Hostname: page-component-8448b6f56d-qsmjn Total loading time: 0 Render date: 2024-04-24T09:39:47.587Z Has data issue: false hasContentIssue false
  • English
  • Français

Investigation of the mechanism of sol-gel formation in the Sr(NO3)2/citric acid/ethylene glycol system by solution state 87 Sr nuclear magnetic resonance spectroscopy

Published online by Cambridge University Press:  31 January 2011

Xiaohua Li ,
Vishal Agarwal ,
Meilin Liu  and
William S. Rees Jr
Xiaohua Li
Affiliation:
School of Chemistry and Biochemistry, and Molecular Design Institute, Georgia Institute of Technology, Atlanta, Georgia 30332-0400
Vishal Agarwal
Affiliation:
School of Materials Science and Engineering, and Molecular Design Institute, Georgia Institute of Technology, Atlanta, Georgia 30332-0245
Meilin Liu*
Affiliation:
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245
William S. Rees Jr*
Affiliation:
School of Chemistry and Biochemistry, and School of Materials Science and Engineering, and Molecular Design Institute, Georgia Institute of Technology, Atlanta, Georgia 30332-0400
*
a)Address all correspondence to this author. e-mail: will.rees@chemistry.gatech.edu e-mail: meilin.liu@mse.gatech.edu
a)Address all correspondence to this author. e-mail: will.rees@chemistry.gatech.edu e-mail: meilin.liu@mse.gatech.edu
Get access

Abstract

The polymerization mechanism of a modified Pechini process was investigated by 87Sr nuclear magnetic resonance spectroscopy for the mixed solution of strontium nitrate, citric acid, and ethylene glycol. The C-ratio (the ratio of citric acid to metal ions in the polymer complex) is suggested to have a strong influence on the quality of the derived film. An analysis of the chemical shift variation, as a function of C-ratio, indicates the presence in the solution of two species: solvated strontium ions and strontium ions bound to the polymer complex, with a stoichiometry of 1:7. A polymeric precursor model based on this stoichiometry is proposed. Through a relaxation rate study of the strontium sites, it was found that the polymerization mechanism is predominantly bimolecular within the concentration region being studied. The equilibrium rate constant for the polymerization was calculated to be 104 s−1. A kinetic study of the fast cation exchange between the two identified strontium sites indicates that the inhomogeneity of the polymeric network leads to film cracking during pyrolysis.

Type
Articles
Information
Journal of Materials Research , Volume 15 , Issue 11 , November 2000 , pp. 2393 - 2399
Copyright
Copyright © Materials Research Society 2000

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1.Matsumoto, Y., Yamada, S., Nishida, T., and Sato, E., J. Electrochem. Soc. 127, 2360 (1980).CrossRefGoogle Scholar
2.Meadowcroft, D.B., Nature 226, 847 (1970);CrossRefGoogle Scholar
Teraoka, Y., Zhang, H.M., Furukawa, S., and Yamazoc, N., Chem. Lett. 1743 (1985).CrossRefGoogle Scholar
3.Bouwmeester, H.J.M, Kruidhof, H., and Burggraaf, A.J., Solid State Ionics 72, 185 (1994).CrossRefGoogle Scholar
4.Huang, X.J., Schoonman, J., Chen, L.Q., Sens. Actuators B 22, 211, 219 (1995).CrossRefGoogle Scholar
5.McNamara, E.A., Montzka, S.A., Barkley, R.M., and Sievers, R.E., J. Chromatogr. 452, 75 (1988).CrossRefGoogle Scholar
6.Steele, B.C.H, Solid State Ionics 75, 157 (1995).CrossRefGoogle Scholar
7.Chen, C.C., Nasrallah, M.M., and Anderson, H.U., J. Electrochem. Soc. 140, 3555 (1993).CrossRefGoogle Scholar
8.Pechini, M.P., U.S. Patent No. 3330697 (1967).Google Scholar
9.Kumar, S. and Messing, G.L., in Better Ceramics Through Chemistry V, edited by Hampden-Smith, M.J., Klemperer, W.G., and Brinker, C.J. (Mater. Res. Soc. Symp. Proc. 271, Pittsburgh, PA, 1992), p. 95.Google Scholar
10.Kucper, W., Visco, S.J., and DeJonghe, L.C., Solid State Ionics 52, 251 (1992).Google Scholar
11.Liu, M. and Wang, D.S., J. Mater. Res. 10, 1 (1995).Google Scholar
12.Delville, A., Stover, H.D., and Detellier, C.J., J. Am. Chem. Soc. 107, 4172 (1985).CrossRefGoogle Scholar
13.Shporer, M. and Luz, Z., J. Am. Chem. Soc. 97, 665 (1975).CrossRefGoogle Scholar
14.Strasser, B.O., Shamsipur, M., and Popov, A.I., J. Phys. Chem. 89, 4822 (1985).CrossRefGoogle Scholar
15.Delville, A., Stover, H.D., and Detellier, C.J., J. Am. Chem. Soc. 109, 7293 (1987).CrossRefGoogle Scholar
16.Schmidt, E. and Popov, A.I., J. Am. Chem. Soc. 105, 1873 (1983).CrossRefGoogle Scholar
17.Ahn, M.K. and Lemox, E., J. Phys. Chem. 93, 4924 (1989).CrossRefGoogle Scholar
18.Holton, D.M., Ellaboudy, A.S., and Edwards, R.N., Proc. R. Soc. London, Ser. A 415, 121 (1988).Google Scholar
19.Rees, W.S. Jr, Alkaline Earth Metals: Inorganic Chemistry, in Encyclopedia of Inorganic Chemistry, edited by King, R.B. (John Wiley & Sons, New York, 1994), Vol. 1, pp. 67–87.Google Scholar
20.Jeffries, C.D. and Sogo, P.B., Phys. Rev. 91, 1286 (1953).CrossRefGoogle Scholar
21.Sandstrom, J., Dynamic NMR Spectroscopy (Academic Press, New York, 1982), p. 14.Google Scholar
22.Becker, E.D., High Resolution NMR Theory and Chemical Applications, 2nd ed. (Academic Press, Orlando, FL, 1980), p. 242.Google Scholar
23.Zdunek, L.Z. and Gold, V., J. Chem. Soc., Faraday Trans. 2 78, 1825 (1982).Google Scholar
24.Delville, A., Stover, H.D., and Detellier, C.J., J. Am. Chem. Soc. 107, 4167 (1985).CrossRefGoogle Scholar
25.Sandstrom, J., Dynamic NMR Spectroscopy (Academic Press, New York, 1982), p. 17.Google Scholar
26.Woessner, D.E., J. Chem. Phys. 35, 41 (1961).CrossRefGoogle Scholar
27.Courty, P., Ajot, H., Marcilly, C., and Delmon, B., Powder Technol. 7, 21 (1973).CrossRefGoogle Scholar
28.Akki, R., Desai, P., and Abhiraman, A.S., J. Appl. Polym. Sci. 54, 1263 (1994).CrossRefGoogle Scholar