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

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

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

3 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

4 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

5 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

6 Products Lumber Engineered Wood Tree Paper Packaging Wood-Polymer Composites

7 Products II Medical: Tree Eating:

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

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

10 Ma et al 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

11 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:

12 Size Scale 1 kilometer mile runway meter 1 centimeter Yard 1 foot 1 inch Apple 1 millimeter inch micrometer nanometer Nanotechnology

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

14 Limin Tong/ Harvard University Human Hair Cellulose Nanocrystal

15 Tree Structure 50 µm Cellulose

16 Nanoparticles from Trees Cellulose Nanocrystals (CNCs)

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

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

19 Nanoparticles from Trees Cellulose Nanocrystals (CNCs)

20 1 millimeter Paper vs. Cellulose Nanocrystals inch 10-4 Paper micrometer 10-6 Visible Light 10-7 Cellulose Nanocrystals Nanotechnology nanometer 10-9

21 Making Paper Stronger Than Steel Paper 50 µm Nano Cellulose film

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

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

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

25 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: Density, g/cm -3

26 Ma et al 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

27 Massively Parallel Manufacturing of? es/private_landowner_assistance.html

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

29

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

31 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!

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

33 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

34 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

35 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

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

37 To Learn More Program Website: 37

38 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 , 10-JV

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