Non–solvent Fractionation of Lignin Enhances Carbon Fiber Performance

Yuan, Joshua S.; Li, Qiang; Li, Mengjie; Lin, Hao -Sheng; Hu, Cheng; Truong, Phuc; Zhang, Tan; Sue, Hung -Jue; Pu, Yunqiao Joseph; Ragauskas, Arthur J.

doi:10.1002/cssc.201901052

Non–solvent Fractionation of Lignin Enhances Carbon Fiber Performance

Journal Article · Wed May 08 00:00:00 EDT 2019 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.201901052· OSTI ID:1545576

Yuan, Joshua S. ^[1]; Li, Qiang ^[1]; Li, Mengjie ^[1]; Lin, Hao -Sheng ^[1]; Hu, Cheng ^[1]; Truong, Phuc ^[1]; Zhang, Tan ^[1]; Sue, Hung -Jue ^[1]; ^[2]; ^[3]

Texas A & M Univ., College Station, TX (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); The Univ. of Tennessee, Knoxville, TN (United States)

Even though lignin carbon fiber has been sought after for several decades, the poor mechanical performance remains to be a major barrier for commercial applications. The low mechanical performance is attributed to the heterogeneity of lignin polymer. Recent advances in fractionation technologies showed the great potential to reduce lignin heterogeneity, but current fractionation methods often depend on costly chemicals and materials such as enzymes, organic solvents, membranes, and dialysis tubes. Here, a new non–solvent strategy was developed to fractionate lignin by autohydrolysis. By using only water, lignin was efficiently fractionated into water–soluble and –insoluble fractions. The latter fraction had increased molecular weight and uniformity and resulted in more β–O–4 interunitary linkages as analyzed by size–exclusion chromatography and 2D heteronuclear single quantum coherence NMR spectroscopy, respectively. In particular, the water–insoluble fraction significantly enhanced the mechanical performances of the resultant carbon fibers. Mechanistic study by differential scanning calorimetry (DSC) revealed that the miscibility of lignin with guest polyacrylonitrile molecules was improved with the reduced lignin heterogeneity. Crystallite analyses by XRD and Raman spectroscopy revealed that the crystallite size and content of the pre–graphitic turbostratic carbon structure were increased. The fundamental understanding revealed how lignin fractionation could modify lignin chemical features to enhance the mechanical performance of resultant carbon fibers. As a result, the autohydrolysis fractionation thus represents a green, economic, and efficient methodology to process lignin waste and boost lignin carbon fiber quality, which could open new horizons for lignin valorization.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1545576

