“Eco-sustainable Food Packaging Based on Polymer Nanomaterials”

Transcription

THE UNIQUE COST FA0904 NETWORK
Complete Life Cycle of the PNFP
Primary Resources
Extraction
&
Processing
Production
Use
Reuse
Recover
Recycle
Analysis of interaction with food; Safety
Disposal
Emission
and Waste
“Eco-sustainable
Food Packaging Based on
Polymer Nanomaterials”
Can Nanotechnology Help Delivering
Good Quality & Safe Food to Everyone?
International Conference
26 - 28 February 2014 CNR Rome Italy
Book of the Abstracts
EUROPEAN COOPERATION IN SCIENCE AND TECHNOLOGY
International
Workshop
“Eco-sustainable
Food Packaging Based on
Polymer Nanomaterials”
Can Nanotechnology Help Delivering
Good Quality & Safe Food to Everyone?
Programme and Extended Abstracts
IInternational
ntern
Conference
26 - 28 February 2014 CNR Rome Italy
of the Abstracts
Book o
Editors
Sossio Cimmino
Marilena Pezzuto
Clara Silvestre
International Workshop
2014 ISBN 978-889-808-545-3
Final International Conference
"Eco-sustainable Food Packaging Based on Polymer Nanomaterials"
COST ACTION FA0904
26 - 28 February 2014, Sala Marconi - CNR - Piazzale A. Moro, 7 - 00185 - ROME
ORGANIZING COMMITTEE
Conference Chairs
Clara Silvestre
Sossio Cimmino
Scientific Board
Cosimo Carfagna
Qasim Chaudhry
Sossio Cimmino
Jeannette Dexpert-Ghys
Donatella Duraccio
Emanuele Fiore
Geoffrey Hunt
Ignacy Jakubowicz
Rumiana Kotsilkova
Marek Kozlowski
Josè Maria Lagaron Cabello
Ramesh Babu Padamati
Marilena Pezzuto
Ramune Rutkaite
Clara Silvestre
Alex Sivan
Mika Vaha-Nissi
Cornelia Vasile
Janis Zicans
Contacts
Sossio Cimmino ([email protected])
Donatella Duraccio ([email protected])
Anna Esposito ([email protected])
Marilena Pezzuto ([email protected])
Clara Silvestre ([email protected])
Local Organizing Committee
Anna Rita Appetito
Pasquale De Luca
Donatella Duraccio
Anna Esposito
Antonella Marra
Marilena Pezzuto
Francesca Proia
Annamaria Randazzo
Final International Conference
"Eco-sustainable Food Packaging Based on Polymer Nanomaterials"
The International Conference is organized in the framework of COST Action FA0904, " Eco-sustainable Food Packaging Based on Polymer Nanomaterials", an International Scientific and Technological Network funded by EC, focused on issues related to polymer nanomaterials for food
packaging (PNFP) application. The Action began on 29 March 2010 for a period of 48 months and
involves 320 participants from 33 Countries. The Action has generated excellent scientific knowledge strongly underlining that post-processing protection through novel packaging based on
nanotechnology is an innovative and valuable methodology to ensure food safety, reduce post
harvest losses and facilitate international trade in a sustainable and environmentally responsible
manner, and to contribute to feed the growing world population with safe and nutrition food,
meeting the 2020 European targets to combat poverty and to reduce waste. The envisioned
direction is to look at the complete life cycle of the PNFP by the combined efforts of leading
research and industrial groups.
The Conference will close the activities of the Action, with the aim at highlighting and disseminating the achievements of the Action with regards to efficiency and effectiveness, environment,
health, safety and cost of novel PNFP.
The Conference will join scientists and technologists working in different fields of PNFP bringing
together methodologies, processing, structure–characterization techniques, properties, health,
regulation, economic and environmental considerations in order to support the design of
innovative PNFP with controlled structures and properties and to face the challenges that still
remain open, identifying the barriers (in research, technology, safety, standardization, eco-sustainability, trained workforce and technology transfer), that prevent a successful development
of PNFP and suggesting strategies necessary to progress. Finally the Conference will constitute a
further opportunity to strengthen the Action Network and will act as launching platform to
establish new fruitful cooperation in Europe.
