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Combustion Characteristics for Producing Titanium Carbonitride Ceramics by Combustion Synthesis
Sang Hwan Kim†, Tae-Sung Kang, June-Bong Kim and Kong Won Kang*
Department of Chemical Engineering, Konkuk University, Seoul 143-701, Korea
*Central Research Laboratory, Aekyung Industrial Co., Daejeon 300-200, Korea (Received 7 March 2001; accepted 24 July 2001)
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Abstract−The combustion synthesis of titanium carbonitride ceramics with excellent hardness and chemical stability to oxi- dation at high temperatures was investigated. The compacted reactants remained at a relatively high temperature for the greater length of time after the passage of combustion front transversing the compact. After-burn time of about 20 to 100 seconds was detected for producing titanium nitride and titanium carbonitride ceramics. After-burn time increased with the increasing ratio of carbon to titanium in the reactants, reached the maximum value at its ratio of 0.7, and thereafter decreased with the further increasing ratio of carbon to titanium. The combustion temperatures as well as the velocity of combustion waves increased with the increasing ratio of carbon to titanium in the reactants. The velocity of combustion waves reached the constant value of 0.4 cm/sec at higher ratio of carbon to titanium than 0.70 in the reactants. The microstructure of combustion-synthesized titanium carbide using the carbon black as carbon source showed the existence of titanium melting during the combustion reaction and the capillary spreading of melted titanium between the interstices of solid carbon. The surface of combustion-synthesized tita- nium carbonitride revealed that the carbon black was active for producing the carbonitride ceramics and the decreasing ratio of carbon to titanium in the reactants enhanced the melting of the titanium during the reaction.
Key words: Titanium Carbonitride, Combustion Synthesis, After-burn Time, Combustion Waves, Ceramics
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†To whom correspondence should be addressed.
E-mail: sanghkim@konkuk.ac.kr
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Fig. 2. Phase diagram of the binary Ti-C system[20].
Fig. 3. Phase diagram of the binary Ti-N system[21].
Table 1. Description of titanium and carbon reactants in the powder
Designation Composition Manufacture Purity(%) Mean particle size(µm)
Ti Titanium Cerac co. 99.5 31
C1 Graphite Cerac co. 99.9 10
C2 Activated carbon Aldrich co. 95.0 33
C3 Carbon black Lucky metals corp. 99.9 0.2
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Fig. 5. Sequential photographs of combustion waves showing (a) the stable combustion and (b) the after-burn reaction for produc- ing titanium carbonitride(TiCxN1−x).
Fig. 6. Effect of particle sizes of titanium on the combustion velocity(,,) and combustion temperature(55) for producing the stoichiomet- ric titanium carbide(TiC). Carbon is graphite(C1).
Fig. 7. Effect of product dilution on the combustion velocity(,,) and combustion temperature(55) for producing the stoichiometric titanium carbide(TiC). Carbon is graphite(C1).
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Fig. 8. Effect of relative density of compacts on the combustion veloc- ity(,,) and combustion temperature(55) for producing the sto- ichiometric titanium carbide(TiC). Carbon is graphite(C1).
Fig. 9. Effect of product dilution on the after-burn time(éé) and weight gain(,,) for producing the stoichiometric titanium nitride(TiN).
Table 2. Comparison of combustion velocity and after-burn time for producing combustion-synthesized titanium products
Product1) Ignition temperature Combustion temperature Combustion wave velocity After-burn time(sec)
TiC 560 1,855 0.57 -
TiCxN1−x2) 550 1,630 0.42 21-51
TiN 980 1,480 0.38 33-102
1)Carbon is graphite(C1).
2)Stoichiometry x is 0.7.
Fig. 10. Effect of the ratio of carbon to titanium on the combustion veloc- ity(,,) and combustion temperature(55) for producing the sub- stoichiometric titanium carbonitride(TiCxN1−x). Carbon is acti- vated carbon(C2).
Fig. 11. Effect of relative density of compacts on the after-burn time(,,) and combustion temperature(55) for producing the substoichio- metric titanium carbonitride(TiCxN1−x, x=0.7). Carbon is graphite (C1).
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Fig. 12. Effect of the ratio of carbon to titanium on the after-burn time (,,) for producing the substoichiometric titanium carbonitride (TiCxN1−x). Carbon is graphite(C1).
