Journal of Applied Spectroscopy, Vol. 76, No.

6, 2009

EFFECT OF TITANIUM ALKOXIDES ON THE PROPERTIES

OF BARIUM-STRONTIUM-CALCIUM TITANATE POWDERS
OBTAINED BY A SOL-GEL METHOD

T. W. Kim,a N. V. Gaponenko,a* E. A. Stepanova,a UDC 621.315.592

T. F. Kuznetsova,b and A. I. Rat’kob

This is a study of the effect of titanium alkoxides on the properties of barium-strontium-calcium titanate pow-
ders produced by a sol-gel method. Sols were synthesized using titanium tetraethoxide, titanium tetraisoprox-
ide, and titanium tetrabutoxide. Xerogels of titanium oxide doped with barium, strontium, and calcium in a
proportion of 60:30:10 were obtained by drying the sols at a temperature of 70oC. Thermogravimetric analy-
sis, along with differential scanning calorimetry, IR spectroscopy, and x-ray phase analysis, were used to
study the changes in the xerogel and the crystallite dimensions in the powder induced by thermal processing.
The morphology and specific surface area of the powders were determined by scanning electron microscopy
and low-temperature physical adsorption-desorption of nitrogen. These studies lead us to recommend sols
based on Ti(OC3H7)4 with a crystallite particle size in the powder of ~63 to 40 nm for creating homogeneous
ceramic materials from barium-strontium-calcium titanate.

Keywords: barium-strontium-calcium titanate, sol-gel method, infrared detector.

Introduction. In recent years active research on the development of barium-strontium-calcium titanate ceramic
technology for use in uncooled thermal detectors has been under way [1]. The pyroelectric coefficient reaches a maxi-
o
mum near the phase transition temperature characterized by the Curie temperature, which is about 130 C for
perovskite BaTiO3. However, when a certain number of barium atoms in BaTiO3 are replaced by strontium, it is pos-
sible to obtain a (Ba1–x, Srx)TiO3 solid solution with a Curie temperature close to room temperature [2]. Adding cal-
cium to the barium-strontium titanate reduces the pyroelectric coefficient only slightly, but greatly reduces the slope of
the dielectric losses, so that basic characteristics of the IR radiation detector, such as its voltage and current sensitivi-
ties and its signal/noise ratio, are improved [3]. For this reason, the ferroelectric compound barium-strontium-calcium
titanate (Ba0.6Sr0.3Ca0.1)TiO3 offers promise as an IR detector material.
Depending on the crystallite sizes, the pyroelectric and dielectric properties of the ceramic (Ba0.6Sr0.3Ca0.1)TiO3
can vary widely [4]. IR detectors require powders with crystallite sizes in the range of 1–3 μm [5]. In recent years
(Ba0.6Sr0.3Ca0.1)TiO3 has been synthesized mainly by sol-gel methods. However, the effect of precursors on the prop-
erties of barium-strontium-calcium titanate powders has not been adequately studied.
In this paper, IR spectroscopy, thermogravimetric analysis, and other methods are used to study the changes
induced by thermal processing in (Ba0.6Sr0.3Ca0.1)TiO3 xerogels created from sols with different compositions. In addi-
tion, the morphology and specific surface area of the powders and the sizes of the crystallites in them are analyzed and
practical recommendations are offered as to the composition of a sol for producing homogeneous (Ba0.6Sr0.3Ca0.1)TiO3
ceramic materials.
Experiment. Three groups of titanium oxide sols containing barium, strontium, and calcium were prepared
using three types of titanium alkoxides as initial components: titanium tetraethoxide (Ti(OC2H5)4), titanium tetraiso-
proxide (Ti(OC3H7)4), and titanium tetrabutoxide (Ti(OC4H9)4). Solutions of Ti(OC2H5)4 and Ti(OC3H7)4 were pre-

∗
To whom correspondence should be addressed.

a
Belarusian State University of Informatics and Radioelectronics, 6 P. Brovki Str., 220013, Minsk, Belarus;
b
e-mail: nik@nano.bsuir.edu.by; Institute of General and Organic Chemistry, National Academy of Sciences of Be-
larus, Minsk. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 6, pp. 884–890, November–December,
2009. Original article submitted September 10, 2009.

