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应用小角X射线散射等方法, 系统、定量地测试表征了聚丙烯腈基碳纤维原丝中纳米孔的尺寸、形状、体积分数、单位体积中纳米孔绝对数量以及纤维总孔洞率等形态结构参量, 并对这些参量在水洗、水洗牵伸、热致密化、高压蒸汽牵伸及热稳定化等工艺过程中的变化规律及原因进行了研究. 结果表明, 纺丝过程中牵伸及高温热处理均可使纤维总孔洞率逐步下降. 纳米孔尺寸体积分数Vi测试表明, 对于小于10 nm3的小纳米孔和大于103 nm3的较大纳米孔, 两者的Vi在纺丝初期水洗牵伸工艺中分别为0.217和0.369, 而在纺丝后期热稳定化处理后发生大幅度改变, 分别为0.948 与0.015. 其原因并不是在高压蒸汽牵伸及热稳定处理中较小纳米孔含量的增加, 而是较大纳米孔含量的大幅度减少. 纳米孔形状研究表明, 纺丝工艺中的多次牵伸处理均使纳米孔的长短轴比加大, 而大于玻璃化温度的热处理均使纳米孔长短轴比收缩, 并且对于较小纳米孔来说这种收缩更为显著.
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关键词:
- 聚丙烯腈基碳纤维原丝 /
- 纳米孔 /
- 纳米孔绝对数量 /
- 小角X射线散射
In this paper, we quantitatively characterize the morphological structure parameters including the nanopore size, shape, volume fraction, absolute number of nanopores and total prosity of polyacrylonitrile based carbon fiber precursor. Meanwhile, the change law and reason in the process of washing, drawing in washing, heat-densification, drawing in high pressure steam and hoting-stabilization are investigated. Results show that spinning drawing and high-temperature heat treatment make the prosity of fibers decline gradually in the process of fabrication. The result of micropore volume fraction Vi shows that at the beginning of the spinning and drawing in washing process the Vi of smaller nanopore which is less than 10 nm3 and the Vi of greater nanopore which is larger than 103 nm3 are 0.217 and 0.369, respectively, while these values sharply turn to 0.948 and 0.015 after the late spinning process of hoting-stabilization. The reason for this is not the increase of content of smaller nanopore content in the drawing process in high pressure steam and hoting-stabilization, but the sharp decrease of the greater nanopore content. The result about nanopore shape shows that the spinning multiple drawing in the process increases the axial (long-axis-to-short-axis) ratio of nanopores, while heat treatment over the glass transition temperature reduces the axial ratio of nanopore, and this shrinkage is more significant for smaller nanopores.-
Keywords:
- polyacrylonitrile based carbon fiber precursor /
- nanopore /
- absolute number of nanopores /
- small angle X-ray scattering
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[2] Wilms C, Seide G, Gries T 2013 Chem. Eng. Trans. 32 1609
[3] Wang Q F 2010 Ph. D. Dissertation (Jinan: Shandong University) (in Chinese) [王启芬 2010 博士学位论文(济南: 山东大学)]
[4] Li X Y, Li X H, Yang C M, Hua W Q, Zhao N, Miao X R, Tian F, Wang Y Z, Bian F G, Wang J 2013 Chin. Phys. B 22 046102
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[6] Wang C G, Zhu B 2011 Polyacrylontrile-Based Carbon Fiber (Beijing: Science Press) pp188-220 (in Chinese) [王成国, 朱波 2011 聚丙烯腈基碳纤维 (北京: 科学出版社) 第188–220页]
[7] Wang D H, Hao J J, Xing X Q, Mo G, Gong Y, Lu C X, Wu Z H 2011 Chin. Phys. C 35 870
[8] Meng Z F 1996 Small Angle X-Ray Scattering Theory and Application (Changchun: Jilin Science and Technology Publisher) pp52-54 (in Chinese) [孟昭富 1996 小角X射线散射理论及应用 (长春: 吉林科学技术出版社) 第52–54页]
[9] Huang Z F, Wang C Z, Wei Y J, Xu Y, Gao Z M, Hua Z, Chen G 2004 Chem. J. Chin. Univ. 25 1124 (in Chinese) [黄祖飞, 王春忠, 魏英进, 徐跃, 高忠民, 华中, 陈岗 2004 高等学校化学学报 25 1124]
[10] Statton W O 1962 J. Polym. Sci. 58 205
[11] Shioya M, Takaku A 1985 J. Appl. Phys. 58 4074
[12] Takaku A, Shioya M 1986 J. Mater. Sci. 21 4443
[13] Gupta A, Harrion R, Lahijani J 1994 J. Appl. Cryst. 27 627
[14] Gupta A, Harrison I R 1996 Carbon 34 1427
[15] Li D H, Wu G P, L C X, Li Y H, He F, Feng Z H, Li X T, Guo Y M 2010 New Carbon Mater. 25 41 (in Chinese) [李登华, 吴刚平, 吕春祥, 李永红, 贺福, 冯志海, 李秀涛, 郭玉明 2010 新型炭材料 25 41]
