Chemically Cross-linked Polysilanes as Stable Polymer Precursors for Conversion to Silicon Carbide

  • Vadapalli Chandrasekhar
  • Venkatasubbaiah Krishnan
  • Palani Sasikumar
  • Varanasi S. R. Murthy

Cross-linked polysilanes were prepared by the co-polymerization of Me2SiCl2 or PhMeSiCl2 with varying amounts of divinylbenzene (2–15% by weight) using molten sodium as the dehalogenating agent. All the cross-linked polysilanes were stable to air and could be processed thermally for conversion to silicon carbide. Polymers containing from 5–15% of the cross-linking agent underwent a uniform shrinkage during thermal treatment (1500 °C) to afford β-SiC in good yields. The ceramic was characterized by a variety of techniques including Raman and infrared spectroscopy, powder XRD, as well as Scanning Electron Microscopy (SEM).


silicon carbide silicon cross-linked polysilanes chemical cross-linking 



We thank MHRD, India for financial support. VK is thankful to CSIR – India for a Senior Research Fellowship. We are thankful to Prof. Kiyohito Okamura, Department of Metallurgy and Materials Science Graduate School of Enggineering, Osaka Prefecture University, Osaka 599–8531, Japan for his help in performing high-temperature pyrolyis.


  1. 1.
    (a) F. Babonneau, and G. D. Soraru, J. Eu. Ceram. Soc. 8, 29 (1991). (b) R. Riedel, M. Seher, J. Mayer, and D. V. Szab’o, J. Eu. Ceram. Soc. 15, 703 (1995). (c) M. D. Sacks, A. A. Morrone, G. W. Scheiffele, and M. Saleem, Ceram. Engg. Sci. Proc. 16, 25 (1995). (d) R. Riedel, A. Kienzle, W. Dressler, L. Rwisch, J. Bill, and F. Aldinger, Nature 382, 796 (1996). (e) N. I. Baklanova, V. N. Kylyukin, N. Z. Lyazhov, G. Yu. Turikina, O. G. Yarosh, and M. G. Voronkov, J. Mater. Syn. Proc. 5, 443 (1997). (f) T. Ishikawa, S. Kajii, T. Hisayuki, K. Matsunga, T. Hogami, and Y. Kohtoku, Proc. Of the Int. Conf. In High Temp. Ceramic Matric Composites, Osaka, Japan, Sep. 6–9, 15 (1998). (g) A. Idesaki, M. Narisawa, K. Okamura, M. Sugimoto, Y. Morita, T. Seguchi, and M. Itoch, Proc. Of the Int. Conf. In High Temp. Ceramic Matric Composites, Osaka, Japan, Sep. 6–9, 39 (1998). (h) C. Yuan, M. Fujino, K. Ebata, and K. Furukawa, Macromolecules 30, 7618 (1997). (i) T. Ishikawa, Silicon Carbide Ceramics, vol. 2 (Elsevier Applied Science, London and New York, 1991). (j) S. Yajima, and K. J. Okamura, Mater. Sci. 16, 3033 (1981). (k) J. B. John, and M. P. Karl, J. Mater. Sci. 17, 2371 (1982)Google Scholar
  2. 2.
    (a) M. Birot, J. Pilot, and J. Dunogues, Chem. Rev. 95, 1443 (1995). (b) Q. Liu, H. J. Wu, R. Lewis, G. E. Maciel, and L. V. Interrante, Chem. Mater. 11, 2038 (1999). (c) A. T. Hemida, M. Pillot, J. Dunogues, and R. Pailler, Chem. Commun. 2337 (1994). (d) H.-P. Baldus and M. Janses, Angew. Chem. Int. Ed. Engl. 36, 328 (1997). (e) A. R. Brunner, D. R. Bujalski, E. S. Moyer, K. Su, and L. G. Sneddon, Chem. Mater. 12, 2770 (2000)Google Scholar
  3. 3.
    (a) S. Yajima, M. Omori, J. Hayashi, K. Okamura, T. Matsuzawa, and C. Liaw, Chem. Lett. 551 (1976). (b) S. Yajima, J. Hayashi, and M. Omori, Chem. Lett. 931 (1975). (c) S. Yajima, K. Okamura, and J. Hayashi, Chem. Lett. 1209 (1975). (d) S. Yajima, J. Hayashi, M. Omori, and K. Okamura, Nature 261, 683 (1976)Google Scholar
