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1

Emballages actifs :

Contexte général et Perspectives

recherches

Pagora Days 2012

Grenoble, 12 Juin 2012

Dr Julien Bras,

Associate Professor, UMR Grenoble INP Pagora-CNRS , France


2

. « From eating more quantity to eating best quality »

diversity, safety, functional food, nutrition

food tracability, tamper proof packaging

SOCIETY IS CHANGING

. Social & economical evolution

- level of life,

- New marketing target : children, old person

- women’s employment:from 40% to 80% between 1965 & 1999,

- New family : mono-parental, single (1 foyer sur 3)

- Less time for shopping: from 1h30 in 1980 to 30 min en 2001

- less time for dinner : 1/3 of population eat « stand up » their

lunch during week

Precooked dish, frozen food, fast food, higher shelf life food

I. Introduction

=>New packaging systems


3

Distribution evolution

- More supermarket & less storage

- Product numbers X2

- Communication multiplication everywhere

- Placed to address distribution

- E-commerce

New requirement

• consummer: easy opening, easy storage, co-use,

• Packaging maker:easy to make, automatisation, palletisation..

• distributeur: storage, presentation, traçability...

• society: recyclability, non toxicity, food contact...

SOCIETY IS CHANGING

I. Introduction

=>New packaging systems


4

Standardized field [DeJong, 2005; DeKruijf, 2002, Veermeiren, 1999]

- Active Packaging: change packaging conditions to

increase shelf life & safety of food by keeping quality

- Intelligent Packaging: monitor the quality of the food

product or its surrounding environment to predict or measure

the safe shelf life better than a best before date

Ex: ITT, leakage Indicator, freshness indicator

Active & Intelligent Packaging

I. Introduction

3 types: 1. Barrier & MAP,

2. Scavenger (O2, humidity, …),

3. Anti-microbial


5

1. Introduction

2. State of the art

3. Research perspectives

4. Conclusion

AGENDA

1. Barrier & MAP,


3. Anti-microbial

4. Intelligent Packaging


6

PVDC

PP

PVC

PA 6,6

EVOH

PVAL

Cellophane

PEHD

PEBD

10-85 8-25

360

145

560

900

1600

2500-3500

3100

2000

40-60

400

15

Water Vapour

Permeability

(38°C, 90%RH)

g.µm.m-2.d-1

Oxygen

Permeability

(23°C, 0%HR)

cm3.µm.m-2.d-1.bar-1

81000

53 000

178 000

750 000

137 000

PET 8001600

PA 6 43002000

PA MXD6 2000250

1. Barrier & MAP

II. State of the art


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Nanoloads with high ratio Length / thickness

increase of tortuosity d’

d

e

Nano & coating

EXAMPLE:

PA 6 or PET + nanoclay :

O2 barrier : + 50 to 80%

CO2 barrier : + 60 to 80%

SUSTAINPACK:

PLA + Nanoclay O2 barrier improvement

Keep transparency

Importance of plasticizer with starch films

1. Barrier & MAP



8

PAPER FIBRE MFC NCC Polymer

L= 200-500nm

D= 5-10nm L= 1000-2000nm

D= 20-70nm

L= 0,7- 10mm

D= 5-50µm

Thickness= 30-400 µm

Basis weight= 15-400g/m²

DP=10000

Z= 0,5nm

Micro-Macro Nano

NanoCellulose

1. Barrier & MAP



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Microfibrillated cellulose MFC

20-60 nm ab.500-1500 nm

Nanocrystals or whiskers

2-15 nm av. 100-500nm

CELLULOSE

FIBER

microfibril

Chemical

Treatment Mechanical

Treatment

NanoCellulose

Pääkkö, et al.,Biomacromol. 2007 Pääkkö, et al.,Biomacromol. 2007


10

1. Barrier & MAP



11

Lenes, PFI conference, 2010

1. Barrier & MAP



12 (Aulin et al., Cellulose, 2010)

=> Best biomaterial barriers

1. Barrier & MAP



13

Impact of the making process on barrier properties

– TEMPO pre-treatment

» TOCN-COOH (acid pH) ≠ TOCN-COONa (basic pH)

*Fukuzumi et al. Carbohydrate Polymers, 2011

1. Barrier & MAP



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• Food industry

- Meat and meat products

- Milk products

- Bakery products

- Beverages

• Pharmaceuticals

• Electronics

2. Scavenger



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a. EVOH film + O2 scavenger b. PA/PE film + O2 scavenger

c. EVOH film + 30% CO2/70% N2 d. PA/PE film + 30% CO2/70% N2 e. LDPE film

2. Scavenger



16

Additional property

Bioactivity

Traditional properties:

• Barrier properties

(O2 , H2O vapor, aroma …)

• Mechanical properties

• Optical properties, etc

Safety problems

Development of antimicrobial

packaging materials

Listeria spp

Salmonella spp

Toxi-infection


3. Anti-microbial

How to increase the security of food? Adapted from Coma et al ,

Pag Days 2009


17

Source: Coma et al, USB2 Univ. Lyon, ISTAB

Nisine

•Cationic Proteins

synthesized by L. lactis.

