effect of multiple cellulose whiskers on mechanical and...
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![Page 1: Effect of multiple cellulose whiskers on mechanical and ...cerig.efpg.inpg.fr/Note/2010/cellulose-polymer-film.pdfcapim dourado (67) flax + hemp hemp (13) flax (15) ramie (6) Mechanical](https://reader036.vdocuments.us/reader036/viewer/2022081621/613107e51ecc5158694479c6/html5/thumbnails/1.jpg)
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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
![Page 2: Effect of multiple cellulose whiskers on mechanical and ...cerig.efpg.inpg.fr/Note/2010/cellulose-polymer-film.pdfcapim dourado (67) flax + hemp hemp (13) flax (15) ramie (6) Mechanical](https://reader036.vdocuments.us/reader036/viewer/2022081621/613107e51ecc5158694479c6/html5/thumbnails/2.jpg)
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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
![Page 3: Effect of multiple cellulose whiskers on mechanical and ...cerig.efpg.inpg.fr/Note/2010/cellulose-polymer-film.pdfcapim dourado (67) flax + hemp hemp (13) flax (15) ramie (6) Mechanical](https://reader036.vdocuments.us/reader036/viewer/2022081621/613107e51ecc5158694479c6/html5/thumbnails/3.jpg)
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• 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
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« 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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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
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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