1

1

Effect of multiple cellulose whiskers on mechanical and barrier properties

of polymer films

Tangi SENECHAL , Ludovic PERRIN, Alain DUFRESNE, Julien BRAS

LGP2 Grenoble

MATBIM2010 March 5th

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Laboratory of paper science & graphic arts

LGP2 - UMR 5518

AGEFPI

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From wood to converted and printed Materials

Multi-disciplinary domains of competences

Wood Chemistry, Fluid mechanics, Physics and Mechani cs of paper, Rheology of suspensions, Chemistry of surface s, interfaces and adhesion, Polymer chemistry, automatic ,

Biocomposites, Nanocomposite…

Laboratory of paper science & graphic arts

LGP2 - UMR 5518

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ChemicalProcesses

Papermaking & environmentengineering

Fibre structure Physics

Converting -Biomaterial -Packaging

Printing Processes

Laboratory of paper science & graphic arts

LGP2 - UMR 5518

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5

• Cellulose whiskers

• Mechanical properties

• Barrier Properties

• Conclusions and perspectives

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Functionnal packaging :barrier, Frozen films, MAP, …

Packaging context

European union

wax2%

PP2%

HDPE2%

PE79%

Other films1%

fluoridepolymer8%

Silicone4%

Water soluble polymers

2%

Challenge :

Replace Petroleum based by Biobased polymers

Source : ATIP 2 juin 2006, « Enjeux et nouveaux défis de l’emballage papier-carton », J. Poustis

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Cellulose

200 billion tons cellulose. 3% explored.

Linear homopolysaccharideβ-D-glucopyranose units: β-1-4-linkages.

Adapted from Pääkkö, et al. 2007

Multiorganizaton

8

« NanoCellulose »?

Microfibrillated cellulose MFC

10-30 nm × 500-1500 nm

Nanocrystals or whiskers

2-20 nm × 100-1000nm

CELLULOSE FIBER

microfibril

ChemicalTreatment

MechanichalTreatment

Birefringent domains.

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9

Baruah, P. P et al. Indian Pulp and Paper (1971), 25(7 ), 438-409543bamboo

Dufresne, Alain et al. Polymer Composites (1997), 18(2)�2645wheatstraw

Paralikar, K. M. Journal of Applied Polymer Science (1 988), 35(8), 2085-9. 12655

sugar cane bagasse

Boruah, R. K et al. Indian Journal of Fibre & Textile Research(1998), 23(2), 76-80.1064banana

Garcia de Rodriguez, Nancy Lis et al. Cellulose (20 06), 13(3), 261-2701665sisal

Li, Guokang. (2003), patent 6 pp. CN1405218 A 200 30326 3268hemp

Cao, Xiaodong; Dong et al. Biomacromolecules (2007), 8(3), 899-9042371flax

de Menezes, A. J.et al. Abstracts of Papers, 235th AC S National Meeting (2008) �1176ramie

Kumar, Ray Ajoy et al. (1994) Patent 14 pp. IN 1743 43 A119941112181pineapple

Huang, G. Journal of the Textile Institute (2005), 96 (1), 11-15886nettle

De Souza Lima et al. Macromolecular Rapid Communicatio ns (2004), 25(7), 771-787.57490cotton

main referencereferencesCellulose (%) �Sources

SciFinder – June 2008

Cellulose

10

Cellulose Nanocrystals

RamieCotton Sugar beet Tunicate

L/D=10 L/D=6 L/D=42 L/D=67Azizi Samir et al., 2005 Lu et al., 2006 Azizi Samir et al., 2004 Favier et al., 1995

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Cellulose Nanocrystals

dLc /

7.0=φ

Percolation Threshold: Favier, V. Ph.D. Thesis, Joseph Fourier University, Grenoble,France, 1995.

Source L (nm) � D (nm) L/d φ c Reference

Cotton 170 15 10 7

[117]Ramie 500 85 6 11.6

[40]

MCC 200 5 40 1.75 [116]

Sugar beet

pulp210 5 42 1.7 [76]

Palm tree 260 6.1 43 1.6 [12]

Wheat straw 225 5 45 1.6 [115]

Tunicin 1000 15 67 1.0 [74]

Lu et al., 2008

Azizi Samir et al., 2005

Azizi Samir et al., 2004

Favier et al., 1995

Helbert et al., 2004

Bendahou et al., 2008

Bondeson et al., 2006

L/D Nanocrystalsamount

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• Cellulose whiskers

• Mechanical properties

• Barrier Properties

• Conclusions and perspectives

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Cellulose Whiskers

Coco

Industrial flax-hemp

MCC

Not PossibleTunicate

Hemp

Not PossibleBacterial Cellulose

Flax

Not PossibleBagasse

Not PossibleRice Straw

Curaua

Cotton

Palm tree

Ramie

Luffa

Sisal

HardWood

UseAnalysisHydrolysisBleachingObtentionSources

14Transparent Films

No whiskers 6 wt% Sisal Whiskers 12 wt% Sisal Whiskers

Whiskerssuspension

Water soluble matrix

Teflon mold

24h-35°C

Conditioning :

24h 23°C - 50%RH

Nanocomposites

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• hydrolized at 88% (hydrophobic PVA)

