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

高导热中间相沥青基碳纤维的氧化行为

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 10076

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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- 文章访问数: 170
- HTML全文浏览量: 85
- 被引次数: 0
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: 2022-11-24

Oxidation Behavior of High Thermal Conductivity Mesophase Pitch-Based Carbon Fibers

Hao WANG^{1, 3},
Gui WANG³,
Xingming ZHOU⁴,
Zhen FAN⁴,
Huang WU³,
Chong YE^{2, 3},
Yuefeng ZHANG^{2, 3},
Dong HUANG^{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 (No. U21 B2067，52202037); Special Fund for Innovative Construction Province of Hunan (No. 2020 GK4029); Natural Science Foundation of Hunan Province China (No. 2021 JJ40144, 2021 JJ40145); Hunan Province Scientific and Technological Talents Support Project (2022 TJ-N11); Guangdong Provincial Key Laboratory of Modern Surface Engineering Technology (No. 2020 B1212060049); Changsha Municipal Science and Technology Project (No. KQ2102005); Ten Key Technical Projects of Hunan Province (2021 GK1140)

摘要

摘要: 高导热C/C复合材料由中间相沥青基碳纤维(CF_MP)和具有良好导热性能的炭基体构成，在兼顾轻质高强、耐高温、抗热震、耐辐照等性能特点的同时，还具有高导热和高化学惰性的特性，是一种极具前景的极端环境热管理材料。高导热C/C复合材料在高温有氧环境下使役时，氧气会扩散至纤维/炭基体界面处和CF_MP发生氧化反应，纤维氧化损伤的程度直接影响了复合材料力学性能和承载能力的衰减程度，但纤维的氧化行为尚不清晰。本文以自制高导热CF_MP为研究对象，采用M55J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。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%。1CF_MP的氧化机制图，M55J为对照组
- 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 weight loss rate is relative lower. In the high temperature oxidation stage, the oxidation behaviors of the fibers are controlled by oxygen diffusion. The oxidation weight 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：(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衍射图：(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 pattern; (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 D in Fig.1(d); (b) Cross section of core, point B in Fig.1(a) and point E 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图 (a) 与DTG图 (b)

Figure 5. TG (a) and DTG (b) diagrams 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：(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) 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：(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 times: (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：(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的氧化机制图

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)两种碳纤维的性能对比图

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)
TYG-3	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	Lc(002)/nm	La(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 is the diffraction angle of the (002) peak; d(002) is the actual measured layer spacing of the carbon material (002) plane; Lc(002) is the stacking height of the messy layer structure organization; La(100) is the size of the graphene plane; g is the graphitization degree; Z is the 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 times

