Abstract
A series of polyimide (PI) fibers synthesized from pyromellitic dianhydride (PMDA), 4,4′-oxydianiline (ODA), and p-phenylenediamine (p-PDA) were prepared by a two-step wet-spinning process. The prepared PI fibers were then carbonized with the increasing temperatures up to 1500 °C under a high-purity nitrogen atmosphere. The effects of ODA/p-PDA molar ratios on the chemical structure, microstructure, chain orientation, and structural evolutions of the PI fibers were systematically investigated. The elemental composition, morphology, and aggregation structure after carbonization were also analyzed. The results showed that different chemical compositions have greatly influenced the aggregation structures of the resulting PI and carbon fibers. The PI fibers showed increased crystallinity and orientation degree with the decreased ODA moieties, while the corresponding PI-based carbon fibers (CFs) exhibited perfect graphitic structures. The CFs derived from PMDA/p-PDA PI backbone with flat chains exhibited a well-defined graphite structure with d 002 of 0.349 nm and I D/I G of 1.442. In addition, the carbon yield of the prepared PI-based carbon fibers reached more than 95 %.
Similar content being viewed by others
References
Kobets LP, Deev IS (1998) Carbon fibres: structure and mechanical properties. Compos Sci Technol 57(12):1571–1580. doi:10.1016/s0266-3538(97)00088-2
Fitzer E (1987) The future of carbon-carbon composites. Carbon 25(2):163–190
Jing M, Wang CG, Wang Q, Bai YJ, Zhu B (2007) Chemical structure evolution and mechanism during pre-carbonization of PAN-based stabilized fiber in the temperature range of 350–600°C. Polym Degrad Stab 92(9):1737–1742. doi:10.1016/j.polymdegradstab.2007.05.020
Inagaki M, Ohta N, Hishiyama Y (2013) Aromatic polyimides as carbon precursors. Carbon 61:1–21. doi:10.1016/j.carbon.2013.05.035
Newell JA, Rogers DK, Edie DD, Fain CC (1994) Direct carbonization of PBO fiber. Carbon 32(4):651–658. doi:10.1016/0008-6223(94)90086-8
Vázquez-Santos MB, Geissler E, László K, Rouzaud J-N, Martínez-Alonso A, Tascón JMD (2012) Comparative XRD, Raman, and TEM study on graphitization of PBO-derived carbon fibers. J Phys Chem C 116(1):257–268. doi:10.1021/jp2084499
Huang SB, Jiang ZY, Ma XY, Qiu XP, Men YF, Gao LX, Ding MX (2013) Properties, morphology and structure of BPDA/PPD/ODA polyimide fibres. Plast, Rubber Compos 42(10):407–415. doi:10.1179/1743289811y.0000000053
Dong J, Yin CQ, Zhang ZX, Wang XY, Li HB, Zhang QH (2014) Hydrogen-bonding interactions and molecular packing in polyimide fibers containing benzimidazole units. Macromol Mater Eng 299(10):1170–1179. doi:10.1002/mame.201400081
Inagaki M, Meng LJ, Ibuki T, Sakai M, Hishiyama Y (1991) Carbonization and graphitization of polyimide film “Novax”. Carbon 29(8):1239–1243. doi:10.1016/0008-6223(91)90042-h
Inagaki M, Hishiyama Y, Kaburagi Y (1994) Effect of heating rate during carbonization on graphitization of carbon films derived from aromatic polyimides. Carbon 32(4):637–639. doi:10.1016/0008-6223(94)90083-3
Inagaki M, Ibuki T, Takeichi T (1992) Carbonization behavior of polyimide films with various chemical structures. Fibre Chem 44(3):521–525. doi:10.1002/app.1992.070440316
Inagaki M, Harada S, Sato T, Nakajima T, Horino Y, Morita K (1989) Carbonization of polyimide film “Kapton”. Carbon 27(2):253–257
Isono Y, Yoshida A, Hishiyama Y, Kaburagi Y (2004) Carbonization and graphitization of shavings filed away from Kapton. Carbon 42(8–9):1799–1805. doi:10.1016/j.carbon.2004.03.012
Inagaki M, Tachikawa H, Nakahashi T, Konno H, Hishiyama Y (1998) The chemical bonding state of nitrogen in kapton-derived carbon film and its effect on the graphitization process. Carbon 36(7–8):1021–1025. doi:10.1016/s0008-6223(97)00236-4
Sazanov YN, Gribanov AV, Lysenko VA (2009) The role of nitrogen atoms in forming the carbon structure in the carbonization of polymer composites. Fibre Chem 40(4):355–364. doi:10.1007/s10692-009-9067-4
