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Strong high-entropy diboride ceramics with oxide impurities at 1800°C

1800°C下具有优异高强度且含氧化物杂质的高熵二 硼化物陶瓷

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Abstract

In this study, a type of high-entropy boride (HEB) ceramics ((Ti0.2Zr0.2Nba0.2Hfa0.2Taa0.2)B2) with ∼2vol% oxides and ∼1 vol% porosity was successfully consolidated by spark plasma sintering at 2000°C under a uniaxial load of 50 MPa for 10 min, using self-synthesized high entropy diboride powders from a boro/carbothermal reduction approach. The residual oxides were determined to be m-(Hf,Zr)O2, which were incorporated with minor amounts of boron and carbon. Elastic modulus, Vickers hardness and fracture toughness of HEBs at room temperature were 508.5 GPa, 17.7 ± 0.4 GPa and 4.2 ± 0.2 MPa m1/2, respectively. The as-obtained ceramics possessed excellent flexural strength, particularly at high temperatures. The four-point flexural strengths of HEBs at room temperature, 1600, and 1800°C are 400.4 ± 47.0, 695.9 ± 55.9, and 751.6 ± 23.2 MPa, respectively. Postmortem analysis was conducted on HEB fractured at 1800°C, in the region near their tensile and fracture surfaces, and microstructure observations show that limited dislocation lines were present adjacent to the crack front and edge of the pore, without noticing any trace for dislocation motions. It is the first report on the high-temperature strength of high-entropy diboride ceramics and the strengthening mechanism at high temperatures was also discussed.

摘要

以硼热/碳热还原合成高熵二硼化物粉体为原料, 在2000°C/单轴 加压50 MPa条件下, 经10分钟放电等离子烧结, 成功制备了含有 ∼2 vol%的氧化物和∼1 vol%气孔的高熵(Ti0.2Zr0.2Nb0.2Hf0.2Ta0.2)B2陶瓷 (HEBs). 经研究确认, 其中残留氧化物是固溶少量硼和碳的m-(Hf,Zr)O2. 室温下HEBs的弹性模量、维氏硬度和断裂韧性分别为 508.5 GPa、17.7 ± 0.4 GPa和4.2 ± 0.2 MPa m1/2. 烧结得到的HEBs具有 优良的抗弯强度, 特别是其高温强度. HEBs在室温、1600和1800°C下 的四点抗折强度分别为400.4 ± 47.0 MPa、695.9 ± 55.9 MPa和751.6 ± 23.2 MPa. 对1800°C下断裂的HEBs样品进行了失效分析, 在其拉伸和断 裂面附近区域, 仅在裂纹尖端和孔隙边缘发现了数量有限的位错线的 存在, 没有观察到位错运动的痕迹. 本研究首次报道了高熵二硼化物陶 瓷的高温强度, 发现其强度直至1800°C并无衰减, 并对其高温下的强韧 化机制进行了有益的探讨.

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References

  1. Binner J, Porter M, Baker B, et al. Selection, processing, properties and applications of ultra-high temperature ceramic matrix composites, UHTCMCs—A review. Int Mater Rev, 2019, 65: 389–444

    Article  Google Scholar 

  2. Fahrenholtz WG, Binner J, Zou J. Synthesis of ultra-refractory transition metal diboride compounds. J Mater Res, 2016, 31: 2757–2772

    Article  CAS  Google Scholar 

  3. Paul A, Binner J, Vaidhyanathan B, et al. UHTC composites for hypersonic applications. Am Ceram Soc Bull, 2012, 91: 22–29

    CAS  Google Scholar 

  4. Fahrenholtz WG, Hilmas GE, Talmy IG, et al. Refractory diborides of zirconium and hafnium. J Am Ceramic Soc, 2007, 90: 1347–1364

    Article  CAS  Google Scholar 

  5. Zhang X, Wang Z, Sun X, et al. Effect of graphite flake on the mechanical properties of hot pressed ZrB2-SiC ceramics. Mater Lett, 2008, 62: 4360–4362

    Article  CAS  Google Scholar 

  6. Wang Z, Wang S, Zhang X, et al. Effect of graphite flake on microstructure as well as mechanical properties and thermal shock resistance of ZrB2-SiC matrix ultrahigh temperature ceramics. J Alloys Compd, 2009, 484: 390–394

