(Hf, Zr, Ta)B2-SiC超高温陶瓷的设计、制备、力学性能与微观结构演变机制

doi:10.15541/jim20260203

无机材料学报

• 研究论文 •

(Hf, Zr, Ta)B₂-SiC超高温陶瓷的设计、制备、力学性能与微观结构演变机制

刘精龙^1,2,3,4, 胡洋^2,3,4, 王晓宇^2,3,4, 陈博文^2,3, 蔡飞燕^2,3, 阚艳梅^2,3, 丁玉生^2,3, 董绍明^2,3, 王震⁵, 倪德伟^1,2,3

1.国科大杭州高等研究院化学与材料科学学院, 杭州 310024;
2.中国科学院上海硅酸盐研究所, 关键陶瓷材料全国重点实验室, 上海 200050;
3.中国科学院上海硅酸盐研究所, 结构陶瓷及复合材料工程研究中心, 上海 200050;
4.中国科学院大学, 北京 100049;
5.浙江航引新材料科技有限公司, 桐乡 314511

收稿日期:2026-05-11 修回日期:2026-06-23
通讯作者: 倪德伟,研究员. E-mail: deweini@mail.sic.ac.cn
作者简介:刘精龙(2000–),男,硕士研究生. E-mail：liujinglong23@mails.ucas.ac.cn
基金资助:
国家自然科学基金(52332003, 52472114, 52402135); 上海市学术/技术带头人项目(23XD1424300); 浙江航引新材料科技有限公司技术开发项目(HY-CG-20250509001) Zhejiang Hangyin New Materials Technology Co., Ltd Technology Development Project(HY-CG-20250509001); 浙江省领军型创业团队项目(2023R02018); 浙江省 “高层次人才特殊支持计划”科技创新领军人才项目(2023R5228); 浙江省"领雁"研发计划项目(2026C02A1055)

(Hf, Zr, Ta)B₂-SiC Ultra-high Temperature Ceramics: Design, Fabrication, Mechanical Properties and Microstructure Evolution Mechanisms

LIU Jinglong^1,2,3,4, HU Yang^2,3,4, WANG Xiaoyu^2,3,4, CHEN Bowen^2,3, CAI Feiyan^2,3, KAN Yanmei^2,3, DING Yusheng^2,3, DONG Shaoming^2,3, WANG Zhen⁵, NI Dewei^1,2,3

1. School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China;
2. State Key Laboratory of High Performance Ceramics, Chinese Academy of Sciences, Shanghai 200050, China;
3. Structural Ceramics and Composites Engineering Research Center, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China;
4. University of Chinese Academy of Sciences, Beijing 100049, China;
5. Zhejiang Hangyin Technology Co., Ltd., Tongxiang 314511, China

Received:2026-05-11 Revised:2026-06-23
Contact: Ni Dewei, Professor. E-mail: deweini@mail.sic.ac.cn
About author:Liu Jinglong (2000-), male, PhD candidate. liujinglong23@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China (52332003, 52472114, 52402135); Shanghai Excellent Academic/Technical Leaders Program(23XD1424300); Zhejiang Provincial Leading Entrepreneurial Team Program(2023R02018); The Leading Scientific and Technological Innovation Talent Project under the Zhejiang Provincial Special Support Program for High-Level Talent(2023R5228); Zhejiang Provincial "Leading Goose" R&D Program (2026C02A1055)

