Materials Science and Engineering B 110 (2004) 202–212

Extended phase homogeneity and electrical properties of barium

calcium titanate prepared by the wet chemical methods
S. Jayanthi, T.R.N. Kutty∗
Materials Research Center, Indian Institute of Science, Bangalore 560012, India

Received 1 September 2003; accepted 4 March 2004

Abstract

Ca-substituted BaTiO3 with extended homogeneity range upto ∼50 mol% CaTiO3 have been prepared by three different chemical routes
namely carbonate-oxalate (COBCT), gel-carbonate (GCBCT), and gel-to-crystallite conversion (GHBCT) followed by heat treatment above
1150 ◦ C. X-ray powder diffraction (XRD) data show continuous decrease in the tetragonal unit cell parameters as well as c0 /a0 ratio with
CaTiO3 content, which are in accordance with the substitution of smaller sized Ca2+ ions at the barium sites. The microstructure as well as
the dielectric properties are greatly influenced by the cationic ratio, α = (Ba + Ca)/Ti. The grain size decreases with CaTiO3 content for the
stoichiometric samples (α = 1), whereas ultrafine microstructure is observed in the case of off-stoichiometric samples (α > 1) for the whole
compositional range of CaTiO3 concentrations. Sharper εr –T characteristics at lower calcium content and broader εr –T with decreased εmax ,
in the higher calcium range are observed in the case of α = 1. Whereas nanometer grained ceramics exhibiting diffuse εr –T characteristics
are obtained in the case of α > 1. The positive temperature coefficient of resistivity (PTCR) is realized for barium calcium titanate ceramics
having 0.3 at.% Sb as the donor dopant for higher CaTiO3 (typically 30 mol%) containing samples (α = 1), indicating that Ca2+ ions do not
behave as acceptors if they were to substitute at the Ti4+ sites. Whereas the off-stoichiometric (α > 1) ceramics retained high resistivity,
indicative of the Ti-site occupancy for Ca2+ in fine grain ceramics.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Ceramics; Permittivity; Stoichiometry and homogeneity; Metastable phases

1. Introduction thermal coefficient of dielectric properties with Z5U char-

The monolithic as well as multilayer capacitors (MLC)
with good integrated circuits (IC) compatibility, excel-
lent dielectric properties, and volume efficiency have be-
come indispensable components in modern electronic cir-
cuits. Success in developing the dielectric materials for
nickel-electroded multilayer capacitors has been achieved
by adding acceptor type dopants to BaTiO3 ceramics, which
reduces the high cost due to electrodes. BaTiO3 has the
ability to form extensive solid solutions by means of which
a variety of materials with continuously changing dielec-
tric properties can be produced as polycrystalline ceramics.
CaTiO3 is one of the common constituents in most of the
commercial ceramic capacitors whose exact role is not de-
fined, although some believe that calcium minimizes the
∗ Corresponding author. Tel.: +91-80-3092784; fax: +91-80-3341683.
E-mail address: kutty@mrc.iisc.ernet.in (T.R.N. Kutty).
acteristics [1]. Ca-substituted BaTiO3 is also found to have
high piezo-coefficient of resistance. It is generally known
that Ca2+ ions are useful for broadening the temperature
dependence of the dielectric constant of BaTiO3 ceramics
[2,3]. The real mechanism causing the diffuse phase tran-
sition (DPT) behavior, however, is not well understood.
Calcium containing titanate ceramic capacitor composi-
tions can be processed in lower oxygen partial pressure
conditions without any significant change in loss factors.
Because of the commercial importance, calcium substituted
BaTiO3 is presently reinvestigated with specific emphasis
on preparative routes.
Phase relations in BaTiO3 –CaTiO3 system were stud-
ied by Devries and Roy [4]. According to their phase dia-
gram, CaTiO3 up to ∼18 mol% forms a homogenous solid
solution with BaTiO3 at 1400 ◦ C. Several subsequent au-
thors have investigated the effect of calcium ion substitu-
tion on the ferroelectric structural transitions and dielectric
properties in BaTiO3 . Berlincourte and Kulesar [5] found

0921-5107/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2004.03.008
 S. Jayanthi, T.R.N. Kutty / Materials Science and Engineering B 110 (2004) 202–212
that Ca2+ substitution in BaTiO3 caused only negligible
changes in the Curie point whereas, Mcquarrie and Behnke
[6] reported that Ca-doped BaTiO3 showed a decrease of
the Curie point. Mitsui and Westpal [7], from the dielectric
and X-ray diffraction (XRD) studies, demonstrated that the
Curie point of (Ba1−x Cax )TiO3 increases from 130.7 ◦ C for
BaTiO3 to 136.1 ◦ C for x = 0.08 and then decreased with
Ca concentration up to 25 mol%. According to Zhuang et al.
[8], the broadened and diffuse dielectric maximum moves
to room temperature for the composition with 11 mol% of
CaTiO3 , whereas Jaffe et al. [9] have indicated that the
Curie temperature does not change with Ca-content upto
25 mol%. Zhuang et al. [8] were the first to report about
the possible occupancy of Ca2+ in the Ba2+ as well as
Ti4+ sites. Subsequently, several authors have tried to es-
tablish the site occupancy of Ca2+ in BaTiO3 prepared by
different processing routes. However, there are no direct
evidences by way of changes in unit cell size, systematic
absences, changes in crystal system or possible topolog-
cal transformations, which give insight into the cation sub-
stitutions and ordering in single crystals of (Ba,Ca,Ti)2 O3 .
