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2222材料工程  2021, Vol. 49 Issue (4): 120-127    DOI: 10.11868/j.issn.1001-4381.2020.000632
  研究论文 本期目录 | 过刊浏览 | 高级检索 |
低温炭化温度梯度对聚丙烯腈预氧纤维结构演变及碳纤维性能的影响
何沐, 王宇(), 徐樑华
北京化工大学 国家碳纤维工程技术研究中心碳纤维及功能高分子教育部重点实验室, 北京 100029
Effect of low-temperature carbonization temperature gradient on structural evolution of PAN stabilized fiber and properties of carbon fiber
Mu HE, Yu WANG(), Liang-hua XU
Cabon Fiber and Functional Polymer Key Laboratory(Ministry of Education), National Carbon Fiber Engineering Technology Research Center, Beijing University of Chemical Technology, Beijing 100029, China
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摘要 

聚丙烯腈(PAN)预氧纤维在低温炭化阶段经热裂解重组而转化为具有乱层石墨结构雏形的低温炭化纤维,此阶段的温度调控对最终碳纤维的结构与性能有着重要影响。采用13C固体核磁共振谱图(13C-NMR)、拉曼光谱(Raman)、X射线衍射(XRD)和力学性能分析等手段,研究预氧纤维在低温炭化阶段的反应进程、温度梯度调控对预氧纤维的结构演变和碳纤维结构及性能的影响。结果表明:PAN预氧纤维在低温炭化过程中,经450℃热处理后碳结构的支链化程度达到最大值0.99,当处理温度达到550℃后,以芳环链段的重组交联为主要反应。低温炭化温度梯度影响预氧纤维的结构演变进程,当采用350—450—650℃的梯度升温模式时,先经450℃处理的低碳纤维中—C=C基团的13C-NMR位移最大,表明纤维内的支化交联反应最多,再经650℃处理的纤维d002以及相应高碳纤维的IA/IG达到最大,说明其无定形碳相对含量最多,因而最终碳纤维的力学性能最差;当采用350—550—650℃的梯度升温模式时,纤维内裂解与重组交联反应有序开展,低碳和高碳纤维的碳结构更优,最终碳纤维的致密性及力学性能得到提升。

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何沐
王宇
徐樑华
关键词 PAN预氧纤维低温炭化温度梯度无定形碳结构演变    
Abstract

In low-temperature carbonization stage, stabilized polyacrylonitrile (PAN) fibers are pyrolyzed and recombined to transform into low-temperature carbonized fiber with rudiment of turbostratic graphite structure. The temperature regulation of low-temperature carbonization has an important influence on the structure and performance of the final carbon fibers. The reaction process of stabilized fiber during low-temperature carbonization stage, the effect of the regulation of low-temperature carbonization temperature gradient on the structural evolution of stabilized fiber and the structure and performance of carbon fiber were studied through 13C-NMR, Raman, XRD and mechanical property analysis. The results indicate that: in the process of low-temperature carbonization heat treatment of stabilized fiber, the carbon structure shows the degree of branched chain reaches a maximum of 0.99, after heat treatment at 450 ℃. When the heat treatment temperature reaches 550 ℃, the main reaction is the recombination crosslinking reaction of stabilized fiber's aromatic chain segments. The low-temperature carbonization temperature gradients affect the structural evolution of stabilized fibers. When the temperature gradient is 350-450-650 ℃, the 13C-NMR shift of the —C C group in the low carbon fiber treated at 450 ℃ is the largest, the branching crosslinking reactions in fiber are the most, causing the d002 of the low carbon fiber treated at 650 ℃ and the IA/IG of the corresponding high-temperature carbon fiber are the largest, the relative content of amorphous carbon is the largest and the mechanical properties of the final carbon fiber are the worst. However, when the temperature gradient is 350-550-650 ℃, the cracking and recombination crosslinking reaction in fiber are carried out in an orderly manner, resulting in the structure of low-temperature carbonized fiber and carbon fiber more perfect, and the density and mechanical properties of carbon fiber are improved.

