Abstract
The mechanism and the kinetics of the oxidation in an air flow of powdery Nb–Si eutectic alloy containing (wt %) 93.0 Nb, 6.7 Si, and 0.27 B are studied by X-ray diffraction (XRD), thermogravimetric (TG), and differential thermal analysis (DTA). The oxidation of alloy proceeds through three stages. At the first stage (600–923 K), the oxidation of a Nb ss solid solution (with the formation of Nb2O5, NbO0.76, NbO, and NbO2 oxides) and boron (to B2O3) released during the conversion of the Nb5Si3–x B x phase (T2 phase) into Nb5SiB y (D88) occurs. At the second stage (923–993 K), the accumulation of the product layer and the formation of borosilicate occur, which prevents the oxidation. At the third stage, Nb3Si and Nb5SiB y (D88) silicides and Nb3B2 niobium boride are oxidized. Under heating above 1023 K, the interaction of boron oxide with niobium oxide occurs with the formation of Nb3BO9. The possible oxidation mechanisms are considered. It is shown that are well described by the model of three successive stages, each one limited by the kinetic regime.
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Bewlay, B.P., Jackson, M.R., Zhao, J.C., and Subramanian, P.R., A review of very-high-temperature Nb–silicide-based composites, Metall. and Mater. Trans., A, 2003, vol. 34, pp. 2043–2052.
Grashchenkov, D.V., Shchetanov, B.V., and Efimochkin, I.Yu., Development of powder metallurgy of refractory materials, Vse Mater., 2011, no. 5. http://www.viam.ru/public.
Kocherzhinskii, Yu.A., Yupko, L.M., and Shishkin, E.A., Equilibrium diagram of the Nb–Si system, Metally (Moscow), 1980, no. 1, pp. 206–210.
Schlesinger, M.E., Okamoto, H., Gokahle, A.B., and Abbaschian, R., The Nb–Si (niobium-silicon) system, J. Phase Equilib., 1993, vol. 14, no. 4, pp. 502–509.
Chumarev, V.M., Leont’ev, L.I., Udoeva, L.Yu., Sel’menskikh, N.I., Gulyaeva, R.I., Zhidovinova, S.V., and Larionov, A.V., Effect of boron and yttrium on the phase composition and the microstructure of natural Nb–Si composites, Russ. Metall., (Engl. Transl.), 2014, vol. 2014, no. 9, pp. 688–696.
Svetlov, I.L., High-temperature Nb–Si composites. Part 1, Inorg. Mater.: Appl. Res., 2011, no. 2, pp. 307–315
Svetlov, I.L., High-temperature Nb–Si composites. Part 2, Inorg. Mater.: Appl. Res., 2011, no. 2, p. 316.
Zelenitsas, K. and Tsakiropoulos, P., Effect of Al,Cr,and Ta additions on the oxidation behavior of Nb–Ti–Si in situ composites at 800°C, Mater. Sci. Eng., A, 2006, vol. 416, pp. 269–280.
Wang, J., Guo, X.P., and Guo, J.M., Effects of B on the microstructure and oxidation resistance of Nb–Ti–Sibased ultrahigh-temperature alloy, Chin. J. Aeronaut., 2009, vol. 22, pp. 544–550.
Geng, J. and Tsakiropoulos, P., A study of the microstructures and oxidation of Nb–Si–Cr–Al–Mo in situ composites alloyed with Ti, Hf, Sn, Intermetallics, 2007, vol. 15, pp. 382–395.
Gulyaeva, R.I., Mansurova, A.N., Chumarev, V.M., Leont’ev, L.I., and Udoeva, L.Yu., Kineticheskii analiz okisleniya evtekticheskogo splava Nb–Si (Kinetic Analysis of the Oxidation of the Eutectic Nb–Si Alloy), Tr. Inst. Metall., Ural. Otd., Ross. Akad. Nauk, Chelyabinsk: Yuzh.-Ural. Knizh. Izd., 2015, pp. 83–91.
Liu, A.Q., Li, S.S., Sun, L., and Han, Y.F., Effect of B on the microstructures and high temperature oxidation resistance of a Nb–Si system in-situ composite, Mater. Sci. Forum, 2007, vols. 546–549, pp. 1489–1494.
Perepezko, J.H., Phase Stability and Microstructure Design in High Temperature (Mo,Nb)–Si–B Alloys, Madison: Univ. of Wisconsin–Madison, 1999.
Liu, Y., Thom, A.J., Kramer, M.J., and Akinc, M., Processing and Oxidation Behavior of Nb–Si–B Intermetallics, Ames: Iowa State Univ, 2004. http://www.osti.gov/scitech/servlets/purl/832901-O4nY3P/webviewable/.
