Journal of Alloys and Compounds 695 (2017) 2870e2877

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Molten-salt synthesis of BaTiO3 powders and their atomic-scale

structural characterization
Piaojie Xue a, Yang Hu a, Weiren Xia a, Heng Wu a, Xinhua Zhu a, b, *
a
National Laboratory of Solid State Microstructures, School of Physics, Nanjing University, Nanjing 210093, China
b
State Key Laboratory of Materials-Oriented Chemical Engineering (MCE), Nanjing University of Technology, Nanjing 210009, China

a r t i c l e i n f o a b s t r a c t

Article history: In this work, BaTiO3 powders were synthesized by molten-salt synthesis method using BaCO3, TiO2, and
Received 2 September 2016 the eutectic salts (NaCl-KCl) as the raw materials. A systematic study indicating the effects of calcination
Received in revised form temperature as well as the molar ratio of NaCl to KCl in the mixed salt with respect to BaCO3 -TiO2 on the
23 November 2016
microstructures of BaTiO3 powders is reported. The results showed that all the powders crystallized in a
Accepted 28 November 2016
Available online 29 November 2016
tetragonal perovskite structure, as confirmed by X-ray diffraction pattern and Raman spectra. With
increasing the calcination temperature, the morphology of the as-prepared BaTiO3 powders developed
from rectangular/spherical aggregates to circular or cubic shapes and the average particle size was also
Keywords:
Molten-salt synthesis
increased from 320 nm to 900 nm. With increasing the molar ratio of BaCO3:TiO2: NaCl: KCl, the average
BaTiO3 powders particle size was slightly decreased from 440 nm to 360 nm, and the morphology of the as-synthesized
Microstructures BaTiO3 powders transformed from rectangular and cubic shapes to sphere shapes. The chemical com-
Atomic-scale characterization positions of the as-synthesized BaTiO3 powders obtained from energy dispersive X-ray analysis are in
agreement with the nominal ratios. The present results provide a generalized methodology to large-scale
synthesize other perovskite transitional metal oxide powders with controllable sizes and shapes.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Perovskite oxides exhibit a variety of interesting physical
properties such as ferroelectric, dielectric, piezoelectric, and pyro-
electric behaviour. Among the perovskite oxides, BaTiO3 is an
important material, which has been widely used in ferroelectric
random access memories, multilayer ceramic capacitors (MLCCs),
positive temperature coefficient of resistivity thermistors and
piezoelectric sensors due to its excellent ferroelectric, dielectric,
and piezoelectric properties [1,2]. The major challenge in
manufacturing BaTiO3 material is the processing of the material
with reliable and reproducible properties [3,4]. Following a similar
trend to the miniaturization as the conventional complementary
metal oxide semiconductor (CMOS) devices, the down-sized elec-
tronic devices based on perovskite oxide ceramic materials have
also been developed. Advances toward nanoscale electronics have
additionally increased the interest in the field of perovskite oxide
powders [5e7]. For example, to develop high volume efficient
* Corresponding author. National Laboratory of Solid State Microstructures,
School of Physics, Nanjing University, Nanjing 210093, China.
E-mail address: xhzhu@nju.edu.cn (X. Zhu).
MLCCs, the sizes of BaTiO3 powders with high purity and uniform
shape used for fabricating the next generation of MLCCs will be
lowered down to tens of nanometers. Therefore, synthesis of high-
purity, ultra-fine and agglomerate-free perovskite nanoparticles
with controlled particle size, morphology and stoichiometry, is the
critical step in processing of perovskite oxide ceramics with desir-
able properties [8,9]. Conventionally, perovskite BaTiO3 powders
are prepared by solid-state reaction using BaCO3 and TiO2 as raw
materials under high temperature above 1000
C [10,11]. However,
the resulting microstructures of perovskite BaTiO3 powders ob-
tained from this method are not suitable for the miniaturization of
electronic devices, due to their significant particle agglomeration,
poor chemical homogeneity, and coarse large particle sizes. To
resolve the above problems, in recent years, wet-chemical routes
such as sol-gel [12e14], oxalate route [15], hydrothermal [16e18],
microwave-hydrothermal [19,20], solvothermal [21], chemical co-
precipitation [22], have been developed to prepare BaTiO3 nano-
powders. The wet-chemical methods usually have some disad-
vantages, e.g., complex synthetic routes and high synthetic cost.
Therefore, it is still a challenge to synthesize well dispersive BaTiO3
powders with controlled size and morphology.
In the past decade, molten-salt synthesis (MSS) has been widely

