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

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

王昊^{1, 3,},
王归³,
周星明⁴,
樊桢⁴,
吴晃³,
叶崇^{2, 3},
张岳峰^{2, 3},
黄东^{1, 2, 3, ,}

1.
广东省科学院新材料研究所　现代材料表面工程技术国家工程实验室，广东省现代表面工程技术重点实验室，广州 510650
2.
湖南东映碳材料科技有限公司　沥青基高性能碳材料湖南省工程研究中心，长沙 410000
3.
湖南大学　材料科学与工程学院，先进炭材料及应用技术湖南省重点实验室，长沙 410082
4.
航天材料及工艺研究所，北京 100076

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
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出版历程
- 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

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

WANG Hao^{1, 3
,},
WANG Gui³,
ZHOU Xingming⁴,
FAN Zhen⁴,
WU Huang³,
YE Chong^{2, 3},
ZHANG Yuefeng^{2, 3},
HUANG Dong^{1, 2, 3
, ,}

1.
Guangdong Provincial Key Laboratory of Modern Surface Engineering Technology, National Engineering Laboratory for Modern Materials Surface Engineering Technology, Institute of New Materials, Guangdong Academy of Sciences, Guangzhou 510650, China
2.
Hunan Province Engineering Research Center for High Performance Pitch-based Carbon Materials, Hunan Toyi Carbon Material Technology CO., LTD., Changsha 410000, China
3.
College of Materials Science and Engineering, Hunan Province Key Laboratory for Advanced Carbon Materials and Applied Technology, Hunan University, Changsha 410082, China
4.
Aerospace Research Institute of Materials and Processing Technology, Beijing 100076, China

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

摘要: 以自制高导热中间相沥青基碳纤维(CF_MP)为研究对象，采用M55J聚丙烯腈基碳纤维作为对照组，研究了CF_MP在不同氧化温度和时间下的氧化行为。结果表明：CF_MP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CF_MP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，CF_MP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，CF_MP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CF_MP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。
- 中间相沥青基碳纤维 /
- 高导热 /
- 氧化行为 /
- 微观结构 /
- C/C复合材料
Abstract: The oxidation behaviors of the homemade high thermal conductive mesophase-pitch-based carbon fiber (CF_MP) at different time and temperature were investigated using the polyacrylonitrile-based carbon fiber (M55J) as the control group. The results show that CF_MP exhibits a fold radiation structure in the outer part and onion skin structure in the inner part. The CF_MP 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 CF_MP 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 CF_MP 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 CF_MP is higher than that of M55J because there are more oxygen diffusion paths in the CF_MP. Moreover, because there are more and larger microstructural defects in CF_MP after oxidation, the strength retention rate of the CF_MP 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.
- mesophase-pitch-based carbon fibers /
- high thermal conductivity /
- oxidation behavior /
- microstructure /
- C/C composites

HTML全文

图 1 CF_MP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) CF_MP截面低倍放大图；(e) CF_MP截面高倍放大图；(f) CF_MP表面形貌

Figure 1. SEM images of CF_MP 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 CF_MP; (e) High magnification image of cross section of CF_MP; (f) Surface of CF_MP

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图 2 CF_MP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 CF_MP and M55 J: (a) Powder diffraction patterns; (b) Azimuth scan

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图 3 CF_MP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 CF_MP 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)

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图 4 CF_MP和M55 J的氧化失重曲线

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

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

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

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图 6 CF_MP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) CF_MP表面；(d) CF_MP表面高倍放大图；(e) CF_MP截面上的氧化凹坑；(f) CF_MP截面的裂纹

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

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图 7 CF_MP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 CF_MP and M55 J surface before (a) and after (b) 90 min oxidation

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图 8 CF_MP氧化不同时间后的SEM图像：(a) CF_MP氧化10 min；(b) CF_MP氧化40 min；(c) CF_MP氧化90 min；(d) CF_MP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 CF_MP oxidized for different time: (a) Oxidation of CF_MP for 10 min; (b) Oxidation of CF_MP for 40 min; (c) Oxidation of CF_MP for 90 min; (d) Oxidation of CF_MP for 240 min; (e) Oxidation of M55 J for 10 min; (f) Oxidation of M55 J for 90 min

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图 9 600℃氧化90 min后纤维原始截面的SEM图像：(a) CF_MP低倍放大图；(b) CF_MP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 CF_MP; (b) High magnification image of CF_MP; (c) Low magnification image of M55 J; (d) High magnification image of M55 J

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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

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图 11 CF_MP的氧化机制

Figure 11. Diagram of oxidation mechanism of CF_MP

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表 1 高导热中间相沥青基碳纤维(CF_MP)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 (CF_MP) and polyacrylonitrile-based carbon fiber (M55 J) carbon fibers

Sample	Strength/GPa	Modulus/GPa	Elongation at break/%	Thermal conductivity/(W·m⁻¹·K⁻¹)
CF_MP	2.8	872	0.32	816
M55 J	4.0	540	0.74	122

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表 2 CF_MP和M55 J的晶格参数表

Table 2. Lattice parameter table of CF_MP and M55 J

Sample	2θ/(°)	d(002)/nm	L_c(002)/nm	L_a(100)/nm	g/%	Z/(°)
CF_MP	26.37	0.3378	19.04	65.16	72.09	8.31
M55 J	26.07	0.3415	4.48	14.08	29.07	15.57
Notes: 2θ—Diffraction angle of the (002) peak; d(002)—Actual measured layer spacing of the carbon material (002) plane; L_c(002)—Stacking height of the messy layer structure organization; L_a(100)—Size of the graphene plane; g—Graphitization degree; Z—Degree of orientation of the graphite crystal parallel to the fiber axis.

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表 3 CF_MP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 CF_MP and M55 J after different oxidation time

Oxidation time/min	Linear density/(g·km⁻¹)				True density/(g·cm⁻³)
Oxidation time/min	CF_MP	Ratio/%	M55 J	Ratio/%	CF_MP	M55 J
0	272.0	—	230.0	—	2.20	1.90
10	260.0	95.6	212.0	92.2	2.19	1.89
40	245.3	90.2	199.0	86.5	2.18	1.88
90	221.4	81.4	181.0	78.7	2.17	1.86

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