This formula is adopted so as to imply no a priori commit-
ment of the place occupancy of Ca2+ ions in BaTiO3 lat-
tice. Notwithstanding the limited evidences presented that
calcium occupies titanium sites, the homogeneity limit has
not been reported when prepared by the low temperature
chemical routes. During the present investigations, varying
amounts of calcium were added to form (Bax Cay Tiz )2 O3
with x + y + z = 1 by three different wet chemical meth-
ods, where the mole fraction of calcium titanate ranges from
zero to 0.6. The A/B ratio [α = (x + y)/z] is varied from
0.98 to 1.02 so that it can be verified whether the mode
of chemical formulation influences the dielectric proper-
ties. The electrical resistivity of donor (Sb5+ ) doped bar-
ium calcium titanate has been studied in order to verify the
acceptor behavior of Ca2+ by way of occupancy at Ti4+
sites.
2. Experimental procedures
2.1. Preparative routes
Barium calcium titanate (Ba,Ca,Ti)2 O3 was prepared by
three different wet chemical methods namely:
(1) Carbonate-oxalate method (COBCT);
(2) Gel-carbonate method (GCBCT);
(3) Gel-to-crystallite conversion method (GHBCT).
For independently comparing the properties, the same
compositions were also prepared by the ceramic method
(CRBCT). In all the preparative routes, the stoichiometry ra-
tio α = (Ba + Ca)/Ti was varied from 0.98 to 1.02 (0.98 <
α < 1.02) and in few cases up to 1.10. α = (x + y)/z = 1
refers to the stoichiometric perovskite. The compositional
203
details and acronyms used for barium calcium titanate pre-
pared by different routes are given in Table 1.
The precursor route involving the alkaline earths metals
titanyl oxalates yielded the highest purity titanate ceramics
powders. However, barium calcium titanyl oxalate could not
be prepared because of the high solubility of the Ca-rich
component in acid media from which BaTiO(C2 O4 )2 ·4H2 O
is precipitated. Therefore, the carbonate-oxalate method was
adapted. Extra pure TiOCl2 (99.99%) and CaCO3 (99.99%)
in the desired stoichiometric ratios were dissolved in di-
lute HCl. The mixed solution was treated with 1 M ammo-
nium carbonate at 40 ◦ C till the pH raised to ∼8, leading
to the precipitation of the voluminous gel of amorphous hy-
drated titania in which the crystalline CaCO3 nanoparticles
were embedded. The precipitate was washed free of chlo-
ride and ammonium ions. It was mixed with barium titanyl
oxalate, BaTiO(C2 O4 )2 ·4H2 O, powder in different ratios,
using an ultrasonic blender while kept in suspension in dis-
tilled ethanol. The mixtures were dried in air-oven, after
filtering off the solvent. They were decomposed at 650 ◦ C
for 7 h. The residues were then homogenized using a plan-
etary mill (Fritz, Germany) for 2 h in ethanol medium and
were dried at 120 ◦ C. The powders were calcined at 850 and
then at 1150 ◦ C to obtain the desired crystalline phase of
(Bax Cay Tiz )2 O3 .
In the case of gel-carbonate method, high purity
BaCl2 ·2H2 O (99.98%) and CaCl2 (99.96%) were dissolved
in distilled water and the solution was mixed with TiOCl2
(aq). The metal ions were coprecipitated using ammonium
carbonate at 40 ◦ C till the pH is ∼8 leading to amorphous
hydrated titania gel in which BaCO3 + CaCO3 nanocrys-
talline particles remain embedded. The precipitate was
washed free of soluble ions using deionised water and
air-dried. Calcination was carried out in steps between 650
and 1150 ◦ C with intermittent mixing after cooling to room
temperature.
In the gel-to-crystallite conversion method [10], the re-
active gels of hydrated TiO2 (TiO2 ·xH2 O where 80 < × <
110) was prepared by the addition of ammonium hydroxide
at 30 ◦ C to the TiOCl2 solution until the pH was around 7.
The gel was washed free of soluble salts, mostly NH4 Cl.
The gel was suspended in ethanol containing Ca(OH)2
+ Ba(OH)2 in the desired ratio in a flask, attached with a
water-cooled reflux condenser and the alkali guard-tube at
the top-end to avoid the ingression of CO2 . The mixture
was maintained at the boiling point (∼85 ◦ C) while kept
agitated with a magnetic stirrer. Ba2+ + Ca2+ ions enter-
ing the gel produce the chemical changes involving the
breakage of –Ti–O–Ti– (or), –Ti–OH–Ti– bridging bonds
accompanied by dehydroxylation leading to heterogeneous
nucleation and growth of the perovskite crystallites within
the gel. The solid phase remaining in the vessel was then
filtered, washed free of Ba(OH)2 and then air-dried. The
powders so prepared were calcined at 900 and then at
1150 ◦ C. In the case of ceramic method, BaCO3 (99.98%),
CaCO3 (99.99%), and TiO2 (99.98%) were taken in the
204 S. Jayanthi, T.R.N. Kutty / Materials Science and Engineering B 110 (2004) 202–212

Table 1
Acronyms used for barium calcium titanate powder prepared from different methods
Preparative route adopted Acronyms for barium Preparative method
calcium titanate powder
obtained
Carbonate-oxalate COBCT CaCl2 + TiOCl2 were precipitated using NH4 CO3 .
method And the gel is homogenized with barium titanyl
oxalate powder.
