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Journal of Advanced Ceramics 2023, 12(1): 49-58 https://doi.org/10.26599/JAC.2023.9220665
Research Article | Open Access | Issue | Published: 02 December 2022

Low thermal conductivity of dense (TiZrHfVNbTa)Cx high-entropy carbides by tailoring carbon stoichiometry

Show Author's Information Lei CHENa,b( ),  Wen ZHANGa,b,  Wenyu LUa,b,  Boxin WEIc,  Sijia HUOa,b,  Yujin WANGa,b( ),  Yu ZHOUa,b
Institute for Advanced Ceramics, School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
Key Laboratory of Advanced Structural–Functional Integration Materials & Green Manufacturing Technology, Harbin Institute of Technology, Harbin 150001, China
School of Materials Science and Chemical Engineering, Harbin University of Science and Technology, Harbin 150001, China
Keywords:
thermal conductivity, high-entropy carbides, compositional complexity, carbon vacancies
Cite this article:
CHEN L, ZHANG W, LU W, et al. Low thermal conductivity of dense (TiZrHfVNbTa)Cx high-entropy carbides by tailoring carbon stoichiometry. Journal of Advanced Ceramics, 2023, 12(1): 49-58. https://doi.org/10.26599/JAC.2023.9220665
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Abstract Full text About this article

Transition metal carbides are promising candidates for thermal protection materials due to their high melting points and excellent mechanical properties. However, the relatively high thermal conductivity is still a major obstacle to its application in an ultra-high-temperature insulation system. In this work, the low thermal conductivity of dense (TiZrHfVNbTa)Cx (x = 0.6–1) high-entropy carbides has been realized by adjusting the carbon stoichiometry. The thermal conductivity gradually decreases from 10.6 W·m−1·K−1 at room temperature to 6.4 W·m−1·K−1 with carbon vacancies increasing. Due to enhanced scattering of phonons and electrons by the carbon vacancies, nearly full-dense (97.9%) (TiZrHfVNbTa)C0.6 possesses low thermal conductivity of 6.4 W·m−1·K−1, thermal diffusivity of 2.3 mm2·s−1, as well as electrical resistivity of 165.5 μΩ·cm. The thermal conductivity of (TiZrHfVNbTa)C0.6 is lower than that of other quaternary and quinary high-entropy carbide ceramics, even if taking the difference of porosity into account in some cases, which is mainly attributed to compositional complexity and carbon vacancies. This provides a promising route to reduce the thermal conductivity of high-entropy carbides by increasing the number of metallic elements and carbon vacancies.


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Low thermal conductivity of dense (TiZrHfVNbTa)Cx high-entropy carbides by tailoring carbon stoichiometry

Show Author's information Lei CHENa,b( ), Wen ZHANGa,b, Wenyu LUa,b, Boxin WEIc, Sijia HUOa,b, Yujin WANGa,b( ), Yu ZHOUa,b
Institute for Advanced Ceramics, School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
Key Laboratory of Advanced Structural–Functional Integration Materials & Green Manufacturing Technology, Harbin Institute of Technology, Harbin 150001, China
School of Materials Science and Chemical Engineering, Harbin University of Science and Technology, Harbin 150001, China

Abstract

Transition metal carbides are promising candidates for thermal protection materials due to their high melting points and excellent mechanical properties. However, the relatively high thermal conductivity is still a major obstacle to its application in an ultra-high-temperature insulation system. In this work, the low thermal conductivity of dense (TiZrHfVNbTa)Cx (x = 0.6–1) high-entropy carbides has been realized by adjusting the carbon stoichiometry. The thermal conductivity gradually decreases from 10.6 W·m−1·K−1 at room temperature to 6.4 W·m−1·K−1 with carbon vacancies increasing. Due to enhanced scattering of phonons and electrons by the carbon vacancies, nearly full-dense (97.9%) (TiZrHfVNbTa)C0.6 possesses low thermal conductivity of 6.4 W·m−1·K−1, thermal diffusivity of 2.3 mm2·s−1, as well as electrical resistivity of 165.5 μΩ·cm. The thermal conductivity of (TiZrHfVNbTa)C0.6 is lower than that of other quaternary and quinary high-entropy carbide ceramics, even if taking the difference of porosity into account in some cases, which is mainly attributed to compositional complexity and carbon vacancies. This provides a promising route to reduce the thermal conductivity of high-entropy carbides by increasing the number of metallic elements and carbon vacancies.

