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MATERIALS RESEARCH

Powder synthesis of barium titanate and barium

orthotitanate via an ethylene glycol complex
polymerization route
S.J. Lee, M.D. Biegalski, and W.M. Kriven
Department of Materials Science and Engineering, University of Illinois at Urbana–Champaign,
Urbana, Illinois 61801

(Received 25 January 1999; accepted 18 March 1999)

Pure and reactive barium titanate (BaTiO3) and barium orthotitanate (Ba2TiO4)
powders have been synthesized by an ethylene glycol (EG), polymerization-
complexation route. The EG content affected the crystallization behavior and powder
morphology. The BaTiO3 powder, which had a particle size of approximately 100 nm,
crystallized from amorphous to tetragonal phase on calcining at 700 °C for 1 h.
Ball-milled BaTiO3 powder sintered to 97% relative density at 1200 °C after 2 h, with
a grain size of approximately 200 nm. Ba2TiO4 powder required longer holding times
or higher temperatures to be crystallized from the amorphous phase than did BaTiO3.
In Ba2TiO4, the phase transformation between low-temperature monoclinic symmetry
to high-temperature orthorhombic symmetry was observed by dilatometry and
differential scanning calorimetry. A volume decrease of ∼0.5% accompanied the
monoclinic-to-orthorhombic transformation on heating. The high-temperature
orthorhombic phase could be retained down to room temperature by the addition of at
least 6 wt% magnesia (MgO) stabilizer.

I. INTRODUCTION methods based on complex polymerization produced

Barium titanate (BaTiO3) has a large polarization and
a high dielectric constant, whose value usually ranges
from 650–8500, depending on the particle size and im-
purities.1– 6 Above 130 °C the crystal structure is cubic,
and when the material is cooled below 130 °C, the ma-
terial changes to tetragonal symmetry. At higher tem-
peratures, above 1450 °C BaTiO 3 also displays a
hexagonal crystal structure. 7 Barium orthotitanate
(Ba2TiO4) has two crystalline structures that are ortho-
rhombic and monoclinic.8 The orthorhombic form has
been reported to exist at high temperatures and the mono-
clinic form at room temperature. The monoclinic form is
suggested to be similar to ␤– Ca2SiO4.9 As with the
␤–Ca2SiO4 crystal structure, Ba2TiO4 could be expected
to undergo a displacive transformation above room tem-
perature. Bland9 surmised that the phase change from
orthorhombic to monoclinic was near room temperature
because the work of Todd and Lorenson10 found a peak
in the heat capacity near room temperature.
BaTiO3 powder is difficult to obtain by a conventional
ceramic process.11 This is due to the formation of many
intermediate compounds that reduce the purity of the
BaTiO3 itself. Chemical methods are preferred because
they can yield powders that are very pure. Previous ex-
periments have yielded BaTiO3 powders of small particle
size by use of various methods.2– 6,12,13 The sol-gel
0.5–0.3 ␮m particle sizes, with specific dielectric con-
stants ranging from 670 to 2600.3,5 Particle sizes of
0.2 ␮m–0.045 ␮m were formed through hydrolysis of
barium hydroxide solution and amorphous titania.2
These powders had specific dielectric constants ranging
from 5000–8500. Homogenous precipitation has also
been used to create fine BaTiO3 powders of 0.2 ␮m
particle size.6 This method involves the precipitation of
barium titanyl oxalate followed by calcining at high
temperatures. Hydrolytic decomposition can be used
to produce a very pure BaTiO3 powder with particle
sizes in the range of 50–150 Å.12 Arima et al.4 made
BaTiO 3 by a polymerized complex method based
on a modified Pechini route,14 –17 wherein a mixed
solution of citric acid, ethylene glycol (EG), and
barium (from barium carbonate) and titanium (from
titanium tetra-isopropoxide) ions was chelated and
polymerized.
Ba2TiO4 powder is very hard to synthesize because the
powder is not as stable as BaTiO3. A common way to
produce this powder is through physical mixing of TiO2
and BaCO 3 and heating at 1350 °C. 18 Controlled
hydrolysis of barium and titanium alkoxide precursors
can also be used to synthesize Ba2TiO4.8 Single crystals
of Ba2TiO4 have been grown from melts containing
barium oxides and titanium oxides.9

J. Mater. Res., Vol. 14, No. 7, Jul 1999 © 1999 Materials Research Society 3001
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 S.J. Lee et al.: Powder synthesis of barium titanate and barium orthotitanate via an ethylene glycol complex polymerization route
The method used in this experiment is based on
complexation-polymerization with EG (HOCH2CH2OH,
EG) as an organic carrier. The Pechini method only
works with systems that are water soluble. However, by
the use of only the polymerizing agent this process can be
extended to even those chemicals that decompose in
water, such as titanium isopropoxide. The polymeriza-
tion agent, EG in this method, acts to capture the metal
ions through a polymerization-complexation mecha-
nism.11,19,20 This serves to decrease the mobility of the
metal ions and constrain the system to prevent precipi-
tation of cation species and agglomeration. At the opti-
mum amount of polymer, the metal ions are dispersed in
solution and a homogeneous polymeric network is
formed. By complex polymerizations with EG it is pos-
sible to synthesize barium-titanium compounds using
common chemicals like barium nitrite and titanium iso-
propoxide. Titanium isopropoxide is not soluble in water,
so other sol-gel methods cannot be used. This method
also has a distinct advantage over other sol-gel methods
in that it is easier and cheaper.
II. EXPERIMENTAL PROCEDURE
A. Powder synthesis
The flowchart for the powder synthesis method is
summarized in Fig. 1. Barium nitrite [Ba(NO2)2 ⭈ H2O,
reagent grade, Alfa Aesar Chem. Co., Ward Hill, MA]
and titanium (IV) isopropoxide [Ti(OC3H7)4, reagent
grade, Alfa Aesar Chem. Co., Ward Hill, MA] were dis-
solved in stoichiometric proportions in liquid EG (Fisher
Chemical, FW:62.07, Fair Lawn, NJ). The amount of EG
was calculated using a ratio of total weight of metal ions
from cation sources to weight of EG. Several ratios (1:1,
1:3, 1:5, and 1:7) were tried. The barium nitrite was first
added to the EG and heated to 80 °C while mixing until
FIG. 1. Flowchart for preparation of barium–titanium compounds by
the EG, polymerization-complexation route.
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it was fully dissolved. Then, the titanium (IV) isopro-
poxide was slowly added while stirring. The solution was
then allowed to gel for 48 h in a drying oven at 50 °C.
The dried gel was then calcined on a zirconia (3Y-TZP)
substrate in a box furnace at various temperatures. The
calcined Ba2TiO4 powders were kept in a dessicator un-
der vacuum to prevent reaction with air.
The stabilization of the high temperature phase of
Ba2TiO4 was investigated with 3, 6, and 10 wt% of MgO.
The stabilizer was added to the sol in the form of mag-
nesium nitrate hexahydrate [Mg(NO3)2 ⭈ 6H2O, reagent
grade, Aldrich Chemical, Milwaukee WI]. In the case of
BaTiO3, the calcined powder was ball-milled with zirco-
nia media for 12 h. Isopropyl alcohol was used as a
solvent for milling. The ball-milled BaTiO3 powders and
as-calcined Ba2TiO4 powders were uniaxially pressed at
20 MPa followed by cold isostatic pressing at 170 MPa
for 10 min. The pellet-shaped green compacts of BaTiO3
and Ba2TiO4 were sintered at 1200 °C for 2 h in an air
atmosphere.
B. Characterization
The crystallization behavior of the gel-type powders
was examined as functions of calcining temperature and
holding time, with an x-ray diffractometer (Rigaku/USA,
Dmax, automated powder diffractometer, Danvers, MA)
with Cu K␣ radiation (40 kV, 40 mA). The measure-
ments were made with a scanning speed of 10°/min and
a sampling interval of 0.02°, over a range of 10–70° at
room temperature. Five-point Brunaver, Emmett, and
Teller (BET) analysis from nitrogen gas absorption (Mi-
crometrics ASAP 2400, Norcross, GA) was used to ob-
tain the BET-specific surface area of the crystalline
powders. The morphological characteristics of the crys-
tallized powders and grains after sintering were exam-
ined by scanning electron microscopy (SEM, Hitachi
S530, Hitachi, Japan). The specimens were mounted on
an aluminum stub and Au–Pd sputtered. To observe the
grain size of sintered BaTiO3, a cross section was pol-
ished and then thermally etched at 1100 °C for
10 min. The pyrolysis and decomposition behavior of the
organic/inorganic precursor were monitored by simulta-
neous differential scanning calorimetry (DSC) and ther-
mogravimetric analysis (TGA) (DSC/TGA, Model STA
409, Netzsch GmbH, Selb, Germany) up to 1200 °C at a
heating rate of 10 °C/min in an air atmosphere. The ther-
mal expansion behavior and volume change at the phase
transformation of sintered Ba2TiO4 samples were de-
termined with a recording dilatometer (Netzsch Dila-
tometer, 402E, Selb, Germany) and DSC up to 1200 °C
at a heating rate of 5 °C/min. The dielectric con-
stant of the sintered BaTiO3 pellet was characterized
with a HP4275A impedance analyzer operated at room
temperature.
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 S.J. Lee et al.: Powder synthesis of barium titanate and barium orthotitanate via an ethylene glycol complex polymerization route
FIG. 2. TGA/DSC curves for the BaTiO3 precursor made by the EG
method (ethylene glycol content was 1:3).
III. RESULTS AND DISCUSSION
After all the chemicals were dissolved in EG, the so-
lution was pale yellow and transparent. During the drying
process at 50 °C, the transparent gel turned to a yellow-
colored solid gel.
A. Barium titanate
The thermal analysis plots for the BaTiO3 precursor
powder derived from the 1:3 ratio is shown in Fig. 2. In
the TGA curve, the mass loss occurred in two stages (i)
120–560 °C and (ii) 560–610 °C, with corresponding or-
ganic mass losses of 25 and 7%, respectively. The DSC
spectrum showed three exothermic peaks at 280, 580,
and 640 °C. In general, polymer decomposition occurs
by two steps.21,22 The first step is degradation of the
polymeric structure by pyrolysis, which is then followed
by oxidation of residual carbon. In the EG method the
first mass loss was due to the pyrolysis of EG, resulting
in breaking of bonds, removal of free organics from
metal-ion sources, and release of NxOy gases. An exo-
therm at 580 °C in the second weight loss was due to the
burn out of residual carbon by oxidation with CO, and
CO2 gases formed. Another exothermic peak appeared at
640 °C, which corresponded to crystallization of BaTiO3.
The metal ion sources [barium nitrite and titanium
(IV) isopropoxide] were dissolved in EG after heating to
80 °C. However, in the case of the solution, which had
the 1:1 ratio, some precipitation occurred despite long
stirring times. The amount of EG was not enough to
TABLE I. Phase development of BaTiO3 powders at various calcination temperatures and average particle sizes corresponding to each lowest crystalli-
zation temperature.
Mixing ratio
(wt cations : wt EG) 700 °C
1:3 Tetragonal
1:5 Amorphous
1:7 Amorphous
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dissolve the cation sources without any solvent media.
Table I lists the XRD results and particle sizes of the
crystallized powders after calcination at each tempera-
ture for 1:3, 1:5, and 1:7 ratios. The powder derived from
the 1:3 ratio crystallized to tetragonal BaTiO3 at the low-
est temperature of 700 °C after 1 h. The other precursors
required higher calcining temperatures to crystallize. Fig-
ure 3 shows the SEM morphological characteristics of
the crystallized powders calcined at their lowest crystal-
lization temperatures. The SEM micrograph of the pow-
der prepared from the 1:3 ratio sol revealed nanosized
particles of about 100 nm, with a narrow particle size
distribution. The powder derived from the 1:5 solution
resulted in a larger particle size of approximately
200 nm. This was attributed to higher activation energies
for particle size growth at the higher crystallization tem-
peratures. The morphological characteristics of the pow-
der made by the 1:7 solution consisted of broken spheres
and had a wide particle size distribution. It is speculated
that the excess polymer caused inhomogeneity in the
precursor as a result of entanglements of the polymer
chains. This resulted in serious agglomeration, large par-
ticle sizes, and a wide particle size distribution. In the
case of the 1:7 ratio powder, 1250 °C was needed for full
crystallization because of the inhomogeneity in the system.
The broken sphere morphological characteristic was pro-
duced by trapped gases, such as CO and CO2 that ex-
panded when heated and fractured the spherical shapes.11
The BET measurement of crystalline powder prepared
from 1:3 ratio sol had a very low specific surface area of
5.6 m2/g despite nanosized particles [Fig. 3(a)]. The
SEM micrograph revealed that the nanosized particles
were already presintered, suggesting that the nanosized
powder was quite reactive even at low temperatures. The
powders, after ball milling for 1 h, increased their surface
area to 15 m2/g, which resulted from breaking up of the
presintered particles.
Figure 4 is an SEM micrograph of the polished and
thermally etched surface of densified BaTiO3 derived
from the 1:3 ratio route. The pellet had a 97% relative
density and a grain size of about 200 nm after sintering at
1200 °C for 2 h. The densification temperature was 100–
150 °C lower than reported to date.3,12,13,23 The dielec-
tric constant for the disk-type, sintered BaTiO3 reached
2100 at room temperature.
900 °C 1250 °C Particle size (nm)
Tetragonal Tetragonal 70 –150
Tetragonal Tetragonal 150 –250
Amorphous Tetragonal Inhomogeneous
3003
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 S.J. Lee et al.: Powder synthesis of barium titanate and barium orthotitanate via an ethylene glycol complex polymerization route