http://dx.doi.org/10.1016/j.jallcom.2016.11.395
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 P. Xue et al. / Journal of Alloys and Compounds 695 (2017) 2870e2877 2871

used to synthesize many perovskite ceramic oxide powders [23e25].
Since the molten salts can form a liquid phase at the temperature
over the melting point of the chosen salts, they act as a solvent for
reactant dissolution, diffusion and precipitation. Therefore, the MSS
method allows melt-solid reacting much faster due to the small
diffusion distances and higher mobility of oxides in the melt, leading
to complete reactions achieved in a relatively short time [26]. Besides
the relatively low processing temperature, the MSS method can also
control the powder morphology as compared to other synthesis
methods [27e29]. Up to date, there are several reports on the syn-
thesis of BaTiO3 nanomaterials by MSS method. For example, some
high-performance modified BaTiO3 composites had been synthe-
sized and investigated. J.Y. Kim et al. reported the synthesis of the
BaTiO3 powder - polymer composites with improved dielectric
properties by using molten salt treatment [30]. Similarly, J. Fu et al.
also reported an improved dielectric properties of PVDF composites
by employing surface modified strong polarized BaTiO3 particles,
which were derived from the MSS method [31]. For 1D nano-
structures, Y.B. Mao et al. synthesized single-crystalline BaTiO3
nanowires by using starting materials of barium oxalate, TiO2, and
NaCl-KCl salt system [32]. B.R. Lin et al. reported the template-free
fabrication of pure single-crystalline BaTiO3 nanowires by MSS
method [33]. P.M. Rørvik et al. reported the synthesis of BaTiO3
nanorods with a precursor mixture containing barium (or lead) and
titanium, which was annealed in the presence of NaCl at 760 or
820
C [34]. H. Zhao et al. reported the fabrication of long BaTiO3
nanowires with lengths of 20e80 mm by molten salt route [35]. K.C.
Huang et al. reported the synthesis of morphology-controlled BaTiO3
nanorods from a reaction of BaO/BaCO3, TiO2 and KCO3 with a
eutectic mixture of NaCl - KCl flux, and studied the factors deter-
mining the shapes of the final products [36]. For 2D nanostructures,
S. Su et al. also reported the synthesis of micrometer-sized (001)-
oriented BaTiO3 platelets (10e20 mm in diameter and 0.5e1.0 mm in
thickness) with a perovskite structure [37]. D. Liu et al. reported the
synthesis of micron-scale barium titanate platelet with an average
size of 5e10 mm and a thickness of 0.5 mm [38]. Apart from all these,
there are many reports on the synthesis of BaTiO3 nanoparticles. For
example, G. K. Sahoo et al. [39] reported on the effects of different
molten salt systems (NaOH - KOH, NaCl - KCl, and LiCl - KCl) on the
growth of BaTiO3 nanoparticles around the melting points of the
selected molten salt systems. They found that pure phase BaTiO3
powders could be prepared at 175
C by using NaOH - KOH based salt
system, and NaCl - KCl based system produced pure phase powders
at 700
C. However, LiCl - KCl based system failed to produce pure
phase BaTiO3 powders. The crystallite sizes of the synthesized BaTiO3
powders were found to be dependent upon the processing temper-
ature and time. J. Miao et al. reported on the synthesis of single-
crystalline BaTiO3 nanoparticles in BaCO3, TiO2, and NaOH - KOH
salt system. Cubic phase BaTiO3 particles with the size of 50e200 nm
were obtained [40]. Y. Zhang et al. synthesized well dispersive BaTiO3
nanoparticles with the starting materials of Ba(OH)2$8H2O, TiO2, and
salt system of NaCl-KCl at a molar ratio of 1:1:20. The mixtures were
calcined at different temperatures for 3 h. Sphere and rectangular
particles with the size of about 50 nm were obtained [41].
In the present work, we focus on the synthesis of tetragonal
BaTiO3 powders by molten salt method based on the molten salt
system of NaCl-KCl. To control the phase structure, morphology, and
particle size of the BaTiO3 powders the effects of calcination tem-
peratures and the molar ratios of NaCl-KCl salt on the growth of
BaTiO3 powders in the NaCl-KCl salt system are systematically
investigated. In addition, the formation mechanism of the tetrag-
onal BaTiO3 powders in the NaCl-KCl molten salt system is also
discussed. The results show that the sizes of BaTiO3 powders are
influenced apparently by calcination temperature, and higher
temperatures lead to larger particles. It is also found that the amount
of molten salt has conspicuous effects on the morphology of BaTiO3
powders. With increasing the molar ratios of molten salt, cubic and
rectangular particles transformed to sphere ones and even some
rod-like structures appeared, which might also be an enlightenment
on synthesizing one-dimension structures. The microstructures of
the BaTiO3 powders are also characterized at atomic-scale by high-
resolution transmission electron microscopy (HRTEM).
2. Experimental
2.1. Preparation of BaTiO3 powders
For the synthesis of BaTiO3 powders, BaCO3 and TiO2 powders
(Sigma Aldrich, Shanghai, China, 99%) were used as the starting
materials, and the mixed NaCl - KCl (Sigma Aldrich, Shanghai, China,
99%) were used as molten salt with equal molar ratio. In a typical
reaction, 1 mmol each of BaCO3 and TiO2 along with 1 mmol of NaCl
and 1 mmol KCl were mixed in a molar ratio of 1:1:1:1, ground for
30 min by hand, and then the mixture was transferred to a high
purity alumina (Al2O3 > 99.5%) crucible, and loaded into a furnace,
heating at a ramp rate of 5
C/min up to the calcination temperature