α = 0.98a COBCT-98
α =1 COBCT-100
α = 1.005 COBCT-1005
α = 1.01 COBCT-101
α = 1.02 COBCT-102
Carbonate-oxalate COBT
barium titanate.
Gel-carbonate method GCBCT BaCl2 + CaCl2 is added to TiOCl2 and are
coprecipitated using NH4 CO3 .
α = 0.98 GCBCT-98
α =1 GCBCT-100
α = 1.005 GCBCT-1005
α = 1.01 GCBCT-101
α = 1.02 GCBCT-102
Gel-carbonate barium GCBT
titanate
Gel to crystallite GHBCT TiO2 ·xH2 O (gel) + CaO + Ba(OH)2 are made to
conversion method react in ethanol medium.
α =1 GHBCT-100
Gel to crystallite GHBT
barium titanate
Solid state method CRBCT BaCO3 + CaCO3 + TiO2 were milled and are
made to react at high temperature.
α = 0.98 CRBCT-98
α =1 CRBCT-100
α = 1.005 CRBCT-1005
α = 1.01 CRBCT-101
α = 1.02 CRBCT-102
a α = (Ba + Ca)/Ti.

desired stoichiometry and mixed in a planetary mill for 2 h.
The mixtures were calcined at 1050 ◦ C (8 h) and then at
1150 ◦ C (6 h) to effect the solid–solid reactions.
In order to study the variation in properties with respect to
off-stoichiometry, α = (Ba + Ca)/Ti was varied from 0.98
to 1.02 in the case of all the preparative methods. The pow-
ders were prepared under identical conditions and were cal-
cined as that of the stoichiometric samples. The acronyms
used for them are shown in Table 1. The sintering and the
grain growth behavior of (Bax Cay Tiz )2 O3 powders from dif-
ferent wet chemical methods are greatly dependent on the
(Ba + Ca)/Ti ratio. Samples with various compositions of
(Ba,Ca,Ti)2 O3 were prepared by the above methods with the
mole fraction of CaTiO3 , ranging from 0.05 to 0.6. The cal-
cined powders were then mixed with 0.16 wt.% poly vinyl
alcohol (PVA) as the binder and 0.12 wt.% poly ethylene
glycol (PEG) as the deflocculant. The granulated powders
were cold pressed into disks of around 2.5 mm thickness
and 14 mm diameter. The green pellets were sintered in the
temperature range of 1380–1450 ◦ C for 4 h and cooled in
a programmable electric furnace (Thermolyne, USA). Ce-
ramic samples of ≥95 theoretical density were obtained dur-
ing sintering.
In order to study the effect of Ca2+ ions on the donor
doped (Ba,Ca,Ti)2 O3 , ceramic powder prepared from
carbonate-oxalate method with CaTiO3 varying from 2 to
30 mol% was chosen for PTCR studies. Sb2 O5 (=0.3 at.%
Sb) was added to (Ba,Ca,Ti)2 O3 and ball-milled for a few
hours. The mixtures were precalcined at 1000 ◦ C for 2 h
for homogenity by way of diffusion of the dopants. The
fine powders were mixed with 2 wt.% of sinter-aiding ad-
ditives, which is Al2 O3 + 2SiO2 + TiO2 (AST). These
mixtures were mixed in a planetary mill with acetone as
the medium. The dry mixtures were mixed with binder and
then pelletizied. The samples were heated at a rate of 2 ◦ C/
min till 650 ◦ C (1 h) for binder burnout and heated at a rate
of 3 ◦ C/min to 1380 ◦ C, with dwell time of 3 h and then
cooled at a rate of 15 ◦ C/min. The sintered ceramics discs
were polished on both sides and ohmic metal contacts were
made by electroless Ni coating.
 S. Jayanthi, T.R.N. Kutty / Materials Science and Engineering B 110 (2004) 202–212
2.2. Characterization
= c, the in-
X-ray diffraction studies were carried out using a Philips
PW 1050/70/76 (Netherlands) or a Scintag (USA) X-ray
diffractometer having nickel filtered, Cu K␣ as the source.
The cell parameters were evaluated from the diffraction
patterns recorded with polycrystalline silicon as the inter-
nal standard. Microstructures of the polished and thermally
etched ceramics were studied using S360 Cambridge (Eng-
land) scanning electron microscope (SEM). The elemental
distribution analyses of the sintered specimens were carried
out using a fully automated quantitative energy dispersive
X-ray analyser (EDX), Links AN10000 (Oxford Instru-
ments, UK) fitted on to the SEM microscope. Electrodes on
the dielectric ceramic discs were produced by silver paint
(Dupont) fired-on at 800 ◦ C for 10 min, which gave good
ohmic contacts. The capacitance values of the ceramic sam-
ples were measured using the HP 4284A precision LCR
meter, in the frequency range from 20 Hz to 1 MHZ, while
the temperature of the specimen was varied at the rate of
0.5 ◦ C/min.
