On-line identification and evolution of active and passive oxidation for SiC-based thermal protection materials in atomic oxygen environment
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摘要: 当前，高超声速飞行器主流SiC基防热材料在1200~1700℃内的防热机制主要依靠SiC被动氧化生成的SiO2保护层，但高超声速飞行带来的高温气体效应使得防热材料遭受高温、低压、原子氧载荷，原子氧的高活性将改变SiC氧化反应类型，导致材料丧失防护能力。因此，判别不同飞行工况下材料主/被动氧化类型将直接决定材料的使用阈值，对于高超声速飞行器防热设计和新型防热材料研制极为重要。基于此，本文打破通过分析氧化反应后材料微观成分辨别主/被动氧化反应的传统方法，基于光谱诊断、射频等离子放电以及高功率激光技术，建立高温、低压、原子氧环境下SiC基防热材料主/被动氧化反应在线识别方法与系统，实现了SiC基防热材料主/被动氧化反应快速在线识别，经过SEM、EDS和XRD等材料分析，验证了在线识别方法的准确性和可靠性，进一步探究了原子氧环境下SiC材料主动氧化的演化规律，并建立了氧化动力学方程，为SiC基防热材料防护阈值以及材料性能改进提供了重要支撑。Abstract: At present, the thermal protection mechanism of SiC-based materials for hypersonic vehicles mainly depends on the SiO2 protective layer formed by SiC passive oxidation at 1200-1700℃. However, the high-temperature gas effect caused by hypersonic flight makes the thermal protection materials subjected to high temperature, low pressure and atomic oxygen loadings. The high activity of atomic oxygen will change the type of SiC oxidation reaction, resulting in the loss of protective ability. Therefore, the identification of active and passive oxidation types of materials under different flight conditions will directly determine the use threshold of materials, which is very important for the TPS design of hypersonic vehicles and the development of new thermal protection materials. Based on it, this paper breaks the traditional method of analyzing the micro-composition of materials after oxidation, and establishes an on-line identification method and system of active and passive oxidation reaction for SiC-based thermal protection materials under high temperature, low pressure and atomic oxygen environment based on spectral diagnosis RF plasma discharge and high power laser technology. The rapid on-line identification of active and passive oxidation reaction for SiC-based thermal protection materials is realized. After material analysis by SEM, EDS and XRD, the accuracy and reliability of this method were verified, and the evolution law for active oxidation of SiC materials in atomic oxygen environment was further explored, which provides an important support for the protection threshold of SiC-based thermal protection materials and the improvement of material properties.
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图 1 原子环境下主/被动氧化在线识别系统
Figure 1. On-line identification system of active and passive oxidation in atomic environment
图 3 SiC主/被动氧化发射光谱对比
Figure 3. Comparison of active and passive oxidation emission spectra of SiC
图 6 不同试验条件下SiC材料表面发射光谱图像
Figure 6. OES images of SiC material surface under different test conditions
图 7 各SiC试样氧化后SEM组织形貌: (a) 试样3#表面; (b) 试样7#表面; (c) 试样3#截面; (d) 试样7#截面; (e) 试样2#表面; (f) 试样4#表面; (g) 试样6#表面; (h) 试样8#表面
Figure 7. Microstructures and morphologies of SEM after oxidation of SiC samples: (a) Sample 3# surface; (b) Sample 7# surface; (c) Sample 3# section; (d) Sample 7# section; (e) Sample 2# surface; (f) Sample 4# surface; (g) Sample 6# surface; (h) Sample 8# surface
图 9 不同温度下SiC材料氧化3 min后试样质量变化
Figure 9. Quality change of SiC material after 3 min oxidation at different temperatures
图 10 不同温度的SiC材料原子氧氧化后显微组织: (a) SiC-O-1350表面; (b) SiC-O-1400表面; (c) SiC-O-1500表面; (d) SiC-O-1600表面; (e) SiC-O-1350截面; (f) SiC-O-1600截面
Figure 10. Microstructures of SiC materials after atomic oxygen oxidation at different temperatures: (a) SiC-O-1350 surface; (b) SiC-O-1400 surface; (c) SiC-O-1500 surface; (d) SiC-O-1600 surface; (e) SiC-O-1350 section; (f) SiC-O-1600 section
图 11 SiC材料在原子氧介质下的氧化质量损失
Figure 11. Oxidation mass loss of SiC materials in atomic oxygen medium
图 12 C-1# 被动氧化反应后的表面微观形貌
Figure 12. Surface morphology after passive oxidation of C-1#
表 1 试验条件
Table 1. Test condition
Condition 1# 2# 3# 4# 5# 6# 7# 8# 9# T/℃ 1160 1300 1375 1375 1430 1430 1500 1500 1500 P/Pa 20 20 20 50 50 100 100 150 250 
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表 2 不同温度下SiC材料的氧化速率
Table 2. Oxidation rates of SiC materials at different temperatures
T/°C k/(g·min−1) 1350 0.00647 1400 0.00694 1500 0.00853 1600 0.01187
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表 3 C/SiC材料主/被动氧化试验条件
Table 3. Active and passive oxidation test conditions of C/SiC materials
Serial T/°C P/Pa Spctral signal Mass change/mg C-1# 1270 28 F −35.2 C-2# 1350 28 F −72.3 C-3# 1400 28 T −90.6 C-4# 1400 100 F −78.4 C-5# 1500 28 T −115.4 C-6# 1600 27 T −134.8 C-7# 1600 100 F −128.4 C-8# 1650 27 T −150.4
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