Information at www.costfa0904.eu
Final Conference
Cost Action FA0904
26 - 28 February, Sala Marconi - CNR - Piazzale A. Moro, 7 - ROME
PROGRAMME
WEDNESDAY 26 FEBRUARY
8:30
Registration
9:00 - 9:30
Welcome
Chair: Sossio Cimmino
Luigi Nicolais, CNR President
Luigi Ambrosio, Head of CNR Department: Chemical Science & Materials Technology
Francesco Loreto, Head of CNR Department: Biology, Agriculture & Food Science
Cosimo Carfagna, Director of ICTP/CNR
Opening
Ioanna Stavridou, COST Science Officer Food and Agriculture Domain, Belgium
9:45 - 10:10
“European Cooperation in Science and Technology- COST”
Clara Silvestre, COST Action FA0904 Chair
“COST ACTION FA0904 "Eco-Sustainable Food Packaging Based on Polymer Nanomaterials": It is
Time for the Final Appraisal”
10:10 - 10:40 Coffee break
10:40
Session 1
WG1: Development of New Safe PNFP
Introduction Key lecture
Mika Vähä-Nissi , VTT Technical Research Centre of Finland
“Atomic Layer Deposited Thin Films For Packaging”
Josè Kenny, University of Perugia, Italy
“Advances in PLA Matrix Nanocomposites for Food Packaging”
Mikko Tuominen, SP Technical Research Institute of Sweden
“Multifunctional Nanoparticle Coating Using (LFS)-Technique”
Hynek Biederman, Charles University in Prague, Czech Republic
“Low Pressure Plasma Coatings for Food Packaging”
Ana Rita Ferreira, Universidade Nova de Lisboa, Portugal
“Characterization of Fucopol Films for Food Packaging”
13:00 - 14:30 Lunch
Chair: Mika Vähä-Nissi
WEDNESDAY 26 FEBRUARY
14:30
Chair: Josè Maria Lagaron
Session 2
WG2: Development of New Processing Technologies
Introduction Key Lecture
Josè Maria Lagaron, Spanish Council for Scientific Research (CSIC), Spain
“Nanocellulose-Based Renewable Packaging Materials”
Mustapha Kaci, University Abderrahmane Mira, Algeria
“A Study of the Combined Effects of PHBV-g-AM Compatibilizer and Cloisite 30B on PHBV/PLA Blends”
Pilic Branka, University of Novi Sad, Serbia
“The Influence of Physical Modification on the Properties of PLA Films as Green Packaging Materials”
Miguel Cerqueira, University of Minho, Portugal
“Reinforcement of Polysaccharide-Based Films: Evaluation of Physic-Chemical Properties”
Daniela Pamfil, “Petru Poni” Institute of Macromolecular Chemistry, Romania
“Thermal Characterization of Hydrogels Based on Anhydride Modified Collagen and 2 - Hydroxyethyl
Methacrylate”
16:40 - 17:00 Coffee break and Networking
Panel 1: Antimicrobial Packaging
Key Lecture
Louise Deschênes, Agriculture & Agri-Food, Canada
Moderator: Mustapha Kaci
“Challenges in Investigating Nanoparticles as Antimicrobial in Food Packaging. ZnO Case Study”
Marc Verelst, Université Paul Sabatier Toulouse III and CNRS, France
“Preparation and Characterization of Several Polymer/Zinc Oxide Microcomposites with Antibacterial
Activity”
Ramune Rutkaite, Kaunas University of Technology, Lithuania
“Production Technologies of Antimicrobial Silver-Containing Packaging Materials”
Bogdanel Silvestru Munteanu, AL.I. Cuza University, Romania
“Antibacterial Membranes Based on Polyurethane and Biological Polymers”
Paola Del Serrone, Consiglio per la Ricerca e la Sperimentazione in Agricoltura CRA, Italy
“Evaluation of a Mono-Component and a Multi-Component Herbal Extracts as Candidate for
Antimicrobial Packaging of Fresh Retail Meat”
Panel Discussion
THURSDAY 27 FEBRUARY
9:00
Chair: Selcuk Yildirim
Session 3
WG 3: Development of New Strategies to Identify any Critical Interaction
of PNFP with Food
Selcuk Yildirim, Zurich University of Applied Sciences, Switzerland
“Critical Interactions between Palladium Based Oxygen Scavenger and the Food”
Stefanie Gaengler, Cyprus University of Technology, Cyprus
“Influential Factors of Bisphenol A Leaching from Polycarbonate Containers into Drinking Water:
a Simulation Study”
Maurizio Avella, Institute of Chemistry and Technology of Polymers, CNR, Italy
“Plasticization of PLA with Esterified Oligo-PLA”
Federica Aureli, Istituto Superiore di Sanità, Italia
“Single Particle-ICP-MS and Asymmetric Flow Field Flow Fractionation-UV-MALS-ICP-MS for the
Analytical Determination of Inorganic Nanoparticles Released from Polymer Nanomaterials
for Food Packaging”
Marit Kvalvåg Pettersen, NOFIMA, Norway
“Evaluation of Suitability of Some Biomaterials for fresh food. Case Study: Biomaterials for
Fresh Products"
Christos Pandis, National Technical University of Athens, Greece
“Water Sorption and Dielectric Study of Chitosan Films with Various Degrees of Deacetylation”
12:00
Panel 2: Foresights: Filling the Gap Between
Scienceand Technology
Key Lecture
Geoffrey Mitchell, Institute Polytechnic Leiria, Portugal
Moderator: Erich Kny
“A Comparison of Nanocomposities and Nanostructured Polymers for Safe and Effective
Food Packaging”
Christoph Schick, University of Rostock, Germany
“Crystal Nucleation in Poly(epsilon-caprolactone) - Multiwalled Carbon Nanotube Composites”
Gaetano Guerra, Nano Active Film S.r.l., Spin-off Company of the University of Salerno, Italy
“Food Packaging Based on Nanoporous-Crystalline Polymers”
Francesco Marandino, Penelope SpA, Italy
“Intelligent Packing to Support Supply Chain Food Traceability”
Remo Merijs Meri, Riga Technical University, Latvia
