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Ammonia Catalyzed Hydrolysis-Condensation Kinetics of Tetraethoxysilane/Dimethyldiethoxysilane Mixtures Studied by 29Si NMR and SAXS

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Abstract

In-situ 29Si liquid-state nuclear magnetic resonance (NMR) was used to investigate the ammonia catalyzed hydrolysis and condensation of the mixed systems of tetraethoxysilane (TEOS) and dimethyldiethoxysilane (DDS) dissolved in methanol. With ammonia catalysis, the hydrolysis reaction orders for TEOS and DDS in the mixed systems remained first order, which is similar to that observed for their corresponding single silane component precursor systems. The hydrolysis rate constant for TEOS in the mixed systems was larger than that of TEOS in the single silane component precursor systems. Meanwhile, the hydrolysis rate constants of DDS in the mixed precursor systems were smaller than those of DDS in the single silane component precursor systems. The hydrolysis and condensation kinetics showed more compatible hydrolysis-condensation relative rates between TEOS and DDS, which remarkably affected the final microstructure of the resulting silica particles. Small angle X-ray scattering (SAXS) experiments showed a typical double fractal structure in the particulate networks.

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References

  1. 1. Brinker, C.J., Scherer, O.W.: Sol-gel Science: the Physics and Chemistry of Sol-gel Processing. Academic Press, San Diego (1990)

  2. 2. Hench, L.L., West, J.K.: The sol-gel process. Chem. Rev. 90, 33–72 (1990)

    Article  CAS  Google Scholar 

  3. 3. Cheetham, A.K., Brinker, C.J., Mecartney, M.L., Sanchez, C. (eds.): Better ceramics through chemistry V. Materials Research Society, Pittsburgh (1994)

  4. 4. Mackenzie, J.D., Bescher, E.P.: Structure, properties and potential application of ormosils. J. Sol-Gel Sci. Tech. 13, 371–377 (1998)

    Article  CAS  Google Scholar 

  5. 5. Mackenzie, J.D.: Sol-gel research – achievements since 1981 and prospects for the future. J. Sol-Gel Sci. Tech. 26, 23–27 (2003)

    Article  CAS  Google Scholar 

  6. 6. Innocenzi, P., Brusotin, G., Guglielmi, M., Bertani, R.: New synthetic route to (3-glycidoxypropyl)triethoxysilane-based hybrid organic-inorganic materials. Chem. Mater. 11, 1672–1679 (1999)

    Article  CAS  Google Scholar 

  7. 7. Schottner, G.: Hybrid sol-gel-derived polymers: applications of multifunctional materials. Chem. Mater. 13, 3422–3435 (2001)

    Article  CAS  Google Scholar 

  8. 8. Zhang, Y., Wang, M.Q.: Mechanical characterization and optical properties analysis of organically modified silicates. J. Non-Cryst. Solids 271, 88–93 (2000)

    Article  CAS  Google Scholar 

  9. 9. Liu, Y., Ren, W., Zhang, L.Y., Yao, X.: New method for making porous SiO2 thin films. Thin Solid Films 353, 124–128 (1999)

    Article  CAS  Google Scholar 

  10. 10. Kuraoka, K., Kubo, N., Yazawa, T.: Microporous silica xerogel membrane with high selectivity and high permanence for carbon dioxide separation. J. Sol-Gel Sci. Tech. 19, 515–518 (2000)

    Article  CAS  Google Scholar 

  11. 11. Green, D.L., Lam, S., Jayasundara, Y.F., Harris, M.T.: Chemical reaction kinetics leading to the first Stober silica nanoparticles-NMR and SAXS investigation. J. Non-Cryst. Solids 315, 166–179 (2003)

    Article  CAS  Google Scholar 

  12. 12. Blaaderen, A.V., Vru, A.: Synthesis and characterization of monodisperse colloidal organo-silica spheres. J. Colloid Interfac. Sci. 156, 1–18 (1993)

    Article  Google Scholar 

  13. 13. Assink, R.A., Kay, B.D.: Sol-gel kinetics I. Functional group kinetics. J. Non-Cryst. Solids 99, 359–370 (1988)

    Article  CAS  Google Scholar 

  14. 14. Kay, B.D., Assink, R.A.: Sol-gel kinetics: II. Chemical speciation modeling. J. Non-Cryst. Solids 104, 112–122 (1988)

    Article  CAS  Google Scholar 

  15. 15. Sadasivan, S., Dubey, A.K., Li, Y.Z., Rasamussen, D.H.: Alcoholic solvent effect on silica synthesis – NMR and DLS investigation. J. Sol-Gel Sci. Tech. 12, 5–14 (1998)

