SiC过渡层对SiC/SiC陶瓷基复合材料表面MoSi2-SABB涂层结合性能的影响

doi:10.15541/jim20240538

无机材料学报 ›› 2025, Vol. 40 ›› Issue (10): 1119-1128.DOI: 10.15541/jim20240538 CSTR: 32189.14.jim20240538

SiC过渡层对SiC/SiC陶瓷基复合材料表面MoSi₂-SABB涂层结合性能的影响

曹路涵¹^,²(), 孟佳¹(), 薛玉冬³^,⁴, 盛晓晨¹, 崔苑苑⁵, 乐军¹, 宋力昕¹^,²()

¹ 中国科学院上海硅酸盐研究所, 中国科学院特种无机涂层重点实验室, 上海 200050
² 中国科学院大学材料科学与光电工程中心, 北京 100049
³ 中国科学院上海硅酸盐研究所, 关键陶瓷材料全国重点实验室, 上海 200050
⁴ 中国科学院上海硅酸盐研究所, 结构陶瓷与复合材料工程研究中心上海 200050
⁵ 上海大学材料科学与工程学院, 上海 200444

收稿日期:2024-12-26 修回日期:2025-03-15 出版日期:2025-10-20 网络出版日期:2025-04-02
通讯作者: 孟佳, 正高级工程师. E-mail: jiameng@mail.sic.ac.cn;
宋力昕, 研究员. E-mail: lxsong@sunm.shcnc.ac.cn
作者简介:曹路涵(2000-), 女, 硕士研究生. E-mail: caoluhan22@mails.ucas.ac.cn

Effect of SiC Transition Layer on Bonding Properties of MoSi₂-SABB Coating on SiC/SiC Ceramic Matrix Composites

CAO Luhan¹^,²(), MENG Jia¹(), XUE Yudong³^,⁴, SHENG Xiaochen¹, CUI Yuanyuan⁵, LE Jun¹, SONG Lixin¹^,²()

¹ Key Laboratory of Inorganic Coating Materials CAS, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
³ State Key Laboratory of High Performance Ceramics, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
⁴ Structural Ceramics and Composites Engineering Research Centre, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
⁵ School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China

Received:2024-12-26 Revised:2025-03-15 Published:2025-10-20 Online:2025-04-02
Contact: MENG Jia, professor. E-mail: jiameng@mail.sic.ac.cn;
SONG Lixin, professor. E-mail: lxsong@sunm.shcnc.ac.cn
About author:CAO Luhan (2000-), female, Master candidate. E-mail: caoluhan22@mails.ucas.ac.cn

摘要/Abstract

摘要：

SiC/SiC陶瓷基复合材料(SiC/SiC CMCs)以其耐高温、低密度、高强度等优点有望被用于可重复使用空天飞行器的热防护系统。鉴于空天飞行器面临的复杂恶劣使用环境, 为满足可重复使用的要求, 亟需在SiC/SiC CMCs表面制备高温抗氧化封严涂层。由于SiC/SiC CMCs表面粗糙且各向异性, 易诱导涂层开裂失效, 有待进一步研究封严涂层设计和涂层结合性能优化。本工作通过化学气相沉积(Chemical Vapor Deposition, CVD)法在SiC/SiC CMCs表面设计制备了SiC过渡层, 解决了MoSi₂掺杂的SiO₂-Al₂O₃-BaO-B₂O₃(MoSi₂-SABB)玻璃陶瓷复合涂层的开裂剥落问题, 使涂层展现出良好的抗热震性能。有限元分析表明SiC过渡层能够有效降低MoSi₂-SABB涂层与基材界面的残余应力, 缓解残余应力的各向异性, 显著提升涂层的结合性能。结合第一性原理计算探究了不同晶型、极性SiC过渡层与MoSi₂-SABB涂层的结合机制, 揭示了SiC过渡层的晶型与极性是影响涂层结合性能的关键因素。本研究为设计SiC/SiC CMCs表面封严涂层与优化涂层结合性能提供了重要依据。

