The influence of β-diketones on the induction times for hydrolysis of zirconium(IV) alkoxides

(Note: The full text of this document is currently only available in the PDF Version )

Matthew J. Percy, John R. Bartlett, James L. Woolfrey, Leone Spiccia and Bruce O. West

The influence of low ligand/Zr mole ratios (ρ=0-0.1) of acetylacetone on the hydrolysis of Zr(OPrn)4 has been examined by investigating its effect on the induction time (ti) before precipitation commences in the system. A remarkable feature of the data is the large increase in the induction time (reduction in hydrolysis/condensation rate) caused by addition of acetylacetone. This occurs even though only a maximum of one in eighty Zr-OR bonds have reacted with ligand and are no longer available for hydrolysis or further condensation. The effects on ti of five other β-diketones having varying steric properties (trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, dibenzoylmethane and dipivaloylmethane) are compared with that of acetylacetone, under similar concentration conditions, with ρ=0.1. Each shows a greater effect than acetylacetone, the largest change being caused by dibenzoylmethane which, under the conditions used, increases the induction time by a factor of 26 relative to acetylacetone. A mechanism rationalising the origin of the effect is discussed.


  1. J. Livage, M. Henry and C. Sanchez, Prog. Solid State Chem., 1988, 4, 259 CrossRef.
  2. M. In and R. K. Prud'homme, Rheol. Acta, 1993, 32, 556 CAS.
  3. P. Papet, N. Le Bars, J. F. Baumard, A. Lecomte and A. Dauger, J. Mater. Sci., 1989, 24, 3850 CAS.
  4. K. Yamada, T. Y. Chow, T. Horihata and M. Nagata, J. Non-Cryst. Solids, 1988, 100, 316 CAS.
  5. J. C. Debsikdar, J. Non-Cryst. Solids, 1986, 86, 231 CAS.
  6. G. De, A. Chatterjee and D. Ganguli, J. Mater. Sci. Lett., 1990, 9, 845 CAS.
  7. D. C. Bradley, R. C. Mehrotra and D. P. Gaur, in Metal Alkoxides, Academic Press, London, 1978, p. 213 Search PubMed.
  8. A. Léaustic, F. Babonneau and J. Livage, Chem. Mater., 1989, 1, 240 CrossRef CAS.
  9. C. D. Chandler, G. D. Fallon, A. J. Koplick and B. O. West, Aust. J. Chem., 1987, 40, 1427 CAS.
  10. P. Toledano, F. Ribot and C. Sanchez, C. R. Acad. Sci. Paris, II, 1990, 311, 1315 Search PubMed.
  11. F. Ribot, P. Toledano and C. Sanchez, Chem. Mater, 1991, 3, 759 CrossRef CAS; P. Ribot, C. Sanchez and J. Livage, in Chemical Processing of Advanced Materials, ed. L. L. Hench and J. K. West., Wiley and Sons, New York, 1992p. 267 Search PubMed.
  12. J. Blanchard, S. Barboux-Doeuff, J. Maquet and C. Sanchez, New. J. Chem., 1995, 19, 929 Search PubMed.
  13. A. Leaustic, F. Babonneau and J. Livage, Chem. Mater., 1989, 1, 248 CrossRef CAS.
  14. P. Toledano, M. In and C. Sanchez, C. R. Acad. Sci. II, 1990, 311, 1161 Search PubMed.
  15. P. Toledano, M. In and C. Sanchez, C. R. Acad. Sci. II, 1991, 313, 1247 Search PubMed.
  16. C. J. Brinker and G. W. Scherer, in Sol–Gel Science: The Physics and Chemistry of Sol–Gel Processing, Academic Press, San Diego, 1990 Search PubMed.
  17. L. Davies, L. Daza and P. Grange, J. Mater. Sci., 1995, 30, 5087 CAS.
  18. K. E. J. Barret and H. R. Thomas, in Dispersion Polymerisation in Organic Media, ed. K. E. K. Barret, Wiley and Sons, 1975, ch. 4 Search PubMed.
  19. M. Ocaña, R. Rodriguez-Clemente and C. J. Serna, Adv. Mater., 1995, 7, 212 CAS.
  20. P. M. Smit, A. Van Zyl and A. I. Kingon, Mater. Chem. Phys., 1987, 17, 507 CAS.
  21. J. R. Bartlett, M. Percy, J. L. Woolfrey, L. Spiccia and B. O. West, J. Sol–Gel. Sci. Technol., 1995, 2, 215 Search PubMed.
  22. G. Rinn and H. Schmidt, Ceram. Powder Sci. II A, 1988, 23 Search PubMed.
  23. M. J. Percy, J. R. Bartlett, J. L. Woolfrey, L. Spiccia and B. O. West, in Sol–Gel Processing of Advanced Ceramics, Ceram. Trans., 1998, 81, 81 Search PubMed.
  24. R. C. Mehrotra, R. Bora and D. P. Gaur, in Metal β-Diketonates and Allied Derivatives, Academic Press, London, 1978 Search PubMed.
  25. R. Amal, J. A. Raper and T. D. Waite, J. Colloid Interface Sci., 1990, 140, 158 CAS.
  26. J.-L. Look and C. F. Zukoski, J. Am. Ceram. Soc., 1995, 78, 21 CAS.
  27. A. Bleuzen, S. Barboux-Doeuff, P. Fland and C. Sanchez, Mater. Res. Bull., 1994, 29, 1223 CAS.
  28. L. G. Van Uitert, W. C. Ferneliu and B. E. Douglas, J. Am. Chem. Soc., 1953, 75, 457 CrossRef CAS.
  29. G. A. Guter and G. S. Hammond, U. S. Atomic Energy Commission ISC-673, 1955 Search PubMed; Chem. Abstr., 1958, 52, 17102 Search PubMed.