Verpackung von Lebensmitteln

8 / 9 September 2011 Freiburg

CH-1700 NH Kongresshotel

I)  Introduction to Polymer Nanocomposites for

Food Packaging Applications

II) Overview on an European Activity in the Field

Cost Action FA0904
Eco-sustainable Food Packaging based on polymer nanomaterials

Clara Silvestre and Donatella Duraccio

Istituto di Chimica e Tecnologia dei Polimeri
Consiglio Nazionale delle Ricerche Italy

1
 Nano-enhanced products increasingly appear in our everyday life,
even if we do not always realise it

1 - Organic Light Emitting Diodes

2 - Photovoltaic film
3 - Scratch-proof self-cleaning glass
4 - Stain resistant fabrics
13
5 - Intelligent clothing
6 - Bucky-tubeframe
7 - Biocompatible hip-joint
8 - Nano-particle paint
13
9 - Thermo-chromic glass
10 - Magnetic data memory
11 - Carbon nanotube fuel cells
Source: BBC
12 - Nano-engineered cochlear implant
13- Nanomaterials for food packaging
2
Polymer nanotechnology
impacts across all sectors of the
global material markets and fits all size
companies

Polymer nanomaterials have the

potential for enhanced product
characteristics
• fire retardancy
•  thermal stability
•  mechanical strength
•  barrier properties
•  Biocompatibility
in industrial sectors where improved
performance together with reduced
cost and weight are essential:

Source: “Innovation: applying knowledge

in development”, UN

3
 Polymer Global Market

Silvestre C, Duraccio D, Cimmino S. Food packaging based on polymer nanomaterials.

Prog Polym Sci (2011), doi:10.1016/j.progpolymsci.2011.02.003

4
Eco-sustainable Food Packaging based on Polymer Nanomaterials
Functions of packaging
1.  Containment
2.  Protection and
preservation
3.  Marketing and
communication
Polymer nanotechnology can
implement the packaging
functions adding sustainability
Sustainable packaging
(according to the Sustainable Packaging Coalition®)
• It is beneficial, safe, and healthy for individuals and
communities throughout its life cycle.
• It is designed to optimize materials and energy. It is
sourced, manufactured, transported and recycled using
renewable energy.
• It maximizes the use of renewable or recycled source
materials.
• It is made from materials healthy in all probable end-of-life
scenarios.
• It meets market criteria for performance and cost.
5
Current status of Polymer Nanomaterials for Food
Packaging (PNFP) Application

The presence of nanoparticles in the polymer

Improved PNFP matrix materials improves the packaging
properties of the polymer: flexibility, gas barrier
properties, temperature/moisture stability; etc

The presence of nanoparticles allows packages

Active PNFP to interact with food and the environment and
play a dynamic role in food preservation;

The presence of nanodevices in the polymer

matrix can monitor the condition of packaged
Smart PNFP
food or the environment surrounding and can
also act as a guard against fraudulent imitation

6
 Improved nanopackaging

Polymers incorporating clay nanoparticles are among the first

polymer nanomaterials to emerge on the market as improved
materials for food packaging

Several different polymers and clay fillers can be used

for obtaining clay –polymer nanomaterials

Polymers; polyamide, nylons, polyolefins, polystyrene, ethylene-

vinylacetate copolymer, epoxy resins polyurethane, polyimides and
polyethylene terephthalate.

Nanoclay : montmorillonite (MMT), a hydrated alumina-silicate layered

clay consisting of an edge-shared octahedral sheet of aluminum
hydroxide between two silica tetrahedral layers
7
Intercalated: Organic component inserts
between the layers of the clay. Inter-
layer spacing is expanded, but the layers
still have a well-defined spatial
relationship to each other
Flocculated-intercalated: is the same
then intercalated, however silicate
layers are some times flocculated due to
hydroxylated edge-edge interaction of
layers.
Exfoliated: Layers of the clay are
completely separated and the individual
layers are distributed throughout the
organic matrix

8
Improved nanopackaging

Clay particles can cut permeability as much as 75%

9
Improved Packaging

10
Eugenia Nunez Nanobiomatter – Valencia Spain
 Improved Packaging

Very recently a new methodology was reported for preparation of a transparent

clay−polymer with very high oxygen barrier: the lowest permeability ever
reported

This improvement is due to a brick wall nanostructure created by the alternate

adsorption of polymeric mortar and highly oriented, exfoliated clay platelets.
Thin films of sodium montmorillonite clay and branched polyethylenimine were
deposited on various substrates using layer-by-layer assembly

For PET the OTR is below the commercial instrumentation detection limit
(<0.005 cc/(m2 day atm).

