C/SiC-BN复合材料的制备及氧化行为

doi:10.15541/jim20230583

无机材料学报 ›› 2024, Vol. 39 ›› Issue (7): 779-786.DOI: 10.15541/jim20230583

C/SiC-BN复合材料的制备及氧化行为

姜灵毅¹^,²(), 庞生洋², 杨超¹, 张悦¹, 胡成龙², 汤素芳²()

1.沈阳工业大学材料科学与工程学院, 沈阳 110870
2.中国科学院金属研究所, 沈阳 110016

收稿日期:2023-12-18 修回日期:2024-01-21 出版日期:2024-02-22 网络出版日期:2024-02-22
通讯作者: 汤素芳, 研究员. E-mail: sftang@imr.ac.cn
作者简介:姜灵毅(1999-), 男, 硕士研究生. E-mail: lyjiang22h@imr.ac.cn
基金资助:
国家自然科学基金(52272075);国家自然科学基金(U20A20242)

Preparation and Oxidation Behaviors of C/SiC-BN Composites

JIANG Lingyi¹^,²(), PANG Shengyang², YANG Chao¹, ZHANG Yue¹, HU Chenglong², TANG Sufang²()

1. School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110870, China
2. Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

Received:2023-12-18 Revised:2024-01-21 Published:2024-02-22 Online:2024-02-22
Contact: TANG Sufang, professor. E-mail: sftang@imr.ac.cn
About author:JIANG Lingyi (1999-), male, Master candidate. E-mail: lyjiang22h@imr.ac.cn
Supported by:
National Natural Science Foundation of China(52272075);National Natural Science Foundation of China(U20A20242)

摘要/Abstract

摘要：

C/SiC复合材料作为一种高温结构材料, 在航空航天热防护领域具有广泛的应用前景。然而, 该材料的中低温抗氧化性能相对较差, 制约了其在更广泛领域的应用。本研究采用料浆抽滤工艺, 通过调节料浆中陶瓷含量在纤维增强体中引入不同含量的抗氧化组元BN, 再通过反应熔体渗透法制备C/SiC-BN复合材料。系统研究了不同BN含量对复合材料结构组成及抗氧化行为的影响, 并分析相关氧化机理。研究结果表明: 引入BN颗粒显著降低了C/SiC的开口孔隙率, 并明显提高了C/SiC的起始氧化温度。引入质量分数3% BN时, C/SiC-BN复合材料(B3样品)的抗氧化性能最优, 其在900、1200和1500 ℃静态氧化1 h的质量损失率分别为0.009%、-0.301%、-0.596%, 显著优于C/SiC。1500 ℃氧化后, B3样品的强度保持率最高, 达到52%。900 ℃氧化时, C/SiC-BN复合材料主要经历C相和BN相的氧化, 以O₂扩散反应控制的缓慢失重为主; 1200 ℃氧化时, C相和BN相氧化速率加快, SiC发显著氧化, 生成的B₂O₃、硼硅酸盐和SiO₂等氧化产物减缓了O₂的扩散速率, 减小了基体碳的损伤; 1500 ℃氧化时, SiC氧化速率加快, 生成的SiO₂在复合材料表面形成的连续氧化膜阻碍了O₂的向内扩散。B₂O₃、CO等气体产物溢出及持续生成SiO₂主导了整个氧化过程。

关键词: 料浆浸渍, C/SiC, BN, 微观结构, 氧化行为

Abstract:

