Abstract
A fluidized-bed nitridation of pelletized silicon grains having a wide size distribution was carried out in the temperature range 1200–1300°C under conditions free of external heat and mass transfer effects. N2(30%–90%)–H2(5%–50%)–Ar (balance) mixtures were used as the nitriding gas at atmospheric pressure. Both the yield of α-Si3N4 and the final overall conversion of silicon are affected by temperature and nitrogen gas concentration in a nitriding atmosphere, but hydrogen gas has a minor effect on either of these. After accounting for some of the structural changes that occur during nitridation, a simple model was derived. The model has shown that the pseudo-asymptotic exponential conversion trend in the second nitridation stage could be explained by various reaction mechanisms, adjusted for properties of the size distribution of silicon grains and the experimentally observed spalling of the product scale from the silicon surface. In the investigated range of experimental conditions, nitridation could be considered as having an apparent activation energy of Eapp≈340 kJ mol-1. © 1998 Chapman & Hall
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References
F. F. Lange, J. Am. Ceram. Soc. 62 (1979) 428.
W. H. Rhodes and S. Natansohn, Ceram. Bull. 68 (1989) 1804.
T. Yamada, Am. Ceram. Soc. Bull. 72(5) (1993) 99.
F. K. Dijen, A. Kerber, U. Vogt, W. Pfeiffer and M. Schulze, “Key Engineering Materials 89–91” (Trans. Tech. Publications, Switzerland, 1994) p. 19.
Dong-Duk Lee, S. L. Kang, G. Petzow and D. N. Yoon, J. Am. Ceram. Soc. 73 (1990) 767.
G. Hillinger and V. Hlavacek, Interceram. 43 (1994) 333.
R. A. L. Drew, Cerâmica 35 (237) (1989) 129.
F. Cambier and A. Leriche, in “The Physics and Chemistry of Carbides; Nitrides and Borides”, edited by R. Freer (Kluwer Academic, The Netherlands, 1990) pp. 13–28.
D. Geldart, Chem. Eng. Sci. 39 (1984) 1481.
D. Kunii and O. Levenspiel, “Fluidization Engineering”, 2nd Edn (Butterworth—Heinemann, Boston, 1991).
M. Shimizu, European Pat. Applic. no. 90 114 382.6 (1991).
M. Shimizu, H. Fukuoka and M. Fukuhira, US Pat. no. 5073 385 (1991).
H. Fukuoka, M. Shimizu, H. Ochiai, H. Shimizu and M. Fukuhira, US Pat. no. 5232 677 (1993).
P. E. D. Morgan, J. Mater. Sci. 15 (1980) 791.
M. Barsoum, P. Kangutkar and M. J. Koczak, J. Am. Ceram. Soc. 74 (1991) 1248.
R. G. Pigeon, A. Varma and A. E. Miller, J. Mater. Sci. 28 (1993) 1919.
M. W. Lindley, D. P. Elias, B. F. Jones and K. C. Pitman, ibid. 14 (1979) 70.
H. Dervisbegovic and F. L. Riley, ibid. 16 (1981) 1945.
W. M. Dawson and A. J. Moulson, ibid. 13 (1978) 2289.
T. Itoh, J. Mater. Sci. Lett. 10 (1991) 19.
H. M. Jennings, J. Mater. Sci. 18 (1983) 951.
Z. R. Jovanovics, S. Kimura and O. Levenspiel, J. Am. Ceram. Soc. 77 (1994) 186.
D. Campos-Loriz and F. L. Riley, J. Mater. Sic. 13 (1978) 1125.
A. Atkinson, A. J. Moulson and E. W. Robert, J. Am. Ceram. Soc. 59 (1976) 285.
H. Dervisbegovic and F. L. Riley, J. Mater. Sci. 14 (1979) 1265.
H. M. Jennings, B. J. Dagleish and P. L. Pratt, ibid. 23 (1988) 2573.
D. S. Thompson and P. L. Pratt, in “Science of Ceramics”, Vol. 3, edited by G. H. Stewart (Academic Press, New York, 1967) p. 33.
Y. Inomata, J. Ceram. Soc. Jpn 83 (1975) 497.
Y. Inomata and Y. Uemura, ibid. 83 (1975) 244.
J. Koike and S. Kimura, J. Am. Ceram. Soc. 79 (1996) 365.
M. N. Rahaman and A. J. Moulson, J. Mater. Sci. 19 (1984) 189.
B. Myhre and K. Motzfeldt, in “The Physics and Chemistry of Carbides; Nitrides and Borides”, edited by R. Freer (Kluwer Academic, The Netherlands, 1990) p. 29.
