ZrB2-HfSi2复相陶瓷显微组织及其核-周结构形成机制

doi:10.15541/jim20250060

摘要/Abstract

摘要： 近年来,ZrB₂作为超高温陶瓷的代表性材料,已成为新一代空天飞行器热端部件重要的候选材料体系。然而,其实际应用受限于材料制备以及复杂构件的加工难题。为此本研究通过引入HfSi₂作为烧结助剂,优化ZrB₂基超高温陶瓷的烧结工艺,重点解决传统ZrB₂基陶瓷因较低的扩散系数而导致致密化困难的难题。研究聚焦于核-周结构硼化物的形成机制以及其对ZrB₂-HfSi₂陶瓷致密化的辅助作用。研究采用1600 ℃热压烧结成功制备了ZrB₂-HfSi₂陶瓷,结果发现：在烧结过程中,HfSi₂相的软化能够有效填充颗粒间隙,从而实现ZrB₂-HfSi₂陶瓷的低温烧结。同时,在保温阶段,Hf与Zr原子通过溶解-再沉淀机制形成具有核-周结构的ZrB₂/(Zr,Hf)B₂,该过程促进了烧结粉体之间物质交换,从而加速了ZrB₂-HfSi₂陶瓷的致密化。此外,该结构主要由核心ZrB₂及其周边(Zr,Hf)B₂组成,具有完全共格界面(P6/mmm六方结构),晶格失配率低(<5%),界面稳定。ZrB₂-HfSi₂陶瓷的抗压强度、显微硬度以及断裂韧性分别为1333 MPa,15.86 GPa以及2.01 MPa·m^1/2。该陶瓷主要表现为典型的沿晶断裂形式,只有少数解理面上出现核-周结构特征。本研究为实现超高温陶瓷低温烧结提供重要参考价值。

关键词: ZrB₂-HfSi₂陶瓷, HfSi₂烧结助剂, 致密化, 核-周结构, 共格界面

Abstract: In recent years, ZrB₂, as a representative material of ultrahigh temperature ceramics, has become an important candidate material system for components of new generation aerospace vehicles. However, its practical application is limited by difficulties in material preparation and processing of complex components. This study aims to optimize the sintering process of ZrB₂-based ultra-high temperature ceramics (UHTCs) by introducing HfSi₂ as a sintering aid, specifically addressing the challenge of densification caused by the low intrinsic diffusion coefficient of traditional ZrB₂ ceramics. The research focuses on elucidating the formation mechanism of core-rim structured borides and their role in enhancing the densification of ZrB₂-HfSi₂ceramics. Dense ZrB₂-HfSi₂ceramics were successfully fabricated via hot-press sintering at 1600 °C. The results reveal that the softening of the HfSi₂phase during sintering effectively fills interparticle gaps, thereby facilitating low-temperature densification. Furthermore, during the holding stage, interdiffusion of Hf and Zr atoms through a dissolution-reprecipitation mechanism facilitates the formation of a core-rim structured ZrB₂/(Zr,Hf)B₂composite. This core-rim structure consists of ZrB₂ core encased by a (Zr,Hf)B₂ rim, characterized by a fully coherent interface (hexagonal P6/mmm symmetry) with low lattice mismatch (<5%), ensuring interfacial stability. The ZrB₂-HfSi₂ ceramic exhibits a compressive strength of 1333 MPa, Vickers hardness of 15.86 GPa, and fracture toughness of 2.01 MPa·m¹/². The ZrB₂-HfSi₂ ceramic demonstrates typical intergranular fracture behavior, with only a limited number of cleavage planes displaying core-rim structural features. These findings provide critical insights into the low-temperature sintering of UHTCs and underscore the potential of core-rim structures in advancing the preparation of high-performance ceramics.

Key words: ZrB₂-HfSi₂ ceramics, HfSi₂ sintering aid, densification, core-rim structures, coherent interface

中图分类号:

TB332

魏志帆, 陈国清, 祖宇飞, 刘渊, 李明浩, 付雪松, 周文龙. ZrB₂-HfSi₂复相陶瓷显微组织及其核-周结构形成机制[J]. 无机材料学报, DOI: 10.15541/jim20250060.

WEI Zhifan, CHEN Guoqing, ZU Yufei, LIU Yuan, LI Minghao, FU Xuesong, ZHOU Wenlong. Microstructure of ZrB₂-HfSi₂ Ceramics and its Core-rim Structure Formation Mechanism[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250060.