Table 1
Barium titanate samples synthesized by molten salt method, lattice parameters determined from XRD patterns and mean particle size.

Sample Calcination temperature (
Hold time Ratio of molten salt Lattice parameters (nm)a Mean particle size by SEM images
group C) (h) (BaCO3:TiO2:NaCl:KCl) (nm)

A 700 2 1:1:1:1 a ¼ 0.39974, c ¼ 0.40252, c/ 320

a ¼ 1.007
800 2 1:1:1:1 a ¼ 0.39974, c ¼ 0.40294, c/ 430
a ¼ 1.008
900 2 1:1:1:1 a ¼ 0.39975, c ¼ 0.40302, c/ 510
a ¼ 1.008
1000 2 1:1:1:1 a ¼ 0.39937, c ¼ 0.40352, c/ 900
a ¼ 1.010
B 800 2 1:1:0.5:0.5 a ¼ 0.39904, c ¼ 0.40088, c/ 420
a ¼ 1.005
800 2 1:1:1:1 a ¼ 0.39974, c ¼ 0.40294, c/ 430
a ¼ 1.008
800 2 1:1:2:2 a ¼ 0.39876, c ¼ 0.40272, c/ 420
a ¼ 1.010
800 2 1:1:5:5 a ¼ 0.39918, c ¼ 0.40260, c/ 440
a ¼ 1.009
800 2 1:1:10:10 a ¼ 0.39878, c ¼ 0.40306, c/ 360
a ¼ 1.011
a
a and c are the lattice parameters of a tetragonal unit cell of BaTiO3.
2872 P. Xue et al. / Journal of Alloys and Compounds 695 (2017) 2870e2877

of 700
C for 2 h before cooling naturally to room temperature in air.

To investigate the effects of the calcination temperature as well as
the molten salt ratios with respect to the starting materials (BaCO3 -
TiO2) on the phase formation and microstructural characteristics of
BaTiO3 powders, two group samples (A and B) were synthesized at
different conditions, details are listed in Table 1. The resulting
products were washed by distilled water to remove NaCl - KCl until
no Cl was detected by using AgNO3 solution. The washed powders
were dried in an oven at 100
C for 24 h.

