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Journal of Advanced Ceramics 2022, 11(7): 1082-1092 https://doi.org/10.1007/s40145-022-0594-2
Research Article | Open Access | Issue | Published: 02 July 2022

Equiatomic 9-cation high-entropy carbide ceramics of the IVB, VB, and VIB groups and thermodynamic analysis of the sintering process

Show Author's Information Yuan QINa,b,  Ji-Xuan LIUb( ),  Yongcheng LIANGc,  Guo-Jun ZHANGa,b( )
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
Institute of Functional Materials, Donghua University, Shanghai 201620, China
College of Science, Donghua University, Shanghai 201620, China
Keywords:
thermodynamic analysis, high-entropy (HE) carbide, oxygen impurity, carbothermal reduction reaction, phase composition
Cite this article:
QIN Y, LIU J-X, LIANG Y, et al. Equiatomic 9-cation high-entropy carbide ceramics of the IVB, VB, and VIB groups and thermodynamic analysis of the sintering process. Journal of Advanced Ceramics, 2022, 11(7): 1082-1092. https://doi.org/10.1007/s40145-022-0594-2
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Abstract Full text Electronic supplementary material About this article

The preparation of high-entropy (HE) ceramics with designed composition is essential for verifying the formability models and evaluating the properties of the ceramics. However, inevitable oxygen contamination in non-oxide ceramics will result in the formation of metal oxide impurity phases remaining in the specimen or even escaping from the specimen during the sintering process, making the elemental compositions of the HE phase deviated from the designed ones. In this work, the preparation and thermodynamic analysis during the processing of equiatomic 9-cation HE carbide (HEC9) ceramics of the IVB, VB, and VIB groups were studied focusing on the removing of the inevitable oxygen impurity existed in the starting carbide powders and the oxygen contamination during the powder mixing processing. The results demonstrate that densification by spark plasma sintering (SPS) by directly using the mixed powders of the corresponding single-component carbides will inhibit the oxygen-removing carbothermal reduction reactions, and most of the oxide impurities will remain in the sample as (Zr,Hf)O2 phase. Pretreatment of the mixed powders at high temperatures in vacuum will remove most part of the oxygen impurity but result in a remarkable escape of gaseous Cr owing to the oxygen-removing reaction between Cr3C2 and various oxide impurities. It is found that graphite addition enhances the oxygen-removing effect and simultaneously prevents the escape of gaseous Cr. On the other hand, although WC, VC, and Mo2C can also act as oxygen-removing agents, there is no metal-containing gaseous substance formation in the temperature range of this study. By using the heat-treated powders with added graphite, equiatomic HEC9 ceramics were successfully prepared by SPS.


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About this article

Equiatomic 9-cation high-entropy carbide ceramics of the IVB, VB, and VIB groups and thermodynamic analysis of the sintering process

Show Author's information Yuan QINa,b, Ji-Xuan LIUb( ), Yongcheng LIANGc, Guo-Jun ZHANGa,b( )
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
Institute of Functional Materials, Donghua University, Shanghai 201620, China
College of Science, Donghua University, Shanghai 201620, China

Abstract

The preparation of high-entropy (HE) ceramics with designed composition is essential for verifying the formability models and evaluating the properties of the ceramics. However, inevitable oxygen contamination in non-oxide ceramics will result in the formation of metal oxide impurity phases remaining in the specimen or even escaping from the specimen during the sintering process, making the elemental compositions of the HE phase deviated from the designed ones. In this work, the preparation and thermodynamic analysis during the processing of equiatomic 9-cation HE carbide (HEC9) ceramics of the IVB, VB, and VIB groups were studied focusing on the removing of the inevitable oxygen impurity existed in the starting carbide powders and the oxygen contamination during the powder mixing processing. The results demonstrate that densification by spark plasma sintering (SPS) by directly using the mixed powders of the corresponding single-component carbides will inhibit the oxygen-removing carbothermal reduction reactions, and most of the oxide impurities will remain in the sample as (Zr,Hf)O2 phase. Pretreatment of the mixed powders at high temperatures in vacuum will remove most part of the oxygen impurity but result in a remarkable escape of gaseous Cr owing to the oxygen-removing reaction between Cr3C2 and various oxide impurities. It is found that graphite addition enhances the oxygen-removing effect and simultaneously prevents the escape of gaseous Cr. On the other hand, although WC, VC, and Mo2C can also act as oxygen-removing agents, there is no metal-containing gaseous substance formation in the temperature range of this study. By using the heat-treated powders with added graphite, equiatomic HEC9 ceramics were successfully prepared by SPS.

