Al表面改性Si-HfO2/YbDS/GYYZO热/环境障涂层的抗CMAS腐蚀性能

doi:10.15541/jim20250452

无机材料学报 ›› 2026, Vol. 41 ›› Issue (7): 923-929.DOI: 10.15541/jim20250452

Al表面改性Si-HfO₂/YbDS/GYYZO热/环境障涂层的抗CMAS腐蚀性能

商森¹^,²(), 姜林文¹(), 董浩², 戴睿², 吴健², 卓学士², 张军贵², 张小锋²()

¹ 宁波大学材料科学与化学工程学院, 宁波 315000
² 广东省科学院新材料研究所, 现代材料表面工程技术国家工程实验室, 广东省现代表面工程技术重点实验室, 广州 510650

收稿日期:2025-11-09 修回日期:2026-01-19 出版日期:2026-02-05 网络出版日期:2026-02-05
通讯作者: 姜林文, 副教授. E-mail: jianglinwen@nbu.edu.cn;
张小锋, 正高级工程师. E-mail: zxf200808@126.com
作者简介:商森(2000-), 男, 硕士研究生. E-mail:2356800464@qq.com
基金资助:
四川省科技计划(2025ZDZX0003)

CMAS Corrosion Resistance of Al-modified Si-HfO₂/YbDS/GYYZO Thermal/Environmental Barrier Coating

SHANG Sen¹^,²(), JIANG Linwen¹(), DONG Hao², DAI Rui², WU Jian², ZHUO Xueshi², ZHANG Jungui², ZHANG Xiaofeng²()

¹ College of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315000, China
² Guangdong Provincial Key Laboratory of Modern Surface Engineering Technology, National Engineering Laboratory for Modern Materials Surface Engineering Technology, Institute of New Materials, Guangdong Academy of Sciences, Guangzhou 510650, China

Received:2025-11-09 Revised:2026-01-19 Published:2026-02-05 Online:2026-02-05
Contact: JIANG Linwen, associate professor. E-mail: jianglinwen@nbu.edu.cn;
ZHANG Xiaofeng, professor. E-mail: zxf200808@126.com
About author:SHANG Sen (2000-), male, Master candidate. E-mail: 2356800464@qq.com
Supported by:
Sichuan Science and Technology Program(2025ZDZX0003)

摘要/Abstract

摘要：

随着航空发动机热端部件服役温度的提升, 钙镁铝硅酸盐(CMAS)腐蚀已成为热/环境障涂层(T/EBCs)失效的关键因素。新型Gd₂O₃-Yb₂O₃-Y₂O₃共稳ZrO₂ (GYYZO)陶瓷因其优异的热物理性能而颇具应用前景, 但在1500 ℃极端高温下, 其抗CMAS腐蚀性能仍需进一步提高。本研究采用表面镀铝+真空热处理方法对等离子喷涂-物理气相沉积(Plasma spray-physical vapor deposition, PS-PVD)制备的Si-HfO₂/Yb₂Si₂O₇/GYYZO涂层体系进行表面改性。首先, 对PS-PVD制备的涂层进行1300 ℃退火处理, 愈合微裂纹; 随后, 利用直流脉冲磁控溅射技术在GYYZO层表面沉积厚度为3~4 μm的铝薄膜; 最后, 通过真空热处理(400 ℃/2.5 h + 660 ℃/2 h + 808 ℃/1.5 h + 980 ℃/1 h)使铝层转化为致密的Al₂O₃阻挡层。系统研究了改性前后涂层在1500 ℃下的CMAS腐蚀演变行为及失效机理。结果表明, 在1500 ℃下, CMAS熔体通过晶界快速渗透至未改性GYYZO涂层内部, 诱使Yb₂Si₂O₇层产生“起泡”损伤及大量裂纹, 最终导致涂层加速失效。与之相比, 经铝改性技术处理后的GYYZO涂层, 得益于表面原位生成的致密Al₂O₃阻挡层, 可有效抑制CMAS的晶界渗透, 从而延缓腐蚀动力学进程。在腐蚀1 h后, 改性涂层仍能保持结构完整性。

关键词: 热/环境障涂层, CMAS腐蚀, 铝改性, GYYZO

Abstract:

The rising service temperature of aero-engine hot-section components makes calcium magnesium aluminum silicate (CMAS) corrosion a key failure mechanism for thermal/environmental barrier coatings (T/EBCs). The novel Gd₂O₃-Yb₂O₃-Y₂O₃ co-stabilized ZrO₂ (GYYZO) ceramic is promising due to its good thermophysical properties. However, its CMAS corrosion resistance at 1500 ℃ needs improvement. In this work, a PS-PVD- fabricated Si-HfO₂/Yb₂Si₂O₇/GYYZO coating system was enhanced via Al deposition and vacuum heat treatment. Firstly, the as-sprayed coating was annealed at 1300 ℃ to heal microcracks. Subsequently, a 3-4 μm thick aluminum film was deposited on the GYYZO layer surface via direct current pulsed magnetron sputtering. Finally, vacuum heat treatment (400 ℃/2.5 h + 660 ℃/2 h + 808 ℃/1.5 h + 980 ℃/1 h) was conducted to promote the formation of a dense Al₂O₃ barrier layer. A comparative study at 1500 ℃ revealed that CMAS rapidly penetrated the unmodified GYYZO coating along grain boundaries, causing blistering and cracking in the Yb₂Si₂O₇ layer and accelerating failure. Conversely, the Al-modified GYYZO coating formed a dense Al₂O₃ barrier in situ, effectively suppressing CMAS penetration and slowing corrosion kinetics, thus maintaining structural integrity after 1 h.

