Functionalized lignin nanofibres: An alternative platform to valueadded lignin-based materials

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1 Functionalized lignin nanofibres: An alternative platform to valueadded lignin-based materials John F. Kadla, Yingjie Li, Li-Ting Lin, Ian Dallmeyer, George Gao, Frank Ko

2 H H 3 C H Introduction - Lignin H 3 C H 3 C 2 nd most abundant terrestrial biopolymer H Complex heteropolymer & NLY natural source of aromatics H H 3 C H H 3 C CH 3 H H 3 C H CH 3 H H H CH 3 H H 3 C H H 3 C H H CH 3 H R H H 3 C H H CH 3 CH 3 H CH 3 H H 3 C H H H H H Pulp & Paper Industry extracts >50 million tonnes/yr ~2% (1.1 million tonnes) used commercially Low-value dispersants/binders Current market ~$700 million Add-on technologies exist to isolate lignin from kraft mills, thereby increasing boiler capacity and pulp production CH 3

3 H H 3 C H Introduction - Lignin H 3 C H 3 C pportunity exists to develop high-value applications H Type of lignin will dictate the value of products derived from it H H 3 C H H 3 C CH 3 H H 3 C H CH 3 H CH 3 H H H H 3 C H H 3 C H CH 3 CH 3 H H R H H 3 C H H CH 3 CH 3 H CH 3 H H 3 C H H H H H Power / Fuel Carbon source for energy production Lime kiln fuel / Lignin Pellets Macromolecules High molecular mass applications Adhesives PF / Foundry / Friction resins Polymers / Alloys Carbon fibres Aromatics Polymer building blocks Aromatic monomers (BTX) Phenol Vanillin

4 Lignin-based Carbon Fibres LBCF have been extensively studied US DE (RNL) has invested enormous resources Automotive / Wind Energy applications Carbon fibre value ~ $ /tonne (estimated lignin value >$2000/tonne) 60-70% of target (1.7GPa/170 GPa) Thermal Insulation (pitch-based CF) Lower value application (estimated lignin value ~$600/tonne) How to Improve Mechanical Performance & Potential Value

5 Lignin-based Carbon Fibres Improve performance/value by reducing fibre diameter i.e. Lignin-based Carbon Nanofibres Improve molecular order/decrease defects & inclusions Increased surface area / aspect ratio Potential in structural & non-structural applications Composites reinforced with continuous nanofibres out perform those containing short fibres, particles or whiskers utstanding Electrical, Thermal & Surface properties Energy storage (Li-ion batteries/supercapacitors) Shielding (EMI/RFI)

6 Lignin-based Carbon Fibres/Nanofibres Fabricated by electrospinning / force spinning Improve performance by fibre alignment / orientation Increasing carbonization temp increase performance Aligned Random Random Nanofibre 10 5 Aligned Nanofibre 0 Modulus (GPa) Conductivity (S/cm) 474 ± 81 nm 368 ± 62 nm

7 Lignin-based Carbon Fibres/Nanofibres Improve performance by inter-fibre bonding Control by heating rate and/or lignin-type Modulus (GPa) NonBonded Bonded Conductivity (S/cm) Tensile Strength (Mpa)!

8 Lignin-based Carbon Fibres/Nanofibres Improve performance by adding functional fillers Incorporation of magnetic nanoparticles (e.g. iron oxide) Coated with an elastomer -> EMI shielding materials 1000 o C lignin nanofiber + iron salt 1379 ± 326 nm lignin carbon nanofiber + magnetic nanoparticles 780 ± 119 nm Broad frequency High shielding efficiency Tune performance with lignin/nanoparticle concentration

9 Lignin-based Carbon Fibres/Nanofibres Improve performance by surface functionalization Creating ionic responsive surfaces Surface grafting of ionic responsive polymer SI-ATRP (PNIPAM) 653 Hydrophobic ± 29 nm 1041 ± Hydrophobic 51 nm Nanofibre mat expand in water & contracted Hydrophilic in Na 2 S 4 Ionic responsive separation / purification devices

10 Lignin-based Carbon Fibres/Nanofibres Improve performance/value by lignin blending Blending lignin fractions with different thermal behaviour Thermal processing of lignin blends resulted in a phase-separated system o C 2 Dry Moist Dry Moisture-responsive materials capable of reversible changes in shape

11 Conclusions Lignin-based nanofibres offer a unique platform to develop value-added materials Fibre alignment / inter-fibre bonding can significantly improve the strength and conductivity of lignin-based carbon nanofibres Potential for supercapacitors/energy storage Electromagnetic properties can be successfully introduced into lignin-based carbon nanofibres (via In-situ method) Shielding effectiveness was higher than that of PAN-based nanofiber Lignins unique chemistry and thermal properties enables the development of functionalized/stimuli-responsive nanofibrous materials Filtration/separation and Sensor applications

12 Thank You

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