    Article  CAS  Google Scholar 

  7. Wang Z, Hong C, Zhang X, et al. Microstructure and thermal shock behavior of ZrB2-SiC-graphite composite. Mater Chem Phys, 2009, 113: 338–341

    Article  CAS  Google Scholar 

  8. Ma HB, Zou J, Lu P, et al. Oxygen contamination on the surface of ZrB2 powders and its removal. Scripta Mater, 2017, 127: 160–164

    Article  CAS  Google Scholar 

  9. Pellegrini C, Balat-Pichelin M, Rapaud O, et al. Oxidation resistance and emissivity of diboride-based composites containing tantalum disilicide in air plasma up to 2600 K for space applications. Ceramics Int, 2022, 48: 27878–27890

    Article  CAS  Google Scholar 

  10. Harrington GJK, Hilmas GE, Fahrenholtz WG. Effect of carbon on the thermal and electrical transport properties of zirconium diboride. J Eur Ceramic Soc, 2015, 35: 887–896

    Article  CAS  Google Scholar 

  11. Lonergan JM, Fahrenholtz WG, Hilmas GE. Zirconium diboride with high thermal conductivity. J Am Ceram Soc, 2014, 97: 1689–1691

    Article  CAS  Google Scholar 

  12. Fu Q, Zhang P, Zhuang L, et al. Micro/nano multiscale reinforcing strategies toward extreme high-temperature applications: Take carbon/carbon composites and their coatings as the examples. J Mater Sci Tech, 2022, 96: 31–68

    Article  Google Scholar 

  13. Ni D, Cheng Y, Zhang J, et al. Advances in ultra-high temperature ceramics, composites, and coatings. J Adv Ceram, 2022, 11: 1–56

    Article  CAS  Google Scholar 

  14. Feng L, Fahrenholtz WG, Hilmas GE. Processing of dense high-entropy boride ceramics. J Eur Ceramic Soc, 2020, 40: 3815–3823

    Article  CAS  Google Scholar 

  15. Qin M, Gild J, Wang H, et al. Dissolving and stabilizing soft WB2 and MoB2 phases into high-entropy borides via boron-metals reactive sintering to attain higher hardness. J Eur Ceramic Soc, 2020, 40: 4348–4353

    Article  CAS  Google Scholar 

  16. Zhang Y, Jiang ZB, Sun SK, et al. Microstructure and mechanical properties of high-entropy borides derived from boro/carbothermal reduction. J Eur Ceramic Soc, 2019, 39: 3920–3924

    Article  CAS  Google Scholar 

  17. Dai FZ, Wen B, Sun Y, et al. Grain boundary segregation induced strong UHTCs at elevated temperatures: A universal mechanism from conventional UHTCs to high entropy UHTCs. J Mater Sci Tech, 2022, 123: 26–33

    Article  Google Scholar 

  18. Feng L, Fahrenholtz WG, Brenner DW. High-entropy ultra-high-temperature borides and carbides: A new class of materials for extreme environments. Annu Rev Mater Res, 2021, 51: 165–185

    Article  CAS  Google Scholar 

  19. Silvestroni L, Kleebe HJ, Fahrenholtz WG, et al. Super-strong materials for temperatures exceeding 2000°C. Sci Rep, 2017, 7: 1–8

    Article  Google Scholar 

  20. Zou J, Zhang GJ, Kan YM. Formation of tough interlocking microstructure in ZrB2-SiC-based ultrahigh-temperature ceramics by pressureless sintering. J Mater Res, 2009, 24: 2428–2434

    Article  CAS  Google Scholar 

  21. 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

    Article  CAS  Google Scholar 

  22. Csanádi T, Vojtko M, Dankházi Z, et al. Small scale fracture and strength of high-entropy carbide grains during microcantilever bending experiments. J Eur Ceramic Soc, 2020, 40: 4774–4782

    Article  Google Scholar 

  23. Han X, Girman V, Sedlak R, et al. Improved creep resistance of high entropy transition metal carbides. J Eur Ceramic Soc, 2020, 40: 2709–2715

