反应热压烧结制备（Zr_0.5Ta_0.5）B₂-SiC 复相陶瓷的 组织结构演化及抗氧化性能

Microstructural evolution and oxidation resistance of (Zr_0.5Ta_0.5)B₂-SiC multiphase ceramics by reactive hot pressing

摘要

超高温陶瓷是应用于 2000 ℃以上极端环境下的重要候选材料之一。为了进一步提升其抗氧化和抗烧蚀性能，采用反应热压烧结工艺，以 TaSi₂、ZrSi₂、B₄C 和 C 为原料通过原位反应制备复相陶瓷，研究复相陶瓷的微观组织结构、硬度、断裂韧性和抗氧化性能。结果表明，在 1200 ℃下，原位反应形成 ZrB₂-TaB₂-SiC 复相陶瓷材料；而在 1500 ℃下，可发生原位固溶反应，并形成（Zr_0.5Ta_0.5）B₂-SiC 固溶复相陶瓷。与 ZrB₂-TaB₂-SiC 复相陶瓷相比，（Zr_0.5Ta_0.5）B₂-SiC 的硬度从 12.59 GPa 提高到 15.11 GPa，断裂韧性从 3.66 MPa·m^1/2 提高到 5.89 MPa·m^1/2。同时，（Zr_0.5Ta_0.5）B₂-SiC 固溶复相陶瓷具有优异的抗氧化性能，大气环境下的热重分析表明，1600 ℃时氧化导致质量增重为 0.48 mg/cm²，其抗氧化性能改善主要归因于多相氧化物的协同作用和稳定氧化物保护膜的形成，从而降低氧在氧化层中的扩散率。

Abstract

Ultra-high temperature ceramics (UHTCs) are regarded as highly promising materials for aerospace applications due to their exceptional thermal and mechanical stability under harsh environmental conditions. In this study， to further enhance the performance of UHTCs across a broad temperature range，multiphase ceramics are fabricated through a combination of in-situ reaction and hot-pressing techniques， utilizing TaSi₂， ZrSi₂， B₄C， and C as raw materials. Subsequently， the microstructure， micromechanical properties，and oxidation resistance of the prepared ceramics are thoroughly investigated. The results reveal that the ZrB₂-TaB₂-SiC multiphase ceramic is formed at 1200 ℃. As the temperature increasing to 1500 ℃，the ZrB₂-TaB₂-SiC ceramic undergoes an in-situ solid-solution reaction，transforming into (Zr_0.5Ta_0.5)B₂-SiC. In terms of mechanical properties，the hardness values are 12.59 GPa for ZrB₂-TaB₂-SiC and 15.11 GPa for (Zr_0.5Ta_0.5)B₂-SiC，respectively. Similarly，the fracture toughness values are 3.66 MPa·m^1/2 for ZrB₂-TaB₂-SiC and 5.89 MPa·m^1/2 for (Zr_0.5Ta_0.5)B₂-SiC， respectively. Thermogravimetric analysis demonstrates that the (Zr_0.5Ta_0.5)B₂-SiC solid-solution multiphase ceramics exhibit outstanding oxidation resistance. Specifically，the mass gain is only 0.48 mg/cm² when the temperature reaches up to 1600 ℃. The mechanism underlying this excellent oxidation resistance can be attributed to synergistic effect of multiphase oxides，which stabilizes oxidation film and reduces diffusion rate of oxygen.

关键词

超高温陶瓷 / 硼化物固溶体 / 复相陶瓷 / 原位反应 / 热压烧结

Key words

ultra-high temperature ceramics / boride solid solution / multiphase ceramics / in-situ reaction / hot pressing sintering

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基金资助

国家自然科学基金(U2241239)

中国博士后科学基金(2024M750314)

国家资助博士后研究人员计划(GZB20230096)

大连市青年科技之星(2024RQ005)