Abstract
The chemical composition of amorphous SiOx has been analyzed by oxidation studies and is found to be SiO1.7. SiO1.7 appears to be a monophasic amorphous material on the basis of 29Si nuclear magnetic resonance, high resolution electron microscopy, and comparative behavior of a physical mixture of Si and SiO2. Carbothermal reduction and nitridation reactions have been carried out on amorphous SiO1.7 and on amorphous SiO2 obtained from oxidation of SiO1.7. At 1623 K reactions of SiO1.7 lead exclusively to the formation of Si2N2O, while those of SiO2 lead exclusively to the formation of Si3N4. Formation of copious fibers of α-Si3N4 was observed in the latter reaction. It is suggested that the partial pressure of SiO in equilibrium with reduced SiO1.7 and SiO2 during the reaction is the crucial factor that determines the chemistry of the products. The differences in the structures of SiO2 and SiO1.7 have been considered to be the origin of the differences in the SiO partial pressures of the reduction products formed prior to nitridation. The effect of the ratios, C:SiO1.7 and C:SiO2, in the reaction mixture as well as the effect of the temperature on the course of the reactions have also been investigated.
Similar content being viewed by others
References
R. T. Sanderson, Polar Covalence (Academic Press Inc., London, 1983), p. 53.
H.R. Philipp, J. Non-Cryst. Solids 8–10, 627 (1972).
R. Engelke, Th. Roy, H. G. Neumann, and K. Hübner, Phys. Status Solidi 65, 271 (1981).
R.J. Temkin, J. Non-Cryst. Solids 17, 215 (1975).
S.C.H. Lin and M. Joshi, Electrochem. Soc. 116, 1740 (1969).
J.A. Yasaitis and R. Kaplow, J. Appl. Phys. 43, 995 (1972).
H. Kawamura and M. Matsumura, Solid State Commun. 32, 83 (1979).
H. Mehner, German Patent 88999, Sept. 30 (1896).
A. Hendry and K. H. Jack, Special Ceramics 6, edited by P. Popper (The Brit. Ceram. Res. Ass., Stoke-on-Trent, England, 1975), p. 199.
J.G. Lee and I.B. Cutler, Nitrogen Ceramics, edited by F.L. Riley (Nordoff International Publishers, Leyden, The Netherlands, 1977), p. 175.
H. Inoue, K. Komeya, and A. Tsuge, J. Am. Ceram. Soc. 65, C-205 (1982).
K. Komeya and H. Inoue, J. Mater. Sci. 10, 1243 (1975).
A. Szweda, A. Henry, and K. H. Jack, Special Ceramics 7, edited by P. Popper (The Brit. Ceram. Res. Ass., Stoke-on-Trent, England, 1981), p. 107.
M. Mori, H. Inoue, and T. Ochiai, Prog, in Nitrogen Ceramics (Martinus Nijhoff, The Hague, The Netherlands, 1983), p. 149.
Y. W. Cho and J.A. Charles, Mater. Sci. Technol. 7, 289 (1991).
S.J.P. Durham, K. Shanker, and R.A.L. Drew, J. Am. Ceram. Soc. 74, 31 (1991).
S.A. Siddiqi and A. Hendry, J. Mater. Sci. 20, 3230 (1982).
D.S. Perera, J. Mater. Sci. 22, 2411 (1985).
S.C. Zhang and W.R. Cannon, J. Am. Ceram. Soc. 67, 691 (1984).
V. Figush and T. Licko, High Tech Ceramics, edited by P. Vincenzini (Elsevier Science, Amsterdam, 1987), p. 517.
M. Mitomo and Y. Yoshioka, Adv. Ceram. Mater. 2, 253 (1987).
J.W. Evans and S.K. Chatterji, J. Phys. Chem. 62, 1064 (1958).
K.J. Huttinger, High Temp. High Press. 1, 221 (1969).