    Article  CAS  Google Scholar 

  16. 16. Bogush, G.H., Zukoski, C.F.: Studies of the kinetics of the precipitation of uniform silica particles through the hydrolysis and condensation of silicon alkoxides. J. Colloid. Interfac. Sci. 142, 1–18 (1991)

    Article  CAS  Google Scholar 

  17. 17. Fyfe, C.A., Zhang, Y., Aroca, P.: An alternative preparation of organofunctionalized silica gel and their characterization by two-dimensional high-resolution solid-state heteronuclear NMR correlation spectroscopy. J. Am. Chem. Soc. 114, 3252–3255 (1992)

    Article  CAS  Google Scholar 

  18. 18. Hook, R.J.: A 29Si NMR study of the sol-gel polymerization rates of substituted ethoxysilanes. J. Non-Cryst. Solids 195, 1–15 (1996)

    Article  CAS  Google Scholar 

  19. 19. Riegel, B., Blittersdorf, S., Kiefer, W., Hofacker, S., Schottner, G.: Kinetic investigations of hydrolysis and condensation of the glycidoxypropyltrimethoxy silane/aminopropyltriethoxy-silane system by means of FT-Raman spectroscopy I. J. Non-Cryst. Solids 226, 76–84 (1998)

    Article  CAS  Google Scholar 

  20. 20. Riegel, B., Blittersdorf, S., Kiefer, W., Husing, N., Schubert, U.: Raman spectroscopic analysis of the sol-gel processing of Rsi(OMe)3/Si(Ome)4 mixtures. J. Molec. Struct. 410/411, 157–160 (1997)

    Google Scholar 

  21. 21. Prabakar, S., Assink, R.A.: Hydrolysis and condensation kinetics of two component organically modified silica sols. J. Non-Cryst. Solids 211, 39–48 (1997)

    Article  CAS  Google Scholar 

  22. 22. Prabakar, S., Assink, R.A., Raman, N.K., Myers, S.A., Brinker, C.J.: Identification of self- and cross-condensation products in organically modified silica sols by 29Si and 17O NMR spectroscopy. J. Non-Cryst. Solids 202, 53–60 (1996)

    Article  CAS  Google Scholar 

  23. 23. Alie, C., Pirard, J.P.: Preparation of low-density xerogels from mixtures of TEOS with substituted alkoxysilanes. I. 17O NMR study of the hydrolysis-condensation process. J. Non-Cryst. Solids 320, 21–30 (2003)

    Article  CAS  Google Scholar 

  24. 24. Brus, J., Dybal, J.: Copolymerization of tetraethoxysilane and dimethyl(diethoxy) silane studied by 29Si NMR and ab initio calculations of 29Si NMR chemical shifts. Polymer, 40 (1999) 6933–6945

    Article  CAS  Google Scholar 

  25. 25. Brus, J.: Solid-state NMR study of phase separation and order of water molecules and silanol groups in polysiloxane networks. J. Sol-Gel Sci. Tech. 25, 17–28 (2002)

    Article  CAS  Google Scholar 

  26. 26. Wonorahardjo, S., Ball, G.E., Hook, J., Moran, G.: 2H NMR relaxation monitoring of gelation in tetramethoxysilane sol-gels. J. Non-Cryst. Solids 271, 137–146 (2000)

    Article  CAS  Google Scholar 

  27. 27. Satoh, T., Akitaya, M., Konno, M, Saito, S.: Particle size distributions produced by hydrolysis and condensation of tetraethylorthosilicate. J. Chem. Eng. Japan 30(4), 759–762 (1997)

    Article  CAS  Google Scholar 

  28. 28. Mine, E., Nagao, D., Kobayashi, Y., Konno, M.: Solvent effects on particle formation in hydrolysis of tetraethyl orthosilicate. J. Sol-Gel Sci. Tech. 35(3), 197–201 (2005)

    Article  CAS  Google Scholar 

  29. 29. Brus, J., Spirkova, M., Hlavata, D., Strachota, A.: Self-organization, structure, dynamic properties, and surface morphology of silica/epoxy films as seen by solid-state NMR, SAXS, and AFM. Macromolecules 37(4), 1346–1357 (2004)

    Article  CAS  Google Scholar 

  30. 30. Brinker, C.J.: Hydrolysis and condensation of silicates: Effects on structure. J. Non-Cryst. Solids 100, 31–50 (1988)

