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Title: A path for lignin valorization via additive manufacturing of high-performance sustainable composites with enhanced 3D printability

Abstract

Here, we report the manufacture of printable, sustainable polymer systems to address global challenges associated with high-volume utilization of lignin, an industrial waste from biomass feedstock. By analyzing a common three-dimensional printing process—fused-deposition modeling—and correlating the printing-process features to properties of materials such as acrylonitrile-butadiene-styrene (ABS) and nylon, we devised a first-of-its-kind, high-performance class of printable renewable composites containing 40 to 60 weight % (wt %) lignin. An ABS analog made by integrating lignin into nitrile-butadiene rubber needs the presence of a styrenic polymer to avoid filament buckling during printing. However, lignin-modified nylon composites containing 40 to 60 wt % sinapyl alcohol–rich, melt-stable lignin exhibit enhanced stiffness and tensile strength at room temperature, while—unexpectedly—demonstrating a reduced viscosity in the melt. Further, incorporation of 4 to 16 wt % discontinuous carbon fibers enhances mechanical stiffness and printing speed, as the thermal conductivity of the carbon fibers facilitates heat transfer and thinning of the melt. We found that the presence of lignin and carbon fibers retards nylon crystallization, leading to low-melting imperfect crystals that allow good printability at lower temperatures without lignin degradation.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1489603
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 12; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Nguyen, Ngoc A., Barnes, Sietske H., Bowland, Christopher C., Meek, Kelly M., Littrell, Kenneth C., Keum, Jong K., and Naskar, Amit K. A path for lignin valorization via additive manufacturing of high-performance sustainable composites with enhanced 3D printability. United States: N. p., 2018. Web. doi:10.1126/sciadv.aat4967.
Nguyen, Ngoc A., Barnes, Sietske H., Bowland, Christopher C., Meek, Kelly M., Littrell, Kenneth C., Keum, Jong K., & Naskar, Amit K. A path for lignin valorization via additive manufacturing of high-performance sustainable composites with enhanced 3D printability. United States. https://doi.org/10.1126/sciadv.aat4967
Nguyen, Ngoc A., Barnes, Sietske H., Bowland, Christopher C., Meek, Kelly M., Littrell, Kenneth C., Keum, Jong K., and Naskar, Amit K. Fri . "A path for lignin valorization via additive manufacturing of high-performance sustainable composites with enhanced 3D printability". United States. https://doi.org/10.1126/sciadv.aat4967. https://www.osti.gov/servlets/purl/1489603.
@article{osti_1489603,
title = {A path for lignin valorization via additive manufacturing of high-performance sustainable composites with enhanced 3D printability},
author = {Nguyen, Ngoc A. and Barnes, Sietske H. and Bowland, Christopher C. and Meek, Kelly M. and Littrell, Kenneth C. and Keum, Jong K. and Naskar, Amit K.},
abstractNote = {Here, we report the manufacture of printable, sustainable polymer systems to address global challenges associated with high-volume utilization of lignin, an industrial waste from biomass feedstock. By analyzing a common three-dimensional printing process—fused-deposition modeling—and correlating the printing-process features to properties of materials such as acrylonitrile-butadiene-styrene (ABS) and nylon, we devised a first-of-its-kind, high-performance class of printable renewable composites containing 40 to 60 weight % (wt %) lignin. An ABS analog made by integrating lignin into nitrile-butadiene rubber needs the presence of a styrenic polymer to avoid filament buckling during printing. However, lignin-modified nylon composites containing 40 to 60 wt % sinapyl alcohol–rich, melt-stable lignin exhibit enhanced stiffness and tensile strength at room temperature, while—unexpectedly—demonstrating a reduced viscosity in the melt. Further, incorporation of 4 to 16 wt % discontinuous carbon fibers enhances mechanical stiffness and printing speed, as the thermal conductivity of the carbon fibers facilitates heat transfer and thinning of the melt. We found that the presence of lignin and carbon fibers retards nylon crystallization, leading to low-melting imperfect crystals that allow good printability at lower temperatures without lignin degradation.},
doi = {10.1126/sciadv.aat4967},
journal = {Science Advances},
number = 12,
volume = 4,
place = {United States},
year = {2018},
month = {12}
}

