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高导热中间相沥青基碳纤维的氧化行为

王昊 王归 周星明 樊桢 吴晃 叶崇 张岳峰 黄东

王昊, 王归, 周星明, 等. 高导热中间相沥青基碳纤维的氧化行为[J]. 复合材料学报, 2023, 40(9): 5189-5200. doi: 10.13801/j.cnki.fhclxb.20221117.002
引用本文: 王昊, 王归, 周星明, 等. 高导热中间相沥青基碳纤维的氧化行为[J]. 复合材料学报, 2023, 40(9): 5189-5200. doi: 10.13801/j.cnki.fhclxb.20221117.002
WANG Hao, WANG Gui, ZHOU Xingming, et al. Oxidation behavior of high thermal conductivity mesophase-pitch-based carbon fibers[J]. Acta Materiae Compositae Sinica, 2023, 40(9): 5189-5200. doi: 10.13801/j.cnki.fhclxb.20221117.002
Citation: WANG Hao, WANG Gui, ZHOU Xingming, et al. Oxidation behavior of high thermal conductivity mesophase-pitch-based carbon fibers[J]. Acta Materiae Compositae Sinica, 2023, 40(9): 5189-5200. doi: 10.13801/j.cnki.fhclxb.20221117.002

高导热中间相沥青基碳纤维的氧化行为

doi: 10.13801/j.cnki.fhclxb.20221117.002
基金项目: 国家自然科学基金(U21 B2067;52202037);湖南省创新建设专项基金(2020 GK4029);湖南省自然科学基金(2021 JJ40144;2021 JJ40145);湖南省科技人才托举工程项目(2022 TJ-N11);广东省现代表面工程技术重点实验室(2020 B1212060049);长沙科技局重大专项(KQ2102005);湖南省十大技术攻关项目(2021 GK1140)
详细信息
    通讯作者:

    黄东,博士,副研究员,研究方向为碳纤维及复合材料 E-mail: hd52923212@hnu.edu.cn

  • 中图分类号: TB321

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

Funds: National Natural Science Foundation of China (U21 B2067; 52202037); Special Fund for Innovative Construction Province of Hunan (2020 GK4029); Natural Science Foundation of Hunan Province China (2021 JJ40144; 2021 JJ40145); Hunan Province Scientific and Technological Talents Support Project (2022 TJ-N11); Guangdong Provincial Key Laboratory of Modern Surface Engineering Technology (2020 B1212060049); Changsha Municipal Science and Technology Project (KQ2102005); Ten Key Technical Projects of Hunan Province (2021 GK1140)
  • 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。

     

  • 图  1  CFMP和M55 J的SEM图像:(a) M55 J截面低倍放大图;(b) M55 J截面高倍放大图;(c) M55 J表面形貌;(d) CFMP截面低倍放大图;(e) CFMP截面高倍放大图;(f) CFMP表面形貌

    Figure  1.  SEM images of CFMP and M55 J: (a) Low magnification image of cross section of M55 J; (b) High magnification image of cross section of M55 J; (c) Surface of M55 J; (d) Low magnification image of cross section of CFMP; (e) High magnification image of cross section of CFMP; (f) Surface of CFMP

    图  2  CFMP和M55 J的XRD图谱:(a) 粉末衍射图谱;(b) 方位角扫描

    Figure  2.  XRD patterns of CFMP and M55 J: (a) Powder diffraction patterns; (b) Azimuth scan

    图  3  CFMP和M55 J的拉曼光谱分析:(a) 截面表层区,图1(a)中A点和图1(d)中C点;(b) 截面芯部,图1(a)中B点和图1(d)中D点

    Figure  3.  Raman spectroscopy analysis of CFMP and M55 J: (a) Cross sectional surface area, point A in Fig.1(a) and point C in Fig.1(d); (b) Cross section of core, point B in Fig.1(a) and point D in Fig.1(d)

    图  4  CFMP和M55 J的氧化失重曲线

    Figure  4.  Oxidative weight loss curves of CFMP and M55 J

    图  5  600℃恒温氧化时CFMP和M55 J的TG曲线 (a) 与DTG曲线 (b)

    Figure  5.  TG (a) and DTG (b) curves of CFMP and M55 J under constant temperature oxidation at 600℃