11
Priolo et al Appl. Mater. Interfaces, 2010, 2 (1), pp 312–320
Improved Packaging
The incorporation of nanoclays into packaging also offers:

•  Reduction in raw materials. Improved stiffness enables the use of less

raw material and down-gauging by 20% can be achieved. Lighter packaging
may lead to savings in the cost of transportation, storage and recycling.

•  Less dependence on speciality products. Polymer-clay nanocomposites

can be alternatives to expensive speciality materials.

•  Elimination of secondary processes. High-cost operations such as

laminations for barrier packaging or mechanical surface finishing can be
eliminated.

•  Less complex structures. Nanocomposites may have, for example, less

complex structures than multi-laminates and this can lead to easier
recycling.

•  Reduction in machine cycle time. By changing the physical and thermal

properties of polymers it is possible to reduce pack production times.

12
Active Packaging
Active packaging allows packages to interact with food and the
environment and play a dynamic role in food preservation

Active nanopackaging includes:

13
 Active Packaging

New nanocomposites based on isotactic polypropylene

(iPP) for food packaging

• 









• 
 

 

  


  

14
Spray Pirolysis apparatus
Active Packaging

PRELIMINARY RESULTS

The thermal stability of iPP/ZnO nanocomposites is improved respect to neat

iPP and increases with the ZnO content.

The incorporation of ZnO particles imparts significant improvements

on the photo-degradation resistance of iPP to UV-irradiation.

iPP/ZnO systems show antibacterical activity against Escherichia-coli.

Bacterical concentration decreases increasing the amount of ZnO

15
Active Packaging
  
 




 

ASTM E 2149-10

Control plate without ZnO Antibacterical effect of ZnO

nanoparticles to measure the in iPP (iPP/ZnO 5%) after 48h
Escherichia-coli grow after 48 h
16
Smart Packaging
Smart food contact materials are intended to monitor the condition of packaged food or
the environment surrounding the food.

•  Indicators Time temperature : they monitor

package integrity and the time-temperature history

effective expiration date

•  The so-called nanosensors: they respond to;

environmental changes
(temperature or humidity in storage rooms, levels of oxygen exposure)

degradation products or microbial contamination

(oxygen indicators, freshness indicators and pathogen sensors gas sensors)

•  Recently advances:
The so-called “Electronic Tongue” technology;

Devices that will provide a basis for intelligent preservative-packaging technology that
will release a preservative if food begins to spoil.

17
Smart humidity nano-sensors in food packaging

Source:Attophotonics

18
 Current status of Polymer Nanomaterials for Food
Packaging application
The Total Nano-packaging Market
2008 US $4.13 bln
2014 (forecasted) over US$ 7 bln (iRAP, Inc and BBC Research)

Which TECHNOLOGY
Now Improved and Active technology represents the largest share.
2014
Active and improved US $ 4.5 bln
Intelligent US $ 2.5 bln.

Which FOOD
Bakery, meat products, carbonated drinks and bottled water and beer, etc.

Where
Asia/Pacific, Japan is the market leader in active packaging, with 45% of the
current market, US $1.86 bln in 2008 and projected to grow to US $3.43 bln
by 2014
In USA and Australia, improved and active packaging are already being
applied to extend shelf-life while maintaining nutritional quality and ensuring
19
microbiological safety.
 Food- Storage products in Woodrow Wilson database

Antibiotic properties
Fresh food storage container, nano-Ag / USA
Refrigerator coatings, nano-Ag / USA, Jap. Korea
Plastic storage bags , nano-Ag/ USA
Baby mug, nano-Ag / Japan
Water bottle/ salad bowl, nano-Ag/ Korea

Packaging
Plastic Wrap, nano-ZnO / China
Beer bottle with Nano modified Imperm (Corona and Hite), nano-clay/USA
Low permeability coating on polyester bag, nano?/ USA

Others
Adhesive for Mc Donalds burger containers, nano-Starch / USA
Non stick coating Al- foil, nano-?/ DE
20
 Current status of PNFP application

In Europe the industrial application are coming slowly

The main reasons are

 Cost: material and processing
 Legislative restrictions
 Acceptability to European consumers
Lack of knowledge on efficacy and environmental impact

Health concerns: Potential risks due to the migration of the nanoparticles into food

21
 Environmental impact

•  Nanomaterials can enter the environment in the course of

their lifecycle. How long they survive there, and in which
form, i.e. how long they persist, is still matter of
investigation

•  Current predictions suggest that the contribution of

nanoparticles used in food packaging to the total of the
environmental concentration seems to be sure trascurabile

22
 Impact on human health

Three different ways of entrance penetration of nanoparticles in the organism

are possible : inhalation, entrance trough skin penetration and ingestion.

•  Growing scientific evidences that free nanoparticles can cross cellular

barriers and that exposure to some of these nanoparticles may lead to
oxidative damage and inflammatory reactions.

•  For food packaging nanomaterials the inhalation and the entrance trough
skin penetration is relative mainly to the workers in the factories producing
the nanomaterials.

•  For the final consumers the first concern is to verify the extend of migration
of nanoparticles from the package into the food and then the effect of the
ingestion of the nanoparticles inside the body

•  Few studies are present in literature on the migration of nanoparticles to

the food. In all cases insignificant detectable migration of nanoclay is
observed. Although these cases seem to give some reassurance about
safety the number of tests is too limited and further investigation need to be
performed before using these materials.
23
Consumer Perception

•  People’s emotions play an important role in perception on new

technologies nanotechnology

•  Latest surveys results that in Europe and USA there are different
consumer perceptions for food nanothecnology.

European consumers whilst are positive about the opportunities of

nanotechnology in several application, they are sceptical of the use
of nanoparticles in food

American consumers expect many advantages of nanotechnology

also for safer and better food

24
Regulation issues

•  As developments in nanotechnology continue to emerge, its

applicability to the food industry is sure to increase. The success of
these advancements will be strictly dependent on exploration of
regulatory issues. A wide variety of government agencies has taken
interest in nanotechnology.

•  The European Food Safety Authority EFSA on February 2009 has

concluded its assessment of the potential risks of nanotechnologies for
food and feed

•  The bad news is that there are no general rules!

Case-by-case approach is needed

There is urgent need for informed public debate on nanotechnology and food

25
 Conclusions: Needs for a successful application of PNFP

– to define the composition/structure/processing/property relationships

-- to improve characterisation and measurement tools
--to identify stable industrial procedures for homogeneous dispersion of
nanoparticles and for inclusion of nanodevices
--to reach the highest level of knowledge of the interaction of the PNFP with food
and of the risks from nanotechnology for human body
--to improve the understanding of the potential environmental impacts of
nanotechnology-based packaging over their life cycle; Improving the
management of health and environmental risks
–  to harmonize classification and standardization; Identifying specific areas which
need new validated test adapted to the industry
–  to provide up-to-date information on the potential toxicological effects of
polymer nanostructured materials on human health for a wide audience and their
risk assessments

“Eco-sustainable Food Packaging based on Polymer Nanomaterials” C. Silvestre, D.

Duraccio, S. Cimmino. Progress in Polymer Science 2011 doi:10.1016/j.progpolymsci.
2011.02.003

26
Eco-sustainable Food Packaging Based on Polymer
Nanomaterials

COST Action FA0904

Start date: 29/03/2010
End date: 28/03/2014
Year: 1
Chair Clara Silvestre
Istituto di Chimica e Tecnologia dei Polimeri
Consiglio Nazionale delle Ricerche/Italy

27
 Scientific context and objectives (1/2)
MoU Objectives

  To constitute an international scientific and technology network on

issues related to eco-sustainable Polymer Nanomaterials for Food
Packaging (PNFP) for the preservation, conservation and
distribution of high quality and safe food

  To contribute to identify the barriers (in research and technology,

safety, standardisation, trained workforce and dissemination) that
prevent a complete successful development of PNFP and the
strategies to proceed further.

28
Scientific context and objectives (2/2)

Research directions Smart

PNFP

Combined efforts of leading

research/industrial groups

29
 Working groups
•  WG1 Development of new safe PNFP
Leader: Dr Mika VAHA-NISSI (FI) – VTT
Vice-leaders: Prof. Alex SIVAN (IL) and Dr Janis ZICANS (LV)
Approximate number of members: 45

•  WG2 Development of new processing technologies including modelling

and simulation
Leader: Prof. Jose Maria LAGARON CABELLO (ES)
Vice-leaders: Dr R. RUTKAITE (LT) and Dr J. DEXPERT-GHYS (FR)
Approximate number of members: 45

•  WG3 Development of new strategies to identify any critical interaction of

PNFP with food
Leader: Dr Qasim CHAUDHRY (UK) –
Vice-leaders: Dr Ignacy JAKUBOWICZ (SE) and Dr Ramesh Babu P (IE)
Approximate number of members: 30

•  WG4 Ethics, Standardization, Science-society dialogue

Leader: Prof. Geoffrey HUNT (UK) –
Vice-leaders: Prof. Marek KOZLOWSKI (PO) and Dr Ruth Schmid (NO) –
Approximate number of members: 30

First meeting of the WGs (Iasi, Romania, June 2010): the WG leaders presented the contest
of the activities and an agreement on the major themes/division of tasks was reached
30
Grant Holder
ICTP/CNR- Italy
Scientific Representative
Dr. Sossio Cimmino

