production and application of cellulose nanomaterials · cellulose nanomaterials michael bilodeau...

Production and Application ofCellulose Nanomaterials

Michael Bilodeau

Director, Process Development Center

University of Maine

Outline

• UMaine Process Development Center

• Introduction to Cellulose Nanomaterials

• Partnerships

• Applications

• Commercialization Activities

May 19, 2015 E2 Tech Meeting - BioBased Maine 2

UMaine Process Development Center

• Department of Chemical and Biological Engineering

• Not-for-Profit Contract Research Group

• Self Supporting

• Professional Staff

• Fee-for-Service Basis


Serving the Needs of Industry Since 1987

Innovation Continuum – R,D,& C Its Cyclical – not Linear


Valley of Death

Basic Research

Applied Research

Production/Public Access

DevelopmentDemonstration Commercialization

-$$

Univ and Non-profit R&D Commercial R&D

+$$

Business & Markets Drive

Science & Technology Drives

$ Fed Grants –NIH,NSF, etc.

$ Fed GrantsDoD ,DOE ,USDA.

$$ -Regional & State Seed Grants, Development Awards, Fed SBIR

$$ VC --Equity-- Debt

$ Company Funds – Family, Fools and Friends

Operating Model

• Partner with Industry

• Collaborate with other Institutions & Agencies

• Coordinate Project Activities


Academia

PrivatePublic

Pilot Capabilities

• Pilot paper machine

6

• Web coater / laminator

May 19, 2015 E2 Tech Meeting - BioBased Maine

Example of Private-Public Partnership

High Speed Pilot Coater - Client Owned and Operated


Example of Private-Public Partnership

Specialty Paper Machine - Client Owned and Operated


Introduction to Cellulose Nanomaterials


Cellulose based nanoparticles

Cellulose Based MaterialsCellulose Derivatives

Functionalize -OH

• Cellulose Acetate• Hydroxyethyl Cellulose• Methyl cellulose• Carboxymethyl Cellulose

Fiber

10

Lumber

Microcrystalline Cellulose


Courtesy Dr. Robert Moon USFS

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Cellulose Nanofibrils

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What are Cellulose Nanomaterials (CNs)?

12

• Nano-sized particles isolated from:• trees, plants, algae

• Highly ordered cellulose chains: • parallel stacking of chains• ordered & disordered domains

“Nano Effect”:• Fewer defects• Aligned chains

Properties:• Length• Aspect ratio• Crystallinity



Dufresne et al., J. App. Poly. Sci., 1997

Cellulose Nanofibrils (CNF)

Cellulose Nanocrystals (CNC)

13

Several “Flavors” of CNs

Acid HydrolysisAll

Biomass

Chem/Mech

Mechanical

Particles:• Source• Method

Properties:• Length• Aspect Ratio• Branching• Crystallinity

Rod-like•D=3-20 nm•L=50-500 nm•Low branching

Fibril-like:•D=3-40 nm•L=100s nm - >1µm•Branching



http://4.bp.blogspot.com/-upi6rmFpi6I/UT2v7_UGkXI/AAAAAAAAMtc/yEE9iFyuTBk/s1600/ice-cream-cone-soap-set.jpghttp://4.bp.blogspot.com/-upi6rmFpi6I/UT2v7_UGkXI/AAAAAAAAMtc/yEE9iFyuTBk/s1600/ice-cream-cone-soap-set.jpg


May 19, 2015E2 Tech Meeting - BioBased Maine14

• Fibril width 10 – 100 nm• Lengths up to 10’s of microns• High aspect ratio (100 – 1000)• Large specific surface area

(100-200 g/m2 )

x 100k 200 nm

SEM image of isolated


History of Nanocellulose

E2 Tech Meeting - BioBased MaineMay 19, 2015

Reduced to practice by ITT Rayonier, 1977Patented in 1983 – Turbak, et. al.

15

CNF Related Patents


CNF Related Publications


http://blog.luxresearchinc.com/blog/wp-content/uploads/2014/11/Insight1_11_23_14.pnghttp://blog.luxresearchinc.com/blog/wp-content/uploads/2014/11/Insight1_11_23_14.png

Why CNF Again?

• Three Major Driving Forces– Breakthrough lower cost manufacturing methods

– New, novel application technology

– National priorities driving federal funding


Scalable

Low Energy

Low Capital

Applications

Overcoming Commercial Barriers

Partnerships


US Forest Service#1 Priority – Forest Fire Suppression

•>$1 MM/hr spent fighting forest fires

•More than ½ of USFS annual Budget

•Millions of acres need “Restoration”

•Only 200,000 acres/yr restored.


UMaine CNF Pilot Facility

• Capability– Refiner CNF

• Pre-treatment

– Mass Colloider Grinder

• Capacity– 1 ton/day

– Slurry form (3% solids)



• Availability– Fee-for-service basis

– Samples available

• Kg to tonne quantities

• CNF & CNC

• Slurry or dry



• Spray Dryer – Several kg/day capacity


Cellulose Nanomaterials Distributed

between April 2013 – February 2015

• Samples provided to – 167 private companies

– 119 academic institutions

– 25 research centers

– In 35 different countries

May 19, 2015 27E2 Tech Meeting - BioBased Maine

Applications


30

Rheology Modifier• Paints• Cosmetics• Food• Adhesives

Separators/Barrier• Filtration• Batteries• Pumps• …

Commercial Application Areas

Specialty Packaging

Herrera et al.

