J. Am. Ceram. Soc.

, 90 [4] 1323–1326 (2007)

DOI: 10.1111/j.1551-2916.2007.01525.x
r 2007 The American Ceramic Society

Journal
Synthesis of Micron-Scale Platelet BaTiO3
Dan Liu,w Yongke Yan, and Heping Zhou
State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China

Micron-scale platelet barium titanate was synthesized using a
twostep molten salt and topochemical technique. Plate-like
BaBi4Ti4O15 was first synthesized as a precursor by molten
salt synthesis. Then, Bi31 in the precursor was replaced by Ba21
and formed perovskite-structure BaTiO3 through a topochemi-
cal reaction. The BaTiO3 single crystals have an average size of
5–10 lm and a thickness of 0.5 lm. The purpose of this article is
to control the particle shape with desired structure. High aspect
ratio BaTiO3 platelets are suitable templates to obtain textured
ceramics (especially Pb(Mg1/3Nb2/3)O3–32.5PbTiO3) by the
templated grain growth process.
perovskites can often be interchanged at low temperatures,
which facilitate their subsequent conversion into new phases.
Using topochemical reactions, it is possible to design the aimed
product with the desired shape and structure using a multistep
sequence of low-temperature reactions.7,8
In this paper, we designed a twostep method to synthesize
plate-like BaTiO3 with a perovskite structure and a nearly per-
fect size for TGG. An aurivillius-structured BaBi4Ti4O15 pre-
cursor is first synthesized. Using this precursor, plate-like
BaTiO3 is synthesized through an ion-exchange process.