Key wordsPAN stabilized fiber    low-temperature carbonization    temperature gradient    amorphous carbon    structural evolution
收稿日期: 2020-07-14      出版日期: 2021-04-21
中图分类号:  TQ342  
基金资助:中央高校基本业务费项目(JD2012)
通讯作者: 王宇     E-mail: wangy@mail.buct.edu.cn
作者简介: 王宇(1981-), 女, 讲师, 研究方向为高性能碳纤维, 联系地址: 北京市朝阳区北三环东路15号北京化工大学34信箱(100029), E-mail: wangy@mail.buct.edu.cn
引用本文:   
何沐, 王宇, 徐樑华. 低温炭化温度梯度对聚丙烯腈预氧纤维结构演变及碳纤维性能的影响[J]. 材料工程, 2021, 49(4): 120-127.
Mu HE, Yu WANG, Liang-hua XU. Effect of low-temperature carbonization temperature gradient on structural evolution of PAN stabilized fiber and properties of carbon fiber. Journal of Materials Engineering, 2021, 49(4): 120-127.
链接本文:  
http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2020.000632      或      http://jme.biam.ac.cn/CN/Y2021/V49/I4/120
Sample No Low temperature carbonization
TNo.1/℃ TNo.2/℃ TNo.3/℃
SF
1# 350 350
2# 350 400
3# 350 450
4# 350 500
5# 350 550
6# 350 600
7# 350 650
8# 350 700
MF-1# 350 400 650
MF-2# 350 450 650
MF-3# 350 500 650
MF-4# 350 550 650
MF-5# 350 600 650
Table 1  低温炭化阶段工艺参数
Fig.1  预氧纤维和1#~8#低碳纤维的核磁谱图
Sample No Relative content of functional groups/%
—CH3 —CH/—CH2 —CCH —C≡N —C=C —CN —CO
SF 39.72 7.98 20.38 9.80 18.42 3.70
1# 1.32 19.08 26.11 6.01 17.86 24.54 5.08
2# 2.01 10.94 31.91 2.94 23.59 26.62 1.99
3# 3.64 3.68 36.80 0.64 26.82 27.59 0.83
4# 2.04 3.01 34.35 31.00 29.60
5# 33.95 32.79 33.26
6# 23.60 43.92 32.48
7# 18.63 49.47 31.90
8# 18.80 55.27 25.93
Table 2  预氧纤维和1#~8#低碳纤维核磁解析结果
Fig.2  —CH/—CH2的结构演变示意图
(a)形成支链甲基;(b)环结构的交联反应
Fig.3  不同热处理温度低碳纤维的支链化程度
Fig.4  不同热处理温度低碳纤维的R—CC/—CCH
Fig.5  不同温度梯度处理后低碳纤维的13C-NMR分析
(a)13C-NMR谱图;(b)—CC基团的13C-NMR化学位移
Fig.6  低碳纤维的Raman谱图(a)MF-1#;(b)MF-2#; (c)MF-3#; (d)MF-4#; (e)MF-5#
Fig.7  不同温度梯度处理后低碳纤维的IA/IG
Fig.8  不同温度梯度处理后低碳纤维的XRD谱图(a),d002Lc的变化趋势(b)
Fig.9  不同温度梯度处理所得碳纤维的Raman谱图(a)和IA/IG(b)
Low-temperature carbonized fiber Carbon fiber
Sample No IA/IG Sample No ρV/(g·cm-3) ρL/(g·m-1) σ/MPa E/GPa
MF-1# 0.62 CF1 1.762 0.171 3820 236
MF-2# 1.35 CF2 1.754 0.172 3540 224
MF-3# 0.53 CF3 1.760 0.169 4150 238
MF-4# 0.32 CF4 1.769 0.169 4400 240
MF-5# 0.94 CF5 1.764 0.166 3660 233
Table 3  低碳纤维结构及碳纤维性能
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