3. Results
3.1. X-ray diffraction
Fig. 1 shows the X-ray diffraction patterns of Ca-
substituted BaTiO3 for the COBCT-100 sample with vary-
ing calcium contents. The extent of splitting and intensity
ratio of (2 0 0) and (0 0 2) reflections are indicative of the
co-existence of cubic and tetragonal phases at room temper-
Fig. 1. X-Ray diffraction patterns of COBCT ceramics sintered at 1380 ◦ C
(a) COBCT5, (b) COBCT30, (c) COBCT50, and (d) COBCT60.
205
ature. For 100% tetragonal BaTiO3 where a = b
tegrated intensity ratio of the reflections I(0 0 2) /[I(2 0 0),(0 2 0)
+ I(0 0 2) ] will be 0.33. If the phase is 100% cubic (a = b =
c), the above intensity ratio will become zero. For a mixture
of tetragonal and cubic phases, the ratio will have values
between 0.33 and zero. Further, when the phase is 100%
cubic, the reflections from (2 0 0), (0 2 0), and (0 0 2) merge
to single diffraction peak. Powders as well as pressed disks
heat treated below 1250 ◦ C show the above intensity rela-
tion with respect to (0 0 2) and (2 0 0) reflections. However,
the XRD of the samples sintered above 1250 ◦ C showed a
reversal with higher intensity for (0 0 2) and lower intensity
for (2 0 0) reflections. Fig. 2 shows the diffraction peaks of
(2 0 0) and (0 0 2) for the samples COBCT5 and COBCT30
heated at 1100 and 1300 ◦ C. The reason for the reversal in
intensity is due to the preferred orientation of the domains
with their c-axis perpendicular to the surface. During sin-
tering, growth of crystallites with preferred orientation is
possible, which leads to domains along c-axis on cooling
below Tc, resulting in changes of XRD intensities of the
tetragonal line pairs.
COBCT-100, having 50 mol% CaTiO3 , retains phase sin-
gularity with tetragonal symmetry. Above 50 mol% CaTiO3 ,
they showed two sets of XRD peaks, corresponding to two
phases of which the lower intensity reflections are more com-
parable to those of CaTiO3 than of BaTiO3 . GCBCT-100
and GHBCT-100, having ∼45 mol% CaTiO3 is found to
retain phase singularity with the tetragonal symmetry. The
Fig. 2. Reversal in intensity of (2 0 0) and (0 0 2) peak for samples heated
at 1100 and 1300 ◦ C (a) COBCT5 (b) COBCT30.
206 S. Jayanthi, T.R.N. Kutty / Materials Science and Engineering B 110 (2004) 202–212
second phase is observed with further increase in calcium
content. The results show that the homogeneity limit of
(Ba,Ca,Ti)2 O3 has broadened in all the samples prepared by
the wet chemical route, although the limit is found to differ
somewhat with the actual processing method adopted. The
solubility limits of (Ba,Ca,Ti)2 O3 is controlled by the pu-
rity as well as the surface energy by way of restricted grain
growth in the chemically prepared specimens. The presently
observed homogeneity limits are much higher than those re-
ported from the phase diagram studies [4], clearly demon-
strating the advantages of chemical methods in preparing
the titanate solid solutions.
The values of lattice constants were obtained from the
XRD data. Fig. 3 shows the plots of c0 , a0 , and (c0 /a0 ) ver-
sus mol% CaTiO3 for the COBCT-100, GCBCT-100, and
GHBCT-100. The values of c0 and a0 decrease continuously
with calcium titanate content. Mitsui and Westpal [6] have
reported that c0 /a0 ratio of Ba1−x Cax TiO3 decreases mono-
tonically with Ca-content. They have reported only upto
6 at.% Ca substitution. However in our samples too, the same
trend is observed over a wider range of calcium content. The
c0 /a0 ratio varies from 1.009 (zero Ca) to 1.006 (50 mol%
CaTiO3 ). Similar trend is observed in the case of specimens
prepared by the three wet chemical routes (Fig. 3). The c0 /a0
ratio remains nearly the same for specimens from all the
routes. It has been reported [6] that when Ca2+ with ionic
2+ xii
radius (rCa ) = 1.35 Å is substituted for Ba2+ (rBa 2+ xii
) =
1.64 Å [11], the unit cell as well as the lattice parameters de-
crease with the Ca-content. The absence of further changes
Fig. 3. Variation of a0 , c0 , c0 /a0 with mol% calcium titanate for
COBCT-100, GCBCT-100, and GHBCT-100.
in lattice parameters above 50 mol% CaTiO3 suggests that
the homogeneity limit has been exceeded which results in
the formation of a second titanate perovskite phase richer in
Ca-content.