2.2. Characterization of BaTiO3 powders

The phase structures of as-synthesized BaTiO3 powders, were

characterized by X-ray diffraction (Rigaku D/Max-RA, Cu Ka radi-
ation). A typical scan rate was 0.01
per second, and the 2q range
was 15e70
. To obtain the structural information of the BaTiO3
powders from vibrational spectra, Raman measurements were
carried out at room temperature using a Jobin Yvon HR800 spec-
trometer (JY Ltd., France) and visible laser light (wavelength
514.5 nm) as the excitation source. The slits were adjusted so that
the resolution was 1 cm1. Morphology and average particle size of
the as-synthesized BaTiO3 powders were examined by scanning
electron microscopy (SEM) (Hitachi, S-3400N II, 30 kV). This in-
strument was equipped with an X-ay energy dispersive spectros-
copy (EDS) (EX-250 spectroscopy, HORIBA Corporation) to perform
chemical analysis of the BaTiO3 powders. The specimens for TEM
and HRTEM observations were obtained by drying droplets of the
as-synthesized BaTiO3 powders from an ethanol dispersion onto a
holey carbon grid. TEM images and the corresponding selected area
electron diffraction (SAED) patterns were taken at an accelerating
voltage of 200 kV on a Philip CM20 TEM (Philips CM20, 200 kV).
The atomic-scale microstructures of the BaTiO3 powders were
revealed by an HRTEM operated 400 kV (JEOL 4000 EX, 400 kV). All
the TEM images and SAED patterns were recorded by a Gatan
multiscan charge-coupled device (CCD) camera system.

