AParadigminNanocelluloseMaterials

Fromnanofiberstonanostructuredfibers

Hiroyuki Yano
Research Institutes for Sustainable Humanosphere,
Kyoto University

NSCF
Nano-Structured Cellulose Fibers

NSCF
Closeupview
NanoStructuredCelluloseFibers

Dissolving pulp (100)

150m

Dissolving pulp 2,000

10m

Dissolving pulp 30,000

500nm

Theadvantageofpulp:NSCF
overCNC,CNFandBCis

cost

$20-100/kg
$0.6-0.8/kg
$0.1-0.2/kg

AParadigminNanocelluloseMaterials
Fromnanofiberstonanostructuredfibers

Opticallytransparentnanocellulose

MechanicalReinforcementof
TransparentPlastic

Acomponentlessthanonetenththesizeofthe
opticalwavelengthcaneliminatescattering

HierarchicalStructureofWood
CelluloseNanofibers
Hemicellulose
Lignin

1050m
CellStructure

1020nm

CellWall
Structure

Microfibril
bundles

Nano fibersandMatrix

NanoStructuredCelluloseFibers

Fibrillation by a Grinder
Never- dried pulp

Cellulose nanofibers
isolated from wood

K. Abe, et al.,
Biomacromolecules,
2007

PreparationofCelluloseNanofiberComposites

Vacuuming filtration
1% Never-dried Pulp Slurry

Grinder treatment

Nanocomposites

UV cure

Acrylic Resin impregnation

Fiber content::5-90 wt%

CelluloseNanofibers:CNF
Semi-crystalline extended chains
Tensile strength:3GPa aramid fibers
(Based on D.H. Page, F., El-Hosseiny J. Pulp Paper Sci. 1983)

Youngs modulus:138-141GPa -200~+200

(T. Nishino et al. J. Polym Sci., Part B, 1995, Proc.2nd Intn'l Cellulose Conf,2007 )

Thermal expansion coefficient0.1 ppm/K quartz glass

(T. Nishino, Personal communication, 2004)

High specific surface area

Wood Nanofiber

Bacterial Cellulose

Light
Density
Transmittance1
(g/cm3)
(%)

CTE2
(10-6oC-1)

E
(GPa)

Tensile
Strength
(MPa)

Wood Nanofiber
Composites

1.4

82.3

9.8

16.3

283

Bacterial Cellulose
Composites

1.4

83.7

6.0

21.0

325

S. Iwamoto, et al., Biomacromolecules (2007)

1600nm220150

Optically Transparent Cellulose Nanofiber

Reinforced Composite

As strong as steel, as thermally stable as glass,

and as bendable as plastics

LuminescenceofanOLED
depositedonthewoodnanofibercomposite
Devicestructure

Passivation Film

Cathode
Organic Layers
Anode
SiON Barrier Film
Resin (Smoothing Layer)

Wood Cellulose Nanocomposites

Y.Okahisa,etal., Comp.Sci.Technol. (2009)

AfutureFPDprocessing;ContinuousRolltoRoll
R2R processsimple and inexpensive.
R2R processing enables the
continuous
deposition
of
functional materials such as
semiconductor,
transparent
conductive films and gas barrier
films on a roll of substrate.

Ademonstrationof
productionofOLEDbyR2Rprocess
(GE,USA,PressRelease,13March,2008)

Transparent materials developed in Kyoto Uni.

Wood
nanofibers

BC

100%
Wood
nanofibers

Transparent
Crab

MicrotoNano StructureofCrab

Chitinmolecule

Schematicpresentationoftheexoskeletonstructureof
crustaceanshell.
(Ifuku,etal.Biomacro,2009)

Crabshellpowder,Redking

Demineralization(CaCO3) byHCl
Deproteinization byNaOH
Pigmentremovalbyethanol
I.Md.ShamsandYano,2009

SEMimageofchitinparticlesheetsurface

1mmx1mmparticleof
matrixremovedcrabshell

SEMimageofchitinparticlesheetsurface

SEMimageofchitinparticlesheetsurface

SEMimageofchitinparticlesheetsurface

1mm

50mm

Light Transmittance, %

100

Acrylic resin
Chitin powder composites

80

Cellulose nanofibers composites

60

40

20

0
200

400

600

800

Wave length, nm
(a) Light transmittance of the chitin powder reinforced acrylic resin sheet
(thickness 190 m, Powder content: 22wt%) and cellulose nanofibers reinforced
acrylic resin sheet (thickness 100 m and Fiber content: 60wt%).

ComparisonofMicrotoNano structures

Crab

Wood

Thetransitionfromnanofibers
tonanostructured fibers

Encouraged by the transparent crab powder

sheet, we undertook the preparation of
optically transparent pulp-fiber composites.

