钽表面 (WMoCrTa)Si ₂ 高熵硅化物涂层制备及 1400 ℃抗氧化性能

Preparation and oxidation resistance at 1400 ℃ of (WMoCrTa)Si ₂ high entropy silicide coatings on tantalum surface

摘要

以硅化物粉末为原料，采用料浆烧结+卤化物活化包埋渗硅两步法在钽金属表面制备了 (WMoCrTa)Si₂ 高熵硅化物涂层，研究了 1400 ℃下涂层的抗氧化性能。结果表明，最终形成的涂层呈现四层结构，由外至内依次为多孔高熵硅化物相层、铬钽硅化物层、致密 TaSi₂ 层及 Ta₅Si₃ 过渡层，总厚度约 186 μm。在 1400 ℃静态氧化环境中，该涂层可作为有效防护屏障为钽基体提供超过 14 h 的高温保护，其氧化增重曲线呈现“缓慢增长-快速增重-趋于稳定”三阶段特征。氧化初期，涂层表面快速形成致密 SiO₂ 保护膜，Cr 元素优先与氧反应生成 Cr₂O₃，进而与 Ta₂O₅ 反应形成 CrTaO₄，二者协同作用显著提升氧化膜的结构稳定性与阻氧能力；氧化后期，受 SiO₂ 膜剥落、内部孔洞增多等缺陷影响，涂层保护效果逐渐变差。

Abstract

The (WMoCrTa)Si ₂ coatings were prepared by two-step process, involving slurry sintering followed by halide-activated pack cementation, with the silicide powders as the raw materials. The oxidation resistance at 1400 ℃ of the coatings on tantalum surface was investigated. In the results, the four-layer structure is present in the final coatings: the porous high-entropy silicide layers, the chromium-tantalum silicide layers, the TaSi ₂ interlayers, and the innermost Ta ₅Si ₃ layers with the overall thickness of 186 μm. Under the static air oxidation at 1400 ℃, the coatings can protect the tantalum substrate for over 14 h, with the mass gain curves showing a three-stage behavior as slow growth, rapid gain, and gradual stabilization. In the initial stage, the dense SiO ₂ scale is formed rapidly, Cr is preferentially oxidized to Cr ₂O ₃, which further reacts with Ta ₂O ₅ to form CrTaO ₄, and the synergy enhances the stability and oxygen-blocking ability of the coatings. In the later stages of oxidation, the protective performance of the coatings finally deteriorates due to the SiO ₂ spallation and the internal pore proliferation.

关键词

涂层 / 高熵硅化物 / 钽金属 / 抗氧化性能

Key words

coatings / high-entropy silicide / tantalum / oxidation deteriorate

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基金资助

湖南省科技创新计划资助项目(2024AQ2039)

湖南省科技创新计划资助项目(2025RC3026)

湖南省自然科学基金资助项目(2026JJ50455)