Abstract
Lignin, as an abundant carbon-rich renewable resource, is a promising precursor for carbon fibers. However, due to the poor spinnability of lignin, a great challenge comes from the spinning of precursor fibers. In this work, a series of lignosulfonate–acrylonitrile (LS–AN) copolymers with different LS contents were prepared by a two-step process consisting of esterification and free radical copolymerization. In this strategy, lignin was used as a macromer and chemically bonded to acrylonitrile segmer, resulting in significant improvement of the spinnability. Continuous long precursor fibers with a dense structure were successfully prepared from these copolymers by a wet spinning technique and then converted into carbon fibers by thermal stabilization and carbonization. The LS–AN copolymers were characterized by FTIR, GPC, and rheological method. The results confirmed the macromolecular characteristic of the LS–AN copolymers. A hanging lantern model was proposed to describe the molecular structure of the LS–AN copolymers. Effect of the LS–AN copolymers on the microstructure and mechanical properties of carbon fibers was investigated by SEM, single fiber tensile testing, XRD, and HRTEM. The results demonstrated the feasibility of developing partially biobased carbon fibers from the novel LS–AN copolymers.
Similar content being viewed by others
References
Morgan P (2005) Carbon fibers and their composites. CRC Press, New York
Ding R, Wu HC, Thunga M, Bowler N, Kessler MR (2016) Processing and characterization of low-cost electrospun carbon fibers from organosolv lignin/polyacrylonitrile blends. Carbon 100:126–136
Mainka H, Täger O, Körner E, Hilfert L, Busse S, Edelmann FT, Herrmann AS (2015) Lignin—an alternative precursor for sustainable and cost-effective automotive carbon fiber. J Mater Res Technol 4(3):283–296
Mainka H, Hilfert L, Busse S, Edelmann F, Haak E, Herrmann AS (2015) Characterization of the major reactions during conversion of lignin to carbon fiber. J Mater Res Technol 4(4):377–391
Baker DA, Rials TG (2013) Recent advances in low-cost carbon fiber manufacture from lignin. J Appl Polym Sci 130(2):713–728
Frank E, Steudle LM, Ingildeev D, Sporl JM, Buchmeiser MR (2014) Carbon fibers: precursor systems, processing, structure, and properties. Angew Chem Int Edit 53(21):5262–5298
Sen S, Patil S, Argyropoulos DS (2015) Thermal properties of lignin in copolymers, blends, and composites: a review. Green Chem 17(11):4862–4887
Schreiber M, Vivekanandhan S, Cooke P, Mohanty AK, Misra M (2014) Electrospun green fibres from lignin and chitosan: a novel polycomplexation process for the production of lignin-based fibres. J Mater Sci 49:7949–7958. doi:10.1007/s10853-014-8481-z
Laurichesse S, Averous L (2014) Chemical modification of lignins: towards biobased polymers. Prog Polym Sci 39(7):1266–1290
Ragauskas AJ, Beckham GT, Biddy MJ, Chandra R, Chen F, Davis MF, Davison BH, Dixon RA, Gilna P, Keller M, Langan P, Naskar AK, Saddler JN, Tschaplinski TJ, Tuskan GA, Wyman CE (2014) Lignin valorization: improving lignin processing in the biorefinery. Science 344:1246813. doi:10.1126/science.1246843
Chatterjee S, Saito T (2015) Lignin-derived advanced carbon materials. Chemsuschem 8(23):3941–3958
Souto F, Calado V, Pereira N (2015) Carbon fiber from lignin: a literature review. Materia-Rio De Janeiro 20(1):100–114
Ogale AA, Zhang M, Jin J (2016) Recent advances in carbon fibers derived from biobased precursors. J Appl Polym Sci 133(45):1–13. doi:10.1002/APP.43794
Thunga M, Chen K, Grewell D, Kessler MR (2014) Bio-renewable precursor fibers from lignin/polylactide blends for conversion to carbon fibers. Carbon 68:159–166
Hatakeyama H, Hatakeyama T (2009) Lignin structure, properties, and applications. Biopolymers. Springer, Berlin
Baker DA, Gallego NC, Baker FS (2012) On the characterization and spinning of an organic-purified lignin toward the manufacture of low-cost carbon fiber. J Appl Polym Sci 124(1):227–234
Sudo K, Shimizu K, Nakashima N, Yokoyama A (1993) A new modification method of exploded lignin for the preparation of a carbon fiber precursor. J Appl Polym Sci 48(8):1485–1491
Kadla JF, Kubo S, Venditti RA, Gilbert RD, Compere AL, Griffith W (2002) Lignin-based carbon fibers for composite fiber applications. Carbon 40(15):2913–2920
Kubo S, Kadla JF (2005) Lignin-based carbon fibers: effect of synthetic polymer blending on fiber properties. J Polym Environ 13(2):97–105
Chatterjee S, Clingenpeel A, McKenna A, Rios O, Johs A (2014) Synthesis and characterization of lignin-based carbon materials with tunable microstructure. Rsc Adv 4(9):4743–4753
Chatterjee S, Jones EB, Clingenpeel AC, McKenna AM, Rios O, McNutt NW, Keffer DJ, Johs A (2014) Conversion of lignin precursors to carbon fibers with nanoscale graphitic domains. ACS Sustain Chem Eng 2(8):2002–2010
Zhang M, Ogale AA (2014) Carbon fibers from dry-spinning of acetylated softwood kraft lignin. Carbon 69:626–629