[16] Liang Y L, Yue Q W, Qin X Y, Li Z H, Wu Z Y, L Y G, Gong Y J 2009 J. Light Scattering 21 341 (in Chinese) [梁颖琳, 岳奇伟, 秦显营, 李志宏, 吴自玉, 吕永根, 巩雁军 2009 光散射学报 21 341]
[17] Zhao X, Zhu Y B 2002 Shanxi Chem. Industy 22 65 (in Chinese) [赵秀, 朱玉斌 2002 山西化工 22 65]
[18] Mo Z S, Zhang H F, Zhang J D 2010 Struture of Crystalline Ploymers by X-Ray Diffraction (2nd Ed.) ( Beijing: Science Press) pp327-331 (in Chinese) [莫志深, 张宏放, 张吉东 2010晶态聚合物结构和X射线衍射 (第二版) (北京: 科学出版社) 第327–331页]
[19] Gao Z M 2009 Chinese Patent 101349543A (in Chinese) [高忠民 2009 中国专利 101349543A]
[20] Pakshver E A, Gerasimova L S 1975 Fiber Chem. 3 38
[21] Dong X G, Wang C G, Chen J 2008 J. Polym. Res. 15 125
[22] Chen J C, Harrison I R 2002 Carbon 40 25
[23] He F 2010 Carbon Fiber and Graphite Fiber (Beijing: Chemical Industry Press) pp100-104 (in Chinese) [贺福 2010 碳纤维及石墨纤维 (北京: 化学工业出版社) 第100–104页]
[24] Wang Q F, Wang C C 2006 Fiber Compos. 1 29 (in Chinese) [王启芬, 王成国 2006 纤维复合材料 1 29]
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[1] Frank E, Hermanutz F, Buchmeiser M 2012 Macromol. Mater. Eng. 297 493
[2] Wilms C, Seide G, Gries T 2013 Chem. Eng. Trans. 32 1609
[3] Wang Q F 2010 Ph. D. Dissertation (Jinan: Shandong University) (in Chinese) [王启芬 2010 博士学位论文(济南: 山东大学)]
[4] Li X Y, Li X H, Yang C M, Hua W Q, Zhao N, Miao X R, Tian F, Wang Y Z, Bian F G, Wang J 2013 Chin. Phys. B 22 046102
[5] Gao Y, Gao Z M, Li X S, Guo J Q, Wen Y F, Yang Y G 2009 Chem. J. Chin. Univ. 30 2100 (in Chinese) [高宇, 高忠民, 李向山, 郭建强, 温月芳, 杨永岗 2009 高等学校化学学报 30 2100]
[6] Wang C G, Zhu B 2011 Polyacrylontrile-Based Carbon Fiber (Beijing: Science Press) pp188-220 (in Chinese) [王成国, 朱波 2011 聚丙烯腈基碳纤维 (北京: 科学出版社) 第188–220页]
[7] Wang D H, Hao J J, Xing X Q, Mo G, Gong Y, Lu C X, Wu Z H 2011 Chin. Phys. C 35 870
[8] Meng Z F 1996 Small Angle X-Ray Scattering Theory and Application (Changchun: Jilin Science and Technology Publisher) pp52-54 (in Chinese) [孟昭富 1996 小角X射线散射理论及应用 (长春: 吉林科学技术出版社) 第52–54页]
[9] Huang Z F, Wang C Z, Wei Y J, Xu Y, Gao Z M, Hua Z, Chen G 2004 Chem. J. Chin. Univ. 25 1124 (in Chinese) [黄祖飞, 王春忠, 魏英进, 徐跃, 高忠民, 华中, 陈岗 2004 高等学校化学学报 25 1124]
[10] Statton W O 1962 J. Polym. Sci. 58 205
[11] Shioya M, Takaku A 1985 J. Appl. Phys. 58 4074
[12] Takaku A, Shioya M 1986 J. Mater. Sci. 21 4443
[13] Gupta A, Harrion R, Lahijani J 1994 J. Appl. Cryst. 27 627
[14] Gupta A, Harrison I R 1996 Carbon 34 1427
[15] Li D H, Wu G P, L C X, Li Y H, He F, Feng Z H, Li X T, Guo Y M 2010 New Carbon Mater. 25 41 (in Chinese) [李登华, 吴刚平, 吕春祥, 李永红, 贺福, 冯志海, 李秀涛, 郭玉明 2010 新型炭材料 25 41]
[16] Liang Y L, Yue Q W, Qin X Y, Li Z H, Wu Z Y, L Y G, Gong Y J 2009 J. Light Scattering 21 341 (in Chinese) [梁颖琳, 岳奇伟, 秦显营, 李志宏, 吴自玉, 吕永根, 巩雁军 2009 光散射学报 21 341]
[17] Zhao X, Zhu Y B 2002 Shanxi Chem. Industy 22 65 (in Chinese) [赵秀, 朱玉斌 2002 山西化工 22 65]
[18] Mo Z S, Zhang H F, Zhang J D 2010 Struture of Crystalline Ploymers by X-Ray Diffraction (2nd Ed.) ( Beijing: Science Press) pp327-331 (in Chinese) [莫志深, 张宏放, 张吉东 2010晶态聚合物结构和X射线衍射 (第二版) (北京: 科学出版社) 第327–331页]
[19] Gao Z M 2009 Chinese Patent 101349543A (in Chinese) [高忠民 2009 中国专利 101349543A]
[20] Pakshver E A, Gerasimova L S 1975 Fiber Chem. 3 38
[21] Dong X G, Wang C G, Chen J 2008 J. Polym. Res. 15 125
[22] Chen J C, Harrison I R 2002 Carbon 40 25
[23] He F 2010 Carbon Fiber and Graphite Fiber (Beijing: Chemical Industry Press) pp100-104 (in Chinese) [贺福 2010 碳纤维及石墨纤维 (北京: 化学工业出版社) 第100–104页]
[24] Wang Q F, Wang C C 2006 Fiber Compos. 1 29 (in Chinese) [王启芬, 王成国 2006 纤维复合材料 1 29]
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