3. Results and discussion

3.1. Effects of MSS parameters on the microstructures of the as-

synthesized BaTiO3 powders

3.1.1. Role of the calcination temperature

In order to examine the role of the calcination temperature,
BaTiO3 powders (denoted by sample group A) were synthesized by
MSS method under different calcination temperatures, details are
presented in Table 1. The XRD patterns of the products synthesized
under different calcination temperatures by MSS (without washing
by diluted HCl) are shown in Fig. 1(a). It is demonstrated that all the
diffraction peaks shown in Fig. 1(a) can be well assigned to a
tetragonal phase of BaTiO3, in good agreement with the literature
data (JCPDS No. 79-2264), except some very weak impurity peaks
marked by # in Fig. 1(a). These weak diffraction peaks observed at
2q ¼ 23.8
, were ascribed to the BaCO3 (JCPDS No. 71-2394). To
remove the little impure phase of BaCO3, all the products were
washed with diluted HCl, and the corresponding XRD patterns are
shown in Fig. 1(b). It is clear that the little impure phase of BaCO3
was completely removed. Therefore, the NaCl-KCl molten salt can
effectively promote the formation of the tetragonal phase of BaTiO3
powders. It is also observed that with increasing the calcination
temperature the splitting of the (200) and (002) diffraction peaks
around 2q ¼ 45
became more apparent, as shown in Fig. 1(c).
Normally, the XRD pattern in the 2q ¼ 45
region is characteristic of
the presence of either cubic or tetragonal BaTiO3 structure. In this
case, a clear splitting of cubic (200) into tetragonal (200) and (002)
reflections near 2q ¼ 45
is be observed in Fig. 1(c). That indicates
Fig. 1. XRD patterns of the BaTiO3 powders (sample group A) prepared by MSS method
under different calcination temperatures. (a) Before and (b) after washing with diluted
HCl, and (c) local XRD patterns near 2q z 45
. The splitting of the (002)/(200)
diffraction peaks is clearly observed.
that the as-prepared BaTiO3 powders have a tetragonal phase
structure, and the lattice parameters a and c are determined from
the XRD patterns, as presented in Table 1. The tetragonality of the
as-prepared BaTiO3 powders (defined by the lattice parameter c/a
ratio) was also determined from the XRD patterns, which was
increased from 1.007 to 1.010 as increasing the calcination tem-
perature from 700
C to 1000
C, which was slightly larger than that
reported in Ref. [39]. The tetragonal structure of the as-prepared
BaTiO3 powders is also confirmed by the following Raman
spectra, in which the characteristic Raman peaks of tetragonal
phase BaTiO3 such as sharp band around 304 cm1 [B1, E(TO1LO)],
and broad bands around 261 cm1 [A1(TO)], 521 cm1 [A1, E(TO)],
and 722 cm1 [A1, E(LO)] are clearly observed.
SEM images of the as-prepared BaTiO3 powders calcined at
different temperatures are shown in Fig. 2. It can be seen from
 P. Xue et al. / Journal of Alloys and Compounds 695 (2017) 2870e2877
Fig. 2(a) that the as-synthesized BaTiO3 powders calcined at 700
C,
exhibit rectangular and sphere shapes, and most of them are
aggregated together. Their particle sizes were in the range from
200 nm to 400 nm approximately. Fig. 2(b) shows the SEM image of
the powders prepared at 800
C, in which rectangular and cubic
particles are observed, and the average particle size is increased to
about 400e500 nm. As increasing the calcination temperature to
900
C, the morphology of the as-prepared powders was trans-
formed to sphere and irregular shapes, and the particle size was
also increased up to 500e600 nm. In the as-synthesized BaTiO3
powders calcined at 1000
C, many large spherical particles were
observed, and their average size was measured to be about 900 nm.
Overall, the average particle size of the as-synthesized BaTiO3