参考文献

[1] PARTHASARATHY T A, PETRY M D, CINIBULK M K, et al. Thermal and oxidation response of UHTC leading edge samples exposed to simulated hypersonic flight conditions. Journal of the American Ceramic Society, 2013, 96(3): 907.
[2] FAHRENHOLTZ W G, HILMAS G E.Ultra-high temperature ceramics: materials for extreme environments.Scripta Materialia, 2017, 129: 94.
[3] FAHRENHOLTZ W G, HILMAS G E, TALMY I G, et al. Refractory diborides of zirconium and hafnium. Journal of the American Ceramic Society, 2007, 90(5): 1347.
[4] MONTEVERDE F, BELLOSI A, GUICCIARDI S.Processing and properties of zirconium diboride-based composites.Journal of the European Ceramic Society, 2002, 22(3): 279.
[5] GOLLA B R, MUKHOPADHYAY A, BASU B, et al. Review on ultra-high temperature boride ceramics. Progress in Materials Science, 2020, 111:100651.
[6] KHANRA A K, GODKHINDI M M.Effect of Ni additives on pressureless sintering of SHS ZrB₂.Advances in Applied Ceramics, 2005, 104(6): 273.
[7] WANG H, CHEN D, WANG C A, et al. Preparation and characterization of high-toughness ZrB2/Mo composites by hot-pressing process. International Journal of Refractory Metals and Hard Materials, 2009, 27(6): 1024.
[8] GUO S Q.Densification of ZrB₂-based composites and their mechanical and physical properties: a review.Journal of the European Ceramic Society, 2009, 29(6): 995.
[9] GUO S.Densification, microstructure, elastic and mechanical properties of reactive hot-pressed ZrB₂-ZrC-Zr cermets.Journal of the European Ceramic Society, 2014, 34(3): 621.
[10] MISHRA S K, PATHAK L C.Effect of carbon and titanium carbide on sintering behaviour of zirconium diboride.Journal of Alloys and Compounds, 2008, 465(1-2): 547.
[11] REZAIE A, FAHRENHOLTZ W G, HILMAS G E.Effect of hot pressing time and temperature on the microstructure and mechanical properties of ZrB₂-SiC.Journal of Materials Science, 2007, 42(8): 2735.
[12] SHA J J, LI J, WANG S H, et al. Toughening effect of short carbon fibers in the ZrB₂-ZrSi₂ ceramic composites. Materials and Design, 2015, 75: 160.
[13] ASL M S, NAYEBI B, AHMADI Z, et al. Effects of carbon additives on the properties of ZrB₂-based composites: a review. Ceramics International, 2018, 44(7): 7334.
[14] SHAHEDI ASL M, FARAHBAKHSH I, NAYEBI B.Characteristics of multi-walled carbon nanotube toughened ZrB₂-SiC ceramic composite prepared by hot pressing.Ceramics International, 2016, 42(1): 1950.
[15] MONTEVERDE F, BELLOSI A.Efficacy of HfN as sintering aid in the manufacture of ultrahigh-temperature metal diborides-matrix ceramics.Journal of Materials Research, 2004, 19(12): 3576.
[16] MONTEVERDE F, BELLOSI A.Effect of the addition of silicon nitride on sintering behaviour and microstructure of zirconium diboride.Scripta Materialia, 2002, 46(3): 223.
[17] MONTEVERDE F, BELLOSI A.Beneficial effects of AlN as sintering aid on microstructure and mechanical properties of hot-pressed ZrB₂.Advanced Engineering Materials, 2003, 5(7): 508.
[18] SILVESTRONI L, SCITI D.Densification of ZrB₂-TaSi₂ and HfB₂-TaSi₂ ultra-high-temperature ceramic composites: Densification of ZrB₂-TaSi₂ and HfB₂-TaSi₂ ceramic composites.Journal of the American Ceramic Society, 2011, 94(6): 1920.
[19] SILVESTRONI L, KLEEBE H J, LAUTERBACH S, et al. Transmission electron microscopy on Zr- and Hf-borides with MoSi₂ addition: Densification mechanisms. Journal of Materials Research, 2010, 25(5): 828.
[20] SCITI D, SILVESTRONI L, CELOTTI G, et al. Sintering and mechanical properties of ZrB₂-TaSi₂ and HfB₂-TaSi₂ ceramic composites. Journal of the American Ceramic Society, 2008, 91(10): 3285.
[21] LAVRENKO V O, PANASYUK A D, GRIGOREV O M, et al. High-temperature (to 1600 °C) oxidation of ZrB₂-MoSi₂ ceramics in air. Powder Metallurgy and Metal Ceramics, 2012, 51(1): 102.
