A Nano Perspective of Cellulose Arthur J. Ragauskas Yunqiao Pu - PowerPoint PPT Presentation

A Nano Perspective of Cellulose Arthur J. Ragauskas Yunqiao Pu Jianguo Zhang School of Chemistry and Biochemistry Institute of Paper Science and Technology Georgia Institute of Technology

World Pulp Production Million metric tons 70 60 50 40 30 20 10 0 U.S.A. Canada Sweden Finland Brazil Chile N.Z. 1995 2002 Source: Pulp & Paper International, Paperloop.com

Wood Chemistry/Pulp Paper Kraft Bleaching Research Trends 2500 2000 1500 1000 ` 500 0 1975 1980 1985 1990 Kraft Bleaching 1995 2000 2005 5000 4500 Citations 180 4000 Brightness Reversion Citations 160 3500 140 3000 120 2500 100 2000 80 1500 1000 60 500 40 0 20 Filler 1975 0 1980 1985 Starch 1990 1995 1965-70 1970-75 1975-80 1980-85 1985-90 1990-95 1995-00 2000-05 2000 2005

Pulp and Paper Trends Newsprint capacity fell 1.3% in 2003, decline another 2.8% in 2004 lowest since 1989. Paper or plastic? Students prefer the latter Bye bye Paper Tickets when it comes to milk containers TICKETLESS travel will become a so schools switching global reality by the end of 2007- IATA Smurfit-Stone Container to cut costs, increase revenues, close plants (11/9/05) AF&PA: U.S. paper and paperboard capacity continues to decline (02/27/04)

Yogi Berra New York Yankees “The Future Ain’t What It Used To Be”

What is The Future Innovation “A change that creates a new dimension of performance” Drucker Sony Corporation and TOPPAN Printing Co., announced the successful development of 25GB paper disc, the recording layer on which the data is stored lies under a protective layer.

Unconventional Manner All These Examples Use Fibers in An And Others `

NanoCellulosic Structures m mm 100 µ m 1 µ m OH OH O OH O OH O HO O HO O-Cellulose HO O HO O OH O OH OH O OH OH O OH OH O OH O HO O HO O-Cellulose HO O HO O OH O OH O OH OH 10 nm 10 µ m 1 nm Surface Area m 2 /g 140 E-Glass Fibers approx.1 Stiffness 120 Specific Stiffness Paper Fibers 4 100 80 Graphite 25 - 300 60 40 Fumed Silica 100 - 400 20 Fully Exfoliated Clay approx. 500 0 s r e e r n s n i p x e l r k F s a m a i o s P i t o a u s l C t i s e F i t h G l J S o a a W H C l s - g o Nanocellulose Whiskers 400 - 700 E e u r o s e D d o n u l o l e l P c o n Carbon Nanotubes approx. 100 a N

NanoCellulosic Structures • Acid Hydrolysis Technique � Bleached softwood kraft pulp � 8% Cellulose + 64% H 2 SO 4 � Stirred at 45 C, 45 min ~ 1 hour � Dilute with water � Centrifuged, wash and neutralize � Re-disperse with ultrasonication � Allowed to stand over a mixed bed resin for 48 h � The mixture was centrifuged and the supernatant was filter through filter paper. The filtrate was colloidal nanowhisker suspension Over 60% of yield could be achieved by this method .

NanoCellulosic Structures AFM images of nanowhisker

NanoCellulosic Structures Nanocellulose Whisker Composite Films � Polystyrene (average Mw ~280,000 ) solution in THF (5% w/w) � Dry nano whiskers. � Polymer films were prepared by solution casting into molds. The films were left for 24 hours at ambient conditions to allow for solvent evaporation. � 3% nanocellulose whiskers were added into polymer solution, sonificated and then cast into molds. The films were left for 24 hours at ambient conditions to allow for solvent evaporation. � Films was of a thickness of 50~110 µm.

NanoCellulosic Structures Nanocellulose Whisker:Polystyrene Composite Film Preliminary Physical Properties TEA*, Elongation, Modulus J/m 2 % (MPa) Polystyrene 8.9 1.3 46.5 Polystyrene/ +70% + 11% + 23% Polystyrene /whisker film NC whisker *: Tensile energy absorption. � Mechanical tests were carried out on an Instron 4400R � 4.5 inch length * 15 mm width

NanoCellulosic Structures Nanocellulose Whisker Acrylic Acid Composite Film Experimental Method • Dow acrylic latex, solids 50% • Add cellulose whiskers or hardwood bleached kraft pulp • Mixture cured at RT • Initial film dried 50 ˚ C for 2 days.

NanoCellulosic Structures Nanocellulose Whisker:Acrylic Acid Composite Film 14 E A , J / m 2 T T ensile strength, 4000 M Pa 12 W hisker Pulp Fiber 10 3000 W hisker 8 Pulp Fiber 2000 6 4 1000 2 0 0 0 5 10 15 20 0 5 10 15 20 Cellulose, % Filler, % 350 300 250 Strain, % 200 W hisker 150 Pulp Fiber 100 50 0 0 5 10 15 20 Filler,%

NanoCellulosic Structures Nanocellulose Whisker:Acrylic Acid Composite Film Latex Film 20% Cellulose Whiskers:Latex Film 5% Cellulose Whiskers:Latex Film 40 Contact angle 35 30 25 20 0 5 10 15 20 25 W hisker content, %

Nanocellulose Balls • SW ECF bleached kraft pulp • Refined to 20-mesh • Swell fibers with 5M NaOH followed by DMSO • Sonicate cellulose with HCl – H 2 SO 4 75 o C • Wash with water, purify by centrafugation • Sonicate cellulose with HCl – H 2 SO 4 75 o C • Wash with water, purify by centrafugation

Nanocellulose Balls 500 450 400 350 Size (nm) 300 250 200 150 100 180 160 50 140 0 120 0 2 4 6 8 10 12 Size (nm) 100 Time (hour) 80 60 40 20 0 0 1 2 3 4 5 Time (hour) First nanocellulose procedure able to provide practical control of particle sphere dimensions!!

Nanocellulose Balls – 76 nm AFM Images

Nanocellulose Balls 76 nm balls S-800 FE SEM 180 nm balls

Nanocellulose Crystallinity Results 13C-CP/MAS NMR Analysis C-2, 3, 5 C-1 C-6 C-4 Crystallinity index Original pulp – Cellulose 1 0.61 300 – 500 nm Nanocellulose Balls 0.65 Cellulose II 50 – 100 nm Nanocellulose Balls 0.70 Cellulose II

NanoCellulosic Structures Nanocellulose Whisker-Balls:Acrylic Acid Composite Film 5% Cellulose Whiskers:Latex Film 5% Cellulose Balls:Latex Film Latex Film 1400 1200 TEA 1000 800 600 400 200 0

Pathforward • Nanocellulose balls – Derivatives to be used for superabsorbers – viscosity modifiers – Artificial blood/drug delivery – Cosmetics – Template for Nanospheres • Nanocellulose whiskers – Composites with plastics – Composites with natural polymers – In-situ polymerization

Where Is This All Going? "Give me a lever, a fulcrum, and place to stand and I will move the world." Consumer Demand Archimedes ∼ 200 BC Value Added Leveraging: Research and Development Products & Partnership Industry, Universities, Materials Government More Relevant Today!!! Forest Products Community Societal Demand for Innovative Products Carbon Neutral, Environmentally Friendly, Renewable and Sustainable “Nano-Inside” Manufacturing Technologies

Acknowledgments GA Research Alliance IPST Industry Consortium arthur.ragauskas@ipst.gatech.edu ragauskas@hotmail.com