PAN基高模量碳纤维成型过程中的结构性能关联性

doi:10.16085/j.issn.1000-6613.2018-1718

化工进展 ›› 2019, Vol. 38 ›› Issue (05): 2276-2283.DOI: 10.16085/j.issn.1000-6613.2018-1718

PAN基高模量碳纤维成型过程中的结构性能关联性

钱鑫(),王雪飞,郑凯杰,张永刚(),李德宏,宋书林

中国科学院宁波材料技术与工程研究所碳纤维制备技术国家工程实验室，浙江宁波 315201

收稿日期:2018-08-27 修回日期:2019-01-09 出版日期:2019-05-05 发布日期:2019-05-05
通讯作者: 张永刚
作者简介:<named-content content-type="corresp-name">钱鑫</named-content>（1984—），男，博士研究生，高级工程师，研究方向为PAN基碳纤维结构与性能。E-mail：<email>qx3023@nimte.ac.cn</email>。|张永刚，教授级高级工程师，研究方向为PAN基碳纤维制备。E-mail：<email>zhangyonggang@nimte.ac.cn</email>。
基金资助:
装备发展部领域基金重点项目(6140922010103);中科院创新基金(CXJJ-17-M160);中科院先导专项(XDA17020405)

Relationship between micro-structure and macro-properties during the formation of PAN-based high modulus carbon fibers

Xin QIAN(),Xuefei WANG,Kaijie ZHENG,Yonggang ZHANG(),Dehong LI,Shulin SONG

National Engineering Laboratory for Carbon Fiber Preparation, Ningbo Institute of Material Technology & Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China

Received:2018-08-27 Revised:2019-01-09 Online:2019-05-05 Published:2019-05-05
Contact: Yonggang ZHANG

摘要/Abstract

摘要：

以实验室自制T800级聚丙烯腈（PAN）基高强中模碳纤维为原料，经连续石墨化处理得到M50J级、M55J级高模量碳纤维，以X射线衍射（XRD）、Raman光谱为表征手段研究了高强碳纤维向高模量碳纤维转变过程中石墨微晶、取向、微孔含量、石墨化度等石墨特征结构的演变规律，并开展了PAN基碳纤维石墨特征结构与力学性能的关联性研究。研究结果表明：在高强碳纤维向高模量碳纤维转变过程中，随着石墨微晶层间距d ₀₀₂的下降以及石墨微晶堆砌厚度L _c的增加，碳纤维的拉伸模量逐渐提升；石墨微晶层间距和微晶取向是影响碳纤维拉伸强度的两个主要因素，石墨微晶层间距d ₀₀₂值增加、石墨微晶取向越高，纤维拉伸强度也越高；在高模量碳纤维的成型过程中，纤维内部微孔含量随着石墨化程度的提高而降低；经过高温石墨化处理后，碳纤维的拉伸强度会随着Raman光谱中无序结构D峰和石墨特征结构G峰积分强度比值I _D /I _G的下降而下降。

关键词: 聚丙烯腈, 高模碳纤维, 石墨结构, 层间距

Abstract:

M50J and M55J grade high modulus carbon fibers were prepared by using carbon fiber of self-made T800 grade polyacrylonitrile(PAN)-based high strength carbon fibers as raw material. In the conversion of high strength carbon fiber to high modulus carbon fiber, the evolution of graphite characteristic features such as microcrystallites, orientation, the relative content of micropore and graphitization degree were investigated by X-ray diffractometer (XRD) and Raman. The relationship between the graphite characteristic features and the mechanical properties of carbon fiber was also studied in detail. Results showed that with decreases in the value of interlayer spacing d ₀₀₂ and increases in the value of graphite thickness L _c, the tensile modulus of carbon fibers were significantly increased. It was also found that the interlayer spacing and crystallite orientation were two important parameters which could affect the tensile strength of high modulus carbon fiber. The tensile strength increased with increasing d ₀₀₂ value and improving crystallite orientation. In the conversion of high strength carbon fiber to high modulus carbon fiber, increased graphitization degree took place which led to decreases in voids or cavities. After high temperature graphitization, decreases in the tensile strength of carbon fiber were accompanied with decrease in the intensity ratio of disordered induced D-band to the graphite structure G-band.

Key words: polyacrylonitrile, high modulus carbon fiber, graphite structure, interlayer spacing

中图分类号:

TQ 342

钱鑫, 王雪飞, 郑凯杰, 张永刚, 李德宏, 宋书林. PAN基高模量碳纤维成型过程中的结构性能关联性[J]. 化工进展, 2019, 38(05): 2276-2283.

Xin QIAN, Xuefei WANG, Kaijie ZHENG, Yonggang ZHANG, Dehong LI, Shulin SONG. Relationship between micro-structure and macro-properties during the formation of PAN-based high modulus carbon fibers[J]. Chemical Industry and Engineering Progress, 2019, 38(05): 2276-2283.

图/表 13

参考文献 23

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样品	石墨化温度 /℃	牵伸倍率 /%	体密度 / g·m^-3	拉伸强度 /GPa	拉伸模量 /GPa
CF1	—	—	1.78	5.60	293
CF2	2400	3	1.84	5.07	482
CF3	2800	5	1.88	4.86	544
M55J	—	—	1.91	4.02	540

样品	石墨化温度 /℃	牵伸倍率 /%	体密度 / g·m^-3	拉伸强度 /GPa	拉伸模量 /GPa
CF1	—	—	1.78	5.60	293
CF2	2400	3	1.84	5.07	482
CF3	2800	5	1.88	4.86	544
M55J	—	—	1.91	4.02	540

样品	2θ (002)/(°)	d ₀₀₂/nm	FWHM(002) /(°)	L _c/nm
CF1	25.50	0.349	1.96	2.77
CF2	25.62	0.347	1.88	2.87
CF3	25.72	0.346	1.57	3.16
M55J	25.73	0.346	1.71	3.44

样品	2θ (002)/(°)	d ₀₀₂/nm	FWHM(002) /(°)	L _c/nm
CF1	25.50	0.349	1.96	2.77
CF2	25.62	0.347	1.88	2.87
CF3	25.72	0.346	1.57	3.16
M55J	25.73	0.346	1.71	3.44

样品	2θ (100)/(°)	FWHM(100)/(°)	L _a/nm	Z/(°)
CF3	42.70	3.32	20.03	13.41
M55J	42.67	3.13	21.21	13.82

PAN基高模量碳纤维成型过程中的结构性能关联性

Relationship between micro-structure and macro-properties during the formation of PAN-based high modulus carbon fibers

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样品	D-band		G-band		A-band和D′-band		I _D /I _G	I _A /I _G和 I _D _′/I _G
样品	峰位 /cm^-1	FWHM /cm^-1	峰位 /cm^-1	FWHM /cm^-1	峰位 /cm^-1	FWHM /cm^-1	I _D /I _G	I _A /I _G和 I _D _′/I _G
CF1	1359.84	238.39	1592.10	90.48	1509.45	86.27	3.457	0.233
CF2	1349.87	39.26	1582.06	32.49	1620.48	18.41	0.731	0.085
CF3	1349.54	36.58	1581.78	27.28	1620.72	15.36	0.513	0.061
M55J	1349.44	36.83	1581.44	27.18	1620.77	15.39	0.579	0.066

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