镍基单晶高温合金表面铝化物涂层高温氧化机理

李艳明; 王全; 刘欢; 胡鹏; 高志坤

doi:10.13224/j.cnki.jasp.20250331

镍基单晶高温合金表面铝化物涂层高温氧化机理

doi: 10.13224/j.cnki.jasp.20250331

中国航发沈阳发动机研究所，沈阳 110015

详细信息

作者简介:
李艳明（1990-），男，工程师，硕士，从事航空发动机材料应用研究。E-mail：260535498@qq.com

中图分类号: V232.4；TG136.1
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出版历程
- 收稿日期: 2025-07-15
- 网络出版日期: 2026-04-05

High-temperature oxidation mechanism of aluminide coatings on the surface of nickel-based single crystal superalloys

Shenyang Engine Research Institute，Aero Engine Corporation of China，Shenyang 110015，China

摘要

摘要:
镍基单晶高温合金基体上沉积Al涂层和Co-Al涂层，针对1000 ℃高温环境中200 h氧化后的实验样品展开系统性研究工作。实验数据表明：合金基体与两种涂层材料的氧化动力学过程均呈现典型的抛物线型变化趋势。相较于未沉积涂层实验样品和单一Al涂层，Co-Al涂层的氧化速率明显降低。经过高温氧化实验后，可以观察到合金基体表面存在大量孔洞结构及裂纹缺陷，内氧化现象和内氮化反应的发生使得材料抗氧化性能显著下降。与单一Al涂层相比，Co-Al涂层在高温氧化后形成的Al₂O₃保护膜展现出更优异的抗高温特性，该保护膜缺陷密度较低且纯净度较高，结构更为致密。实验还发现Co元素的引入有效延缓了β-NiAl相向γ'-Ni₃Al相的转变过程，难熔金属元素的外扩散行为受到明显抑制，有力促进连续致密Al₂O₃保护膜的形成。
- Al涂层 /
- Co-Al涂层 /
- 高温氧化 /
- 相转变 /
- Al₂O₃保护膜
Abstract:
Al coatings and Co-Al coatings are generally deposited on the substrate of nickel-based single crystal superalloys. A systematic study was conducted on the experimental samples after 200 h of oxidation in a high-temperature environment at 1000 ℃. The experimental data showed that the oxidation kinetics of both the alloy substrate and the two coatings materials exhibited a typical parabolic variation trend. Compared with the alloy substrate and Al coating, the oxidation rate of the Co-Al coating was significantly reduced. After the high-temperature oxidation experiment, a large number of hole structures and crack defects can be observed on the surface of the alloy substrate. The occurrence of internal oxidation and internal nitridation reactions significantly reduced the oxidation resistance of the material. Compared with the Al coating, the Al₂O₃ protective film formed by the Co-Al coating after high-temperature oxidation exhibited more excellent high-temperature resistance, with lower defect density, higher purity, and a denser structure. The experiment also found that the introduction of Co effectively delayed the phase transformation process from β-NiAl phase to γ'-Ni₃Al phase, and the outward diffusion behavior of refractory metal elements was significantly inhibited, providing favorable conditions for the formation of a continuous and dense Al₂O₃ protective film.
- Al coating /
- Co-Al coating /
- high-temperature oxidation /
- phase transformation /
- Al₂O₃ protective film

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图 1 Al涂层和Co-Al涂层沉积态表面XRD图

Figure 1. Surface XRD patterns of Al coating and Co-Al coating in the deposited state

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图 2 原始涂层结构形貌

Figure 2. Original coating structure morphology

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图 3 氧化后基体合金XRD图谱

Figure 3. XRD pattern of the oxidized base alloy

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图 4 氧化后Al涂层XRD图谱

Figure 4. XRD pattern of the oxidized Al coating

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图 5 氧化后Co-Al涂层XRD图谱

Figure 5. XRD pattern of the oxidized Co-Al coating

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图 6 基体合金、Al涂层和Co-Al涂层氧化动力学曲线

Figure 6. Oxidation kinetics curves of base alloy, Al coating and Co-Al coating

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图 7 合金基体、Al涂层和Co-Al涂层表面形貌

Figure 7. Surface morphologies of the alloy substrate, Al coating, and Co-Al coating

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图 8 合金基体、Al涂层和Co-Al涂层截面形貌

Figure 8. Cross-sectional morphologies of the alloy substrate, Al coating, and Co-Al coating

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图 9 合金基体氧化机理示意图

Figure 9. Schematic diagram of the oxidation mechanism of the alloy matrix

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图 10 涂层氧化机理示意图

Figure 10. Schematic diagram of coating oxidation mechanism

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表 1 基体合金、Al涂层和Co-Al涂层氧化速率

Table 1. Oxidation rates of base alloy, Al coating and Co-Al coating

材料	氧化速率/（g²/（m⁴·h））	拟合区间/h	拟合优度
合金基体	0.69838±0.05428	50～200	0.962
Al涂层	0.21491±0.01676	25～200	0.968
Co-Al涂层	0.19199±0.01469	25～200	0.971

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表 2 不同表面区域化学组成

Table 2. Chemical composition of different surface areas

区域	质量分数/%
区域	Al	O	Ni	Cr	Co
图8（a）	21.0	23.4	32.3	15.8	7.5
图8（c）（深色）	62.6	30.9	5.5	0.1	0.9
图8（c）（明亮）	53.4	25.3	17.1	1.1	3.1
图8（e）（深色）	62.9	32.9	3.3	0.4	0.5
图8（e）（明亮）	54.8	21.8	15.4	2.5	5.5

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表 3 不同截面区域化学组成

Table 3. Chemical composition of different cross-sectional areas

样品	区域	质量分数/%
样品	区域	Al	O	Ni	Cr	Co	Ta	W	Re	Mo	N
基体合金	Al₂O₃	64.3	33.2	1.7	0.5	0.3
基体合金	AlN	56.6		21.9	3.4	3.3					14.7
Al涂层	β-NiAl	16.4		73.5	3.9	6.1
	γ′-Ni₃Al	6.0		70.4	2.0	7.5	12.1	1.4		0.6
	Al₂O₃	56.9	40.3	2.2	0.4	0.2
	MC	0.9		18.8	10.4	9.7	3.9	26.8	24.9	4.6
Co-Al涂层	β -（Ni,Co）Al	17.1		71.6	3.5	7.8
	γ′-（Ni,Co）₃Al	6.0		71.1	2.0	7.6	11.6	1.4		0.4
	Al₂O₃	61.0	32.7	5.1	0.6	0.6
	MC	0.7		12.9	12.8	10.8	2.4	27.8	26.8	5.9

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