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

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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_at_utk.edu

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Presentation Topics

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

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The Biorefinery as a Unifying Concept
Outputs (Conversion)
Inputs (Supply)
Butadiene Polylactic acid Pentanes,
pentene BTX Succinic acid Phenolics Ethanol Organi
c acids Furfural Polyols Resorcinol Levulinic
acid Levoglucosan Peracetic acid Tetrahydrofuran A
nthraquinone 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
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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
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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.
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Impacts of Product Integration with Fuels
Scenario 1 Fossil Fuel and PDO Scenario 2 Independent BioPDO and EtOH Scenario 3 Integrated Corn Biorefinery
Economic Pretax Return 11 3 20
Environment Total Energy Down 72 vs scenario 1
Petroleum Down 90 vs scenario 1
Natural gas Down 54 vs scenario 1
R. Dorsch and R. Miller, World Congress on
Industrial Biotechnology and Bioprocessing, April
2004, Orlando, FL
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What Product Should We Make?

• 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.

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/355
23.pdf
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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

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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
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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
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Natural Polymers as Templates
Review H. Sieber, Mat. Sci. Engineering 2005,
412, 43
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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
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Cellulose/CaCO3 Nanocomposites as Artificial Bone
J. Biomater. Sci. Polym. Ed. 06/17/435
Biomaterials 06/27/4661

• Organized polymers can template CaCO3
• Bacterial cellulose forms a fine, highly
  organized template
• Acid functionalization promotes biomineralization

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Biological and Polymer Applications

• Medical diagnostics, biochips, biosensors
• Nanomolar sensitivity for detection of
  biotin-containing species
• Cellulose provides a new set of support properties

Angew. Chem. Int. Ed. 06/45/2883

• PVA/cellulose composites
• Magnetic alignment of cellulose nanofibers
• Improved mechanical properties

AFM
Appl. Phys. A 07/87/641
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Bolaforms As Self Assembling Systems
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Carbohydrate and glycal based bolaforms
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Glycal Based Bolaform Research Schematic
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Ferrier Bolaform Synthesis
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Bolaform Synthesis Summary
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TEM Images of Nanostructures
Thompson, Kim (Purdue), Dunlap, Tice
Shimizu et al, Adv. Mater. 2005, 17, 2732
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Hypothetical Assembly Process
T. Shimizu, Macromol. Rapid Commun. 2002, 23, 311
T. Shimizu, Carb. Res. 2000, 326, 56
Glycal analog
Parallel
Antiparallel
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X-ray Structures of Bolaform Crystals
Glucal ?,?-diastereomer
Glucal ?,?-diastereomer
Galactal, ?,?-diastereomer
Masuda, Shimizu, Carb. Res. 2000, 326, 56
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Comparative Hydrogen Bonding Networks
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Disaccharide Bolaform Headgroups
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Chemical Stabilization and Bioactive Materials
Patterning Hesse and Kondo, Carb. Polym. 2005,
60, 457 Kondo et al, PNAS 2002, 99, 14008
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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
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SEM of Cellulose Films
No bolaform added
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AFM Images of Bola/Cellulose Film
4 avicel in DMAc/LiCl
4 avicel in DMAc/LiCl, 5 bola
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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?
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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