高导热中间相沥青基碳纤维的氧化行为

Oxidation behavior of high thermal conductivity mesophase-pitch-based carbon fibers

  • 摘要: 以自制高导热中间相沥青基碳纤维(CFMP)为研究对象,采用M55J聚丙烯腈基碳纤维作为对照组,研究了CFMP在不同氧化温度和时间下的氧化行为。结果表明:CFMP表现出“外层褶皱辐射+内层洋葱皮”状结构特征,石墨微晶发育程度好,取向度高,发生氧化时氧气分子优先沿着CFMP褶皱辐射状炭织构之间的微裂纹或微孔扩散和反应,形成具有径向裂纹和局部凹坑的氧化特征。在低温氧化阶段,纤维的氧化行为受碳-氧化学反应控制,CFMP石墨微晶的活性位浓度低,所以起始反应温度比M55J高,氧化失重率比M55J低;在高温氧化阶段,纤维的氧化行为受扩散控制,CFMP内部的氧扩散路径多,所以氧化失重率比M55J高;同时氧化造成了CFMP微观缺陷尺寸更大、数量更多,氧化后纤维强度保留率仅为78%,低于M55J的85%。本文为高导热C/C复合材料的结构设计和实际服役提供一定的技术和理论参考。

     

    Abstract: The oxidation behaviors of the homemade high thermal conductive mesophase-pitch-based carbon fiber (CFMP) at different time and temperature were investigated using the polyacrylonitrile-based carbon fiber (M55J) as the control group. The results show that CFMP exhibits a fold radiation structure in the outer part and onion skin structure in the inner part. The CFMP has a well-developed graphite crystallite and a high degree of orientation. Oxygen atoms preferentially diffuse in the microcracks and micropores in the fold radiation carbon textures of CFMP and react with them resulting in radial cracks and localized pits. In the low temperature oxidation stage, the oxidation behaviors of the fibers are controlled by the carbon-oxygen chemical reaction. Because the active site concentration in graphite crystallite of CFMP is lower, its initial reaction temperature is higher than that of M55J, and its oxidation mass loss rate is relative lower. In the high temperature oxidation stage, the oxidation behaviors of the fibers are controlled by oxygen diffusion. The oxidation mass loss rate of CFMP is higher than that of M55J because there are more oxygen diffusion paths in the CFMP. Moreover, because there are more and larger microstructural defects in CFMP after oxidation, the strength retention rate of the CFMP is only 78%, which is lower than that of M55J (85%). This study provides certain technical and theoretical references for the structural design and actual service of high thermal conductive C/C composites.

     

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