Oxidation time/min	Linear density/(g·km⁻¹)				True density/(g·cm⁻³)
Oxidation time/min	CF_MP	Ratios	M55 J	Ratios	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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[1]	SHI L, SESSIM M, TONKS M R, et al. High-temperature oxidation of carbon fiber and char by molecular dynamics simulation[J]. Carbon,2021,185:449-463. doi: 10.1016/j.carbon.2021.09.038
[2]	FUKUNAGA A, UEDA S, NAGUMO M. Air-oxidation and anodization of pitch-based carbon fibers[J]. Carbon,1999,37(7):1081-1085. doi: 10.1016/S0008-6223(98)00307-8
[3]	SESSIM M, SHI L Y, PHILLPOT S R, et al. Phase-field modeling of carbon fiber oxidation coupled with heat conduction[J]. Computational Materials Science,2022,204:1-17.
[4]	李贺军, 史小红, 沈庆凉, 等. 国内C/C复合材料研究进展[J]. 中国有色金属学报, 2019, 29(9):2142-2154. doi: 10.19476/j.ysxb.1004.0609.2019.09.15 LI Hejun, SHI Xiaohong, SHEN Qingliang, et al. Research and development of C/C composites in China[J]. The Chinese Journal of Nonferrous Metals,2019,29(9):2142-2154(in Chinese). doi: 10.19476/j.ysxb.1004.0609.2019.09.15
[5]	HUANG D, LIU Q L, ZHANG Y F, et al. Ablation behavior and thermal conduction mechanism of 3 D ZrC–SiC-modified carbon/carbon composite having high thermal conductivity using mesophase-pitch-based carbon fibers and pyrocarbon as heat transfer channels[J]. Composites Part B,2021,224:1-14.
[6]	HUANG D, TAN R X, LIU L, et al. Preparation and properties of the three-dimensional highly thermal conductive carbon/carbon-silicon carbide composite using the mesophase-pitch-based carbon fibers and pyrocarbon as thermal diffusion channels[J]. Journal of the European Ceramic Society,2021,41(8):4438-4446. doi: 10.1016/j.jeurceramsoc.2021.03.011
[7]	ZHANG X, LI X, YUAN G, et al. Large diameter pitch-based graphite fiber reinforced unidirectional carbon/carbon composites with high thermal conductivity densified by chemical vapor infiltration[J]. Carbon,2017,114(Complete):59-69.
[8]	LI T Q, XU Z H, HU Z J, et al. Application of a high thermal conductivity C/C composite in a heat-redistribution thermal protection system - ScienceDirect[J]. Carbon,2010,48(3):924-925. doi: 10.1016/j.carbon.2009.10.043
[9]	刘宇峰, 李同起, 冯志海, 等. 薄层化碳布缝合碳/碳复合材料制备与性能[J]. 复合材料学报, 2021, 38(4):1210-1222. doi: 10.13801/j.cnki.fhclxb.20200713.005 LIU Yufeng, LI Tongqi, FENG Zhihai, et al. Preparation and properties of spreading carbon cloth stitched C/C composites[J]. Acta Mater. Compositae Sin.,2021,38(4):1210-1222(in Chinese). doi: 10.13801/j.cnki.fhclxb.20200713.005
[10]	YE C, HUANG D, LI B L, et al. Ablation Behavior of the SiC-Coated Three-Dimensional Highly Thermal Conductive Mesophase-Pitch-Based Carbon-Fiber-Reinforced Carbon Matrix Composite under Plasma Flame[J]. Materials,2019,12(17):1-15.
[11]	ZHUANG L, FU Q G, MA W H, et al. Oxidation protection of C/C composites: Coating development with thermally stabile SiC@PyC nanowires and an interlocking TaB2-SiC structure[J]. Corrosion Science,2019,148:307-316. doi: 10.1016/j.corsci.2018.12.024
[12]	王玲玲, 肖春, 王坤杰, 等. 不同制备方法下(C/C)/ZrB₂-SiC复合材料的抗烧蚀性能[J]. 复合材料学报, 2019, 36(12):2878-2886. WANG Lingling, XIAO Chun, WANG Kunjie, et al. Ablation performance of (C/C)/ZrB₂-SiC composites by different fabrication methods[J]. Acta Mater. Compositae Sin.,2019,36(12):2878-2886(in Chinese).
[13]	王玲玲, 闫联生, 郭春园, 等. 不同ZrC含量的(C/C)/SiC-ZrC复合材料的抗烧蚀性能[J]. 复合材料学报, 2020, 37(9):2250-2257. doi: 10.13801/j.cnki.fhclxb.20200110.003 WANG Lingling, YAN Liansheng, GUO Chunyuan, et al. Anti-ablative property of (C/C)/SiC-ZrC composites with different ZrC content[J]. Acta Mater. Compositae Sin.,2020,37(9):2250-2257(in Chinese). doi: 10.13801/j.cnki.fhclxb.20200110.003
[14]	李昭锐, 张东, 徐樑华, 等. 碳纤维形貌结构对其电化学氧化行为及其复合材料界面性能的影响[J]. 复合材料学报, 2015, 32(4):1218-1224. doi: 10.13801/j.cnki.fhclxb.20141204.002 LI Zhaorui, ZHANG Dong, XU Lianghua, et al. Influence of carbon fiber morphology structure on electrochemical oxidation behaviors and interfacial properties of its composites[J]. Acta Mater. Compositae Sin.,2015,32(4):1218-1224(in Chinese). doi: 10.13801/j.cnki.fhclxb.20141204.002