“Characterization of Polyethylene Terephthalate Based Hybrid Nanocomposites”
Panel Discussion
13:30 - 15:00 Lunch
THURSDAY 27 FEBRUARY
15:00
Chair: Geoffrey Hunt
Session 4
WG4: Ethics, Environment , Standardization, Science-Society Dialogue,
International Cooperation
Geoffrey Hunt, St Mary’s University College, United Kingdom
“The Convergence of New Food Technologies: Social & Ethical Issues”
Eddo Hoekstra, Joint Research Centre of the European Commission, Italy
“Eco-sustainable Plastic Food Contact Materials Using Nanomaterials from
Development to Final Product”
Marlena Kwiatkowska, Wroclaw University of Technology, Poland
“Biodegradation of PLA and PLA Composites”
Tiziana Maria P. Cattaneo, Consiglio per la Ricerca e la Sperimentazione in Agricoltura, Italy
“New Features in Food Packaging Sector: Italian Research Updating”
Emanuele Fiore, Embassy of Italy, Canada
“International Cooperation in Science and Technology: the Example of Italy and Canada”
17:00 - 18:30 Panel 3: Complementary Platforms
Moderator: Clara Silvestre
for Interactions
Key Lecture
Agnes Safrany, International Atomic Energy Agency UN, Austria
“Preparation of New Food Packaging Materials by Radiation-Initiated Reactions and IAEA Support
to Member States Institutions”
Erich Kny, Kemyk, Austria
“COST Action MP1206 on Electrospinning Nanofibers”
Robert van Otterdijk, Food & Agriculture Organization- UN, Italy
”FAO Activities in the Field of Food Waste and Loss”
Cecilia Bartolucci, National Research Council (CNR), Italy
“A Foresight Perspective to the Role of Packaging in the Sustainability of Food and Environment”
Andrea Porcari, Center for Nanotechnologies and KETs, Italian Association for Industrial
Research (AIRI/Nanotec IT), Italy
“Nanotechnology in Italy and the Role of Nanotec IT”
20:00
Panel Discussion
Dinner
FRIDAY 28 FEBRUARY
9:00 - 10:30
MC Meeting
10:30 - 11:00 Coffee break
11:00 - 12:30 Action Evaluation
9:00 - 12:30 Session: Poster Presentation
Chairs: Cornelia Vasile
Donatella Duraccio
Lorena Affatato, Institute of Chemistry and Technology of Polymers, CNR, Italy
“Smart City”
Aida Benhamida, University of Bejaia, Algeria
“Morphology and Mechanical Properties Polyamide 11/OMMT Nanocomposites Prepared by
Melt Mixing”
Isabel Bourbon, Universidade do Minho, Campus de Gualtar, Portugal
“Incorporation of Nanohydrogels in Polysaccharide-Based Films: Effect on
Physic-Chemical Properties”
Andrei Choukourov, Charles University in Prague, Czech Republic
“Effect of DBD Plasma Treatment on Properties of Poly(ethylene terephthalate) Foils”
Doina Constantinescu, SC ICEFS COM SRL, Romania
“Project Eureka- Compounding with Alimentary Additives For Layers with Antimicrobial
and Antioxidant Properties – Pilot Phases”
Elena Fortunati, University of Perugia, Italy
“Combined Effect of Cellulose Nanocrystals Extracted from Phormium Tenax Leaves and
Limonene on the Properties of PLA Films”
Jan Hanuš, Charles University in Prague, Czech Republic
“Fabrication and Characterization of a-C:H/Cu Nanocomposites Prepared
by PECVD Combined with Gas”
Evgeni Ivanov, Bulgarian Academy of Sciences, Bulgaria
“Polypropylene Composites Based on MWCNT and Organoclay”
Tatjana Ivanova, Riga Technical University, Latvia
“Structure and Properties of Zinc Oxide Containing Polymer Nanocomposites”
Claudio Larosa, University of Genoa, Italy
“Ceria oxide nanoparticles in Lexan polycarbonate: new films nanocomposite prospective
for food container”
Artur Martins, University of Minho, Portugal
“Diffusion of Different Molecular Weight Proteins through Poly ε-caprolactone Films
With Encapsulated Trypsin”
Ramesh Babu Padamati, Trinity College Dublin, Ireland
“Effect of Layered Nanomaterials and Nanofibers on Mechanical and Barrier Properties of Biobased
Polymer Composites”
Elena Paslaru, “Petru Poni” Institute of Macromolecular Chemistry, Romania
“Lactofferin –Coated Poly(Lactic Acid)”
FRIDAY 28 FEBRUARY
9:00 - 12:30
Elisa Passaglia, Istituto di Chimica dei Composti OrganoMetallici-UOS-CNR, Italia
“The Use of Plasticizers as Coupling Agents in Preparation of PLA-based Nanocomposites”
Marilena Pezzuto, Institute of Chemistry and Technology of Polymers, CNR, Italy
“Study of the Effetc of Ionizing Radiation on the Properties of Polypropylene Nanocomposites
for Food Packaging Applications”
Ana Cristina Pinheiro, University of Minho, Portugal
“Κ-Carrageenan/Chitosan Nanolayered Coating as a Vehicle for Incorporation
of Bioactive Compounds”
Frederika Popovska-Pavlovska, Integrated Business Institute, R.Macedonia
“A Contribution to Rheological And Relaxation Properties of Polymer Nanocomposite Materials”
Tanja Radusin, University of Novi Sad, Serbia
“Development of New PLA/Silica Nano Composites with Potential Use for Packaging of Fresh Meat”
Marcella Salvatore, Institute of Chemistry and Technology of Polymers, CNR, Italy
“Effect of Ionizing Radiation on the Nanocomposites Based on Polylactic Acid/Montmorillonite
for Food Packaging Applications”
Amhed Swilem, Ain Shams University, Cairo, Egypt
“Development and Radiation Processing of Polycaprolactone/Chitosan (Pcl/Cs) Blend for
Active Food Packaging”
Cornelia Vasile, “P.Poni” Institute of Macromolecular Chemistry, Romania
