Production and Application of Cellulose Nanomaterials · Production and Application of Cellulose...

Production and Application of Cellulose Nanomaterials

Michael Bilodeau

Director, Process Development Center

University of Maine

Sean Ireland

Manager, New Technologies

Verso Paper Corp.

Outline • UMaine Process Development Center

• Cellulose Nanotechnology o Production methods

o Applications

o Corn Fiber

• Commercial Status

2 April 29, 2014 Tate & Lyle Meeting - Nashville, TN

UMaine Process Development Center

• Department of Chemical and Biological Engineering

• Professional Staff

• Self Supporting

• Not-for-Profit Contract Research Group

• Fee-for-Service Access

3

Serving the Needs of Industry Since 1987

April 29, 2014 Tate & Lyle Meeting - Nashville, TN

UMaine Pilot Plant

4

Stock Preparation and

Refining Loop

CNF Pilot Plant


UMaine Pilot Plant

5

Pilot paper machine with

advanced control systems

Web coater with

laminating station


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

6 Valley of Death

Basic Research

Applied Research

Production/ Public Access

Development Demonstration Commercialization

-$$

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

+$$

Business & Markets Drive

Science & Technology

Drives

$ Fed Grants – NIH,NSF, etc.

$ Fed Grants DoD ,DOE

,USDA.

$$ -MTI Seed Grants, Development Awards, ACF ,

Fed SBIR

$ SEGF--VC --Equity-- Debt

$ Company Funds – Family, Fools and Friends


Innovation

• Awarded five US

patents in last three

years

• All have industrial

co-inventor(s)

• All are licensed or in

the licensing process

7

Commercialize

Validate

Innovate


Operating Model

• Partner with Industry

• Collaboration with

other Institutions &

Agencies

• Example - J/V with

USDA Forest Products

Laboratory

8

Academia

Private Public


Cellulose Nanotechnology Research Consortium


11

Cellulose Nanofibrils


12




• Fibril width 3 – 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

13

SEM image of isolated



14

Cellulose Nanotechnology

Source : Akira Isogai, University of Tokyo

CN

F


Production Methods

• Cellulose Nanofibrils

• Cellulose Nanocrystals

• Other cellulose materials

April 29, 2014 Tate & Lyle Meeting - Nashville, TN 15

Plant Matter Pre-

treatment Fibrillation

Post-treatment

Cellulose NanoFibers

Preparation of Cellulose NanoFibrils

Wood

Corn Stover

Grass

Bagasse

Tunicates

Kraft Pulping

Refining

Enzymatic

TEMPO

Carboxy

Methylation

Refining

Grinding

Homogenization

Extrusion

Cryo-Crushing

Collision

Refining

Grinding

Cationization

Siloxane treatment

Drying

Early Cellulose Nanofibril Process

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Reduced to practice by

ITT Rayonier, 1977

Patented in 1983 – Turbak, et. al.


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Preparation Process

Homogenizer Mass Colloider/ Grinder Microfluidizer


19

Preparation Process

Reference: Rojas, et. al., 2010 Tappi International Nanotechnology Conference

27,800 4,170 1,390

Energy consumption (kW Hr/Tonne)


Preparation Process

• Mechanical Processes o Broader size distribution

o Wider fibril diameters

o Native surface chemistry

o Lower cost

Mass Colloider/Grinder

Microfluidizer

Pohler, Tiina et.al., 2012 Tappi International Conference on Nanotechnology for Renewable Materials, Montreal, Canada. June 5-7, 2012.


Preparation Process

• Chemical Processes o Narrow size distribution

o Smaller fibril diameters

o Highly charged surfaces

o Chemically modified surfaces

o More transparent films

TEMPO Oxidation

Carboxymethylation Cationization

Pohler, Tiina et.al., 2012 Tappi International Conference on Nanotechnology for Renewable Materials, Montreal, Canada. June 5-7, 2012.


