Abstract
The relationship between the microstructure and phase composition of a product obtained by selfpropagating high-temperature synthesis (SHS) and different reaction mechanisms is studied using the example of silicon nitride. The formation of nanosized silicon nitride particles upon the combustion of silicon in nitrogen and other phenomena typical of substances of this class, such as self-organization and self-assembly, are observed. The chemical condensation SHS of silicon nitride is studied in the presence of inorganic salts as modifying additives. The resulting Si3N4 powders have a structure of secondary spherical particles being composed of primary ultrafine and nanosized ones. The Si3N4 powders under study were fractionated depending on the particles size and microstructure by chemical dispersion. Ultrafine particles of the light fraction form as homogeneous rods by the conventional vapor–liquid–crystal mechanism. The fine-crystalline fractions are formed by hollow crystals assembled into globules. Microstructural analysis shows that the crystal walls consist of nanosized Si3N4 particles. The effects of organic additives introduced into the charge stock on the phase formation, microstructure formation, and particle size of SHS silicon nitride are studied. The combustion products are found to be composite powders whose phase compositions depend on the additive and the synthesis conditions. According to the data from X-ray powder diffraction and chemical analysis, the final products can contain up to 100% of β-Si3N4, up to 60% of α-Si3N4, up to 80% of SiC, and up to 70% of Si2N2O. It is shown that silicon nitride-based composite powders containing silicon carbide and/or silicon oxynitride can be obtained in one step. The role of ferric chloride hexahydrate as the SHS catalyst is studied. An ultrafine structurally homogeneous powder of β-Si3N4 is obtained in the presence of FeCl3 · 6H2O.
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References
G. Ziegler, J. Heinrich, and W. Wotting, “Relationships between processing, microstructure and properties of dense and reaction-bonded silicon nitride,” J. Mater. Sci. 22, 3041–3086 (1987).
F. L. Riley, “Silicon nitride and related materials,” J. Am. Ceram. Soc. 83, 245–265 (2000).
F. Munakata, K. Matsuo, K. Furuya, Y. Akimune, and I. Ishikawa, “Optical properties of β-Si3N4 single crystals grown from a Si melt in N2,” Appl. Phys. Lett. 74, 3498–3500 (1999).
J. Zaman and A. Chakma, “Inorganic membrane reactors,” J. Membr. Sci. 92, 1–28 (1994).
A. Jonker and J. H. Potgieter, “An evaluation of selected waste resources for utilization in ceramic materials applications,” J. Eur. Ceram. Soc. 25, 3145–3149 (2005).
F. C. Peillon and F. Thevenot, “Microstructural designing of silicon nitride related to toughness,” J. Eur. Ceram. Soc. 22, 271–278 (2002).
A. Tsuge, K. Nishida, and M. Komatsu, “Effect of crystallising the grain-boundary glass phase on the high temperature strength of hot-pressed Si3N4 containing Y2O3,” J. Am. Ceram. Soc. 58, 323–326 (1975).
M. K. Cinibulk, G. Thomas, and S. M. Johnson, “Fabrication and secondary-phase crystallization of rareearth disilicate–silicon nitride ceramics,” J. Am. Ceram. Soc. 75, 2037–2043 (1992).
H. J. Kleebe, G. Pezzotti, and G. Ziegler, “Microstructure and fracture toughness of Si3N4 ceramics: combined roles of grain morphology and secondary phase chemistry,” J. Am. Ceram. Soc. 82, 1857–1867 (1999).
G. Pezzotti and H. J. Kleebe, “Effect of residual microstresses at crystalline multigrain junctions on the toughness of silicon-nitride,” J. Eur. Ceram. Soc. 19, 451–455 (1999).
S. Q. Guo, N. Hirosaki, Y. Yamamoto, T. Nishimura, and M. Mitomo, “Strength retention in hot-pressed Si3N4 ceramics with Lu2O3 additives after oxidation exposure in air at1500degrees C,” J. Am. Ceram. Soc. 85, 1607–1609 (2002).
S. Q. Guo, N. Hirosaki, T. Nishimura, Y. Yamamoto, and M. Mitomo, “Hot-pressed silicon nitride with Lu2O3 additives: oxidation and its effect on strength,” J. Am. Ceram. Soc. 86, 1900–1905 (2003).
S. Q. Guo, N. Hirosaki, Y. Yamamoto, T. Nishimura, and Y. Kagawa, “Hot-pressed Si3N4 ceramics with Lu2O3 additives: grain-boundary phase and strength,” Mater. Sci. Eng. A 408, 9–18 (2005).
A. G. Merzhanov, “Self-propagating high-temperature synthesis,” in Physical Chemistry: Modern Problems, Ed. by Ya. M. Kolotyrkin (Khimiya, Moscow, 1983), pp. 5–45 [in Russian].
A. G. Merzhanov, “Combustion: new manifestation of an ancient process,” in Chemistry of Advanced Materials, Ed. by C. N. R. Rao (Blackwell Scientific, 1992), pp. 19–39.
K. Hirao, V. Miamoto, and M. Koizumi, “Synthesis of silicon nitride by a combustion reaction under high nitrogen pressure,” J. Am. Ceram. Soc. 69(4), 60–65 (1986).
