Mechanosynthesis and Solid-phase Synthesis of Ceramics Based on Hafnium and Zirconium Carbonitride
DOI:
https://doi.org/10.2298/SOS250814042KAbstract
Ceramics based on hafnium carbonitride and zirconium carbonitride were obtained on the basis of commercial powders of hafnium and zirconium carbides and nitrides by mechanochemical synthesis during processing in a high-energy planetary ball milling, as well as solid-phase synthesis during spark plasma sintering. It was shown that with increasing processing time in a high-energy ball milling the formation of carbonitrides increases and a change in the lattice parameters characteristic of the process of carbonitride formation is observed, correlating according to Vegard's rule. When spark plasma sintering was carried out at a temperature of 2000 ºC, a complete solid-phase reaction with the formation of hafnium carbonitride and zirconium carbonitride was observed. It was found that the solid-phase reaction of hafnium carbonitride formation starts at a temperature of 1347 ºC, and zirconium carbonitride at 1562 ºC. Bulk samples were obtained by spark plasma sintering. The hardness, Young's modulus and fracture toughness measured on the consolidated samples were: 19.51 ± 0.22 GPa, 448.26 ± 3.41 GPa, 7.03 ± 0.26 MPa∙m1/2 for HfCN; 16 ± 0.12 GPa, 343.44 ± 4.25 GPa, 3.57 ± 0.14 MPa∙m1/2 for ZrCN, respectively.
References
1. R.W. Harrison, W.E. Lee, Processing and properties of ZrC, ZrN and ZrCN ceramics: a review, Adv. Appl. Ceram. 115 (2016) 294-307.
https://doi.org/10.1179/1743676115Y.0000000061.
2. S.V. Ushakov, A. Navrotsky, Q.J. Hong, A. van de Walle, Carbides and nitrides of zirconium and hafnium, Mater. 12 (2019) 2728.
https://doi.org/10.3390/ma12172728.
3. W.G Fahrenholtz, G.E. Hilmas, Ultra-high temperature ceramics: materials for extreme environments, Scr. Mater. 129 (2017) 94-99,
https://doi.org/10.1016/j.scriptamat.2016.10.018.
4. V. Suvorova, A. Nepapushev, D. Suvorov, K. Kuskov, P. Loginov, D. Moskovskikh, Investigation of the Effect of Molybdenum Silicide Addition on the Oxidation Behavior of Hafnium Carbonitride, J. Compos. Sci. 7 (2023) 25.
https://doi.org/10.3390/jcs7010025
5. El Azhari, Multiscale mechanical and microstrutural characterization of titanium and zirconium carbonitride hard coatings [PhD thesis] (2020).
6. C.M. Silva, K.J. Kondrat, K.S. Holliday, S.J. McCormack, Crystallographic Study of Product Phases of Carbothermic Reduction and Nitridation of Hafnium Dioxide, Inorg. Chem. 62 (2023) 11910-11919.
https://doi.org/10.1021/acs.inorgchem.3c01333.
7. Y.H.R. Chang, T.L. Yoon, Effects of nitrogen addition and growth condition on the enhanced mechanical properties of transition metal carbides TMC (TM= Zr, Hf), Ceram. Int. 46 (2020) 1124-1136.
https://doi.org/10.1016/j.ceramint.2019.09.081.
8. Q. Yang, W. Lengauer, T. Koch, M. Scheerer, I. Smid, Hardness and elastic properties of Ti(CxN1−x), Zr(CxN1−x) and Hf(CxN1−x), J. Alloys Compd. 309 (2000) L5-L9.
https://doi.org/10.1016/S0925-8388(00)01057-4.
9. X. Zhang, X. Li, J. Zuo, R. Luo, J. Wang, Y. Qian, J. Xu, Characterization of thermophysical and mechanical properties of hafnium carbonitride fabricated by hot pressing sintering, J. Mater. Res. Technol. 23 (2023) 4432-4443.
https://doi.org/10.1016/j.jmrt.2023.02.099.
10. A.P. Zavjalov, P.A. Nikiforov, D.Y. Kosyanov, A.M. Zakharenko, V.O. Trukhin, K.Y. Talskikh, E.K. Papynov, Phase formation and densification peculiarities of Hf–C–N solid solution ceramics during reactive spark plasma sintering, Adv. Eng. Mater. 22 (2020) 2000482.
https://doi.org/10.1002/adem.202000482.
11. V.S. Buinevich, A.A. Nepapushev, D.O. Moskovskikh, G.V. Trusov, K.V. Kuskov, S.G. Vadchenko, A.S. Mukasyan, Fabrication of ultra-high-temperature nonstoichiometric hafnium carbonitride via combustion synthesis and spark plasma sintering, Ceram. Int. 46 (2020) 16068-16073.
https://doi.org/10.1016/j.ceramint.2020.03.158.