Fig. 13. Photographs of (a) TiC, (b) TiCxN1−x and(c) TiNceramics pro- duced by combustion synthesis. Carbon is graphite(C1).
Fig. 14. Scanning electron micrograph of combustion-synthesized stoi- chiometric titanium carbide(TiC) using the (a) carbon black (C3) and (b) graphite(C1).
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Fig. 15. Scanning electron micrograph of combustion-synthesized tita- nium nitride(TiN) in the (a) exterior and (b) interior surface of the products.
Fig. 16. Scanning electron micrograph of combustion-synthesized sub- stoichiometric titanium carbonitride(TiCxN1−x) with the ratios of (a) C/Ti=0.7 and (b) C/Ti=0.65. Carbon is carbon black(C3).
Fig. 17. X-ray diffraction patterns of combustion-synthesized substoi- chiometric titanium carbonitride(TiCxN1−x, x=0.65) using the (a) carbon black(C3) and (b) activated carbon(C2).
Fig. 18. X-ray dot maps of combustion-synthesized substoichiometric titanium carbonitride(TiCxN1−x, x=0.6) for the elements of (b) titanium, (c) carbon and (d) nitrogen.
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1. Merzhanov, A. G. and Borovinskaya, I. P.: Combust. Sci. & Tech., 10, 195(1975).
2. Crider, J. F.: Ceram. Eng. Sci. Proc., 3, 519(1982).
3. McCauley, J. W.: Ceram. Eng. Sci. Proc., 11, 1137(1990).
4. Hlavecek, V.: Am. Ceram. Soc. Bull., 69, 537(1990).
5. Munir, Z. A. and Anselmi-Tamburini, V.: Mater. Sci. Report, 3, 277(1989).
6. Munir, Z. A.: Ceram. Bull., 67, 342(1988).
7. McCauley, J. W.: Ceram. Eng. Sci. Proc., 9, 503(1988).
8. Frankhouser, W. L.: “Advanced Processing of Ceramic Compounds,”
Noyes Data Corp., Park Ridge, New Jersey(1987).
9. Toth, L. E.: “Transition Metal Carbides and Nitrides,” Academic Press, New York(1971).
10. Storms, E. K.: “The Rafractory Carbides,” Academic Press, New York(1967).
11. Stasyuk, L. F. and Neshpor, V. S.: Sov. Powder Metall. Ceram., 18, 851(1988).
12. Kim, S. H.: Chemical Industry and Technology, 8, 506(1990).
13. Shkiro, V. M., Borovinskaya, I. P. and Merzhanov, A. G.: Sov. Pow- der Metall. Ceram., 18, 684(1979).
14. Arbuzov, M. P., Moshkovskii, E. I. and Lyashchenko, A. B.: Sov.
Powder Metall. Ceram., 20, 426(1981).
15. Kirdyashkin, A. I., Maksimov, Yu. M. and Nekrasov, E. A.: Com- bust. Explos. & Shock Waves, 17, 377(1981).
16. Nekrasov, E. A., Smolyakov, V. K. and Maksimov, Yu. M.: Comb.
Explos. & Shock Waves, 17, 513(1982).
17. Holt, J. B. and Munir, Z. A.: J. Mat. Sci., 21, 251(1986).
18. Sarian, S.: J. of Appl. Phys., 39, 3305(1968).
19. Sarian, S.: J. of Appl. Phys., 40, 3515(1969).
20. Baldoni, J. G. and Buljan, S. T.: Ceram. Bull., 67, 381(1988).
21. Pierson, H. O.: “Handbook of Chemical Vapor Deposition,” pp. 213 (1992).
22. Munir, Z. A., Deevi, S. D. and Eslamloo-Grami, M.: High Tempera- ture-High Pressure, 20, 19(1988).
23. Deevi, S. and Munir, Z. A.: J. Mater. Res., 5, 2177(1990).
24. Munir, Z. A. and Holt, J. B.: J. Mater. Sci., 22, 710(1987).
25. Eslamloo-Grami, M. and Munir, Z. A.: J. Am. Ceram. Soc., 73, 2222 (1990).
26. Eslamloo-Grami, M. and Munir, Z. A.: J. Am. Ceram. Soc., 73, 1235 (1990).
27. Agrafiotis, C. C., Puzynski, J. A. and Hlavacek, V.: Combust. Sci. &
Tech., 76, 187(1991).