0021-9037/09/7606-0833 ©2009 Springer Science+Business Media, Inc. 833

 Fig. 1. TG, DTG, and DSC curves for (Ba0.6Sr0.3Ca0.1)TiO3 xerogels obtained
from sols based on Ti(OC2H5)4 (a), Ti(OC3H7)4 (b), and Ti(OC4H9)4 (c).

pared by dissolving Ti(OC2H5)4 and Ti(OC3H7)4 in monomethyl ethylene glycol ether (HOCH2CH2OCH3) and a so-
lution of Ti(OC4H9)4, by dissolving Ti(OC4H9)4 in butyl spirit. In order to obtain a solution with a 60:30:10 proportion
of barium, strontium, and calcium, the calculated amounts of the acetic salts Ba(CH3COO)2, Sr(CH3COO)2⋅1/2H2O, and
o
Ca(CH3COO)2⋅H2O were dissolved in acetic acid with boiling by a reflux condenser at a temperature of 110 C until
they were fully dissolved. After cooling to room temperature the barium, strontium, and calcium solution was mixed
with each of the respective prepared solutions of titanium alkoxides. A mixture of water with HOCH2CH2OCH3 was
added for a hydrolysis reaction. After retention for several days at room temperature all the resulting sols had con-
o
verted into transparent gels. Then the xerogel (Ba0.6Sr0.3Ca0.1)TiO3 was formed by drying the gels at 70 C.
The changes induced in the xerogel by thermal processing were studied using thermogravimetric analysis
(TGA) and differential scanning calorimetry (DSC), IR spectroscopy, and x-ray diffraction. TGA was performed on a

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 Fig. 2. IR spectra of samples after annealing for 60 min at temperatures of
70 (1), 200 (2), 400 (3), 600 (4), and 800oC (5).

o o
TGA/DSC-1 analyzer (Mettler Toledo, Switzerland) over 25–1000 C with a heating rate of 10 C/min. Samples for IR
o –1
spectroscopy prepared by tableting with KBr were obtained by annealing at 200–800 C. IR spectra over 4000–450 cm
were recorded on a FT-IR-M2000 (Midac, USA) Fourier transform IR spectrometer. Samples for x-ray phase analysis
o
were obtained using an annealing temperature of 500–800 C for 1 h. The x-ray phase analysis was done on a D8 Ad-
vance (Bruker) diffractometer, with probing by CuKα radiation. The measurements were conducted on the reflected
o o
beam by stepwise scanning with a step size of 0.1 in the angle 2θ for the phase analysis and a step size of 0.01
for the angle 2θ for analyzing the crystallite dimensions. Analysis of the specific surface area of the powders was
o
done using low-temperature (–196 C) phase absorption-desorption of nitrogen [6] on an ASAP 2020 MP (Micromet-
rics, USA) sorption surface and porosity analyzer. The pore surface area per unit mass of the solid, or the specific
surface area was, was estimated by the Brunauer–Emmett–Teller (BET) method. Before analysis the samples were out-
gassed at a 523 K for 1 h. The powder morphology was analyzed with an S-806 f scanning electron microscope (Hi-
tachi, Japan).
Discussion. Figure 1 illustrates the thermal characteristics of the (Ba0.6Sr0.3Ca0.1)TiO3 xerogel obtained from
three different sols. The DSC curve has three exothermic peaks associated with thermal decomposition of organic
o o
groups and the intermediate carbonate phase at temperatures of 418, 674, and 723 C (Fig. 1a), 415, 679, and 711 C
o
(Fig. 1b), and 415, 505, and 671 C (Fig. 1c). According to the differential thermogravimetric data (DTG curve), the
o
mass loss can be divided into three stages. Mass loss occurs in the first stage (up to 190 C) because of evaporation
of residual organic solvents. The mass losses in this stage is 5.43 (Fig. 1a), 9.93 (Fig. 1b), and 8.66 mass % (Fig. 1c).
o
In the second stage (190–600 C) the mass losses owing to decomposition of organic groups are 28.84 (Fig. 1a), 28.14
o
(Fig. 1b), and 28.55 mass % (Fig. 1c). The third stage (600–760 C) yields mass losses of 9.19 (Fig. 1a), 9.31 (Fig.
o
1b), and 9.19 mass % (Fig. 1c) caused by decomposition of the carbonate. Above 760 C mass loss is observed only
in the material obtained from a sol based on Ti(OC2H5)4 (Fig. 1a), while the samples prepared from the other two
sols underwent no further mass loss (Fig. 1b and c).
o
Figure 2 shows IR spectra of the xerogel based on Ti(OC3H7)4, dried at 70 C with subsequent thermal proc-
o o
essing at 200, 400, 600, and 800 C. Within the measured range, the spectrum of the sample formed at 70 C contains
–1
distinct absorption bands. The absorption band at 3420–3460 cm is caused by valence vibrations of the O–H bond of
surface hydroxyl groups and O–H groups in physically adsorbed water contained in the gel [7]. The absorption bands at
–1
2800–3000 cm belong to symmetric and antisymmetric valence vibrations of CH3 groups and CH2 groups of
–1
Ti(OC3H7)4, HOCH2CH2OCH3, acetic acid, and salts of carboxylic acid. The absorption band around 1701 cm belongs
–1
to C=O valence vibrations of acetic acid and the absorption bands at 1570 and 1417 cm , to symmetric and antisymmet-
ric valence vibrations of C–O carboxyl groups [8]. The absorption band of the deformation vibration of the COO group
–1 –1
at 1326 cm belongs to acetate anions [9]. The three bands in the 900–1100 cm range are caused by the presence

