Exclusive: Marking 100 years since Shi Changxu's birth

Recent progress in high performance PAN based carbon fibers

  • LIU Ruigang ,
  • XU Jian
  • Institute of Chemistry, Chinese Academy of Sciences;Beijing National Laboratory for Molecular Sciences, Beijing 100190, China

Received date: 2018-09-10

  Revised date: 2018-10-08

  Online published: 2018-11-13


Recent progresses in the production of high performance polyacrylonitrile (PAN) based carbon fibers are reviewed in this paper, focusing on the polymerization, the production of PAN precursors, the stabilization and carbonization procedures for the production of PAN based carbon fibers. The polymerizing method is the key procedure for the distribution of co-monomers on the PAN line and the homogeneity of the spinning solution. Compared with the bath and semi-continuous polymerizing process, the continuous polymerizing process can produce a homogeneous and stabilizing PAN solution, reducing the formation of PAN microgels, which is beneficial for producing high quality PAN carbon fiber precursors and hereafter the PAN based carbon fibers. The coagulating parameters, as well as the phase separation process of the PAN solutions, determine the formation, the development, and the content of the microvoids in the PAN precursor fibers, which in turn influences the performance of the PAN precursors and thereafter the carbon fibers. The drawing and drying parameters are critical for the optimization of the orientation and the crystallization, as well as the quality of PAN precursor fibers. The heating rate, the highest temperature, and the tensile strength determine the core-shell structure and the cyclization index, which influences the carbonizing process and the properties of the resultant carbon fibers. The strength and the modulus of the carbon fibers are closely related with the temperature and the strength of the carbonizing procedure. The correlation between the structure and the properties of PAN based carbon fibers remains an issue to be further explored, as well as the technology of the production of high performance carbon fibers in China. The combination of fundamental and applied researches are critically needed.

Cite this article

LIU Ruigang , XU Jian . Recent progress in high performance PAN based carbon fibers[J]. Science & Technology Review, 2018 , 36(19) : 32 -42 . DOI: 10.3981/j.issn.1000-7857.2018.19.006