The samples with off-stoichiometry, GCBCT101 and CR-
BCT101, with c0 /a0 = 1.000, show cubic symmetry. In the
case of higher composition of calcium, such as GCBCT30,
minor increase in (α = 1.005) is sufficient to render the
material cubic. Therefore, from any one of the method of
preparation and for a wider range of Ca-substitution, the
phase contents remain completely cubic at room temper-
ature (RT) for all the compositions having α > 1. The
XRD of the sintered specimens with α > 1.05 show ad-
ditional peaks corresponding to two phases i.e. Ba-rich
(Ba3 Ca2 Ti2 O9 ) as well as Ca-rich (Ca3 Ba2 Ti2 O9 ) phases
matching with the JCPDS File No. 42-0535. The compo-
sitions of the secondary phases have been ascertained by
EDX analyses. With α < 1.05, the presence of secondary
phases is not discernible by XRD. However preferential
segregation of calcium towards the grain boundary layer
regions could be deciphered from EDX studies. In a typical
case of (Ba0.3 Ca0.21 Ti0.5 )2 O3 sintered ceramics, the grain
interiors showed Ba = 42.3, Ca = 8.2 and Ti = 24.6 wt.%
whereas the composition of the grain boundary regions
showed a wider range: Ba = 42.3–54.2, Ca = 8.2–18.1,
and Ti = 14.5–24.6 wt.%. The contents of Ba and Ca in
the higher ranges approach the compositions of the sec-
ondary phases mentioned earlier i.e. (Ba3 Ca2 Ti2 O9 and
Ca3 Ba2 Ti2 O9 ). For ceramics containing >50 mol% CaTiO3 ,
segregation of Ca-rich titanate perovskite is conspicuous in
the case of off-stoichiometric samples with α > 1.02.
Zhuang et al. [8] have reported that c0 /a0 decreases
with increasing amount of calcium and that the tetrag-
onality diminishes to approach a cubic unit cell due to
the internal lattice distortion of the materials caused by
the substitution of Ca at the Ti-site, for the composition
of Ba0.95 Ti1−x Ca0.05+x O3−x , where x (0.01–0.04) is the
amount of calcium occupying titanium sites. However the
value of x (referred to as the amount of Ca substituting in
Ti-site) presented by Zhuang et al. [8] is the same as of the
off-stoichiometric samples with α ranging from 1.02–1.08,
wherein the c0 /a0 ratio decreases with α-value, approaching
cubic symmetry. Therefore, the decrease in c0 /a0 observed
by Zhuang et al. is due to the variation in α value and does
not reflect the occupancy of Ca2+ in Ti4+ -sites.
3.2. Microstructural studies
The microstructural features of sintered specimens of
(Ba,Ca,Ti)2 O3 show diversity with the methods of prepa-
ration. When sintered at 1380 ◦ C, COBT-100 having zero
calcium content acquires large grain size of ∼100 ␮m. With
the incorporation of 5 mol% CaTiO3 , the average grain size
reduces to 80 ␮m. Further addition of CaTiO3 to 30 mol%
decreases the grain size to =10 ␮m. With 60 mol% CaTiO3 ,
which is in the inhomogeneity range, the grain size decreases
 S. Jayanthi, T.R.N. Kutty / Materials Science and Engineering B 110 (2004) 202–212
to 1–4 ␮m. In the case of GCOBT-100, the grain size varies
from 45–60 ␮m. When the CaTiO3 content is increased to
30 mol% the grain size decreases to 5–6 ␮m which further
goes down to sub-micrometer range with CaTiO3 con-
tent of ∼45 mol%. (Ba,Ca,Ti)2 O3 ceramic prepared from
gel-to-crystallite method, having <10 mol% CaTiO3 , pos-
sess average grains size <5 ␮m, and exhibit wavy grain
boundaries. Grain growth is improved at higher CaTiO3
contents. With 30 mol% CaTiO3 , the ceramics have larger
grain size of 10–25 ␮m with a broader size-distribution.
Ferroelectric domains are observed within the individual
grains for all the specimens with grain size ≥ 2 ␮m.
Fig. 4 shows the SEM picture of COBT, COBCT10-100
as compared to the off-stoichiometric samples (α =
1.005–1.01). The grain size reduces drastically to 0.1–1.0 ␮m
range when the α-value is increased to 1.005. The grain
growth is affected by different parameters such as α-value,
processing conditions and the preparative routes. This af-
fects the ferroelectric domain stability, and inhibits the
grain growth. For a given method of powder preparation,
increasing α-value is the most crucial parameter in lowering
the grain size to nanometer ranges.
3.3. Dielectric properties of (Ba,Ca,Ti)2 O3 ceramics
The dielectric-temperature characteristics (εr –T) of
(Ba,Ca,Ti)2 O3 are greatly dependent on the preparative
methods as well as the processing conditions. The εr –T
for BaTiO3 corresponding to tetragonal–cubic transition is
Fig. 4. Microstructure of stoichiometric (a) COBT (b) COBCT10 and off-stoichiometric ceramic samples (c) COBCT10–1005 (d) COBCT10–101.
207
about 131 ◦ C with εmax ≈ 12, 000. Dielectric properties of
Ca substituted BaTiO3 ceramics is not a linear function of
the concentration of the substituent. The dielectric behav-
ior of (Ba,Ca,Ti)2 O3 ceramics prepared by wet chemical
methods measured in the temperature range of 20–180 ◦ C
are shown in Fig. 5. As the CaTiO3 content is increased,
max decreases and the dielectric maxima broaden for sam-
ples prepared by all the routes. The εr –T characteristics are
intimately related to their microstructure. Those samples,
which possess sharp r peaks around the Curie temperature,
were found to have coarser grain sizes while those showing
broad and diffuse dielectric response are fine-grained.