• hydrosoluble matrix

• grease and O2 barrier

• easily degradable

PVA matrices:

• Petroleum based

Polyvinylalcohol

Polyvinyl acetate hydrolysis

16Transparent and regular films

Nanocomposite

PVA/ Sisal whiskersnanocomposites

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0,00E+00

2,00E+06

4,00E+06

6,00E+06

8,00E+06

1,00E+07

1,20E+07

1,40E+07

0 100 200 300 400 500 600 700

strain (%)

Stre

ss (P

a)

NR-W0%1

NR-W1%2

NR-W2,5%4

NR-W5%1

NR-W10%2

NR-W15%2

[A. Bendahou, 2007]

Mechanical Properties

Percolation threshold in NR/ Palm treewhiskers nanocompositeφφφφw~1.1%

φw= φc*ρm/ ρw

•Density : PVA = 1,30 g/cm3Whiskers = 1,50 g/cm3

Percolation in a matrix

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Mechanical Properties

Young’s modulus increase above percolation threshold

0,9

capimdourado

10.144,71,21,45,1φw

ramieflaxhempwoodsisalcottonPVA matrix

PVA/whiskers nanocomposites

0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

not filled wh hemp 4,5% wh hemp 6,5% wh ramie 11,6% wh ramie 13,6%

You

ng's

mdu

lous

(GP

a)

hemp(13)

ramie(28,6)

=> Comparison of whiskers at different concentration = φw+2%

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0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

PVA PVA + whcotton15%

PVA + whHW 3,4%

PVA + whCD 3,5%

PVA + whflax+hemp

6,5%

PVA + whhemp6,5%

PVA + whflax 6,5%

PVA + whramie13,6%

You

ng's

mod

ulou

s (M

Pa)

cotton(10)

wood(50)

capim dourado

(67)

flax + hemp

hemp(13)

flax(15)

ramie(6)

Mechanical Properties

Reinforcement with each type of whiskers

No clear effect of aspect ratio/ Percolation is more imp ortant

X 4,5

Percolation threshold + 2%

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Mechanical Properties

Strain at Break

Strain divided by 5 with ramie and flax whiskers

0

50

100

150

200

250

300

350

PVA PVA + wh cotton10%

PVA + wh hemp6,5%

PVA + wh flax6,5%

PVA + wh ramie11,6%

stra

in (

%)

cotton(10)

hemp(13)

flax(15)

ramie(6)

1/5

Percolation threshold + 2%

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• Cellulose whiskers

• Mechanical properties

• Barrier Properties

• Conclusions and perspectives

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Barrier Properties

Cloisite 20 A

Rhim J W et al. 2009

Tortuosity = Barrier

tortuosity0 1

Physical barrier

O2 and CO2 transmission rates halved compared with standard films

PA 6 or PET + nanoclay :

� O2 barrier : + 50 to 80%

� CO2 barrier : + 60 to 80%

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10% 20% 15%

PVA / Cotton Whiskers nanocomposite

Paralikar, Simonsen, Lombardi ; Journal of membrane s cience, 2008

Barrier Properties

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0

1E-11

2E-11

3E-11

4E-11

5E-11

6E-11

7E-11

8E-11

PVA

W co

tton

10

W H

W 1

W h

emp

6,5

W fl

ax 6

,5

W C

D 1,5

W R

amie 13

,6

W fla

x/he

mp 6,

5

W M

CC 4

WV

P g

/(m.P

a.s)

00,511,5

22,533,5

44,55

WV

TR

g/(m

².24h

)

WVP

WVTR

Barrier Properties

HR= 0%

FilmWater vapor

HR= 0%

CaCl 2

FilmWater vapor

23°C-50%RH

300%Global decreaseof WVP withwhiskers

WVP divided by 3

Better organisation during mixing (surface energy) ?

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Conclusion

• Obtention of Cellulose whiskers with different aspect r atios

• Improvement of mechanical and barrier properties ofnanocomposites with the whiskers above percolation thres hold

• No direct correlation between aspect ratio and propert iesimprovement

=> PERCOLATION IS THE KEY PARAMETER

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Perspectives• Improvement of barrier properties of other packagin g

� coated paper

� non-water soluble matrices

• Comprehension of tortuosity mechanism with different film processing & influence of process parameters

• Evolution of matrix cristallinity with whiskers

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Thanks For Your Attention!

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EXTRA SLIDE

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Isolation of Cellulose Nanocrystals

microfibril

Fiber

H2SO4 Heating

Centrifugation Dialysis

Sonication

Bleached Fiber

500 nm500 nm

NanocrystalsLD

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• Impurities at the surface

• Differences in whiskers surface groups

monodisperse

polydisperse

E

%Wφw φw+2

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BiopolymerPetrochemichal

polymers

7,27

8,6

5,18

9,12

0,106 0,026 0,079 0,020,252

0

1

2

3

4

5

6

7

8

9

10

C el lo phane M C HPC HPM C HPM C / A S ( 1,1/ 1)

HPM C / A S( 0 ,8 / 1)

LD PE HD PE EV OH

WVP (g.mm.m

-2.d-1.kPa

-1)�

Barrier Properties