835
 Fig. 3. Diffraction patterns for a xerogel powder obtained from sol based on
Ti(OC3H7)4 after annealing at temperatures of 500 (1), 600 (2), 700 (3),
750 (4), and 800oC (5).

–1
of C–O and C–O–C bonds. The absorption bands at 938 and 1050 cm belong to symmetric and antisymmetric C–O–C
i
valence vibrations [8]. These C–O–C bonds are caused by the formation of derivative Ti(O Pr)4–x(OCH2CH2OCH3)x(x =
–1
1–4) during the reaction of Ti(OC3H7)4 with HOCH2CH2OCH3 in a colloidal solution [10]. The 1023 cm absorption
band is attributable to C–O vibrational bonds of the monomethyl ether ethylene glycol [8] and the bands at 800–400
–1
cm , to the intrinsic vibrations of the metal oxide lattices [9, 11].
o
In the spectra of samples obtained after thermal processing at 200 C the intensities of the absorption bands in
–1 –1
the regions 3420–3460 and 2800–3000 cm decrease, while the absorption band near 1701 cm essentially vanishes.
o
This is because of the evaporation of acetic acid and HOCH2CH2OCH3 as the temperature is raised to 200 C.
o –1
After thermal processing at 400 C there is an absorption band in the spectrum at 1387 cm owing to defor-
–1
mation vibrations of CH3 of the carboxyl group [8]. In the 900–1100 cm range there is only one absorption band at
–1 –1
1059 cm ; this may indicate rupture of the C–O–C bond. The absorption band near 865 cm is related to the for-
mation of a carbonate phase owing to a decomposition reaction [12]. As the thermal processing temperature is raised
o
to >600 C this band vanishes, which is an indication that salts of the carboxylic acid have been dissociated and
o
(Ba0.6Sr0.3Ca0.1)TiO3 has crystallized. When the processing temperature for the samples is increased to 800 C, an in-
–1
tense band with a peak at 539 cm shows up in the spectrum. This is evidence of the conversion of the amorphous
oxides into a crystalline structure. Similar spectral behavior has been observed for xerogels obtained from sols based
on Ti(OC2H5)4 and Ti(OC4H9)4.
Figure 3 is a series of diffraction patterns for (Ba0.6Sr0.3Ca0.1)TiO3 powders obtained from Ti(OC3H7)4 sol
o o
after annealing at temperatures of 500–800 C. The spectrum of the samples annealed at 500 C indicates that they have
an amorphous structure with an intermediate phase present. An analysis of the decomposition reaction [12] has shown
o
that this phase is a complex carbonate phase with the formula (Ba,Sr,Ca)2Ti2O5CO3. The pattern obtained at 600 C
corresponds to a sample with a partial crystalline structure owing to incomplete formation of a perovskite phase. Rais-
ing the annealing temperature leads to an improvement in the crystalline structure of the samples and to the appear-
o
ance of sharper reflections peaks. It was found that with annealing temperatures ≤750 C the sample becomes
completely crystallized, and further increases in temperature do not yield more intense lines in the diffraction pattern.
In terms of position and relative intensity, all the lines observed in the spectra coincide with standards for a structure
of the type (Ba0.6Sr0.4)TiO3 (PDF Card No. 00-034-041). Other crystalline phases were not detected here. Thus, the
xerogel being analyzed here is a solid solution with a composition (Ba0.6Sr0.3Ca0.1)TiO3 that corresponds to the com-
position of the synthesized sol. Similar diffraction patterns have been obtained for powders formulated from sols based
on Ti(OC2H5)4 and Ti(OC4H9)4.
Figure 4 shows the diffraction patterns for (Ba0.6Sr0.3Ca0.1)TiO3 powder based on different alkoxides of tita-
o
nium with annealing at a temperature of 800 C. The magnified part near the (110) peak shows that the diffraction pat-