摘要/Abstract

摘要： 新一代高速飞行器的发展对高性能热结构材料提出了迫切需求。本研究通过反应热压和Ta : Hf(Zr)比例调控,制备了系列(Hf, Zr, Ta)B₂-SiC超高温陶瓷(UHTCs),并系统研究了其力学性能与微观结构演变机制。首先,采用硼热/碳热还原法合成了不同Ta : Hf(Zr)比例的(Hf, Zr, Ta)B₂固溶粉体;随后以Si为烧结助剂,在1800 ℃下通过反应热压工艺,利用Si与C的原位反应在较低温度(1800 ℃)下实现了材料的致密化,并同步原位生成SiC;接着,系统探究了反应热压过程中陶瓷的微观结构演变机制,明确了Si含量对致密化行为与力学性能的影响规律。结果表明,当Si质量分数为7%时,(Hf, Zr)B₂-SiC陶瓷的开口气孔率仅为0.5%,弯曲强度与断裂韧性分别为386 MPa和2.71 MPa·m^1/2。此外,本工作系统研究了Ta : Hf(Zr)比例对(Hf, Zr, Ta)B₂-SiC陶瓷微观结构及力学性能的影响,发现Ta的引入可有效抑制晶粒长大、细化显微组织。随着Ta : Hf(Zr)比例增加,陶瓷的硬度与弯曲强度均有所升高。本工作为多组元UHTCs的设计、制备和性能优化奠定了基础。

关键词: (Hf,Zr,Ta)B₂, SiC, 反应热压, 致密化, 力学性能

Abstract: The development of next-generation high-speed aircraft has created an urgent demand for high-performance thermal structure materials. In this study, a series of (Hf, Zr, Ta)B₂-SiC ultra-high temperature ceramics (UHTCs) were fabricated by reactive hot pressing (RHP) with different Ta : Hf(Zr) ratios, and their mechanical properties and mechanisms were systematically studied. First, (Hf, Zr, Ta)B₂ solid solution powders with different Ta : Hf(Zr) ratios were synthesized by boro/carbothermal reduction. Subsequently, the addition of Si enabled low-temperature (1800 °C) densification via RHP, with SiC formed in situ. The microstructural evolution during RHP was systematically analyzed, which clarified the effect of Si content on densification behavior and mechanical properties. Results show that with 7% (in mass) Si, the apparent porosity of (Hf, Zr)B₂-SiC ceramics was only 0.5%. The flexural strength and fracture toughness reached 386 MPa and 2.71 MPa·m^1/2, respectively. Furthermore, the effect of the Ta : Hf(Zr) ratio on the microstructure and mechanical properties of (Hf, Zr, Ta)B₂-SiC ceramics was systematically investigated. The addition of Ta effectively suppressed grain growth and refined the microstructure. As the Ta : Hf(Zr) ratio increased, the hardness and flexural strength of the ceramics improved. This work establishes a foundation for the design, fabrication, and performance optimization of multicomponent UHTCs.

Key words: (Hf,Zr,Ta)B₂, SiC, reactive hot pressing, densification, mechanical property

中图分类号:

TQ174.1

刘精龙, 胡洋, 王晓宇, 陈博文, 蔡飞燕, 阚艳梅, 丁玉生, 董绍明, 王震, 倪德伟. (Hf, Zr, Ta)B₂-SiC超高温陶瓷的设计、制备、力学性能与微观结构演变机制[J]. 无机材料学报, DOI: 10.15541/jim20260203.

LIU Jinglong, HU Yang, WANG Xiaoyu, CHEN Bowen, CAI Feiyan, KAN Yanmei, DING Yusheng, DONG Shaoming, WANG Zhen, NI Dewei. (Hf, Zr, Ta)B₂-SiC Ultra-high Temperature Ceramics: Design, Fabrication, Mechanical Properties and Microstructure Evolution Mechanisms[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260203.

