硅酸盐学报

氧化钇稳定的氧化锆热障涂层表面磁控溅射TiAl膜的抗CaO-MgO-Al₂O₃-SiO₂腐蚀性能

PDF下载

刘若愚 ¹ , 舒朝玺 ² , 李璞 ³ , 李克 ¹ , 云海涛 ¹ , 殷倩楠 ¹ , 吕亮 ¹ , 陈勇国 ¹ , 汪云程 ¹ , 曹学强 ²

硅酸盐学报 | 第14届无机非金属材料专题研讨会专题—研究论文 2025,53(4): 828-838

收起

硅酸盐学报 |第14届无机非金属材料专题研讨会专题—研究论文 2025 , 53 (4) : 828 -838

氧化钇稳定的氧化锆热障涂层表面磁控溅射TiAl膜的抗CaO-MgO-Al₂O₃-SiO₂腐蚀性能

全屏

刘若愚¹, 舒朝玺², 李璞³, 李克¹, 云海涛¹, 殷倩楠¹, 吕亮¹, 陈勇国¹, 汪云程¹, 曹学强²

作者信息

^1．中国航发南方工业有限公司，湖南株洲 412002

^2．武汉理工大学，硅酸盐建筑材料国家重点实验室，武汉 430070

^3．中国航发湖南动力机械研究所，湖南株洲 412000

通讯作者:

舒朝玺（1998—），男，博士研究生；

曹学强（1964—），男，教授。

作者简介:

刘若愚（1993—），男，工程师。

TiAl Film Deposited by Magnetron Sputtering on YSZ Thermal Barrier Coating and Its Anti-Corrosion Property Against CaO-MgO-Al₂O₃-SiO₂

Ruoyu LIU¹, Chaoxi SHU², Pu LI³, Ke LI¹, Haitao YUN¹, Qiannan YIN¹, Liang LV¹, Yongguo CHEN¹, Yuncheng WANG¹, Xueqiang CAO²

Affiliations

^1.AECC South Industry Co. Ltd., Zhuzhou 412002, Hunan, China

^2.State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China

^3.AECC Hunan Aviation Powerplant Research Institute, Zhuzhou 412000, Hunan, China

Corresponding Author:

SHU Chaoxi (1998-), male, Doctoral candidate. E-mail: 317256@whut.edu.cn;

CAO Xueqiang (1964-), male, Professor. xcao@whut.edu.cn

LIU Ruoyu (1993-), male, Engineer. E-mail: 931801509@qq.com

出版时间: 2025-04-20 doi: 10.14062/j.issn.0454-5648.20240823

文章导航

摘要

收起

热障涂层是高温下具有良好隔热性能的陶瓷涂层，在航空发动机和燃气轮机高温防护方面有重要应用。大气中的硅酸盐沙尘（CaO-MgO-Al₂O₃-SiO₂，CMAS）在熔化状态时对热障涂层有较强的腐蚀作用，是影响发动机安全运行的一个重要因素。采用大气等离子喷涂方法制备氧化钇稳定的氧化锆（YSZ）涂层，通过磁控溅射在YSZ表面分别沉积Al和TiAl膜并原位氧化生成Al₂O₃和TiO₂-Al₂O₃，研究Ti和Al对YSZ抗CMAS腐蚀性能的协同作用。研究表明，Ti能显著加快CMAS与Al₂O₃反应生成钙长石和尖晶石等高熔点产物，并促进腐蚀产物结晶，能有效阻碍熔融CMAS向YSZ涂层内部渗透。分析了TiO₂-Al₂O₃-YSZ抗CMAS腐蚀机理，为YSZ抗CMAS腐蚀技术提供新的思路。

关键词

热障涂层 / 氧化钇稳定氧化锆 / 硅酸盐沙尘 / 腐蚀机理

Abstract

收起

Introduction

Thermal barrier coatings (TBCs), primarily composed of yttria-stabilized zirconia (YSZ), are critical materials for protecting the hot section components of gas turbine engines due to their high fracture toughness, melting point, and thermal stability. However, increasing operational temperatures has some challenges, particularly from molten CMAS (CaO-MgO-Al₂O₃-SiO₂) deposits that can penetrate TBCs, reduce their strain tolerance, and accelerate failure. The performance of YSZ deteriorates upon interaction with CMAS, leading to phase transformation and coating detachment. Research efforts focus on modifying YSZ with TiO₂, Cr₂O₃, or Al₂O₃ based on sacrificial protection strategies, enhancing resistance to CMAS via promoting the crystallization of compounds such as gehlenite (CaAl₂Si₂O₈). This study was to investigate the effect of Ti on the reactivity of sacrificial protective Al₂O₃ coatings with CMAS. Al and Ti layers were deposited on YSZ by magnetron sputtering and heat treatment to form mixed oxide layers to improve the protective efficacy against CMAS attack.

Methods

In this study, graphite was utilized as a substrate for YSZ coatings. After degreasing and cleaning, graphite substrates were roughened with alumina sand (WA22). A YSZ powder (KF231) was sprayed onto the substrates in Ar-H₂ as a plasma gasby a model Multicoat APS system (Oerlikon Metco Co., Switzerland) to deposit a YSZ coating with the thickness of 1500 μm. The graphite substrate was removed by heat treatment at 750 ℃ for 3 h. Subsequently, Al and Ti films were deposited on the YSZ surface via magnetron sputtering, and followed via annealing at 1000 ℃ for 2 h to form TiO₂-Al₂O₃ modified YSZ (TA-YSZ) coatings. An additional control group of Al₂O₃-modified YSZ (A-YSZ) without Ti deposition was also prepared.