    图  6  CFMP和对照组M55 J静态空气中氧化60 min的SEM图像:(a) M55 J表面;(b) M55 J截面;(c) CFMP表面;(d) CFMP表面高倍放大图;(e) CFMP截面上的氧化凹坑;(f) CFMP截面的裂纹

    Figure  6.  SEM images of CFMP and M55 J oxidized in static air for 60 min: (a) Surface of M55 J; (b) Cross section of M55 J; (c) Surface of CFMP; (d) High magnification image of surface of CFMP; (e) Oxidation pits on cross section of CFMP; (f) Cracks on cross section of CFMP

    图  7  CFMP和M55 J纤维氧化90 min前 (a) 和后 (b) 表面的拉曼光谱分析

    Figure  7.  Raman spectroscopy analysis of CFMP and M55 J surface before (a) and after (b) 90 min oxidation

    图  8  CFMP氧化不同时间后的SEM图像:(a) CFMP氧化10 min;(b) CFMP氧化40 min;(c) CFMP氧化90 min;(d) CFMP氧化240 min;(e) 对照组M55 J氧化10 min;(f) 对照组M55 J氧化90 min

    Figure  8.  SEM images of CFMP oxidized for different time: (a) Oxidation of CFMP for 10 min; (b) Oxidation of CFMP for 40 min; (c) Oxidation of CFMP for 90 min; (d) Oxidation of CFMP for 240 min; (e) Oxidation of M55 J for 10 min; (f) Oxidation of M55 J for 90 min

    图  9  600℃氧化90 min后纤维原始截面的SEM图像:(a) CFMP低倍放大图;(b) CFMP高倍放大图;(c) M55 J低倍放大图;(d) M55 J高倍放大图

    Figure  9.  SEM images of the original section of fibers after oxidation at 600℃ for 90 min: (a) Low magnification image of CFMP; (b) High magnification image of CFMP; (c) Low magnification image of M55 J; (d) High magnification image of M55 J

    图  10  氧化前后纤维拉伸强度保留率:(a) 氧化前后的拉伸强度;(b)氧化前后的强度保留率

    Figure  10.  Tensile strength retention of fiber before and after oxidation: (a) Tensile strength before and after oxidation; (b) Strength retention rate before and after oxidation

    图  11  CFMP的氧化机制

    Figure  11.  Diagram of oxidation mechanism of CFMP

    表  1  高导热中间相沥青基碳纤维(CFMP)和聚丙烯腈基碳纤维(M55 J)的性能对比

    Table  1.   Comparison of properties of high thermal conductive mesophase-pitch-based carbon fiber (CFMP) and polyacrylonitrile-based carbon fiber (M55 J) carbon fibers

    SampleStrength/GPaModulus/GPaElongation at break/%Thermal conductivity/(W·m−1·K−1)
    CFMP2.88720.32816
    M55 J4.05400.74122
    下载: 导出CSV

    表  2  CFMP和M55 J的晶格参数表

    Table  2.   Lattice parameter table of CFMP and M55 J

    Sample/(°)d(002)/nmLc(002)/nmLa(100)/nmg/%Z/(°)
    CFMP26.370.337819.0465.1672.09 8.31
    M55 J26.070.3415 4.4814.0829.0715.57
    Notes: —Diffraction angle of the (002) peak; d(002)—Actual measured layer spacing of the carbon material (002) plane; Lc(002)—Stacking height of the messy layer structure organization; La(100)—Size of the graphene plane; g—Graphitization degree; Z—Degree of orientation of the graphite crystal parallel to the fiber axis.
    下载: 导出CSV

    表  3  CFMP和M55 J不同氧化时间后的线密度与真密度

    Table  3.   Data table of linear density and true density of CFMP and M55 J after different oxidation time

    Oxidation time/minLinear density/(g·km−1)True density/(g·cm−3)
    CFMPRatio/%M55 JRatio/%CFMPM55 J
    0272.0230.02.201.90
    10260.095.6212.092.22.191.89
    40245.390.2199.086.52.181.88
    90221.481.4181.078.72.171.86
    下载: 导出CSV
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  • 收稿日期:  2022-09-21
  • 修回日期:  2022-10-27
  • 录用日期:  2022-11-06
  • 网络出版日期:  2022-11-19
  • 刊出日期:  2023-09-15

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