[15]	徐翊桄, 靳玉伟, 张海龙, 等. 碳纤维热氧化行为及其机理[J]. 合成纤维工业, 2010(6):5-7. doi: 10.3969/j.issn.1001-0041.2010.06.002 XU Yiguang, JIN Yuwei, ZHANG Hailong, et al. Thermal oxidation behavior and mechanism of carbon fiber[J]. China Synthetic Fiber Industry,2010(6):5-7(in Chinese). doi: 10.3969/j.issn.1001-0041.2010.06.002
[16]	TJC A, RRU B, GO C, et al. Nanoscale oxidation behavior of carbon fibers revealed with in situ gas cell STEM[J]. Scripta Materialia,2021,199:1-6.
[17]	SerfSERF P, FIGUEIREDO J L. An investigation of vapor-grown carbon fiber behavior towards air oxidation[J]. Carbon,1997,35(5):675-683. doi: 10.1016/S0008-6223(97)00023-7
[18]	MERINO C, BRANDL W. Oxidation behaviour and microstructure of vapour grown carbon fibres[J]. Solid State Sciences,2003,5(4):663-668. doi: 10.1016/S1293-2558(03)00039-6
[19]	MANOCHA L M, WARRIER A, MANOCHA S, et al. Oxidation behaviour of ribbon shape carbon fibers and their composites[J]. Materials Science and Engineering B,2006,132(1/2):121-125.
[20]	DHAMI T L, MANOCHA L M, BAHL O P. Oxidation behaviour of pitch based carbon fibers[J]. Carbon,1991,29(1):51-60. doi: 10.1016/0008-6223(91)90094-Y
[21]	NAKAMURA K, TANABE Y, FUKUSHIMA M, et al. Analysis of surface oxidation behavior at 500℃ under dry air of glass-like carbon heat-treated from 1200 to 3000℃[J]. Materials Science and Engineering B,2009,161(1-3):40-45. doi: 10.1016/j.mseb.2008.11.012
[22]	GUO W M, XIAO H N, ZHANG G J. Kinetics and mechanisms of non-isothermal oxidation of graphite in air[J]. Corrosion Science,2008,50(7):2007-2011. doi: 10.1016/j.corsci.2008.04.017
[23]	NAITO K, TANAKA Y, YANG J. M, et al. Tensile Properties of Ultrahigh Strength PAN-Based, Ultrahigh Modulus Pitch-Based and High Ductility Pitch-Based Carbon Fibers[J]. Carbon,2008,46(2):189-195. doi: 10.1016/j.carbon.2007.11.001
[24]	YE C, WU H, ZHU S P, et al. Microstructure of high thermal conductivity mesophase pitch-based carbon fibers[J]. New Carbon Materials,2021,36(5):980-986. doi: 10.1016/S1872-5805(21)60050-1
[25]	EMMERICH F G. Young’s modulus, thermal conductivity, electrical resistivity and coefficient of thermal expansion of mesophase pitch-based carbon fibers[J]. Carbon,2014,79:274-293. doi: 10.1016/j.carbon.2014.07.068
[26]	YUAN G M, LI X K, DONG Z J, et al. The structure and properties of ribbon-shaped carbon fibers with high orientation[J]. Carbon,2014,68:426-439. doi: 10.1016/j.carbon.2013.11.019
[27]	马兆昆, 宁淑丽, 宋怀河. 高导热炭纤维的研究进展[J]. 北京化工大学学报:自然科学版, 2014(1):1-13. MA Zhaokun, NING Shuli, SONG Huaihe. Recent progress in the study of carbon fibers with high thermal conductivity[J]. Journal of Beijing University of Chemical Technology (Natural Science),2014(1):1-13(in Chinese).
[28]	MOCHIDA I, YOON S. H, TAKANO N, et al. Microstructure of mesophase pitch-based carbon fiber and its control[J]. Carbon,1996,34(8):941-956. doi: 10.1016/0008-6223(95)00172-7
[29]	WU H, HUANG D, YE C, et al. Engineering microstructure toward split-free mesophase pitch-based carbon fibers[J]. Journal of Materials Science,2022,57(4):2411-2423. doi: 10.1007/s10853-021-06770-9
[30]	HUANG D, LIU Q L, ZHANG P, et al. Thermal response of the two-directional high-thermal-conductive carbon fiber reinforced aluminum composites with low interface damage by a vacuum hot pressure diffusion method[J]. Journal of Alloys and Compounds,2022,905:1-11.
[31]	中华人民共和国国家质量监督检验检疫总局;中国国家标准化管理委员会. 碳纤维单丝拉伸性能的测定: GB/T 31290-2014[S]. 北京: 中国标准出版社, 2014. General Administration of Quality Supervision Inspection and Quarantine of the People's Republic of China; Standardization Administration of the People’s Republic of China. Carbon fibre-Determination of the tensile properties of single-filament specimens: GB/T 31290-2014[S]. Beijing: China Standards Press, 2014(Chinese).