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A Nano Perspective of Cellulose
Arthur J. RagauskasYunqiao Pu
Jianguo Zhang
School of Chemistry and BiochemistryInstitute of Paper Science and Technology
Georgia Institute of Technology
World Pulp ProductionMillion metric tons
010203040506070
U.S.A. Canada Sweden Finland Brazil Chile N.Z.
1995 2002Source: Pulp & Paper International,
Paperloop.com
Wood Chemistry/Pulp PaperResearch Trends
1975 1980 1985 1990 1995 2000 2005
StarchFiller
0500
100015002000250030003500400045005000
Citations
1975 1980 1985 1990 1995 20002005
Kraft Bleaching
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Kraft Bleaching
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1965-70 1970-75 1975-80 1980-85 1985-90 1990-95 1995-00 2000-05
Brightness Reversion Citations
Pulp and Paper Trends
Paper or plastic? Students prefer the latter when it comes to milk containersso schools switching
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)
Bye bye Paper Tickets TICKETLESS travel will become a global reality by the end of 2007- IATA
Newsprint capacity fell 1.3% in 2003,decline another 2.8% in 2004lowest since 1989.
“The Future Ain’t What It Used To Be”
Yogi BerraNew York Yankees
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.
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All These ExamplesAnd Others
Use Fibers in AnUnconventional Manner
NanoCellulosic Structures
m
10 µm
1 µm
10 nm
1 nm
100 µmmm
OO
HOOH
OO
HOOH
OH
OH
O
HOOH
OO
HOOH
O-Cellulose
OH
OH
O
OO
HOOH
OO
HOOH
OH
OH
O
HOOH
OO
HOOH
O-Cellulose
OH
OH
O
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E-Glas
sHem
p
Flax
Jute
Sisal
CoirCott
on
Nanoc
ellulo
se W
hiske
rsDou
glas F
ir
Pond
erosa
Pine
StiffnessSpecific Stiffness
approx. 100Carbon Nanotubes400 - 700Nanocellulose Whiskers
approx. 500Fully Exfoliated Clay100 - 400Fumed Silica25 - 300Graphite
4Paper Fibersapprox.1
Surface Area m2/gE-Glass Fibers
• Acid Hydrolysis Technique
Bleached softwood kraft pulp 8% Cellulose + 64% H2SO4
Stirred at 45 C, 45 min ~ 1 hourDilute with waterCentrifuged, wash and neutralizeRe-disperse with ultrasonicationAllowed to stand over a mixed bed resin for 48 hThe 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
Polystyrene /whisker film
Mechanical tests were carried out on an Instron 4400R4.5 inch length * 15 mm width
+ 23%+ 11%+70%Polystyrene/NC whisker
46.51.38.9Polystyrene
Modulus (MPa)
Elongation, %
TEA*, J/m2
*: Tensile energy absorption.
Preliminary Physical Properties
NanoCellulosic Structures
NanoCellulosic StructuresNanocellulose 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.
0
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0 5 10 15 20Filler,%
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in, %
WhiskerPulp Fiber
NanoCellulosic StructuresNanocellulose Whisker:Acrylic Acid Composite Film
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0 5 10 15 20Cellulose, %
Tensile strength, MPa
WhiskerPulp Fiber
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Filler, %
TEA, J/m2
WhiskerPulp Fiber
Nanocellulose Whisker:Acrylic Acid Composite Film
NanoCellulosic Structures
Latex Film 20% Cellulose Whiskers:Latex Film
5% Cellulose Whiskers:Latex Film
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Whisker content, %
Contact angle
Nanocellulose Balls
• SW ECF bleached kraft pulp• Refined to 20-mesh • Swell fibers with 5M NaOH followed by DMSO• Sonicate cellulose with HCl – H2SO4 75 oC • Wash with water, purify by centrafugation• Sonicate cellulose with HCl – H2SO4 75 oC• Wash with water, purify by centrafugation
First nanocellulose procedure able to provide practical control of particle sphere dimensions!!
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Time (hour)
Siz
e (n
m)
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100120140160180
0 1 2 3 4 5
Time (hour)
Size
(nm
)
Nanocellulose Balls
Nanocellulose Balls – 76 nmAFM Images
Nanocellulose Balls
S-800 FE SEM
180 nm balls
76 nm balls
Nanocellulose Crystallinity Results 13C-CP/MAS NMR Analysis
0.7050 – 100 nm Nanocellulose BallsCellulose II
0.65300 – 500 nm Nanocellulose BallsCellulose II
0.61Original pulp – Cellulose 1
Crystallinity index
C-1
C-4
C-2, 3, 5
C-6
Nanocellulose Whisker-Balls:Acrylic Acid Composite Film
NanoCellulosic Structures
Latex Film
5% Cellulose Whiskers:Latex Film5% Cellulose Balls:Latex Film
0200400600800
100012001400
TEA
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."
Archimedes ∼200 BC
Forest Products CommunityInnovative Products“Nano-Inside”
Societal Demand forCarbon Neutral, Environmentally Friendly, Renewable and SustainableManufacturing Technologies
Consumer DemandValue Added
Products &
Materials
More Relevant Today!!!Leveraging: Research and Development
Partnership Industry, Universities,
Government
