硅酸盐学报

氧化铝-氧化锆预应力陶瓷的抗钙镁铝硅酸盐腐蚀性能

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张旭阳 ¹ , 王秀芳 ¹^,² , 万德田 ³^,⁴ , 李海燕 ³^,⁴ , 包亦望 ³^,⁴ , 贾志杰 ³^,⁴ , 马华超 ³^,⁴

硅酸盐学报 | 研究论文 2024,52(12): 3815-3823

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硅酸盐学报 |研究论文 2024 , 52 (12) : 3815 -3823

氧化铝-氧化锆预应力陶瓷的抗钙镁铝硅酸盐腐蚀性能

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张旭阳¹, 王秀芳¹^,², 万德田³^,⁴, 李海燕³^,⁴, 包亦望³^,⁴, 贾志杰³^,⁴, 马华超³^,⁴

作者信息

^1．北京建筑大学土木与交通工程学院，北京 102616

^2．北京建筑大学理学院，建筑结构与环境修复功能材料北京市重点实验室，北京 102616

^3．中国国检测试控股集团股份有限公司，北京 100024

^4．绿色建材国家重点实验室，中国建筑材料科学研究总院，北京 100024

通讯作者:

王秀芳（1984—），女，高级实验师。

万德田（1978—），男，教授。

作者简介:

张旭阳（1998—），女，硕士研究生。

Corrosion Resistance of Alumina Zirconia Prestressed Ceramics to Calcium Magnesium Aluminosilicate

Xuyang ZHANG¹, Xiufang WANG¹^,², Detian WAN³^,⁴, Haiyan LI³^,⁴, Yiwang BAO³^,⁴, Zhijie JIA³^,⁴, Huachao MA³^,⁴

Affiliations

^1.School of Civil and Transportation Engineering, Beijing University of Civil engineering and Architecture, Beijing 102616, China

^2.Beijing Key Laboratory of Building Structure and Environmental Restoration Functional Materials, School of Science, Beijing University of Civil engineering and Architecture, Beijing 102616, China

^3.China National Inspection and Testing Holding Group Co., Ltd., Beijing 100024, China

^4.State Key Laboratory of Green Building Materials, China Building Materials Academy, Beijing 100024, China

Corresponding Author:

WANG Xiufang (1984-), female, Senior Engineer; E-mail: wangxiufang@bucea.edu.cn;

WAN Detian (1978-), male, Professor. dtwan@ctc.ac.cn

ZHANG Xuyang (1998-), female, Master candidade. E-mail: 18736768339@163.com

出版时间: 2024-12-20 doi: 10.14062/j.issn.0454-5648.20240381

文章导航

摘要

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氧化锆（ZrO₂）陶瓷因其优异的性能常被用于航空发动机高温部件，然而在服役过程中常面临钙镁铝硅酸盐（CMAS）腐蚀，严重影响其服役寿命。为减缓CMAS对陶瓷构件的腐蚀，采用预应力增强的方法在ZrO₂陶瓷表层引入一层含压应力的氧化铝（Al₂O₃）涂层，形成ZrO₂基体的Al₂O₃-ZrO₂预应力陶瓷，为研究其对CMAS腐蚀的抑制作用，通过选用ZrO₂陶瓷为参照样，研究了不同服役温度下CMAS渗透和腐蚀反应机理。结果表明，Al₂O₃-ZrO₂预应力陶瓷抵抗CMAS腐蚀效果显著优于ZrO₂，这主要归因于2点：1）高温下CMAS与Al₂O₃涂层发生了反应，生成了高熔点化合物钙长石（CaAl₂Si₂O₈）、尖晶石（MgAl₂O₄）和少量的钙铝黄长石（Ca₂Al₂SiO₇），从而有利于阻止CMAS熔体渗透；2）表层的压应力能够抑制裂纹的扩展，从而阻碍了通过裂纹进入的氧化深入效应，提高ZrO₂陶瓷构件在CMAS腐蚀环境下的使用寿命。