[22] MUSA C, LICHERI R, ORRù R, et al. Synthesis, sintering, and oxidative behavior of HfB₂-HfSi₂ ceramics. Industrial and Engineering Chemistry Research, 2014, 53(22): 9101.
[23] SAJDAK M, KORNAUS K, ZIENTARA D, et al. Processing, microstructure and mechanical properties of TiB₂-MoSi₂-C ceramics. Crystals, 2024, 14(3): 212.
[24] GROHSMEYER R J, SILVESTRONI L, HILMAS G E, et al. ZrB₂ -MoSi₂ ceramics: A comprehensive overview of microstructure and properties relationships. Part I: Processing and microstructure. Journal of the European Ceramic Society, 2019, 39(6): 1939.
[25] NIIHARA K.A fracture mechanics analysis of indentation-induced Palmqvist crack in ceramics.Journal of Materials Science Letters, 1983, 2(5): 221.
[26] ZU Y, CHEN G, FU X, et al. Effects of liquid phases on densification of TiO₂-doped Al₂O₃-ZrO₂ composite ceramics. Ceramics International, 2014, 40(3): 3989.
[27] MELéNDEZ-MARTíNEZ J J, DOMíNGUEZ-RODRíGUEZ A, MONTEVERDE F, et al. Characterisation and high temperature mechanical properties of zirconium boride-based materials. Journal of the European Ceramic Society, 2002, 22(14-15): 2543.
[28] SUN X, HAN W, HU P, et al. Microstructure and mechanical properties of ZrB₂-Nb composite. International Journal of Refractory Metals and Hard Materials, 2010, 28(3): 472.
[29] GUO S Q, KAGAWA Y, NISHIMURA T.Mechanical behavior of two-step hot-pressed ZrB₂-based composites with ZrSi₂.Journal of the European Ceramic Society, 2009, 29(4): 787.
[30] ORLOVSKAYA N, STADELMANN R, LUGOVY M, et al. Mechanical properties of ZrB₂-SiC ceramic composites: room temperature instantaneous behaviour. Advances in Applied Ceramics, 2013, 112(1): 9.
[31] LI W, ZHANG X, HONG C, et al. Microstructure and mechanical properties of zirconia-toughened ZrB₂-MoSi₂ composites prepared by hot-pressing. Scripta Materialia, 2009, 60(2): 100.
[32] ASL M S, KAKROUDI M G, NOORI S.Hardness and toughness of hot pressed ZrB₂-SiC composites consolidated under relatively low pressure.Journal of Alloys and Compounds, 2015, 619: 481.
[33] GUI K, HU P, HONG W, et al. Microstructure, mechanical properties and thermal shock resistance of ZrB₂-SiC-C_f composite with inhibited degradation of carbon fibers. Journal of Alloys and Compounds, 2017, 706: 16.
[34] YANG Y, QIAN Y H, XU J[J] , et al. Effects of TaSi₂ addition on room temperature mechanical properties of ZrB₂-20SiC composites. Ceramics International, 2018, 44(14): 16150.
[35] MONTEVERDE F.Hot pressing of hafnium diboride aided by different sinter additives.Journal of Materials Science, 2008, 43(3): 1002.
[36] LANG Q, LI N, LIU X,et al. Regulating Mg/Fe interfacial compound formation by in-situ alloying with Gd and Y. Journal of Magnesium and Alloys, 2024,12(12): 5179.
[37] SONG G, LI T, ZHANG Z, et al. Investigation of unequal thickness Mg/steel butt-welded plate by hybrid laser-tungsten inert gas welding with a Ni interlayer. Journal of Manufacturing Processes, 2017, 30: 299.
[38] HU D L, GU H, ZOU[J] , et al. Core-rim structure, bi-solubility and a hierarchical phase relationship in hot-pressed ZrB₂-SiC-MC ceramics (M=Nb, Hf, Ta, W). Journal of Materiomics, 2021, 7(1): 69.
[39] ZHU S, LI J, XING[J] , et al. Cathodoluminescence characteristics of a novel core-rim structure in bi-doped (Sr,Ba)TiO₃ ceramics. Ceramics International, 2019, 45(6): 8027.
[40] ENGSTRöM I, LöNNBERG B. Thermal expansion studies of the group IV-VII transition-metal disilicides.Journal of Applied Physics, 1988, 63(9): 4476.
[41] KEIHN F G, KEPLIN E J.High-temperature thermal expansion of certain group IV and group V diborides.Journal of the American Ceramic Society, 1967, 50(2): 81.

ZrB₂-HfSi₂复相陶瓷显微组织及其核-周结构形成机制

Microstructure of ZrB₂-HfSi₂ Ceramics and its Core-rim Structure Formation Mechanism

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