    Article  CAS  Google Scholar 

  24. Shen XQ, Liu JX, Li F, et al. Preparation and characterization of diboride-based high entropy (Tia0.2Zr0.2Hfa0.2Nba0.2Ta0.2)B2-SiC particulate composites. Ceramics Int, 2019, 45: 24508–24514

    Article  Google Scholar 

  25. Qin Y, Liu JX, 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. J Adv Ceram, 2022, 11: 1082–1092

    Article  CAS  Google Scholar 

  26. Gild J, Zhang Y, 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

    Article  CAS  Google Scholar 

  27. Zhang Y, Sun SK, Guo WM, et al. Fabrication of textured (Hf0.2Zr0.2-Ta0.2Cr0.2Ti0.2)B2 high-entropy ceramics. J Eur Ceramic Soc, 2021, 41: 1015–1019

    Article  CAS  Google Scholar 

  28. Zhang Y, Guo WM, Jiang ZB, et al. Dense high-entropy boride ceramics with ultra-high hardness. Scripta Mater, 2019, 164: 135–139

    Article  CAS  Google Scholar 

  29. Zhang SC, Hilmas GE, Fahrenholtz WG. Pressureless densification of zirconium diboride with boron carbide additions. J Am Ceramic Soc, 2006, 89: 1544–1550

    Article  CAS  Google Scholar 

  30. Zou J, Zhang G, Kan Y, et al. Pressureless densification of ZrB2-SiC composites with vanadium carbide. Scripta Mater, 2008, 59: 309–312

    Article  CAS  Google Scholar 

  31. 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

    Article  CAS  Google Scholar 

  32. Murchie AC, Watts JL, Fahrenholtz WG, et al. Room-temperature mechanical properties of a high-entropy diboride. Int J Appl Ceramic Tech, 2022, 19: 2293–2299

    Article  CAS  Google Scholar 

  33. Zhang Z, Zhu S, Liu Y, et al. Phase structure, mechanical properties and thermal properties of high-entropy diboride (Hf0.25Zr0.25Ta0.25Sc0.25)B2. J Eur Ceramic Soc, 2022, 42: 5303–5313

    Article  CAS  Google Scholar 

  34. Gu J, Zou J, Sun SK, et al. Dense and pure high-entropy metal diboride ceramics sintered from self-synthesized powders via boro/carbothermal reduction approach. Sci China Mater, 2019, 62: 1898–1909

    Article  CAS  Google Scholar 

  35. Spencer PJ. Development of a thermodynamic database for refractory boride, carbide, nitride and silicide systems. In: Materials Science & Technology 2017 Conference & Exhibition. Pittsburgh, 2017: 1230–1238

  36. Saxena S, Spencer P, Drozd V. An alternative, environmentally friendly production process for refractory metal carbides and syngas using methane reduction of the oxide ores. Monatsh Chem, 2018, 149: 411–422

    Article  CAS  Google Scholar 

  37. Li H, Bradt RC. The microhardness indentation load/size effect in rutile and cassiterite single crystals. J Mater Sci, 1993, 28: 917–926

    Article  CAS  Google Scholar 

  38. Liu L, Hou Z, Zhao Y, et al. Fabrication of ZrB2 ceramics by reactive hot pressing of ZrB and B. J Am Ceram Soc, 2018, 101: 5294–5298

    Article  CAS  Google Scholar 

  39. Li LH, Kim HE, Son Kang E. Sintering and mechanical properties of titanium diboride with aluminum nitride as a sintering aid. J Eur Ceramic Soc, 2002, 22: 973–977

    Article  CAS  Google Scholar 

  40. Zou J, Zhang GJ, Hu CF, et al. Strong ZrB2-SiC-WC ceramics at 1600°C. J Am Ceram Soc. 2012, 95: 874–878

    CAS  Google Scholar 

  41. Zou J, Zhang GJ, Hu CF, et al. High-temperature bending strength, internal friction and stiffness of ZrB2-20 vol% SiC ceramics. J Eur Ceramic Soc, 2012, 32: 2519–2527