Sun, Z., Yang, Y., Guo, X., Zhang, C., and Chang, Y.A., Thermodynamic modeling of the Nb-rich corner in the Nb–Si–B system, Intermetallics, 2011, vol. 19, pp. 26–34.
Katrych, S., Grytsiv, A., Bondar, A., Rogl, P., Velikanova, T., and Bohn, M., Structural materials: metal–silicon–Boron. The Nb-rich corner of the Nb–Si–B system, J. Solid State Chem., 2004, vol. 177, pp. 493–497.
Joubert, J.-M., Colinet, C., Rodrigues, G., Suzuki, P.A., Nunes, C.A., Coelho, G.C., and Tedenac, J.-C., The T2 phase in the Nb–Si–B system studied by abinitio calculations and synchrotron X-ray diffraction, J. Solid State Chem., 2012, vol. 190, pp. 111–117.
Cheng, J., Yi, S., and Sik Park, J., Oxidation behavior of Nb–Si–B alloys with the NbSi2 coating layer formed by a pack cementation technique, Int. J. Refract. Met. Hard Mater., 2013, vol. 41, pp. 103–109.
Ukegawa, M., Yamauchi, A., Kobayashi, A., and Kurokawa, K., Interfacial reaction sin Nb/NbSi2 and Nb/NbSi2–B systems, Vacuum, 2009, vol. 83, pp. 157–160.
Cheng, J., Yi, S., and Sik Park, J., Simultaneous coating of Si and B on Nb–Si–B alloys by a halide activated pack cementation method and oxidation behaviors of the alloys with coating sat 1100°C, J. Alloys Compd., 2015, vol. 644, pp. 975–981.
Zhang, F., Zhang, L.T., Shan, A.D., and Wu, J.S., Microstructural effect on oxidation kinetics of NbSi2 at 1023 K, J. Alloys Compd., 2006, vol. 422, pp. 308–312.
Sun, Z., Yang, Y., Guo, X., Zhang, C., and Chang, Y.A., Thermodynamic modeling of the Nb-rich corner in the Nb–Si–B system, Intermetallics, 2011, vol. 19, pp. 26–34.
Junior, D.M.P., Nunes, C.A., Coelho, G.C., and Ferreira, F.V., Liquidus projection of the Nb–Si–B system in the Nbrich region, Intermetallics, 2003, vol. 11, pp. 251–255.
Kurokawa, K., Yamauchi, A., and Matsushita, S., Improvement of oxidation resistance of NbSi2 by addition of boron, Mater. Sci. Forum, 2005, vol. 502, pp. 243–248.
Murakami, T., Xu, C.N., Kitahara, A., Kawahara, M., Takahashi, Y., Inuy, H., and Yamaguchi, M., Microstructure,mechanical properties and oxidation behavior of power compacts of the Nb–Si–B system prepared by spark plasma sintering, Intermetallics, 1999, vol. 7, pp. 1043–1048.
Behrani, V., Thom, A.J., Kramer, M.J., and Akinc, M., Microstructure and oxidation behavior of Nb–Mo–Si–B alloys, Intermetallics, 2006, vol. 14, pp. 24–32.
Proc. 20th Annual Conf. on Composites, Advanced Ceramics, Materials, and Structures, A: Ceramic Engineering and Science Proceedings, Wachtman, J.B., Eds., New York: Wiley, 2008, vol. 17, no. 3, p. 131.
Upolovnikova, A.G., Zhidovinova, S.V., and Larionov, A.V., Oxidation of eutectic Nb–Si alloys doped with boron, Privolzhsk. Nauch. Vestn., 2015, no. 10, pp. 33–36.
International Centre for Diffraction Data–ICDD, 2013. http://www.icdd.com/.
Vyazovkin, S., Burnham, A.K., Criado, J.M., Perez-Maqueda, L.A., Popescu, C., and Sbirrazzuoli, N., ICTAC kinetics committee recommendations for performing kinetic computations on thermal analysis data, Thermochim. Acta, 2011, vol. 520, pp. 1–19.
Brown, M.E., Dollimore, D., and Galway, A.K., Reaction in the solid state, in Comprehensive Chemical Kinetics, Bamford, C.H. and Tipper, C.F.H., Eds., Amsterdam: Elsevier, 1980, pp. 87–91.
Kofstad, P., High-Temperature Oxidation of Metals, New York: Wiley, 1966.
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Original Russian Text © A.N. Mansurova, R.I. Gulyaeva, V.M. Chumarev, 2016, published in Perspektivnye Materialy, 2016, No. 8, pp. 37–47.
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Mansurova, A.N., Gulyaeva, R.I. & Chumarev, V.M. Kinetic analysis of the oxidation of Nb–Si eutectic alloy doped with boron. Inorg. Mater. Appl. Res. 8, 318–326 (2017). https://doi.org/10.1134/S2075113317020150
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DOI: https://doi.org/10.1134/S2075113317020150