12. V.S. Buinevich, A.A. Nepapushev, D.O. Moskovskikh, G.V. Trusov, K.V. Kuskov, A.S. Mukasyan, Mechanochemical synthesis and spark plasma sintering of hafnium carbonitride ceramics, Adv. Powder Technol. 32 (2021) 385-389.
https://doi.org/10.1016/j.apt.2020.12.018.
13. E. Kuzmenko, S. Matrenin, Y. Liang, G. Voronova, Characterization and densification of hot pressed ZrCN-ZrO2 ceramics, Sci. Sint. (2025) 8,
https://doi.org/10.2298/SOS241128008K.
14. Q.J. Hong, A. Van De Walle, Prediction of the material with highest known melting point from ab initio molecular dynamics calculations, Phys. Rev. B. 92 (2015) 020104.
https://doi.org/10.1103/PhysRevB.92.020104.
15. V.S. Buinevich, A.A. Nepapushev, D.O. Moskovskikh, K.V. Kuskov, S.N. Yudin, A.S. Mukasyan, Ultra-high-temperature tantalum-hafnium carbonitride ceramics fabricated by combustion synthesis and spark plasma sintering, Ceram. Int. 47 (2021) 30043-30050.
https://doi.org/10.1016/j.ceramint.2021.07.180.
16. J. Yuan, M.L. Galetz, X.G. Luan, C. Fasel, R. Riedel, E. Ionescu, High-temperature oxidation behavior of polymer-derived SiHfBCN ceramic nanocomposites, J. Eur. Ceram. Soc. 12 (2016) 3021-3028.
https://doi.org/10.1016/j.jeurceramsoc.2015.12.006.
17. Z. Yu, Y. Pei, S. Lai, S. Li, Y. Feng, X. Liu, Single-source-precursor synthesis, microstructure and high temperature behavior of TiC-TiB2-SiC ceramic nanocomposites, Ceram. Int. 8 (2017) 5949-5956.
https://doi.org/10.1016/j.ceramint.2017.01.117.
18. S. Chen, Y. Gou, H. Wang, J. Wang, Fabrication and characterization of precursor-derived non-oxide ZrC-SiC multiphase ultrahigh temperature ceramics, J. Eur. Ceram. Soc. 36 (2016) 3843-3850.
https://doi.org/10.1016/j.jeurceramsoc.2016.06.047.
19. L. Wang, B. Wei, M. Zhang, W. Fang, L. Chen, Y. Wang, Oxidation behavior and kinetics of (Zr,Ti)(C, N)–SiC ceramics with enhanced oxidation resistance at 850°C–950°C, J. Mater. Res. Technol. 27 (2023) 6744-6755.
https://doi.org/10.1016/j.jmrt.2023.11.140.
20. Bellosi, F. Monteverde, R. Calzavarini, C. Zancolo, Factors influencing the milling performances of Ti (C,N)-based tools against carbon steel, Int. J. Refract. Met. Hard Mater. 19 (2001) 191-202.
https://doi.org/10.1016/S0263-4368(01)00049-X.
21. Y. Wang, High Entropy Transition Metal Carbides [PhD thesis] (2022).
22. Khadyrova, V. Suvorova, A. Nepapushev, D. Suvorov, K. Kuskov, D. Moskovskikh, Hafnium-Zirconium Carbonitride (Hf,Zr)(C,N) by One Step Mechanically Induced Self-Sustaining Reaction: Powder Synthesis and Spark Plasma Sintering, Ceram. 6 (2023) 1129-1138.
https://doi.org/10.3390/ceramics6020067.
23. V. Suvorova, I. Khadyrova, A. Nepapushev, K. Kuskov, D. Suvorov, D. Moskovskikh, Fabrication and investigation of novel hafnium-zirconium carbonitride ultra-high temperature ceramics, Ceram. Int. 49 (2023) 23809-23816.
https://doi.org/10.1016/j.ceramint.2023.04.222.
24. A.B. Peters, C. Wang, D. Zhang, A. Hernandez, D.C. Nagle, T. Mueller, J.B. Spicer, Reactive laser synthesis of ultra-high-temperature ceramics HfC, ZrC, TiC, HfN, ZrN, and TiN for additive manufacturing, Ceram. Int. 49 (2023) 11204-11229.
https://doi.org/10.1016/j.ceramint.2022.11.319.
25. K. Gürcan, E. Ayas, I. Yurdabak, S. Güngören, Effect of Y3Al5O12 addition on the microstructural evaluation and mechanical properties of spark plasma sintered ZrB2-SiC composites, Sci. Sint. 54 (2022) 1-9.
https://doi.org/10.2298/SOS2201001G.
