric field
S.H. Jin et al. Journal of the European Ceramic Society 41 (2021) 4826–4834

Fig. 9. (a)–(c) SEM micrographs for BM-1000, BM-1100, and BM-1200 powders, respectively. (d)–(f) Corresponding particle size distributions measured from (a)–
(c), respectively.

Fig. 10. SEM micrographs of the fractured surfaces of (a) SC-1100 and (b) BM-1100 ceramics.

of 30 kV/cm, and Ps were measured to be almost the same value of 26.2
μC/cm2 for both ceramics. The remnant polarization (Pr) and coercive
field (Ec) were 14.7 μC/cm2 and 3.50 kV/cm, respectively, for SC-1100
ceramic, and those for BM-1100 ceramic were in a practically compa­
rable range (Pr: 14.1 μC/cm2 and Ec: 3.95 kV/cm). Since these dielectric
and ferroelectric properties are strongly affected by many factors, such
as the grain size and distribution, density, tetragonality and non­
stoichiometry, these results demonstrate that the quality of SC-1100 is
almost identical to that of BM-1100 both in powders and ceramics.

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Fig. 11. (a) Temperature-dependent dielectric constants and losses and (b)
room temperature P-E hysteresis loops of SC-1100 and BM-1100 ceramics.
4. Conclusions
In summary, the sonochemical mixing effect on the solid-state syn­
thesis of BaTiO3 powders was systematically investigated. When
increasing the ultrasonic power, the phase conversion ratio to the
BaTiO3 phase was increased exponentially. This sonochemical activa­
tion was attributed to the preferential fragmentation of micron-sized
BaCO3 raw powder in the sonochemical mixtures, leading to particle
size reduction and homogeneous mixing between the raw materials.
Consequently, even if coarse BaCO3 powders were used, submicron-
sized BaTiO3 powder with high tetragonality could be prepared suc­
cessfully through the sonochemically activated solid-state reaction. The
role of the sonochemical fragmentation of BaCO3 on the accelerated
solid-state reaction was discussed based on the thermogravimetric
analysis. Moreover, structural, dielectric and ferroelectric character­
izations of the resulting powders and ceramics revealed that sono­
chemical mixing can replace the conventional ball mill mixing for the
solid-state synthesis of BaTiO3 powders. We believe that this sono­
chemically activated solid-state synthesis of BaTiO3 will be effective in
developing a time-saving, contamination-free, and cost-effective process
in highly competitive MLCC and related ceramic industries, through
further process optimization.
Declaration of Competing Interest
The authors declare no conflict of interest.
Acknowledgments
This work was supported by the Competency Development Program
for Industry Specialist (P0012451) through the Korea Institute for
Advancement of Technology (KIAT) funded by the Ministry of Trade,
Industry and Energy (MOTIE), and also supported by the Basic Science
Research Program (2020R1I1A3052042) through the National Research
Foundation of Korea (NRF) funded by the Ministry of Education,
4833
Journal of the European Ceramic Society 41 (2021) 4826–4834
Republic of Korea.
References
[1] G.H. Haertling, Ferroelectric ceramics: history and technology, J. Am. Ceram. Soc.
82 (1999) 797–818.
[2] H. Kishi, Y. Mizuno, H. Chazono, Base-metal electrode-multilayer ceramic
capacitor: past, present and future perspectives, Jpn. J. Appl. Phys. Part 1 (42)
(2003) 1–15.
[3] C. Pithan, D. Hennings, R. Waser, Progress in the synthesis of nanocrystalline
BaTiO3 powders for MLCC, Int. J. Appl. Ceram. Technol. 2 (2005) 1–14.
[4] K. Hong, T.H. Lee, J.M. Suh, S.–H. Yoon, H.W. Jang, Perspectives and challenges in
multilayer ceramic capacitors for next generation electronics, J. Mater. Chem. C 7
(2019) 9782–9802.
[5] V. Buscaglia, C.A. Randall, Size and scaling effects in barium titanate. An overview,
J. Eur. Ceram. Soc. 40 (2020) 3744–3758.
[6] T. Tsurumi, T. Sekine, H. Kakemoto, T. Hoshina, S. –M. Nam, H. Yasuno, S. Wada,
Evaluation and statistical analysis of dielectric permittivity of BaTiO3 powders,
J. Am. Ceram. Soc. 89 (2006) 1337–1341.
[7] B. Jiang, J. Iocozzia, L. Zhao, H. Zhang, Y. –W. Harn, Y. Chen, Z. Lin, Barium
titanate at the nanoscale: controlled synthesis and dielectric and ferroeletric
properties, Chem. Soc. Rev. 48 (2019) 1194–1228.