    Article  CAS  Google Scholar 

  31. 31. Liu, R., Xu, Y., Wu, D., Sun, Y., Gao, H., Yuan, H., Deng, F.: Comparative study on the hydrolysis kinetics of substituted ethoxysilanes by liquid-state 29Si NMR. J. Non-Cryst. Solids 343, 61–70 (2004)

    Article  CAS  Google Scholar 

  32. 32. Iler, R.K.: The Chemistry of Silica. Wiley, New York (1979)

  33. 33. Keefer, K.D.: In: C.J. Brinker, D.E. Clark, D.R. Ulrich (eds.) Better ceramics through chemistry, p. 15. North-Holland, New York (1984)

    Google Scholar 

  34. 34. Pohl, E.R., Osterholtz, F.D.: In: Ishida, H., Kumar, G. (eds.) Molecular Characterization of Composite Interfaces, p. 157. Plenum, New York (1985)

  35. 35. Voronkov, M.G., Mileshkevich, V.P., Yuzhelevski, Y.A.: The Siloxane Bond. Consultants Bureau, New York (1978)

  36. 36. Assink, R.A., Kay, B.D.: Sol-gel kinetics III. Test of the statistical reaction model. J. Non-Cryst. Solids 107, 35–40 (1988)

    Article  CAS  Google Scholar 

  37. 37. Assink, R.A., Kay, B.D.: In: Brinker, C.J., Clark, D.E., Ulrich, D.R. (eds.) Better Ceramics through Chemistry, p. 301. North-Holland, New York (1984)

    Google Scholar 

  38. 38. Lee, K., Look, J.L., Harris, M.T., McCormick, A.V.: Assessing extreme models of the Stöber synthesis using transients under a range of initial composition. J. Colloid. Interfac. Sci. 194, 78–88 (1997)

    Article  CAS  Google Scholar 

  39. 39. Xu, Y., Liu, R., Wu, D., Sun, Y., Gao, H., Yuan, H., Deng, F.: Ammonia-catalyzed hydrolysis kinetics of mixture of tetraethoxysilane with methyltriethoxysilane by 29Si NMR. J. Non-Cryst. Solids 351, 2403–2413 (2005)

    Article  CAS  Google Scholar 

  40. 40. Boukari, H., Lin, J.S., Harris, M.T.: Probing the dynamics of the silica nanostructure formation and growth by SAXS. Chem. Mater. 9, 2376–2384 (1997)

    Article  CAS  Google Scholar 

  41. 41. Boukari, H., Long, G., Harris, M.T.: Polydispersity during the formation and growth of the Stober silica particles from small angle X-ray scattering measurements. J. Colloid. Interf. Sci. 229, 129–139 (2000)

    Article  CAS  Google Scholar 

  42. 42. Berthon, S., Barbieri, O., Ehrburger-Dolle, F.: DLS and SAXS investigations of organic gels and aerogels. J. Non-Cryst. Solids 285, 154–161 (2001)

    Article  CAS  Google Scholar 

  43. 43. Krakovsky, I., Urakawa, H., Kajiwara, K., Kohjiya, S.: Time resolved small angle X-ray scattering of inorganic-organic gel formation kinetics. J. Non-Cryst. Solids 231, 31–40 (1998)

    Article  CAS  Google Scholar 

  44. 44. Keefer, K.D., Schaefer, D.W.: Growth of fractal rough colloids. Phys. Rev. Lett. 56, 2376–2379 (1986)

    Article  CAS  Google Scholar 

  45. 45. Craievich, A.F.: SAXS study of the porous fractal structure of tricalcuim silicate dry gels. J. Appl. Crystallogr. 20, 327–329 (1987)

    Article  CAS  Google Scholar 

  46. 46. Marliere, C., Despetis, F., Etienne, P., Phalippou, J.: Two fractal structures in aerogel. J. Non-Cryst. Solids 285, 175–180 (2001)

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, China

    Yao Xu, Xianyong Sun, Dong Wu & Yuhan Sun

  2. State Key Laboratory of Magnetic Resonance & Atomic & Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan, 430071, China

    Yongxia Yang, Hanzhen Yuan & Feng Deng

  3. Laboratory of Synchrotron Radiation, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100039, China

    Zhonghua Wu

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  1. Yao Xu
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Correspondence to Yao Xu.

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Xu, Y., Sun, X., Wu, D. et al. Ammonia Catalyzed Hydrolysis-Condensation Kinetics of Tetraethoxysilane/Dimethyldiethoxysilane Mixtures Studied by 29Si NMR and SAXS. J Solution Chem 36, 327–344 (2007). https://doi.org/10.1007/s10953-006-9117-y

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  • DOI: https://doi.org/10.1007/s10953-006-9117-y

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