“Study of Thermal Properties and Heat-Induced Denaturation of Hybrid Hydrogels Based Collagen”
Cornelia Vasile, “P.Poni” Institute of Macromolecular Chemistry, Romania
“PLA Nanocomposites as Potential Antimicrobial Materials”
Selcuk Yildirim, Zurich University of Applied Sciences, Switzerland
“Electrospun Nanofibers as A Food Contact Layer for Iron Based Oxygen Scavenging Films”
12:30 - 13:00 Concluding Remarks and Closure
Clara SILVESTRE and Rumiana KOTSILKOVA
Lunch and farewell
LECTURES
CHEMICAL SCIENCE & MATERIALS TECHNOLOGY DEPARTMENT
L. Ambrosio
Chemical Science and materials technology department, CNR, Roma, Italy
[email protected]
The needs of the modern society and the fast growth of several emerging economics that are characterized by
continuous investments in research and development, are pushing the Europe and related Member States to define a
research and development strategy to address grand societal challenges in the coming years. In this directions, Key
Enabling Technologies (nanotechnology, micro-nanoelectronics, photonics, advanced materials, industrial
biotechnology and advanced manufacturing systems) have been identified to strengthening Europe’s capacity for
industrial innovation and the development of new products and services needed to deliver smart, sustainable and
inclusive European growth. Moreover, excellence science are implemented of by the Future Emerging Technology (FET)
programs. In Italy, the National Research Council, is one of the main institution promoting this strategy by identifying
the main objective: ....to produce values by the knowledge generate from research". Based on this the Department of
Chemical Science & Materials Technology has defined as own main missions the Chemical Manufacturing & Advanced
Materials Technology. In this context, the Chemical and Material Science are crucial for the sustainable development
based on integrate and dynamic innovation to respond to the social end technological challenges as defined by the
demand pull of the modern society. In this directions, the department has defined and integrated the competences and
knowledge to meet a research and innovation agenda in the following strategic area: Sustainable Chemistry, Advanced
Materials and Enabling Technologies, Health Science.
The Unique COST FA0904 Network
18
THE DEPARTMENT OF BIOLOGY, AGRICULTURE AND FOOD SCIENCES (DISBA) OF THE
NATIONAL RESEARCH COUNCIL OF ITALY, AND ITS ACTIVITES
F. Loreto
Department of Biology, Agriculture and Food Sciences (DISBA-CNR), Piazzale Aldo Moro 7 00185 Roma, ITALY
[email protected]
The mission of the Department of Biology, Agriculture and Food Sciences (DISBA) of the National Research Council of
Italy is to contribute to the progress of the scientific and technological knowledge, for the development and valorization
of an innovative and sustainable agricultural system.
In a planetary frame this is now a very important mission, as it has to cope with: growing anthropic pressures over the
territory; past, present and future climate change including growing frequencies of extreme events; resources
shortages, with special attention to the water resource which is already limiting agriculture in wide areas of the planet,
including the South of Italy; and, last but not least, repeated and heavy variations of the prices of the commodities,
eventually feed-backing on the use of soils and resources.
Moreover, agriculture and forestry are the main tools to win the global challenges of the next decades, such as the
preservation of the environment and the food security. There is an urgent need to increase quality and quantity of
agriculture and forestry productions, yet preserving environmental and biological resources, and the income of farmers
and agro-industry. Coherently with the above societal, economical, environmental and production challenges, the
research activities of DISBA are in line with the priorities of the European programmes (namely Horizon 2020 and the
specific societal challenge on Food and Sustainable Agriculture), of the Common Agriculture Policy (PAC), and of
National Programme of Research (PNR).
The research activities at DISBA are broken into 52 research lines which are carried out in 22 Institutes CNR. Nine
Institutes belong to DISBA, supplying a critical mass of around 700 researchers and technologists over the entire Italian
territory. The research lines are gathered into 3 department projects in the fields of “Biology”, “Food science” and
“Sustainable agriculture”. These projects cover about all production fields in agriculture and forestry, with remarkable
examples of excellence in the fields of: precision agriculture, climate change impacts and responses, food quality, safety
and security (including relevant food technologies), plant, animal and microorganism biology, protection and
valorization of the biodiversity, sustainable plant protection, and wood technology. There are many CNR Institutes of
different areas that collaborate with DISBA activities, indicating the excellent interdisciplinary research in agriculture
and food sciences at CNR, in particular in the areas of green chemistry, nutraceutics, food science and health, and
environmental protection.