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Preparation Process

Low Consistency Refiners @ UMaine


University of Maine Proprietary

Cellulose Nanofiber Process

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• Novel method to produce CNF

• Commercially scalable

• Low cost

• Patent pending technology

• High performance additive

• Wide range of applications


UMaine CNF Pilot Facility

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• Capability o Refiner CNF

• Pre-treatment

o Mass Colloider Grinder

• Capacity o 1 ton/day

o Slurry form (3% solids)



28

• Spray Dryer o Several kg/day

capacity



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• Availability o Fee-for-service basis

o Samples available

• Kg to tonne

quantities

• CNF & CNC

• Slurry or dry


Samples of Cellulose Nanomaterials Distributed

April 2013 – April 2014

• Total 160 Entities – 28 Countries o 60 Universities/Government Labs

o 100 Companies

• CNF / CNC split fairly even


Applications

•Cellulose Nanofibrils

•Cellulose Nanocrystals


CNF Applications

Paper and Paper Coating

• CNF addition to paper furnish o Lowers air permeability

o Improves sheet smoothness

o Improves bond dependent properties

• Targeted applications o Release Papers

o Barrier and Packaging

o Printing and Writing


CNF as a Furnish Additive

164%

61%

11%

30%

-6% -6% -25%

25%

75%

125%

175%

Porosity Bond Stiffness Tensile Tear Bulk

% Change from Control

90 gsm Uncoated Freesheet


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Commercial Scale-up

Release Base Paper Surface

Control – 208 X CN 200 – 245 X

5% CNF added


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 µm April 29, 2014

Tate & Lyle Meeting - Nashville, TN 36

Ink density of Flexo Printed Samples

37

Printed with a water-based pigment ink

by flexographic printing tester

0.6

0.7

0.8

0.9

1

1.1

uncoated 0.5 1.5 3

Ink

den

sity

Coat weights with CNF, g/m2


Ink density of Ink Jet Printed Samples

CNF improves ink jet print quality

April 29, 2014

EKA Chemicals Inc.

Tate & Lyle Meeting - Nashville, TN 38

CNF Applications

Composites

• CNF properties o Strength to weight ratio

o High L/D ratio

o High surface area

o Relatively low cost

o Renewable material

o Promising EHS profile

• Targeted applications o Thermoplastics reinforcing and filling

o Thermoset resin reinforcing and filling

o Paints, inks and coatings


Polypropylene-based Composites

• Polypropylene with 10% CNF added

o Increased flexural stress by more than 30%

o Increased flexural modulus by more than 50%

o Maintained impact strength

• CNF addition compatible with existing processing

equipment

• Incorporated as much as 20% CNF in PP


Polypropylene-based Composites


6 wt% CNF in polypropylene

CNF Applications

• Other applications under development

o Rheology modifier

o Structural Products

o Insulating foams

o Cement additive

o Acoustical panels


CNC Applications

• CNC properties

o Strength to weight ratio

o Low thermal expansion

o Strong hydrogen bonding – no additional binder required

o Relatively high cost

o Renewable material

o Promising EHS profile

• Targeted applications o Transparent films

o Printed electronics

o High strength cement


Commercialization Status

• Three existing commercial CNF installations

o All refiner-based

o Two domestic, one foreign

o Two paper applications, one consumer products

o One operating for more than 10 years

• Commercial activity

o Seven commercial paper machine evaluations since Q2

2012

o Additional trial scheduled for Q3 2014

o CNF backlog exceeds 2,000 lbs.

o Robust activity in validating paper property and process improvements


Contacts

Michael Bilodeau, Director

Email: [email protected]

Phone: 207-581-2387

Pros Bennett, Managing Director


Phone: 207-949-4176

www.umaine.edu/pdc


mailto:[email protected]:[email protected]

Questions

Sean Ireland


Phone: 207-944-03267

mailto:[email protected]

Production and Application of Cellulose Nanomaterials · Production and Application of Cellulose...

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