a nano perspective of cellulose final presentation.pdfo-cellulose oh oh 0 20 40 60 80 100 120 140 e-...

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

0

500

1000

1500

2000

2500

Kraft Bleaching

`

020406080

100120140160180

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.

`

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

0

20

40

60

80

100

120

140

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

50

100

150

200

250

300

350

0 5 10 15 20Filler,%

Stra

in, %

WhiskerPulp Fiber

NanoCellulosic StructuresNanocellulose Whisker:Acrylic Acid Composite Film

0

2

4

6

8

10

12

14

0 5 10 15 20Cellulose, %

Tensile strength, MPa

WhiskerPulp Fiber

0

1000

2000

3000

4000

0 5 10 15 20

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

20

25

30

35

40

0 5 10 15 20 25

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!!

050

100150200250300350400450500

0 2 4 6 8 10 12

Time (hour)

Siz

e (n

m)

020406080

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

arthur.ragauskas@ipst.gatech.edu

ragauskas@hotmail.com

AcknowledgmentsGA Research AllianceIPST Industry Consortium