Smirnova VE, Gofman IV, Maritcheva TA, Yudin VE, Eto K, Takeichi T, Kaburagi Y, Hishiyama Y (2007) The effect of different orientations in rigid rod polyimide films on the graphitized products. Carbon 45(4):839–846. doi:10.1016/j.carbon.2006.11.012
Takeichi T, Endo Y, Kaburagi Y, Hishiyama Y, Inagaki M (1996) Carbonization and graphitization of polyimide films: polyamide acid methyl ester of PMDA/PDA as a precursor. J Appl Polym Sci 61(9):1571–1578
Takeichi T, Eguchi Y, Kaburagi Y, Hishiyama Y, Inagaki M (1998) Carbonization and graphitization of Kapton-type polyimide films prepared from polyamide alkyl ester. Carbon 36(1–2):117–122. doi:10.1016/s0008-6223(97)00155-3
Takeichi T, Endo Y, Kaburagi Y, Hishiyama Y, Inagaki M (1998) Carbonization and graphitization of polyimide films: effect of size of leaving group at imidization. Appl Polym Sci 68(10):1613–1620
Takeichi T, Eguchi Y, Kaburagi Y, Hishiyama Y, Inagaki M (1999) Carbonization and graphitization of BPDA/PDA polyimide films: effect of structure of polyimide precursor. Carbon 37(4):569–575
Takeichi T, Zuo M, Hasegawa M (2001) Role of the in-plane orientation of polyimide films in graphitization. J Polym Sci 39(23):3011–3019. doi:10.1002/polb.10050
Yang KS, Edie DD, Lim DY, Kim YM, Choi YO (2003) Preparation of carbon fiber web from electrostatic spinning of PMDA-ODA poly(amic acid) solution. Carbon 41(11):2039–2046. doi:10.1016/s0008-6223(03)00174-x
Chung GS, Jo SM, Kim BC (2005) Properties of carbon nanofibers prepared from electrospun polyimide. J Appl Polym Sci 97(1):165–170. doi:10.1002/app.21742
Niu HQ, Huang MJ, Qi SL, Han EL, Tian GF, Wang XD, Wu DZ (2013) High-performance copolyimide fibers containing quinazolinone moiety: preparation, structure and properties. Polymer 54(6):1700–1708. doi:10.1016/j.polymer.2013.01.047
Zhang MY, Niu HQ, Lin ZW, Qi SL, Chang JJ, Ge QY, Wu DZ (2015) Preparation of high performance copolyimide fibers via increasing draw ratios. Macromol Mater Eng 300(11):1096–1107. doi:10.1002/mame.201500126
Chang JJ, Niu HQ, He M, Sun M, Wu DZ (2015) Structure-property relationship of polyimide fibers containing ether groups. J Appl Polym Sci 132(34):42474
Chang JJ, Niu HQ, Zhang MY, Ge QY, Li Y, Wu DZ (2015) Structures and properties of polyimide fibers containing ether units. J Mater Sci 50(11):4104–4114. doi:10.1007/s10853-015-8966-4
Zhang MY, Niu HQ, Qi SL, Tian GF, Wang XD, Wu DZ (2014) Structure evolutions involved in the carbonization of polyimide fibers with different chemical constitution. Mater Today Commun 1(1–2):1–8. doi:10.1016/j.mtcomm.2014.08.001
Wang S, Chen ZH, Ma WJ, Ma QS (2006) Influence of heat treatment on physical–chemical properties of PAN-based carbon fiber. Ceram Int 32(3):291–295. doi:10.1016/j.ceramint.2005.02.014
Belenkov EA (2001) Formation of graphite structure in carbon crystallites. Inorg Mater 37(9):928–934. doi:10.1023/a:1011601915600
Jawhari T, Roid A, Casado J (1995) Raman spectroscopic characterization of some commercially available carbon black materials. Carbon 33(11):1561–1565. doi:10.1016/0008-6223(95)00117-v
Niu HQ, Qi SL, Han EL, Tian GF, Wang XD, Wu DZ (2012) Fabrication of high-performance copolyimide fibers from 3,3′,4,4′-biphenyltetracarboxylic dianhydride, p-phenylenediamine and 2-(4-aminophenyl)-6-amino-4(3H)-quinazolinone. Mater Lett 89:63–65. doi:10.1016/j.matlet.2012.08.088
Zhao S, Shi ZQ, Wang CY, Chen MM (2008) Structure and surface elemental state analysis of polyimide resin film after carbonization and graphitization. J Appl Polym Sci 108(3):1852–1856. doi:10.1002/app.27697
Acknowledgements
The authors gratefully acknowledge the financial supports from the National Natural Science Foundation of China (NSFC, Project No. 51373008) and the Higher School Specialized Research Fund for Doctoral Priority Areas of Development Project (No. 20130010130001).
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Cao, L., Zhang, M., Niu, H. et al. Structural relationship between random copolyimides and their carbon fibers. J Mater Sci 52, 1883–1897 (2017). https://doi.org/10.1007/s10853-016-0477-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-016-0477-4