II. Experimental Procedures

I. Introduction
A Bi2O2(Ban
m
1BimTinO3n11) structured precursor was first

P LATELET-shaped single crystals have drawn considerable at-

tention recently because of their use as template seeds in the
templated grain growth (TGG) process, which is an effective
synthesized. Reaction starting from oxides as Formula (1) re-
sulted in a Ba2Bi4Ti5O18 phase and defected morphology. A
large BaBi4Ti4O15 template was obtained by reaction of Bi4-
method for producing highly textured ceramics. During the Ti3O12 and oxides (Formula (2) and (3)). As the precursor was
TGG process, platelet particles were mixed with matrix pow- prepared, perovskite-structured BaTiO3 was achieved by a topo-
ders and aligned by tape casting. Matrix grains grew epitaxially chemical reaction (Formula (4)).
on the templates and resulted in textured ceramics after thermal
treatment. The characters of the template particles, including 2BaCO3 þ 2Bi2 O3 þ 5TiO2 ! Ba2 Bi4 Ti5 O18 þ CO2 (1)
structure, shape, and size, are critical factors to the final prod-
uct. Platelet Bi3Ti4O12, SrTiO3, BaTiO3, etc., had already been
used to texture Na1/2Bi1/2TiO3–BaTiO3, Pb(Mg1/3Nb2/3)O3– 2Bi2 O3 þ 3TiO2 ! Bi4 Ti3 O12 (2)
32.5PbTiO3 (PMNT), and Al2O3.1–3
To date, although platelet SrTiO3 prepared by a twostep Bi4 Ti3 O12 þ BaCO3 þ 4TiO2 ! BaBi4 Ti4 O15 þ CO2 (3)
molten salt synthesis and BaTiO3 by the Reimaka method4 have
been used to obtain textured PMNT,1,5,6 both these templates BaBi4 Ti4 O15 þ BaCO3 ! 2BaTiO3 þ 2Bi2 O3 þ CO2 (4)
have disadvantages. For SrTiO3 templates, it has a large lattice
mismatch with PMNT, and it would dissolve into the PMNT
matrix because of its instability in a Pb-rich environment. A
Platelet Bi4Ti3O12 particles were synthesized by molten salt
maximum Logtering factor of 0.705 was reported and difficult to
synthesis.9 Stoichiometric amounts of Bi2O3 and TiO2 were
improve. For BaTiO3 templates, although BaTiO3 showed a
mixed by ball milling for 8 h. Same weights of NaCl and KCl
smaller lattice difference than SrTiO3, the platelet morphology
(1:1 mol) were added as salts. The slurry was dried at 1201C with
would be destroyed when BaTiO3 was crushed into small pieces
stirring. The mixture was heated to 11001C and held for 1 h. The
because of the large size. The corrosive KF molten salt was not
NaCl and KCl salts were removed by washing with deionized
eco-friendly and needed a costly platinum crucible. Although
water several times.
Sabolsky et al.6 showed enhanced performance, texturing
To obtain a BaBi4Ti4O15 precursor, the Bi4Ti3O12 particles
PMNT ceramics with large BaTiO3 templates resulted in
were reacted with BaCO3 and TiO2 in a ration of 1:1.1:1.1 mol.
extremely coarse microstructures and thus too low a strength
Equal weights of BaCl2–KCl (1:1 mol) were added as salts.
for most applications. There is an urgent demand for finding a
These raw materials were mixed by magnetic stirring on a hot
template with low lattice difference and appropriate size.
disk to avoid destroying the plate-like shape of Bi4Ti3O12. The
Soft chemistry offers potentially powerful tools for control-
reactants were reacted at 10801C for 1 h. The salts were removed
ling thermodynamically inaccessible structural and morpho-
in a manner similar to the previous step. A platelet BaBi4Ti4O15
logical features at the kinetic level. In recent years, perovskites
precursor was obtained in this step.
have been the target of many low-temperature chemical trans-
In the second step, BaTiO3 seeds were obtained by a topo-
formations.7 The interlayer cations or structural units of layered
chemical reaction between BaBi4Ti4O15 and BaCO3 without
changing the plate-like morphology. The BaBi4Ti4O15 particles
E. Suvaci—contributing editor were reacted with BaCO3 by a ratio of 1:4 mol in NaCl–KCl
molten salts. The mixture was magnetically stirred in ethanol
medium. The slurry was dried and subsequently reacted at
Manuscript No. 22261. Received September 21, 2006; approved November 17, 2006. 9501C for 3 h. BaTiO3 seeds were separated by washing with
w
Author to whom correspondence should be addressed. e-mail: liudan99@gmail.com deionized water and ethanol.
1323
1324 Communications of the American Ceramic Society
The microstructure was observed by a scanning electron
microscope (model JMS 6460LV, JEOL, Tokyo, Japan). The
crystalline phases were determined by X-ray diffraction (XRD)
(model Rigaku 2500, Tokyo, Japan).
III. Results and Discussion
(1) BaBi4Ti4O15 Precursor Preparation by Molten Salt
Synthesis
The entire process of synthesis is illustrated in Fig. 1. The first
step is designed to synthesize a precursor that has a pseudo-pe-
rovskite structure and can easily be transformed to BaTiO3. Ac-
cording to the literature, Aurivillius-structured compositions are
reasonable candidates.10 Aurivillius families with a formula of
Bi2O2(An
2BnO3n11) have a structure of a [Bi2O2] interlayer and
a perovskite sub-lattice. One interesting feature of the Aurivillius
phases is the compositional flexibility of the perovskite blocks
that allows to incorporate various cations such as Na1, K1,
Ca21, Sr21, Ba21, Pb21, Bi31, or Ln31 for the A site and Fe31,
Cr31, Ti41, Nb51, or W61 for the B site. The [Bi2O2] slabs can
easily be removed during a high-temperature treatment. A-site
ions can be replaced by other elements through topochemical
techniques and form a perovskite phase. The Ba-based Aurivil-
lius Ba2Bi4Ti5O18 (B2BT) and BaBi4Ti4O15 (BBT) are supposed
to degrade to BaTiO3 through these reactions.
Figure 2(a) shows the XRD patterns of the specimen pre-
pared by Formula (1) at 10801C for 3 h. All of the diffraction
peaks are assigned to JCPDS No. 741663 Ba2Bi4Ti5O18 phase,
which is different from Kimura and Yoshida.11 This means that
B2BT was synthesized by a direct reaction of raw oxides. Figure
3(a) shows the microstructure of B2BT. The microstructure is
composed of small plate-like grains that have defects and holes
in the middle area. The average size is about 4 mm, and the
thickness is less than 0.5 mm. B2BT has a tendency to become a
platelet because of the anisotropic structure. But the irregular
shape and small size suggest that this candidate may not be
suitable for the next ion-exchange step.
Figure 2(b) shows the XRD pattern of BBT that was pre-
pared by the reaction of Bi4Ti3O12 and BaCO3 at 10801C for 3 h.
All the peaks were assigned to JCPDS No. 350757. The strong
intensities of (0010), (0016), and (0018) peaks indicate that the
surface of the BBT platelet was parallel to (00l). Figures 3(b) and
(c) show the microstructure of Bi4Ti3O12 and BBT. BBT shows a
microstructure of plate-like morphology with a size of about
6B10 mm and a thickness of 0.5 mm. Compared with Fig. 3(a),
BBT has a more regular rectangle shape and a cleaner surface.
Most of the crystallographic studies12 reported the necessity to
partially substitute Bi for Ba in the [Bi2O2]21 slabs, especially for
Ba-based Aurivillius compounds such as BBT and B2BT. The
Fig. 1. Illustration of the designed twostep reactions: Bi4Ti3O12 was
transformed to BaBi4Ti4O15 by molten salt synthesis in the first step;
BaBi4Ti4O15 was transformed to BaTiO3 by a topochemical reaction in
the second step.
Vol. 90, No. 4
Fig. 2. X-ray diffraction patterns of (a) Ba2Bi4Ti5O18, (b) BaBi4Ti4O15,
and (c) BaTiO3.
incompatibility between the Ba21 anionic environment and the
configuration of the [Bi2O2] slabs is so important that, at a local
scale, the continuity of the [Bi2O2] slabs cannot be ensured. In
the B2BT compound, the substitution for Ba in [Bi2O2] slabs is
in evidence.13 The defective morphology of B2BT may be due to
the existence of faults or mismatch in the layers stacking within
the crystal. The platelet Bi4Ti3O12 precursor also took part in
the growth of large BBT grains. Bi4Ti3O12 played a role as nu-
cleation centers and reacted with BaCO3 without altering the
plate-like shape. Another reason for the large size of BBT may
be attributed to the use of BaCl2–KCl molten salts. The con-
centration of Ba21 ions was much higher in BaCl2–KCl than in
the NaCl–KCl system, which provides sufficient materials to
build up the Aurivillius structure. Large size and regular shape
BBT was a suitable precursor for the next step of synthesis.
(2) BaTiO3 Prepared by Topochemical Reaction
Using BBT as a precursor, plate-like BaTiO3 particles were syn-
thesized by a topochemical reaction. Soft chemical reactions
must be carried out at a temperature that is sufficiently low to
prevent extensive bond breaking and rearrangement of the
structural framework. The reaction temperature was set to
9501C. Bismuth oxide sublayers were first removed at this tem-
perature and formed Bi2O3. BaCO3 dissolved into the lattice and
replaced the Bi ions with a preserved particle morphology and a
developed {001} plane of the perovskite. Figure 2(c) shows the
XRD pattern of as-prepared phase-pure perovskite BaTiO3 par-
ticles. The split of (200) and (002) peaks near 451 indicates that
the BaTiO3 particles have a tetragonal structure rather than cu-
bic. Figure 3(d) shows the microstructure of BaTiO3. The par-
ticles show a regular quadrate shape with a narrow size
distribution. The mean size is about 7 mm and the thickness is
about 0.5 mm, which is nearly the ideal size for the TGG process.
The EDX analysis possessed a pattern like that of pure BaTiO3,
but a small amount of Bi (about 1 atomic %) was detected. The
remnant Bi in the final products may be due to the nature of the
topochemical reaction in which Bi in the BBT lattice could not
be completely replaced by Ba. The residual Bi shows no fatal
influence on the TGG process. For the TGG process, another
criterion for templates is that the template should be thermo-
dynamically stable at high temperatures. The sample was heated
at 11001C for 1 h to test the thermal stability. The morphology
of the platelets remained unchanged throughout the high-tem-
perature treatment (Fig. 4), which indicated the applicability of
these templates for the TGG-type processes.
Figure 5 shows the differential thermal analysis (DTA) of this
step. The DTA test was applied on the mixture of BBT, BaCO3,
and BaCl2–KCl salts. The sample was heated to 9501C at 101C/
April 2007 Communications of the American Ceramic Society 1325

