原位反应/热压合成Ti2AlC-20TiB2复合材料在1000~1300 ℃空气中的高温氧化行为

doi:10.15541/jim20240352

无机材料学报 ›› 2025, Vol. 40 ›› Issue (1): 31-38.DOI: 10.15541/jim20240352 CSTR: 32189.14.10.15541/jim20240352

原位反应/热压合成Ti₂AlC-20TiB₂复合材料在1000~1300 ℃空气中的高温氧化行为

王文婷¹^,²(), 徐敬军¹(), 马科¹, 李美栓¹, 李兴超³, 李同起³

1.中国科学院金属研究所, 沈阳 110016
2.中国科学技术大学材料科学与工程学院, 沈阳 110016
3.航天材料及工艺研究所先进功能复合材料技术重点实验室, 北京 100076

收稿日期:2024-07-27 修回日期:2024-09-23 出版日期:2025-01-20 网络出版日期:2024-09-27
通讯作者: 徐敬军, 副研究员. E-mail: jjxu@imr.ac.cn
作者简介:王文婷(1992-), 女, 博士研究生. E-mail: wtwang16s@imr.ac.cn
基金资助:
国家自然科学基金(52071318)

Oxidation Behavior at 1000-1300 ℃ in air of Ti₂AlC-20TiB₂ Synthesized by in-situ Reaction/Hot Pressing

WANG Wenting¹^,²(), XU Jingjun¹(), MA Ke¹, LI Meishuan¹, LI Xingchao³, LI Tongqi³

1. Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2. School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
3. Science and Technology on Advanced Functional Composite Laboratory, Aerospace Research Institute of Materials & Processing Technology, Beijing 100076, China

Received:2024-07-27 Revised:2024-09-23 Published:2025-01-20 Online:2024-09-27
Contact: XU Jingjun, associate professor. E-mail: jjxu@imr.ac.cn
About author:WANG Wenting (1992-), female, PhD candidate. E-mail: wtwang16s@imr.ac.cn
Supported by:
National Natural Science Foundation of China(52071318)

摘要/Abstract

摘要：

Ti₂AlC是MAX相材料中抗氧化性能最好的化合物之一, 在高温结构材料和高温抗氧化防护涂层领域具有潜在的应用前景, 然而其强度和硬度不足, 在高温领域的应用受到限制。为了提升Ti₂AlC的性能, 本研究采用原位固-液相反应/热压方法成功合成了Ti₂AlC-20%TiB₂(体积分数)复合材料(简称Ti₂AlC-20TiB₂), 分析了其在1000~1300 ℃的高温氧化行为, 揭示了其高温抗氧化机理。结果表明: Ti₂AlC-20TiB₂复合材料的氧化动力学符合自然对数规律, 比单相Ti₂AlC具有更优异的抗氧化性能。1200 ℃以下, 氧化膜主要由Al₂O₃(内层)和TiO₂(外层)组成, 而在1300 ℃时, 氧化膜的外层则是TiO₂与Al₂TiO₅混合物。复合材料形成的Al₂O₃保护层比单相Ti₂AlC形成的更为致密, 这是抗氧化性能优异的关键。引入的TiB₂颗粒减小了材料的晶粒尺寸, 增加了短路扩散的晶界数量, 有利于Al的选择性氧化, 从而加速了Al₂O₃保护层的形成。TiB₂氧化过程中生成的B₂O₃能够填充微孔并修复微裂纹, 有效阻止了O的内扩散, 进一步提高了复合材料的抗氧化性能。

关键词: Ti₂AlC-TiB₂复合材料, 高温氧化行为, 氧化保护层, 高温抗氧化机理

Abstract:

Ti₂AlC is considered to be one of the compounds with the best antioxidant properties in MAX phase materials, with potential application prospects in the field of high-temperature structural materials and high-temperature antioxidant protective coatings. However, the low hardness and strength of single phase Ti₂AlC limit its wide application in the field of high-temperature material. In order to improve the properties of Ti₂AlC, Ti₂AlC-20%TiB₂(in volume) composites (referred to as Ti₂AlC-20TiB₂) were synthesized by the in-situ solid-liquid phase reaction/hot pressing method. Besides, the high temperature oxidation behavior in the temperature range of 1000-1300 ℃ was studied, and the oxidation resistance mechanism at high temperature was analyzed. The results show that the oxidation kinetics of Ti₂AlC-20TiB₂ composites is logarithmic, exhibiting superior oxidation resistance compared to single phase Ti₂AlC. Below 1200 ℃, the oxide scale is mainly composed of an inner layer of Al₂O₃ and an outer layer of TiO₂, while the outer layer of oxide scale is a mixture of TiO₂ and Al₂TiO₅ at 1300 ℃. The Al₂O₃ protective layer formed in the composite is denser than that in single-phase Ti₂AlC, which is the key to its excellent antioxidant performance. The addition of TiB₂ reduces the grain size of the material and increases the number of grain boundaries for short-circuit diffusion, which facilitates the selective oxidation of Al and accelerates the formation of Al₂O₃ protective layer. Additionally, B₂O₃ produced during the oxidation of TiB₂ can effectively fill the micropores and repair microcracks, thereby preventing the internal diffusion of O and further enhancing the antioxidant properties of the composites.

