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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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NANOCELLULOSE PRODUCTION

STABLE SUSPENSION

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NANOCELLULOSE PRODUCTION

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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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