Abstract
The Partial Charge Model has been applied to analyse quantitatively experimental data on the process of hydrolysis and condensation, leading to gelation of Al3+ and Zr4+ cations in acidic concentrated inorganic sols. Both Al3+ and Zr4+ can condense to high polymeric species, but Zr4+ requires a higher ratio of hydrolysis than aluminium to initiate polymerization. Oxolation may occur in both aluminium and zirconium precursors. The role of anions in the polymerization process may also be calculated by this model and is assessed. In mixed Al-Zr gel systems, 27Al nuclear magnetic resonance shows that Al3+ does not participate in the initial polymerization, but instead decomposes to low polymer species upon mixing. Ageing has little effect on the polymerization of Al3+. Calorimetry shows that the polymerization of Zr4+, initiated by aluminium, accelerates at the beginning and gradually slows down after passing through a rate maximum. For mixtures of aluminium and zirconium precursors, temperature, composition (Al/Zr ratio) and concentration can significantly affect the rate of polymerization, as estimated from the rate of heat evolution.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
R. W. Davidge and J. L. Woodhead, UK Pat. 2094 779B, March 1982.
C. J. Brinker, D. E. Clark and D. R. Ulrich, in “Better Ceramics Through Chemistry”, MRS Symposia Proceedings, Vol. 73 (Materials Research Society, Pittsburgh, PA, 1986) pp. 820.
Idem, ibid., 1988) pp. 900.
J. J. Z. Brian, C. J. Brinker, D. E. Clark, and D. R. Ulrich, ibid.in “, 1990) pp. 1099.
R. C. Mehrotra, in “Sol-Gel Science and Technology”, Proceedings of the Winter School on Glasses and Ceramics from Gels, edited by M. A. Aeger, M. Jr. Jafelicci, D. F. Souza and E. E. Zanotto, Sao Carlos (SP), Brazil, August 1989, p. 1.
W. B. Zhang and F. P. Glasser, J. Euro. Ceram. Soc., in press.
Idem, ibid.
J. Livage, and M. Henry, in “Ultrastructure Processing of Advanced Ceramics”, edited by J. D. Mackenzie (Wiley, New York, 1988) p. 183.
J. Livage, M. Henry and C. Sanchez, Prog. Solid State Chem. 18 (1988) 259.
J. L. Woodhead, J. Mater. Educ. 6 (1984) 887.
T. Assih, A. Ayral, M. Abenoza and J. Phalippou, J. Mater. Sci. 23 (1988) 3326.
L. Nazar and L. Klein, J. Amer. Ceram. Soc. 71 (2) (1988) C-85.
L. Nazar, L. C. Klein and D. Napier, in “Better Ceramics Through Chemistry”, MRS Symposia Proceedings, Vol. 121 (Materials Research Society, Pittsburg, PA, 1988) p. 133.
R. E. Mesmer, C. F. Base Jr and F. N. Sweeton, in “Proceeding of 32nd International Water Conference”, Pittsburgh PA, 1971, p. 55.
G. Johansson, Acta Chem. Scand. 14 (1960) 771.
J. Akitt and A. Farthing, J. Chem. Soc. Dalton Trans. (1980) 1606.
Idem, ibid. (1981) 1617.
Idem, ibid. (1981) 1624.
J. Akitt and J. Mann, J. Magn. Reson. 44 (1981) 584.
B. F. Clarles, “Hydrolysis of Cations”, (Wiley Interscience, New York, 1980) pp. 112–22, 152–8.
J. Mason, “Multinuclear NMR” (Plenum Press, New York, 1987) p. 259.
K. J. Laidle and J. H. Meiser, “Physical Chemistry” (Benjamin/ Cumming USA, 1982) p. 821.
J. Livage, M. Henry, J. P. Jolivet and C. Sanchez, MRS Bull. XVI (1990) 18.
L. Klein, Ann. Rev. Mater. Sci. 15 (1985) 227.
C. J. Brinker, and G. W. Scherer, “Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing” (Academic Press, San Diego, CA, 1990) p. 331.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Zhang, W., Glasser, F.P. Condensation and gelation of inorganic ZrO2-Al2O3 sols. Journal of Materials Science 28, 1129–1135 (1993). https://doi.org/10.1007/BF00400902
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/BF00400902