Alternate ID(s):: OSTI ID: 1560165

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 14 Vol. 12; ISSN 1864-5631

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Carbonfasern: Präkursor-Systeme, Verarbeitung, Struktur und Eigenschaften Frank, Erik; Steudle, Lisa M.; Ingildeev, Denis Angewandte Chemie, Vol. 126, Issue 21 https://doi.org/10.1002/ange.201306129	journal	March 2014
Carbon Fibers: Precursor Systems, Processing, Structure, and Properties Frank, Erik; Steudle, Lisa M.; Ingildeev, Denis Angewandte Chemie International Edition, Vol. 53, Issue 21 https://doi.org/10.1002/anie.201306129	journal	March 2014
Carbon fibers based on pyrolytic lignin Qin, W.; Kadla, J. F. Journal of Applied Polymer Science, Vol. 126, Issue S1 https://doi.org/10.1002/app.36554	journal	April 2012
Recent advances in low-cost carbon fiber manufacture from lignin Baker, Darren A.; Rials, Timothy G. Journal of Applied Polymer Science, Vol. 130, Issue 2 https://doi.org/10.1002/app.39273	journal	April 2013
Recent advances in carbon fibers derived from biobased precursors Ogale, Amod A.; Zhang, Meng; Jin, Jing Journal of Applied Polymer Science, Vol. 133, Issue 45 https://doi.org/10.1002/app.43794	journal	May 2016
Methanol Fractionation of Softwood Kraft Lignin: Impact on the Lignin Properties Saito, Tomonori; Perkins, Joshua H.; Vautard, Frederic ChemSusChem, Vol. 7, Issue 1 https://doi.org/10.1002/cssc.201300509	journal	November 2013
Lignin-Derived Advanced Carbon Materials Chatterjee, Sabornie; Saito, Tomonori ChemSusChem, Vol. 8, Issue 23 https://doi.org/10.1002/cssc.201500692	journal	November 2015
Lignin biochemistry: Biosynthesis and biodegradation Higuchi, T. Wood Science and Technology, Vol. 24, Issue 1 https://doi.org/10.1007/BF00225306	journal	January 1990
Conversion of technical lignins to functional materials with retained polymeric properties Matsushita, Yasuyuki Journal of Wood Science, Vol. 61, Issue 3 https://doi.org/10.1007/s10086-015-1470-2	journal	April 2015
Carbon fibres from mesophase pitch Singer, Leonard S. Fuel, Vol. 60, Issue 9 https://doi.org/10.1016/0016-2361(81)90147-2	journal	September 1981
Molecular organization of lignin during carbonization Davé, Vipul; Prasad, Abaneshwar; Marand, Hervé Polymer, Vol. 34, Issue 15 https://doi.org/10.1016/0032-3861(93)90382-K	journal	January 1993
Lignin-based carbon fibers for composite fiber applications Kadla, J.F; Kubo, S; Venditti, R.A Carbon, Vol. 40, Issue 15, p. 2913-2920 https://doi.org/10.1016/S0008-6223(02)00248-8	journal	January 2002
The effect of processing on the structure and properties of carbon fibers Edie, D. D. Carbon, Vol. 36, Issue 4 https://doi.org/10.1016/S0008-6223(97)00185-1	journal	January 1998
Kinetics and mechanism of autohydrolysis of hardwoods Chen, Xiaowen; Lawoko, Martin; Heiningen, Adriaan van Bioresource Technology, Vol. 101, Issue 20 https://doi.org/10.1016/j.biortech.2010.05.006	journal	October 2010
Effect of structural changes of lignin during the autohydrolysis and organosolv pretreatment on Eucommia ulmoides Oliver for an effective enzymatic hydrolysis Zhu, Ming-Qiang; Wen, Jia-Long; Su, Yin-Quan Bioresource Technology, Vol. 185 https://doi.org/10.1016/j.biortech.2015.02.061	journal	June 2015
Processing and characterization of low-cost electrospun carbon fibers from organosolv lignin/polyacrylonitrile blends Ding, Rui; Wu, Hongchao; Thunga, Mahendra Carbon, Vol. 100 https://doi.org/10.1016/j.carbon.2015.12.078	journal	April 2016
Tuning hydroxyl groups for quality carbon fiber of lignin Li, Qiang; Naik, Mandar T.; Lin, Hao-Sheng Carbon, Vol. 139 https://doi.org/10.1016/j.carbon.2018.07.015	journal	November 2018
Comparative study of lignin fractionation by ultrafiltration and selective precipitation Toledano, A.; Serrano, L.; Garcia, A. Chemical Engineering Journal, Vol. 157, Issue 1 https://doi.org/10.1016/j.cej.2009.10.056	journal	February 2010
Lignin-based polymer blends: analysis of intermolecular interactions in lignin–synthetic polymer blends Kadla, John F.; Kubo, Satoshi Composites Part A: Applied Science and Manufacturing, Vol. 35, Issue 3 https://doi.org/10.1016/j.compositesa.2003.09.019	journal	March 2004
Improved lignin properties and reactivity by modifications in the autohydrolysis process of aspen wood Li, Jiebing; Gellerstedt, Göran Industrial Crops and Products, Vol. 27, Issue 2 https://doi.org/10.1016/j.indcrop.2007.07.022	journal	March 2008
Biochemical and molecular characterization of a novel laccase from selective lignin-degrading white-rot fungus Echinodontium taxodii 2538 Shi, Lili; Yu, Hongbo; Dong, Tianbao Process Biochemistry, Vol. 49, Issue 7 https://doi.org/10.1016/j.procbio.2014.03.028	journal	July 2014