Otani S, Fukuoka Y, Igarashi B, Sasaki K (1969) Method for producing carbonized lignin fiber. US patent 3461082
Ago M, Okajima K, Jakes JE, Park S, Rojas OJ (2012) Lignin-based electrospun nanofibers reinforced with cellulose nanocrystals. Biomacromolecules 13(3):918–926
Kubo S, Kadla JF (2004) Poly(ethylene oxide)/organosolv lignin blends: relationship between thermal properties, chemical structure, and blend behavior. Macromolecules 37(18):6904–6911
Brodin I, Ernstsson M, Gellerstedt G, Sjoholm E (2012) Oxidative stabilisation of kraft lignin for carbon fibre production. Holzforschung 66(2):141–147
Imel AE, Naskar AK, Dadmun MD (2016) Understanding the impact of poly(ethylene oxide) on the assembly of lignin in solution toward improved carbon fiber production. ACS Appl Mater Interfaces 8(5):3200–3207
Dallmeyer I, Lin LT, Li YJ, Ko F, Kadla JF (2014) Preparation and characterization of interconnected, kraft lignin-based carbon fibrous materials by electrospinning. Macromol Mater Eng 299(5):540–551
Svinterikos E, Zuburtikudis I (2016) Carbon nanofibers from renewable bioresources (lignin) and a recycled commodity polymer poly(ethylene terephthalate). J Appl Polym Sci 133(37):1–12. doi:10.1002/APP.43936
Kubo S, Yoshida T, Kadla JF (2007) Surface porosity of lignin/PP blend carbon fibers. J Wood Chem Technol 27(3–4):257–271
Wang SC, Li Y, Xiang HX, Zhou Z, Chang TK, Zhu MF (2015) Low cost carbon fibers from bio-renewable lignin/poly(lactic acid) (PLA) blends. Compos Sci Technol 119:20–25
Liu HC, Chien AT, Newcomb BA, Davijani AAB, Kumar S (2016) Stabilization kinetics of gel spun polyacrylonitrile/lignin blend fiber. Carbon 101:382–389
Husman G (2014) Development and commercialization of a novel low-cost carbon fiber. Presentation at 2014DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting, Oak Ridge National Laboratory
Oroumei A, Fox B, Naebe M (2015) Thermal and rheological characteristics of biobased carbon fiber precursor derived from low molecular weight organosolv lignin. ACS Sustain Chem Eng 3(4):758–769
Liu HC, Chien AT, Newcomb BA, Liu YD, Kumar S (2015) Processing, structure, and properties of lignin- and CNT-incorporated polyacrylonitrile-based carbon fibers. ACS Sustain Chem Eng 3(9):1943–1954
Dong XZ, Lu CX, Zhou PC, Zhang SC, Wang LY, Li DH (2015) Polyacrylonitrile/lignin sulfonate blend fiber for low-cost carbon fiber. Rsc Adv 5(53):42259–42265
Seydibeyoglu MO (2012) A novel partially biobased PAN-lignin blend as a potential carbon fiber precursor. J Biomed Biotechnol 2012:1–8. doi:10.1155/2012/598324
Xia KQ, Ouyang Q, Chen YS, Wang XF, Qian X, Wang L (2016) Preparation and characterization of lignosulfonate–acrylonitrile copolymer as a novel carbon fiber precursor. ACS Sustain Chem Eng 4(1):159–168
Ouyang Q, Wang XH, Wang XL, Huang J, Huang XW, Chen YS (2016) Simultaneous DSC/TG analysis on the thermal behavior of PAN polymers prepared by aqueous free-radical polymerization. Polym Degrad Stab 130:320–327
Maradur SP, Kim CH, Kim SY, Kim BH, Kim WC, Yang KS (2012) Preparation of carbon fibers from a lignin copolymer with polyacrylonitrile. Synth Met 162(5–6):453–459
Cifre JGH, La Torre JGD (2004) Orientation of polymer chains in dilute solution under shear: effect of chain model and excluded volume. Macromol Theor Simul 13(3):273–279
Ouyang Q, Chen Y, Wang X, Ma H, Li D, Yang J (2015) Supramolecular structure of highly oriented wet-spun polyacrylonitrile fibers used in the preparation of high-performance carbon fibers. J Polym Res 22(12):1–10
Ren FZ, Lu CX, Liang XY, Wu GP, He F, Ling LC (2004) Influence of amination on the structure of a PAN nascent filament during wet spinning. New Carbon Mater 19(4):268–274
Wang H, Xiao H, Lu Y, Jiang J (2016) The catalytic effect of boron nitride on the mechanical properties of polyacrylonitrile-based carbon fiber. J Mater Sci 51:10690–10700. doi:10.1007/s10853-016-0079-1
Chae HG, Newcomb BA, Gulgunje PV, Liu Y, Gupta KK, Kamath MG, Lyons KM, Ghoshal S, Pramanik C, Giannuzzi L (2015) High strength and high modulus carbon fibers. Carbon 93:81–87
Kubo S, Uraki Y, Sano Y (1998) Preparation of carbon fibers from softwood lignin by atmospheric acetic acid pulping. Carbon 36(7–8):1119–1124
Iwashita N (2016) Chapter 2—X-ray powder diffraction, materials science and engineering of carbon. Tsinghua University Press, Beijing
Cuesta A, Dhamelincourt P, Laureyns J, Martinez-Alonso A, Tascon JMD (1998) Comparative performance of X-ray diffraction and Raman microprobe techniques for the study of carbon materials. J Mater Chem 8(12):2875–2879
Acknowledgements
Financial support by the National Natural Science Foundation of China (No. 21404111) is gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Ouyang, Q., Xia, K., Liu, D. et al. Fabrication of partially biobased carbon fibers from novel lignosulfonate–acrylonitrile copolymers. J Mater Sci 52, 7439–7451 (2017). https://doi.org/10.1007/s10853-017-0977-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-017-0977-x