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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
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UMaine Process Development Center
• Department of Chemical and Biological Engineering
• Professional Staff
• Self Supporting
• Not-for-Profit Contract Research Group
• Fee-for-Service Access
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Serving the Needs of Industry Since 1987
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UMaine Pilot Plant
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Stock Preparation and
Refining Loop
CNF Pilot Plant
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UMaine Pilot Plant
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Pilot paper machine with
advanced control systems
Web coater with
laminating station
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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
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Innovation
• Awarded five US
patents in last three
years
• All have industrial
co-inventor(s)
• All are licensed or in
the licensing process
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Commercialize
Validate
Innovate
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Operating Model
• Partner with Industry
• Collaboration with
other Institutions &
Agencies
• Example - J/V with
USDA Forest Products
Laboratory
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Academia
Private Public
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Cellulose Nanotechnology Research Consortium
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Cellulose Nanofibrils
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Cellulose Nanofibrils
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Cellulose Nanofibrils
• 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
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SEM image of isolated
Cellulose Nanofibrils
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Cellulose Nanotechnology
Source : Akira Isogai, University of Tokyo
CN
F
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Production Methods
• Cellulose Nanofibrils
• Cellulose Nanocrystals
• Other cellulose materials
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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
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Preparation Process
Reference: Rojas, et. al., 2010 Tappi International Nanotechnology Conference
27,800 4,170 1,390
Energy consumption (kW Hr/Tonne)
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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.
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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
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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
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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)
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UMaine CNF Pilot Facility
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• Spray Dryer o Several kg/day
capacity
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UMaine CNF Pilot Facility
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• Availability o Fee-for-service basis
o Samples available
• Kg to tonne
quantities
• CNF & CNC
• Slurry or dry
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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
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Applications
•Cellulose Nanofibrils
•Cellulose Nanocrystals
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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
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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
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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
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Ink density of Flexo Printed Samples
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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
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Ink density of Ink Jet Printed Samples
CNF improves ink jet print quality
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EKA Chemicals Inc.
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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
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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
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Polypropylene-based Composites
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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
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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
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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
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Contacts
Michael Bilodeau, Director
Email: mbilodeau@maine.edu
Phone: 207-581-2387
Pros Bennett, Managing Director
Email: pbennett@maine.edu
Phone: 207-949-4176
www.umaine.edu/pdc
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mailto:mbilodeau@maine.edumailto:pbennett@maine.edu
Questions
Sean Ireland
Email: sean.ireland@versopaper.com
Phone: 207-944-03267
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mailto:mbilodeau@maine.edu