powders is increased with increasing the calcined temperatures,
details are given out in Table 1. And the particle size was larger than
that of many products previously reported in Refs. [39e41]. The
chemical compositions of the as-synthesized BaTiO3 powders are
also examined by EDS spectra. Quantitative EDS measurements
from the as-synthesized BaTiO3 powders demonstrate that the
atomic concentration (atomic percentage %) of Ba: Ti: O is
21.19:19.89:58.92. Therefore, the atomic ratios of Ba: Ti: O is
1.00:0.94:2.78, close to the nominal values in the composition of
BaTiO3.
3.1.2. Molten salt ratio of NaCl to KCl with respect to the starting
materials
Generally, the molten salt ratio with respect to the starting
materials is also an important factor in the MSS process. In this
work, the effect of molten salt ratio with respect to the starting
materials on the sample phase structure and microstructural
characteristics was investigated by the sample group B, which was
synthesized under different molten salt ratios. Details are pre-
sented in Table 1. Fig. 3 shows the XRD patterns of the BaTiO3
powders synthesized at 800
C for 2 h under different molten salt
ratios. It is clear that all the strong diffraction peaks can be well
assigned to a tetragonal phase of BaTiO3 except minor weak peaks
associated with the BaCO3. This result indicates that almost pure
tetragonal BaTiO3 can be formed under the molten salt ratio (NaCl:
KCl) range from 1:1 to 10:10. With increasing the molar ratios of
BaCO3: TiO2: NaCl: KCl from 1:1:0.5:0.5 to 1:1:10:10, the tetra-
gonality of the as-prepared BaTiO3 powders was found to be
Fig. 2. SEM images of the BaTiO3 powders (sample group A) prepared by MSS method under different calcination temperatures. (a) 700
C, (b) 800
C, (c) 900
C, and (d) 1000
C.
2873
increased from 1.005 to 1.011, details are shown in Table 1.
Fig. 4 shows the SEM images of the products prepared under
different molar ratios of molten salt. As shown in Fig. 4(a), the
BaTiO3 powders prepared under the molar ratio of BaCO3:TiO2:-
NaCl: KCl equal to 1:1:0.5:0.5, exhibit rectangular and cubic mor-
phologies, and their particle sizes are not very uniform. Some small
particles are about 200e300 nm while some large ones are up to
500 nm, whose average size was about 360 nm. Similar
morphology of the particles was also observed in the BaTiO3
powders prepared under the molar ratio of BaCO3: TiO2: NaCl: KCl
equal to 1:1:1:1, and their average particles size was also about
430 nm. Fig. 4(c) reveals the products prepared under BaCO3: TiO2:
NaCl: KCl equal to 1:1:2:2. Some particles exhibit sphere
morphology with an average particle size about 420 nm. Fig. 4(d)
demonstrates the product prepared under the molar ratio of BaCO3:
TiO2: NaCl: KCl equal to 1:1:5:5, in which some smaller and bigger
particles are observed, and some rod-like structures with the
length about 1.0 mm are also observed. The average size of the
particles was about 440 nm. In Fig. 5(e) the products prepared
under BaCO3: TiO2: NaCl: KCl equal to 1:1:10:10, exhibit sphere
morphology. The average particle size of the products was about
360 nm. Therefore, with increasing the molten salt ratio, the
morphology of the particles could be evolved from rectangular and
cubic shapes to sphere morphology, which can be ascribed to the
effect of surface tension of molten salt liquid. With less molten salt
ratio, the particles tended to grow into the morphology consistent
with their crystal structures. When the molten salt ratio was
increased, the raw materials were dissolved and surrounded by
molten salt, surface tension of molten salt liquid would induce
sphere shape of the products. The BaTO3 nanoparticles synthesized
in Refs. [40,41] under different temperatures and holding time did