The incorporation of CaTiO3 by the carbonate-oxalate
method in the range of 5–10 mol% shows a marginal increase
in Curie point to 138 ◦ C. With higher CaTiO3 content up to
50 mol%, the Curie temperature remains unchanged around
130 ◦ C. Very slight dip in the Curie point is noticed with
60 mol% calcium titanate. The εr –T behavior of samples pre-
pared by gel-to-carbonate method shows a nearly unchanged
Tc ∼130 ◦ C till 30 mol% CaTiO3 . The Curie temperature
dips to 124 ◦ C, accompanied by the decrease in ⑀max for
45 mol% CaTiO3 . Whereas, ceramics having CaTiO3 con-
tent of 60 mol% show the diffuse εr –T curve, without any
peak maximum. In the case of gel-to-crystallite method, the
samples exhibit decrease in Tc up to 12 mol% CaTiO3 . Tc
increases with further CaTiO3 content up to 30 mol% and
remains the same without much variation at higher calcium
contents. Slightest increase in α > 1.00 causes downward
shift in Tc for the composition of GHBCT5 and GHBCT12
208 S. Jayanthi, T.R.N. Kutty / Materials Science and Engineering B 110 (2004) 202–212
Fig. 5. The dielectric vs. temperature for samples sintered at 1380 ◦ C for stoichiometric (Ba,Ca,Ti)2 O3 : (a) carbonate-oxalate; (b) gel-carbonate; and (c)
gel-to-crystallite method.
from gel-to-crystallite and GCBCT45, from gel-carbonate
route. Correspondingly, the εr –T characteristics are modified
for a given composition, prepared by any one of the chem-
ical methods. However, in general, for stoichiometric sam-
ples (α = 1.00), the Tmax remains around 115–138 ◦ C. The
tan δ as a function of temperature for different Ca-content
is shown in Fig. 6. Tan δ lies between 0.02 and 0.08 at room
temperature and is almost unchanged with temperature. The
εr –T characteristics are nearly flat between room tempera-
ture to 80 ◦ C. The temperature coefficient of relative permit-
tivity (TCC) lies within a few parts per million in the same
temperature range.
To study the effect of stoichiometric variations on
the εr –T characteristics, ␣ = (Ba + Ca)/Ti was var-
ied for (i) the gel-carbonate and (ii) ceramic route while
maintaining the same CaTiO3 content at 10 mol%. The
samples prepared with α = 0.98 retains the εr –T be-
havior as that of α = 1 specimens. However, for α =
1.005–1.02, the corresponding εr –T characteristics are
very different (Fig. 7). The curves show shifts in Tc for
cubic–tetragonal (C–T), tetragonal–orthorhombic (T–O),
and orthorhombic–rhombohedral (O–R) transformations
which might result in the merging of two or more fer-
roelectric phases with the decrease in max as well as
shift in Tmax to lower temperature region. In the case of
gel-carbonate route, the Tmax is around 90 and 27 ◦ C for the
GCBCT10–101 and GCBCT10–102, respectively. The εmax
also decreases as shown in Fig. 7. The reason for the dif-
ference in the εr –T characteristics for the off-stoichiometry
samples with respect to the GCBCT10 could be explained
as follows: During the formation of sintered bodies of
GCBCT101 and GCBCT102 with sub-micrometer sized
grains, the excess A-cations near the grain boundary may
occupy the titanium sites, thereby acting as acceptors.
Although it restricts the grain growth, the ferroelectric
domains are still prevalent. Therefore unlike CRBCT10,
 S. Jayanthi, T.R.N. Kutty / Materials Science and Engineering B 110 (2004) 202–212
Fig. 6. Variation in tan δ with temperature for sintered ceramics (a) COBCT
(b) GCBCT and (c) GHBCT.
with broad εr maxima, which is indicative of diffuse tran-
sition, the sharper εr –T maximum in GCBCT10 reflects
ferroelectric domain development with first order transition
characteristics.
Specimens prepared by the ceramic route, CRBCT10–101
and CRBCT10–102, show broad εr maxima which is in con-
trast to the characteristics of the corresponding stoichiomet-
ric samples i.e. with α = 1.00. This can be attributed to the
effect of higher surface energy arising from the fine grains
as seen in the SEM micrographs (Fig. 4). For the CRBCT10
off-stoichiometry samples, different contributions of ferro-
electric domain stability such as, elastic strains, impurity
pinning, point defects, depolarization effects, and the free
surface accumulation of compensating charges might result
in the suppression of cubic–tetragonal phase transition [12].