关键词: SiC/SiC陶瓷基复合材料, SiC过渡层, 玻璃陶瓷复合涂层, 结合性能

Abstract:

SiC/SiC ceramic matrix composites (SiC/SiC CMCs) are expected to be used in the thermal protection system of reusable aerospace vehicles due to their advantages of high temperature resistance, low density and high strength. Given the complex and harsh working environment of aerospace vehicles, it is urgent to develop a high-temperature anti-oxidation sealing coating on the surface of SiC/SiC CMCs to meet the requirements for reusability. In this work, a SiC transition layer was designed and prepared on the surface of SiC/SiC CMCs by chemical vapor deposition (CVD), which is supposed to solve the cracking and spalling problems of the MoSi₂-doped SiO₂-Al₂O₃-BaO-B₂O₃ (MoSi₂-SABB) glass-ceramic composite coating, and enable the coating to exhibit excellent thermal shock resistance. Finite element analysis showed that the SiC transition layer could effectively reduce the residual stress at the interface between the MoSi₂-SABB coating and the substrate, alleviate anisotropy of the residual stress, and significantly improve bonding performance of the coating. This binding mechanism of SiC transition layer with different crystal structures and polarities and MoSi₂-SABB coating was investigated by the first principles calculation. The results showed that crystal structure and polarity of SiC transition layer were key factors affecting the coating bonding performance, providing a basis for design and optimization of bonding performance for surface sealing coating of SiC/SiC CMCs.

Key words: SiC/SiC ceramic matrix composite, SiC transition layer, glass-ceramic composite coating, bonding performance

中图分类号:

TQ174

曹路涵, 孟佳, 薛玉冬, 盛晓晨, 崔苑苑, 乐军, 宋力昕. SiC过渡层对SiC/SiC陶瓷基复合材料表面MoSi₂-SABB涂层结合性能的影响[J]. 无机材料学报, 2025, 40(10): 1119-1128.

CAO Luhan, MENG Jia, XUE Yudong, SHENG Xiaochen, CUI Yuanyuan, LE Jun, SONG Lixin. Effect of SiC Transition Layer on Bonding Properties of MoSi₂-SABB Coating on SiC/SiC Ceramic Matrix Composites[J]. Journal of Inorganic Materials, 2025, 40(10): 1119-1128.

图/表 14

表1 相关材料的热物性质

Table 1 Thermophysical properties of the relevant materials

Sample	Temperature, T/℃	Density, ρ/(kg·m⁻³)	Elastic modulus/GPa	Poisson’s ratio	Thermal expansion coefficient, α/ (×10⁻⁶, K^-1)	Thermal conductivity/ (W·m^-1·K^-1)	Specific heat capacity/ (J·kg^-1·K^-1)
MoSi₂-SABB coating	25	2192	33.370	0.208	3.30	1.130	716
	100	-	33.805	0.208	3.30	1.206	789
	200	-	34.125	0.208	3.51	1.277	883
	300	-	34.499	0.208	3.66	1.368	975
	400	-	34.824	0.208	3.70	1.475	1068
	500	-	34.861	0.208	3.64	1.702	1159
	600	-	35.246	0.208	3.59	1.849	1252
CMCs	25	2600	150	0.130	2.929	4.83	759
	200	-	150	0.130	4.128	/	706
	400	-	150	0.130	3.880	/	299
	600	-	150	0.130	3.831	/	410
	800	-	150	0.130	4.124	4.68	805
	1000	-	150	0.130	4.157	4.57	963
SiC layer^[22-23]		3200	340	0.142	4.0	39	700

