添加Si对(Ti0.2Zr0.2Hf0.2Ta0.2Mo0.2)C基高熵陶瓷等温氧化行为的影响及其机理

doi:10.15541/jim20260322

摘要/Abstract

摘要： 过渡金属碳化物高熵陶瓷在高温氧化环境中的失效问题严重制约了其作为耐磨材料的应用,添加第二相进行改性是一种有效的解决途径。本研究通过在(Ti_0.2Zr_0.2Hf_0.2Ta_0.2Mo_0.2)C(HEC)高熵陶瓷中添加不同质量分数(0、2.5%、5.0%、10.0%)的Si,经放电等离子烧结原位生成SiC及MoSi₂第二相,系统研究了Si添加量对HEC陶瓷1500 ℃等温氧化行为的影响规律和内在机理。结果表明,未添加Si的HEC陶瓷氧化层疏松多孔,并因MoO₃(g)和CO(g)的逸出而呈现氧化失重行为。添加Si后,所有复相陶瓷均转为轻微的氧化增重行为。其中,添加5%Si的HEC陶瓷表现出最优的抗氧化性能,其氧化表面平整且较致密,从最外侧到基体之间共形成了具有四层结构的氧化层。其中,富Ti氧化物最外层和(Zr,Hf)₆Ta₂O₁₇次外层均较致密,有效抑制了氧的内扩散和挥发性MoO₃(g)的形成。然而,过量添加Si(10%)会生成过多SiO₂液相,导致氧化层内形成大量连通孔隙,削弱保护效果。本研究为高熵碳化物陶瓷的抗氧化组分设计提供了实验依据。

关键词: 高熵碳化物, 碳化硅, 二硅化钼, 等温氧化, 抗氧化性能

Abstract: The failure of transition metal carbide high-entropy ceramics in high-temperature oxidative environments severely limits their application as wear-resistant materials. Incorporating secondary phases to modify them represents an effective strategy to address this issue. In this study, different mass fractions (0, 2.5%, 5%, 10%) of Si were added to (Ti_0.2Zr_0.2Hf_0.2Ta_0.2Mo_0.2)C (HEC) high-entropy ceramics, and SiC and MoSi₂ secondary phases were generated in-situ via spark plasma sintering. The effects of Si content on the isothermal oxidation behavior of HEC ceramics at 1500 ℃ and its underlying mechanism were systematically investigated. The results indicate that the oxidation scale of Si-free HEC ceramic is loose and porous, exhibiting mass loss due to the release of MoO₃ (g) and CO (g). Upon Si addition, all composite ceramics exhibited a slight mass gain. Among them, the HEC ceramic with 5%Si addition exhibited the best oxidation resistance, characterized by a flat and relatively dense oxide scale surface, along with a four-layered oxide scale structure extending from the outermost layer to the substrate. Both the outermost Ti-rich oxide layer and the subouter (Zr,Hf)₆Ta₂O₁₇ layer are relatively dense, which effectively suppresses inward oxygen diffusion and the formation of volatile MoO₃ (g). However, excessive Si addition (10%) led to the formation of an excessive SiO₂ liquid phase, generating numerous interconnected pores within the oxide scale and thereby weakened the protective effect. These findings provide experimental evidence for the design of oxidation-resistant high-entropy carbide ceramics.

Key words: high-entropy carbide, silicon carbide, molybdenum disilicide, isothermal oxidation, oxidation resistance

中图分类号:

TB35

刘吉轩, 卢凯峰, 秦渊, 王靖媛, 程伟强, 张国军. 添加Si对(Ti_0.2Zr_0.2Hf_0.2Ta_0.2Mo_0.2)C基高熵陶瓷等温氧化行为的影响及其机理[J]. 无机材料学报, DOI: 10.15541/jim20260322.

LIU Jixuan, LU Kaifeng, QIN Yuan, WANG Jingyuan, CHENG Weiqiang, ZHANG Guojun. Isothermal Oxidation Behavior and Mechanism of (Ti_0.2Zr_0.2Hf_0.2Ta_0.2Mo_0.2)C-Based High-entropy Ceramics Modified by Si Addition[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260322.

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