Difficultyintheproductionof
nanocellulosereinforcedcomposites

Nanofibrillation
of Pulp

Slow
Dewatering
Speed

Low
Productivity

Opticallytransparentpulpsheet

The pulpfiber sheet was acetylated, with care taken to

maintain a neverdried condition, and it was then dried
and impregnated with acrylic resin.
CNFofNever
DriedPulp
Drying

Acetylation

Acetyl
Group

Resin
Impregnation

Neverdried Acetylated Resin

Pulp
drypulp
impregnated
acetylated
drypulp

AcetylatedPulpSheet

Acetylated
PulpSheet
Beforeresinimpregnation

Afterresinimpregnation

Effectofsurfacefibrillationusingbeadsmill
Pulp,NBKP

Surfacefibrillatedpulp

Surface
fibrillation
200um

Pulpsheet

200um

Surfacefibrillatedpulpsheet

Linearlighttransmittance%

Changesintransparencyofacrylicresinimpregnatedpaper
100
90
80
70
60
50
40
30
20
10
0

Acrylicresin
CNF+resin

+Surfacefibrillation
Acetylation
UntreatedPulp
Beforeresin
impregnation
300

Afterresin
impregnation

500
700
Wavelengthnm

Thickness
um

Fiber
content
%

CTE

Acetylatedsurface
fibrillated pulp

60

18.0

11.9

70.0

88.1

Acetylatedpulp

100

26.0

8.30

54.1

87.8

Untreated pulp

100

28.5

3.64

43.7

87.0

Nanofiber1)

100

3540 12.1

82.0

90.0

Resin1)

91.0

92.0

ppm/K

213.0

Linear
Light
Transmit.
%

Total
Light
Transmit.
(%)

CTE:20150

1)Y.Okahisa,etal.,CompositeScienceandTechnology,2009

Theadvantageofpulp:NSCF
overCNC,CNFandBCis

cost&performance

20-100US$/kg
0.6-0.8US$/kg
0.1-0.2US$/kg

AnotherexampleusingNSCF

Chemicallymodifiedsurfacefibrillatedpulp
orChemicallymodifiedNSCF

NEDO Green Sustainable Chemical Process Programs

from 2009 to 2013
NEDO: New Energy and Industrial Technology
Development Organization of Japan

Project Title

Development of highperformancecellulose nanofibers reinforced

plastics for automotive parts
Organizations: Kyoto University, Kyoto Municipal Institute, Oji Paper,
Mitsubishi Chemical , DIC, Seiko PMC
Advisers:ToyotaAutobody,Nissan,Suzuki,Denso,NipponPaint,Panasonic,
JapanSteelWorks
CO2Fixation

SustainableForest

AutomotiveParts

Disintegrationandwelldispersionofchemicallymodified
pulpinHDPE,PPandPA12duringmeltcompounding
Chemicallymodified
CNF reinforcedplastic

Twinscrewextruder

Injectionmolding
Chemicallymodified

drypulp

Nanofibrillation
& Compounding

PE,PP,PApellets
+
Additives
Samples

Xraytomographyof
injectionmoldedsamples
ModifiedPulp

UnmodifiedPulp

SEMImages

ModifiedCNF

HDPE

UnmodifiedPulp
afterremovalofHDPE

Pulp(Surfacefibrillated)

10m
ModifiedPulp
afterremovalofHDPE

10m

10m

Tensileproperties
(PulporCNF10%)
HDPE+ModifiedPulp
E:3.3GPa,:57MPa

Stress(MPa)

HDPE+ModifiedCNF
E:3.5GPa,:56MPa
HDPE+UnmodifiedPulp
E:1.6GPa,:38MPa
NeatHDPE
E:0.8GPa,:23MPa

Stain(%)

ChemicallymodifiedCNFreinforcedBioHDPE
Pulp10%

60.0

Modified CNF/HDPE
E: 2.4GPa, : 48MPa

50.0

Stress (MPa)

40.0
30.0
20.0

Neat Bio-HDPE
E: 0.7GPa, : 21MPa

10.0
0.0
0

10

Strain (%)

12

14

16

ChemicallymodifiedCNFreinforcedPP
Pulp10%

60

Modified CNF/PP
E: 1.7GPa, : 46MPa

50

Stress (MPa)

40
30
20

Neat PP
E: 0.7GPa, : 26MPa

10
0
0

10

12

14

16

Strain (%)

ChemicallymodifiedCNFreinforcedPA12

stress[MPa]

Pulp10%

Modified CNF/PA12
E: 3.0GPa, : 63MPa

70
60
50
40
30
20
10
0

Unmodified CNF/PA12
E: 1.8GPa, : 42MPa

Neat PA12
E: 1.3GPa, : 35MPa

10
strain[%]

15

20

ChemicallymodifiedCNFreinforcedPA12
500
Deformation(m)
(m)

Polymer
Composites

400

Modified CNF/PA12

300
PA12

200
100
0
0

20

40
60
80
Temperature()
()

100

CTE(0100)
ppm/K
PA12

92

ModifiedCNF/PA12

24

Aluminumalloy

23

Thankyouverymuchforyourkindattention!

49