Key words: Ti₂AlC-TiB₂ composite, high-temperature oxidation behavior, oxidation protective layer, high-temperature oxidation resistance mechanism

中图分类号:

TB332

王文婷, 徐敬军, 马科, 李美栓, 李兴超, 李同起. 原位反应/热压合成Ti₂AlC-20TiB₂复合材料在1000~1300 ℃空气中的高温氧化行为[J]. 无机材料学报, 2025, 40(1): 31-38.

WANG Wenting, XU Jingjun, MA Ke, LI Meishuan, LI Xingchao, LI Tongqi. Oxidation Behavior at 1000-1300 ℃ in air of Ti₂AlC-20TiB₂ Synthesized by in-situ Reaction/Hot Pressing[J]. Journal of Inorganic Materials, 2025, 40(1): 31-38.

图/表 9

图1 Ti2AlC-20TiB2复合材料的表面形貌以及Al、C、B元素的EDS面扫描结果

Fig. 1 Surface morphology of Ti2AlC-20TiB2 composite and EDS element mappings of Al, C, and B

图2 材料的蚀刻表面形貌(内插图为粒径统计分布图)

Fig. 2 Morphologies of the etched surface with inserts showing the statistical distribution of particle size (a) Ti2AlC; (b) Ti2AlC-20TiB2

图3 Ti2AlC-20TiB2在1000~1300 ℃空气中的氧化动力学曲线

Fig. 3 Oxidation kinetics of Ti2AlC-20TiB2 composite at 1000-1300 ℃ in air (a) Δm/A vs. t; (b) Δm/A vs. ln(t/t0+1)

表1 图3(a)氧化动力学曲线拟合得到的k、t0和R2, 以及Ti2AlC[8]的kc

Table 1 k, t0, R2 by fitting the oxidation kinetics curves in Fig. 3(a) and kc of Ti2AlC[8]

Temperature		1000 ℃	1100 ℃	1200 ℃	1300 ℃
Ti₂AlC- 20TiB₂	k	0.0656	0.1355	0.0920	0.2849
	t₀	0.0918	0.0488	0.1313	0.6860
	R²	99.50	99.47	99.72	99.77
Ti₂AlC	k_c	2.38×10^-12	1.54×10^-11	1.12×10^-10	2.13×10^-10

图4 Ti2AlC-20TiB2氧化前和在1000~1300 ℃空气中氧化10 h后的XRD图谱

Fig. 4 XRD patterns of Ti2AlC-20TiB2 composite before and after oxidation at 1000-1300 ℃ in air for 10 h (a) Before oxidation; (b) 1000 ℃; (c) 1100 ℃; (d) 1200 ℃; (e) 1300 ℃

图5 Ti2AlC-20TiB2复合材料在1000~1300 ℃空气中氧化10 h后的表面形貌以及O、Al、Ti元素的EDS面扫描结果

Fig. 5 Surface morphologies of Ti2AlC-20TiB2 composite oxidized at 1000-1300 ℃ in air for 10 h and EDS element mappings of O, Al, and Ti (a) 1000 ℃; (b) 1100 ℃; (c) 1200 ℃; (d) 1300 ℃

图6 Ti2AlC在1000~1300 ℃空气中氧化10 h后的表面形貌以及O、Al、Ti元素的EDS面扫描结果

Fig. 6 Surface morphologies of Ti2AlC oxidized at 1000-1300 ℃ in air for 10 h and EDS element mappings of O, Al, and Ti (a) 1000 ℃; (b) 1100 ℃; (c) 1200 ℃; (d) 1300 ℃

图7 Ti2AlC-20TiB2复合材料在1000~1300 ℃空气中氧化10 h后的截面形貌以及O、Al、Ti元素的EDS面扫描结果

Fig. 7 Cross-sectional morphologies of Ti2AlC-20TiB2 composite oxidized at 1000-1300 ℃ in air for 10 h and EDS element mappings of O, Al, and Ti (a) 1000 ℃; (b) 1100 ℃; (c) 1200 ℃; (d) 1300 ℃

图8 Ti2AlC在1000~1300 ℃空气中氧化10 h后的截面形貌以及O、Al、Ti元素的EDS面扫描结果

Fig. 8 Cross-sectional morphologies of Ti2AlC oxidized at 1000-1300 ℃ in air for 10 h and EDS element mappings of O, Al, and Ti (a) 1000 ℃; (b) 1100 ℃; (c) 1200 ℃; (d) 1300 ℃

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原位反应/热压合成Ti₂AlC-20TiB₂复合材料在1000~1300 ℃空气中的高温氧化行为

Oxidation Behavior at 1000-1300 ℃ in air of Ti₂AlC-20TiB₂ Synthesized by in-situ Reaction/Hot Pressing

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