Keywords: thermodynamic analysis, high-entropy (HE) carbide, oxygen impurity, carbothermal reduction reaction, phase composition

References(58)

[1]
Rost CM, Sachet E, Borman T, et al. Entropy-stabilized oxides. Nat Commun 2015, 6: 8485.
DOI Google Scholar
[2]
Wang YC. Processing and properties of high entropy carbides. Adv Appl Ceram 2021, .
DOI Google Scholar
[3]
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
[4]
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
[5]
Braic V, Vladescu A, Balaceanu M, et al. Nanostructured multi-element (TiZrNbHfTa)N and (TiZrNbHfTa)C hard coatings. Surf Coat Technol 2012, 211: 117-121.
DOI Google Scholar
[6]
Castle E, Csanádi T, Grasso S, et al. Processing and properties of high-entropy ultra-high temperature carbides. Sci Rep 2018, 8: 8609.
DOI Google Scholar
[7]
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
[8]
Wei XF, Liu JX, Li F, et al. High entropy carbide ceramics from different starting materials. J Eur Ceram Soc 2019, 39: 2989-2994.
DOI Google Scholar
[9]
Gild J, Zhang YY, Harrington T, et al. High-entropy metal diborides: A new class of high-entropy materials and a new type of ultrahigh temperature ceramics. Sci Rep 2016, 6: 37946.
DOI Google Scholar
[10]
Chen H, Xiang HM, Dai FZ, et al. Porous high entropy (Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)B2: A novel strategy towards making ultrahigh temperature ceramics thermal insulating. J Mater Sci Technol 2019, 35: 2404-2408.
DOI Google Scholar
[11]
Liu JX, Shen XQ, Wu Y, et al. Mechanical properties of hot-pressed high-entropy diboride-based ceramics. J Adv Ceram 2020, 9: 503-510.
DOI Google Scholar
[12]
Qin Y, Liu JX, Li F, et al. A high entropy silicide by reactive spark plasma sintering. J Adv Ceram 2019, 8: 148-152.
DOI Google Scholar
[13]
Gild J, Braun J, Kaufmann K, et al. A high-entropy silicide: (Mo0.2Nb0.2Ta0.2Ti0.2W0.2)Si2. J Materiomics 2019, 5: 337-343.
DOI Google Scholar
[14]
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
[15]
Zhang Y, Sun SK, Guo WM, et al. Optimal preparation of high-entropy boride-silicon carbide ceramics. J Adv Ceram 2021, 10: 173-180.
DOI Google Scholar
[16]
Shen XQ, Liu JX, Li F, et al. Preparation and characterization of diboride-based high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2-SiC particulate composites. Ceram Int 2019, 45: 24508-24514.
DOI Google Scholar
[17]
Lu K, Liu JX, Wei XF, et al. Microstructures and mechanical properties of high-entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C ceramics with the addition of SiC secondary phase. J Eur Ceram Soc 2020, 40: 1839-1847.
DOI Google Scholar
[18]
Cai FY, Ni DW, Chen BW, et al. Fabrication and properties of Cf/(Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C-SiC high-entropy ceramic matrix composites via precursor infiltration and pyrolysis. J Eur Ceram Soc 2021, 41: 5863-5871.
DOI Google Scholar
[19]
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
[20]
Harrington TJ, Gild J, Sarker P, et al. Phase stability and mechanical properties of novel high entropy transition metal carbides. Acta Mater 2019, 166: 271-280.
DOI Google Scholar
[21]
Wang F, Yan XL, Wang TY, et al. Irradiation damage in (Zr0.25Ta0.25Nb0.25Ti0.25)C high-entropy carbide ceramics. Acta Mater 2020, 195: 739-749.
DOI Google Scholar
[22]