[8] S. Wada, T. Suzuki, T. Noma, Preparation of barium titanate fine particles by
hydrothermal method and their characterization, J. Ceram. Soc. Jpn. 103 (1995)
1220–1227.
[9] D. Hennings, S. Schreinemacher, Characterization of hydrothermal barium
titanate, J. Eur. Ceram. Soc. 9 (1992) 41–46.
[10] D.F.K. Hennings, C. Metzmacher, B.S. Schreinemacher, Defect chemistry and
microstructure of hydrothermal barium titanate, J. Am. Ceram. Soc. 84 (2001)
179–182.
[11] G. Dale, M. Strawhorne, D.C. Sinclair, J.S. Dean, Finite element modeling on the
effect of intra-granular porosity on the dielectric properties of BaTiO3 MLCCs,
J. Am. Ceram. Soc. 101 (2017) 1211–1220.
[12] K. Lieselotte, K. Templeton, J.A. Pask, Formation of BaTiO3 from BaCO3 and TiO2
in air and in CO2, J. Am. Ceram. Soc. 42 (1959) 212–216.
[13] A. Beauger, J.C. Mutin, J.C. Niepce, Synthesis reaction of metatitanate BaTiO3 Part
1 Effect of the gaseous atmosphere upon the thermal evolution of the system
BaCO3-TiO2, J. Meter. Sci. 18 (1983) 3041–3046.
[14] A. Beauger, J.C. Mutin, J.C. Niepce, Synthesis reaction of metatitanate BaTiO3 Part
2 Study of solid-solid reaction interfaces, J. Mater. Sci. 18 (1983) 3543–3550.
[15] D.F.K. Hennings, B.S. Schreinemacher, H. Schreinemacher, Solid-state preparation
of BaTiO3-Based dielectrics, using ultrafine raw materials, J. Am. Ceram. Soc. 84
(2001) 2777–2782.
[16] M.T. Buscaglia, M. Bassoli, V. Buscaglia, Solid-state synthesis of ultrafine BaTiO3
powders from nanocrystalline BaCO3 and TiO2, J. Am. Ceram. Soc. 88 (2005)
2374–2379.
[17] M.T. Buscaglia, N. Bassoli, V. Buscaglia, Solid-state synthesis of nanocrystalline
BaTiO3: reaction kinetics and powder properties, J. Am. Ceram. Soc. 91 (2008)
2862–2869.
[18] S.–S. Ryu, D.–H. Yoon, Solid-state synthesis of nano-sized BaTiO3 powder with high
tetragonality, J. Mater. Sci. 42 (2007) 7093–7099.
[19] T.–T. Lee, C.–Y. Huang, C.–Y. Chang, I.–K. Cheng, C.–L. Hu, M. Fujimoto, Phase
evolution of solid-state BaTiO3 powder prepared with the ultrafine BaCO3 and
TiO2, J. Mater. Res. 27 (2012) 2495–2502.
[20] L.B. Kong, J. Ma, H. Huang, R.F. Zhang, W.X. Que, Barium titanate derived from
mechanochemically activated powders, J. Alloys. Compd. 337 (2002) 226–230.
[21] S.–S. Ryu, S.–K. Lee, D.–H. Yoon, Synthesis of fine Ca-doped BaTiO3 powders by
solid-state reaction method–part I: mechanical activation of starting materials,
J. Electroceram. 18 (2007) 243–250.
[22] R. Yanagawa, M. Senna, C. Ando, H. Chazono, H. Kishi, Preparation of 200 nm
BaTiO3 particles with their tetragonality 1.010 via a solid-state reaction preceded
by agglomeration-free mechanical activation, J. Am. Ceram. Soc. 90 (2007)
809–814.
[23] R. Rotaru, C. Peptu, P. Samoila, V. Harabagiu, Preparation of ferroelectric barium
titanate through an energy effective solid state ultrasound assisted method, J. Am.