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Works referenced in this record:

Lignin Valorization: Improving Lignin Processing in the Biorefinery
journal, May 2014

  • Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.
  • Science, Vol. 344, Issue 6185, p. 1246843-1246843
  • DOI: 10.1126/science.1246843

Plant oil renewable resources as green alternatives in polymer science
journal, January 2007

  • Meier, Michael A. R.; Metzger, Jürgen O.; Schubert, Ulrich S.
  • Chemical Society Reviews, Vol. 36, Issue 11
  • DOI: 10.1039/b703294c

Turning renewable resources into value-added polymer: development of lignin-based thermoplastic
journal, January 2012

  • Saito, Tomonori; Brown, Rebecca H.; Hunt, Marcus A.
  • Green Chemistry, Vol. 14, Issue 12, p. 3295-3303
  • DOI: 10.1039/c2gc35933b

Rotational 3D printing of damage-tolerant composites with programmable mechanics
text, January 2018


Biomimetic 4D printing
journal, January 2016

  • Sydney Gladman, A.; Matsumoto, Elisabetta A.; Nuzzo, Ralph G.
  • Nature Materials, Vol. 15, Issue 4
  • DOI: 10.1038/nmat4544

A 3D bioprinting system to produce human-scale tissue constructs with structural integrity
journal, February 2016

  • Kang, Hyun-Wook; Lee, Sang Jin; Ko, In Kap
  • Nature Biotechnology, Vol. 34, Issue 3
  • DOI: 10.1038/nbt.3413

The Temperature Dependence of Relaxation Mechanisms in Amorphous Polymers and Other Glass-forming Liquids
journal, July 1955

  • Williams, Malcolm L.; Landel, Robert F.; Ferry, John D.
  • Journal of the American Chemical Society, Vol. 77, Issue 14
  • DOI: 10.1021/ja01619a008

Rotational 3D printing of damage-tolerant composites with programmable mechanics
journal, January 2018

  • Raney, Jordan R.; Compton, Brett G.; Mueller, Jochen
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 6
  • DOI: 10.1073/pnas.1715157115

Omnidirectional Printing of Flexible, Stretchable, and Spanning Silver Microelectrodes
journal, March 2009


Direct Ink Writing of Three-Dimensional Ceramic Structures
journal, December 2006

  • Lewis, Jennifer A.; Smay, James E.; Stuecker, John
  • Journal of the American Ceramic Society, Vol. 89, Issue 12, p. 3599-3609
  • DOI: 10.1111/j.1551-2916.2006.01382.x

Enzymatic "Combustion": The Microbial Degradation of Lignin
journal, October 1987


Additive manufacturing of multi-directional preforms for composites: opportunities and challenges
journal, November 2015


Additive manufacturing: scientific and technological challenges, market uptake and opportunities
journal, January 2018


4D printing of polymeric materials for tissue and organ regeneration
journal, December 2017


Instrumented cardiac microphysiological devices via multimaterial three-dimensional printing
journal, October 2016

  • Lind, Johan U.; Busbee, Travis A.; Valentine, Alexander D.
  • Nature Materials, Vol. 16, Issue 3
  • DOI: 10.1038/nmat4782

3D printing of polymer matrix composites: A review and prospective
journal, February 2017


Recent developments in 3D printable composite materials
journal, January 2016

  • Kalsoom, Umme; Nesterenko, Pavel N.; Paull, Brett
  • RSC Advances, Vol. 6, Issue 65
  • DOI: 10.1039/C6RA11334F

Coupling 3D printing with hot-melt extrusion to produce controlled-release tablets
journal, March 2017


The performance of the hot end in a plasticating 3D printer
journal, January 2017