Wang HX, Wang SY, Cao YJ, et al. Oxidation behaviors of (Hf0.25Zr0.25Ta0.25Nb0.25)C and (Hf0.25Zr0.25Ta0.25Nb0.25)C-SiC at 1300-1500 ℃. J Mater Sci Technol 2021, 60: 147-155.
Google Scholar
[23]
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
[24]
Wang XF, Wang XG, Yang QQ, et al. High-strength medium-entropy (Ti,Zr,Hf)C ceramics up to 1800 ℃. J Am Ceram Soc 2021, 104: 2436-2441.
DOI Google Scholar
[25]
Demirskyi D, Borodianska H, Suzuki TS, et al. High-temperature flexural strength performance of ternary high-entropy carbide consolidated via spark plasma sintering of TaC, ZrC and NbC. Scripta Mater 2019, 164: 12-16.
DOI Google Scholar
[26]
Peng C, Tang H, He Y, et al. A novel non-stoichiometric medium-entropy carbide stabilized by anion vacancies. J Mater Sci Technol 2020, 51: 161-166.
DOI Google Scholar
[27]
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
[28]
Dusza J, Švec P, Girman V, et al. Microstructure of (Hf-Ta-Zr-Nb)C high-entropy carbide at micro and nano/ atomic level. J Eur Ceram Soc 2018, 38: 4303-4307.
DOI Google Scholar
[29]
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
[30]
Wang F, Zhang X, Yan XL, et al. The effect of submicron grain size on thermal stability and mechanical properties of high-entropy carbide ceramics. J Am Ceram Soc 2020, 103: 4463-4472.
DOI Google Scholar
[31]
Chicardi E, García-Garrido C, Gotor FJ. Low temperature synthesis of an equiatomic (TiZrHfVNb)C5 high entropy carbide by a mechanically-induced carbon diffusion route. Ceram Int 2019, 45: 21858-21863.
DOI Google Scholar
[32]
Li F, Lu Y, Wang XG, et al. Liquid precursor-derived high-entropy carbide nanopowders. Ceram Int 2019, 45: 22437-22441.
DOI Google Scholar
[33]
Zhang W, Chen L, Xu CG, et al. Grain growth kinetics and densification mechanism of (TiZrHfVNbTa)C high-entropy ceramic under pressureless sintering. J Mater Sci Technol 2022, 110: 57-64.
DOI Google Scholar
[34]
Zhang W, Chen L, Xu CG, et al. Densification, microstructure and mechanical properties of multicomponent (TiZrHfNbTaMo)C ceramic prepared by pressureless sintering. J Mater Sci Technol 2021, 72: 23-28.
DOI Google Scholar
[35]
Wang YC, Csanádi T, Zhang HF, et al. Enhanced hardness in high-entropy carbides through atomic randomness. Adv Theory Simul 2020, 3: 2000111.
DOI Google Scholar
[36]
Mellor WM, Kaufmann K, Dippo OF, et al. Development of ultrahigh-entropy ceramics with tailored oxidation behavior. J Eur Ceram Soc 2021, 41: 5791-5800.
DOI Google Scholar
[37]
Kaufmann K, Maryanovsky D, Mellor WM, et al. Discovery of high-entropy ceramics via machine learning. npj Comput Mater 2020, 6: 42.
DOI Google Scholar
[38]
Zhou JY, Zhang JY, Zhang F, et al. High-entropy carbide: A novel class of multicomponent ceramics. Ceram Int 2018, 44: 22014-22018.
DOI Google Scholar
[39]
Wang K, Chen L, Xu CG, et al. Microstructure and mechanical properties of (TiZrNbTaMo)C high-entropy ceramic. J Mater Sci Technol 2020, 39: 99-105.
DOI Google Scholar
[40]
Wei XF, Liu JX, Bao WC, et al. High-entropy carbide ceramics with refined microstructure and enhanced thermal conductivity by the addition of graphite. J Eur Ceram Soc 2021, 41: 4747-4754.
DOI Google Scholar
[41]
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
[42]
Backman L, Opila EJ. Thermodynamic assessment of the group IV, V and VI oxides for the design of oxidation resistant multi-principal component materials. J Eur Ceram Soc 2019, 39: 1796-1802.