参考文献

[1] WYATT B C, NEMANI S K, HILMAS G E, et al. Ultra-high temperature ceramics for extreme environments. Nature Reviews Materials, 2024, 9(11): 773.
[2] ZHANG X H, WANG Y M, CHENG Y,et al. Research progress on ultra-high temperature ceramic composites. Journal of Inorganic Materials, 2024, 39(6): 571.
[3] XU Y X, YU L, ZHAO T, et al. Composition design of oxidation resistant non-equimolar high-entropy ceramic materials: an example of (Zr-Hf-Ta-Ti) B₂ ultra-high temperature ceramics. Journal of Advanced Ceramics, 2024, 13(12): 2087.
[4] CHEN S Y, WANG J M, CHEN Z K,et al. Nb-and Ta-doped (Hf, Zr, Ti)C multicomponent carbides with enhanced oxidation resistance at 2500 ℃. Journal of Advanced Ceramics, 2024, 13(3): 332.
[5] 赵涛, 刘吉轩, 徐以祥, 等. 添加SiC对高熵硼化物陶瓷抗激光烧蚀性能的影响. 现代技术陶瓷, 2024, 45(5): 417.
[6] ZHU Z J, LIU Y W, QIN Y B,et al. Tough and strong bioinspired high-entropy all-ceramics with a contiguous network structure. Nature Communications, 2025, 16: 4587.
[7] 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 Materialia, 2020, 197: 81.
[8] FENG L, FAHRENHOLTZ W G, HILMAS G E,et al. Strength retention of single‐phase high‐entropy diboride ceramics up to 2000 ℃. Journal of the American Ceramic Society, 2024, 107(3): 1895.
[9] WEN Z H, LIU Y W, YANG J,et al. Exceptional oxidation resistance of high‐entropy carbides up to 3600 ℃. Advanced Materials, 2025, 37(34): 2507254.
[10] OTANI S, AIZAWA T, KIEDA N.Solid solution ranges of zirconium diboride with other refractory diborides: HfB₂, TiB₂, TaB₂, NbB₂, VB₂ and CrB₂.Journal of Alloys and Compounds, 2009, 475(1/2): 273.
[11] BALAK Z.Shrinkage, hardness and fracture toughness of ternary ZrB₂-SiC-HfB₂ composite with different amount of HfB₂.Materials Chemistry and Physics, 2019, 235: 121706.
[12] HASSAN R, OMAR S, BALANI K.Solid solutioning in ZrB₂ with HfB₂: effect on densification and oxidation resistance.International Journal of Refractory Metals and Hard Materials, 2019, 84: 105041.
[13] YANG B L, KUANG C L, LIU Z L, et al. Oxidation resistance and physical properties of ZrB₂-SiC-HfB₂ coating reinforced with diboride. Ceramics International, 2024, 50(24): 55429.
[14] YU Y, LI L, MA C L,et al. Oxidation resistance, oxidation mechanism and mechanical properties of ZrB₂-SiC-TaB₂ ceramics. Ceramics International, 2025, 51(10): 13522.
[15] TONG K, ZHANG M Y, SU Z A,et al. Ablation behavior of (Zr, Ta) B₂-SiC coating on carbon/carbon composites at 2300 ℃. Corrosion Science, 2021, 188: 109545.
[16] GOLLA B R, MUKHOPADHYAY A, BASU B,et al. Review on ultra-high temperature boride ceramics. Progress in Materials Science, 2020, 111: 100651.
[17] NI D W, CHENG Y, ZHANG J P, et al. Advances in ultra-high temperature ceramics, composites, and coatings. Journal of Advanced Ceramics, 2022, 11(1): 1.
[18] NI D W, ZHANG G J, KAN Y M,et al. Hot pressed HfB₂ and HfB₂-20 vol% SiC ceramics based on HfB₂ powder synthesized by borothermal reduction of HfO₂*. International Journal of Applied Ceramic Technology, 2010, 7(6): 830.
[19] KURBATKINA V V, PATSERA E I, SMIRNOV D V,et al. Part 2. Structure, mechanical and thermophysical properties of consolidated ceramics based on (Hf, Ta) B₂. Ceramics International, 2019, 45(3): 4076.
[20] ZHANG Y, TAN D W, GUO W M,et al. Improvement of densification and microstructure of HfB₂ ceramics by Ta/Ti substitution for Hf. Journal of the American Ceramic Society, 2020, 103(1): 103.
