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Hybrid Nanocellulose-Clay Composites for Controlled Release
Supervisors: Peter SZABO, Anders Egede DAUGAARD, Ole HASSAGER
ESR: Jon TRIFOL GUZMAN
Danish Polymer Center
Department of Chemical and Biochemical Engineering
Technical University of Denmark
Kongens Lyngby, Denmark
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INTRODUCTION
- PLA (Polylactic acid)√ Renewable source√ Biodegradable√ Suitable for industry√ Good Mechanical properties√ Transparent
~ CostX Barrier propertiesX Thermomech. propertiesX Slow crystallizationX Brittleness
NANOCOMPOSITE
C30B CNF
Improvement of properties?
Comparisson vsSynergetic
When? How? How much?
NEED TO BE FIXED
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PLA BASED NANOCOMPOSITES
PLA & PLA +C30B
PLA +CNF
PLA +CNF +C30B
DMF + 15 h 80 °CDCM15 h 23 °C
SOLVENT CASTING BETTER FOR THE ”PROOF OF THE HYPOTHESIS” ”UPSCALING” NEXT RESEARCH MULTIPLE POSSIBILITES
BEST CONDITIONS FOR EACH NANOCOMPOSITE
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TRANSPARENCY
400 600 800 10000.0
0.2
0.4
0.6
0.8
1.0
Tra
nsm
ittan
ce
Wavelenght
PLA PLA CNF 1% PLA CNF 1% C30B 1%
HOT PRESSEDNANOCOMPOSITES
PLA/CNF 1%/C30B 1% TRANSPARENT
AND CLEAR
INFRAREDUV
UVBLOCKING?
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CRYSTALLIZATION: XRD, MDSC & POM
PLA/C30B 1%t1/2 = 3 min
PLA CNF 1%t1/2 = 9 min
PLA CNF 1%C30B 1%
t1/2 = 5 min
PLA t1/2 = 25 min
Kinetic IMPROVEMENTSize and shape ?
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THERMOMECHANICAL PROPERTIES
40 60 80 100 120 140 160
1E8
1E9
Sto
rage
mod
ulu
s (P
a)
Temperature (°C)
Neat PLA PLA CNF 5% PLA CNF 5% C30B 1% PLA CNF 5% C30B 5%
Neat PLA PLA CNF/C30B 1% 1%
There is also a synergetic behaviour
The improvement is really meaningful even at low load
PLA CNF 5%
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BARRIER PROPERTIES
PLAPLA/C30B 1%
PLA/CNF 1%
PLA/CNF/C30B 1% 1%
0
5000
10000
15000
20000
25000
0
500
1000
1500
2000
2500
WV
TR
(m
g µ
m m
-2 d
ay-1
)
OT
R (
mL
µm
m-2 d
ay-1
)
OTR WVTR
PLA/CNF 5%/C30B 5%- 89% REDUCTION OTR- 75% REDUCTION WVTR
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POLARIZED OPTICAL MICROSCOPY
PLA PLA C30B 1% PLA CNF 1% PLA CNF C30B 1%
AFTER SOLVENT CASTING
AFTER ISOTHERMAL CRYSTALLIZATION @ 100 C(COMPARABLE DEGREE OF CRYSTALLINITY)
100 µm 100 µm 100 µm 100 µm
100 µm100 µm 100 µm 100 µm
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CRYSTALLINITY AND BARRIER PROPERTIES
PLA
PLA/C30B 1%
PLA/CNF 1%
PLA/CNF/C30B 1% 1%
SOLVENT CASTING
AMORPHOUS
FULLY CRYSTALLIZED
5 MINUTES AT 170 °C - FAST COOLING
120 MINUTES 120 °C
AMORPHOUS MOBILE/RIGID UNDER INVESTIGATION
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WATER DIFFUSIVITY
PLAPLA/C30B 1%
PLA/CNF 1%
PLA/CNF/C30B 1% 1%
0.00E+000
5.00E-009
1.00E-008
1.50E-008
2.00E-008
2.50E-008
3.00E-008
3.50E-008
4.00E-008
4.50E-008
Diff
usiv
ity (
cm2 /s
)
Annealed Solvent Casting Fully Crystallized
DIFFUSIVITY CONTROLLED
QUARTZ SPRING MICROBALANCE
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GRAFTING OF BZAA (SOLREACT)
+
Small vacuumT= 130 °CTb(water) < T < Tb (agent to graft)
Removal of water critical!Not removal of the agent to graftAcetate groups acetic acid removed ?
ABSORBANT
Improve dispersion +
GIVE AN EXTRA FUNCTION
ESTERIFICATION
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CONTROLLED RELEASE95% MeOH on water fatty food simulant.
PLA + 6% CARVACROLPLA CNF 3% + 6% CARVACROLPLA gCNF 3% + 6% CARVACROLPLA gCNF 3% C30B 5% + 6% CARVACROL
SOLVENT CASTING
ISOTHERMAL CRYSTALLIZATION7,5 min at 120 ºC
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CONTROLLED RELEASE
2 4 6 8 10
5000
10000
15000
20000
25000
INT
EN
SIT
Y2
PLA CNF 3% C30B 5%
BAD CLAY DISPERSION!0 20 40 60 80 100 120 140 160 180 200
0.0
0.2
0.4
0.6
0.8
1.0
Abs
orba
nce/
Abs
orba
nce
at e
quili
briu
m
Time (min)
PLA SC PLA CNF 3% SC PLA gCNF 3% SC PLA gCNF C30B 3% 5% SC PLA ISO PLA CNF 3% ISO PLA gCNF 3% ISO PLA gCNF C30B 3% 5% ISO
RELEASE OF CARVACROL ON FATTY FOOD (MeOH 95% V/V)
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INTRODUCTION
- PLA (Polylactic acid)√ Renewable source√ Biodegradable√ Suitable for industry√ Good Mechanical properties√ Transparent
~ CostX Barrier propertiesX Thermomech. propertiesX Slow crystallizationX Brittleness
NANOCOMPOSITE
C30B CNF
Improvement of properties?
Comparisson vsSinergetic
When? How? How much?
NEED TO BE FIXED
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INTRODUCTION
- PLA (Polylactic acid)√ Renewable source√ Biodegradable√ Suitable for industry√ Good Mechanical properties√ Transparent
~ CostX Barrier propertiesX Thermomech. propertiesX Slow crystallizationX Brittleness
NANOCOMPOSITE
C30B CNF
Improvement of properties?
Comparisson vsSinergetic
When? How? How much?
ENHANCED
ENHANCED
ENHANCED
MANTAINED
ENHANCED
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Langowski, H.-C., (2008) Permeation of Gases and Condensable Substances through Monolayer and Multilayer Structures. In: Plastic Packaging: Interactions with Food and Pharmaceuticals (Eds. Piringer O.G., Baner A.L.) 2008: Wiley-VCH, 297-347.
ACKNOWLEDGEMENTS• To my supervisor board for guiding me during my PhD.
• To my coauthors for helping me and their valuable advices.
• In memoriam to Prof. Iñaki Mondragón Egaña, whose dedication for the science is a inspiration for me.
• To the Marie Curie (ITN) Program (Project: NewGenPak project No: 290098) for the financial support.
• To this COST Action FP1105 for the invitation to several meetings where I have learnt a lot (I got some inspirations during meeting at Thesalonniki)
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