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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
2
Laboratory of paper science & graphic arts
LGP2 - UMR 5518
AGEFPI
2
3
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
4
ChemicalProcesses
Papermaking & environmentengineering
Fibre structure Physics
Converting -Biomaterial -Packaging
Printing Processes
Laboratory of paper science & graphic arts
LGP2 - UMR 5518
3
5
• Cellulose whiskers
• Mechanical properties
• Barrier Properties
• Conclusions and perspectives
6
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
4
7
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.
5
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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11
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
12
• Cellulose whiskers
• Mechanical properties
• Barrier Properties
• Conclusions and perspectives
7
13
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
8
15
• 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
9
17
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
18
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%
10
19
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%
20
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%
11
21
• Cellulose whiskers
• Mechanical properties
• Barrier Properties
• Conclusions and perspectives
22
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%
12
23
10% 20% 15%
PVA / Cotton Whiskers nanocomposite
Paralikar, Simonsen, Lombardi ; Journal of membrane s cience, 2008
Barrier Properties
24
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) ?
13
25
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
26
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
14
27
Thanks For Your Attention!
28
EXTRA SLIDE
15
29
Isolation of Cellulose Nanocrystals
microfibril
Fiber
H2SO4 Heating
Centrifugation Dialysis
Sonication
Bleached Fiber
500 nm500 nm
NanocrystalsLD
30
• Impurities at the surface
• Differences in whiskers surface groups
monodisperse
polydisperse
E
%Wφw φw+2
16
31
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