Abstract
An aqueous, all nitrate, solution-based preparation of BaTiO3 is reported here. Rapid freezing of a barium and titanyl nitrate solution, followed by low temperature sublimitation of the solvent, yielded a freeze-dried nitrate precursor which was thermally processed to produce BaTiO3. XRD revealed that 10 min at temperatures ≧600 °C resulted in the formation of phase pure nanocrystalline BaTiO3. TEM revealed that the material was uniform and nanocrystalline (10–15 nm). The high surface to volume ratio inherent in these small particles stabilized the cubic phase of BaTiO3 at room temperature. It was also found that the average particle size of the BaTiO3 produced was highly dependent upon calcination temperature and only slightly dependent upon annealing time. This result suggests a means of selection of particle size of the product through judicious choice of calcination temperature. The experimental details of the freeze-dried precursor preparation, thermal processing of the precursor, product formation, and product morphology are discussed.
Similar content being viewed by others
References
K. Kiss, J. Magder, M. S. Vukasovich, and R. J. Lockhart, J. Am. Ceram. Soc. 49, 291 (1966).
M. Stockenhuber, H. Mayer, and J. A. Lercher, J. Am. Ceram. Soc. 76, 1185 (1993).
M. P. Pechini, U.S. Patent No. 3330 697, July 11, 1967.
K. S. Mazdiyasni, R. T. Dolloff, and J. S. Smith II, J. Am. Ceram. Soc. 52, 523 (1969).
G. Pfaff, J. Mater. Chem. 2, 591 (1992).
C. Zhixiong, Z. Fangqiao, L. Meidong, W. Guoan, and P. Xiang-sheng, Ferroelectrics 123, 61 (1991).
S. S. Flachen, J. Am. Chem. Soc. 77, 6194 (1955).
W. Hertl, J. Am. Ceram. Soc. 71, 879 (1988).
P. P. Phule and S. H. Risbud, J. Mater. Sci. 25, 1169 (1990).
M. Alvazzi Delfrate, M. Leoni, L. Nanni, E. Melioli, B. E. Watts, and F. Leccabue, J. Mater. Sci., Mater. Elec. 5, 153 (1994).
H. G. Lee and H. G. Kim, J. Appl. Phys. 67, 2024 (1990).
K. S. Mazdiyasni, R. T. Dolloff, and J. S. Smith II, J. Am. Ceram. Soc. 52, 523 (1969).
J. F. Schnettler, F. R. Monforte, and W. W. Rhodes, in Science of Ceramics, edited by G. H. Stewart (British Ceramics Society, Manchester, 1968).
A. C. C. Tseung and H. L. Bevan, J. Mater. Sci. 5, 604 (1970).
J. Barksdale, Titanium, Its Occurrence, Chemistry, and Technology (Ronald Press, New York, 1966).
H. B. Weiser, Inorganic Colloid Chemistry, Volume II, The Hydrous Oxides and Hydroxides (John Wiley and Sons, London, 1935).
A. W. Hixson and W. W. Plechner, Ind. Eng. Chem. 25, 262 (1933).
H. Yamamura, A. Watanabe, S. Shirasaki, Y. Moriyoshi, and M. Tanada, Ceram. Int. 11, 17 (1985).
D. M. DeLeeuw, C. A. H. A. Mutsaers, C. Langereis, H. C. A. Smoorenberg, and P. J. Rommers, Physica C 152, 39 (1988).
E. Ruckenstein, S. Narain, and N. L. Wu, J. Mater. Res. 4, 267 (1989).
T. M. Shaw, D. Dinos, P. E. Batson, A. G. Shrott, D. R. Clarke, and P. R. Duncombe, J. Mater. Res. 5, 1176 (1990).
J. M. McHale and N. V. Coppa, unpublished work.
N. V. Coppa, Doctoral Dissertation, Temple University, Philadelphia, PA (1990).
T. M. Ozra, J. C. Jha, and E. I. Ezekiel, J. Indian Chem. Soc. 45, 420 (1968).
N. V. Coppa, G. H. Myer, R. E. Salomon, A. Bura, J. W. O’Reilley, J. E. Crow, and P. K. Davies, J. Mater. Res. 7, 2017 (1992).
E. L. Brosha, E. Sanchez, P. K. Davies, N. V. Coppa, A. Thomas, and R. E. Salomon, Physica C 184, 353 (1991).
CRC Handbook of Physics and Chemistry, 56th ed., edited by R. C. Weast (CRC Press, Cleveland, OH, 1976).
L. K. Templeton and J. A. Pask, J. Am. Ceram. Soc. 42, 212 (1959).
As prepared in Ref. 22.
T. Takemuchi, K. Ado, T. Asai, H. Kageyama, Y. Saito, C. Masqueleir, and O. Nakamura, J. Am. Ceram. Soc. 77, 1665 (1994).
The possible ternary impurity, Ba2TiO4, is reported to have a d-spacing of 3.54 Å.
S. Andersson and L. Jahnberg, Ark. Kemi 21, 413 (1964).
H. F. Kay and P. Vousdan, Philos. Mag. 7, 1019 (1949).
B. D. Cullity, Elements of X-Ray Diffraction (Addison-Wesley, Reading, MA, 1978).
S. Naka, F. Nakakita, Y. Suwa, and M. Inagaki, Bull. Chem. Soc. Jpn. 47, 1168 (1974).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
McHale, J.M., McIntyre, P.C., Sickafus, K.E. et al. Nanocrystalline BaTiO3 from freeze-dried nitrate solutions. Journal of Materials Research 11, 1199–1209 (1996). https://doi.org/10.1557/JMR.1996.0154
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1557/JMR.1996.0154