耐高温氧化Fe-Cr-Ni中熵合金氧化层的微结构与力学性能分布

杜晓洁, 丁骁, 马新元, 张威, 贾玺泉, 范光伟, 何宜柱

表面技术 ›› 2022, Vol. 51 ›› Issue (8) : 363-374.

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表面技术 ›› 2022, Vol. 51 ›› Issue (8) : 363-374. DOI: 10.16490/j.cnki.issn.1001-3660.2022.08.032
腐蚀与防护

耐高温氧化Fe-Cr-Ni中熵合金氧化层的微结构与力学性能分布

  • 杜晓洁1, 丁骁1, 马新元1, 贾玺泉1, 何宜柱1, 张威2, 范光伟2
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Microstructure and Micro-mechanical Distribution of Oxide Layer Formed on Fe-Cr-Ni Medium Entropy Alloy with Excellent High-temperature Oxidation Resistance

  • DU Xiao-jie1, DING Xiao1, MA Xin-yuan1, JIA Xi-quan1, HE Yi-zhu1, ZHANG Wei2, FAN Guang-wei2
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摘要

目的 开发有优异抗高温氧化性的低成本Fe-Cr-Ni中熵合金,研究其高温氧化层微结构与力学性能分布。方法 通过连续氧化增重试验研究了Fe-Cr-Ni中熵合金在1 150~1 240 ℃空气中的氧化动力学,结合SEM、EDS、XRD、XPS等分析技术与微米划痕试验,对经1 150 ℃氧化4 h后的氧化层形貌、成分、相分布与微米力学性能分布进行了分析。结果 Fe-Cr-Ni中熵合金在空气中高温氧化增重遵循抛物线规律,氧化激活能为417.64 kJ/mol,抗氧化性优异;经1 150 ℃氧化4 h后,Fe-Cr-Ni中熵合金氧化层形成双层结构,外层主要由致密的Mn(Fe/Cr)2O4尖晶石氧化物、Fe2O3和少量MnO2组成,内层由致密且连续的Cr2O3组成,在基体与氧化层界面弥散分布着SiO2内氧化物颗粒。氧化层的力学分布特征体现了其分层结构,外层与内层的结合力约为10 N,氧化内层与基体的结合性好,结合力约为24 N。随着划痕深度的增加,压头从氧化层表面划动至基体,塑性变形比例逐层降低,断裂韧性则随着划痕深度的增加逐层增大。结论 开发的低成本Fe-Cr-Ni中熵合金具有优异的耐高温氧化性能,经高温氧化后在表面形成致密的氧化层有效阻碍了O2?的向内扩散和合金元素的向外扩散,同时SiO2内氧化物颗粒增加了氧化层与基体的结合力,这是Fe-Cr-Ni中熵合金具有优异抗氧化性的重要原因。

Abstract

This work aims to develop a low cost Fe-Cr-Ni medium entropy alloy with excellent high temperature oxidation resistance, and then, the microstructure and micro-mechanical distribution of oxide layer formed on Fe-Cr-Ni medium entropy alloy were studied. The oxidation kinetics in the air at 1 150-1 240 ℃ was obtained by continuous oxidation and weight gain experiment. The morphology, composition and phase composition of the oxide film oxidized at 1 150 ℃ for 4 h were analyzed by SEM, EDS, XRD and XPS techniques. The micro-mechanical distribution of oxide layer was studied by micro-scratch method. The result show that, the oxidation resistance of Fe-Cr-Ni medium entropy alloy is excellent with a high oxidation activation energy that is 417.64 kJ/mol. The weight gain at high temperature in air follows a parabolic rule. After being oxidized at 1 150 ℃ for 4 h, the entropy alloy oxide film of Fe-Cr-Ni formed a double-layer structure. The outer oxide layer was mainly composed of dense Mn(Fe/Cr)2O4 spinel, Fe2O3 and a small mount MnO2 oxides, the inner oxide layer was composed of dense and continuous Cr2O3. Meanwhile, internal oxide particles SiO2 were dispersed at the interface between the matrix and the oxide film. The micro-mechanical distribution characteristics of the oxide layer reflect its layered structure, the binding force between the outer oxide layer and the inner oxide layer is about 10 N, while the binding force between the inner oxide layer and the matrix is about 24 N. With the increase of scratch depth, the indentation moves from outer oxide layer to matrix, the plastic deformation ratio decreases, while the fracture toughness increases from outer oxide layer to matrix. The developed low cost Fe-Cr-Ni medium entropy alloy really show an excellent high temperature oxidation resistance. After high temperature oxidation, the dense oxide layer formed on the surface effectively hinders the inward diffusion of O2? and the outward diffusion of alloying elements. Meanwhile, the internal oxide particles in SiO2 increase the binding force between the oxide layer and matrix, this is an important reason for the excellent oxidation resistance of the entropy alloy in Fe-Cr-Ni. The dense and continuous Cr2O3 layer effectively impedes the growth of the oxide layer, while the internal oxide particles SiO2 increase the binding force between the oxide film and the matrix, which is an important reason for the excellent oxidation resistance of Fe-Cr-Ni MEA.

关键词

Fe-Cr-Ni中熵合金;高温氧化;氧化动力学;氧化层;微结构;力学性能分布;微米划痕

Key words

Fe-Cr-Ni MEA; high temperature oxidation; oxidation kinetics; oxide layer; microstructure; micro-mechanical distribution; micro-scratch

引用本文

导出引用
杜晓洁, 丁骁, 马新元, 张威, 贾玺泉, 范光伟, 何宜柱. 耐高温氧化Fe-Cr-Ni中熵合金氧化层的微结构与力学性能分布[J]. 表面技术. 2022, 51(8): 363-374
DU Xiao-jie, DING Xiao, MA Xin-yuan, ZHANG Wei, JIA Xi-quan, FAN Guang-wei, HE Yi-zhu. Microstructure and Micro-mechanical Distribution of Oxide Layer Formed on Fe-Cr-Ni Medium Entropy Alloy with Excellent High-temperature Oxidation Resistance[J]. Surface Technology. 2022, 51(8): 363-374

基金

安徽省高校研究生科学研究项目(YJS20210335);山西省科技重大专项资助项目(20181101016)

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