Journal of Sol-Gel Science and Technology 15, 263–270 (1999)

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c 1999 Kluwer Academic Publishers. Manufactured in The Netherlands.

Sol-Gel Processing of Some Electroceramic Powders

SRIDHAR KOMARNENI, ISAAC ROBIN ABOTHU AND ALAMANDA V. PRASADA RAO

Materials Research Laboratory, The Pennsylvania State University, University Park, PA 16802, USA

Received February 18, 1998; Accepted March 20, 1998

Abstract. This review deals with the solution-sol-gel processing (SSG) of powders such as BaTiO3 , MgTiO3 ,
PbTiO3 , Bi4 Ti3 O12 , La2 Ti2 O7 , Pb(Zr0.52 Ti0.48 )O3 , Pb(Mg1/3 Nb2/3 )O3 and Ba(Mg1/3 Ta2/3 )O3 . Fine powders of good
sinterability can be easily obtained at low temperatures although the process can be expensive and time consuming.
We propose a nanocomposite route which utilizes nanophases of different components as a cost-effective alternative
to sol-gel process for powder preparation.

Keywords: processing, sol-gel, barium titanate, magnesium titanate, lead titanate, bismuth titanate, lanthanum
titanate, lead zirconium titanate, lead magnesium titanate, barium magnesium tantalate

1. Introduction of some of the most important electroceramic materials

in our laboratory.
Purity, particle size and homogeneity are the most
important characteristics of electroceramic powders
2. Experimental
which determine the electrical properties such as di-
electric loss, dielectric constant and curie temperature
The preparation of BaTiO3 , MgTiO3 , PbTiO3 ,
of the sintered ceramics. There are numerous pow-
Bi4 Ti3 O12 , La2 Ti2 O7 , Pb(Zr0.52 Ti0.48 )O3 [PZT],
der preparation techniques which are well known. Of
Pb(Mg1/3 Nb2/3 )O3 [PMN], and Ba(Mg1/3 Ta2/3 )O3
these, solution-sol-gel (SSG) and hydrothermal meth-
[BMT] ceramics from various precursors is described
ods are of the low temperature type. The SSG process
below. The SSG powders were calcined at various tem-
is highly versatile which can lead to powders, films,
peratures and their purity was checked by powder x-ray
fibers, spheres, monoliths, aerogels, xerogels etc. of
diffraction (XRD) using a Scintag Pad V X-ray diffrac-
high purity and homogeneity. Purity of the SSG de-
tometer with CuK α radiation. Particle size and mor-
rived powders can be controlled by the purity of the
phology was checked by scanning electron microscope
starting chemicals and homogeneity can be controlled
(SEM) using an ISI-DS 130 instrument. Surface ar-
by precisely controlling the hydrolysis, condensation
eas of the various crystalline powders were determined
and polymerization reactions. The starting precursors
by multipoint N2 adsorption using an Autosorb-1
in the SSG process can be metal organics, metals, in-
apparatus.
organic salts etc. The key, however, is to achieve ul-
tra homogeneous mixing at atomic to molecular level.
Mazdiyasni et al., [1–3] probably were the first to re- 3. Results and Discussion
port the preparation of high purity electroceramic pow-
ders via the SSG process. Since then there are literally 3.1. BaTiO3 Powders
thousands of papers which utilized some type of SSG
process in the preparation of powders, fibers, films, Barium titanate is the most widely used material in
sintered ceramics etc. of various electroceramic mate- capacitor industry. Barium titanate powders have been
rials. The objective of the present paper is to review the prepared [4] using powdered Ba metal and titanium iso-
SSG processes utilized in the fine powder preparation propoxide as depicted in Fig. 1. This procedure yielded
264 Komarneni and Abothu
Figure 1. Flow chart for sol-gel preparation of BaTiO3 powder.
highly crystalline BaTiO3 at 700◦ C as can be seen in
Fig. 2. This method is highly suitable for fine pow-
der preparation. An alternative method to prepare fine
powder as well as films has recently been shown by
us [5] using barium hydroxide and titanium butox-
ide, Ti(OC4 H9 )4 . Stoichiometric amount of Ba(OH)2
to prepare 100 cm3 of 0.25 molar BaTiO3 was first dis-
solved in 30 g of glacial acetic acid at 90◦ C and then
the solution was heated to 110◦ C to evaporate water
in argon atmosphere. This clear Ba precursor solution
Figure 2. Powder x-ray diffraction pattern of BaTiO3 crystallized
at 700◦ C/2 h.
Figure 3. Scanning electron micrograph of BaTiO3 crystallized at
700◦ C/1 h.
was cooled and 1.55 g of ethylene glycol was added and
stirred followed by the addition of the required amount
of titanium butoxide under constant stirring. Butanol
was added to the solution to make it 0.25 molar with
respect to BaTiO3 . This precursor solution was then hy-
drolyzed with distilled water and heated at 700◦ C/1 h to
yield fine crystalline BaTiO3 powder (Fig. 3; Table 1).
This procedure using Ba hydroxide has been found to
be highly suitable to prepare stable Ba titanate pre-
cursor coating solutions in addition to cost-effectively
prepare BaTiO3 because it is the largest amount of elec-
troceramic material used in the capacitor industry.
3.2. MgTiO3 Powders
Magnesium titanate ceramics are used in the industry
as chip capacitors, dew sensors and high frequency and
temperature compensating capacitors. Sol-gel process
has been previously used to prepare MgTiO3 [6]. Fine
 Sol-Gel Processing of Some Electroceramic Powders 265

