Production and Application of Cellulose Nanomaterials

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1 Production and Application of Cellulose Nanomaterials Sean Ireland Manager, New Technologies Verso Paper Corp. Michael Bilodeau Director, Process Development Center University of Maine

2 Outline UMaine Process Development Center Cellulose Nanotechnology o Production methods o Applications o Corn Fiber Commercial Status 2

3 UMaine Process Development Center Serving the Needs of Industry Since 1987 Department of Chemical and Biological Engineering Professional Staff Self Supporting Not-for-Profit Contract Research Group Fee-for-Service Access 3

4 UMaine Pilot Plant CNF Pilot Plant Stock Preparation and Refining Loop 4

5 UMaine Pilot Plant Web coater with laminating station Pilot paper machine with advanced control systems 5

6 Innovation Continuum R,D,& C Its Cyclical not Linear Production/ Public Access Basic Research Applied Research Development Demonstration Commercialization +$$ $ Fed Grants DoD,DOE,USDA. $ SEGF--VC --Equity-- Debt $ Fed Grants NIH,NSF, etc. $$ -MTI Seed Grants, Development Awards, ACF, Fed SBIR -$$ Science & Technology Drives Univ and Non-profit R&D $ Company Funds Family, Fools and Friends Valley of Death Business & Markets Drive Commercial R&D 6

7 Innovation Awarded five US patents in last three years All have industrial co-inventor(s) All are licensed or in the licensing process Validate Innovate Commercialize 7

8 Operating Model Partner with Industry Collaboration with other Institutions & Agencies Example - J/V with USDA Forest Products Laboratory Public Academia Private 8

9 Cellulose Nanotechnology Research Consortium 10

10 Cellulose Nanofibrils 11

11 Cellulose Nanofibrils 12

12 Cellulose Nanofibrils Fibril width nm Lengths up to 10 s of microns High aspect ratio ( ) Large specific surface area ( g/m 2 ) x 100k 200 nm SEM image of isolated Cellulose Nanofibrils 13

13 CNF Cellulose Nanotechnology Source : Akira Isogai, University of Tokyo 14

14 Production Methods Cellulose Nanofibrils Cellulose Nanocrystals Other cellulose materials 15

15 Preparation of Cellulose NanoFibrils Plant Matter Fibrillation Pretreatment Posttreatment Cellulose NanoFibers Wood Corn Stover Kraft Pulping Refining Refining Grinding Homogenization Refining Grinding Grass Enzymatic Extrusion Cationization Bagasse TEMPO Cryo-Crushing Siloxane treatment Tunicates Carboxy Methylation Collision Drying

16 Early Cellulose Nanofibril Process Reduced to practice by ITT Rayonier, 1977 Patented in 1983 Turbak, et. al. 17

17 Preparation Process Homogenizer Mass Colloider/ Grinder Microfluidizer 18

18 Preparation Process 27,800 4,170 1,390 Energy consumption (kw Hr/Tonne) Reference: Rojas, et. al., 2010 Tappi International Nanotechnology Conference 19

19 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,

20 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 Pohler, Tiina et.al., 2012 Tappi International Conference on Nanotechnology for Renewable Materials, Montreal, Canada. June 5-7, Cationization 21

21 Preparation Process Low Consistency UMaine 23

22 University of Maine Proprietary Cellulose Nanofiber Process Novel method to produce CNF Commercially scalable Low cost Patent pending technology High performance additive Wide range of applications 25

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24 UMaine CNF Pilot Facility Capability o Refiner CNF Pre-treatment o Mass Colloider Grinder Capacity o 1 ton/day o Slurry form (3% solids) 27

25 Spray Dryer UMaine CNF Pilot Facility o Several kg/day capacity 28

26 UMaine CNF Pilot Facility Availability o Fee-for-service basis o Samples available Kg to tonne quantities CNF & CNC Slurry or dry 29

27 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 30

28 Applications Cellulose Nanofibrils Cellulose Nanocrystals 31

29 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 32

30 CNF as a Furnish Additive 175% 125% 164% % Change from Control 90 gsm Uncoated Freesheet 75% 61% 25% 11% 30% -25% -6% -6% Porosity Bond Stiffness Tensile Tear Bulk 33

31 Commercial Scale-up Release Base Paper Surface Control 208 X CN X 5% CNF added 34

32 Paper Coated with CNF X µm 1.5 g/m2 coating X µm 0.5 g/m 2 coating 3.0 g/m2 coating X µm 36

33 Ink density Ink density of Flexo Printed Samples uncoated Coat weights with CNF, g/m 2 Printed with a water-based pigment ink by flexographic printing tester 37

34 Ink density of Ink Jet Printed Samples EKA Chemicals Inc. CNF improves ink jet print quality 38

35 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 CNF Applications Composites o Thermoplastics reinforcing and filling o Thermoset resin reinforcing and filling o Paints, inks and coatings 39

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37 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 41

38 Polypropylene-based Composites 6 wt% CNF in polypropylene 42

39 CNF Applications Other applications under development o Rheology modifier o Structural Products o Insulating foams o Cement additive o Acoustical panels 43

40 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 44

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43 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 Q o Additional trial scheduled for Q o CNF backlog exceeds 2,000 lbs. o Robust activity in validating paper property and process improvements 47

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45 Contacts Michael Bilodeau, Director Phone: Pros Bennett, Managing Director Phone:

46 Questions Sean Ireland Phone: