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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
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. « 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
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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
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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
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1. Introduction
2. State of the art
3. Research perspectives
4. Conclusion
AGENDA
1. Barrier & MAP,
2. Scavenger (O2, humidity, …),
3. Anti-microbial
4. Intelligent Packaging
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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
II. State of the art
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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
II. State of the art
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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
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Lenes, PFI conference, 2010
1. Barrier & MAP
II. State of the art
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12 (Aulin et al., Cellulose, 2010)
=> Best biomaterial barriers
1. Barrier & MAP
II. State of the art
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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
II. State of the art
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• Food industry
- Meat and meat products
- Milk products
- Bakery products
- Beverages
• Pharmaceuticals
• Electronics
2. Scavenger
II. State of the art
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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
II. State of the art
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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
II. State of the art
3. Anti-microbial
How to increase the security of food? Adapted from Coma et al ,
Pag Days 2009
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Source: Coma et al, USB2 Univ. Lyon, ISTAB
Nisine
•Cationic Proteins
synthesized by L. lactis.
•antibacterienne
Active Packaging :
- HPMC-Nisine (Coma et al)
II. State of the art
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.
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II. State of the art
3. Anti-microbial
Chitosan
THC= tetrahydrocurcuminoid derivatives
Source: E. Portes et al. / Carbohydrate Polymers
76 (2009) 578–584
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3. Anti-microbial
II. State of the art
Example: Bioswitch [Thijssen et al 2003]
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II. State of the art
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
II. State of the art
4. Intelligent
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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
II. State of the art
4. Intelligent
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1. Introduction
2. State of the art
3. Research & perspectives
4. Conclusion
AGENDA
1. Barrier & MAP,
2. Scavenger (O2, humidity, …),
3. Anti-microbial
4. Intelligent Packaging
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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
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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
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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
III. Research examples 1. Barrier
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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
III. Research examples 1. Barrier
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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
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=> 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
III. Research examples 2. Scavenger
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30 30
Active packaging test
=> Very interesting results with acid ascorbic coated paper
Pap2
Pap1
III. Research examples 2. Scavenger
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Cyclodextrine
- Trapping system thanks to cellulose
cyclodextrin grafting
- Positive impact on prolonged release
Cusola et al., JAPS. submitted, 2012*
III. Research examples 3. Antimicrobial
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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
III. Research examples 3. Antimicrobial
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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 »
III. Research examples 3. Antimicrobial
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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
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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
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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
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