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 Laboratories University of Tennessee Knoxville, TN 37996 [email protected] Presentation Topics. Renewables and the biorefinery

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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 LaboratoriesUniversity of Tennessee

Knoxville, TN 37996

[email protected]


Presentation topics
Presentation Topics Forest Products Industry?

  • Renewables and the biorefinery

  • A few examples of carbohydrate nanotechnology opportunities

  • Self assembling carbohydrate based bolaforms and their interaction with cellulose


The biorefinery as a unifying concept
The Biorefinery as a Unifying Concept Forest Products Industry?

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


Forest products matrix
Forest Products Matrix Forest Products Industry?

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


Strategic goals for the use of renewable feedstocks and biorefinery development
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.


Impacts of product integration with fuels
Impacts of Product Integration with Fuels Biorefinery Development

R. Dorsch and R. Miller, World Congress on Industrial Biotechnology and Bioprocessing, April 2004, Orlando, FL


What product should we make

The DOE “Top 12” products from sugars: Biorefinery Development

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


Potential market impact of nanotechnology
Potential Market Impact of Nanotechnology Biorefinery Development

  • 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


What will the forest products biorefinery look like
What Will The Forest Products Biorefinery Look Like? Biorefinery Development

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”


What will the forest products biorefinery look like1
What Will The Forest Products Biorefinery Look Like? Biorefinery Development

Woody

biomass

Lignin based aromatic

chemicals

Sugar/cellulose based

chemicals

Balance point?

Biobased

fuels

Pulp and paper

products


Natural polymers as templates
Natural Polymers as Templates Biorefinery Development

Review: H. Sieber, Mat. Sci. Engineering2005, 412, 43


Artificial fossils from cellulose templates
“Artificial Fossils” from Cellulose Templates Biorefinery Development

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


Cellulose caco 3 nanocomposites as artificial bone
Cellulose/CaCO Biorefinery Development3 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


Biological and polymer applications

Medical diagnostics, biochips, biosensors Biorefinery Development

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


Bolaforms as self assembling systems
Bolaforms As Self Assembling Systems Biorefinery Development




Ferrier bolaform synthesis
Ferrier Bolaform Synthesis Biorefinery Development


Bolaform synthesis summary
Bolaform Synthesis Summary Biorefinery Development


Tem images of nanostructures
TEM Images of Nanostructures Biorefinery Development

Thompson, Kim (Purdue), Dunlap, Tice

Shimizu et al, Adv. Mater.2005, 17, 2732


Hypothetical assembly process
Hypothetical Assembly Process Biorefinery Development

T. Shimizu, Macromol. Rapid Commun.2002, 23, 311

T. Shimizu, Carb. Res.2000, 326, 56

Glycal analog

Antiparallel

Parallel


X ray structures of bolaform crystals
X-ray Structures of Bolaform Crystals Biorefinery Development

Glucal; ,-diastereomer

Glucal; ,-diastereomer

Galactal, ,-diastereomer

Masuda, Shimizu, Carb. Res. 2000, 326, 56


Comparative hydrogen bonding networks
Comparative Hydrogen Bonding Networks Biorefinery Development


Disaccharide bolaform headgroups
Disaccharide Bolaform Headgroups Biorefinery Development


Chemical stabilization and bioactive materials
Chemical Stabilization and Bioactive Materials Biorefinery Development

Patterning:

Hesse and Kondo, Carb. Polym.2005, 60, 457;

Kondo et al, PNAS2002, 99, 14008


Bolaform crystal formation in presence of cellulose
Bolaform Crystal Formation in Presence of Cellulose Biorefinery Development

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


Sem of cellulose films
SEM of Cellulose Films Biorefinery Development

No bolaform added


Afm images of bola cellulose film
AFM Images of Bola/Cellulose Film Biorefinery Development

4% avicel in DMAc/LiCl

4% avicel in DMAc/LiCl, 5% bola


Alignment of carbohydrates
Alignment of Carbohydrates Biorefinery Development

Hypothetical organization of cellobiose

Organization/self assembly into

nanostructures

Maintenance of

H-bonding network

Additional stabilization

through -bonding and

alignment of hydrophobic

chains?


Conclusions and acknowledgements
Conclusions and Acknowledgements Biorefinery Development

  • 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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