全谱拟合法研究聚丙烯腈基碳纤维形成过程中晶态结构演变

张彩红; 盛毅; 田红; 徐耀; 吕春祥; 吴忠华

doi:10.7498/aps.60.036101

摘要

通过全谱拟合法对碳纤维制备过程中不同阶段纤维的XRD谱图进行处理,得到不同阶段纤维的微观结构参数,研究了聚丙烯腈(PAN)基碳纤维制备过程中晶态结构的演变.全谱拟合法基于晶体衍射的严格物理理论,拟合目标为整个衍射谱,并不是个别衍射峰,所得结果具有更高的可信度.研究结果表明:PAN原丝中的高分子链沿纤维轴高度取向,表观晶粒尺寸为6.5 nm左右;经过预氧化处理,纤维中的有序结构遭到破坏,表观晶粒尺寸锐减.纤维中逐渐形成梯形结构并沿纤维轴取向,从而形成新的有序结构;经过碳化处理后,环状梯形结构转变为碳的层状结

关键词:

碳纤维 /
晶体结构 /
XRD /
全谱拟合法

Abstract

Based on the Rietveld theory and Maud software, the evolution of crystalline structure of PAN-based carbon fibers was studied by investigating the different stages in the preparation of carbon fibers. The microstructure parameters of PAN fibers, oxidative fibers, and carbon fibers, including cell parameters, apparent crystal grain sizes, textural structure and micro-strain, were obtained from the named whole powder pattern fitting method for XRD result. Based on rigorus theory of crystallography, the whole powder pattern fitting treats the whole XRD powder diffraction pattern rather than individual diffraction peaks, resulting in higher credibility and precision. The results indicated that polymer chains were arranged along the axis of PAN fiber and the apparent crystallite size was about 6.4 nm. After pre-oxidation, the originally ordered structure in PAN fiber was damaged and new less-ordered cyclic ladder structure was formed in the pre-oxidized PAN fibers, while the apparent crystallite size of fiber decreased obviously. With the carbonization process, the cyclic ladder structure of per-oxidized fibers transferred into layer structure similar to that of graphite. The layers were oriented along the axis of carbonized fiber that contributed to the X-ray diffraction, which comprised the apparent crystallite grains. As the carbonization temperature increased, size of the layer structure in the direction perpendicular to fiber axis increased clearly, the preferential orientation was enhanced and the layer structure became much more ordered.

Keywords:

作者及机构信息

(1)中国科学院高能物理所同步辐射实验室,北京 100049; (2)中国科学院山西煤炭化学研究所,中国科学院炭材料重点实验室,太原 030001

基金项目: 国家自然科学基金(批准号:10835008)资助的课题.

Authors and contacts

(1)Key Laboratory of carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China; (2)Laboratory of Synchrotron Radiation, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

参考文献

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[25]	Zhang L Z, Lü C X, Lü Y G, Wu G P, He F 2005 New Carbon Materials 20 144 (in Chinese) [张利珍、吕春祥、吕永根、吴刚平、贺福 2005 新型炭材料 20 144]
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[28]	Perret R, Ruland W 1970 J. Appl. Cryst. 3 525
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施引文献

