Journal of Non-Crystalline Solids 351 (2005) 976–980

www.elsevier.com/locate/jnoncrysol

Barium titanate sols prepared by a diol-based sol–gel route

a,* b
Supin Tangwiwat , Steven J. Milne
a
Metallurgy and Materials Science Research Institute, Chulalongkorn University, Bangkok 10330, Thailand
b
Department of Materials, University of Leeds, Leeds, LS2 9JT, UK

Available online 2 March 2005

Abstract

A diol-based sol–gel route for preparing barium titanate precursor sols has been developed. The sols were prepared using 1,3
propanediol, barium acetate, and titanium isopropoxide, modified by acetylacetonate. The decomposition behavior of samples of
gel, dried at 120 °C, was studied by GC–MS, TGA and DSC; phase formation was investigated by XRD and FTIR techniques.
From the XRD results for calcined gel powders, crystalline barium titanate began to form at
600 °C. FTIR spectra showed
two absorption bands at 538 cm1 and 400 cm1 in samples calcined at 600 °C; these peaks are assigned to barium titanate, in
accord with the XRD results. There was also FTIR evidence of a carbonate phase, which persisted until a calcination temperature
of
1000 °C. The sols have been kept in a closed container for
6 months without any evidence of precipitation or gel formation.
Ó 2005 Elsevier B.V. All rights reserved.

1. Introduction butoxide is usually sensitive to moisture in the air.

Barium titanate (BT) and related compositions find
extensive use in electronic components such as capaci-
tors; there is now growing interest in using thin film ana-
logues in micro-electronics applications [1]. Sol–gel is
one method of fabricating the films. Barium titanate sols
may be prepared from several different types and combi-
nations of starting reagents. Generally a short chain tita-
nium alkoxide is employed, together with various types
of barium reagent. Routes include: Barium metal in eth-
anol, with acetylacetone and diethylamine as stabilizers
[2]; barium ethoxide in dehydrated methanol, and 2-
methoxyethanol as solvents [3–7]; barium acetate dis-
solved in acetic acid [8–10]; barium hydroxide and
isopropanol or 2-methoxyethanol [11,12]; barium chlo-
ride dissolved in deionized water [13]; barium nitrate dis-
solved in nitric acid [13]. The short chain titanium
alkoxide such as titanium isopropoxide or titanium
Therefore it has to be handled under inert atmospheres.
To make it more stable to air, the titanium alkoxide can
be modified by reaction with acetylacetone [14]. One of
the modified titanium alkoxides, titanium diisopropox-
ide bisacetylacetonate (TIAA), has been used to prepare
lead titanate and lead zirconate titanate sols for thin film
deposition [15,16].
In the present research, a diol-based sol–gel route has
been developed for preparing a barium titanate precur-
sor sol. The sols were prepared using 1,3 propanediol,
barium acetate, and titanium isopropoxide, modified
by acetylacetonate. Previously this chemical approach
has proved to be successful in preparing lead zirconate
titanate (PZT) precursor sols [16,17].
2. Experimental

Barium acetate (Aldrich, purity >99%) was dissolved

*
Corresponding author. Tel.: +662 218 4243; fax: +662 611 7586. in acetic acid (J.T Baker, purity >99.9%) and heated
E-mail address: supin.t@chula.ac.th (S. Tangwiwat). under reflux conditions for 90 min. In another flask,

0022-3093/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2004.12.008
 S. Tangwiwat, S.J. Milne / Journal of Non-Crystalline Solids 351 (2005) 976–980 977

titanium diisopropoxide bisacetylacetonate, abbreviated ever present in the starting TIAA solution. The building
TIAA, (75 wt% in isopropanol, Aldrich) was mixed with block of the BT gel structure is probably analogous to
1,3 propanediol (Aldrich, purity >98%), in a 1:1 molar that of Ti sols made from TIAA and 1,3 propanediol
ratio of titanium to diol, then maintained under reflux (i.e. the system [Ti(acac)2(OiPr)2]/propane-1,3 diol [20]).
conditions for 60 min. Afterwards, distillation was car-
ried out, at a temperature of
80 °C. Finally, the bar-
ium acetate solution was added to the TIAA solution,
to give a 1:1 molar ratio of Ba and Ti. This mixture
was maintained under reflux for 60 min.
The freshly synthesized sol was converted to a dried
gel by heating the sol at
70 °C, and then heating at