[21] GUO W M, TAN D W, ZENG L Y,et al. Synthesis of fine ZrB₂ powders by solid solution of TaB₂ and their densification and mechanical properties. Ceramics International, 2018, 44(4): 4473.
[22] KANNAN R, RANGARAJ L.Densification, mechanical, and tribological properties of ZrB₂‐ZrC_x composites produced by reactive hot pressing. Journal of the American Ceramic Society, 2020, 103(11): 6120.
[23] SU C, WANG B Z, GUO H,et al. Reactive hot-pressing induced low temperature densification of (Zr, Ta)B₂-SiC ceramics: microstructure and strengthening. Ceramics International, 2025, 51(20): 32049.
[24] GHADAMI S, TAHERI-NASSAJ E, BAHARVANDI H R,et al. Improvement of mechanical properties of HfB₂-based composites by incorporating in situ SiC reinforcement through pressureless sintering. Scientific Reports, 2021, 11: 9835.
[25] EVANS A G, CHARLES E A.Fracture toughness determinations by indentation.Journal of the American Ceramic Society, 1976, 59(7/8): 371.
[26] ZHOU Y C, XIANG H M, FENG Z H,et al. General trends in electronic structure, stability, chemical bonding and mechanical properties of ultrahigh temperature ceramics TMB₂(TM= transition metal). Journal of Materials Science & Technology, 2015, 31(3): 285.
[27] HIGGINS G T, WIRYOLUKITO S, NASH P. The kinetics of coupled phase coarsening in two-phase structures. Materials Science Forum, 1992, 94/95/96: 671.
[28] ZHANG W, ZHANG Y, GUO W M,et al. Powder synthesis, densification, microstructure and mechanical properties of Hf-based ternary boride ceramics. Journal of the European Ceramic Society, 2021, 41(7): 3922.
[29] CHUNG F H.Quantitative interpretation of X-ray diffraction patterns of mixtures. I. Matrix-flushing method for quantitative multicomponent analysis.Journal of Applied Crystallography, 1974, 7(6): 519.
[30] CHUNG F H.Quantitative interpretation of X-ray diffraction patterns of mixtures. II. Adiabatic principle of X-ray diffraction analysis of mixtures.Journal of Applied Crystallography, 1974, 7(6): 526.
[31] CHUNG F H.Quantitative interpretation of X-ray diffraction patterns of mixtures. III. Simultaneous determination of a set of reference intensities.Journal of Applied Crystallography, 1975, 8(1): 17.
[32] BALAK Z, ZAKERI M, RAHIMIPUR M R,et al. Effect of open porosity on flexural strength and hardness of ZrB2-based composites. Ceramics International, 2015, 41(7): 8312.
[33] RICE R W.Comparison of stress concentration versus minimum solid area based mechanical property-porosity relations.Journal of Materials Science, 1993, 28(8): 2187.
[34] DUTTA S K, MUKHOPADHYAY A K, CHAKRABORTY D.Assessment of strength by Young's modulus and porosity: a critical evaluation.Journal of the American Ceramic Society, 1988, 71(11): 942.
[35] SELSING J.Internal stresses in ceramics. Journal of the American Ceramic Society, 1961, 44(8): 419.
[36] LIU Y W, MA M D, WANG W,et al. Lattice distortion enhanced hardness in high‐entropy borides. Advanced Functional Materials, 2025, 35(11): 2416992.
[37] ZHU Q Q, ZHANG Z, ZHANG Y,et al. Effects of TaB₂ and TiB₂ on the grain growth behavior and kinetics of HfB₂ ceramics during pressureless sintering. Journal of the American Ceramic Society, 2020, 103(5): 3330.
[38] ENGEL U, HÜBNER H. Strength improvement of cemented carbides by hot isostatic pressing (HIP).Journal of Materials Science, 1978, 13(9): 2003.

(Hf, Zr, Ta)B₂-SiC超高温陶瓷的设计、制备、力学性能与微观结构演变机制

(Hf, Zr, Ta)B₂-SiC Ultra-high Temperature Ceramics: Design, Fabrication, Mechanical Properties and Microstructure Evolution Mechanisms

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