Fig. 3. Scanning electron microscope images of (a) Ba2Bi4Ti5O18, (b) Bi4Ti3O12, (c) BaBi4Ti4O15, and (d) BaTiO3.

Fig. 4. Scanning electron microscope images of BaTiO3 particles heat-

ed at 11001C for 1 h. Fig. 5. Differential thermal analysis of a BBT/BaCl2/KCl mixture from
room temperature to 9501C.

min and held for 1 min. The strong thermal absorption peak 1 at
about 6501C is the melting point of the mixture of BaCl2–KCl,
and peak 4 at about 8001C is the melting point of Bi2O3. The
yellow Bi2O3 residual was found in the resultant mixture. The
decomposition temperature of BaCO3 is 13001C, which suggests
that BBT reacted with BaCO3 before BaCO3 decomposed to
BaO. During this step, [Bi2O2] sublayers decompounded from
BBT and Ba took the place of Bi. The inconspicuous peaks 2
and 3 between 7001 and 8001C could be attributed to these re-
actions. The detailed reaction consequence needs further re-
search. In the BBT lattice, mixed Bi/Ba atomic positions exist
within the perovskite blocks but specific Ba or Bi sites cannot be
evidenced. The difference in the ionic radii of the Ba21 and Bi21
cations causes different local cation environments. The rotation
of the TiO6 octahedral caused by the smaller Bi cations increases
the instability of the lattice and provides the driving force in ion-
exchange reactions.
IV. Conclusions
In this paper, we converted a layered Aurivillius structure into a
perovskite phase using a twostep method. BaBi4Ti4O15 was first
synthesized by the reaction of Bi4Ti3O12 and BaCO3 in BaCl2–
KCl molten salts. This Aurivillius phase, BaBi4Ti4O15, is an
1326 Communications of the American Ceramic Society
intergrowth of perovskite and bismuth oxide and has a covalent
network of [Bi2O2] between the two-dimensional perovskite
slabs. [Bi2O2] sublayers were removed and Bi31 was replaced
by Ba21 in the topochemical condensation reaction. BaTiO3
platelets with a perovskite structure and micron sizes were suc-
cessfully synthesized. The potential to synthesize other perovs-
kite-structured template seeds (SrTiO3, PbTiO3, etc.) by the
same routine exists. These platelet seeds should be very suitable
templates for (reactive-) templated grain growth.
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