| 引用本文: | 章凯,辛丽,程玉贤,彭新,王博.AlCr(Si)N和CrAl(Si)N涂层对TiAl合金900℃循环氧化性能的影响*[J].中国表面工程,2023,36(4):185~195 |
| ZHANG Kai,XIN Li,CHENG Yuxian,PENG Xin,WANG Bo.Influence of AlCr(Si)N and CrAl(Si)N Coatings on the Cyclic Oxidation of TiAl Alloys at 900 ℃[J].China Surface Engineering,2023,36(4):185~195 |
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| AlCr(Si)N和CrAl(Si)N涂层对TiAl合金900℃循环氧化性能的影响* |
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章凯1, 辛丽2, 程玉贤1, 彭新3, 王博1
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1.中国航发沈阳黎明航空发动机有限责任公司 沈阳 110043;2.中国科学院金属研究所 沈阳 110016;3.空装驻沈阳地区第二军事代表室 沈阳 110042
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| 摘要: |
| TiAl 合金作为新型高温结构材料在航空航天和汽车工业领域已获应用，然而在 850 ℃及以上温度服役时抗氧化性不足， 施加氮化物涂层在提高 TiAl 合金抗氧化性和耐磨性等综合性能方面独具优势，目前关于氮化物涂层对 TiAl 基合金抗氧化性影响的研究有限。采用多弧离子镀方法在 TiAl 合金表面分别制备 AlCrN 涂层、AlCrSiN 涂层、CrAlN 涂层和 CrAlSiN 涂层， 研究涂层对 TiAl 合金 900℃循环氧化行为的影响。XRD 结果表明，AlCrN 和 AlCrSiN 涂层主要呈现 AlN 结构，而 CrAlN 和 CrAlSiN 涂层为 CrN 结构。在 AlCrSiN 和 CrAlSiN 涂层中，Si 可能固溶于晶格中形成(Al, Cr, Si)N 和(Cr, Al, Si)N 固溶体。在 900 ℃经过 300 个周期的循环氧化，AlCrN 和 AlCrSiN 涂层表面氧化膜主要由 Al2O3组成，热循环过程中涂层中形成大量裂纹。CrAlN 和 CrAlSiN 涂层表面氧化膜主要由 Cr2O3 组成，连续致密，无开裂剥落。其中 CrAlN 涂层表面 Cr2O3膜下面形成了 Al 的内氧化物，其氧化增重高于 CrAlSiN 涂层。此外，CrAlN 和 CrAlSiN 涂层均与 TiAl 合金发生较严重的互扩散，在 CrAlN / TiAl 界面和 CrAlSiN / TiAl 界面处形成较厚的互扩散层。可见，CrAlN 和 CrAlSiN 涂层显著提高了 TiAl 合金的抗高温氧化性能，而涂层中 Si 的添加使得涂层抗氧化性得到进一步的提升。研究结果可为 TiAl 合金施加氮化物涂层高温防护提供潜在可能。 |
| 关键词: 氮化物涂层 金属间化合物 高温氧化 互扩散 |
| DOI：10.11933/j.issn.1007?9289.20221102002 |
| 分类号:TG156；TB114 |
| 基金项目:国家自然科学基金（51871229）；辽宁“百千万人才工程”培养经费资助项目 |
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| Influence of AlCr(Si)N and CrAl(Si)N Coatings on the Cyclic Oxidation of TiAl Alloys at 900 ℃ |
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ZHANG Kai1, XIN Li2, CHENG Yuxian1, PENG Xin3, WANG Bo1
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1.AECC Shenyang Liming Aero-Engine Co.Ltd., Shenyang 110043 , China;2.Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 , China;3.Shenyang Area 2nd Military Representative Room of Air Force Equipment Department,Shenyang 110042 , China
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| Abstract: |
| TiAl-based alloys are used in the aerospace and automotive industries because of their low density, reliable strength, and good oxidation resistance. However, the Al content of the TiAl-based alloys is approximately 50 at.%; thus, it cannot form a protective alumina scale when oxidized over 850 ℃, resulting in poor high-temperature oxidation resistance. Many coatings such as metallic, ceramic, aluminide or silicide diffusion, and glass coatings have been investigated to improve the oxidation resistance of TiAl alloys. Furthermore, the effects of alloying or halogens on the oxidation of TiAl alloys have been studied. Nitride coatings have unique advantages for improving the comprehensive properties of TiAl alloys owing to their wear and oxidation resistance. However, studies on the effect of nitride coatings on the oxidation resistance of TiAl-based alloys are limited. In this study, a multi-arc ion plating system was used to deposit AlCrN, AlCrSiN, CrAlN, and CrAlSiN coatings on a TiAl alloy. The influence of AlCr(Si)N and CrAl(Si)N coatings on the cyclic oxidation of the TiAl alloy