Journal of Sol-Gel Science and Technology

, Volume 5, Issue 1, pp 5–14 | Cite as

EXAFS study of zirconium alkoxides as precursors in the sol-gel process: II. The influence of the chemical modification

  • D. Peter
  • T. S. Ertel
  • H. Bertagnolli
Article

Abstract

EXAFS studies of primary zirconium alkoxides Zr(OR)4 with OR = n-propoxide and n-butoxide, dissolved in their corresponding alcohols and chemically modified with acetylacetone (Hacac) and acetic acid (HOAc) in different molal ratios, are presented. The EXAFS-spectroscopic results, supported by FT-IR-studies, indicate a different chemical behavior of the complexing agents. In contrast to acetylacetone, the addition of acetic acid does not change the oligomeric structure of the zirconium alkoxides. Amazingly, the modification with acetic acid leads, in comparison to the pure compounds, to a shortened metal centre distance, whereas in the reaction with acetylacetone the Zr-Zr distance is not changed. With the determined distances and a rough quantitative inclusion of the coordination numbers it was possible to deduce detailed structure models.

Keywords

X-ray absorption zirconium alkoxides sol-gel process precursor chemical modification 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    C.J. Brinker and G.W. Scherer, Sol-Gel Science—The Physics and Chemistry of Sol-Gel Processing (Academic Press, San Diego, 1990).Google Scholar
  2. 2.
    E. Wu, K.C. Chen, and J.D. Mackenzie, in Better Ceramics through Chemistry I. Vol. 32, edited by C.J. Brinker, D.E. Clark, and D.R. Ulrich (Material Research Soc., Elsevier Science Publ., New York, 1984), p. 169.Google Scholar
  3. 3.
    L.C. Klein (ed.), Sol Gel Technology for thin Films, Fibres, Preforms, Electronics and Speciality Shapes (Noyes Publications, Park Ridge, N.Y., 1988).Google Scholar
  4. 4.
    B.E. Yoldas, J. Non-Cryst. Solids 63, 145 (1984).CrossRefGoogle Scholar
  5. 5.
    C. Sanchez, U. Livage, M. Henry, and F. Babonneau, J. Non-Cryst. Solids 100, 65 (1988).CrossRefGoogle Scholar
  6. 6.
    W.C. LaCourse and S. Kim, in Science of Ceramic Chemical Processing, edited by L.L. Hench and D.R. Ulrich (Wiley, New York, 1986), p. 310.Google Scholar
  7. 7.
    J. Livage, in Ultrastructure Processing of Advanced Ceramics, Vol. 73, edited by L.L. Hench and D.R. Ulrich (Wiley, New York, 1986), p. 717.Google Scholar
  8. 8.
    K. Yamada, T.Y. Chow, T. Horihata, and M. Nagata. J. Non-Cryst. Solids 100, 316 (1988).CrossRefGoogle Scholar
  9. 9.
    F. Bobonneau, A. Leaustic, and J. Livage, in Better Ceramics through Chemistry III, Vol. 121, edited by C.J Brinker, D.E. Clark, and D.R. Ulrich (Pittsburgh, Pa, 1988), p. 317.Google Scholar
  10. 10.
    J. Livage, C. Sanchez, M. Henry, and S. Doeuff, Solid State Ionics 32, 633 (1989).CrossRefGoogle Scholar
  11. 11.
    A. Leaustic, F. Babonneau, and J. Livage, Chem. Mat. 1, 248 (1989).CrossRefGoogle Scholar
  12. 12.
    I. Laaziz, A. Larbot, A. Julbe, C. Guizard, and L. Cot, J. Solid State Chem. 98, 393 (1992).CrossRefGoogle Scholar
  13. 13.
    D. Peter, T.S. Ertel, and H. Bertagnolli, J. Sol-Gel Sci. Techn. 3, 91 (1994).CrossRefGoogle Scholar
  14. 14.
    R.C. Mehrotra and R. Bohara, Metal Carboxylates (Academic Press, London, 1993).Google Scholar
  15. 15.
    R.C. Mehrotra, R. Bohra, and D.P. Gaur, Metal β-Diketonates and Allied Derivatives (Academic Press, London, 1978).Google Scholar
  16. 16.
    D.C. Bradley, R.C. Mehrotra, and D. P. Gaur, Metal Alkoxides (Academic Press, London, 1978).Google Scholar
  17. 17.
    S. Doeff and M. Henry, J. Non-Cryst. Solids 89, 206 (1987).CrossRefGoogle Scholar
  18. 18.
    K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds (Wiley, New York, 1978).Google Scholar
  19. 19.
    K.H. Thiele and M. Panse, Z. Anorg. Allg. Chem. 441, 23 (1978).CrossRefGoogle Scholar
  20. 20.
    T.S. Ertel and H. Bertagnolli, Nucl. Instrum. Methods Phys. Res., Sect. B 73, 199 (1993).CrossRefGoogle Scholar
  21. 21.
    T.S. Ertel, H. Bertagnolli, S. Hückmann, U. Kolb, and D. Peter, Appl. Spectrosc. 46, 690 (1992).CrossRefGoogle Scholar
  22. 22.
    J.K. Silverton and J.L. Hoard, Inorg. Chem. 2, 243 (1963).CrossRefGoogle Scholar
  23. 23.
    M. Kaupp and P. von Ragué Schleyer, J. Am. Soc. 112, 11202 (1993).CrossRefGoogle Scholar

Copyright information

© Kluwer Academic Publishers 1995

Authors and Affiliations

  • D. Peter
    • 1
  • T. S. Ertel
    • 2
  • H. Bertagnolli
    • 2
  1. 1.Institut für Physikalische Chemie der Universität WürzburgWürzburgGermany
  2. 2.Institut für Physikalische Chemie der Universität StuttgartStuttgartGermany

Personalised recommendations