A. S. Mukas’yan, V. M. Martynenko, A. G. Merzhanov, I. P. Borovinskaya, and M. Yu. Blinov, “Mechanism and principles of silicon combustion in nitrogen,” Fiz. Goreniya Vzryva, No. 5, 43–49 (1986).
A. S. Mukas’yan, B. V. Stepanov, Yu. A. Gal’chenko, and I. P. Borovinskaya, “Mechanism of structure formation of silicon nitride with combustion of silicon in nitrogen,” Fiz. Goreniya Vzryva 5, 45–52 (1990).
V. V. Zakorzhevskii and I. P. Borovinskaya, “Some regularities of α-Si3N4 sythesis in a commercial SHS reactor,” Int. J. SHS 9, 171–192 (2000).
V. V. Grachev, B. N. Shatalov, and I. P. Borovinskaya, “Characteristics of silicon powder combustion process in gaseous nitrogen,” in Proceedings of the All-Russia Conference on Processes of Combustion and Explosion in Physicochemistry and Technology of Inorganic Materials, Moscow, June 24–27, 2002, pp. 89–93.
G. H. Peng, G. J. Jiang, H. R. Zhuang, W. L. Li, and S. Y. Xu, “Fabrication of a-Si3N4 whiskers by combustion synthesis with MgSiN2 as additives,” Mater. Res. Bull. 40, 2139–2143 (2005).
I. G. Cano, S. P. Baelo, M. A. Rodriguez, and S. de Aza, “Self-propagating high-temperature synthesis of Si3N4: role of ammonium salt addition,” J. Eur. Ceram. Soc. 21, 291–295 (2001).
A. G. Merzhanov, I. P. Borovinskaya, V. V. Zakorzhevskii, L. P. Savenkova, and T. I. Ignat’eva, “A method for producing a silicon nitride with a high content of a-phase,” Inventor’s Certificate RU2137708C1 No. 98104981/25, Byull. Izobret. No.26(1999).
I. P. Borovinskaya, T. I. Ignat’eva, V. I. Vershinnikov, O. M. Miloserdova, and V. N. Semenova, “SHS of ultra- and nano-dispersive tungsten and titanium carbide powders,” Poroshk. Metallurg., No. 9, 3–12 (2008).
T. I. Ignat’eva, O. M. Miloserdova, V. N. Semenova, and I. P. Borovinskaya, “Extraction of ultra- and nanodispersive titanium carbide powders by chemical dispergation,” Perspekt. Mater., No. 3,82(2009).
I. P. Borovinskaya, T. V. Barinova, V. I. Vershinnikov, and T. I. Ignat’eva, “SHS of ultrafine and nanosized refractory powders: an autoreview,” Int. J. SHS 19, 116–121 (2010).
I. M. Maslov, I. P. Borovinskaya, and A. G. Merzhanov, “Experimental deriving of maximum temperatures of SHS processes,” Fiz. Goreniya Vzryva14(5), 79–85 (1978).
T. I. Ignat’eva, “Some features of chemical analysis of SHS materials,” in Self-Propagating High-Temperature Synthesis: Theory and Practice (Territoria, Chernogolovka, 2001), pp. 385–397 [in Russian].
V. V. Zakorzhevskii and I. P. Borovinskaya, “SHS of a-Si3N4 from fine Si-powders in the presence of blowing agents,” Int. J. SHS 20, 156–160 (2011).
W. Yang, Z. Xie, H. Miao, L. Zhang, H. Ji, and L. An, “Synthesis of single-crystalline silicon nitride nanobelts via catalyst assisted pyrolysis of a polysilazane,” J. Am. Ceram. Soc. 88,466(2005).
M. Ahmad, J. Zhao, C. Pan, and J. Zhu, “Ordered arrays of high-quality single-crystalline α-Si3N4 nanowires: synthesis, properties and applications,” J. Cryst. Growth 311, 4486–4490 (2009).
H. Remy, Course of Inorganic Chemistry, (Inostr. Liter., Moscow, 1966; Akademische Verlaggsellschaft Geest and Portig, Leipzig, 1954).
T. V. Barinova and I. P. Borovinskaya, “Combustion of silicon powders containing organic additives in nitrogen gas under pressure. 1: Effect of Dopants on combustion phenomenology,” Int. J. SHS 18, 25–29 (2009).
T. V. Barinova and I. P. Borovinskaya, “Combustion of silicon powders containing organic additives in nitrogen gas under pressure. 2: Composition of combustion products,” Int. J. SHS 18, 30–33 (2009).
A. N. Nesmeyanov and N. A. Nesmeyanov, Beginnings of Organic Chemistry (Khimiya, Moscow, 1974), Vol. 2, p.491[in Russian].
P. A. Tesner, Carbon Formation from Hydrocarbons in the Gas Phase (Khimiya, Moscow, 1972), p.136[in Russian].
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Original Russian Text © I.P. Borovinskaya, T.V. Barinova, T.I. Ignatieva, 2015, published in Rossiiskie Nanotekhnologii, 2015, Vol. 10, Nos. 9–10.
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Borovinskaya, I.P., Barinova, T.V. & Ignatieva, T.I. SHS of ultrafine and nanosized Si3N4 powders: The effect of inorganic and organic additives on the microstructures, morphology, and phase compositions of products. Nanotechnol Russia 10, 763–776 (2015). https://doi.org/10.1134/S199507801505002X
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DOI: https://doi.org/10.1134/S199507801505002X