Chemical modification of lignins: Towards biobased polymers Laurichesse, Stéphanie; Avérous, Luc Progress in Polymer Science, Vol. 39, Issue 7, p. 1266-1290 https://doi.org/10.1016/j.progpolymsci.2013.11.004	journal	July 2014
Lignin separation and fractionation by ultrafiltration Toledano, A.; García, A.; Mondragon, I. Separation and Purification Technology, Vol. 71, Issue 1 https://doi.org/10.1016/j.seppur.2009.10.024	journal	January 2010
Dehydrogenative Polymerization of Coniferyl Alcohol in Artificial Polysaccharides Matrices: Effects of Xylan on the Polymerization Li, Qiang; Koda, Keiichi; Yoshinaga, Arata Journal of Agricultural and Food Chemistry, Vol. 63, Issue 18 https://doi.org/10.1021/acs.jafc.5b01070	journal	May 2015
Advanced Chemical Design for Efficient Lignin Bioconversion Xie, Shangxian; Sun, Qining; Pu, Yunqiao ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 3 https://doi.org/10.1021/acssuschemeng.6b02401	journal	January 2017
Lignin as Renewable and Superior Asphalt Binder Modifier Xie, Shangxian; Li, Qiang; Karki, Pravat ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 4 https://doi.org/10.1021/acssuschemeng.6b03064	journal	March 2017
Lignin/Polyacrylonitrile Carbon Fibers: The Effect of Fractionation and Purification on Properties of Derived Carbon Fibers Liu, Huan; Dai, Zhong; Cao, Qiping ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 7 https://doi.org/10.1021/acssuschemeng.8b00868	journal	May 2018
Relationship between the glass transition temperature and the interaction parameter of miscible binary polymer blends Lu, Xinya; Weiss, R. A. Macromolecules, Vol. 25, Issue 12 https://doi.org/10.1021/ma00038a033	journal	June 1992
Correlation between the glass transition temperatures of polymer mixtures and intermolecular force parameters Kwei, T. K.; Pearce, Eli M.; Pennacchia, John R. Macromolecules, Vol. 20, Issue 5 https://doi.org/10.1021/ma00171a055	journal	September 1987
Fractional Precipitation of Softwood Kraft Lignin: Isolation of Narrow Fractions Common to a Variety of Lignins Cui, Chengzhong; Sun, Runkun; Argyropoulos, Dimitris S. ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 4 https://doi.org/10.1021/sc400545d	journal	February 2014
How biotech can transform biofuels Lynd, Lee R.; Laser, Mark S.; Bransby, David Nature Biotechnology, Vol. 26, Issue 2, p. 169-172 https://doi.org/10.1038/nbt0208-169	journal	February 2008
Sustainable carbon materials Titirici, Maria-Magdalena; White, Robin J.; Brun, Nicolas Chemical Society Reviews, Vol. 44, Issue 1, p. 250-290 https://doi.org/10.1039/C4CS00232F	journal	January 2015
Quality carbon fibers from fractionated lignin Li, Qiang; Xie, Shangxian; Serem, Wilson K. Green Chemistry, Vol. 19, Issue 7 https://doi.org/10.1039/C6GC03555H	journal	January 2017
Molecular weight and uniformity define the mechanical performance of lignin-based carbon fiber Li, Qiang; Serem, Wilson K.; Dai, Wei Journal of Materials Chemistry A, Vol. 5, Issue 25 https://doi.org/10.1039/C7TA01187C	journal	January 2017
Lignin Valorization: Improving Lignin Processing in the Biorefinery Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J. Science, Vol. 344, Issue 6185, p. 1246843-1246843 https://doi.org/10.1126/science.1246843	journal	May 2014
Lignin Biosynthesis Boerjan, Wout; Ralph, John; Baucher, Marie Annual Review of Plant Biology, Vol. 54, Issue 1, p. 519-546 https://doi.org/10.1146/annurev.arplant.54.031902.134938	journal	June 2003
Comparative genome analysis of lignin biosynthesis gene families across the plant kingdom Xu, Zhanyou; Zhang, Dandan; Hu, Jun BMC Bioinformatics, Vol. 10, Issue Suppl 11 https://doi.org/10.1186/1471-2105-10-S11-S3	journal	January 2009
Solvent screening for the fractionation of industrial kraft lignin Duval, Antoine; Vilaplana, Francisco; Crestini, Claudia Holzforschung, Vol. 70, Issue 1 https://doi.org/10.1515/hf-2014-0346	journal	January 2016
Fractionation of Technical Lignin: Molecular Mass and pH Effects Helander, Mikaela; Theliander, Hans; Lawoko, Martin BioResources, Vol. 8, Issue 2 https://doi.org/10.15376/biores.8.2.2270-2282	journal	January 2013
Lignin carbon fiber: The path for quality Li, Qiang; Ragauskas, Arthur; Yuan, Joshua TAPPI Journal, Vol. 16, Issue 03 https://doi.org/10.32964/TJ16.3.107	journal	January 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
autohydrolysis
carbon fibers
fractionation
lignin
mechanical performance

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