关键词

钙镁铝硅酸盐腐蚀 / 预应力陶瓷 / 弯曲强度 / 腐蚀机理

Abstract

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Introduction

Zirconium dioxide (ZrO₂)ceramics have superior properties such as high hardness, high thermal expansion coefficient and low thermal conductivity, which are widely used in high-temperature components like aircraft engines, gas turbines and combustion power plants. However, ZrO₂ ceramics in the use can be CMAS (i.e., CaO, MgO, Al₂O₃ and SiO₂) and other small particles corrosion, resulting in the decrease of ZrO₂ ceramics performance. The problem of CMAS corrosion becomes a challenge. The technologies used to protect the CMAS corrosion of ZrO₂ ceramics are the use of a non-permeable protective layer, the use of a top layer of laser glazing treatment, a thermal spray nanostructure coating and a rare-earth co-doped coating. Although these methods have a certain anti-CMAS corrosion effect, they still have some shortcomings of complex preparation process and high cost. To further investigate and improve the high-temperature corrosion resistance of ZrO₂ ceramics, Al₂O₃-ZrO₂ prestressed ceramics were prepared with Al₂O₃ as a coating and ZrO₂ as a matrix. The flexural strength at different temperatures and the behavior of CMAS penetration and element diffusion were investigated via comparative analysis of Al₂O₃-ZrO₂ prestressed ceramics and ZrO₂ ceramics. The effect of prestressed enhancement, the CMAS penetration and the corrosion mechanism of Al₂O₃-ZrO₂ prestressed ceramics against CMAS at a high temperature were analyzed.

Methods

The thermal corrosion experiment was carried out in a high-temperature sintering furnace. The samples of ZrO₂ ceramics and Al₂O₃-ZrO₂ prestressed ceramics with CMAS powder were heated at different temperatures (i.e., 1 200, 1 250, 1 300, 1 350 ℃ and 1 400 ℃), respectively, for 10 h, and then cooled in the furnace. In the analysis of corrosion resistance of ZrO₂ ceramics and Al₂O₃-ZrO₂ prestressed ceramics, the mechanical properties of ZrO₂ ceramics and Al₂O₃-ZrO₂ prestressed ceramics before and after corrosion were tested by a model C45 machine controlled electronic universal testing machine. During the test, the span of 30 mm and the loading rate of 0.5 mm/min were set, and the data of 5 samples in each group were collected to obtain the three-point flexural strength of the samples affected by corrosion. The corrosion and morphology characteristics of the sample in a macro-scale were determined by a model KEYENCE VHX-970F optical microscope. The depth of CMAS corrosion of ZrO₂ ceramics and the change of the state of Al₂O₃ coating at different corrosion temperatures were analyzed via adjusting different magnifications. The microstructure of the sample was characterized by a model QUANTA 250FEG scanning electron microscope in order to further analyze the corrosion mechanism of CMAS. The morphology and distribution area of corrosion products generated by Al₂O₃-ZrO₂ prestressed ceramics were determined, and the corrosion mode of ZrO₂ ceramics was analyzed. Also, the element composition ratio and distribution of the sample cross-section were analyzed by an EDS scanning system. The phase of Al₂O₃ ceramic particles corroded by CMAS was analyzed by a model Rigaku SmartLab SE X-ray diffractometer.

Results and discussion

Before corrosion, the flexural strength of Al₂O₃-ZrO₂ prestressed ceramics reaches (1 038±41) MPa, which is 35.6% higher than that of ZrO₂ ceramics. After CMAS corrosion, the flexural strength of Al₂O₃-ZrO₂ prestressed ceramics decreases with the increase of corrosion temperature, but it is still higher than that of ZrO₂ ceramics. This is because the residual stress formed during the cooling process enhances the strength of ZrO₂ ceramics after sintering Al₂O₃ coating and ZrO₂ ceramics.