DOI Google Scholar
[43]
Wang HX, Cao YJ, Liu W, et al. Oxidation behavior of (Hf0.2Ta0.2Zr0.2Ti0.2Nb0.2)C-xSiC ceramics at high temperature. Ceram Int 2020, 46: 11160-11168.
DOI Google Scholar
[44]
Backman L, Gild J, Luo J, et al. Part II: Experimental verification of computationally predicted preferential oxidation of refractory high entropy ultra-high temperature ceramics. Acta Mater 2020, 197: 81-90.
DOI Google Scholar
[45]
Tan YQ, Chen C, Li SG, et al. Oxidation behaviours of high-entropy transition metal carbides in 1200 ℃ water vapor. J Alloys Compd 2020, 816: 152523.
DOI Google Scholar
[46]
Zhu YB, Chai JL, Wang ZG, et al. Microstructural damage evolution of (WTiVNbTa)C5 high-entropy carbide ceramics induced by self-ions irradiation. J Eur Ceram Soc 2022, 42: 2567-2576.
DOI Google Scholar
[47]
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
[48]
Zhou YC, Zhao B, Chen H, et al. Electromagnetic wave absorbing properties of TMCs (TM = Ti, Zr, Hf, Nb and Ta) and high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C. J Mater Sci Technol 2021, 74: 105-118.
DOI Google Scholar
[49]
Guo WJ, Hu J, Ye YC, et al. Ablation behavior of (TiZrHfNbTa)C high-entropy ceramics with the addition of SiC secondary under an oxyacetylene flame. Ceram Int 2022, 48: 12790-12799.
DOI Google Scholar
[50]
Wang XG, Guo WM, Kan YM, et al. Densification behavior and properties of hot-pressed ZrC ceramics with Zr and graphite additives. J Eur Ceram Soc 2011, 31: 1103-1111.
DOI Google Scholar
[51]
Zhu SM, Fahrenholtz WG, Hilmas GE, et al. Pressureless sintering of carbon-coated zirconium diboride powders. Mater Sci Eng A 2007, 459: 167-171.
DOI Google Scholar
[52]
Gild J, Kaufmann K, Vecchio K, et al. Reactive flash spark plasma sintering of high-entropy ultrahigh temperature ceramics. Scripta Mater 2019, 170: 106-110.
DOI Google Scholar
[53]
Barbarossa S, Orrù R, Garroni S, et al. Ultra high temperature high-entropy borides: Effect of graphite addition on oxides removal and densification behaviour. Ceram Int 2021, 47: 6220-6231.
DOI Google Scholar
[54]
Anstis GR, Chantikul P, Lawn BR, et al. A critical evaluation of indentation techniques for measuring fracture toughness: I, direct crack measurements. J Am Ceram Soc 1981, 64: 533-538.
DOI Google Scholar
[55]
Zou J, Zhang GJ, Sun SK, et al. ZrO2 removing reactions of Groups IV-VI transition metal carbides in ZrB2 based composites. J Eur Ceram Soc 2011, 31: 421-427.
DOI Google Scholar
[56]
Zhang L, Gao KW, Elias A, et al. Porosity dependence of elastic modulus of porous Cr3C2 ceramics. Ceram Int 2014, 40: 191-198.
DOI Google Scholar
[57]
Nino A, Tanaka A, Sugiyama S, et al. Indentation size effect for the hardness of refractory carbides. Mater Trans 2010, 51: 1621-1626.
DOI Google Scholar
[58]
Zhang Y, Zhou YJ, Lin JP, et al. Solid-solution phase formation rules for multi-component alloys. Adv Eng Mater 2008, 10: 534-538.
DOI Google Scholar
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Publication history

Received: 16 January 2022
Revised: 25 March 2022
Accepted: 29 March 2022
Published: 02 July 2022
Issue date: July 2022

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© The Author(s) 2022.

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 52032001 and 51872045).

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