836
 Fig. 4. Diffraction pattern for a xerogel powder obtained from a (Ba0.6Sr0.3Ca0.1)TiO3
sol based on Ti(OC2H5)4 (1), Ti(OC3H7)4 (2), and Ti(OC4H9)4 (3) after annealing
at 800oC.

Fig. 5. Diffraction pattern measured after annealing of a powder based on

Ti(OC2H5)4 at 750oC.

tern line for the powder obtained from Ti(OC2H5)4 is shifted relative to the lines for the samples obtained from the
two other sols. This means that homogeneity of the elements in this powder is not ensured.
o
Figure 5 is a diffraction pattern obtained after annealing of a powder based on Ti(OC2H5)4 at 750 C. Besides
a perovskite phase (Ba0.6Sr0.3Ca0.1)TiO3, a small amount of a titanium oxide Ti0.784O2 phase in the form of anatase
was detected. Raising the annealing temperature leads to a lower intensity for the Ti0.784O2 phase and to a higher in-
tensity for the perovskite phase.
The most intense (110) peak was analyzed to determine the sizes of the crystallites. For cubic crystals (in the
absence of microstresses) the crystallite size L can be found using the formula [13]

L = 0.94λ ⁄(β cos θ) , β = √

⎯⎯⎯⎯⎯
B2 − b2 ,

where λ is the wavelength of the radiation, θ is the diffraction angle, B is the width (half maximum) of the x-ray line,
and b is the instrumental broadening. This formula yielded crystallite sizes of 37, 41, and 50 nm for Ti(OC2H5)4,
Ti(OC3H7)4, and Ti(OC4H9)4, respectively.

837
 Fig. 6. Scanning electron microscope pictures of (Ba0.6Sr0.3Ca0.1)TiO3 powders
based on Ti(OC2H5)4 (a), Ti(OC3H7)4 (b), and Ti(OC4H9)4 (c).

Figure 6 shows pictures of powders obtained using a scanning electron microscope. The powders obtained
from the three types of sols consist of fairly homogeneous particles, with the particles obtained from the sol based on
Ti(OC3H7)4 having the smallest size d and those from the sol based on Ti(OC2H5)4, the largest.
The specific area of the samples, measured by the BET method using sorption isotherms obtained with a
2
sorption surface and porosity analyzer, are 12.86, 16.92, and 15.15 m /g for the sols based on Ti(OC2H5)4,
Ti(OC3H7)4, and Ti(OC4H9)4, respectively.
In the case of spherically shaped particles with equal diameter d, the specific surface area S can be used to
calculate the diameter using the formula [6]

d = 6 ⁄ Sρ ,

where ρ is the density of the solid.

For real powders consisting of particles with different sizes and arbitrary shapes, this equation can be used to
3
estimate the average particle diameter. Given the additively calculated density of (Ba0.6Sr0.3Ca0.1)TiO3 at 5.587 g/cm ,
the average particle diameters are 84, 63, and 71 nm for the powders obtained from the Ti(OC2H5)4, Ti(OC3H7)4, and
Ti(OC4H9)4 sols, respectively.
Conclusions. According to x-ray phase analysis data, the powders produced from sols based on Ti(OC3H7)4
and Ti(OC4H9)4 are characterized by better homogeneity than the powder obtained from the sol based on Ti(OC2H5)4,
where titanium oxide in the form of an anatase phase is present in addition to the perovskite phase. At 41 nm, the
size of the crystallites of the powder produced from the Ti(OC3H7)4 based sol is smaller than that of the powder
based on Ti(OC4H9)4. Electron microscopy data and an analysis of the specific surface area show that the particles of
the powder formed from the sol based on Ti(OC3H7)4 are the smallest with a size of 63 nm, while the other two sols
yield larger average particle sizes of 84 and 71 nm for the sols based on Ti(OC2H5)4 and Ti(OC4H9)4. As a result of
these studies, we can recommend a sol based on Ti(OC3H7)4 for the production of homogeneous ceramic materials
from barium-strontium-calcium titanate by the sol-gel method.

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