    Article  CAS  Google Scholar 

  42. Zou J, Zhang GJ, Vleugels J, et al. High temperature strength of hot pressed ZrB2–20 vol% SiC ceramics based on ZrB2 starting powders prepared by different carbo/boro-thermal reduction routes. J Eur Ceramic Soc, 2013, 33: 1609–1614

    Article  CAS  Google Scholar 

  43. Ando K, Houjyou K, Chu MC, et al. Crack-healing behavior of Si3N4/SiC ceramics under stress and fatigue strength at the temperature of healing (1000°C). J Eur Ceramic Soc, 2002, 22: 1339–1346

    Article  Google Scholar 

  44. Lange FF, Gupta TK. Crack healing by heat treatment. J Am Ceramic Soc, 1970, 53: 54–55

    Article  CAS  Google Scholar 

  45. Lange FF, Radford KC. Healing of surface cracks in polycrystalline Al2O3. J Am Ceramic Soc, 1970, 53: 420–421

    Article  CAS  Google Scholar 

  46. Luo W, Yan S, Zhou J. Ceramic-based dielectric metamaterials. Interdisciplinary Mater, 2022, 1: 11–27

    Article  Google Scholar 

  47. Nabarro FRN. Fifty-year study of the Peierls-Nabarro stress. Mater Sci Eng-A, 1997, 234–236: 67–76

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (52022072, 51972243, 92060202 and 52202067), the National Key R&D Programs (2021YFB3701400), Hubei Provincial Natural Science Foundation of China (Distinguished Young Scholars 2022CFA042), Independent Innovation Projects of Hubei Longzhong Laboratory (2022ZZ-10), and the Research Fund for Central Universities (2020IVB074 and 2021IVA094). The authors appreciate Dr. Junfeng Gu and Dr. Haiyue Xu for their help with sample preparations.

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Authors and Affiliations

  1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China

    Jie Liu  (柳洁), Qing-Qing Yang  (杨青青), Ji Zou  (邹冀), Wei-Min Wang  (王为民) & Zheng-Yi Fu  (傅正义)

  2. Hubei Longzhong Laboratory, Xiangyang, 441000, China

    Jie Liu  (柳洁), Ji Zou  (邹冀), Wei-Min Wang  (王为民) & Zheng-Yi Fu  (傅正义)

  3. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 201899, China

    Qing-Qing Yang  (杨青青) & Xin-Gang Wang  (王新刚)

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  1. Jie Liu  (柳洁)
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Contributions

All authors participated in the discussion of the results. Zou J conceived the idea of this work. Liu J, Yang QQ and Zou J performed the main experiments. Fu ZY and Wang WM provided resources and helped construct the framework of the manuscript. Yang QQ and Wang XG measured the high-temperature strength. Liu J and Zou J wrote the paper, which was revised by Wang WM and Fu ZY.

Corresponding authors

Correspondence to Ji Zou  (邹冀), Xin-Gang Wang  (王新刚) or Zheng-Yi Fu  (傅正义).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Jie Liu is currently a Master’s student at the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology. Her research focuses on the strengthening mechanisms and properties of high-entropy diboride ceramics.

Qing-Qing Yang is currently a research assistant at the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology. Her research focuses on the microstructure control and ultra-high temperature mechanical properties of high-entropy ceramics.

Ji Zou is a professor at Wuhan University of Technology. He received his PhD degree from Shanghai Institute of Ceramics, Chinese Academy of Sciences. He has been active in the processing-structure-property correlation of ceramics and composites, especially for borides.

Xin-Gang Wang is a senior engineer at Shanghai institute of Ceramics, Chinese Academic of Sciences. He graduated from the same institute and worked from there since then. His current research interests include ceramics for extreme environments and the mechanical performances for coatings and fibers.

Zheng-Yi Fu is a chief professor and an academician of Chinese Academy of Engineering at the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology. He received his PhD degree from Wuhan University of Technology in 1994. His current research interests include advanced ceramics, composites and their bioprocess-in-spired fabrication.

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Liu, J., Yang, QQ., Zou, J. et al. Strong high-entropy diboride ceramics with oxide impurities at 1800°C. Sci. China Mater. 66, 2061–2070 (2023). https://doi.org/10.1007/s40843-022-2287-7

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