D. R. Meisser and P. Wong, J. Am. Ceram. Soc. 56, 480 (1973).
A. Atkinson, A.J. Moulson, and E.W. Roberts, J. Am. Ceram. Soc. 59, 285 (1976).
A. J. Moulson, J. Mater. Sci. 14, 1017 (1979).
H. M. Jennings, J. Mater. Sci. 18, 951 (1983).
S. M. Boyer and A. J. Moulson, J. Mater. Sci. 13, 1637 (1978).
W.M. Dawson and A.J. Moulson, J. Mater. Sci. 13, 2289 (1978).
H. Dervibegovic and F. L. Riley, J. Mater. Sci. 14, 1265 (1979).
F.L. Riley, Nitrogen Ceramics, edited by F. L. Riley (Nordoff International Publishers, Leyden, The Netherlands, 1977), p. 265.
Y. Kaneko, K. Ameyama, and H. Iwasaki, J. Soc. Mater. Sci. Jpn. 37, 65 (1988).
W. E. Knippenberg and Verspui, Silicon Carbide–1968, edited by H. K. Henisch and R. Roy (Pergamon Press, London, 1969), p. 33.
S.B. Hanna, A.L.N. Mansour, and A.S. Taha, Trans. J. Brit. Ceram. Soc. 84, 18 (1985).
R. C. Johnson, J. K. Alley, W. H. Warwick, H. Wilbur, and H. R. Shell, U.S. Patent 3 244 480, April 5 (1966).
M.J. Wang and H. Wada, J. Mater. Sci. 25, 1690 (1990).
H. Saito, T. Hayashi, and K. Miura, Nippon Kagaku Kaishi, 401 (1982).
T. Hayashi, S. Kawabe, and H. Saito, Yogyo Kyokaishi 94, 19 (1986).
M. Mizuhara, M. Noguchi, T. Ishihara, A. Satoh, K. Hiramatsu, and Y. Takita, J. Am. Ceram. Soc. 74, 846 (1991).
A. L. Cunningham and L. G. Davis, SAMPLE 15, 120 (1969).
M. Tanaka and T. Kawabe, Japanese Patent 1324479 (1986).
Y. Kohtoku and K. Masunaga, Japanese Patent Provisional Publication, 61–275199 (1986).
T. Isoda and M. Arai, Jpn. Kokai Tokkyo Koho, Jpn. Patent No. 60–145903 (1985).
K. Niwano, Silicon Nitride-1, edited by S. Sömiya, M. Mitomo, and M. Yoshimura (Elsevier Applied Sciences, London and New York, 1990), Chap. 10.
K. Kijima, N. Setaka, and H. Tanaka, J. Cryst. Growth 24/25, 183 (1974).
S. Motojima, S. Ueno, T. Hattori, and H. Iwanaga, J. Cryst. Growth 96, 383 (1989).
G. Brauer, Handbook of Preparative Inorganic Chemistry (Academic Press, New York, 1963), Vol. 1, p. 458.
L. Brewer and R. K. Edwards, J. Phys. Chem. 58, 351 (1954).
R. Dupree, D. Holland, and D. S. Williams, Philos. Mag. 50, L13 (1984a).
R. Dupree, M.H. Lewis, and M. E. Smith, J. Am. Chem. Soc. 111, 5125 (1989).
R. Dupree, M.H. Lewis, G. Leng-ward, and D.S. Williams, J. Mater. Sci. Lett. 4, 393 (1985).
N. Wada, S. A. Solin, J. Wong, and S. Prochazka, J. Non-Cryst. Solids 43, 7 (1981).
K.V. Damodaran, V.S. Nagarajan, and K.J. Rao, J. Non-Cryst. Solids 124, 233 (1990).
O. Kubaschewski and C.B. Alcock, Metallurgical Thermochemistry, 5th ed. (Pergamon Press, New York, 1989), p. 221.
J. C. Brice, The Growth of Crystals from Liquids (North-Holland Publishing Co., Amsterdam, The Netherlands, 1973), Chap. 3.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Ramesh, P.D., Rao, K.J. Carbothermal reduction and nitridation reaction of SiOx and preoxidized SiOx: Formation of α-Si3N4 fibers. Journal of Materials Research 9, 2330–2340 (1994). https://doi.org/10.1557/JMR.1994.2330
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1557/JMR.1994.2330