[1]	He F 2004 Carbon fibers and applied technology (Beijing:Chemical Industry Press) (in Chinese) [贺福 2004 碳纤维及其应用技术(北京:化学工业出版社)]
[2]	Dalton S, Heatley F, Budd P M 1999 Polymer 40 5531
[3]	Wang P H, Liu J, Yue Z R, Li R Y 1992 Carbon 30 113
[4]	Bohn C R, Schaefgen J R, Sratton W O 1961 J. Polym. Sci. 55 531
[5]	Ko T H, Lin C H 1989 J. Appl. Polym. Sci. 37 553
[6]	Lü C X, Wu G P, Lü Y G, Li K X, Li Y H, Liang X Y, He F, Ling L C 2003 New Carbon Materials 18 186 (in Chinese) [吕春祥、吴刚平、吕永根、李开喜、李永红、梁晓怿、贺福、凌立成 2003 新型炭材料 18 186]
[7]	Johnson D J 1980 Phil. Trans. R. Soc. Lond. A 294 443
[8]	Zickler G A, Smarsly B, Gierlinger N, Herwig P, Oskar P 2006 Carbon 44 3239
[9]	Perret R, Ruland W 1970 J. Appl. Cryst. 3 525
[10]	Yang Y, Hou J G, Yu W H 1990 Acta Phys. Sin. 39 561 (in Chinese) [杨原、侯建国、俞文海 1990 物理学报 39 561]
[11]	Wu X M, Wu Q C, Sui Y F 1992 Acta Phys. Sin. 41 1132 (in Chinese) [吴雪梅、邬钦崇、隋毅峰 1992 物理学报 41 1132 ]
[12]	Chen Z J, Wang W, Cai Q, Chen X, Wu Z H, Li R P, Che C Q, Pan W 2008 Acta Phys. Sin. 57 5793 (in Chinese) [陈中军、王维、蔡泉、陈兴、吴忠华、李蓉萍、车传强、潘伟 2008 物理学报 57 5793]
[13]	Dieter L, Oskar P, Rennhofer H, Martin M, Herwig P 2007 Carbon 45 2801
[14]	Oskar P, Dieter L, Herwig P 2002 Carbon 40 551
[15]	Oskar P, Dieter L, Martin M, Lichtenegger H, Peterlik H 2001 J. Appl. Cryst. 34 473
[16]	Li D F, Wang H J, Xue L B, Wang X K 2006 Chemical Industry and Engineering Progress 25 1101 (in Chinese) [李东风、王浩静、薛林兵、王心葵 2006 化工进展 25 1101]
[17]	Chen J, Wang C g, Ding H Y, Ge G Y, Cai X J 2006 Science & Technology in Chenmical Industry 14 9 (in Chinese) [陈娟、王成国、丁海燕、葛曷一、蔡相军 2006 化工科技 14 9]
[18]	Li XS, Wang W Y, Fan X P, Zhu Y X 1995 Carbon Technicals 2 11(in Chinese) [李向山、王文宇、樊希平、朱永萱 1995 炭素技术 2 11]
[19]	Li X S, Hua Z, Wang W Y, Zhang R L 1997 New Carbon Materials 12 1 (in Chinese) [李向山、华中、王文宇、张瑞林 1997 新型碳材料 12 1]
[20]	Ma L D 1996 Progress in Physics 16 251 (in Chinese) [马礼敦 1996 物理学进展 16 251]
[21]	Ma L D 2004 Modern polycrystalline X-ray diffraction-Experim-ental technology and data analysis (Beijing:Chemical Industry Press) (in Chinese) [马礼敦 2004 近代X射线多晶体衍射-实验技术与数据分析(北京:化学工业出版社)]
[22]	Warren B E, Bodenstein P 1965 Acta Cryst. 18 282
[23]	Klug H P, Alexander L E 1986 X-Ray diffraction procedures for polycrystalline and amorphous materials (Beijing:Metallurgical Industry Press) p442 (in Chinese) [克鲁格H P、亚历山大L E著、盛世雄译 1986 X射线衍射技术(多晶体和非晶质材料)(北京:冶金工业出版社)第442页]
[24]	Ko T H, Phaichit C, Ting H Y, Lin C H 1989 J. Appl. Polym. Sci. 37 541
[25]	Zhang L Z, Lü C X, Lü Y G, Wu G P, He F 2005 New Carbon Materials 20 144 (in Chinese) [张利珍、吕春祥、吕永根、吴刚平、贺福 2005 新型炭材料 20 144]
[26]	Qiu L, Hu Y H 1999 (Metallurgical Industry Press) (in Chinese) [丘利、胡玉和 1999 (冶金工业出版社)]
[27]	Li D F, Wang HJ, He F, Wang X K 2007 New Carbon Materials 22 59 (in Chinese) [李东风、王浩静、贺福、王心葵 2007 新型炭材料 22 59]
[28]	Perret R, Ruland W 1970 J. Appl. Cryst. 3 525
[29]	Ji M X, Wang C G 2005 Materials Review 21 111 (in Chinese) [季敏霞、王成国 2005 材料导报 21 111]

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