  • Mackay, Michael E.; Swain, Zachary R.; Banbury, Colby R.
  • Journal of Rheology, Vol. 61, Issue 2
  • DOI: 10.1122/1.4973852

Lignin-Based Thermoplastic Materials
journal, April 2016

  • Wang, Chao; Kelley, Stephen S.; Venditti, Richard A.
  • ChemSusChem, Vol. 9, Issue 8
  • DOI: 10.1002/cssc.201501531

An approach towards tailoring interfacial structures and properties of multiphase renewable thermoplastics from lignin–nitrile rubber
journal, January 2016

  • Bova, Tony; Tran, Chau D.; Balakshin, Mikhail Y.
  • Green Chemistry, Vol. 18, Issue 20
  • DOI: 10.1039/C6GC01067A

A study of poplar organosolv lignin after melt rheology treatment as carbon fiber precursors
journal, January 2016

  • Sun, Qining; Khunsupat, Ratayakorn; Akato, Kokouvi
  • Green Chemistry, Vol. 18, Issue 18
  • DOI: 10.1039/C6GC00977H

A New Class of Renewable Thermoplastics with Extraordinary Performance from Nanostructured Lignin-Elastomers
journal, March 2016

  • Tran, Chau D.; Chen, Jihua; Keum, Jong K.
  • Advanced Functional Materials, Vol. 26, Issue 16, p. 2677-2685
  • DOI: 10.1002/adfm.201504990

An Acrylonitrile–Butadiene–Lignin Renewable Skin with Programmable and Switchable Electrical Conductivity for Stress/Strain-Sensing Applications
journal, December 2017


Poly(ethylene oxide)-Assisted Macromolecular Self-Assembly of Lignin in ABS Matrix for Sustainable Composite Applications
journal, November 2015


Effect of fiber surface-treatments on the properties of laminated biocomposites from poly(lactic acid) (PLA) and kenaf fibers
journal, February 2008


A general method to improve 3D-printability and inter-layer adhesion in lignin-based composites
journal, September 2018


On the structure of softwood kraft lignin
journal, January 2017

  • Crestini, Claudia; Lange, Heiko; Sette, Marco
  • Green Chemistry, Vol. 19, Issue 17
  • DOI: 10.1039/C7GC01812F

Softwood Lignin-Based Methacrylate Polymers with Tunable Thermal and Viscoelastic Properties
journal, February 2016


Syringyl Methacrylate, a Hardwood Lignin-Based Monomer for High- T g Polymeric Materials
journal, April 2016


Correlation of dynamic and steady flow viscosities
journal, April 1958


Effect of Ideal, Organic Nanoparticles on the Flow Properties of Linear Polymers:  Non-Einstein-like Behavior
journal, September 2005

  • Tuteja, Anish; Mackay, Michael E.; Hawker, Craig J.
  • Macromolecules, Vol. 38, Issue 19
  • DOI: 10.1021/ma050974h

Microfluidic Printheads for Multimaterial 3D Printing of Viscoelastic Inks
journal, April 2015

  • Hardin, James O.; Ober, Thomas J.; Valentine, Alexander D.
  • Advanced Materials, Vol. 27, Issue 21
  • DOI: 10.1002/adma.201500222

From zero to hero – Production of bio-based nylon from renewable resources using engineered Corynebacterium glutamicum
journal, September 2014


Unsaturated PA X,20 from Renewable Resources via Metathesis and Catalytic Amidation: Unsaturated PA X,20 from Renewable Resources via Metathesis and …
journal, May 2009

  • Mutlu, Hatice; Meier, Michael A. R.
  • Macromolecular Chemistry and Physics, Vol. 210, Issue 12
  • DOI: 10.1002/macp.200900045

Theory, practice and prospects of X-ray and neutron scattering for lignocellulosic biomass characterization: towards understanding biomass pretreatment
journal, January 2015

  • Cheng, Gang; Zhang, Xin; Simmons, Blake
  • Energy & Environmental Science, Vol. 8, Issue 2
  • DOI: 10.1039/C4EE03147D