[1] Liang H W, Liu J W, Qian H S, et al. Multiplex templating process in one-dimensional nanoscale:Controllable synthesis, macroscopic assemblies, and applications[J]. Accounts of Chemical Research, 2013; 46(7):1450-1461.
[2] Liang H W, Guan Q F, Chen L F, et al. Macroscopic-scale template synthesis of robust carbonaceous nanofiber hydrogels and aerogels and their applications[J]. Angewandte Chemie-International Edition, 2012, 51(21):5101-5105.
[3] Chen L F, Huang Z H, Liang H W, et al. Flexible all-solidstate high-power supercapacitor fabricated with nitrogen-doped carbon nanofiber electrode material derived from bacterial cellulose[J]. Energy & Environmental Science, 2013, 6(11):3331-3338.
[4] Liang H W, Guan Q F, Zhu Z, et al. Highly conductive and stretchable conductors fabricated from bacterial cellulose[J]. Npg Asia Materials, 2012, 4(6):e19.
[5] Chen L F, Zhang X D, Liang H W, et al. Synthesis of nitrogendoped porous carbon nanofibers as an efficient electrode material for supercapacitors[J]. ACS Nano, 2012, 6(8):7092-7102.
[6] Liang H W, Cao X, Zhang W J, et al. Robust and highly efficient free-standing carbonaceous nanofiber membranes for water purification[J]. Advanced Functional Materials, 2011, 21(20):3851-3858.
[7] Chen P, Liang H W, Lü X H, et al. Carbonaceous nanofiber membrane functionalized by beta-cyclodextrins for molecular filtration[J]. ACS Nano, 2011, 5(7):5928-5935.
[8] Liang H W, Zhang W J, Ma Y N, et al. Highly active carbonaceous nanofibers:A versatile scaffold for constructing multifunctional free-standing membranes[J]. ACS Nano, 2011, 5(10):8148-8161.
[9] Liang H W, Wang L, Chen P Y, et al. Carbonaceous nanofiber membranes for selective filtration and separation of nanoparticles[J]. Advanced Materials, 2010, 22(42):4691-4695.
[10] Wu Z Y, Li C, Liang H W, et al. Ultralight, flexible, and fireresistant carbon nanofiber aerogels from bacterial cellulose[J]. Angewandte Chemie-International Edition, 2013, 52(10):2925-2929.
[11] Chen L F, Huang Z H, Liang H W, et al. Bacterial-cellulosederived carbon nanofiber@MnO2 and nitrogen-doped carbon nanofiber electrode materials:An asymmetric supercapacitor with high energy and power density[J]. Advanced Materials, 2013, 25(34):4746-4752.
[12] Frank E, Steudle L M, Ingildeev D, et al. Carbon fibers:Precursor systems, processing, structure, and properties[J]. Angewandte Chemie-International Edition, 2014, 53(21):5262-5298.
[13] Li Q, Xie S X, Serem W K, et al. Quality carbon fibers from fractionated lignin[J]. Green Chemistry, 2017, 19(7):1628-1634.
[14] Li Q, Ragauskas A J, Yuan J S. Lignin carbon fiber:The path for quality[J]. Tappi Journal, 2017, 16(3):107-108.
[15] Steudle L M, Frank E, Ota A, et al. Carbon fibers prepared from melt spun peracylated softwood lignin:An integrated approach[J]. Macromolecular Materials and Engineering, 2017, 302(4):1700195.
[16] Barton B E, Behr M J, Patton J T, et al. High-modulus lowcost carbon fibers from polyethylene enabled by boron catalyzed graphitization[J]. Small, 2017, 13(36):1701926.
[17] Behr M J, Landes B G, Barton B E, et al. Structure-property model for polyethylene-derived carbon fiber[J]. Carbon, 2016, 107:525-535.
[18] Kim K W, Lee H M, An J H, et al. Effects of cross-linking methods for polyethylene-based carbon fibers:Review[J]. Carbon Letters, 2015, 16(3):147-170.
[19] Younker J M, Saito T, Hunt M A, et al. Pyrolysis pathways of sulfonated polyethylene, an alternative carbon fiber precursor[J]. Journal of the American Chemical Society, 2013, 135(16):6130-6141.
[20] Dalton S, Heatley F, Budd P M. Thermal stabilization of polyacrylonitrile fibres[J]. Polymer, 1999, 40(20):5531-5543.
[21] Ouyang Q, Cheng L, Wang H J, et al. Mechanism and kinetics of the stabilization reactions of itaconic acid-modified polyacrylonitrile[J]. Polymer Degradation and Stability, 2008, 93(8):1415-1421.
[22] Watt W, Johnson W. Mechanism of oxidization of polyacrylonitrile fibers[J]. Nature, 1975, 257(5523):210-212.
[23] Nunna S, Naebe M, Hameed N, et al. Evolution of radial heterogeneity in polyacrylonitrile fibres during thermal stabilization:An overview[J]. Polymer Degradation and Stability, 2017, 136:20-30.
[24] Grassie N, McGuchan R. Pyrolysis of polyacrylonitrile and related polymer-VⅢ. Copolymers of acrylonitrile with vinylacetate, vinyl formate, acrolein and methyl vinyl ketone[J]. European Polymer Journal, 1973, 9(2):113-124.
[25] Grassie N, McGuchan R. Pyrolysis of polyacrylonitrile and related polymers-Ⅱ Effect of sample preparation on thermal behaviour of polyacrylonitrile[J]. European Polymer Journal, 1971, 7(8):1091-1104.
