Journal of Crystal Growth 41(1977) 317—320

© North-Holland Publishing Company

CRYSTAL GROWTH OF BISMUTH TITANATES AND TITANIUM OXIDE FROM MELTS IN THE SYSTEM
Bi203—V205—Ti02

Shiro SHIMADA, Kohei KODAIRA and Toru MATSUSHITA

Department of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060, Japan

Received 7 June 1977; manuscript received in final form 5 July 1977

Single crystals of Bi4Ti3O12, Bi2Ti2O7, B12T14O11 and Ti02 were grown from the melt with various compositions in the
system Bi203—V205—Ti02. The crystal growth regions can be divided into three parts designated I, II, and HI in the ternary dia-
gram of the system: Bi4Ti3O12 growth in the region I, Bi2Ti4O1 1 in II, Bi2Ti2O7 on the boundary between land II and Ti02 in
region III. The V205 content in the Bi203, V205 and Ti02 mixture was increased according to the sequence I —~ 11 -. III. The
increase in V205 content reduced the Bi content in the grown crystal to 0% in the case of the Bi-free crystal of Ti02. It was con-
cluded that the increase in V205 content leads to complexing between bismuth oxide and vanadium oxide in the melt and thus
reduces the Bi content in the grown crystal.

1. Introduction 2. Experimental

Single crystals of bismuth titanates and rutile
(Ti02) are of great interest because they have many
applications in the field of dielectrics [1—3]. The
Bi4Ti3O12, Bi2Ti4O1 1 and Ti—sillenite crystals have
been grown under hydrothermal conditions [4] and
Bi4Ti3O12 from a melt of excess Bi203 in the sys-
tern Bi2O3—Ti02 [5] and also from bismuth borate
solution [6]. However, none is reported on the flux
growth of the Bi2Ti4O1 1 and Bi2Ti2O7 single crystals.
Rutile single crystals have been grown by many fluxes
[7—9] but no reference has been found on its growth
from a Bi203 flux. Wanklyn [10,11] has reported the
application of a bismuth vanadate flux (composition:
4Bi2O3 V205) to the growth of a number of simple
and complex oxides. We tried to carry out experi-
ments for the growth of bismuth titanate crystals
from
Bi melts of oxide mixtures in the ternary system
203—V205—Ti02. As a result of these experiments,
single
Ti0 crystals of Bi4Ti3O12, Bi2Ti2O7, Bi2Ti4O11 and
2 were grown from melts with various composi-
tions in this system. This paper describes the growth
conditions for these single crystals and a considera-
tion of the crystallization process involved.
The Bi203, V205 or Ti02 starting materials were
of reagent grade. The powder mixtures of Bi203,
V205 and Ti02, which weighed 13—16 g, were placed
in tightly covered 30 mQ platinum crucibles. The con-
tent of hO2 in the mixture ranged from 8 to 53
mol% for V205/Bi203 ratios of 0—4.0. They were
soaked at 1200 or 1300°Cfor 20 h in air and then
cooled down to 900°Cat a rate of 5°C/h.After cool-
ing, the melt was immediately poured onto a stainless
steel tray. The grown crystals were removed from the
crucible by leaching the remaining flux in a hot 20%
nitric acid. The crystals were identified by means of
the X-ray powder diffraction and from measurement
of the Ti/Bi ratio. The ratio was determined by quan-
titative chemical analysis. The bismuth titanate crys-
tals were dissolved in asolution
3~in the HF—H2S04 solution. The
was determined by
amount of Bi
titration withcolorimetrically
4~was a standard solution of EDTA
determined. Theand that
amount
of Ti
of V205 in the solidified flux, which was dissolved in
HNO3 solution, was determined by the potentio-
metric method.

317
318 S. Shimada et al. / Crystal growth of bismuth titanates and titanium oxides

3. Results and discussion V 0,

‘
Table 1 illustrates the Ti/Bi ratios of the
Bi4Ti3O12, Bi2Ti2O7 and Bi2Ti4O1 crystals, which
are near to those calculated from the above corn- a \
pound. The compositions of the melts from which b 0 \

the
phasesingle crystals
diagram were
of the grown
system are plotted on the
Bi203—V205—Ti02, as ~\ .0 \
shown in fig. 1. Lines a and b indicate the V205 corn-
dpositions
and e the
V2O5/Bi203.
for Ti02
a fixed ratio of Ti02/Bi2O3
It is compositions
seen from fig.for1 athat
andratio
fixed linesof
c,
the crystal
/\ / 0
0
growth region is divided into three parts labelled I, II,
and III on the diagram: Bi4Ti3O12 in region I, —

Bi2Ti4O11 in II and TiO2 in III. 20 J_~. 60

40 80 810
TiO~ mol %

3.1. Region I Fig. 1. The phase relation in Bi203—V205—Ti02 system for

the crystal growth of Bi4Ti3O12, Bi2Ti2O7, Bi2Ti4O1 and
Single crystals of Bi4Ti3O12 were grown in this Ti02 :(v) Bi4Ti3O12, (o) Bi~Ti2O7,(A) Bi2Ti4O1 ~, (0) Ti02
(X) no yield of crystal. Lines a—b indicate a change in V205
region. In the V205-free case, the crystals were composition for a fixed ratio of Ti02/Bi203. Lines c—e
slightly grayish with the sheet-like habit of 10—15 change in Ti02 composition for a fixed ratio of V205/
mm in size. A Laue photograph showed that the Bi203. The mixture of Bi203 and Ti02 was soaked at
(001) plane of the crystal develops. An increase in the 1200°Cand that of Bi203, V205 and hO2 at 1300°C.
V2O5 content along line a leads to a reduction in
crystal size and a change in its color from gray to cubic unit cell of a = 20.68A, differing from the
reddish brown. This tendency is also valid for the case normal pyrochlore a = 10.4A [12].
of a small amount of Ti02 on line d or e. Crystals of
Bi2Ti4O11, in addition to the small sheet-like crystals 3.2. Region II
of Bi4bi3012, were simultaneously grown in the 13
and 17 mol% V205 compositions along lines a and d, Single crystals of Bi2Ti4O11 were grown in this
which illustrate the boundary for the crystal growth region. The crystals in the boundary region were
of Bi4Ti3O12 and Bi2Ti4O11. Fig. 2 shows the simul-
taneously grown crystals of Bi4Ti3O12 and Bi2Ti4O11
for the case of 13 mol% V205.
The addition of 10 mol% ZnO to the composition
of 13 mol% V205 resulted in the crystallization of
Bi2Ti2O7. Fig. 3 shows the reddish brown crystals of
Bi2Ti2O7 with the block-like habit. The X-ray powder
pattern showed that the crystal has a face-centered

Table 1
The Bi/Ti ratio of bismuth titanate crystals determined from
the chemical analysis

Bi4Ti3O12 Bi2Ti2O7 Bi2Ti4O1 1

Measured 0.8 1.1 2.1 Fig. 2. The simultaneously grown crystals of Bi4Ti3O12 and
Calculated 0.75 1.0 2.0 Bi2Ti4O1 1 in the case of 13 mol% V~O5on line a (1 divi-
__________________________________________________ sion 1 mm).
 S. Shimada et al. / Crystal growth of bismuth
~ mol% V205 composition, as shown in fig. 4. An
___________
Fig. 3. The crystals of Bi2Ti2O7 with the block-like habit
(1 division = 1 mm).
black with a needle habit of 1 X 15 mm in maximum
size, as shown in fig. 2. However, the crystals became
blackish brown and trellis-like aggregates with an
increase of TiO2 content along line d. The result of an
X-ray rotation photograph showed that the long axis
of the crystal is the c-axis in agreement with the
result of Petushkova [13].
3.3. Region III
Single crystals of Ti02 were grown beyond the
composition of about 20 mol% V205 on line a.
Striated black crystals were obtained from a melt
containing 22 mol% V2O5, which had a rod form and
a size of 15 X 3 mm. An increase in V205 content
decreased the size of the rod crystal down to 2 X 0.5
~ occur owing to the increase of the Ti content in the
.
Fig. 4. The crystals of Ti02 in the case of 53 mol% V205 on
line a (1 division = 1 mm).
titanates and titanium oxides 319
mm for a 68 mol% V205 composition. However,
larger crystals of 25 X 3 mm were obtained for a 53
increase of Ti02 content along line c decreased the
crystal size. The result of rotation and Laue photo-
graphs showed that the long axis of the crystal is the
c-axis and that the main faces on the crystal are of
the ~ii0} family.
3.4. A consideration for the crystallization process
An X-ray powder diffraction analysis was made of
the solidified flux obtained from melts containing
greater than 16 mol% V2O5 along line a, which was
poured onto a stainless steel tray after the growth
experiments. BiVO4 (high temp.) and tetragonal M
phases crystallized out from compositions where the
V205/Bi203 ratio was less than 1 .0, BiVO4 alone at a
ratio of 1.0 and BiVO4 and V2O5 phases where the
ratio was greater than 1.0. The stoichiometry of the
M phase was not determined but the M phase was
found to contain Bi, V and Ti elements by the means
of X-ray fluorescence and had an V/Bi ratio of about
0.4 by chemical analysis. The formation of BiVO4
and M phases in the solidified flux suggests the
linkage of V2O5 to Bi2O3 in the melt. As described
above, each crystal of Bi4Ti3O12, Bi2bi4011 or biO2
was successively obtained by an increase in V205 con-
tent along line a. It may be concluded that the
increase of V2O5 content increases the Bi consump-
tion through a linkage between bismuth oxide and
vanadium oxide in the melt and thus reduces the Bi
content in the grown crystal. The growth of the Ti02
crystals from the 20 mol% V205 composition may be
due to the complexing of all the bismuth oxide with
the vanadium oxide in the melt. The simultaneous
growth of Bi4Ti3O12 and Bi2Ti4O11 on line d may
melt.
Acknowledgements
We express our thanks to Dr. T. Okutani, Govern-
ment Industrial Development Laboratory, Hokkaido,
for the X-ray fluorescence measurement. Financial
support for this work was given by The Sakkokai
Fundation.
320 S. Shimada et al. / Crystal growth of bismuth titanates and titanium oxides

References
[1] G.W. Taylor, Ferroelectrics 1(1970) 79.
[2] J.M. Herbert, Proc. Brit. Ceram. Soc. No. 18 (1970)
157.
[3] O.W. Johnson, J.W. De Ford and S. Myhra, J. Appl.
Phys. 43 (1972) 807.
[4] M.L. Barsukova, V.A. Kuznetsov, A.N. Lobachev and
Yu. V. Shaldin, J. Crystal Growth 13/14 (1972) 530.
[5] L.G. Van Uitert and L. Egerton, J. Appl. Phys. 32
(1961) 959.
[6] TM. Bruton, J. Crystal Growth 36 (1976) 36.
[7] J.S. Berkes, W.B. Whife and R.Roy, J. Appl. Phys. 36
(1965) 3276.
[8] T. Sugai and S. Hasegawa, J. Ceram. Assoc. Japan 77
(1969) 65.
[9] I.N. Anikin, 1.1. Naumova and G.V. Rumyantseva,
Soviet Phys.-Cryst. 10 (1965) 172.
[10] G. Garton, S.H. Smith and B.M. Wanklyn, J. Crystal
Growth 13/14 (1972) 588.
[11] B.M. Wanklyn, J. Crystal Growth 7 (1970) 368.
[12] E. Aleshin and R. Roy, J. Am. Ceram. Soc. 45 (1962)
18.
[13] LN. Petushkova, S.P. Dmitrieva, E.A. Pobedimskaya
and N.V. Belov, Chem. Abstracts 81(1974) 69590g.