DISBA currently holds 63 international projects, including 27 projects of the 7FP of the European Commission; 8 projects
of the programme Life+; 4 projects of the programme COST, and one European Science Foundation – Eurocores
programme. The Department is member of the European Plant Science Organization (EPSO), the Safe Consortium, and
the European Food Safety Authority (EFSA). The Department also participates many European technology platforms
such as: Food for Life, Plants for the Future, Biofuels, and TP-Organics.
DISBA has published in 2013 more than a thousand research papers on ISI international journals, and holds 48 patents
representing the most relevant and innovative technological results in the fields of agriculture and food science. About
half of the patents have met industrial expectancies, and are licensed to specific agro-industrial enterprises, spanning
plant nurseries to food industry, to medical applications of functional foods.
19
Rome Italy 26 - 28 February 2014
EUROPEAN COOPERATION IN SCIENCE AND TECHNOLOGY- COST
I. Stavridou
COST Office, Avenue Louise 149, Brussels
[email protected]
COST- the acronym for European Cooperation in Science and Technology – is the oldest and widest intergovernmental
framework dedicated to the networking of nationally funded research projects. Established by the Ministerial
Conference in November 1971, COST is presently used by the scientific communities in 36 European Countries, and
contributes to closing the gap between science, policy makers and society throughout Europe and beyond.
COST key features are a ‘bottom-up’, ‘inclusiveness and equality of access’ and ‘flexible structure’. All these make COST
unique and instrumental for successful innovation strategies and global cooperation. COST allows European researchers
to tackle from their own perspective the current and future scientific or societal challenges leading to defragmentation
of knowledge and of European research investment. There are currently around 300 networks with a 20000 total yearly
participants that share, create, apply, and disseminate knowledge,thereby contributing to the objective of
strengthening the scientific and technological bases of the European Research Area.
COST fosters the establishment of scientific excellence in the nine key domains:
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COST covers basic and more applied research and also addresses issues of pre-normative nature or of societal
importance.
20
COST ACTION FA0904 "ECO-SUSTAINABLE FOOD PACKAGING BASED ON POLYMER
NANOMATERIALS": IT IS TIME FOR THE FINAL APPRAISAL
C. Silvestre, S. Cimmino
Institute of Chemistry and Technology of Polymers, (ICTP-CNR), Italy
[email protected]
[email protected]
COST Action FA0904 is a 48-month European research activity involving 320 participants from 33 Countries started on
March 2010, aimed at creating an open network at regional, national and international level with top experts for full
exploitation of nanotechnology in the field of polymer nanomaterials for food packaging (PNFP).
The envisioned direction is to look at the complete life cycle of the PNFP by the combined efforts of leading research and
industrial groups, identifying at each stage the barriers (in research and technology, safety, standardisation, trained
workforce and technology transfer) that prevent a complete successful development of PNFP and indicating the
strategies to proceed further.
The Action brought together methodologies, processing, structure–characterization techniques, properties, health,
regulation, economic and environmental considerations in order to support the design of innovative and
eco-sustainable polymer nanomaterials with controlled structures and properties to be used in the food packaging
sector.
The Action has fully achieved the objectives and technical goals as shown by the elevated numbers of measurable
scientific deliverables achieved by the Action, that prove the strong networking among the COST Action participants:
over 180 publications, 33 joint projects, 6 books with ISBN.
The Action has generated excellent scientific knowledge strongly underlining that post-processing protection through
novel packaging based on nanotechnology is an innovative and valuable methodology to ensure food safety, reduce
post harvest losses and facilitate international trade in a sustainable and environmentally responsible manner, and to
contribute to feed the growing world population with safe and nutrition food, meeting the 2020 European targets to
combat poverty and to reduce waste. The Action has reached a very high involvement of ESRs in the Action activities and
an excellent balance in term of female participation and among senior and ESR researchers (almost 50%).
Moreover some important issues for a complete exploitation of the nanotechnology in the field of food packaging still
remain open. In particular the challenges of the scientific/industrial community needs to face are: 1. the design of the
morphology and structure of the nanomaterials by directing the structure and properties of the polymer nanomaterial
during crystallisation/solidification taking into consideration the material characteristics, the composition, the
nanoparticles shape as well as the conditions of the manufacturing packaging process (extrusion, blowing, etc); 2. the
contribution to develop harmonized standardization measures valid worldwide to ensure regulatory compliance for a
faster penetration into the global the market of food. The Action has demonstrated that, in order to achieve valuable
results the fundamental point is the synergistic combination of multidisciplinary teams and complimentary high level
skill sets with networks of top-experts sharing instrumentation/expertise and working together, (almost) irrespective
of the institute/ company/country they are located.
Finally COST Action FA0904 can be considered a successful pilot initiative aiming at contributing to the identification of
the key factors in the development of innovative PNFP and is an example that it is not always necessary to have
big-scale organizations of departments, universities and companies to reach competitive and innovative results.
References
1. C.Silvestre, S.Cimmino Eds, "Eco-sustainable polymer nanomaterials for food packaging” ISBN 978-90-04-207373-0 Taylor and
Francis Press -2013.
2. C.Silvestre, D. Duraccio, S.Cimmino, Food packaging based on polymer nanomaterials, Progress in Polymer Science 2011, 36,
1766–1782.
21
ATOMIC LAYER DEPOSITED THIN FILMS FOR PACKAGING
M. Vähä-Nissi, E. Salo, J. Sievänen, M. Pitkänen, E. Kenttä, M. Putkonen, M. Rättö, A. Harlin
VTT Technical Research Centre of Finland, Espoo, Finland
[email protected]
Atomic layer deposition (ALD) is a layer-by-layer thin film deposition process based on repeated self-limiting gas-solid
reactions by using volatile precursors1-3. ALD is suited for producing pinhole-free and uniform thin films in nanoscale as
seen in microelectronics industry which is today the most important application area for ALD. Although industrial ALD
is today carried out in single wafer or batch mode, the current development of roll-to-roll processes will enhance the
techno-economic feasibility of ALD also for packaging materials. There are significant efforts to develop ALD processes
for web materials4-6. The purpose of this presentation is to demonstrate the potential and the challenges of using ALD to
create functional thin films for packaging materials.
ALD metal oxide thin films can have a profound effect on the barrier properties of polymer films. The relative
improvement in oxygen and water vapor barriers with 25 nm of Al2O3 was the most significant with cellulose and
polyester films, while certain plastic processing additives in polyolefin films prevented thin layer growth. Proper surface
chemistry, and oxygen containing groups in specific, enhances thin layer uniformity. Cellophane is rich in hydroxyl
groups, while polyesters have also -(C=O)-O- groups in the main molecule chain available for reactions with the
precursors. Chemically favorable surfaces also improved the mechanical properties of polymers with thin oxide layers. It
is therefore not surprising that the final thin film properties were affected by polymer pretreatments and choice of
oxidizing precursor. However, it is important, as with polymer films to be metallized, to prevent polymers from
attracting contaminants prior to ALD. ALD was also used to create antimicrobial thin films.
Adequate barrier or antimicrobial properties are only part of the key requirements set for packaging materials.
Whenever a new packaging solution is developed safety of the novel material should be confirmed. As also presented
earlier it is our opinion that uniform thin barrier films, such as Al2O3, chemically bonded to the base polymer do not fall
under the European Commission’s definition of nanomaterial7 resembling metallized layers used for packaging
materials for tens of years. Although migration of Al2O3 from the ALD layer was lower than the limit set by the current
European regulations, the oxygen barrier was strongly impaired due to film dissolution. It is therefore obvious that
polymers coated with ALD thin films require an additional protective and heat sealing top layer. Only polymers with low
melting temperature/viscosity and certain surface roughness provided heat sealability with the ALD oxide thin film. In
addition, the unique possibility to prepare nanolaminates with ALD enabled controlled mechanical and surface
characteristics by combining inorganic oxide and organic-inorganic hybrid layers. For example, adhesion of polylactide
onto oxide thin film could be improved with a lactic acid based hybrid top layer.
References
1. Leskelä, M.; Ritala, M. Thin Solid Films 2002, 409 (1), pp. 138-146.
2. George, S.M. Chem. Rev. 2010, 110 (1), pp. 111-131.
3. Puurunen, R., J. Appl. Phys. 2005, 97 (12), 121301.
4. Poodt, P.; Cameron, D.C.; Dickey, E.; George, S.M.; Kuznetsov, V.; Parsons, G.N.; Roozeboom, F.; Sundaram, G.; Vermeer, A. J. Vac. Sci.
Technol. A 2012, 30 (1), 010802.
5. Lahtinen, K.; Maydannik, P.; Kääriäinen, T.; Seppänen, T.; Cameron, D.C.; Johansson, P.; Kraft, M.; Kuusipalo, J. TAPPI International
Conference on Nanotechnology for Renewable Materials, 24-27 June 2013, Stockholm, Sweden.
6. Hirvikorpi, T.; Laine, R.; Vähä-Nissi, M.; Kilpi, V.; Salo, E.; Li, W.-M.; Lindfors, S.; Vartiainen, J.; Kenttä, E.; Nikkola, J.; Harlin, A.;
Kostamo, J. Thin Solid Films 2014, 550, pp. 164-169.
7. Vähä-Nissi, M.; Sievänen, J.; Salo, E.; Pitkänen, M.; Harlin, A. International COST FA0904 Workshop ”Development of new safe
PNFP”, February 7-8, 2013, Praque, Czech Republic.
22
ADVANCES IN PLA MATRIX NANOCOMPOSITES FOR FOOD PACKAGING
J.M. Kenny1,2, I. Armentano1, E. Fortunati1, F. Dominici1, F. Luzi1
(1)
Department of Civil and Environmental Engineering, University of Perugia, Terni, Italy
(2)
Institute of Polymer Science and Technology, CSIC, Madrid, Spain
[email protected]
The research illustrated here deals with the development and characterization of innovative packaging films based on
fully sustainable and biodegradable PLA matrix materials for the packaging of fresh food from different origins. The
innovation produced in this field will provide the food industry with customizable, ecoefficient, biodegradable
packaging solutions with direct benefits for both the environment and consumers in terms of food quality and safety.