Vartiainen et al.

Flexible Electronics• Self Powered• Display• Solar• LED• … Yano et al.

Tissue Engineering

• Scaffolds• Bandages• Ligament• Blood Vessels• Drug Delivery

Deng et al.

Continuous Fibers

Dong et al., 2012

• Reinforcement• Textiles• Woven• …

Specialty Cements

Cao et al.

• Foamed• Panel• Siding• …

Foams

Paakko et al., Soft Matter, 2008

• Acoustic• Structural• Thermal• …

Production• Yields• Process• Costs

May 19, 2015 E2 Tech Meeting - BioBased MaineCourtesy Dr. Robert Moon USFS

http://heavenlyhomemakers.com/wp-content/uploads/2013/06/maple_syrup.pnghttp://heavenlyhomemakers.com/wp-content/uploads/2013/06/maple_syrup.pnghttp://www.innventia.com/en/http://www.innventia.com/en/http://www.performancebiofilaments.com/http://www.performancebiofilaments.com/


Commercial Scale-upRelease Base Paper Surface

Control – 208 X CN 200 – 245 X

5% CNF added

Stain ResultsSilicone Coated Release Base


A. Control Base B. CN 200 Base

Pilot paper machine samples 5% CNF

Paper Coated with CNF

X 500

X 500

X 500

0.5 g/m2 coating

1.5 g/m2 coating

3.0 g/m2 coating

20 µm 20 µm

20 µmMay 19, 2015

E2 Tech Meeting - BioBased Maine 33

Ink density of Ink Jet Printed Samples


CNF improves ink jet print quality

EKA Chemicals Inc.

Polymer Composites

Neat Silicone 1% L-CNC 2% L-CNC

1% CNC in PLA

Agglomerates

1% TEMPO CNF in PLA

Conventional Bleached CNC & CNFVery poor dispersion

Neat PE 1% L-CNC in PE

Neat PHB 1% L-CNC in PHB

BioPlus L-CNCVery uniform dispersion

Neat PS 1% L-CNC in PS0.3% L-CNC in PLA


BioPlus Compostable Bags● Strong ● Renewable ● Compostable ● PLA + BioPlus L-CNC


Vehicle Light Weighting Project• Objective: Development of a sprayable binder resin

system containing nanocellulose as a reinforcing phase to replace steel in seating assemblies– Opportunity to achieve commercial application on

electric vehicles

• Results: Clark ATL has successfully dispersed L-CNC in the hydrophobic resin system of choice

• Impact: Reducing a vehicle’s weight by just 10 percent can improve fuel economy by 6-8 percent

– U.S. DOE’s target vehicle weight reduction is 50% by 2050.

– According to the DOE the limiting factor in use of lightweight materials in vehicles is availability of sufficient quantities at affordable cost1

ReinforcingMaterial Density (g/cm3)

Calcium carbonate 2.71

Talc 2.69

E-glass fiber 2.5

Carbon fiber 1.8

Nanocellulose 1.5


3D Printing Project

• Objective: Reinforce 3D printing feedstock with high temperature stability, highly dispersableBioPlus-L™ to obtain desired mechanical properties for load-bearing parts

• Impact: Replace high cost, peutroleum–based carbon fiber as reinforcing agent for high temperature polymers like ABS, PLA, Nylon 6,6, and PC with renewable, biobased nanocellulose.

• Phase II Goal: Print a golf cart from nanocellulose reinforced polymer using Oak Ridge’s Big Area Manufacturing (BAAM) facility.


CNF Films


Industrial Epoxy Coatings

40Link

Link

Link

Link


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Commercialization Activities



Ref: Shatkins, JTappi Nano ConferenceVancouver, BC 2014.

Commercial Start-ups

• American Process Inc. – Thomaston, GA

– BioPlus “Pre-commercial” plant - 0.5 tpd capacity

– CNF and CNC capacity

– Started-up April 2015


API’s Thomaston Biorefinery

Fractionation and Cellulose Separation

Biomass

Was

he

d

cellu

lose

Regenerated Solvent, SO

2

Liquor (hemicelluloses solvent, SO

2, lignin)

Enzymatic Hydrolysis

Glucose to

chemicals conversion Hemicelluloses Sugars to Ethanol / Butanol

Lignin to energy and chemical applications

Hemicelluloses Auto Hydrolysis

Chemical Regeneration

Cellulose products


BioPlus Demonstration Line

Screening & Cleaning

Mechanical Treatment

Product Cooling & Storage

Bleach Plant

½ ton per dayStart-up in April 2015

Located at Thomaston Biorefinery


Commercial Start-ups

• Paperlogic Paper – Turners Falls, MA

– Commercial CNF plant - 2 tpd capacity

– Internal and merchant sales

– Started-up May 14, 2015


Contacts

Michael Bilodeau, Director

Email: [email protected]

Phone: 207-581-2387

Pros Bennett, Managing Director

Email: [email protected]

Phone: 207-949-4176

www.umaine.edu/pdc

mailto:[email protected]:[email protected]

production and application of cellulose nanomaterials · cellulose nanomaterials michael bilodeau...

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