硅酸盐学报

碳化硅复合材料的水氧腐蚀机理

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曾雨琪 ¹ , 李归 ² , 宋阁 ¹ , 罗潇 ¹ , 黄晶琪 ² , 陈文博 ² , 李坚 ¹ , 徐友良 ¹ , 曹学强 ²

硅酸盐学报 | 研究论文 2024,52(6): 1978-1986

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硅酸盐学报 |研究论文 2024 , 52 (6) : 1978 -1986

碳化硅复合材料的水氧腐蚀机理

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曾雨琪¹, 李归², 宋阁¹, 罗潇¹, 黄晶琪², 陈文博², 李坚¹, 徐友良¹, 曹学强²

作者信息

^1．中国航发湖南动力机械研究所，湖南株洲 412000

^2．武汉理工大学，硅酸盐建筑材料国家重点实验室，武汉 430070

通讯作者:

陈文博（1991—），男，博士，副研究员；

曹学强（1964—），男，博士，教授。

作者简介:

曾雨琪（1994—），女，硕士。

Corrosion Mechanism of Silicon Carbide Composite by H₂O-O₂

Yuqi ZENG¹, Gui LI², Ge SONG¹, Xiao LUO¹, Jingqi HUANG², Wenbo CHEN², Jian LI¹, Youliang XU¹, Xueqiang CAO²

Affiliations

^1.Hunan Aviation Powerplant Research Institute, Aero Engine Corporation of China, Hunan Zhuzhou 412000, China

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

Corresponding Author:

CHEN Wenbo (1991-), male, PH.D., Associate Professor. E-mail: wchen@whut.edu.cn;

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

ZENG Yuqi (1994-), female, Master. E-mail: nikki27@163.com

出版时间: 2024-06-20 doi: 10.14062/j.issn.0454-5648.20230780

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摘要

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为阐明碳化硅复合材料（SiC_f/SiC）航空发动机燃气环境中被H₂O和O₂的腐蚀机理，本工作研究了SiC_f/SiC复合材料在水热（无氧）和水氧耦合环境的腐蚀行为。结果表明，SiC_f/SiC复合材料连通孔隙是腐蚀介质/产物的进出通道；在200 ℃无氧水热环境中，SiC被水腐蚀是一个体积膨胀过程，形成乳白色产物H₂SiO₃；在1 300 ℃水氧耦合腐蚀环境中，SiC_f/SiC复合材料的纤维与界面层被腐蚀，结构变疏松，腐蚀中间产物为H₂SiO₃，最终产物为方石英SiO₂。

关键词

碳化硅 / 复合材料 / 水氧腐蚀

Abstract

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Introduction

SiC_f/SiC ceramic matrix composites can replace high-temperature alloys in manufacturing high-temperature structural parts of aerospace engines due to their excellent properties. In a gas environment, SiC_f/SiC composite materials have a challenge from corrosion by water vapor and oxygen. The specific process of SiC_f/SiC corrosion by water vapor-oxygen coupling is not yet clarified. Therefore, investigating its corrosion behavior is of extremely important significance in guiding the protection of SiC_f/SiC from corrosion and ensuring the application of high-temperature components.

In this paper, the water-oxygen corrosion behavior of SiC_f/SiC was simulated via hydrothermal corrosion experiment in water environment and water-oxygen corrosion experiment in water-oxygen coupling environment, respectively.

Methods

In the hydrothermal corrosion experiment, SiC_f/SiC was placed in deionized water in a closed container and kept in an oven at 200 ℃ for 2 450 h. The pressure inside the container was approximately 2 MPa. After the corrosion was completed, the aqueous solution was taken out and dried in an oven at 35 ℃, and the dried powder was characterized. In the water-oxygen corrosion experiment, SiC_f/SiC was placed in a closed high-temperature furnace tube, and water vapor-oxygen mixed gas (A volume ratio of 90%∶10%) was injected into the furnace tube. The pressure inside the furnace tube was normal pressure, the temperature was maintained at 1 300 ℃ for 50-200 h.

The crystal structure of water-oxygen corrosion products was analyzed by X-ray diffraction (XRD, Smart Lab., Japan). The morphology and composition of SiC_f/SiC and its corrosion products were determined by scanning electron microscopy (SEM, Zeiss Co., Germany). The Si content in hydrothermal corrosion products dissolved in aqueous solution was measured by inductively coupled plasma (ICP, Leeman Prodigy 7, USA). The electronic states of Si and O in the hydrothermal corrosion products were characterized by X-ray photoelectron spectroscopy (ESCALAB 250Xi, XPS). The thermal stability of hydrothermal corrosion products was analyzed by thermal gravimetric analysis-differential scanning calorimetry (TGA-DSC, Netzsch Co., Germany).

Results and discussion

Based on the observation of the microstructure, the connected pores of SiC_f/SiC composite materials are the entry and exit channels for corrosion media/products. Corrosion products mainly exist in three types of areas, i.e., pores remaining during the precursor impregnation process, lamellar holes produced in the gaps between fiber cloths, and suture holes in the z direction.

In a hydrothermal environment at 200 ℃, the corrosion of SiC_f/SiC in water is a volume expansion process, the matrix becomes loose, and the pores are filled with corrosion products. After hydrothermal corrosion for 2 450 h, the Si content in the milky white colloid measured is 1 045.4 mg/L. According to the EDS analysis, the O/Si atomic number ratio is 2.9, and the chemical composition is close to H₂SiO₃ (SiO₂·H₂O). The comprehensive analysis by XRD (PDF 38-0448) and XPS (O 1s has two chemical states, namely Si—O and Si—O—H) indicates that the milky white product is H₂SiO₃.

In the water-oxygen coupled corrosion environment at 1 300 ℃, the fibers and interface layers of the SiC_f/SiC composite material are corroded, and cracks are formed. After corrosion for 200 h, the thickness of the sample expands from 4.85 mm to 6.66 mm, which is increased by 37%. The internal structure of the sample becomes loose, the corrosion intermediate product is H₂SiO₃, and the final product is cristobalite SiO₂.

Conclusions

This article studied the corrosion process of SiC_f/SiC composite materials in hydrothermal (oxygen-free) and water-oxygen coupling environments. The connected pores of SiC_f/SiC composite materials were channels for corrosive media/products, which could not be avoided. In an oxygen-free hydrothermal environment at 200 ℃, the corrosion of SiC_f/SiC by water was a volume expansion process, forming a milky white product H₂SiO₃. In a water-oxygen coupled corrosion environment at 1 300 ℃, the SiC_f/SiC composite material expanded in volume and formed cracks. The fibers and interface layers were corroded and the structure became loose. The corrosion product was cristobalite SiO₂.

Key words

silicon carbide fiber-reinforced silicon carbide matrix / ceramic matrix composite / water vapor corrosion

引用本文

曾雨琪, 李归, 宋阁, 罗潇, 黄晶琪, 陈文博, 李坚, 徐友良, 曹学强. 碳化硅复合材料的水氧腐蚀机理. 硅酸盐学报, 2024 , 52 (6) : 1978 -1986 . DOI: 10.14062/j.issn.0454-5648.20230780

Yuqi ZENG, Gui LI, Ge SONG, Xiao LUO, Jingqi HUANG, Wenbo CHEN, Jian LI, Youliang XU, Xueqiang CAO. Corrosion Mechanism of Silicon Carbide Composite by H₂O-O₂[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (6) : 1978 -1986 . DOI: 10.14062/j.issn.0454-5648.20230780

基金

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国家自然科学基金重点项目(U2241238)
中国航发集团自主创新专项基金项目(ZZCX-2017-016)

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2024年第52卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230780

接收时间：2023-10-10
首发时间：2026-10-22
出版时间：2024-06-20

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收稿日期：2023-10-10
修回日期：2024-01-11

基金

国家自然科学基金重点项目(U2241238)

中国航发集团自主创新专项基金项目(ZZCX-2017-016)

作者信息

^1．中国航发湖南动力机械研究所，湖南株洲 412000

^2．武汉理工大学，硅酸盐建筑材料国家重点实验室，武汉 430070

通讯作者:

陈文博（1991—），男，博士，副研究员；

曹学强（1964—），男，博士，教授。

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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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