Keywords: thermal conductivity, high-entropy carbides, compositional complexity, carbon vacancies

References(36)

[1]
Padture NP. Advanced structural ceramics in aerospace propulsion. Nat Mater 2016, 15: 804–809.
DOI Google Scholar
[2]
Savino R, de Stefano Fumo M, Paterna D, et al. Aerothermodynamic study of UHTC-based thermal protection systems. Aerosp Sci Technol 2005, 9: 151–160.
DOI Google Scholar
[3]
Ni DW, Cheng Y, Zhang JP, et al. Advances in ultra-high temperature ceramics, composites, and coatings. J Adv Ceram 2022, 11: 1–56.
DOI Google Scholar
[4]
Xiang HM, Xing Y, Dai FZ, et al. High-entropy ceramics: Present status, challenges, and a look forward. J Adv Ceram 2021, 10: 385–441.
DOI Google Scholar
[5]
Sarker P, Harrington T, Toher C, et al. High-entropy high-hardness metal carbides discovered by entropy descriptors. Nat Commun 2018, 9: 4980.
DOI Google Scholar
[6]
Tan YQ, Teng Z, Jia P, et al. Diverse oxidation behaviors of metal carbide solutions in high-temperature water vapor. Corros Sci 2021, 191: 109758.
DOI Google Scholar
[7]
Lun HL, Zeng Y, Xiong X, et al. Oxidation behavior of non-stoichiometric (Zr,Hf,Ti)Cx carbide solid solution powders in air. J Adv Ceram 2021, 10: 741–757.
DOI Google Scholar
[8]
Yan XL, Constantin L, Lu YF, et al. (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics with low thermal conductivity. J Am Ceram Soc 2018, 101: 4486–4491.
DOI Google Scholar
[9]
Moskovskikh DO, Vorotilo S, Sedegov AS, et al. High-entropy (HfTaTiNbZr)C and (HfTaTiNbMo)C carbides fabricated through reactive high-energy ball milling and spark plasma sintering. Ceram Int 2020, 46: 19008–19014.
DOI Google Scholar
[10]
Liu DQ, Zhang AJ, Jia JG, et al. Phase evolution and properties of (VNbTaMoW)C high entropy carbide prepared by reaction synthesis. J Eur Ceram Soc 2020, 40: 2746–2751.
DOI Google Scholar
[11]
Schwind EC, Reece MJ, Castle E, et al. Thermal and electrical properties of a high entropy carbide (Ta, Hf, Nb, Zr) at elevated temperatures. J Am Ceram Soc 2022, 105: 4426–4434.
DOI Google Scholar
[12]
Zhang WM, Xiang HM, Dai FZ, et al. Achieving ultra-broadband electromagnetic wave absorption in high-entropy transition metal carbides (HE TMCs). J Adv Ceram 2022, 11: 545–555.
DOI Google Scholar
[13]
Yan NN, Fu QG, Zhang YY, et al. Preparation of pore-controllable zirconium carbide ceramics with tunable mechanical strength, thermal conductivity and sound absorption coefficient. Ceram Int 2020, 46: 19609–19616.
DOI Google Scholar
[14]
Chen H, Xiang HM, Dai FZ, et al. High porosity and low thermal conductivity high entropy (Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)C. J Mater Sci Technol 2019, 35: 1700–1705.
DOI Google Scholar
[15]
Wei BX, Chen L, Wang YJ, et al. Densification, mechanical and thermal properties of ZrC1−x ceramics fabricated by two-step reactive hot pressing of ZrC and ZrH2 powders. J Eur Ceram Soc 2018, 38: 411–419.
DOI Google Scholar
[16]
Zhang YH, Liu B, Wang JM, et al. Theoretical investigations of the effects of ordered carbon vacancies in ZrC1−x on phase stability and thermo-mechanical properties. Acta Mater 2016, 111: 232–241.
DOI Google Scholar
[17]
Rost CM, Borman T, Hossain MD, et al. Electron and phonon thermal conductivity in high entropy carbides with variable carbon content. Acta Mater 2020, 196: 231–239.
DOI Google Scholar
[18]
Chen L, Zhang W, Tan YQ, et al. Influence of vanadium content on the microstructural evolution and mechanical properties of (TiZrHfVNbTa)C high-entropy carbides processed by pressureless sintering. J Eur Ceram Soc 2021, 41: 60–67.
DOI Google Scholar
[19]
