Technical Challenges Nano-fractionalization and nano-catalysis for separations;

1. Focus Areas 2/3Forest Nanomaterials/Control of Water Lignocellulosic Interactions for Modification of Properties

2. Technical Challenges Nano-fractionalization and nano-catalysis for separations; Non covalent disassembly/re-assembly Entropic effects in the assembly and disassembly of nanomaterials in forest materials Focus Area 2: Forest Nanomaterials Target: Liberation and use of nanocellulose building blocks

3. Cellulose Morphology(William T. Winter, Cellulose Research Institute, SUNY – ESF, Syracuse NY) Fiber (cell) White pine tracheids ESF archives Wood Cell Schematic Cote -ESF Microfibril Hanna, ESF

4. Cellulose Nanowhiskers Field-emission electron micrograph of freeze-dried cellulose whiskers of nanoscale cross-sectional dimensions prepared at Paprican’s Vancouver laboratory from H2SO4 hydrolyzed bleached Kraft softwood pulp W. Hamad. Can. Jour. Chem. Eng. 84. Oct. 2006. pp513 – 519

5. 200 nm Nanocrystalline Cellulose William T. Winter, Cellulose Research Institute, SUNY – ESF, Syracuse NY 13210 25% - 30% strength of Carbon Nanotubes

6. Surface Area vs. Aspect Ratio Montmorillonite Clay: Length: 1 nm Diameter: 200 – 400 nm Aspect Ratio: 0.005 – 0.0025 (200 – 400) Cellulose Nanocrystals: Length: 100 nm – several mm Diameter: 3 – 20 nm Aspect Ratio: 10 – 10,000 William T. Winter, Cellulose Research Institute, SUNY – ESF, Syracuse NY 13210

7. Microfibrils + Acid Nanocrystals Crystal and Microfibril Preparation(William T. Winter, Cellulose Research Institute, SUNY – ESF, Syracuse NY) Extraction, Bleaching: • Dewax- Soxhlet • Mill • Alkali solution • Sodium chlorite • homogenize Hydrolysis (for nanocrystals): • acid (HCl, H2SO4) • concentrations ( 65%) • temperature (40°C) • hydrolysis time (1 – 2 h) • acid-to-substrate ratio (0.1 – 0.5 mol/g)

8. Liberation and Use of Nanocellulose • Need • Identify/develop more commercially attractive methods to liberate nanocellulose, in either the whisker or crystalline forms • Once liberated, nanomaterials must be: • Characterized • Stabilized • Incorporated into existing and new applications

9. Focus Area 3 : Understand the control of water-lignocellulose interaction for modification of properties Target Understand water forest materials interactions Control effects of water on wood and paper properties Shed water more efficiently Technical Challenges Interfacial properties at nanoscale Production of hydrophilic/hydrophobic switchable surfaces Biological activity control

10. Background • The response of lignocellulosics to moisture (liquid and vapor) is due almost entirely to the supermolecular structure of the biopolymers and nanoscale structures of the composites that comprise the wood fiber • Primary microfibrils – 4 –10 nm in cross-section • Microfibril angle • Degree of crystallinity • Species, growing conditions, processing conditions – all affect interactions between water and lignocellulosics

11. Background • Control/modification of surfaces of lignocellulosic materials using nano coatings or impregnation of nano particles can be used to provide physical/chemical barriers to modify the effect of moisture by changing wetting (hydrophilicity/hydrophobicity) and adhesion forces. • Durability and other end use properties of wood and paper products closely tied to the response to moisture • Interfiber bond strength - paper • Dimensional stability – wood and paper • Decay, fungi, rot, UV stability - wood • Very large volumes of water are handled in the manufacture of forest products. Nano materials which can modify drainage rates and drying could result in significant reductions in energy requirements.

12. WATER VAPOR AS A PROBE TO CHARACTERIZE SURFACES AND NANOSTRUCTURES

15. WATER VAPOR ACCESSIBLE SURFACE AREA AND SURFACE ENERGY OF ADSORPTION FOR SELECTED MODEL COMPOUNDS AND PULPS

16. Summary Lignocellulosic fiber is a nanocomposite • Water accessible surface area determined by nanostructure which is dependent on species and pulping processes • Surface energy of adsorption • Model compounds show impact of different functional groups and the concentration of those groups on the surface • Pulps show differences due to both pulping process and species • Eucalyptus has a lower accessible surface area, but a significantly higher surface energy of adsorption indicating a higher concentration of hydrophilic groups on the accessible surface

17. Examples

18. Growth rings 1 cm 50 mm Cell wall layers Relate to Macroscopic Properties

19. News, 45 g/m² Moisturized sheet Dry sheet ESEM - Environmental Scanning Electron Microscope G. A. Baum 2003

20. Water Droplets on “Nanoseal” Treated Wood Nanoparticles adhere directly to the substrate molecules (molecular bonding) and assemble into an invisible ultra-thin nanoscopic mesh providing a long lasting, self-cleaning, hydrophobic surface. The wood is protected against decay, fungi and rot. It is dimensionally and UV stable. It will not wear off and cannot be removed by water, normal cleaning agents or high pressure equipment.

21. Wood Surface Repels Water Droplets Water droplets rest on a wood surface impregnated with BASF’s “Lotus Spray” The surface is superhydrophobic . Thus contact area between the surface of the wood and the water is reduced to a minimum, and the adhesive forces are greatly decreased making the water drops assume a globular form.