B. Barium orthotitanate
Because the Ba2TiO4 powder reacted with an alumina
substrate during calcination, a zirconia (3Y-TZP) sub-
strate was used instead. The Ba2TiO4 was found to de-
compose when exposed to air at ambient temperatures.18
Hence, the calcined powder was kept in a dessicator un-
der vacuum. The Ba2TiO4 precursor powders formed the
best crystallinity with a 1:5 ratio solution. Unlike the
BaTiO3, the barium nitrite would not completely dissolve
in the 1:3 solution. The powder derived from the 1:5 ratio
solution crystallized at lower temperatures than did the
powder produced from 1:7 ratio solution. The phase
changes of Ba2TiO4 powders at various temperatures are
summarized in Table II. The powder produced from 1:5
ratio solution crystallized to monoclinic phase after heat-
ing at 1000 °C for 5 h or at 1200 °C for 1 h. During
calcination tetragonal barium titanate (t-BaTiO3) formed,
before the appearance of monoclinic barium orthotitanate
(m-Ba2TiO4).
Figure 5 shows the powder morphological character-
istic of the m-Ba2TiO4 (from 1:5 ratio solution) calcined
at 1200 °C for 1 h. The SEM micrograph revealed an
average particle size of ∼0.6 ␮m, as well as presintered
particles with glassy phase. XRD indicated that the
amount of glassy phase gradually increased as a function
of temperature above 1200 °C. The Ba2TiO4 powder was