not show apparent differences in shapes, which might imply that
the amount of salt plays a more important role in affecting the
morphology of the products.
The morphology and fine structures of the as-synthesized
BaTiO3 powders with different molar ratios of molten salt were
further examined by TEM. As depicted in Fig. 5(a), the BaTiO3
powders were synthesized under the molar ratio of BaCO3: TiO2:
NaCl: KCl equal to 1:1:0.5:0.5, in which many rectangular particles
were observed. Fig. 5(b) showed the BaTiO3 powders that were
synthesized under the molar ratio of BaCO3: TiO2: NaCl: KCl equal
2874 P. Xue et al. / Journal of Alloys and Compounds 695 (2017) 2870e2877
Fig. 3. XRD patterns of the BaTiO3 powders (sample group B) prepared by MSS method
under different molar ratios of BaCO3:TiO2:NaCl:KCl. The molar ratios of BaCO3:-
TiO2:NaCl:KCl are equal to (a) 1.0:1.0:0.5:0.5, (b) 1.0:1.0:1.0:1.0, (c) 1.0:1.0:2.0:2.0, (d)
1.0:1.0:5.0:5.0, and (e) 1.0:1.0:10.0:10.0.
to 1:1:1:1, lots of rectangular and cubic particles were observed.
Some large ones grew to 400e500 nm and some small ones grew to
about 200 nm. The average size of the particles were about 430 nm.
In Fig. 5(c) the BaTiO3 powders were synthesized under the molar
ratio of BaCO3: TiO2: NaCl: KCl equal to 1:1:2:2, the sizes of the
particles became larger than the ones synthesized under less salt
molar ratios. Some large particles grew over 500 nm and some
small ones grew up to 200e300 nm. The average size was about
Fig. 4. SEM images of the BaTiO3 powders (sample group B) prepared by MSS method under different molar ratios of BaCO3:TiO2:NaCl:KCl. The molar ratios of BaCO3:TiO2:NaCl:KCl
are equal to (a) 1.0:1.0:0.5:0.5, (b) 1.0:1.0:1.0:1.0, (c) 1.0:1.0:2.0:2.0, (d) 1.0:1.0:5.0:5.0, and (e) 1.0:1.0:10.0:10.0.
420 nm and most of the particles exhibit rectangular and cubic
morphology. Fig. 5(d) showed the BaTiO3 powders synthesized
under the molar ratio of BaCO3: TiO2: NaCl: KCl equal to 1:1:5:5,
and the average particle sizes were about 380 nm. In addition, some
sphere particles began to appear. With further increasing the molar
ratio of BaCO3: TiO2: NaCl: KCl up to 1:1:10:10, more and more
BaTiO3 powders exhibit spherical morphology, and a few rod-like
structures with a diameter of 125 nm is also occasionally
observed. The average particle size of the BaTiO3 powders particles
was around 370 nm. The single crystalline nature of the as-
synthesized BaTiO3 powders was confirmed by the selected area
electron diffraction (SAED) pattern taken from single BaTiO3 pow-
der, which was illustrated as the inset of Fig. 5(b). The SAED pattern
exhibits the characteristics of single crystal diffraction pattern,
which was taken from the [010] direction of the tetragonal BaTiO3.
The c/a ratio of the tetragonal BaTiO3 powder was determined to be
1.008 from the SAED pattern, which was in well agreement with the
XRD result. In addition, the single crystalline nature of the as-
synthesized BaTiO3 powders was also confirm by an HRTEM im-
age of individual BaTiO3 powder synthesized under the molar ratio
of BaCO3:TiO2:NaCl:KCl equal to 1:1:0.5:0.5, as depicted in Fig. 5(f).
As shown in Fig. 5(f) lattice fringes were clearly resolved, and their
interplanar spacing was measured to be 0.39 nm, which corre-
sponds to the (100) lattice spacing of the tetragonal BaTiO3. The
formation of rod-shaped BaTiO3 structures that are occasionally
observed in Fig. 5(e), can be interpreted as followings. Under high
temperature (800
C) and large ratios of the molten salt to the
starting materials (e.g., NaCl:KCl:BaCO3:TiO2 ¼ 10:10:1:1), due to a
high solubility of barium oxide in the eutectic salt of NaCl-KCl much
 P. Xue et al. / Journal of Alloys and Compounds 695 (2017) 2870e2877 2875