[26] Grassie N, McGuchan R. Pyrolysis of polyacrylonitrile and related polymers-VI. Acrylonitrile copolymers containing carboxylic-acid and amide structures[J]. European Polymer Journal, 1972; 8(2):257-269.
[27] 李悦生, 李百祥, 张贵宝, 等. 一种链结构均匀的丙烯腈二元共聚物纺丝液及制备方法:CN101413153A[P]. 2009-04-22. Li Yuesheng, Li Baixiang, Zhang Guibao, et al. Acrylonitrile biopolymer spinning fluid having homogeneous chain structure and preparation thereof:CN101413153A[P]. 2009-04-22.
[28] Liu X F, Zhu C Z, Dong H X, et al. Effect of microgel content on the shear and extensional rheology of polyacrylonitrile solution[J]. Colloid and Polymer Science, 2015, 293(2):587-596.
[29] 徐坚, 刘瑞刚. 高性能纤维基本科学原理[M]. 北京:国防工业出版社, 2018. Xu Jian, Liu Ruigang. Fundamentals of high performance fibers[M]. Beijing:National Defense Industry Press, 2018.
[30] 余晓兰. 聚丙烯腈基材料的制备、表征及应用[D]. 北京:中国科学院化学研究所, 2011. Yu Xiaolan. The preparation, characterization, and applications of polyacrylnitril based materials[D]. Beijing:Institute of Chemistry, Chinese Academy of Sciences, 2011.
[31] 刘小芳. 聚丙烯腈溶胶-凝胶转变及其纤维结构演变的研究[D]. 北京:中国科学院化学研究所, 2014. Liu Xiaofang. Researches on the sol-gel transition of polyacrylnitril solution and the structure formation and development of polyacrylnitril fibers[D]. Beijing:Institute of Chemistry, Chinese Academy of Sciences, 2014.
[32] Marinesco S, Carew T J. Improved electrochemical detection of biogenic amines in Aplysia using base-hydrolyzed cellulose-coated carbon fiber microelectrodes[J]. Journal of Neuroscience Methods, 2002, 117(1):87-97.
[33] Ko T H. Influence of continuous stabilization on the physicalproperties and microstructure of PAN-based carbon-fibers[J]. Journal of Applied Polymer Science, 1991, 42(7):1949-1957.
[34] Huang X S. Fabrication and properties of carbon fibers[J]. Materials, 2009, 2(4):2369-2403.
[35] Sedghi A, Farsani R E, Shokuhfar A. The effect of commercial polyacrylonitrile fibers characterizations on the produced carbon fibers properties[J]. Journal of Materials Processing Technology, 2008, 198(1/2/3):60-67.
[36] Dunham M G, Edie D D. Model of stabilization for PANbased carbon-fiber precursor bundles[J]. Carbon, 1992, 30(3):435-450.
[37] Houtz R C. "Orlon" acrylic fiber:Chemistry and properties[J]. Textile Research Journal, 1950, 20(11):786-801.
[38] Schurz J. Discoloration effects in acrylonitrile polymers[J]. Journal of Polymer Science, 1958, 28(117):438-439.
[39] Standage A E, Matkowsky R D. Thermal oxidation of polyacrylonitrile[J]. European Polymer Journal, 1971, 7(7):775-783.
[40] Friedlander H N, Peebles L H, Brandrup J, et al. On the chromophore of polyacrylonitrile. VI. Mechanism of color formation in polyacrylonitrile[J]. Macromolecules, 1968, 1(1):79-86.
[41] Henrici-Olivé G, Olivé S. Molecular interactions and macroscopic properties of polyacrylonitrile and model substances[M]//Chemistry. Berlin, Heidelberg:Springer Berlin Heidelberg, 1979:123-152.
[42] Ganster J, Fink H P, Zenke I. Chain conformation of polyacrylonitrile-A comparison of model scattering and radial-distribution functions with experimental wide-angle X-ray-scattering results[J]. Polymer, 1991; 32(9):1566-1573.
[43] Gupta A, Harrison I R. New aspects in the oxidative stabilization of PAN-based carbon fibers:Ⅱ[J]. Carbon, 1997, 35(6):809-818.
[44] Gupta A, Harrison I R. New aspects in the oxidative stabilization of PAN-based carbon fibers[J]. Carbon, 1996, 34(11):1427-1445.
[45] Liu X R, Chen W, Hong Y L, et al. Stabilization of atacticpolyacrylonitrile under Nitrogen and air as studied by solidstate NMR[J]. Macromolecules, 2015, 48(15):5300-5309.
[46] Liu X R, Makita Y, Hong Y L, et al. Chemical reactions and their kinetics of atactic-polyacrylonitrile as revealed by solidstate 13C NMR[J]. Macromolecules, 2017, 50(1):244-253.
[47] Wang Y S, Xu L H, Wang M Z, et al. Structural identification of polyacrylonitrile during thermal treatment by selective 13C labeling and solid-state 13C NMR spectroscopy[J]. Macromolecules, 2014, 47(12):3901-3908.
[48] Layden G K. Retrograde core formation during oxidation of polyacrylonitrile filaments[J]. Carbon, 1972, 10(1):59-60.
[49] Liu X F, Zhu C Z, Guo J, et al. Nanoscale dynamic mechanical imaging of the skin-core difference:From PAN precursors to carbon fibers[J]. Materials Letters, 2014, 128:417-420.
[50] Lian F, Liu J, Ma Z K, et al. Stretching-induced deformation of polyacrylonitrile chains both in quasicrystals and in amorphous regions during the in situ thermal modification of fibers prior to oxidative stabilization[J]. Carbon, 2012, 50(2):488-499.
[51] Fitzer E, Frohs W, Heine M. Optimization of stabilization and carbonization treatment of PAN fibers and structural characterization of the resulting carbon-fibers[J]. Carbon, 1986, 24(4):387-395.