120 °C for 12 h in an oven. The dried gel powders were
analyzed by gas chromatography–mass spectrometry
(GC–MS). The dried gel was first heated up to 800 °C
and soaked for 9 s using a Fischer Curie Point Pyrolyzer
0316M, the vapor products were then introduced into
the MS ion chamber after chromatographic separation.
A Fison GC 8000 series chromatograph with MD 800 Fig. 1. Chromatograms of vapor products from dried gel pyrolyzed at
800 °C for 9 s.
was employed, using: A fused silica capillary column
(L = 30 m) with polymethyl siloxane, DB-1, as station-
ary phase; initial column temperature, 35 °C; final col-
umn temperature, 240 °C; heating rate, 10 °C/min;
injection temperature 250 °C; carrier gas, helium
10 ml/min. The compounds separated by GC were iden-
tified by recording their mass spectra and compared
with spectra in the NIST library [18].
The thermal decomposition characteristics of the
dried barium titanate gel were also determined by ther-
mogravimetric analysis (TGA) using a Netzsch STA
409C instrument; the heating rate was 5 °C/min to a
maximum temperature of 900 °C, with a gas flow rate
of 50 ml/min of an air/nitrogen (50/50) mixture.
Phase analysis of calcined gels were performed using
a Philips PW3710 diffractometer (CuK(radiation) and
FTIR-Perkin Elmer 1760x.

3. Results and discussion

After the barium titanate gel was pyrolyzed at 800 °C

and analyzed by GC, there were four dominant peaks in
the chromatogram, Fig. 1, at retention times of 2.76,
5.42, 12.49, and 15.11 min. The peaks at 2.76 and
5.42 min gave mass spectra, Fig. 2(a) and (b), matching
carbon dioxide and acetic acid, respectively, whereas the
mass spectra of the peaks at 12.49 and 15.11 min, Fig.
2(c) and Fig. 2(d), were similar to isopropyl acetate
((CH3)2CHOCOCH3) and trimethylene acetate (CH3
COO(CH2)3COOCH3), respectively, [18].
The acetic acid formed during pyrolysis is thought to
include products of barium acetate decomposition and
unreacted acetic acid in starting sol. The isopropyl ace-
tate vapor signifies esterification of acetic acid and iso-
propanol, the latter would be formed by exchange Fig. 2. Mass spectra for vapor products from dried gel pyrolyzed at
reactions of propanediol (OHCH2CH2CH2OH) with 800 °C for 9 s at several retention times: (a) 2.76 min, (b) 5.42 min, (c)
the isopropoxy groups on TIAA; isopropanol was how- 12.49 min, and (d) 15.11 min.
978 S. Tangwiwat, S.J. Milne / Journal of Non-Crystalline Solids 351 (2005) 976–980
O The combined DSC and TGA plots are shown in Fig.
n(acac)2Ti (CH2)3 [-O-Ti(acac)2-O-(CH2)3-]n
O to be due to the expulsion of residual water and acetic
Proposed molecular structure of gel precursors in the
TIAA–propanediol system [20].
The trimethylene acetate found here is possibly a
byproduct of thermal decomposition of the acetyl acet-
onate groups on the [–O–Ti(acac)2–O–(CH2)3–]n chain,
where, acac = CH3COCHCOCH3, [20]. There are litera-
ture reports of the evolution of barium containing gel
made from barium acetate in acetic acid; the gel was
composed of an interconnecting 3D network of
Ba4(CH3COO)8 units [19]. It is plausible that in the
present BT gels, prior to pyrolysis, similar Ba units co-
exist with the more linear [–O–Ti(acac)2–O–(CH2)3–]n
species. However detailed analysis of molecular struc-
ture in the new BT diol gels has not yet been carried out.
From TGA and DTG data, Fig. 3(a), the largest
weight loss occurred in the second of three principal
decomposition steps, with a corresponding DTG peak
at 323 °C. The total weight loss from dried gel was

