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Biobased Nanostructural Materials: New Opportunities for the Forest Products Industry?

Biobased Nanostructural Materials: New Opportunities for the Forest Products Industry?. Joseph J. Bozell Forest Products Center – Biomass Chemistry Laboratories University of Tennessee Knoxville, TN 37996 jbozell@utk.edu. Presentation Topics. Renewables and the biorefinery

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Biobased Nanostructural Materials: New Opportunities for the Forest Products Industry?

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  1. Biobased Nanostructural Materials: New Opportunities for the Forest Products Industry? Joseph J. Bozell Forest Products Center – Biomass Chemistry LaboratoriesUniversity of Tennessee Knoxville, TN 37996 jbozell@utk.edu

  2. Presentation Topics • Renewables and the biorefinery • A few examples of carbohydrate nanotechnology opportunities • Self assembling carbohydrate based bolaforms and their interaction with cellulose

  3. The Biorefinery as a Unifying Concept Outputs (Conversion) Inputs (Supply) Butadiene Polylactic acid Pentanes, pentene BTX Succinic acid Phenolics Ethanol Organic acids Furfural Polyols Resorcinol Levulinic acid Levoglucosan Peracetic acid Tetrahydrofuran Anthraquinone Sorbitol others Building blocks (Separation) Corn Switchgrass Potatoes Sorghum Soybeans Apple pomace Jerusalem artichoke Guayule Beet molasses Sugar cane Wood Residues Starch Cellulose Lignin Other Carbohydrates Oils

  4. Forest Products Matrix Wood processing Timber products, plywood, OSB, etc. Wood as wood; relative value low Conventional Kraft Wood for paper and fuel; relative value low to mid Cellulose Black liquor Forest (renewable) resource Alkali extraction Cellulose Hemicellulose Black liquor Wood for paper, fuel, and commodities; relative value low to mid Advanced fractionation Emerging Cellulose Hemicellulose Lignin Sugars Extractives Wood for chemicals; relative value mid to high

  5. Strategic Goals for the Use of Renewable Feedstocks and Biorefinery Development • Dramatically reduce, or even end, dependence on foreign oil (a displacement and energy component) • Spur the creation of a domestic bioindustry (an enabling and economic component) Integration of chemicals with fuels will simultaneously address both goals.

  6. Impacts of Product Integration with Fuels R. Dorsch and R. Miller, World Congress on Industrial Biotechnology and Bioprocessing, April 2004, Orlando, FL

  7. The DOE “Top 12” products from sugars: Biomass as a feedstock for products is an issue of current high interest to a wide range of industrial segments. Develop technology to make inexpensive building blocks of defined carbon number and businesses will develop. Lignin product development is important. What Product Should We Make? Technology development will have more impact than pre-identification of products with both fundamental and applied research needed! Available at http://www.nrel.gov/docs/fy04osti/35523.pdf

  8. Potential Market Impact of Nanotechnology • NSF: $1 trillion by 2015 • BCC research (www.bccresearch.com): • $9.4 billion (2005) • $10.5 billion (2006) • $25.2 billion (2011) • UK estimate: $1.275 trillion by 2010 (www.uktradeinvest.gov.uk) • Draper Fisher Jarvetson: $600 billion by 2012

  9. What Will The Forest Products Biorefinery Look Like? Woody biomass Lignin based aromatic chemicals Sugar/cellulose based chemicals Balance point? Biobased fuels Pulp and paper products 2005: “Nanotechnology for the Forest Products Industry”

  10. What Will The Forest Products Biorefinery Look Like? Woody biomass Lignin based aromatic chemicals Sugar/cellulose based chemicals Balance point? Biobased fuels Pulp and paper products

  11. Natural Polymers as Templates Review: H. Sieber, Mat. Sci. Engineering2005, 412, 43

  12. “Artificial Fossils” from Cellulose Templates ZrO2 - Chem. Comm. 05/795 catalysts Au/TiO2 - Chem. Comm. 04/1008 photocatalysts Chem. Mater. 05/17/3513 SnO2, gas sensing ITO - J. Mat. Chem. 06/16/292 electronics Ag - Chem. Comm. 05/795

  13. Cellulose/CaCO3 Nanocomposites as Artificial Bone • Organized polymers can template CaCO3 • Bacterial cellulose forms a fine, highly organized template • Acid functionalization promotes biomineralization J. Biomater. Sci. Polym. Ed. 06/17/435 Biomaterials 06/27/4661

  14. Medical diagnostics, biochips, biosensors Nanomolar sensitivity for detection of biotin-containing species Cellulose provides a new set of support properties PVA/cellulose composites Magnetic alignment of cellulose nanofibers Improved mechanical properties Biological and Polymer Applications Angew. Chem. Int. Ed. 06/45/2883 AFM Appl. Phys. A 07/87/641

  15. Bolaforms As Self Assembling Systems

  16. Carbohydrate and glycal based bolaforms

  17. Glycal Based Bolaform Research Schematic

  18. Ferrier Bolaform Synthesis

  19. Bolaform Synthesis Summary

  20. TEM Images of Nanostructures Thompson, Kim (Purdue), Dunlap, Tice Shimizu et al, Adv. Mater.2005, 17, 2732

  21. Hypothetical Assembly Process T. Shimizu, Macromol. Rapid Commun.2002, 23, 311 T. Shimizu, Carb. Res.2000, 326, 56 Glycal analog Antiparallel Parallel

  22. X-ray Structures of Bolaform Crystals Glucal; ,-diastereomer Glucal; ,-diastereomer Galactal, ,-diastereomer Masuda, Shimizu, Carb. Res. 2000, 326, 56

  23. Comparative Hydrogen Bonding Networks

  24. Disaccharide Bolaform Headgroups

  25. Chemical Stabilization and Bioactive Materials Patterning: Hesse and Kondo, Carb. Polym.2005, 60, 457; Kondo et al, PNAS2002, 99, 14008

  26. Bolaform Crystal Formation in Presence of Cellulose 200µm 200µm No avicel, 20% bola in DMAc/LiCl 4% avicel, 20% bola (based on avicel) in DMAc/LiCl 200µm 200µm 2% avicel, 20% bola in DMAc/LiCl, edge of drop. Note transition from crystals to greater structure. Trunk and branches

  27. SEM of Cellulose Films No bolaform added

  28. AFM Images of Bola/Cellulose Film 4% avicel in DMAc/LiCl 4% avicel in DMAc/LiCl, 5% bola

  29. Alignment of Carbohydrates Hypothetical organization of cellobiose Organization/self assembly into nanostructures Maintenance of H-bonding network Additional stabilization through -bonding and alignment of hydrophobic chains?

  30. Conclusions and Acknowledgements • Renewable sources of carbon offer unique opportunities for the production of chemicals, fuels and materials. • The forest biorefinery of the future must integrate new product opportunities with their traditional product lines • Carbohydrate based bolaforms could offer an entry into the rapidly growing field of nanostructural materials, but more work is needed to control the process • Interaction of bolaforms with natural polymers may lead to new families of uniquely patterned materials • Thanks! To Thomas Elder, David Thompson, John Dunlap, Sebastien Vidal, Joseph Bullock Funding: • USDA/NRI

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