was investigated at 900 ℃. Furthermore, the influence of the Al content on the coating structure and thermal cycle resistance was investigated. The as-deposited AlCr(Si)N and CrAl(Si)N coatings were homogeneous, compact, and well combined with the matrix alloy. Compared with the CrAl(Si)N coatings, the AlCr(Si)N coatings exhibited a deeper contrast in scanning electron micro scopes back scattered electron pattern, which might be related to the higher Al content. X-ray diffraction patterns showed that the AlCrN and AlCrSiN coatings exhibited an AlN structure, whereas the CrAlN and CrAlSiN coatings exhibited CrN structures. Si may have dissolved into the crystal lattice of the AlCrSiN and CrAlSiN coatings to form (Al, Cr, Si)N and (Cr, Al, Si)N solid solutions. During oxidation for 300 cycles at 900 ℃, oxide scales primarily composed of Al2O3 formed at the surface of AlCrN and AlCrSiN coatings, and numerous cracks formed in the coatings. Aluminum and titanium reacted with oxygen through cracks to form many ridged oxides on the surface of the coatings. However, the matrix was severely oxidized. Therefore, the AlCr(Si)N coatings exhibited poor thermal cycle resistance, which could not improve the cycle oxidation resistance of TiAl alloys. Therefore, research on the development of coatings should consider not only the improvement of oxidation resistance, but also other properties to adapt to complex environmental conditions in the actual service process. After oxidation, continuous and dense oxide scales without cracking or peeling formed on the surface of the CrAlN and CrAlSiN coatings primarily composed of Cr2O3. The weight gain of the CrAlN coating was higher than that of the CrAlSiN coating, which was attributed to the formation of an internal oxidation zone under the outer Cr2O3 layer. Therefore, the addition of Si efficiently inhibited the formation of an inner oxidation zone in the CrAlSiN coating. In addition, the CrAl(Si)N coating decomposed into CrN, Cr2N, Cr, and h-AlN after annealing. After oxidation, thick interdiffusion zones formed at both the CrAlN / TiAl and CrAlSiN / TiAl interfaces owing to the significant interdiffusion between the CrAlN or CrAlSiN coatings and the TiAl matrix. TiN and Ti2AlN beneath the CrAlSiN coating in the interdiffusion zone (IDZ) at the CrAlSiN / TiAl interfaces were primarily formed by the diffusion of N from CrAlSiN to TiAl. Moreover, the released Al diffused from the TiN and Ti2AlN layers to form TiAl2. In the discontinuous Laves phase, Ti5Si3 and Al3Nb were formed between the TiAl2 and nitride layers, and the diffusion barrier of Si addition for N to the TiAl alloy was not apparent, which might be due to the lack of formation of a continuous Ti5Si3 layer in the IDZ. It could be concluded that both the CrAlN and CrAlSiN coatings significantly improved the high-temperature oxidation resistance of the TiAl alloy, and the addition of Si to the coating further improved the oxidation resistance. These results provide prospects for the application of nitride coatings for high-temperature oxidation protection of TiAl-based alloys. |
| Key words: nitride coating intermetallics high-temperature oxidation interdiffusion |
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