B. W. Sheldon. J. Szekely and J. S. Hagerty, J. Am. Ceram. Soc. 75 (1992) 677.
Y. D. Liu and S. Kimura, Powder Technol. 75 (1993) 189.
Z. R. Jovanovic, PhD dissertation, Oregon State University, Corvallis, OR, USA (1994).
Z. R. Jovanovic and S. Kimura, J. Am. Ceram. Soc. 77 (1994) 2226.
R. G. Pigeon and A. Varma, J. Mater. Sci. 28 (1993) 2999.
W. Ku, O. Gregory and H. M. Jennings, J. Am. Ceram. Soc. 73 (1990) 286.
J. Szekely, J. W. Evans and H. Y. Sohn, “Gas-Solid Reactions” (Academic Press, New York, 1976).
J. Heinrich, Eur. Space Agency Report no. N–81–22113, December 1990.
N. J. Shaw and F. J. Zeleznik, Commun. Am. Ceram. Soc. 65 (1982) C-180.
J. Heinrich and G. Streb, J. Mater. Sci. 14 (1979) 2083.
S. Kimura, personal communication, Chemical Engineering Department, Oregon State University, Corvallis, OR 97331, USA (1995).
I. J. R. Baumvol, F. C. Stedile, J. J. Ganem, S. Rigo and I. Trimaille, J. Electrochem. Soc. 142 (1995) 1205.
K. Kijima, and S. Shirsaki, J. Chem. Phys. 65 (1976) 2668.
J. W. Christian, in “The Theory of Transformations in Metals and Alloys; Part I-Equilibrium and General Kinetic Theory”, 2nd Edn (Pergamon Press, Oxford, 1975) pp. 410–17.
R. M. Barrer, “Dissusion in and through Solids” (Cambridge University Press, Cambridge, 1951).
S. M. Sze, “Physics of Semiconductor Devices” (Wiley, New York, 1981).
A. F. Wells, “Structural Inorganic Chemistry”, 3rd Edn (Oxford University Press, New York, 1962).
A. T. Fromhold Jr, in “Defects in Crystalline Solids: Fundamentals”, Vol. 9, edited by S. Amelinckx, R. Gevers and J. Nihoul (North-Holland, Amsterdam, New York, Oxford, 1976) p. 28.
Y. Hayafuji and K. Kajiwara, J. Electrochem. Soc. Solid State Sci. Technol. 129 (1982) 2102.
O. Kubaschewski and B. E. Hopkins, “Oxidation of Metals and Alloys”, 2nd Edn (Butterworths, London, 1962).
M. I. Mendelson, J. Mater. Sci. 14 (1979) 1752.
H. M. Jennings and M. H. Richman, ibid. 11 (1976) 2087.
U. R. Evans, “The Corrosion and Oxidation of Metals: Scientific Principles and Practical Applications” (Edward Arnold, London, 1967).
G. A. Rossetti Jr and R. P. Denkewicz Jr, J. Mater. Sci. 24 (1989) 3081.
S. Yagi and D. Kunii, in “Proceedings of the Fifth International Symposium on Combustion (1955)” (Van Nostrand Reinhold, New York, 1955) p. 231.
G. Valensi, Comput. Rend. 202 (1936) 309.
R. E. Carter, J. Chem. Phys. 34 (1961) 2010.
Z. R. Jovanovic, J. Mater. Sci. Lett. 14 (1995) 1263.
PSI-PLOT, “Technical Plotting and Data Processing” (Poly Software International Ltd, Salt Lake City, 1993).
O. Levenspiel, “The Chemical Reactor Omnibook” (OSU Book Stores, Corvallis, OR 97331, 1993).
S. Kimura, Y. Takagi, S. Tone and T. Otake, J. Chem. Eng. Jpn 16 (3) (1983) 217.
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Jovanovic, Z.R. Kinetics of direct nitridation of pelletized silicon grains in a fluidized bed: experiment, mechanism and modelling. Journal of Materials Science 33, 2339–2355 (1998). https://doi.org/10.1023/A:1004395506202
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DOI: https://doi.org/10.1023/A:1004395506202