Participating countries
COST Countries
AT, BE, BG, CH, CZ, DE, DK,
ES, FI, FR, GR, IE, IL, IS, IT,
LT, LV, MK, NL, NO, PL, RO,
RS, SI, SE, UK.
Non COST Countries
USA, CA, NZ
Interested Countries:
TR (pending), CY, PT
31
32
Use of COST Instruments
Progress includes several successful
Activity (No.) Year 1 Year 2 Year 3 Year 4
activities

MC/WG 2/5   Kick-off meeting (Brussels 29-30 /3/2010),

Meetings where procedures and / tools to guarantee the
Action development were set;
STSMs 7   Plenary conference (Iasi , Romania
29/30-6-2010), that included the 1° WGs meeting
Training - and a Round Table dedicated to industry;
Schools   Technological Seminar London (1/2 -9-2010)
on Ethical Issues.
Workshops or 3
  International Workshop (Pozzuoli Italy
Conferences 3/4-3-2011) with a session dedicated to WG1,
MC meeting and a Round Table for ESRs.
Joint 20  Involvement of ESRs: 7 STSMs grants,
Publications organization of a round table, constitution of an
intergroup Entity.

33
Results vs. Objectives

The focus of the activities performed was mainly to build, to

strengthen and to enlarge the Network and to plant the seeds
for innovative knowledge in the field of PNFP

The Action has fully achieved the objectives and technical

goals for this first period, with results well above those
planned

34
Innovative networking (1/3)

In the short time of life some interesting results were already obtained,
mainly through the STSMs, with formation of new networks:
 investigation of morphological/structural properties (degree of dispersion of
nanoparticles in the matrix and their influence on properties);
 study of recyclability of some PNFP for increase ecosustainability;
 new approach for setting up novel nanosensors to measure temperature/humidity
based on fibre optic sensor;
 identification of the shape and minimum amount of nanoparticles required to
influence properties and processing conditions for nano-platelets or spherical
nanoparticles.

Improved packaging: Films of polypropylene (a)

and with embedded clay nanoparticles (dark
objects) b), used for food packigning

35
 Innovative networking (2/3)
Significant highlights in Science

 Analysis of dispersion and alignment of nanoparticles.

The flakes align parallel to film surface, exactly the

arrangement required to increase the tortuosity of gas paths,
which provides higher barrier properties.
This activity resulted also in a formation of a new
network

Significant scientific breakthrough SAXS patterns for a polymer films with 0.5%
flakes for (A) parallel plate shear cell, (B) a
Development of a new film based on polypropylene and Couette cell.
zinc oxide with antibacterial activity (Escherichia-coli
DSM498). This breakthroughs, still in a preliminary stage
was obtained with a multidisciplinary approach (8
institutions/ 4 countries) This activity resulted also in a
bilateral project CNR/CNRS and formation of new
network
Active packaging:
Antibacterial effect of ZnO in
iPP films a) Control plate; b) 36
iPP/ZnO 5%
Innovative networking (3/3)

• Tangible medium term socio-economic impacts achieved

 The networking has already stimulated participants to submit joint projects.

At the moment 10 proposals obtained financial support
Funded proposals

AGREEMENT CNR/BAS JOINT PROJECT 2010-2012

Proposal n° 20101056 “Soleil Parigi France
Accord Cnr/Cnrs Conjoints De researche 2010-2011

Project within the frame of programme Nanotechnologies for Society by

Academy of Science Czech Republic 2011

Proposal n° 20100458 for Elettra TRIESTE

Consortium Emilia-Romagna Region, Universities, Chamber of Commerce and
industrial association, CNR and ENEA,

Proposal n° 23868 “– ESRF Grenoble

Project for Elettra beam time n. 2010/5480

37
Project supported by Tukitak Turkey 2011-2012
Future Plan
Organization of

International Workshop
“Novel nanostructured polymeric materials for food packaging and beyond”
Espoo, FINLAND, September 15-16 2011
Venue: Technical Research Centre of Finland
http://www.vtt.fi/files/vtt/vtt_karttaespoo.pdf

Training school Skopie November 2011

Spain (WG2- March ‘12)

• Plan for the future includes a seminar (late in 2012) on migration, food impact and
food quality (WG3) and the preparation of a booklet for consumers that explains the
development of safe nanomaterials-based (WG4).

• Plan for the future includes presentation of demonstrator projects, to go beyond the
materials development/processing/characterization and to evaluate food shelf-life,
biodegradability.

38
 Verpackung von Lebensmitteln

8. / 9. September 2011Freiburg
CH-1700 NH Kongresshotel

Polymer Nanocomposites for Food Packaging Applications

Further information:
www.cost.esf.org (FA0904)
www.nanocomposites-cost.eu
duraccio@ictp.cnr.it silvestre@ictp.cnr.it

Thank you for your attention

Clara Silvestre and Donatella Duraccio

ISTITUTO DI CHIMICA E TECNOLOGIA DEI POLIMERI CNR Italy 39