Table 1. Surface areas of crystalline powders prepared by sol-gel

processing.

Ceramic powder Preparation conditions Surface area (m2 /g)

BaTiO3 700◦ C/1 h 11.2

MgTiO3 650◦ C/0.5 h 10.1
PbTiO3 600◦ C/2 h 4.8
Bi4 Ti3 O12 700◦ C/2 h 0.7
La2 Ti2 O7 700◦ C/2 h 11.6
PZT 600◦ C/2 h 2.6
PMN 900◦ C/2 h 0.4
BMT 650◦ C/2 h 12.2

Figure 5. Scanning electron micrograph of MgTiO3 crystallized at

650◦ C/0.5 h.

3.3. PbTiO3 Powders

Lead titanate is a good candidate ferroelectric mate-

Figure 4. Flow chart for the synthesis of MgTiO3 powder.
powders of MgTiO3 with a surface area of 10.1 m2 /g
(Table 1) have been prepared [7] using Mg ethox-
ide, Mg(OC2 H5 )2 and Ti isopropoxide, Ti(OC3 H7 )4
as shown in Fig. 4. This procedure yielded fine crys-
talline powder in the temperature range of 560–650◦ C.
Figure 5 shows the scanning electron micrograph of
fine MgTiO3 powder prepared at 650◦ C/0.5 h.
rial for high-temperature and high frequency trans-
ducer applications and it has been previously prepared
by sol-gel by many investigators [8–13]. One of the
main problems with this material, however, is micro-
cracking during cubic to tetragonal transformation. To
prevent micro-cracking, PbTiO3 is normally modified
with dopants such as Sm and Mn. Here we report the
sol-gel synthesis of Sm and Mn doped PbTiO3 using Pb,
Sm and Mn acetates and titanium isopropoxide [11].
These acetates were first dissolved in methoxyethanol
and water was distilled off. To the above solution, tita-
nium isopropoxide in methoxyethanol was added and
refluxed in argon at 125◦ C for 6 h to obtain a homo-
geneous mixture of all the chemicals. This solution
was cooled and its pH was adjusted to 10 before hy-
drolyzing with water in 2-methoxyethanol using a wa-
ter to Pb-Ti molar ratio of 3 : 1. Hydrolysis led to gels
which were calcined to obtain fine crystalline powder
at 600–650◦ C. Figure 6 shows the scanning electron
micrograph of fine but agglomerated PbTiO3 powder
prepared at 600◦ C/2 h. This powder showed a surface
area of 4.8 m2 /g (Table 1).
3.4. Bi4 Ti3 O12 Powders
Bismuth titanate, Bi4 Ti3 O12 (BIT) is a ferroelectric
with electro-optic switching behavior. Its piezoelec-
tric coefficient is quite high and thus it may be useful
266 Komarneni and Abothu

