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?

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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

  • 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

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

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

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:

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

  • 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?

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?

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

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


Artificial fossils from cellulose templates

“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


Cellulose caco 3 nanocomposites as artificial bone

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


Biological and polymer applications

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


Bolaforms as self assembling systems

Bolaforms As Self Assembling Systems


Carbohydrate and glycal based bolaforms

Carbohydrate and glycal based bolaforms


Glycal based bolaform research schematic

Glycal Based Bolaform Research Schematic


Ferrier bolaform synthesis

Ferrier Bolaform Synthesis


Bolaform synthesis summary

Bolaform Synthesis Summary


Tem images of nanostructures

TEM Images of Nanostructures

Thompson, Kim (Purdue), Dunlap, Tice

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


Hypothetical assembly process

Hypothetical Assembly Process

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

Glucal; ,-diastereomer

Glucal; ,-diastereomer

Galactal, ,-diastereomer

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


Comparative hydrogen bonding networks

Comparative Hydrogen Bonding Networks


Disaccharide bolaform headgroups

Disaccharide Bolaform Headgroups


Chemical stabilization and bioactive materials

Chemical Stabilization and Bioactive Materials

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

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

No bolaform added


Afm images of bola cellulose film

AFM Images of Bola/Cellulose Film

4% avicel in DMAc/LiCl

4% avicel in DMAc/LiCl, 5% bola


Alignment of carbohydrates

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?


Conclusions and acknowledgements

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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