The production of innovative “green materials” derived from natural sources is currently one of the main points of
interest in the academic and industrial areas of material research. Packaging, including flexible films and rigid
containers, is the largest single market for plastic material consumption and post-consumption. Biodegradable
polymers represent an alternative to non-degradable polymers currently used in film production for different industrial
applications1-2. Moreover, the active food-packaging concepts provide some additional functions in comparison with
traditional materials that are limited to protect food product against external influences.
In this context, the research field illustrated here deals with the development and characterization of innovative
packaging films based on fully sustainable and biodegradable materials for the packaging of fresh food from different
origins. The innovation produced in this field will provide the food industry with customizable, ecoefficient,
biodegradable packaging solutions with direct benefits both for the environment and consumers in terms of food
quality and safety.
In particular, the main idea is to combine biopolymers already used in industrial packaging (mainly polylactic acid
(PLA)) with bio-based fillers, with the aim to develop multifunctional, cost-effective, and sustainable composites. One
of the main interests of this research is to minimize the current limitations offered by polylactic acid (PLA) for packaging
applications such as low thermal resistance and flexibility, water permeability, difficult processability, and insufficient
food protection. The addition of specific and innovative reinforcing materials, antimicrobials and biodegradable
plasticizers will solve these drawbacks3-5.
The integrated framework presented here for packaging materials design, aims to assist packaging designers by
illustrating main drivers and most important aspects related to a successful and innovative packaging solution. These
drivers have strong interdependences: changes improving one aspect certainly will bring improvement or worsening of
other aspects at the same time. Packaging design needs to take place inside this complex system, where every factor
interacts with each other, taking into account standards, regulations, lab testing and procedures supporting each issue.
References
1. A.P. Gupta, V. Kumar, European Polymer Journal, 43, 4053-4074, 2007.
2. L.T. Lim, R. Auras, M. Rubino, Progress Polym. Sci, 33, 820-852, 2008.
3. P. Bordes, E. Pollet, L. Averous, Progress Polym Sci, 34, 125-155, 2009.
4. E. Fortunati, I Armentano, Q. Zhou et al., Carbohyd Polym, 87, 1596-1605, 2012.
5. E. Fortunati; M. Peltzer; I. Armentano; A. Jiménez; J.M. Kenny, J Food Eng, 118, 117-124, 2013.
23
MULTIFUNCTIONAL NANOPARTICLE COATING USING LFS-TECHNIQUE
M. Tuominen1, H. Teisala2, J. Kuusipalo2, J. Haapanen2, J. Mäkelä2, M. Stepien3, J. Saarinen3, M. Toivalla3
(1)
SP, Swedish Technical Research Institute
Tampere University of Technology (TUT)
(3)
Abo Akademi University
[email protected]
(2)
Introduction
Liquid flame spray (LFS)-technique was used to create multifunctional nanoparticle coatings. LFS process is continuous
roll-to-roll process and it operates in ambient conditions. The LFS-process is presented in Figure 1.
Figure 1. LFS coating process.
Results and Discussion
Titanium dioxide (TiO2) nanoparicle coatings were generated on heat sensitive packaging materials, i.e. board, paper,
and low density polyethylene (LDPE), as seen in the Figure 2. LFS-coatings have several functionalities, for example
permanent superhydrophobicity (CAW >150°), self-cleanability and adjustable wettability, as seen in the Figure 2.
Figure 2. FEG-SEM images of LFS/TiO2 coated board, paper and LDPE coating (upper row). Images of superhydrophobic paper
surface, self cleanable board surface and patterned wetting on board (lower row).
LFS/TiO2 coating has also SLIPS (Slippery Liquid Infused Porous Surface)-properties, whereas LFS/SiO2 nanoparticle
coating has permanent superhydrophilicity (CAW <10°).
Conclusions
LFS-process is potential for industrial use because it operates roll-to-roll at high line speeds (> 200 m/min). In addition,
coating amounts are very low (< 50 mg/m2) and the coatings have several beneficial functionalities.
Acknowledgements
Tekes (Finnish Funding Agency for Technology and Innovation), Stora Enso, UPM and Beneq. Mikko Tuominen acknowledges also the
financial support of Nils and Dorthi Troëdsson Foundation for Scientific Research
24
LOW PRESSURE PLASMA COATINGS FOR FOOD PACKAGING
H. Biederman, O. Kylian, J.Hanuš, O.Polonskyi, A. Choukourov, A. Shelemin, A. Kuzminova, D. Slavínká,
L. Hanyková
Charles University, Faculty of Mathematics and Physics, Prague, Czech Republic
[email protected]
Use of conventional polymers for food packaging has some limitations that are connected for instance with their low
hardness, relatively low barrier properties towards oxygen or water vapor and relatively high contact angle of water.
Promising and often employed approach for improvement of properties of polymeric foils is their coating by a thin
barrier film using low temperature plasma methods - RF sputtering or PECVD1. The most commonly used materials are
metal oxides (e.g. TiOx, AlxOy) or SiOx films, that were all reported to significantly increase the barrier properties of
polymeric foils. An interesting alternative to these materials is represented by hydrogenated amorphous carbon (a-C:H)
thin films2. In comparison with metal oxides or SiO2 films, a-C:H coatings offer combination of high hardness
comparable to ceramic materials and high elasticity of polymer-like materials. Furthermore, these films have high
chemical and thermal stability, optical transparency and facilitate the recycling process.
