DEVELOPMENT OF HIGH-ENTROPY ALLOY COMPOSITIONS FOR THE PRO- DUCTION OF SUPERHARD COMPOSITES BASED ON CUBIC BORON NITRIDE
DOI:
https://doi.org/10.15407/plit2025.04.062Keywords:
cubic boron nitride, high-entropy alloys, superhard composites, thermodynamic analysis, nitrides, boridesAbstract
This work explores the prospects of developing new composite materials based on cubic boron nitride (cBN) using high-entropy alloys (HEAs) as a binding matrix. The research is driven by the need for next-generation tool materials capable of efficiently machining modern structural materials under extreme conditions where the properties of traditional cBN-based composites are no longer sufficient. The unique properties of cBN make it a key enabling material for cutting tools. However, the consolidation of cBN presents fundamental challenges due to its strong covalent bonds, which require the application of extreme pressures and temperatures, thus necessitating the use of binding materials. Existing traditional metallic and ceramic binding agents have significant drawbacks: metallic binders have low softening temperatures, while ceramic binders are brittle and exhibit low thermal conductivity. In contrast, high-entropy alloys combine high strength, wear resistance, and, crucially, exceptional thermal stability inherent to their specific structure. Nevertheless, the successful development of HEA/cBN composites depends on overcoming a number of critical challenges: controlling interfacial interactions, managing porosity, and minimizing residual stresses. This necessitates predictive methods, including the application of thermodynamic modeling to forecast interactions across a wide temperature range. Given the fragmented and limited availability of specialized thermodynamic databases for HEA systems, this work proposes a combinatorial method of thermodynamic analysis. This approach is designed to predict optimal compositions of high-entropy alloys (HEAs) intended for the creation of composites based on cubic boron nitride (cBN). The developed model accounts for changes in the Gibbs free energy of the system during the formation of nitrides and borides at the HEA/cBN phase boundary, enabling assessment of the thermodynamic likelihood of their formation. The method is based on calculations of the mixing entropy of the HEA components and the formation energies of compounds of the AnBm type. A five-component system (Ni–Cr–Fe–Co–Al–Ti) was used for the analysis, where the contribution of each element to the change in Gibbs free energy upon interaction with cBN was taken into account. Calculations showed that aluminium, titanium, and zirconium are the most active elements that form stable nitrides and borides (AlN, TiB₂, ZrN) at temperatures up to 2000 °C. Results indicate that adding 5–10 at. % Al and Ti to the HEA promotes formation of a strong interfacial bond with cBN through the creation of thermally stable intermediate phases. Thermodynamic calculations also confirm that an excess of these elements can lead to undesirable delamination and failure of the composite. The proposed method makes it possible to reduce the number of experimental studies by pre-selecting promising systems via thermodynamic screening.
References
Ji, H., Li, Z., & Liu, M. (2021). Structural and mechanical properties of cBN composites by regulating particle size distribution and holding time. International Journal of Refractory Metals and Hard Materials, 100, Article 105635. https://doi.org/10.1016/j.ijrmhm.2021.105635
Daoush, W. M., Alkhuraiji, T. S., & Alshammri, A. D. (2021). Fabrication of polycrystalline cubic boron nitride/metal composite particles by surface metallization followed by electroless deposition technique. Materials, 14, 7906. https://doi.org/10.3390/ma14247906
Rathinasabapathy, S., Santhosh, M. S., & Asokan, M. (2020). Significance of boron nitride in composites and its applications. In Recent Advances in Boron-Containing Materials. IntechOpen. https://doi.org/10.5772/intechopen.81557.
Li, H., et al. (2024). Surface Topography: Metrology and Properties, 12, 025013. https://doi.org/10.1088/2051-672X/ad4403.
Solozhenko, V. L. (1995). Boron nitride phase diagram: State of the art. High Pressure Research, 13, 199–214.
Solozhenko, V. L., & Gavrichev, K. S. (1995). Thermodynamic properties of boron nitride. In M. A. Preals, P. Gielisse, G. Popovichi, B. V. Spitsyn, & T. Stacy (Eds.), Wide Band Gap Electronic Materials (NATO ASI Series — High Technology, Vol. 1, pp. 377–392). Dordrecht, Boston, London: Kluwer Academic Publishers.
Haynes, W. M. (Ed.). (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, FL: CRC Press.
NIST–JANAF Thermochemical Tables. National Institute of Standards and Technology. Retrieved from https://janaf.nist.gov.
Kosolapova, T. Ya. (Ed.). (1986). Svoystva, poluchenie i primenenie tugoplavkikh soedinenii [Properties, production and application of refractory compounds]. Moscow: Metallurgiya. [in Russian].
Mirković, D., Gröbner, J., Schmid-Fetzer, R., Fabrichnaya, O., & Lukas, H. (2004). Experimental study and thermodynamic re-assessment of the Al–B system. Journal of Alloys and Compounds, 384, 168–174.
Pankratz, L. B., Stuve, J. M., & Gokcen, N. A. (1984). Thermodynamic Data for Mineral Technology (Bulletin 677). Washington, DC: United States Bureau of Mines.
Van Ende, M.-A., & Jung, I.-H. (2013). Critical thermodynamic evaluation and optimization of the Fe–B, Fe–Nd, B–Nd and Nd–Fe–B systems. Journal of Alloys and Compounds, 548, 133–154.
Yamada, K., Ohtani, H., & Hasebe, M. (2008). Thermodynamic analysis of the Fe–Cr–B ternary system. High Temperature Materials and Processes, 27(4), 269–283.
Widenmeyer, M., Hansen, T. C., Meissner, E., & Niewa, R. (2014). Formation and decomposition of iron nitrides observed by in situ powder neutron diffraction and thermal analysis. Zeitschrift für Anorganische und Allgemeine Chemie, 640(7), 1265–1274.
Tessier, F., Navrotsky, A., Niewa, R., Leineweber, A., Jacobs, H., Kikkawa, S., Takahashi, M., Kanamaru, F., & DiSalvo, F. J. (2000). Energetics of binary iron nitrides. Solid State Sciences, 2, 457–462.
Stoeckl, P., Swatek, P. W., & Wang, J.-P. (2024). Theoretical study of thermal stability of α″-Fe₁₆N₂ against other iron nitrides. AIP Advances, 14, 015047.
Göhring, H., Fabrichnaya, O., Leineweber, A., & Mittemeijer, E. J. (2016). Thermodynamics of the Fe–N and Fe–N–C systems: The Fe–N and Fe–N–C phase diagrams revisited. Metallurgical and Materials Transactions A, 47, 6173–6186.
Triana, T., Brooks, G. A., Rhamdhani, M. A., & Pownceby, M. I. (2024). Iron oxide direct reduction and iron nitride formation using ammonia: Review and thermodynamic analysis. Journal of Sustainable Metallurgy, 10, 1428–1445.
Liu, Y. Q., Zhao, X. S., Yang, J., & Shen, J. Y. (2011). Thermodynamic optimization of the B–Co–Fe (boron–cobalt–iron) system. Journal of Alloys and Compounds, 509, 4805–4810.
Kartal, L. (2023). Cobalt boride (Co₂B) particle synthesis by one-step carbothermic reduction. Hittite Journal of Science and Engineering, 10(3), 229–235.
Phase Diagrams. (n.d.). Co–N. Retrieved from https://sites.google.com/rictsystems.com/phase-diagrams/metal/co/co-n
F. R. de Boer, F. R., Boom, R., Mattens, W. C. M., Miedema, A. R., & Niessen, A. K. (1988). Cohesion in Metals: Transition Metal Alloys. Amsterdam: North-Holland.
Hahn, H., & Konrad, A. (1951). Über die Bindungswärme des Ni₃N [On the bond heat of Ni₃N]. Zeitschrift für Anorganische und Allgemeine Chemie, 264, 181–183. [in German].