Figure 6. Scanning electron micrograph of PbTiO3 crystallized at

600◦ C/2 h.

as a lead free ceramic in high temperature transducer

applications. Many papers have been published [14–
19] on the sol-gel processing of Bi titanate. Bi titanate
has been prepared in our laboratory [19] using Bi ac-
etate and Ti isopropoxide as the starting precursors and
the procedure is depicted in Fig. 7. The calcined gel
powders yielded a crystalline powder of Bi titanate at
700◦ C/2 h as shown in Fig. 8. The fine particles of BIT
appear to be sintered (Fig. 8) and gave a small surface Figure 7. Flow chart for the synthesis of Bi4 Ti3 O12 powder.
area of 0.7 m2 /g (Table 1).

3.5. La2 Ti2 O7 Powders

The La2 Ti2 O7 ceramic belongs to the A2 B2 O7 com-

pounds with perovskite layered structure. These ceram-
ics have useful ferroelectric properties up to 1500◦ C
and may be useful as electronic sensors/transducers in
hostile environments. The La2 Ti2 O7 ceramic powders
or thin films have been prepared [20–22] by using La
acetylacetonate and titanium isopropoxide as shown in
Fig. 9. The gel calcined at 700◦ C/2 h yielded a fine
crystalline powder of La2 Ti2 O7 with a surface area of
11.6 m2 /g (Table 1) as can be seen from Fig. 10.

Figure 8. Scanning electron micrograph of Bi titanate crystallized

3.6. PZT Powders at 700◦ C/2 h.

Next to BaTiO3 , PZT is the most widely used elec-

troceramic material in industrial applications as actua- oratory using lead acetate, zirconium n-butoxide and
tors and transducers. There are many ways of prepar- titanium isopropoxide as depicted in Fig. 11. Scan-
ing PZT powders and thin films by sol-gel [23–28]. ning electron micrograph of PZT powder prepared at
PZT ceramic powder has been prepared in our lab- 600◦ C/2 h is shown in Fig. 12. The micrograph shows
 Sol-Gel Processing of Some Electroceramic Powders
Figure 9. Flow chart for the synthesis of La2 Ti2 O7 powder by sol-
gel processing.
Figure 10. Scanning electron micrograph of La2 Ti2 O7 crystallized
at 700◦ C/2 h.
267
Figure 11. Flow chart for the synthesis of Pb(Zr0.52 Ti0.48 )O3 pow-
der by sol-gel processing.
that the powder is coarse and exhibited a surface area
of 2.6 m2 /g (Table 1).
3.7. PMN Powders
Ferroelectric PMN has a broad maximum dielectric
constant just below room temperature and is a poten-
tial alternative to BaTiO3 in multilayer ceramic ca-
pacitors and electrostrictive actuators. PMN has been
prepared by sol-gel process by some investigators
[29–36]. The process that we have developed uti-
lizes lead acetate, magnesium ethoxide and niobium
268 Komarneni and Abothu

Figure 12. Scanning electron micrograph of PZT crystallized at Figure 14. Scanning electron micrograph of PMN crystallized at
600◦ C/2 h. 900◦ C/2 h.

ethoxide as starting precursors and is shown in Fig. 13. ogy of PMN powder crystallized at 900◦ C is given in
The PMN powder prepared by calcining the gel at Fig. 14 which reveals that the particles are very large
900◦ C/2 h showed a small amount of pyrochlore as which was reflected in its surface area of only 0.4 m2 /g
determined by XRD. The particle size and morphol- (Table 1).