In the high-temperature service environment, the EDS analysis results show that CMAS exists an element diffusion in ZrO₂ ceramics. Based on the analysis of the cross section of ZrO₂ ceramics after corrosion, the corrosion mode of ZrO₂ ceramics is a grain boundary corrosion. The penetration depth of CMAS gradually increases from 24 μm to 143 μm with the increase of corrosion temperature, thus bringing a serious harm to ZrO₂ ceramic components. Al₂O₃ coating in Al₂O₃-ZrO₂ prestressed ceramics effectively blocks a direct contact between CMAS and ZrO₂ ceramics, avoids the diffusion of elements Ca, Mg, Al and Si in CMAS to ZrO₂ ceramics, and effectively protects the microstructure of ZrO₂ ceramics. The results indicate that Al₂O₃ coating can improve the strength and CMAS corrosion resistance of ZrO₂ ceramics.

Based on the analysis of the corroded section of Al₂O₃-ZrO₂ prestressed ceramics as well as the analysis of EDS and XRD results, Al₂O₃ coating reacts with CMAS at a high temperature. The high melting point compounds calc feldspar (CaAl₂Si₂O₈), spinel (MgAl₂O₄) and a small amount of calc aluminite (Ca₂Al₂SiO₇) are generated. The diffusion channel is clogged and the penetration depth of CMAS is greatly reduced due to these substances with a high melting point and a good chemical stability as well as the increased viscosity of molten CMAS, thus having a positive effect on preventing CMAS corrosion. In addition, the compressive stress in the Al₂O₃ coating can also inhibit the expansion of cracks, prevent the deep oxidation effect entering through cracks, and improve the service life of ZrO₂ ceramic components in CMAS corrosion environment.

Conclusions

The mechanism of resistance of Al₂O₃-ZrO₂ prestressed ceramics to CMAS corrosion at a high temperature was investigated, and ZrO₂ ceramics were taken as a reference sample. The results showed that in Al₂O₃-ZrO₂ prestressed ceramics, Al₂O₃ coating with compressive stress could effectively improve the flexural strength of ZrO₂ ceramics, and help to slow down the action of CMAS corrosion, thus having the superior resistance to CMAS corrosion. This was mainly attributed to that the compressive stress of the surface layer of the material could improve the strength and toughness of the ceramic, effectively inhibiting the crack propagation; and at high temperatures, Al₂O₃ coating in Al₂O₃-ZrO₂ prestressed ceramics could react with CMAS, producing a high melting point calcium feldspar, spinel and a small amount of calcium-aluminum feldspar at the interface, and forming a stable and dense reaction layer, which inhibited the continuous penetration of CMAS melt.

Key words

calcium-magnesium-alumino-silicate corrosion / prestressed ceramics / flexural strength / corrosion mechanism

引用本文

张旭阳, 王秀芳, 万德田, 李海燕, 包亦望, 贾志杰, 马华超. 氧化铝-氧化锆预应力陶瓷的抗钙镁铝硅酸盐腐蚀性能. 硅酸盐学报, 2024 , 52 (12) : 3815 -3823 . DOI: 10.14062/j.issn.0454-5648.20240381

Xuyang ZHANG, Xiufang WANG, Detian WAN, Haiyan LI, Yiwang BAO, Zhijie JIA, Huachao MA. Corrosion Resistance of Alumina Zirconia Prestressed Ceramics to Calcium Magnesium Aluminosilicate[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (12) : 3815 -3823 . DOI: 10.14062/j.issn.0454-5648.20240381

基金

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国家重点研发计划(2021YFB3702300)
国家自然科学基金(52032011; 52072356; 51808025)
北京建筑大学金字塔人才培养工程(JDYC20200329)

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2024年第52卷第12期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240381

接收时间：2024-05-30
首发时间：2026-10-22
出版时间：2024-12-20

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收稿日期：2024-05-30
修回日期：2024-07-07

基金

国家重点研发计划(2021YFB3702300)

国家自然科学基金(52032011; 52072356; 51808025)

北京建筑大学金字塔人才培养工程(JDYC20200329)

作者信息

^1．北京建筑大学土木与交通工程学院，北京 102616

^2．北京建筑大学理学院，建筑结构与环境修复功能材料北京市重点实验室，北京 102616

^3．中国国检测试控股集团股份有限公司，北京 100024

^4．绿色建材国家重点实验室，中国建筑材料科学研究总院，北京 100024

通讯作者:

王秀芳（1984—），女，高级实验师。

万德田（1978—），男，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240381

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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

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