Zhang W, Chen L, Lu WY, et al. Non-stoichiometry of (TiZrHfVNbTa)Cx and its significance to the microstructure and mechanical properties. J Eur Ceram Soc 2022, 42: 6347–6355.
DOI Google Scholar
[20]
Pierson HO. Handbook of Refractory Carbides and Nitrides: Properties, Characteristics, Processing and Applications. New Jersey, USA: Noyes Publications, 1996.
DOI
[21]
Song JT, Chen GQ, Xiang HM, et al. Regulating the formation ability and mechanical properties of high-entropy transition metal carbides by carbon stoichiometry. J Mater Sci Technol 2022, 121: 181–189.
DOI Google Scholar
[22]
Taylor RE, Morreale J. Thermal conductivity of titanium carbide, zirconium carbide, and titanium nitride at high temperatures. J Am Ceram Soc 1964, 47: 69–73.
DOI Google Scholar
[23]
Williams WS. High-temperature thermal conductivity of transition metal carbides and nitrides. J Am Ceram Soc 1966, 49: 156–159.
DOI Google Scholar
[24]
Yang Y, Ma L, Gan GY, et al. Investigation of thermodynamic properties of high entropy (TaNbHfTiZr)C and (TaNbHfTiZr)N. J Alloys Compd 2019, 788: 1076–1083.
DOI Google Scholar
[25]
Katoh Y, Vasudevamurthy G, Nozawa T, et al. Properties of zirconium carbide for nuclear fuel applications. J Nucl Mater 2013, 441: 718–742.
DOI Google Scholar
[26]
Storms EK, Wagner P. Thermal conductivity of substoichiometric ZrC and NbC. High Temp Sci 1973, 5: 454–462.
Google Scholar
[27]
Williams WS. Electrical properties of hard materials. Int J Refract Met Hard Mater 1999, 17: 21–26.
DOI Google Scholar
[28]
Peng C, Gao X, Wang MZ, et al. Diffusion-controlled alloying of single-phase multi-principal transition metal carbides with high toughness and low thermal diffusivity. Appl Phys Lett 2019, 114: 011905.
DOI Google Scholar
[29]
Elliott RO, Kempter CP. Thermal expansion of some transition metal carbides. J Phys Chem 1958, 62: 630–631.
DOI Google Scholar
[30]
Zhang BH, Yin J, Wang YC, et al. Low temperature densification mechanism and properties of Ta1−xHfxC solid solutions with decarbonization and phase transition of Cr3C2. J Materiomics 2021, 7: 672–682.
DOI Google Scholar
[31]
Ye BL, Chu YH, Huang KH, et al. Synthesis and characterization of (Zr1/3Nb1/3Ti1/3)C metal carbide solid solution ceramic. J Am Ceram Soc 2019, 102: 919–923.
Google Scholar
[32]
Ye BL, Wen TQ, Nguyen MC, et al. First-principles study, fabrication and characterization of (Zr0.25Nb0.25Ti0.25V0.25)C high-entropy ceramics. Acta Mater 2019, 170: 15–23.
DOI Google Scholar
[33]
Liu DQ, Zhang AJ, Jia JG, et al. Reaction synthesis and characterization of a new class high entropy carbide (NbTaMoW)C. Mater Sci Eng A 2021, 804: 140520.
DOI Google Scholar
[34]
Qin MD, Gild J, Hu CZ, et al. Dual-phase high-entropy ultra-high temperature ceramics. J Eur Ceram Soc 2020, 40: 5037–5050.
DOI Google Scholar
[35]
Wang YC. Processing and properties of high entropy carbides. Adv Appl Ceram 2022, 121: 57–78.
DOI Google Scholar
[36]
Zhao SJ. Lattice distortion in high-entropy carbide ceramics from first-principles calculations. J Am Ceram Soc 2021, 104: 1874–1886.
DOI Google Scholar
Publication history
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Publication history

Received: 21 July 2022
Revised: 03 September 2022
Accepted: 23 September 2022
Published: 02 December 2022
Issue date: January 2023

Copyright

© The Author(s) 2022.

Acknowledgements

This work is financially supported by the National Natural Science Foundation of China (Nos. 52032002 and 51972081), National Safety Academic Foundation (No. U2130103), Science and Technology on Particle Transport and Separation Laboratory, and Heilongjiang Touyan Team Program.

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