CMAS powders with a composition of 33%CaO-9%MgO-13%AlO_1.5-45%SiO₂ (in mole fraction) were synthesized via melt quenching. The melting and crystallization temperatures of CMAS and its mixtures with Al₂O₃ and TiO₂ were characterized by differential scanning calorimetry (DSC). The thermal corrosion test was performed by painting the coated surface with a CMAS slurry and exposing it to 1300 ℃ for 5 min or 1250 ℃ for 2 h and 10 h (after 2 h heat treatment, the temperature was lowered in a furnace and then raised to 1250 ℃ for 2 h, and this was repeated for 5 times). The phase structure was determined by X-ray diffraction (XRD, Rigaku Smart Lab., Japan). The surface and cross-sectional microstructures of the corroded samples were analyzed by a model Phenom ProX field emission scanning electron microscope (SEM, Thermo Scientific, Netherlands) equipped with an energy-dispersive X-ray spectroscopy (EDS) system. The corroded samples were embedded in epoxy resin, cut and diamond-polished before performing the SEM analysis of the coating cross-section. The phase structure of YSZ was determined by a model InVia-Reflex Fourier-transform Raman spectroscopy (Renishaw Co., UK).

Results and discussion

Al and Ti films are sequentially deposited on the surface of YSZ coatings via magnetron sputtering. Al film exhibits a typical physical deposition structure. After heat treatment, the Ti element shows a dotted band above Al layer and forms an oxide layer. The results of DSC analysis reveal that the crystallization and melting characteristic temperatures of the three powder samples (i.e., CMAS, CMAS+Al₂O₃, and CMAS+Al₂O₃+TiO₂) shift towards lower temperatures in such an order. This indicates that the addition of Al₂O₃ and TiO₂ effectively reduces the crystallization temperature of CMAS and affects its melting characteristics.

TA-YSZ and A-YSZ coatings coated with CMAS and subjected to treatments at 1300 ℃ for 5 min or 1250 ℃ for up to 2 h and 10 h show that Ti promotes reactions between CMAS and Al₂O₃ to form high-melting-point crystalline phases such as gehlenite (CaAl₂Si₂O₈) and spinel (MgAl₂O₄). The introduction of Ti significantly enhances the interfacial reaction kinetics between the coating and the CMAS melt. Ti facilitates the formation of high-melting-point crystalline phases. Also Ti accelerates the crystallization process of corrosion products, forming a dense reaction barrier layer that effectively consumes molten CMAS and inhibits its penetration into the YSZ substrate. Moreover, the time and spatial distribution characteristics of the reaction products can occur during corrosion testing due to the different reaction kinetics characteristics of high-melting-point crystalline phases. Under the sacrificial protection mechanism of the surface coating, no phase transformation appears in the YSZ substrate.

Conclusions

YSZ coatings prepared by the atmospheric plasma spraying method were subjected to magnetron sputtering to deposit Al and TiAl films on their surface, which were then in-situ oxidized to form Al₂O₃ and TiO₂-Al₂O₃ (TA-YSZ) layers. The synergistic effect of Ti and Al on the enhancement of the CMAS corrosion resistance of YSZ coatings was investigated. The results showed that Ti significantly accelerated the reaction between CMAS and Al₂O₃, leading to the formation of high-melting-point products such as gehlenite and spinel, and promoted the crystallization of corrosion products. These actions effectively hindered the penetration of molten CMAS into the YSZ coating interior.

Key words

thermal barrier coatings / yttria stabilized zirconia / silicate dust / corrosion mechanism

引用本文

刘若愚, 舒朝玺, 李璞, 李克, 云海涛, 殷倩楠, 吕亮, 陈勇国, 汪云程, 曹学强. 氧化钇稳定的氧化锆热障涂层表面磁控溅射TiAl膜的抗CaO-MgO-Al₂O₃-SiO₂腐蚀性能. 硅酸盐学报, 2025 , 53 (4) : 828 -838 . DOI: 10.14062/j.issn.0454-5648.20240823

Ruoyu LIU, Chaoxi SHU, Pu LI, Ke LI, Haitao YUN, Qiannan YIN, Liang LV, Yongguo CHEN, Yuncheng WANG, Xueqiang CAO. TiAl Film Deposited by Magnetron Sputtering on YSZ Thermal Barrier Coating and Its Anti-Corrosion Property Against CaO-MgO-Al₂O₃-SiO₂[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (4) : 828 -838 . DOI: 10.14062/j.issn.0454-5648.20240823

基金

收起

国家自然科学基金重点项目(92060201)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

2025年第53卷第4期

PDF下载

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20240823

接收时间：2024-12-26
首发时间：2026-10-22
出版时间：2025-04-20

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2024-12-26
修回日期：2025-02-20

基金

国家自然科学基金重点项目(92060201)

作者信息

^1．中国航发南方工业有限公司，湖南株洲 412002

^2．武汉理工大学，硅酸盐建筑材料国家重点实验室，武汉 430070

^3．中国航发湖南动力机械研究所，湖南株洲 412000

通讯作者:

舒朝玺（1998—），男，博士研究生；

曹学强（1964—），男，教授。

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240823

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

关闭全屏

BibTeX
EndNote
RefWorks
TxT