Figure 13. Flow chart for the synthesis of PMN powder by sol-gel processing.
 Sol-Gel Processing of Some Electroceramic Powders
Figure 15. Scanning electron micrograph of BMT crystallized at
650◦ C/2 h.
3.8. BMT Powders
Perovskite oxides of BMT composition have been ex-
tensively investigated for their microwave dielectric
properties. A few sol-gel studies have been carried
out [37–39] to prepare this ceramic powder. The SSG
process that we have utilized involves barium metal,
magnesium ethoxide and tantalum(v)ethoxide. Tan-
talum(v)ethoxide and magnesium ethoxide were sep-
arately dissolved in 2-methoxyethanol (2-MOE) and
refluxed at 125◦ C for 8 and 6 h, respectively in argon
atmosphere. These two precursor solutions were mixed
and refluxed for 8 h at 125◦ C in argon to form double
alkoxide of tantalum and magnesium. Ba metal was
dissolved in 2-MOE by refluxing in a separate flask at
125◦ C for 8 h. This Ba precursor solution was cooled
and then mixed with Ta and Mg double alkoxide solu-
tion followed by refluxing at 125◦ C for 8 h in argon.
This process yielded a clear Ba-Mg-Ta precursor solu-
tion. The pH of this precursor solution was adjusted to
10 using concentrated HNO3 . Hydrolysis was carried
out by adding 1 : 4 ratio of water and 2-MOE at a slow
rate to prepare a homogeneous BMT gel. The gel was
then heated in an oven at 60◦ C to prepare a xerogel
which was then calcined at 650◦ C/2 h to prepare crys-
talline BMT powder. Figure 15 shows the scanning
electron micrograph of the above crystallized powder
which reveals a uniform, fine powder with a surface
area of 12.2 m2 /g (Table 1).
4. Conclusion
Although almost all electroceramic powders can be
prepared by some type of sol-gel process, this method
269
is time consuming and expensive. The use of nanocom-
posite powders may be a cost-effective alternative [40].
The SSG process, however, is eminently suited for thin
films.
Acknowledgment
This research was supported by the Division of Materi-
als Research, National Science Foundation under grant
no. DMR-9319809.
References
1. K.S. Mazdiyasni, R.T. Dolloff, and J.S. Smith II, J. Am. Ceram.
Soc. 52, 523 (1969).
2. K.S. Mazdiyasni, R.T. Dolloff, and J.S. Smith II, J. Am. Ceram.
Soc. 53, 91 (1970).
3. L.M. Brown and K.S. Mazdiyasni, J. Am. Ceram. Soc. 55, 541
(1972).
4. F. Selmi, Ph.D. Thesis, The Pennsylvania State University, Uni-
versity Park, PA 16802, 1993, pp. 122.
5. D.S. Paik, A.V. Prasada Rao, and S. Komarneni, J. Sol-Gel Sci.
Tech. 10, 213 (1997).
6. J. Moreno, J.M.D.A. Montoya, L. Vicente, and T. Viveros, J.
Mater. Chem. 5, 509 (1995).
7. I.R. Abothu, A.V. Prasada Rao, and S. Komarneni, in Proceed-
ings of 7th National Seminar on Crystal Growth (Crystal Re-
search Centre, Alagappa University, Karaikudi-630003, India,
Jan. 6–8, 1997).
8. S.R. Gurkovich and J.B. Blum, in Ultrastructure Processing of
Ceramics, Glasses and Composites, edited by L.L. Hench and
D.R. Ulrich (Wiley, New York, 1984), pp. 152–160.
9. U. Selvaraj, A.V. Prasada Rao, S. Komarneni, K. Brooks, and