Microfabricated Deposition Nozzles for Direct-Write Assembly of Three-Dimensional Periodic Structures
journal, February 2005


Polymer Dielectrics for 3D-Printed RF Devices in the K a Band
journal, May 2016

  • Lis, Michael; Plaut, Maxwell; Zai, Andrew
  • Advanced Materials Technologies, Vol. 1, Issue 2
  • DOI: 10.1002/admt.201600027

3D Bioprinting of Vascularized, Heterogeneous Cell-Laden Tissue Constructs
journal, February 2014

  • Kolesky, David B.; Truby, Ryan L.; Gladman, A. Sydney
  • Advanced Materials, Vol. 26, Issue 19
  • DOI: 10.1002/adma.201305506

Embedded 3D Printing of Strain Sensors within Highly Stretchable Elastomers
journal, June 2014

  • Muth, Joseph T.; Vogt, Daniel M.; Truby, Ryan L.
  • Advanced Materials, Vol. 26, Issue 36, p. 6307-6312
  • DOI: 10.1002/adma.201400334

3D-Printing of Lightweight Cellular Composites
journal, June 2014

  • Compton, Brett G.; Lewis, Jennifer A.
  • Advanced Materials, Vol. 26, Issue 34, p. 5930-5935
  • DOI: 10.1002/adma.201401804

Crystal structure of nylon 12
journal, June 1973

  • Inoue, Kazuo; Hoshino, Sadao
  • Journal of Polymer Science Part A-2: Polymer Physics, Vol. 11, Issue 6
  • DOI: 10.1002/pol.1973.180110604

Crystalline Transitions in Nylon 12
journal, August 1999


Orientation of the lamellar crystals in polyamide 12
journal, January 1993


Nanoparticle Agglomeration in Polymer-Based Solar Cells
journal, October 2010

  • Kiel, Jonathon W.; Eberle, Aaron P. R.; Mackay, Michael E.
  • Physical Review Letters, Vol. 105, Issue 16, Article No. 168701
  • DOI: 10.1103/PhysRevLett.105.168701

Shear-Induced Solution Crystallization of Poly(3-hexylthiophene) (P3HT)
journal, May 2014

  • Wie, Jeong Jae; Nguyen, Ngoc A.; Cwalina, Colin D.
  • Macromolecules, Vol. 47, Issue 10
  • DOI: 10.1021/ma500040k

Works referencing / citing this record:

An Ionomeric Renewable Thermoplastic from Lignin-Reinforced Rubber
journal, July 2019

  • Barnes, Sietske H.; Goswami, Monojoy; Nguyen, Ngoc A.
  • Macromolecular Rapid Communications, Vol. 40, Issue 13
  • DOI: 10.1002/marc.201970030

A fundamental understanding of whole biomass dissolution in ionic liquid for regeneration of fiber by solution-spinning
journal, January 2019

  • Nguyen, Ngoc A.; Kim, Keonhee; Bowland, Christopher C.
  • Green Chemistry, Vol. 21, Issue 16
  • DOI: 10.1039/c9gc00774a

Desirable plant cell wall traits for higher-quality miscanthus lignocellulosic biomass
journal, April 2019

  • da Costa, Ricardo M. F.; Pattathil, Sivakumar; Avci, Utku
  • Biotechnology for Biofuels, Vol. 12, Issue 1
  • DOI: 10.1186/s13068-019-1426-7

An Ionomeric Renewable Thermoplastic from Lignin‐Reinforced Rubber
journal, April 2019

  • Barnes, Sietske H.; Goswami, Monojoy; Nguyen, Ngoc A.
  • Macromolecular Rapid Communications
  • DOI: 10.1002/marc.201900059

3D Printing of Amylopectin‐Based Natural Fiber Composites
journal, August 2019

  • Jiang, Yijie; Raney, Jordan R.
  • Advanced Materials Technologies, Vol. 4, Issue 11
  • DOI: 10.1002/admt.201900521