Fig. 5. TEM images of the BaTiO3 powders (sample group B) prepared by MSS method under different molar ratios of BaCO3:TiO2:NaCl:KCl. The molar ratios of BaCO3:TiO2:NaCl:KCl
are equal to (a) 1:1:0.5:0.5; (b) 1.0:1.0:1.0:1.0; (c) 1.0:1.0:2.0:2.0; (d) 1.0:1.0:5.0:5.0, and (e) 1.0:1.0:10.0:10.0. The inset in Fig. (b) is a SAED pattern taken from a single BaTiO3 powder
along the [010] direction of the tetragonal BaTiO3. (f) HRTEM image of an individual BaTiO3 powder synthesized under the molar ratio of BaCO3:TiO2:NaCl:KCl equal to 1:1:0.5:0.5,
where the (100) lattice fringes are clearly observed.

barium oxide can be dissolved in the molten salt. During the
solution-precipitation process of barium oxide, the insoluble TiO2
particles with sphere-like shape have chance to reunite into rods-
like particles in the molten salt environment, which act as tem-
plates for further growth [42]. Therefore, in this case the dissolved
barium oxide can diffuse to the surfaces of rod-like TiO2 and react
with TiO2 in situ to form BaTiO3 rod-like structure. On the contrary,
in the case of low temperature and small ratios of the salt to the
starting materials, imperfect dispersion of both barium and tita-
nium oxide particles cannot be avoided in spite of the hand-milling.
Therefore, the agglomerated particles can reduce the dissolved rate
of barium oxide in salt, leading to the left barium oxide in the
starting materials reacting with titanium oxide to synthesize
BaTiO3 particles directly by particle-to-particle contact. That is very
similar to the normal solid-state mechanism. As a consequence,
both the particles and rod-like structures are usually observed in
the final products. However, the formation of rod-like BaTiO3
structure is usually difficult due to the isotropy of the BaTiO3
tetragonal crystal structure and the anisotropy of the one dimen-
sional rod-like structure [33]. That is the reason why the rod-
shaped BaTiO3 structures are occasionally observed in the final
products.
3.2. Raman spectra of the as-synthesized BaTiO3 powders
To probe the local structure and dynamic symmetry of the as-
synthesized BaTiO3 powders, Raman spectra were collected from
the as-synthesized BaTiO3 powders under different molten salt
2876 P. Xue et al. / Journal of Alloys and Compounds 695 (2017) 2870e2877
Fig. 6. Raman spectra of the BaTiO3 powders (sample group B) prepared by MSS
method under different molar ratios of BaCO3:TiO2:NaCl:KCl. The molar ratios of
BaCO3:TiO2:NaCl:KCl are equal to (a) 1.0:1.0:0.5:0.5, (b) 1.0:1.0:1.0:1.0, (c)
1.0:1.0:2.0:2.0, (d) 1.0:1.0:5.0:5.0, and (e) 1.0:1.0:10.0:10.0.
ratios with respect to the starting oxides, as shown in Fig. 6. The
observed Raman bands centered near 261, 304, 521 and 722 cm1
are clearly observed. It is well known that the cubic phase structure
of BaTiO3 has no Raman active modes whereas the tetragonal phase
structure of BaTiO3 has. Tetragonal BaTiO3 unit cell contains 15
vibrational modes, including 12 optical modes, which can be rep-
resented as Gopt ¼ 3A1þB1þ4E [43]. From theoretical analysis, B1
mode is only Ramen active and resulted from the relative move-
ment between O4 and O5 along Z-axis. A1 mode and E soft mode
split from F1u mode in cubic BaTiO3, which contributed a lot to the
ferroelectricity in tetragonal BaTiO3. The observed Raman peak
near 261 cm1 could be ascribed to A1(TO) mode, Raman peak near
304 cm1 assigned to B1 and E(TO þ LO) modes, and Raman peak
near 521 cm1 assigned to E and A1(TO) modes. Raman peak near
722 cm1 was assigned to A1 and E(LO) modes. Cubic BaTiO3 does
not have Raman active modes, whereas broad Raman peaks near
261 cm1 and 521 cm1 would appeared when the cubic phase
transformed into tetragonal phase, which could be ascribed to the
position linearity of Ti atom in lattices. Raman peaks near 304 cm1
is characteristic peak of tetragonal BaTiO3 [44]. As shown in Fig. 6,
the characteristic peak of the tetragonal BaTiO3 near 304 cm1 is
present in all samples, indicating that all the BaTiO3 powders have
tetragonal phase structure, as confirmed by the XRD patterns. In
addition, the intensity of the Raman peak at 304 cm1 was also
increased with increasing the molar ratios of BaCO3: TiO2: NaCl: KCl
from 1:1:0.5:0.5 and 1:1:10:10, indicating that the tetragonality of
the BaTiO3 powders was increased, in well agreement with the XRD
results. Similar phenomenon was also observed in the Raman peak
near 722 cm1.
4. Conclusions
BaTiO3 powders were synthesized by molten-salt method from
a reaction of BaCO3 and TiO2 with a eutectic mixture of NaCl - KCl
flux as molten salt. The influence of the molar ratio of NaCl to KCl in
the mixed salt with respect to the starting oxides (BaCO3: TiO2:
NaCl: KCl) and the calcination temperature on the phase structure,
composition, particle size, and morphology of the BaTiO3 powders
were systematically studied. The XRD patterns and Raman spectra
demonstrated that the as-synthesized BaTiO3 powders have a
tetragonal phase structure. The chemical compositions of the as-
synthesized BaTiO3 powders determined from EDS spectra were
closed to 1:1:3, in agreement with the nominal ratio. SEM and TEM
images displayed that the morphology of the as-prepared BaTiO3
powders evolved from rectangular/spherical aggregates to circular
or cubic shapes with increasing the calcination temperature, and
the average particle size was increased from 320 nm to 900 nm.
Meanwhile, with increasing the molar ratio of BaCO3: TiO2: NaCl:
KCl, the average particle size was slightly decreased from 440 nm to
360 nm, and the morphology of the as-synthesized BaTiO3 trans-
formed from rectangular and cubic shapes to sphere shapes. That
could be ascribed to the effect of surface tension of the molten-salt
liquid of NaCl - KCl mixture. HRTEM images of individual BaTiO3
powder reveal the lattice fringes clearly, indicating a good crys-
tallinity of the as-prepared BaTiO3 powders. Due to the simplicity
and versatility of the approach used, it is expected that this
methodology can be generalized to the large-scale synthesis of
other perovskite transitional metal oxides with controllable sizes
and shapes.
Acknowledgements
This research is financially supported by the National Natural
Science Foundation of China (grant nos. 11174122 and 11134004);
National Basic Research Program of China (grant nos.
2015CB654900); open projects from State Key Laboratory of
Materials-Oriented Chemical Engineering (MCE), Nanjing Univer-
sity of Technology (grant no. KL14-10), six big talent peak project
from Jiangsu Province (grant no. XCL-004), and open project (grant
no. M28026) of National Laboratory of Solid State Microstructures,
Nanjing University.
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