S. Kurtz, J. Mat. Res. 7, 992 (1992).
10. U. Selvaraj, A.V. Prasada Rao, and S. Komarneni, Mat. Lett. 20,
71 (1994).
11. A.V. Prasada Rao, A.I. Robin, and S. Komarneni, Ferroelectric
Lett. 21, 141 (1996).
12. D.S. Paik, A.V. Prasada Rao, and S. Komarneni, Mat. Lett. 32,
97 (1997).
13. D.S. Paik and S. Komarneni, Mat. Res. Bull. 32, 109 (1997).
14. P.C. Joshi, A. Mansingh, M.N. Kamalasanan, and S. Chandra,
Appl. Phys. Lett. 59, 2390 (1991).
15. P.C. Joshi, S.B. Krupanidhi, J. Appl. Phys. 72, 5827 (1992).
16. E. Dayalan, C.H. Pang, and S.B. Desu, Ceram. Trans. 25, 279
(1992).
17. N. Tohge, Y. Fukuda, and T. Minami, Jpn. J. Appl. Phys. 31,
4016 (1992).
18. M. Toyoda, Y. Hamaji, K. Tomono, and D.A. Payne, Jpn. J.
Appl. Phys. 32, 4158 (1993).
19. A.V. Prasada Rao, A.I. Robin, and S. Komarneni, Mat. Lett. 28,
469 (1996).
20. A.V. Prasada Rao, U. Selvaraj, and S. Komarneni, Mat. Lett. 12,
306 (1991).
21. A.V. Prasada Rao, U. Selvaraj, S. Komarneni, and A.S. Bhalla,
J. Mat. Res. 7, 2859 (1992).
22. A.V. Prasada Rao, U. Selvaraj, S. Komarneni, and A.S. Bhalla,
Ferroelectric Lett. 14, 65 (1992).
270 Komarneni and Abothu
23. Z.Q. Zhuang, M.J. Haun, and S.J. Jang, Advanced Ceramic Ma-
terials 3, 485 (1988).
24. R.A. Lipeles, N.A. Ives, and M.S. Leung, in Science of Ceramic
Chemical Processing, edited by L.L. Hench and D.R. Ulrich
(John Wiley, New York, 1996), pp. 320–326.
25. U. Selvaraj, K. Brooks, A.V. Prasada Rao, S. Komarneni, R. Roy,
and L.E. Cross, J. Am. Ceram. Soc. 76, 1441 (1993).
26. D.S. Paik, S. Komarneni, I.R. Abothu, and A.V. Prasada Rao, J.
Mat. Chem. 7, 1831 (1997).
27. P. Poosanas, A. Dogan, A.V. Prasada Rao, S. Komarneni, and
K. Uchino, J. Electroceramics 1, 105 (1997).
28. A.V. Prasada Rao, A.I. Robin, and S. Komarneni, in Intl. Sym-
posium on Manufacturing Practices and Technologies, Ceramic
Transactions (Am. Ceram. Soc., 1996), Vol. 70, pp. 253–260.
29. P. Ravindranathan, S. Komarneni, A.S. Bhalla, R. Roy, and L.E.
Cross, Ceramic Transactions, Ceramic Powder Science (Am.
Ceram. Soc., Columbus, 1988), Vol. 1, pp. 182–189.
30. P. Ravindranathan, E. Breval, S. Komarneni, and R. Roy, Mat.
Lett. 8, 161 (1989).
31. P. Ravindranathan, S. Komarneni, and R. Roy, J. Am. Ceram.
Soc. 73, 1024 (1990).
32. P. Ravindranathan, S. Komarneni, A.S. Bhalla, and R. Roy, Fer-
roelectric Lett. 11, 137 (1990).
33. P. Ravindranathan, S. Komarneni, A.S. Bhalla, and R. Roy, Fer-
roelectric Lett. 12, 29 (1990).
34. P. Ravindranathan, S. Komarneni, A.S. Bhalla, and R. Roy, J.
Am. Ceram. Soc. 74, 2996 (1991).
35. K. Kikuta, W. Sakamoto, and S. Hirano, Ceramic Transactions
12, 717 (1990).
36. L.F. Francis, Y.J. Oh, and D.A. Payne, J. Mat. Sci. 25, 5007
(1990).
37. D. Ravichandran, B. Jin, R. Roy, and A.S. Bhalla, Mat. Lett. 25,
257 (1995).
38. D. Ravichandran, R. Meyer, Jr., R. Roy, R. Guo, A.S. Bhalla,
and L.E. Cross, Mat. Res. Bull. 31, 817 (1996).
39. Z. Ji, Q-X Su, K.M. Moulding, and D.J. Barber, J. Mat. Sci. Lett.
15, 1808 (1996).
40. S. Komarneni, J. Mat. Chem. 2, 1219 (1992).