42 wt%, with all but 2% occurring below 740 °C
(TGA); the final slight weight loss occurred at

1060 °C. It is speculated that the 740 °C and 1060 °C
losses may represent decomposition of different forms
of carbonate phase.
Fig. 3. (a) TGA and DTG curve for dried barium titanate gel. (b)
TGA and DSC curve for dried barium titanate gel.
3(b). The first DSC endotherm (
100 °C) is considered
acid volatilization (the boiling point of the acid is
117 °C). This is followed by a series of exotherms and
losses at intermediate temperatures, associated with
pyrolysis of the major organic components. The small
weight loss, and DSC endotherm at
1060 °C is consis-
tent with the decomposition of a residual carbonate
phase. The DSC anomaly at
820 °C is close to the re-
ported transition temperature of gamma to beta barium
carbonate, 811 °C [21].
Fig. 4 shows XRD diffraction patterns for a dried gel,
and after calcination at 300–1000 °C, for 2 h in air. The
first crystalline phases to appear, at 300 °C, were barium
acetate and barium carbonate, which could be derived
from partial decomposition of the barium acetate start-
ing reagent. After treatments at 400 °C or 500 °C, only
BaCO3 was detected; BaTiO3, first appeared in the
600 °C sample, co-existing with BaCO3. The oxycarbon-
ate phase, Ba2Ti2O5CO3, has been reported for other
metallo-organic systems [22]; here there was some evi-
dence of the latter in the 600 °C sample. For the
800 °C sample, pervoskite BaTiO3 and a small amount
of BaCO3 were detected in XRD plots. A small amount
of Ba2TiO4 appeared in the 900 °C sample, but heating
at 1000 °C produced a pattern of single phase BaTiO3.
FTIR spectra of the dried gel, Fig. 5, showed charac-
teristic peaks due to acetate groups, at 1567 cm1 (ace-
tate asymmetric stretching) and 1421 cm1 (acetate
symmetric stretching), which may correspond to unre-
acted barium acetate and acetic acid starting reagent.
The 1028 cm1 peak is assigned to be due to C–H bend-
ing. The broad bands at
3500 cm1 are attributed to
O–H stretching, which decreased in intensity as calcina-
tion temperature increased, but persisted to
900 °C.
The 657 cm1 and 550 cm1 peaks may be due to Ti–O
5 5 5
5 5 5 5 5 o
1000 C
4 o
900 C
2 o
800 C
Relative intensity
o
700 C
3
o
600 C
o
2 2 2 2 22 500 C
2
o
1 1 1 400 C
o
300 C
gel
10 20 30 40 50 60 70 80
Degree two thetha
Fig. 4. XRD pattern for dried gel and products derived from BT gel
calcined at 300–1000 °C for 2 h. Note: 1 = Ba(CH3COO)2, 2 = BaCO3,
3 = Ba2Ti2O5CO3, 4 = Ba2TiO4, 5 = BaTiO3.
 S. Tangwiwat, S.J. Milne / Journal of Non-Crystalline Solids 351 (2005) 976–980
Absorbance (arbitary unit)
1440
1431
1028
3429 1567 1421
4000 3600 3200 2800 2400 2000 1600 1200
Wavenumber (cm-1)
Fig. 5. FTIR spectra for dried gel and products derived from BT gel
calcined at 300–1000 °C for 2 h.
bonds [18] in the [–O–Ti(acac)2–O–(CH2)3–]n gel-
forming chain. Noticeably the intensity of the bands
representing Ti–O decreased after the gel was calcined
at 300 °C or higher. The 690 cm1 peak which could
be TiO2 was found between 400 °C and 700 °C. When
the gel was heated up to 400 °C the acetate peaks de-
creased in intensity, and evidence of carbonate groups
appeared, as signified by the peaks at 1431 cm1 (C@O
1
stretching of CO2 3 ) and 860 cm (out of plane defor-
2
mation of CO3 ); these decreased in intensity with
increasing calcination temperature, but persisted until