图1 界面模型界面处原子示意图

Fig. 1 Schematic diagram of atoms at the interface according to interface model

图2 制备SiC过渡层前后CMCs基底的表面形貌结构与在其表面制备的MoSi2-SABB涂层形貌

Fig. 2 Surface morphologies and structures of CMCs substrates before and after preparation of the SiC transition layer, along with morphology of the MoSi2-SABB coating prepared on its surface (a-d) SEM images of (a) CMCs, (b) CMCs/MoSi2-SABB coating, (c) CMCs/SiC, and (d) CMCs/SiC/MoSi2-SABB coating; (e) Surface profile curves of CMCs and CMCs/SiC; (f) Surface 3D profile curves of CMCs/SiC

图3 CMCs/MoSi2-SABB与CMCs/SiC/MoSi2-SABB模型中MoSi2-SABB涂层界面在波峰、波谷处的温度与残余应力曲线

Fig. 3 Curves of temperature and residual stress at peaks and valleys of MoSi2-SABB coating interfaces in CMCs/MoSi2- SABB and CMCs/SiC/MoSi2-SABB models (a) Radial stress; (b) Axial stress

图4 CMCs/MoSi2-SABB(a, c)和CMCs/SiC/MoSi2-SABB(b, d)涂层界面的径向应力(a, b)和轴向应力(c, d)

Fig. 4 Radial stress (a, b) and axial stress (c, d) of coating interface of CMCs/MoSi2-SABB (a, c) and CMCs/SiC/MoSi2-SABB (b, d) S11: radial stress; S22: axial stress. Colorful figures are available on website

图5 CMCs/SiC/MoSi2-SABB涂层热震循环测试前(a, c)后(b, d)的表面(a, b)和截面(c, d)SEM照片

Fig. 5 (a, b) Surface and (c, d) cross-sectional SEM images of CMCs/SiC/MoSi2-SABB coating before (a, c) and after (b, d) thermal shock cycle

图6 不同CVD工艺制备的三种SiC过渡层表面的MoSi2-SABB涂层宏观形貌

Fig. 6 Macroscopic morphologies of MoSi2-SABB coatings on the surface of three SiC transition layers prepared by different CVD processes (a) 1# sample; (b) 2# sample; (c) 3# sample

图7 1#~3# CMCs/SiC基底表面SEM照片、AFM图像与水接触角示意图

Fig. 7 SEM, AFM and water contact angle images of the surface of 1#-3# CMCs/SiC substrates (a) 1# CMCs/SiC; (b) 2# CMCs/SiC; (c) 3# CMCs/SiC

图8 CMCs和1#~3# CMCs/SiC表面的XRD图谱

Fig. 8 XRD patterns of CMCs and 1#-3# CMCs/SiC surfaces

表2 6H-SiC、3C-SiC与MoSi2、SiO2界面的黏附强度

Table 2 Adhesion strength of 6H-SiC, 3C-SiC and MoSi2, SiO2 interfaces

W_sep/(J·m^-2)	6H-SiC/ MoSi₂	6H-SiC/ SiO₂	3C-SiC/ MoSi₂	3C-SiC/ SiO₂
Si termination	3.64	6.67	2.91	4.79
C termination	4.80	1.60	7.41	0.49

图9 1#~3# CMCs/SiC表面MoSi2-SABB涂层的SEM照片

Fig. 9 SEM images of MoSi2-SABB coatings on the surfaces of 1#-3# CMCs/SiC (a) 1# CMCs/SiC; (b) 2# CMCs/SiC; (c) 3# CMCs/SiC

图10 MoSi2-SABB涂层受力分析

Fig. 10 Force analysis of MoSi2-SABB coating

图11 2# CMCs/SiC表面玻璃改性前(a)后(b)的MoSi2-SABB涂层的SEM照片

Fig. 11 SEM images of MoSi2-SABB coating on 2# CMCs/SiC substrate before (a) and after (b) modification of glass

图12 SABB玻璃改性前后的软化温度

Fig. 12 Softening temperature before and after modification of SABB glass

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SiC过渡层对SiC/SiC陶瓷基复合材料表面MoSi₂-SABB涂层结合性能的影响

Effect of SiC Transition Layer on Bonding Properties of MoSi₂-SABB Coating on SiC/SiC Ceramic Matrix Composites

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