Teppa, O., & Taskinen, P. (1993). Thermodynamic assessment of the Ni–B phase diagram. Materials Science and Technology, 9(3), 205–212.
Ma, X., Li, C., Du, Z., & Zhang, W. (2004). Thermodynamic assessment of the Ti–B system. Journal of Alloys and Compounds, 370, 149–158.
Linstrom, P. J., & Mallard, W. G. (Eds.). NIST Chemistry WebBook, NIST Standard Reference Database Number 69. National Institute of Standards and Technology. Retrieved from https://webbook.nist.gov/.
Liao, P. K., & Spear, K. E. (1986). The B–Cr (boron–chromium) system. Bulletin of Alloy Phase Diagrams, 7(3), 232–237.
Sirota, N. N., Vinokurov, V. A., Zinakov, D. V., Matovnikov, A. V., Novikov, V. V., & Siniy, Y. E. (2004). Thermodynamic functions of Cr₂B in the range 5–300 K [Termodinamicheskie funktsii Cr2B v intervale 5–300 K]. Zhurnal Fizicheskoi Khimii (Journal of Physical Chemistry),78(1), 23–26. [in Russian].
Tojo, M., Tokunaga, T., Ohtani, H., & Hasebe, M. (2010). Thermodynamic analysis of phase equilibria in the Cr–Mo–B ternary system. CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry, 34, 263–270.
Musameh, S. M., & Jodeh, S. W. (2007). Tribological behavior of chromium nitride coating by unbalanced magnetron sputtering. Journal of Active and Passive Electronic Devices, 2, 93–103.
Greenwood, N. N., & Earnshaw, A. (1997). Chemistry of the Elements (2nd ed.). Oxford: Butterworth-Heinemann.
Rogl, P. (2009). Boron–carbon–vanadium. In G. Effenberg & S. Ilyenko (Eds.), Refractory Metal Systems (Landolt–Börnstein — Group IV: Physical Chemistry, Vol. 11E1, pp. 551–578). Berlin, Heidelberg: Springer.
Spear, K. E., Liao, P. K., & Smith, J. F. (1987). The B–V (boron–vanadium) system. Bulletin of Alloy Phase Diagrams, 8(5), 447–454.
Storms, E., & Mueller, B. (1977). Phase relations and thermodynamic properties of transition metal borides. I. The molybdenum–boron system and elemental boron. The Journal of Physical Chemistry, 81(4), 318–324.
Ferro, N. (1980). The Mo–N (molybdenum–nitrogen) system. Bulletin of Alloy Phase Diagrams, 1(2), 82–85.
Cheng, X.-Y., Chen, X.-Q., Li, D.-Z., & Li, Y.-Y. (2014). Computational materials discovery: The case of the W–B system. Acta Crystallographica Section C: Structural Chemistry, 70, 85–103.
Takeuchi, A., & Inoue, A. (2005). Classification of bulk metallic glasses by atomic size difference, heat of mixing and period of constituent elements and its application to characterization of the main alloying element. Materials Transactions, 46(12), 2817–2829.
Chen, L., Wang, S., Zhang, J., & Zhang, Z. (2021). Microstructure and mechanical properties of TiN–TiB₂–hBN composites fabricated by reactive hot pressing using TiN–B mixture. Materials Science and Engineering: A, 821, 141602.
Zhang, Y., Zhang, J., Wang, S., & Liu, X. (2023). Effect of NiTi content on the mechanical properties and microstructure of TiB₂–TiN-based composite ceramic material prepared using spark plasma sintering. Ceramics International, 49(12), 20415–20423. https://doi.org/10.1016/j.ceramint.2023.03.123
Angseryd, J., Elfwing, M., Olsson, E., & Andrén, H.-O. (2009). Detailed microstructure of a cBN-based cutting tool material. International Journal of Refractory Metals and Hard Materials, 27, 249–255. https://doi.org/10.1016/j.ijrmhm.2008.09.008
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