900 °C.
Considering the barium titanate formation reaction
during gel decomposition, the results suggest that
BaTiO3 principally forms by the reaction: BaCO3 +
TiO2 ! BaTiO3 + CO2 at temperatures between 600 °C
and 800 °C. The BaCO3 phase was identified in XRD
patterns for heat treatments between 300 °C and
700 °C, indeed FTIR confirmed that small amounts of
carbonate containing phase were present until at least
900 °C. X-ray diffraction did not reveal any TiO2 phase,
which indicates that any TiO2 formed by decomposition
of TIAA–propanediol species was amorphous, or pres-
ent as very small crystallites which were below the criti-
cal size for Bragg reflection. The presence of Ba2TiO4
after calcining at 900 °C could point to a minor reaction
involving unreacted BaCO3 and the main BaTiO3 phase
to give minor amounts of Ba2TiO4 (+CO2) which then
goes on to react with residual TiO2 at higher tempera-
tures, to form BaTiO3.
The thermochemical analysis experiments (at differ-
ing heating rates), indicate that the reaction sequence
to form BaTiO3 commences directly after the comple-
tion of organic decomposition (Fig. 3). Gel decompo-
sition requires sufficient thermal energy to break C–H,
C–C, and C–O bonds, and then to volatilize any byprod-
ucts. It appears that
500 °C represents the minimum
temperature for this to be achieved in the BT-diol sol–
gel system, and it is noted that the boiling point of tri-
979
methylene acetate, identified as a late decomposition
o
1000 C
product by GC–MS, is 482 °C.
Due to the thermal stability of BaCO3, the formation
900oC
of CO2 during pyrolysis is a particular problem.
800oC
Although XRD suggested that barium carbonate had
534423700oC
600oC
decomposed at
800 °C, FTIR proved a more sensitive
500oC indicator, revealing carbonate in samples calcined at
690
900 °C, and possibly a faint trace even in the 1000 °C
400oC
860
300oC
sample. There was a co-existence of OH stretching (at
gel
3500 cm1) with the carbonate absorptions (at
657 550

1440 cm1), Fig. 5, suggesting that the carbonate
800 400 may be in the form of a hydroxy carbonate. However
further work is required to validate this point and to
investigate the possibility that reactions with air after
calcination (and before FTIR experiments) may contrib-
ute to carbonate (or hydroxycarbonate) phases in the gel
powders, especially in high surface area powders formed
at low calcination temperatures.
The sols have been kept in a closed container for six
months without any evidence of precipitation: In future
work, the capability of the sol for fabricating barium
titanate thin films will be evaluated.
4. Conclusions
A diol-based sol–gel route has been demonstrated for
BaTiO3. On heating, the dried gel powders initially
decomposed to give crystalline barium carbonate and
barium acetate at 300 °C. A temperature of at least
500 °C was required to eliminate all organic residues
from the gel products. Acetic acid, isopropyl acetate,
and trimethylene acetate were among the main byprod-
ucts. Perovskite BaTiO3 first appeared after calcination
at 600 °C, but because of the stability of the intermedi-
ate barium carbonate phase, calcination at
1000 °C
was required to produce carbonate-free BaTiO3
powders.
Acknowledgements
The authors wish to thank ÔDevelopment Grants for
New Faculty/ResearchersÕ from Chulalongkorn Univer-
sity, The Thailand Research Fund and the Thai Govern-
ment for financial support.
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