Due to one or more contributions mentioned above, the grain
size decreases drastically, and the R–O transition moves
towards higher temperature region. As also, the O–T tran-
sition temperature shifts upwards (≥25 ◦ C) while the T–C
transition moves down due to near identical values of free
energy of formation for different phases. This results in the
merging of the transitions giving rise to broad and diffuse
εr –T characteristics. The variations in εmax and Tmax for ce-
ramics from all the three wet chemically prepared samples
are shown in Fig. 8. It can be seen that the stoichiometric ra-
tio, (Ba + Ca)/Ti, plays a major role in determining the mi-
crostructure of the sample as well as the εr –T characteristics
of the samples. According to Zhuang et al. [8], the transition
temperature depends on the concentration of Ca on the B-site
209
Fig. 7. εr vs. T for (a) GCBCT10 and (b) CRBCT10.
or on both A and B-sites, and that Tc lies near room temper-
ature for ceramics containing 6% Ca on the A-site and 5%
Ca on the B-site. The lowering of Tc with the concentration
of Ca-ion on the B-site (BaTi1−x Cax O3−x ) or on both the A
and B-sites (Ba0.95 Ti1−x Ca0.05+x O3−x , x ranging from 0.01
to 0.04) as discussed by Zhuang et al. [8] is found to be due
to the variation in off-stoichiometry (α > 1), where α ranges
from 1.02 to 1.08. However there are no direct evidences, to
differentiate the site occupancy of Ca2+ in BaTiO3 . More-
over, the total concentration of substituted Ca2+ has been
restricted to <8 at.% in most of the earlier investigations.
Whereas in our studies, the homogeneity limit is nearly up
to 50 mol% in all the wet chemical route with well-defined
splitting in XRD reflection, indicating nearly 100% tetrag-
onality. The εr –T peaks are sharp for the stoichiometric
samples with depression in εmax for higher calcium con-
tents, and minor variations in Tc depending upon the
processing routes.
Nearly uniform microstructure with large grain size and
εr –T relations similar to those of BaTiO3 are obtained for
α = 1 irrespective of the Ca-content. In contrast, ceram-
ics with ultrafine-grain microstructure accompanied by the
shift in Tc and diffuse phase transition characteristics are
observed for α = 1.005–1.02 as seen in GCBCT10 and
CRBCT10. Therefore, the results given by Zhuang et al. [8]
could be considered to arise from the stoichiometric varia-
tions and can be explained in terms of sharper εr –T curve
for stoichiometric and diffuse εr –T for off-stoichiometric
210 S. Jayanthi, T.R.N. Kutty / Materials Science and Engineering B 110 (2004) 202–212
Fig. 8. Variation in Tmax and εmax with calcium titanate mol% for the
chemically prepared samples from different routes.
samples respectively. It could be concluded that α-value
is the determining factor for the sharper or diffuse εr –T
characteristics. The method of formulation by Zhuang
et al. [8] is, in fact, identical to the off-stoichiometric
samples.
3.4. Electrical conductivity of donor doped
(Ba,Ca,Ti)2 O3 ceramics
The semiconducting polycrystalline BaTiO3 is charac-
terized by its positive temperature coefficient of resistivity
(PTCR) around the Curie temperature. The effect of iso-
valent substituents in BaTiO3 namely those of Sr2+ and
Pb2+ are known to shift the Tc to opposite temperature
regions [13]. The typical curve for n-BaTiO3 shows sharp
PTCR characteristics around Tc with a well-defined resis-
tivity maximum (ρmax ), followed by a continuous decrease
in resistivity with further increase in temperature. PTCR of
La-doped (Ba,Ca,Ti)2 O3 prepared by ceramic route as well
as hydrothermal method have been reported by Voltzke and
Abicht [14]. However, they have reported resistivity jump of
around three orders of magnitude for 4 mol% Ca although
no ρ–T curves have been presented. The PTCR effect in
(Ba,Ca,Ti)2 O3 has been seldom reported in literature. In
order to verify the acceptor behavior of Ca2+ by way of
Fig. 9. ρ vs. T for (Ba,Ca,Ti)2 O3 –(0.3Sb–200Mn) + 2AST; COBCT10-
without AST.
occupancy in Ti4+ sites, the conductivity of donor doped
barium calcium titanate has been studied.
Fig. 9 gives the electrical resistivity of (Ba,Ca,Ti)2 O3
ceramics for 2–30 mol% CaTiO3 substitution. PTCR of the
ceramics with composition of 10 mol% CaTiO3 contain-
ing 0.3 at.% Sb show four orders of magnitude with room
temperature resistivity to around 800  cm. Addition of
the sinter-aids enhances the magnitude of the PTCR jump
to six orders and also brings down the room temperature
resistivity to 56–154  cm for the compositions ranging
from 2–30 mol% CaTiO3 (Fig. 9). The electrical resistivity
at room temperature, the broadening of ρ–T characteristics
as well as the magnitude of the electrical resistivity at high
temperatures (>200 ◦ C) are found to depend on the calcium
content. Electronic compensation of the donor dopants
takes place in limited concentration range of 0.15–0.4 at.%.
