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Received 6 January 2000; received in revised form 10 April 2000; accepted 29 April 2000
Abstract
In this work, the synthesis of BaTiO3 powder from BaCO3TiO2 reaction at high temperatures is studied. In order to improve the
kinetics of this reaction, successive modications on the powder processing have been implemented. The contribution of the
mechanochemical activation to the BaTiO3 formation is analysed. It was found that the use of a mechanochemical activation
favours the decomposition of BaCO3 at low temperatures and improves the barium ion diusion through the BaTiO3 layer. In
consequence, a BaTiO3 product free of secondary phases can be obtained at lower temperatures. # 2000 Elsevier Science Ltd. All
rights reserved.
Keywords: BaTiO3 and titanates; Milling; Powders-solid-state reaction
0955-2219/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0955-2219(00)00148-5
2348 E. Brzozowski, M.S. Castro / Journal of the European Ceramic Society 20 (2000) 23472351
Hence, the formation of Ba2TiO4 proceeds by the heating rate of 10 C/min. Size particle distributions of
reaction between BaO and the prior-formed BaTiO3. the raw materials, milled products and calcined samples
iii. Finally, TiO2 and Ba2TiO4 react to produce were determined by the Sedigraph technique with a
BaTiO3, which is the nal phase: Micromeritics. The surface area measurements were
carried out using the BET method with a Monosorb
Ba2 TiO4 ! BaTiO3 BaO 4 Quantachrome, employing a mixture of He/N2 gasses in
a relation 70/30.
TiO2 BaO ! BaTiO3 5
Fig. 1. X-ray diraction patterns of samples S1 and S2. *BaCO3, &TiO2 anatase, &TiO2 rutile, *BaTiO3, /Ba TiO , !Ba TiO .
2 4 2 5
Then, when the decomposition of the carbonate is pro- Fig. 2 shows the DTA diagrams for samples S1, S2,
duced, a diminution in the particle size is observed (see and S3. Signicant dierences in the systems appear as
Table 2). temperature is increasing. Sample S2 does not present
Due to the use of TiO2 with high specic area, sam- an important variation in the DTA diagram respect to
ples S1 and S3 present an elevated value of specic area. S1. However, in sample S3, a displacement of the
Moreover, sample S3 does not present an important BaTiO3 peak respect to S1 is observed. Moreover, the
increase in the specic area as consequence of the signal corresponding to the transition g!b in BaCO3
milling step, because in this mixture the activation pro- (827 C)15,16 does not appear in sample S3. This dier-
cess presents a diminution in the BaCO3 particle sizes. ence is due to an increase in the reactivity of the BaCO3
Table 2
Particle size distributions and specic area of samples S1, and S3
As milled Calcined
2
Sample D80 (mm) D20 (mm) D50 (mm) W Specic area (m /g) D80 (mm) D20 (mm) D50 (mm) W
decomposition. This is favoured by the catalytic eect 4. Caballero, A. C., Fernandez, J. F., Moure, C. and Duran, P.,
of a very reactive TiO2. In a second stage, the BaTiO3 ZnO-doped BaTiO3: microestructure and electrical properties. J.
Eur. Ceram. Soc., 1997, 17, 513523.
formation is controlled by the barium diusion through
5. Tzing, W. H., Tuan, W. H. and Lin, H. L., The eect of the
barium titanate layer. In this stage, secondary phases microestructure on the electrical properties of NiO-doped
are formed. An eective way of limiting the existence of BaTiO3. Ceramics International, 1999, 25, 425430.
secondary phases consists of departing from a system in 6. Tzing, W. H. and Tuan, W. H., The eect of NiO addition on the
which the reactivities of the raw materials are similar. In sintering and grain growth behaviour of BaTiO3. Ceramics Inter-
this work, such goal was achieved by making modica- national, 1999, 25, 6975.
7. Li, X. and Heng, S. W., Size eects in barium titanate particles
tions on the processing of the powders. The application and clusters. J. Am. Ceram. Soc., 1997, 80(11), 28442853.
of a rigorous mill step allows an increase of the 8. Stojanovic, B. D., Pavlovic, V. B., Pavlovic, V. P., Djuric, S.,
reactivity of BaCO3. This reactivity avoids that the Marinkovic, B. A. and Ristic, M. M., Dielectric properties of
barium carbonate decomposition and the barium barium titanate sintered from tribophysically activated powders.
diusion control the course of the reaction. J. Eur. Ceram. Soc., 1999, 19, 10811083.
9. Beauger, A., Mutin, J. C. and Niepce, J. C., Synthesis reaction of
metatitanate BaTiO3. Part 2: study of solidsolid reaction inter-
faces. J. Matt. Sci., 1983, 18, 35433550.
Acknowledgements 10. Mutin, J. C. and Niepce, J. C., About stoichiometry of poly-
crystaline BaTiO3 synthesized by solidsolid reaction. J. Mat.
Financial support from Fundacion Antorchas and Sci. Letter, 1984, 3, 591592.
11. Hamano, A., Atake, T. and Saito, Y., Succesive phase transitions
CONICET are gratefully acknowledged. The authors of BaTiO3 ceramics synthesized by powder calcination. Int. J.
would also like to thank to Dr. B. Stojanovic for her High Tech. Ceram., 1988, 4, 4150.
valuable discussions. 12. Amin, A., Spears, M. A. and Kulwicki, B. M., Reaction of anatase
and rutile with barium carbonate. J. Am. Ceram. Soc., 1983, 66, 733.
13. Gomez-Yanez, C., Benitez, C. and Balmori-Ramirez, H., Mechan-
References ical activation of the sysnthesis of BaTiO3 from a mixture of BaCO3
and TiO2 powders. Ceramics International, 2000, 26, 271277.
1. Hill, D. C. and Tuller, H. L., Ceramics sensors: theory and prac- 14. Beauger, A., Mutin, J. C. and Niepce, J. C., Role and behaviour
tice. In Ceramic Materials for Electronics: Processing Properties of orthotitanate Ba2TiO4 during the processing of BaTiO3 based
and Applications, ed. R. C. Buchanan. Marcel Dekker, Inc., New ferroelectric ceramics. J. Mat. Sc., 1984, 19, 195210.
York and Basel, 1986, pp. 265372. 15. Templeton, L. K. and Pask, J. A., Formation of BaTiO3 from
2. Hozer, L., Semiconductor Ceramics Grain Boundary Eects. BaCO3 and TiO2 in air and in CO2. J. Am. Ceram. Soc., 1959, 42,
PWN Polish Scientic Publishers, Warsaw, Poland, 1994 pp. 3 212216.
41, 109143. 16. Fernandez, J. F., Duran, P. and Moure, C., Reaction kintetics in
3. Rae, A., Chu, M. and Ganine, V., Barium titanatepast, present the BaTiO3 synthesis: inuence of the TiO3 crystalline structure
and future. In Dielectric Ceramic Materials, ed. K. M. Nair and and morphologies. In Ceramics Today-Tomorrow's Ceramics,
A. S. Bhalla. The American Ceramic Society, Westerville, OH, ed. E. D. Vicenzini. Elsevier Science Publishers, Amsterdam,
1998, pp. 112. 1991, pp. 19731982.