FIG. 4. SEM micrograph of polished and thermally etched (1100 °C

for 10 min) cross section of BaTiO3 sintered at 1200 °C for 2 h.

TABLE II. Phase change of Ba2TiO4 powders at each calcination tem-

perature (EG content ⳱ 1:5).

Calcination temp. (°C) 800 1000 1200 1400

Holding time (h) 1 5 1 5 1 5 1 5
FIG. 3. SEM micrographs of BaTiO3 powders calcined at their lowest
crystallization temperatures (Table I). (a) Powder from 1:3 solution Phase T T T+M M M M M+G M<G
calcined at 700 °C for 1 h, (b) powder from 1:5 solution calcined at
900 °C for 1 h, and (c) powder from 1:7 solution calcined at 1250 °C T: tetragonal barium titanate (t-BaTiO3), M: monoclinic barium orthoti-
for 1 h. tanate (m-Ba2TiO4), G: glass.

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 S.J. Lee et al.: Powder synthesis of barium titanate and barium orthotitanate via an ethylene glycol complex polymerization route

FIG. 5. SEM micrograph of the Ba2TiO4 powder calcined at 1200 °C

for 1 h (ethylene glycol content was 1:5).

found to slowly decompose on contact with air. After

several hours in an air atmosphere, the Ba2TiO4 powder
decayed into crystalline t-BaTiO3 and amorphous by-
products. Excess BaO after decomposition to t-BaTiO3
was not detected by XRD.
The dilatometric and DSC analysis of sintered, poly-
crystalline Ba2TiO4 indicated a phase transformation
from monoclinic to orthorhombic symmetry. The dilato-
metric and DSC plots for Ba2TiO4 are given in Fig. 6.
The initial transformation on heating occurred at around
710 °C and was accompanied by a volume decrease of
∼0.5%. On cooling, only an ∼0.2% volume increase was
observed, however. A smaller exothermic peak occurred
in the DSC compared with the corresponding larger en-
dothermic peak on heating. These results may be attrib-
uted to the decreasing amount of Ba 2 TiO 4 and
corresponding increase in glassy phase during the ther-
mal analysis cycle. As mentioned previously in Table II
and Fig. 5, glassy phase was formed from the Ba2TiO4 at
temperatures above 1200 °C.
The high-temperature orthorhombic form could be re-
tained down to room temperature. The use of MgO as
stabilizer and its effects are summarized in Table III.
By the addition of 6 and 10 wt% MgO, the high-
temperature orthorhombic phase was obtained at room
temperature. With only a 3 wt% MgO addition, pure or-
thorhombic phase was not obtained at all temperature
ranges. Above 1500 °C the 3 wt% stabilized powder
would begin to melt. In the 6 and 10 wt% MgO stabilized
powders, t-BaTiO3 phase was detected after long anneal-
ing times at 1000 °C. It was reported9 that for BaTiO3
and Ba2TiO4 the ratio of the number of oxygen atoms to
barium atoms is not sufficient to allow a close-packed
framework. In particular, this effect was much more
important in Ba2TiO4 than in BaTiO3.9 In Ba2TiO4, the
Ti–O bond became the predominant factor that pro-
FIG. 6. (a) Dilatometry and (b) DSC curves for polycrystalline
Ba2TiO4 sintered at 1200 °C for 2 h.
duced a tetrahedral environment around titanium, and
the result was a loosely packed structure of barium
atoms. This implies that BaO is easily released from
the unstable Ba2TiO4, resulting in the formation of
stable BaTiO3.
The tetragonal BaTiO3 transformed to the hexagonal
form above 1300 °C (Table III). The addition of MgO
stabilizer forms a solid solution with Ba2TiO4, and hence
the decomposition product BaTiO3. This lowers the te-
tragonal to hexagonal transformation temperature rela-
tive to pure BaTiO3 (in an air atmosphere it is 1550 °C
and in a hydrogen atmosphere it is 1325 °C).7,24 Conse-
quently, hexagonal barium titanate (h-BaTiO3) forms at
1300 °C, as seen by its retention down to room tempera-
ture. The orthorhombic phase was more stable in the
10 wt% MgO compared with 6 wt% MgO stabilized
powder. Comparison of Tables II and III implies that the
addition of MgO can make the Ba2TiO4 phase more
chemically stable by inhibition of BaO release. The char-
acteristic x-ray patterns of the pure monoclinic and or-
thorhombic phases of Ba2TiO4 are presented in Fig. 7.

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 S.J. Lee et al.: Powder synthesis of barium titanate and barium orthotitanate via an ethylene glycol complex polymerization route

TABLE III. Phase changes of stabilized Ba2TiO4 with different MgO contents after several annealing conditions.

Annealing temp. (°C) 800 1000 1100 1200 1300 1500

Annealing time (h) 2 5 2 6 24 50 5 15 2 5

3 wt% MgO M+T M+T M+T O+M+T O+M<T O<T O+T O<T O+H Melt
6 wt% MgO M+T O+T O O>T O>T O+T O>T O>T O>H O<H
10 wt% MgO O+T O>T O O O>T O>T O O>T O>H O>H

O: orthorhombic barium orthotitanate (o-Ba2TiO4), M: monoclinic barium orthotitanate (m-Ba2TiO4), T: tetragonal barium titanate (t-BaTiO3),
H: hexagonal barium titanate (h-BaTiO3).

FIG. 7. X-ray diffraction patterns of synthesized Ba2TiO4 (a) pure
monoclinic phase formed by calcining at 1200 °C for 1 h and (b) pure
orthorhombic phase (stabilized with 6 wt% MgO) calcined at 1000 °C
for 2 h.
IV. CONCLUSIONS
BaTiO3 and Ba2TiO4 have been successfully synthe-
sized by the EG polymerization-complexation route by
use of water-insoluble chemicals as a source of titanium
ions. The crystalline powders calcined at relatively low
temperatures were nanoscale in size and possessed high
sinterability. Direct dissolution of chemicals in EG sim-
plified the process and showed that chelation was not
necessary to form a homogeneous barium–titanium com-
pound. In sintered BaTiO3, a nanoscale grain size re-
sulted from the homogeneous, amorphous-type precursor
and relatively low sintering temperature. In Ba2TiO4, the
high temperature orthorhombic phase could be retained
at room temperature by addition of MgO. In the MgO-
doped Ba2TiO4 structure, the release of BaO during long
annealing times resulted in formation of stable t-BaTiO3.
As the MgO content increased, BaO release was retarded.
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