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(UHTCs)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UHTCs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。采用1600 ℃热压烧结制备了ZrB₂-HfSi₂陶瓷, 结果表明, 在烧结过程中, HfSi₂相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, 促进了烧结粉体之间的物质交换, 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), 晶格失配度低(<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±83) MPa、(15.86±0.72) GPa以及(2.01±0.36) 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UHTCs低温烧结提供了重要的参考价值。

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 ultra-high temperature ceramics (UHTCs), 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 sintering process of ZrB₂-based UHTCs by introducing HfSi₂ as a sintering aid, specifically addressing the challenge of densification caused by low intrinsic diffusion coefficient of traditional ZrB₂ ceramics. The research focuses on elucidating formation mechanism of core-rim structured borides and their role in enhancing densification of ZrB₂-HfSi₂ ceramics. Dense ZrB₂-HfSi₂ ceramics were successfully fabricated via hot-press sintering at 1600 ℃. The results reveal that softening of HfSi₂ phase 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 formation of a core-rim structured ZrB₂/(Zr,Hf)B₂ composite. 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 a low lattice mismatch (<5%), ensuring interfacial stability. The ZrB₂-HfSi₂ ceramic exhibits a compressive strength of (1333±83) MPa, a Vickers hardness of (15.86±0.72) GPa, and a fracture toughness of (2.01±0.36) MPa·m^1/2. 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 low-temperature sintering of UHTCs and underscore potential of core-rim structures in advancing the preparation of high-performance ceramics.

Key words: ZrB₂-HfSi₂ ceramic, HfSi₂ sintering aid, densification, core-rim structure, 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, 2025, 40(7): 817-825.

WEI Zhifan, CHEN Guoqing, ZU Yufei, LIU Yuan, LI Minghao, FU Xuesong, ZHOU Wenlong. ZrB₂-HfSi₂ Ceramics: Microstructure and Formation Mechanism of Core-rim Structure[J]. Journal of Inorganic Materials, 2025, 40(7): 817-825.

图/表 11

图1 (a) ZrB2-HfSi2陶瓷致密化曲线; (b)其他ZrB2基陶瓷的烧结温度及相对密度[27-34]

Fig. 1 (a) Densification curve of ZrB2-HfSi2 ceramic; (b) Sintering temperature and relative density of other ZrB2 based ceramics[27-34]

图2 ZrB2-HfSi2陶瓷的XRD图谱

Fig. 2 XRD patterns of ZrB2-HfSi2 ceramic

图3 (a, b) ZrB2-HfSi2陶瓷的显微组织(a)及其局部放大图(b); (c) ZrB2-HfSi2陶瓷的EDS结果; (d)反应(6)的吉布斯自由能

Fig. 3 (a) Microstructure and (b) partial enlarged microstructure of ZrB2-HfSi2 ceramic; (c) EDS results of ZrB2-HfSi2 ceramic; (d) Gibbs free energy of the reaction (6)

图4 ZrB2-HfSi2陶瓷核-周结构的EBSD分析图

Fig. 4 EBSD analysis diagrams of ZrB2-HfSi2 ceramic with core-rim structure (a) Core-rim structure microstructure; (b) Phase distribution of core-rim structure; (c) IPF of core-rim structure; (d) Orientation angle difference of interface position

图5 (a) ZrB2-HfSi2陶瓷的STEM照片及其元素分布图; (b)核-周结构界面处的显微组织及SAED图案; (c)图5(b)中界面选取位置的HRTEM照片

Fig. 5 (a) STEM image and element distribution of ZrB2-HfSi2 ceramic; (b) Microstructure at the interface of core-rim structure and SAED patterns; (c) HRTEM images of the selected interface position in Fig. 5(b)

表1 晶面间距及失配度的测量值和理论值

Table 1 Measured and theoretical values of the interplanar spacing and misfit ratio

Crystalline plane	Plane spacing measured/ theoretical value	Crystalline plane	Plane spacing measured/ theoretical value	Mismatch ratio measured/theoretical value	Interface
(1¯10¯1)_ZrB2	0.213/0.216 nm	(1¯10¯1)_(Zr,Hf)B2	0.216/0.215 nm	1.4%/0.4%	Common lattice interface
(01¯1¯1)_ZrB2	0.209/0.216 nm	(01¯1¯1)_(Zr,Hf)B2	0.213/0.215 nm	1.9%/0.4%	Common lattice interface
(01¯11)_(Zr,Hf)B2	0.214/0.215 nm	(0¯20)_(Zr,Hf)Si2	0.730/0.734 nm	228.5%/243.4%	Noncommon lattice interface
(¯1102)_(Zr,Hf)B2	0.146/0.148 nm	(1¯1¯1)_(Zr,Hf)Si2	0.260/0.258 nm	78.1%/74.3%	Noncommon lattice interface

图6 (a)(Zr,Hf)Si2/(Zr,Hf)B2界面处的显微组织及SAED图案; (b)图6(a)中界面选取位置的HRTEM照片

Fig. 6 (a) Microstructure at the interface of (Zr,Hf)Si2/ (Zr,Hf)B2 and SAED patterns; (b) HRTEM images of the selected interface position in Fig. 6(a)

图7 ZrB2-HfSi2核-周结构界面形成机理图

Fig. 7 Formation mechanism diagram of core-rim structure interface in ZrB2-HfSi2 During the initial stage, the surface of ZrB2 melts, and Hf partially dissolves in the transient liquid phase to form a core. During the middle stage, Hf solute diffuses through the transient liquid phase to the surface of the unmelted ZrB2 nucleus, and then precipitates to form a high Hf solubility (Zr,Hf)B2 peripheral layer. During the later stage, the remaining Zr-rich transient liquid phase precipitates to form (Zr,Hf)Si2 phase, and finally forms the hierarchical relationship of ZrB2-(Zr,Hf)B2-(Zr,Hf)Si2.

图8 ZrB2-HfSi2陶瓷烧结过程中微观结构的演变过程

Fig. 8 Process of microstructure evolution during the sintering of ZrB2-HfSi2 ceramic

图9 (a) ZrB2、(Zr,Hf)B2和(Zr,Hf)Si2纳米压痕试验的载荷-位移曲线; (b)显微组织中ZrB2、(Zr,Hf)B2和(Zr,Hf)Si2的硬度

Fig. 9 (a) Load-displacement curves of ZrB2, (Zr,Hf)B2 and (Zr,Hf)Si2 in nano indentation experiment; (b) Hardnesses of ZrB2, (Zr,Hf)B2 and (Zr,Hf)Si2 in the microstructures

图10 (a) ZrB2-HfSi2陶瓷的断口组织形貌; (b)核-周结构的解理平台; (c)放大的断口组织及其(d) EDS元素分布

Fig. 10 (a) Fracture microstructure of ZrB2-HfSi2 ceramics; (b) Cleavage platform of core-rim structure; (c) Enlarged drawing of fracture and (d) corresponding EDS element distributions

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ZrB₂-HfSi₂复相陶瓷显微组织及其核-周结构形成机制

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

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