From the ionic size considerations, Sb5+ will occupy the
Ti4+ sites. There is definite difference in the extent of elec-
tronic versus vacancy compensation when both A and B
sub-lattices are substituted with donor impurities simulta-
neously [15]. If Ca2+ were to substitute in Ti4+ site, the
electron compensation by donor (e.g. Sb5+ ) will not be
effective to yield specimens of lower resistance ranges. The
oxygen vacancy due to CaTi would have resulted in the
barium calcium titanate with high resistivity. However the
 S. Jayanthi, T.R.N. Kutty / Materials Science and Engineering B 110 (2004) 202–212
semiconducting behavior around RT with lower resistiv-
ity and six orders of magnitude of PTCR jump show that
the electron compensation are predominant in the grain
interior by the substitution of Sb5+ in the Ti4+ site. The
ferroelectric domain characteristics were retained by the
PTCR ceramics. The magnitude of PTCR jump is further
increased by the addition of limited concentrations of Mn,
which enhances the acceptor states. Attempts to prepare
PTCR samples from the off-stoichiometric compositions
(higher α-value) for a given Ca-content only led to capac-
itive specimens. In brief, the present results do not support
the suggestion that Ca2+ ions occupy the Ti4+ -sites, partic-
ularly in the stoichiometric barium calcium titanate over a
wider range of calcium content (0–50 mol%).
4. Discussion
The substitution of Ca2+ in BaTiO3 is seen to influence
the microstructure and the electrical properties of these ce-
ramics to a great extent. It is evident from the above results
that the routes adapted for the processing of (Ba,Ca,Ti)2 O3
powders as well as the sintered disks can influence the homo-
geneity limit of the solid solutions. The fact that the speci-
mens prepared from the ceramic methods show limited range
of homogeneity suggests that the solid state reactions taking
place in the mixture of BaCO3 , CaCO3 , and TiO2 particles
results in nonuniform distribution of Ba2+ and Ca2+ ions at
the unit cell level [16]. One way of looking at the problem is
in terms of the microscopic chemical inhomogenities ensu-
ing from the slow reaction kinetics due to diffusional limita-
tions, which will restrict the solubility of CaTiO3 in BaTiO3
when prepared by the ceramic method. The alternate way
is to treat the system in terms of metastability wherein the
path dependent kinetics modify the criteria of phase stability
in multinary ceramics. The methods adapted for preparation
become very important in such cases.
In the wet chemical routes, the distribution of differ-
ent cationic constituents takes place in the atomic level to
start-with; the compositional inhomogenities originate from
exsolutions in the solid state during calcination as well as
sintering. Unlike in the ceramic method where the initial
reaction is rapid but further reaction becomes increasingly
slower as the product layer builds up, the kinetics restric-
tions in the wet chemical route will be by way of seggre-
gations into Ca-rich or Ba-rich titanate perovskite phases.
This drastically reduces the possibility of the compositional
inhomogenities and leads to metastable phases.
The c0 /a0 ratio of samples obtained from all the wet chem-
ical routes shows nearly constant value for a broader range
of CaTiO3 content. This shows that the solubility level of
CaTiO3 in BaTiO3 is higher in the case of wet chemical
routes, possibly due to large surface area of the resulting
powders, which leads to high reactivity. εr –T behavior simi-
lar to that of BaTiO3 is observed for stoichiometric (α = 1)
samples. Whereas, the ultrafine-grained microstructure ac-
211
companied by surface contributions affecting the stability
of ferroelectrics domains, results in the diffuse-phase trans-
formation characteristics for the off-stoichiometric (α > 1)
samples. Ca-excess conditions lead to restrictions in grain
boundary movements and limited grain growth. Ca2+ may
occupy Ti-sites near the surface regions and thereby acting
as acceptors. Surface contributions due to depolarization ef-
fect give rise to modified εr –T behavior.
Lin and Lin [17], also have studied Ca- modified barium
titanate ceramics and have reported that the cationic ratio
α = (Ba + Ca)/Ti is the predominant factor which results
in the variation of dielectric constant as well as the shift
in Curie point. Thus, εr –T relations are strongly influenced
by the cationic ratio α = (Ba + Ca)/Ti rather than the
occupancy of Ca2+ ions in Ba2+ or Ti4+ site in the bulk
of the grains. The mode of formulation of the composition
does not reflect the exact site occupy of Ca2+ ions. Han et al.
[18,19] suggested that Ca2+ could partially occupy the Ti
sites in the BaTiO3 lattice in the case of (Ba + Ca)/Ti >
1. However, Ca2+ with significant difference in the ionic
charge as well as radius makes it difficult to substitute at the
Ti4+ sites. The PTCR exhibited by barium calcium titanate
with 2–50 mol% CaTiO3 shows that the acceptor behavior
of Ca2+ by way of substitution at the Ti4+ sites does not
prevail in these materials. For the off-stoichiometric samples
with α > 1, there can be metastable occupancy of Ca2+
at Ti4+ sites, at the surface regions, which results in the
increase of the grain boundary surface energy preventing the
grain coarsening. Whereas, for the stoichiometric samples,
Ca2+ substitution at Ba2+ site dominates which leads to
grain growth in the sintered specimens.
5. Conclusions
The fabrication of either conductive (PTCR) or capaci-
tive barium calcium titanate ceramics is dependent on the
stoichiometric ratio, (Ba + Ca)/Ti. Capacitor ceramics of
nanometer grain size can be sintered in atmosphere of lower
partial pressures of oxygen if the α-value is maintained
above unity. This may arise from the dual site occupancy
of Ca2+ ions in fine-grained specimens. Similar complexity,
related to compositional deviations, may be present in other
substitutional solid solutions of barium titanate.
Acknowledgements
The Naval Research Board, Government of India is
thanked for a research grant.
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