26. Taha Yilmaz, U. Taşcı, A. Naci Tanis, H. Gokmese, M. Kocak, B. Bostan Investigation of microstructural, mechanical and tribological properties of NiTi/nB4C metal matrix composites produced by spark plasma sintering, Sci. Sint. 57 (2025). 53-68.
https://doi.org/10.2298/SOS240502023Y.
27. J. David, G. Trolliard, M. Gendre, A. Maitre, TEM study of the reaction mechanisms involved in the carbothermal reduction of zirconia, J. Eur. Ceram. Soc. 33 (2013) 165-179.
https://doi.org/10.1016/j.jeurceramsoc.2012.07.024.
28. R. Harrison, O. Ridd, D.D. Jayaseelan, W.E. Lee, Thermophysical characterisation of ZrCxNy ceramics fabricated via carbothermic reduction–nitridation, J. Nucl. Mater. 454 (2014) 46-53.
https://doi.org/10.1016/j.jnucmat.2014.07.030.
29. B.B. Bokhonov, D.V. Dudina, Synthesis of ZrC and HfC nanoparticles encapsulated in graphitic shells from mechanically milled Zr-C and Hf-C powder mixtures, Ceram. Int. 43 (2017) 14529-14532.
https://doi.org/10.1016/j.ceramint.2017.07.164.
30. M.A. Roldan, M.D. Alcala, C. Real, Mechanically induced self-propagating reaction of vanadium carbonitride, Ceram. Int. 41 (2015) 4688-4695.
https://doi.org/10.1016/j.ceramint.2014.12.016.
31. Chernyavskii A. S. Synthesis of ceramics based on titanium, zirconium, and hafnium nitrides, Inorg. Chem. 55 (2019) 1303-1327,
https://doi.org/10.1134/S0020168519130016.
32. F. Frank, M. Tkadletz, C. Saringer, A. Stark, N. Schell, M. Deluca, N. Schalk, In-Situ Investigation of the Oxidation Behaviour of Chemical Vapour Deposited Zr(C,N) Hard Coatings Using Synchrotron X-ray Diffraction, Coatings. 11 (2021) 264.
https://doi.org/10.3390/coatings11030264.
33. Ul-Hamid A. Microstructure, properties and applications of Zr-carbide, Zr-nitride and Zr-carbonitride coatings: a review, Mater. Adv. 1 (2020) 1012-1037.
https://doi.org/10.1039/D0MA00233J.
34. W. Aperador, J. Bautista-Ruiz, J. Sanchez-Molina, Effect of Temperature on the Tribological Properties of Hafnium Carbonitrides Coatings, Met. 13 (2023) 818.
https://doi.org/10.3390/met13040818.
35. M.T. Konnik, T. Oldham, A. Rzepka, V. Le Maout, K.A. Stephani, F. Panerai, High-temperature oxidation and nitridation of substoichiometric zirconium carbide in isothermal air, J. Eur. Ceram. Soc. 44 (2024) 6771-6776.
https://doi.org/10.1016/j.jeurceramsoc.2024.04.006.
36. Dai Y., F. Zeng, H. Liu, Y. Gao, Q. Yang, M. Chen, Y. Gu, Controlled nitrogen content synthesis of hafnium carbonitride powders by carbonizing hafnium nitride for enhanced ablation properties, Ceram. Int. 49 (2023) 33265-33274.
https://doi.org/10.1016/j.ceramint.2023.08.035.
37. D.Y. Kosyanov, A.P. Zavjalov, A.A. Vornovskikh, Some approaches for residual porosity estimating, Mater. Sci. Eng. 1093 (2021) 012015.
https://doi.org/10.1088/1757-899X/1093/1/012015.
38. Moradkhani, V. Panahizadeh, M. Hoseinpour, Indentation fracture resistance of brittle materials using irregular cracks: A review, Heliyon (2023).
https://doi.org/10.1016/j.heliyon.2023.e19361.
39. Kucheryavaya, Z. Lences, P. Sajgalík, H. Harmuth, Zirconium oxycarbides and oxycarbonitrides: A review, Int. J. Appl. Ceram. Technol. 20 (2023) 541-562.
40. M.N. Magomedov, On deviations from Vegard’s law at increasing pressure in alloys, Inorg. Mater. 56 (2020) 953-958.
https://doi.org/10.1134/S0020168520090125.
41. A.V. Kasimtsev, S.N. Yudin, A.V. Shuitsev, On the possibility of synthesizing zirconium carbonitride at a temperature of 1200 ℃, Trends in the development of science and education 31 (2017) 46-52.
https://doi.org/10.18411/lj-31-10-2017-12.
42. M. Gendre, A. Maitre, G. Trolliard, A study of the densification mechanisms during spark plasma sintering of zirconium (oxy-)carbide powders, Acta Mater. 58 (2010) 2598-2609.
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