  4. 4.
    (a) K. S. Mazdiyasni, R. West, and L. D. David, J. Am. Cerm. Soc. 61, 504 (1978). (b) R. West, L. D. David, P. I. Djurovich, K. L. Sterky, K. S. V. Srinivasan, and H. Yu, J. Am. Chem. Soc. 103, 7352 (1981). (c) R. West, L. D. David, P. I. Djurovich, and H. Yu, Ceramic Bull. 62, 899 (1983)Google Scholar
  5. 5.
    (a) S. Prochazka, and R. M. Scanlan, J. Am. Ceram. Soc. 58, 72 (1975). (b) C. Greskovich, and J. H. Rosolowski, J. Am. Ceram. Soc. 59, 336 (1976). (c) H. Suzuki, and T. Hase, J. Am. Ceram. Soc. 63, 349 (1980). (d) D. H. Stutz, S. Prochazka, and J. Lorenz, J. Am. Ceram. Soc. 68, 479 (1985). (e) K. Negita, J. Am. Ceram. Soc. 69, C-308 (1986). (f) G. Passing, R. Riedel, and G. Petzow, J. Am. Ceram. Soc. 74, 642 (1991). (g) J. J. Cao, W. J. MoberlyChan, L. C. De Jonghe, C. J. Gilbert, and R. O. Ritchie, J. Am. Ceram. Soc. 79, 461 (1996). (h) R. Vassen, A. Kaiser, J. Forster, H. P. Buchkremer, and D. J. Stover, Mater. Sci. 31, 3623 (1996). (i) H. Tenailleau, X. Bourrat, R. Naslain, R. E. Tressler, and L. A. Giannuzzi, J. Am. Ceram. Soc. 81, 2037 (1998). (j) H. Gu, Y. Shinoda, F. Wakai, J. Am. Ceram. Soc. 82, 469 (1999)Google Scholar
  6. 6.
    (a) M. T. Hsu, T. S. Chen, and S. R. Riccitiello, J. Appl. Polym. Sci. 42, 851 (1991). (b) V. P. Gutenberger, W. Abel, C. Nover, and P. Sartori, J. Organomet. Chem. 543, 1 (1993). (c) M. Eber, and L. E. Jones, Ceram. Eng. Sci. Proc. 19, 485 (1998). (d) G. T. Burns, and G. A. Zank, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 34, 343 (1993). (e) A. R. Puerta, E. E. Remsen, M. G. Bradley, W. Sherwood, and L. G. Sneddon, Chem. Mater. 15, 478 (2003)Google Scholar
  7. 7.
    (a) J. A. Rabe, J. Lipowitz, and P. P. Lu, U.S. Patent 5,051,215,1991. (b) D. C. Deleeuw, J. Lipowitz, and P. P. Lu, U.S. Patent 5,071,600,1992. (c) J. Lipowitz, T. Barnard, D. Bujalski, J. Rabe, G. Zank, A. Zangvil, and Y. Xu, Comput. Sci. Technol. 51, 167 (1994). (d) J. Lipowitz, J. A. Rabe, A. Zangvil, and Y. Xu, Ceram. Eng. Sci. Proc. 18, 147 (1997). (e) A. Tazi Hemida, R. Pailler, M. Birot, J. P. Pillot, and J. Dunogues, J. Mater. Sci. 32, 3237 (1997). (f) A. Tazi Hemida, H. Tennailleau, L. Bardeau, R. Pailler, M. Birot, J. P. Pillot, and J. Dunogues, J. Mater. Sci. 32, 5791 (1997)Google Scholar
  8. 8.
    V. Krishnan, R. Bindu, V. Chandrasekhar, V. S. R. Murthy (2002) J. Am. Ceram. Soc. 85:504CrossRefGoogle Scholar
  9. 9.
    B.S. Furniss, A. J. Hannaford, P. W. G. Smith, A. R. Tatchell, Vogel’s Textbook of Practical Organic Chemistry, 5th ed. (Longman, London, 1989)Google Scholar
  10. 10.
    M. Rama Rao, S. Packirisamy, P. V. Ravindran, P. K. Narendranath (1992) Macromolecules 25:5165CrossRefGoogle Scholar
  11. 11.
    T. S. Radhakrishnan (2006) J. Appl. Polym. Sci. 99:2679CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2007

Authors and Affiliations

  • Vadapalli Chandrasekhar
    • 1
  • Venkatasubbaiah Krishnan
    • 1
  • Palani Sasikumar
    • 1
  • Varanasi S. R. Murthy
    • 2
  1. 1.Department of ChemistryIndian Institute of Technology – KanpurKanpurIndia
  2. 2.Department of Materials and Metallurgical EngineeringIndian Institute of Technology – KanpurKanpurIndia

Personalised recommendations