As thermal structural materials operating at high temperatures, C/SiC composites have extensive applications as thermal protection systems in aerospace vehicles. However, their limited antioxidant performance at low and medium temperatures restricts their utilization in diverse fields. In this work, an improved slurry impregnation technique was employed to introduce antioxidant component BN at different contents into the carbon fiber felts by adjusting the ceramic content in the slurry, and then densified the felts to prepare C/SiC-BN composites using reaction melt infiltration method. Effects of BN content on the composition, microstructure and oxidation behaviors of the composites were systematically studied, and relevant oxidation mechanisms were explored. Experimental results indicate that introduction of BN particles significantly reduces the open porosity of C/SiC and enhances the initial oxidation temperature of C/SiC. The C/SiC-BN composite with 3% BN (mass fraction, sample B3) has optimal antioxidant performance, and the corresponding mass loss rates in static air at 900, 1200 and 1500 ℃ for 1 h are 0.009%, -0.301%, and -0.596%, respectively. After oxidation at 1500 ℃, the strength retention rate of sample B3 is up to 52%. At 900 ℃, the mass change is dominated by slow weight loss controlled by O₂diffusion and oxidation of C and BN. At 1200 ℃, the oxidation rates of C and BN phases increase while SiC begins to undergo significant oxidation. New formed oxidation products, such as B₂O₃, borosilicate and SiO₂, gradually slow the diffusion of O₂and reduce the damage of carbon. At 1500 ℃, the oxidation rate of SiC is accelerated obviously. Finally, a continuous oxidation film formed by generated SiO₂ retards the inward diffusion of O₂, and overflow of gas products (such as B₂O₃ and CO) and continuous formation of SiO₂ dominate the oxidation process.

Key words: slurry impregnation, C/SiC, BN, microstructure, oxidation behavior

中图分类号:

TB332

姜灵毅, 庞生洋, 杨超, 张悦, 胡成龙, 汤素芳. C/SiC-BN复合材料的制备及氧化行为[J]. 无机材料学报, 2024, 39(7): 779-786.

JIANG Lingyi, PANG Shengyang, YANG Chao, ZHANG Yue, HU Chenglong, TANG Sufang. Preparation and Oxidation Behaviors of C/SiC-BN Composites[J]. Journal of Inorganic Materials, 2024, 39(7): 779-786.

图/表 11

图1 C/SiC-BN复合材料的制备过程示意图

Fig. 1 Schematic preparation process of C/SiC-BN composites

图2 料浆浸渍BN后低密度C/C预制体的SEM照片

Fig. 2 SEM images of low-density C/C preforms after slurry impregnation with BN (a) Sample B1; (b) Sample B3; (c) Sample B5; (d) Enlarged image of sample B5

图3 C/SiC和C/SiC-BN截面形貌和纤维间区域放大图

Fig. 3 Cross-sectional morphologies of C/SiC and C/SiC-BN composites and their magnification images (a, b) Sample B0; (c, d) Sample B5

表1 C/SiC和C/SiC-BN复合材料的密度及孔隙率

Table 1 Densities and porosities of C/SiC and C/SiC-BN composites

Sample	Density/(g·cm^-3)	Porosity/%
B0	2.29	8.5
B1	2.37	5.6
B3	2.34	6.3
B5	2.37	6.7

图4 C/SiC和C/SiC-BN在不同温度氧化后质量的变化曲线

Fig. 4 Oxidation weight loss curves of C/SiC and C/SiC-BN oxidated at different temperatures (a) 900 ℃; (b) 1200 ℃; (c) 1500 ℃

图5 不同BN含量复合材料的TG-DSC曲线

Fig. 5 TG-DSC curves of composites with different BN contents Colorful figure is available on website

图6 C/SiC-BN(B3)在不同温度氧化1 h后的表面形貌

Fig. 6 Surface morphologies of C/SiC-BN(B3) after oxidation at different temperatures for 1 h (a) 900 ℃; (b) 1200 ℃; (c) 1500 ℃

表2 C/SiC-BN复合材料氧化前后的弯曲强度和模量

Table 2 Flexural strength and modulus of C/SiC-BN composites before and after oxidation

Sample	Flexural strength/MPa	Strength after oxidation/MPa	Strength retention rate/%	Modulus/GPa
B1	172	70	41	18.2
B3	198	103	52	19.3
B5	181	78	43	17.3

图7 C/SiC-BN(B3)在不同温度氧化后的表面XRD谱图

Fig. 7 XRD patterns of the surface of C/SiC-BN(B3) after oxidation at different temperatures

图8 C/SiC-BN(B3)在不同温度氧化1 h后的截面形貌

Fig. 8 Cross-sectional morphologies of C/SiC-BN(B3) after oxidation at different temperatures for 1 h (a) 900 ℃; (b) 1200 ℃; (c) 1500 ℃

图9 B2O3和SiO2蒸气压随温度的变化曲线

Fig. 9 Vapor pressure-temperature curves of B2O3 and SiO2

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C/SiC-BN复合材料的制备及氧化行为

Preparation and Oxidation Behaviors of C/SiC-BN Composites

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