Key words: thermal/environmental barrier coating, CMAS corrosion, aluminum modification, GYYZO

中图分类号:

TQ174

商森, 姜林文, 董浩, 戴睿, 吴健, 卓学士, 张军贵, 张小锋. Al表面改性Si-HfO₂/YbDS/GYYZO热/环境障涂层的抗CMAS腐蚀性能[J]. 无机材料学报, 2026, 41(7): 923-929.

SHANG Sen, JIANG Linwen, DONG Hao, DAI Rui, WU Jian, ZHUO Xueshi, ZHANG Jungui, ZHANG Xiaofeng. CMAS Corrosion Resistance of Al-modified Si-HfO₂/YbDS/GYYZO Thermal/Environmental Barrier Coating[J]. Journal of Inorganic Materials, 2026, 41(7): 923-929.

图/表 11

表1 PS-PVD喷涂参数

Table 1 PS-PVD spraying parameters

Parameter	Si-HfO₂	YbDS	GYYZO
Spray distance/mm	300	350	280
Current/A	650	700	630
Ar/(L•min^-1)	40	40	50
H₂/(L•min^-1)	5	12	8
Feeding rate/(r•min^-1)	2.5	2.8	3
Chamber pressure/mbar	40	50	60
Carrier gas/(L•min^-1)	3	2.5	2.5

表2 CMAS的组成成分

Table 2 Compositions of CMAS

Oxide	CaO	MgO	Al₂O₃	SiO₂	Fe₂O₃+Na₂O+K₂O+ZrO₂
Mole/%	34.91	4.44	10.58	46.20	3.87

图1 GYYZO涂层的微观截面形貌

Fig. 1 Cross-sectional morphologies of GYYZO coating (a) Cross-sectional view of Si-HfO2/Yb2Si2O7/GYYZO coating system; (b) Interface between Si-HfO2 and Yb2Si2O7 layers; (c) Interface between Yb2Si2O7 and GYYZO layers; (d) High-magnification view of GYYZO layer

图2 GYYZO与Al-GYYZO涂层的XRD图谱

Fig. 2 XRD patterns of GYYZO and Al-GYYZO coatings

图3 GYYZO涂层在1500 ℃下经过不同CMAS腐蚀时间的截面形貌

Fig. 3 Cross-sectional morphologies of GYYZO coating after CMAS corrosion at 1500 ℃ for different time (a) 1 min; (b) 10 min; (c) 30 min; (d) 1 h

图4 GYYZO涂层在1500 ℃下经CMAS腐蚀10 min后的截面微观形貌

Fig. 4 Cross-sectional morphologies of GYYZO coating after CMAS corrosion at 1500 ℃ for 10 min (a) Cross-sectional morphology; (b) Reaction layer; (c) EDS elemental mappings of Fig. (b); (d) Transverse cracks in the intermediate layer

图5 Al-GYYZO涂层的微观截面形貌

Fig. 5 Cross-sectional morphologies of Al-GYYZO coating (a) As-sprayed cross-section; (b) Interface between bond coat and interlayer; (c) Al-modified layer; (d) Interface between GYYZO and interlayer; (e) EDS elemental mappings of Fig. (a)

图6 Al-GYYZO涂层在1500 ℃下经过不同时间CMAS腐蚀后的截面形貌

Fig. 6 Cross-sectional morphologies of Al-GYYZO coating after CMAS corrosion at 1500 ℃ for different time (a) 1 min; (b) 10 min; (c) 30 min; (d) 1 h

表3 图6(d)标记点的EDS元素组成

Table 3 EDS elemental compositions of the marked spots in Fig. 6(d)

Element	Content/% (in atom)
Element	Spot 1	Spot 2	Spot 3
Si	20.85	99.04	27.10
Hf	17.58	0.91	18.84
O	61.58	0.05	52.28
Ca	0	0	0.20
Mg	0	0	0.17
Al	0	0	1.41

图7 Al-GYYZO涂层在1500 ℃下经CMAS腐蚀10 min后的微观截面形貌

Fig. 7 Cross-sectional morphologies of Al-GYYZO coating after CMAS corrosion at 1500 ℃ for 10 min (a) Cross-sectional morphology; (b) Reaction layer; (c) EDS elemental mappings of Fig. (b)

图8 Al-GYYZO涂层在1500 ℃下经CMAS腐蚀30 min后的微观截面形貌

Fig. 8 Cross-sectional morphologies of Al-GYYZO coating after CMAS corrosion at 1500 ℃ for 30 min (a) Cross-sectional morphology; (b) Reaction layer; (c) EDS elemental mappings of Fig. (a)

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Al表面改性Si-HfO₂/YbDS/GYYZO热/环境障涂层的抗CMAS腐蚀性能

CMAS Corrosion Resistance of Al-modified Si-HfO₂/YbDS/GYYZO Thermal/Environmental Barrier Coating

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