Ceram. Soc. 100 (2017) 4511–4518.
[24] H.Z. Akbas, Z. Aydin, O. Yilmaz, S. Turgut, Effects of ultrasonication and
conventional mechanical homogenization processes on the structures and
dielectric properties of BaTiO3 ceramics, Ultrason. Sonochem. 34 (2017) 873–880.
[25] N. Döbelin, R. Kleeberg, Profex: a graphical user interface for the Rietveld
refinement program BGMN, J. Appl. Crystallogr. 48 (2015) 1573–1580.
[26] K.S. Suslick, Sonochemisty, Science 247 (1990) 1439–1445.
[27] J.H. Bang, K.S. Suslick, Applications of ultrasound to the synthesis of
nanostructured materials, Adv. Mater. 22 (2010) 1039–1059.
[28] T. Chatier, E. Jorge, P. Boch, Ultrasonic deagglomeration of Al2O3 and BaTiO3 for
tape casting, J. Phys. III 1 (1991) 689–695.
[29] S. Marković, M. Mitrić, G. Starčević, D. Uskoković, Ultrasonic de-agglomeration of
barium titanate powder, Ultrason. Sonochem. 15 (2008) 16–20.
[30] K.A. Kusters, S.E. Pratsinis, S.G. Thoma, D.M. Smith, Energy-size reduction laws for
ultrasonic fragmentation, Powder Tech. 80 (1994) 253–263.
[31] M.T. Buscaglia, V. Buscaglia, R. Allessio, Coating of BaCO3 crystals with TiO2:
versatile approach to the synthesis of BaTiO3 tetragonal nanoparticles, Chem.
Mater. 19 (2007) 711–718.
[32] K. Uchino, E. Sadanaga, T. Hirose, Dependence of the crystal structure on particle
size in barium titanate, J. Am. Ceram. Soc. 72 (1989) 1555–1558.
S.H. Jin et al.
[33] P.R. Rios, T. Yamamoto, T. Kondo, T. Sakuma, Abnormal grain growth kinetics of
BaTiO3 with an excess TiO2, Acta Mater. 46 (1998) 1617–1623.
[34] Y.K. Cho, S.-J.L. Kang, D.Y. Yoon, Dependence of grain growth and grain-boundary
structure on the Ba/Ti ratio in BaTiO3, J. Am. Ceram. Soc. 87 (2004) 119–124.
[35] K. Kinoshita, A. Yamaji, Grain-size effects on dielectric properties in barium
Titanate ceramics, J. Appl. Phys. 47 (1976) 371–373.
[36] G. Arlt, D. Hennings, G. de With, Dielectric properties of fine-grained barium
titanate ceramics, J. Appl. Phys. 58 (1985) 1619–1625.
[37] A.V. Polotai, A.V. Ragulya, C.A. Randall, Preparation and size effect in pure
nanocrystalline barium titanate ceramics, Ferroelectrics 288 (2003) 93–102.
[38] Z. Zhao, V. Buscaglia, M. Viviani, M.T. Buscaglia, L. Mitoseriu, A. Testino,
M. Nygren, M. Johnsson, P. Nanni, Grain-size effects on the ferroelectric behavior
of dense nanocrystalline BaTiO3 ceramics, Phys. Rev. B 70 (2004), 024107.
4834
Journal of the European Ceramic Society 41 (2021) 4826–4834
[39] M.T. Buscaglia, M. Viviani, V. Buscaglia, L. Mitoseriu, A. Testino, P. Nanni,
Z. Zhao, M. Nygren, C. Harnagea, D. Piazza, C. Galassi, High dielectric constant and
frozen macroscopic polarization in dense nanocrystalline BaTiO3 ceramics, Phys.
Rev. B 73 (2006), 064114.
[40] T. Hoshina, K. Takizawa, J. Li, T. Kasama, H. Kakemoto, T. Tsurumi, Domain size
effect on dielectric properties of barium titanate ceramics, Jpn. J. Appl. Phys. 47
(2008) 7607–7611.
[41] S.-H. Yoon, M.-Y. Kim, C.-H. Nam, J.-W. Seo, S.-K. Wi, K.-H. Hur, Grain-growth
effect on dielectric nonlinearity of BaTiO3-based multi-layer ceramic capacitors,
Appl. Phys. Lett. 107 (2015), 072906.