NanoTrees: Making Paper Stronger than Steel. Robert Moon, PhD and Greg Schueneman, PhD Forest Biopolymer Science & Engineering

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NanoTrees: Making Paper Stronger than Steel Robert Moon, PhD and Greg Schueneman, PhD Forest Biopolymer Science & Engineering

What do they do? Parks & Forests Recreation Camping Forest Fires Wildlife & Ecosystem Wood Science R&D US Forest Service

US Forest Service Mission: Use science and technology to conserve and extend our nation's forest resources Promote healthy forests Promote forest-based economies Forest Products Laboratory: Established in 1910 Largest Federal Forestry Research Lab 55 Scientists, 190 total employees $19M/yr budget, ~$5M/yr on Nano

United States Forest Resource* 749 Million Acres 2/3 of America s forests are east of the Mississippi River Standing Forest Biomass >22 Billion Metric tons Growth to Harvest >2:1 Harvest ~236 million Metric tons/year (1%) *Forestland > 10% tree cover * Includes Alaska & Hawaii

Comparison of Selected Industries* Percent of Total Manufacturing GDP Chemical products 13.8% Computer and electronic products 8.9% Fabricated metal products 8.6% Machinery 7.3% Motor vehicles, bodies and trailers, and parts 6.3% Forest Products 6.2% Other transportation equipment 4.7% Plastics and rubber products 4.5% Petroleum and coal products 4.2% Electrical equipment, appliances and components 3.2% * Data from the U.S. Department of Commerce, 2005

Products Lumber Engineered Wood Tree Paper Packaging Wood-Polymer Composites

Products II Medical: Tree Eating:

Nanotechnology In Forestry For Forest Products Industry Incorporation of Nanomaterials Improve Performance & Function From Forest Products Industry Cellulose Nanomaterials New Applications & Products

New Products from Trees Chemicals Plastics Tree Fuels/Materials Materials:

Ma et al. 2011 Filtration Systems Printing Aerospace Industry Biomedical Packaging Chemical Industry Materials Opportunities Engineered Composites Battery Technology Automotive Industry Bio plastics Flexible Electronics Automation Machinery Okahisa et al., 2009

How to Do This? Nanotechnology: The understanding and control of matter at dimensions of 1 to 100 nanometers, where unique phenomena enable novel applications. New Properties/Functionality:

Size Scale 1 kilometer 10 3 1 mile runway 10 2 10 1 1 meter 1 centimeter 10 0 10-1 10-2 1 Yard 1 foot 1 inch Apple 1 millimeter 10-3 1 16 inch 10-4 10-5 1 micrometer 10-6 10-7 1 nanometer 10-8 10-9 Nanotechnology

Size Scale 1 millimeter 10-3 1 16 inch 10-4 Red Blood Cell 10-5 Bacteria 1 micrometer 10-6 Visible Light 1 μm Cellulose Nanocrystal (CNC) 10-7 Nanotechnology 10-8 1 nanometer 10-9 1 nm

Limin Tong/ Harvard University Human Hair Cellulose Nanocrystal

Tree Structure 50 µm Cellulose

Nanoparticles from Trees Cellulose Nanocrystals (CNCs)

Cellulose Microfibrils in Wood After chemical treatment that removes material surrounding microfibrils

Paper from Trees Isolated Wood Fibers > 95% Cellulose Other Pulps: Plants Cotton Hemp

Nanoparticles from Trees Cellulose Nanocrystals (CNCs)

1 millimeter Paper vs. Cellulose Nanocrystals 10-3 1 16 inch 10-4 Paper 10-5 1 micrometer 10-6 Visible Light 10-7 Cellulose Nanocrystals Nanotechnology 10-8 1 nanometer 10-9

Making Paper Stronger Than Steel Paper 50 µm Nano Cellulose film

Why? Smaller = Difference Paper Strength U Defects CNC film Less Defects Particle Films More Surface Bonding area

Tensile Strength, MPa High Strength Carbon Fiber Fiber Composites Paper Titanium HS Steel LS Steel Density, g/cm -3

See Through Nogi et al., Adv. Mater, 2009 Cellulose Film Paper 50 µm Nanosized Microsized Solar Rx

Tensile Strength, MPa New Properties Transparent: High Strength: Carbon Fiber Cellulose Film Paper Fiber Composites Titanium HS Steel LS Steel Paper Nogi et al., Adv. Mater, 2009, 20:1-4. Thermal Stability: Okahisa et al., Comp. Sci. Tech., 2009, 69:1958-1961. Density, g/cm -3

Ma et al. 2011 Filtration Systems Printing Aerospace Industry Biomedical Packaging Chemical Industry Materials Opportunities Engineered Composites Battery Technology Automotive Industry Bio plastics Flexible Electronics Automation Machinery Okahisa et al., 2009

Massively Parallel Manufacturing of? http://www.blpole.com/products_servic es/private_landowner_assistance.html

WOOD Chemistry Cellulose ~40% (crystalline and amorphous) Hemicellulose ~20-30% branched, hydrophilic Xylan, HW Galactoglucomannans, SW Lignin ~20-30% (Phenolic, hydrophobic) Extractives (1-10%)

FPL Cellulose Nanomaterials Project Capability to prepare semi-commercial scale batches of cellulose nano-crystals and nanofibrillar cellulose CNC/CNF Production @FPL ($1.7 M) CNC-SO4/-OH and CNF-COOH Containment facility Freeze drying CNF Production @ U of Maine ($1.5 M) NFC and Tempo NFC Spray drying

Current USA Nanocellulose Research Cellulose Nanotechnology Research Led by the USDA Forest Service Member of National Nanotechnology Initiative (NNI) Formal Industry Liaison to NNI Additional work through grants from NSF Supported by industry - Adv. Novel Materials Task Group - Standards & Annual International Cond. Industry and USDA Forest Service have formed an Industry- Government-Academia Cellulose Nanotechnology Research Consortium New NC Book!

Recyclable Materials - Possible Impact Solar Device: Reduce Environmental Footprint!! (COPE) Zhou, Y.H. et al.,. Sci. Rep. 3, 1536; DOI:10.1038/srep01536 (2013). 32

Nanoparticle Decoration of CNC s Emulsion deposition of nanoparticles onto CNC s Metals: Ag, Au, Cu, Pd, etc. Semiconductors: CdS, PdS, ZnS Sonal Padalkar,, J. R. Capadona,,),^ S. J. Rowan,),^,3 C. Weder,#,),3 Yu-Ho Won, Lia A. Stanciu,*,, and Robert J. Moon

Nanocomposites CNC/Epoxy 5 wt% CNC 2 wt% CNC Neat Epoxy + Stiffness = + 100% + Abrasion Resistance = +32% + Thermal Expansion = -25% + Thermal Stability = Maintained Moisture Uptake = Accelerated/Increased

Nanocellulose Reinforced Cement 20% increase in strength 0.7 wt.% Cellulose Nanocrystals 3,300 million tones of cement WW Complete conversion = 23 million tones of CNC used

Key Points Cellulose Nanoparticles (Trees & Plants) Size Matters New Properties New Composites Transparent High Strength Steel Nogi et al., Adv. Mater, 2009

To Learn More http://www.fpl.fs.fed.us/research/research_emphasis_areas/introduction.php?rea_id=4 http://www.tappinano.org/ Program Website: https://engineering.purdue.edu/nanotrees/ 37

Acknowledgements Rick Reiner & Alan Rudie of FPL for CNC s Momentive for epoxy & Hexion for amine Air Products for epoxy & amine U.S. Forest Service Grants 11-JV-11111129-117, 10-JV-11111104-066