Review of high-temperature oxidation properties for carbon fiber toughened ceramic matrix composites: oxidation mechanisms, oxidation damage experiments and models
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摘要: 碳纤维增韧陶瓷基复合材料兼具陶瓷材料优良的抗氧化腐蚀性能和碳纤维材料增强增韧的力学性能，已成为最有潜力的高超声速飞行器热防护候选材料。碳纤维增韧陶瓷基复合材料在多物理场耦合服役环境下的高温氧化损伤失效机理对热防护材料设计及性能表征与评价至关重要，也一直是国内外学者研究的热点。本文从高温氧化机理、耦合失效实验、高温氧化模型三个方面对C/SiC和C/ZrB2-SiC复合材料进行详细论述和总结，对相应的研究方法的局限性和适用范围进行分析和评价，并展望了碳纤维增韧陶瓷基复合材料氧化损伤研究的发展趋势，进而为碳纤维增韧陶瓷基复合材料在热力氧耦合条件下的热/力响应及性能评价研究奠定理论模型基础。
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关键词:
- 碳纤维增韧陶瓷基复合材料 /
- 氧化机理 /
- 损伤失效 /
- 实验 /
- 氧化模型
Abstract: Carbon fiber toughened ceramic matrix composites inherit the excellent mechanical properties of carbon fibers and the high oxidation and corrosion resistance of ceramics, become the most promising candidate thermal protection materials for hypersonic vehicles. The high-temperature oxidation mechanisms and damage mechanical behaviors of carbon fiber toughened ceramic matrix composites in coupled service environments are important topics in the study of design, property characteristic and evaluation of thermal protection material. This provides a detailed discussion and summary of the research and analysis methods employed to characterize the oxidation damage of C/SiC and C/ZrB2-SiC composites in three aspects: high-temperature oxidation mechanisms, coupled failure experiment, and high-temperature oxidation model. The limitations and applicability of various research methods are analyzed and evaluated. In addition, the development trend of investigation of oxidation damage in carbon fiber toughened ceramic matrix composites is provided. It lays a theoretical foundation of thermal/mechanical response analysis and performance evaluation of carbon fiber toughened ceramic matrix composites in the thermal/mechanical/oxygen environment. -
图 2 ZrB2-SiC高温氧化行为研究：(a)采用DNE-TGA分析ZrB2-SiC在1600℃空气氧化不同时间后的材料微结构演化[8]；(b)基于SEM与XEDS的ZrB2-SiC在1627℃空气中氧化后扫描分析结果[11]；(c)基于实验结果建立氧化产物演化模型示意图[17]
Figure 2. Study on high temperature oxidation behavior of ZrB2-SiC: (a) DNE-TGA was used to analyze the microstructure evolution of ZrB2-SiC after oxidation in air at 1600℃ for different times[8]; (b) Scanning analysis results of ZrB2-SiC after oxidation in air at 1627℃ based on SEM and XEDS[11];(c) Schematic diagram of oxidation product evolution model based on experimental results[17]
图 3 数据驱动的方法在陶瓷氧化损伤研究中的应用[29, 30]：(a)使用从文献中提取的实验数据库训练ML以预测氧化损伤； (b)模型预测氧化层厚度随温度变化和实际值的比较
Figure 3. Application of data-driven methods in the study of ceramic oxidation damage[29, 30]: (a) ML trained by the experimental database extracted from the literature to predict oxidative damage; (b) Comparison of model prediction and actual oxide scale thickness values vs. temperature
图 4 碳纤维与C/SiC复合材料的高温氧化行为研究：(a)T300碳纤维的恒温氧化失重曲线[31]；(b)平纹C/SiC复合材料的恒温氧化失重曲线[31]；(c)基体裂纹提供氧气通道诱导局部纤维的氧化[31]；(d)在裂纹尖端形成的碳纤维消耗区[33]
Figure 4. High temperature oxidation behavior of carbon fiber and c/sic composite: (a) Isothermal oxidation weight loss curve of T300 carbon fiber[31];(b) Isothermal oxidation weight loss curve of plain c/sic composite[31]; (c) Matrix crack provides oxygen channel to induce local fiber oxidation[31]; (d) Carbon fiber consumption zone formed at the crack tip[33]
图 6 C/ZrB2-SiC复合材料的高温氧化行为研究：(a)不同深度的氧化层微结构成分与形貌[36]；(b)轴向纤维和横向纤维在空气中的氧化行为示意图[34]
Figure 6. Study on high temperature oxidation behavior of C/ZrB2-SiC composites: (a) Microstructure composition and morphology of oxide layers at different depths[36]; (c) Oxidation behavior of axial fibers and transverse fibers in air[34]
图 8 C/SiC复合材料的应力氧化行为[45]：(a)均匀与非均匀氧化共存形貌，归一化应力NS=0.32；(b)非均匀氧化形貌, 归一化应力NS=0.64；(c) 在不同应力氧化机制下C/SiC复合材料的长度变化
Figure 8. Study on stress oxidation behavior of C/SiC composites[45]: (a) Uniform/non-uniform fiber oxidation coexistence, NS=0.32; (b) Non-uniform fiber oxidation, NS=0.64; (c) Length changes of C/SiC composites under different stress oxidation mechanisms
图 9 C/SiC复合材料的耦合失效研究：(a)拉伸载荷作用下裂纹的演化与局部纤维结构相关[47]；(b)，(c)基于原位Micro-CT表征SiC/SiC的应力氧化力学行为和结构特征[53]
Figure 9. Study on coupling failure behavior of ceramic matrix composites: (a) The evolution of cracks under tensile load is related to local fiber structure[47]; (b) and (c) Characterization of stress oxidation mechanical behavior and structural characteristics of sic/sic based on in-situ Micro-CT[53]
图 10 陶瓷基复合材料冲击损伤实验以及剩余性能研究: (a)氧乙炔对冲击后C/C复合材料和SiC-C/C复合材料氧化测试与损伤表征[59]；(b)氧化质量损失与涂层冲击损伤面积的关系以及C/SiC复合材料剩余弯曲性能[59]
Figure 10. The impact damage experiment and residual performance study of ceramic matrix composites: (a) Oxidation test and damage characterization of oxyacetylene on C/C composites and SiC-C/C composites after impact [59]; (b) Relationship between oxidation mass loss and impact damage area of coating and C/SiC residual bending properties of composites [59]
图 11 陶瓷基复合材料的宏细观氧化模型：(a)基于不同控制因素的宏观氧化模型[61]；(b)建立考虑预制裂纹的纤维横向氧化细观有限元模型[63]；(c)基于剪滞理论的细观氧化损伤模型[66]
Figure 11. Macro and meso scale oxidation models of ceramic matrix composites: (a) Macro oxidation model based on different control factors[61]; (b) Meso finite element model of fiber transverse oxidation considering prefabricated cracks[63]; (c) Meso oxidation damage model based on shear lag theory[66]
图 12 陶瓷基复合材料的耦合失效模型：(a)非线性宏-微观耦合二维有限元模型[69]；(b)氧气浓度计算结果[69]；(c)基于Micro-CT建立的细观单胞模型[71]；(d)基于用户子程序的氧化损伤模拟云图[71]；(e)结合氧化动力学和渐近损伤模型的失效分析方法[73]
Figure 12. Coupling failure model of ceramic matrix composites: (a) Nonlinear macro micro coupled two-dimensional finite element model[69]; (b) Oxygen concentration calculation[69]; (c) Meso model based on Micro-CT[71]; (d) Oxidation damage cloud figure simulated by user subroutine[71]; (e) Failure analysis method combining oxidation kinetics and asymptotic damage models[73]
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