•antibacterienne

Active Packaging :

- HPMC-Nisine (Coma et al)


3. Anti-microbial

-Antimicrobial effectiveness of lysozyme immobilized on polyvinylalcohol-based

film against Alicyclobacillus acidoterrestris

By Conte, Amalia; Sinigaglia, Milena; Del Nobile, Matteo Alessandro

From Journal of Food Protection (2006), 69(4), 861-865.


18


3. Anti-microbial

Chitosan

THC= tetrahydrocurcuminoid derivatives

Source: E. Portes et al. / Carbohydrate Polymers

76 (2009) 578–584


19

3. Anti-microbial


Example: Bioswitch [Thijssen et al 2003]


20


4. Intelligent

INTELLIGENT PACKAGING

monitor the quality of the food product or its surrounding environment

to predict or measure the safe shelf life better than a best before date

EXTRA Packaging system INTRA Packaging system

Indicator Principle Objective

Time temperature Chemistry or enzymes Storage Conditions

O2 redox Pigments, pH sensitive pigment,

enzymes Storage & leakage Conditions

CO2 Chemistry Storage & leakage Conditions

Freshness pH sensitive pigment , specific molecule

Pigments Microbial degradation

bactéries Chemistry or immunocemistry Pathogènes bacterie presence


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Pathogenes Detection

VTT Technical Research Centre of Finland, 2006. Disponible sur :

www.vtt.fi/inf/pdf/workingpapers/2006/W51.pdf


4. Intelligent

http://www.vtt.fi/inf/pdf/workingpapers/2006/W51.pdf


22

Temperature Logger

• Status

– Proof of principle achieved

– Mock up will be used, because real system will be ready in May 2008?

• Focus

– Development towards requirements (T range and accuracy)

– Changing data allowed by law

– Start button

– Read-out


4. Intelligent


23

1. Introduction

2. State of the art

3. Research & perspectives

4. Conclusion

AGENDA

1. Barrier & MAP,


3. Anti-microbial

4. Intelligent Packaging


24

L = 210 nm

d = 5 nm

L/d = 42

Sugar Beet

Scale bars : 50 nm

T1 : Bio-nano-particules &

their use: Cellulose nanocristals, starch, chitine ; NFC,

Bio-nanocomposites, mechanical

reinforcement, characterisation

T2 : New biomaterial : from surface

treatments to composites Biopolymer ; Bio-composites ; chemical grafting ; Rheology

of enduction sauce ;adhesion & coating ; Multilayer ;

Microencapsulation ; Specialty paper, extrusion

T3 : Functionnal Packaging : 3D

process & end-use properties Cardboard, Core ; Thermoforming ; embossing ; Shelf life &

barrier properties ; Mechanical similution & humidity

conditions, RFID, functionnal material & coating, food contact

PEM+functional Fibres

Converting

Biomaterial Packaging

Dpt

Laboratory of paper science & graphic arts

LGP2 - UMR 5518

20 researchers

(10 PhD, 2 post-doc)

Ab. 100 employees staff, 40 PhD


25

0

1E-11

2E-11

3E-11

4E-11

5E-11

6E-11

7E-11

8E-11

PVA

W c

otto

n 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 fl

ax/h

emp

6,5

W M

CC 4

WV

P g

/(m

.Pa

.s)

0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

5

WV

TR

g/(

m².

24

h)

WVP

WVTR

HR= 0% HR= 0%

CaCl 2

Film Water vapor

23°C-50%RH

300%

Global decrease of WVP (till divided by 3)

AGROBAR

Sénéchal et al, MATBIM, 2010*

PVA

Paper

NCC

III. Research examples 1. Barrier


26

5 m

Gel Films Biopolymer

(e.g. starch...)

Starch Nanocrystals

Final Uses

Initial

Products

Product

Product

Coated Paper

Product

Commercial message

Properties

FlexPakRenew

Most commun

application



27

Xylan Starch

408

358337

227

102

67

340

50

100

150

200

250

300

350

400

450

Wa

ter

Va

po

r T

ran

sm

iss

ion

Ra

te (g

/m².

d)

691

484449

8

115

0

100

200

300

400

500

600

700

800

Ref Handsheet S/PEG S/PEG/Nanoclays A S/PEG/SNC

Wa

ter

Va

po

r T

ran

sm

iss

ion

Ra

te (

g/m

².d

)Phase 1:

Industrial paper(42g/m²)

Phase 2:

Medium barrier coating

(10-12 g/m²)

Phase 3:

PVA coating (2.5g/m²)

& GraftingLS Demonstrator 1

Starch / PEG / Nanoclays

LS Demonstrator 2Starch / PEG / SNC

Phase 1:

Industrial paper(42g/m²)

Phase 2:

Medium barrier

coating (10-12 g/m²)Medium Barrier 2

Xylan / Glycerol / SNC

Medium Barrier 1

Xylan / Glycerol / Nanoclays



28

Immersion on TiO2

nanoparticles aqueous

suspension

(5-15% TiO2)

TiO2 nanoparticles adhere to fibres surfaces without polyelectrolytes

ASSEMBLY OF TiO2/CELLULOSE NANOCOMPOSITES WITH PREVIOUS

FIBRE PROTECTION

Source: Bras & Neto, 2008

III. Research examples 2. Scavenger


29

=> Important anti-ripening effect with addition of Aveiro fibre treatment

even when used in composites

PEM+classic Fibre(30%) PEM+AveiroFibres(30%)

AFTER 12 days

Test at 25°C / 22

hours of UV

irradiation in total

/during 12 days



30 30

Active packaging test

=> Very interesting results with acid ascorbic coated paper

Pap2

Pap1



31

Cyclodextrine

- Trapping system thanks to cellulose

cyclodextrin grafting

- Positive impact on prolonged release

Cusola et al., JAPS. submitted, 2012*

III. Research examples 3. Antimicrobial


32

Ref : 0 g/m² (MFC weight coat) 2 coats : 3 g/m² 5 coats : 6 g/m²

0

2

4

6

0 2 4 6 8 10 12 14 16

MFC weight coat (g/m²)

Air

per

mea

bili

ty (

cm3 /m

².P

a.s)

0

40

80

120

160

200

Air p

ermeab

ility (cm3/m

².Pa.s)

Bar coating

Size press

Wet multilayer

Bar coating

-95%

Size press

- 61%

Multilayer

-77%

Burst index (kPa.m²/g) X

Young modulus (Gpa) + 75%

Bending stiffness (N.mm) + 54%

Lavoine et al., Tappi Nano, 2011*

Mechanical & Barrier improvement

Paper Paper+MFC

GR

EA

SE

BA

RR

IER



33

Paper/cardboard

MFC

Active molecule

? ?

? ?

? ?

Prolonged Release

Liquid

Oil

Gaz

? ? ?

Barrier properties

Antimicrobial property

?

• MFC coating => Barrier due to « nanoporosity »

BiopackFun Project (2010-2013)

• Expect for High value added materials

=> prolonged release due to « nanoporosity »



34

3 different kind of MFC 3 different kind of MFC + caffein

Kinetic release Successive release

Films immersion

+ caféine

MFC > 1 year collaboration > Furnish of MFC suspensions > Release study with films

III. Perspectives


35

MFC

+

I

II +

IV

+

?

?

Couchage

Couchage

III

III. Perspectives


36

Obtention

NC

Grafting

Grafted NC

Nanocomposite preparation

Active nanocomposite Multilayers

One phase

PVA, starch PLA PBS PCL paper

Amines Phenolic compounds Pesticides Anisol*

Aqueous media Solvent

• Silanes (NOTES)

• Others

• Copolymers

Direct reaction

Nanomicelles

SiSi

∆T

Freeze-drying

SiSi

SiSi

SiSi

SiSi

MCC

Where

Migration, Characterization, Application

Australia Grenoble Paris

1

2

3

4

6 5

Radical polymerization Esterification Cyclodextrin*

WMS CNC Redispersible

Ozonolysis

CAN

Vapor media reaction

+ NOTES ∆T

∆T

III. Perspectives


37

IV. Conclusion

- Society expectation => More & more important field

-Only bio or only active is not sufficient

-Difficult to have test for all kind of packaging

-Interesting possibilities with nanocellulose

-New legislation


38 38

THANK My CO-WORKERS (N.Lavoine, I.Desloges, E. Espino, N.Belgacem, A. Dufresne, K.Missoum, G.Siqueira, T.Senechal)

And

THANK YOU FOR YOUR ATTENTION

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