The first objective of this study is to compare properties of a-C:H and SiOx films. Both of these materials were deposited
by means of PECVD on PET foils: in case of a-C:H a mixture of Ar and nHexane was used, in case of SiOx films a mixture of
HMDSO and O2 was used. It was observed that both a-C:H and SiOx films are capable to increase barrier properties of PET
foils. In addition it was found that this improvement depends strongly on the thickness of the barrier film and optimal
thickness is in order of tens of nanometers.
As the second objective, we test possibility to tailor wettability of a-C:H and SiOx coatings either by subsequent plasma
treatment or by roughening the surface by incorporation of hydrocarbon nanoparticles. It is shown that this strategy
allows to fabricate surfaces with super-hydrophobic and super-hydrophilic character.
Finally, a method that allows incorporation of metallic nanoclusters into the growing a-C:H or SiOx matrix is introduced.
It is based on gas aggregation sources of metallic nanoparticles combined with PECVD. Possible application of this
method for production of functional coatings (e.g. for fabrication of antibacterial barrier films) is discussed.
Acknowledgements
This work was performed under the COST Action FA 0904 and was supported by the grant LD 11032 from the program COST CZ
financed by the Ministry of Education, Youth and Sports of the Czech Republic.
References
1. O. Kylián, A. Choukourov, L. Hanyková, H.Biederman: Plasma Technology for Polymer Food Packaging Materials In: Ecosustainable
Polymer Nanomaterials for Food Packaging, Eds. C. Silvestre, S. Cimmino, CRC Press Taylor & Francis Group, Boca Raton FL 2013,
119-142.
2. O. Polonskyi, O. Kylián, M. Petr, A. Choukourov, J. Hanuš, H. Biederman, Gas barrier properties of hydrogenated amorphous carbon
films coated on polyethylene terephthalate by plasma polymerization in argon/n-hexane gas mixture, Thin Solid Films 540 (2013)
65–68.
25
CHARACTERIZATION OF FUCOPOL FILMS FOR FOOD PACKAGING
A. R. V. Ferreira1, C. Torres1, F. Freitas1, M. Reis1, V. D. Alves2, I. M. Coelhoso1
(1)
(2)
REQUIMTE/CQFB, Chemistry Department, FCT/Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
CEER-Biosystems Engineering, Instituto Superior de Agronomia, Universidade de Lisboa, Tapada da Ajuda, 1349-017 Lisbon,
Portugal
[email protected]
Introduction
In the recent years, many researchers have driven their attention to the use of natural/bio-based polymers as new
materials to replace or reduce the use of petrochemical-based plastics. This is due to the fact that the later are
non-degradable and non-totally recyclable, which causes a highly negative environmental impact.
Films of different polysaccharide materials have been studied, including, chitosan, starch, alginate and carrageenan,
mainly because polysaccharides are biodegradable, nontoxic and widely available.1
Microbial polysaccharides represent an alternative to other recovered from animals or plants, because they are
independent on climate and season of the year, being only dependent on microbial cultivation parameters which may
be easily controlled. Some microbial polysaccharides have been studied to produce biodegradable films with potential
final use on packaging materials, which is the case of gellan, kefiran and xanthan 2.
In this work, FucoPol, an exopolysaccharide, produced by an Enterobacter strain grown in a bioreactor with glycerol as
carbon source, was used to produce biodegradable films. FucoPol is a high molecular weight heteropolysaccharide,
composed mainly of neutral sugars (fucose, galactose and glucose in nearly equimolar proportion). The presence of
glucuronic acid, as well as pyruvyl and succinyl groups, confer the polymer an anionic character. Both product and
process are innovative and were patented 3.
FucoPol revealed the capacity to produce cohesive and dense films, quite transparent and with a good physical integrity,
presenting though a high hydrophilic character being completely soluble in water.
The mechanical properties revealed a low tensile strength at break (3.10 MPa), a high elongation at break (55 %) and
a Young Modulus of 2.8 MPa, which are characterisitic of a material with a rather low stiffness and a high plasticity.
Regarding the barrier properties, in what concerns the water vapour permeability the results revealed a value similar to
other polysaccharides (1.01x10-11 mol/m s Pa) such as corn starch when similar driving force is applied [4]. Regarding
gas permeability (CO2 and O2), it was much lower than that of water vapour. However, FucoPol films demostrated a
higher permeability to CO2 (42.70x10-16 mol m/m2 s Pa) than to O2 (0.69x10-16 mol m/m2 s Pa). This behaviour is also
characteristic of films from polysaccharides such as starch or chitosan.
Conclusion
FucoPol films are transparent, with brown tone. They are hydrophilic with poor barrier properties to water vapour, which
can be enhanced by using nanoclays.The good barrier properties to gases (oxygen and carbon dioxide) makes them
good candidates to apply on packaging, namely as one layer in a multilayer packaging material.
References
1. Siracusa, V., Rocculi, P., Romani, S., Rosa, M. D., 2008, Biodegradable polymers for food packaging: a review, Trends in Food
Science & Technology, 19, 634-643.
2. Freitas, F., Alves, V., Reis, M., Crespo, J., