硅酸盐学报

C/C复合材料高温抗氧化陶瓷防护涂层的研究进展与展望

PDF下载

王麓焱 ¹ , 刘荣军 ² , 王衍飞 ² , 李端 ² , 缪花明 ²

硅酸盐学报 | 综合评述 2025,53(3): 688-699

收起

硅酸盐学报 |综合评述 2025 , 53 (3) : 688 -699

C/C复合材料高温抗氧化陶瓷防护涂层的研究进展与展望

全屏

王麓焱¹, 刘荣军², 王衍飞², 李端², 缪花明²

作者信息

^1．南昌航空大学材料科学与工程学院，南昌 330063

^2．国防科技大学，空天科学学院新型陶瓷纤维及其复合材料重点实验室，长沙 410073

通讯作者:

刘荣军（1978—），男，博士，研究员。

作者简介:

王麓焱（2000—），男，硕士研究生。

Research Progress on High-Temperature Ceramic Protective Coatings on C/C Composite Materials

Luyan WANG¹, Rongjun LIU², Yanfei WANG², Duan LI², Huaming MIAO²

Affiliations

^1.School of Materials Science and Engineering, Nanchang Hangkong University, Nanchang 330063, China

^2.Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China

Corresponding Author:

LIU Rongjun (1978-), male, Ph.D., Researcher. E-mail: rongjunliu@163.com

WANG Luyan (2000-), male, Master candidate. E-mail: wangluyan123892@163.com

出版时间: 2025-03-20 doi: 10.14062/j.issn.0454-5648.20240585

文章导航

摘要

收起

C/C复合材料具有优异的力学性能，在航天航空、核能、化工、汽车、医疗等多个领域具有较高的应用潜力，但由于高温下会被迅速氧化，限制了其应用极限，在C/C复合材料表面制备抗氧化陶瓷涂层是提高其高温抗氧化性能的有效手段之一。本文依据不同抗氧化机理对当前C/C复合材料高温陶瓷防护涂层进行了归类讨论，并对C/C复合材料高温陶瓷抗氧化涂层的未来发展方向进行了适当展望。

关键词

碳/碳复合材料 / 抗氧化 / 表面涂层 / 抗氧化机理

Abstract

收起

C/C composite materials have several advantages, i.e., low density, high thermal conductivity, low thermal expansion coefficient, and resistance to ablation, which can be used in various fields such as aerospace and nuclear chemical engineering. However, the susceptibility of C/C composite materials to oxidation in high-temperature environments is a primary concern for their further application. One effective solution is the fabrication of high-temperature oxidation-resistant ceramic coatings on the surface of C/C composite materials. The existing high-temperature oxidation-resistant ceramic coatings for C/C composites are gradually transited from single-layer to multi-layer. Typically, these composite coatings consist of three components, i.e., a mitigating layer, an intermediate layer and a sealing layer. The mitigating layer serves to alleviate the thermal expansion coefficient mismatch between the substrate and the coating, while an oxygen-blocking layer characterized by a low oxygen diffusion rate prevents external oxygen from penetrating the substrate. The sealing layer with low porosity, high-temperature fluidity, and self-healing properties protects against environmental medium erosion.

This review categorizes the existing high-temperature oxidation-resistant coatings of C/C composites based on different oxidation resistance mechanisms of ceramic coatings, i.e., ceramic coatings based on self-healing glass phase protection mechanisms, ceramic coatings based on enhanced glass phase protection mechanisms, and antioxidant coatings based on composite glass phases. The ceramic coatings based on enhanced glass phase protection mechanisms are further divided into ion-enhanced glass phases, microporous-inclusion structure enhanced glass phases, and particle-enhanced glass phases. In the self-healing glass phase protection mechanism coatings, SiO₂ and B₂O₃ are the most common glass phases. However, single-layer SiO₂ or B₂O₃ coatings are restricted in their application at > 1000 ℃ due to the volatilization of the generated B₂O₃ glass phase. It is thus necessary to incorporate both silicides and borides into the coating to facilitate the formation of a silicon-boron glass phase from their high-temperature oxidation products (i.e., SiO₂ and B₂O₃), thereby enhancing the oxidation resistance at > 1000 ℃. In addition, SiOC glass phases can also improve oxidation resistance at > 1000 ℃.

In ion-enhanced glass phases, Ta and Hf ions exhibit significant reinforcement effects on the glass phase. Specifically, Ta ions due to its intense ionic complexation form a coral-like oxide framework with Hf ions, acting as a supporting scaffold in the Ta-Hf-Si-O glass phase. This enhances the viscosity and strength of the glass layer and the oxygen barrier capability of the coating. Hf cations diffuse into the SiO₂ lattice, creating more stable chemical bonds that increase the thermal stability of SiO₂ glass, allowing the glass phase to continue protecting the substrate from oxidation in a wider temperature range for an extended period. In microporous-inclusion structure enhanced glass phases, the microporous structure can inhibit crack propagation, while the inclusion structure can suppress the tendency for coating cracking, thereby also enhancing oxidation resistance. A research indicates that SiC-Si coatings with microporous structures can protect C/C composites from oxidation at 1500 ℃ for 846 h, with a mass loss of only 0.16%. In particle-enhanced glass phases, the SiO₂ glass phase generated upon oxidation of the coating becomes stable due to the incorporation of Zr compound particles as reinforcing phases, reducing the formation of cracks in the glass phase. This results in superior high-temperature oxidation resistance. For instance, La₂O₃-modified ZrB₂-SiC coatings yield a Zr compound particle distribution in La-Si-O glass that forms a dense oxidation film, demonstrating the oxidation resistance at 1500 ℃ for 550 h and at 1600 ℃ for 107 h, while enduring 50 thermal cycles from 1500 ℃ to room temperature with a mass gain of 0.35%. Researchers develop the coatings that can resist oxidation at 1700 ℃ for 415 h based on the aforementioned antioxidant mechanism.

In coatings based on composite glass phases, silicate and aluminate composite glass phases synergistically utilize the advantages of different glass phases. In addition to exhibiting self-healing functions, they also possess a superior oxidation resistance, remaining stable under high-temperature and oxidative conditions. Moreover, elements such as Zr, Y, and Al can capture oxygen molecules, forming a stable oxide layer that further protects the C/C substrate from oxidation damage. In addition, this review also represents the specific preparation processes and oxidation resistance effects for coatings based on oxide-generated glass phase protection mechanisms, enhanced glass phase protection mechanisms, and silicate glass phase coatings.

Summary and Prospects

This review offers a prospective outlook on the development of oxidation-resistant coatings for C/C composites. Firstly, novel reinforcing phases, such as one-dimensional and two-dimensional materials, can be doped to design and optimize the synthesis of ultra-high-temperature oxidation-resistant ceramic materials via efficient artificial intelligence approaches. This involves more complex combinations of the existing oxidation-resistant coatings or mechanisms to actively explore new systems of oxidation-resistant coatings for C/C composites capable of withstanding at > 1700 ℃. Secondly, constructing a complete and reliable performance database for the existing C/C composite oxidation-resistant coatings can elucidate the related protective mechanisms, establish reasonable evaluation mechanisms, and explore key control methods, thereby providing design parameters and theoretical support for practical applications. Finally, a research should focus on the adaptability of oxidation-resistant coatings on C/C composite components of various sizes and configurations, optimizing preparation processes, revealing critical control factors, forming stable process control pathways, and developing relevant process standards.

Key words

carbon/carbon composites / antioxidant / surface coating / antioxidation mechanism

引用本文

王麓焱, 刘荣军, 王衍飞, 李端, 缪花明. C/C复合材料高温抗氧化陶瓷防护涂层的研究进展与展望. 硅酸盐学报, 2025 , 53 (3) : 688 -699 . DOI: 10.14062/j.issn.0454-5648.20240585

Luyan WANG, Rongjun LIU, Yanfei WANG, Duan LI, Huaming MIAO. Research Progress on High-Temperature Ceramic Protective Coatings on C/C Composite Materials[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (3) : 688 -699 . DOI: 10.14062/j.issn.0454-5648.20240585

基金

收起

新型陶瓷纤维及其复合材料重点实验室基金(6142907220301)

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3期

PDF下载

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20240585

接收时间：2024-09-06
首发时间：2026-10-22
出版时间：2025-03-20

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2024-09-06
修回日期：2024-10-23

基金

新型陶瓷纤维及其复合材料重点实验室基金(6142907220301)

作者信息

^1．南昌航空大学材料科学与工程学院，南昌 330063

^2．国防科技大学，空天科学学院新型陶瓷纤维及其复合材料重点实验室，长沙 410073

通讯作者:

刘荣军（1978—），男，博士，研究员。

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240585

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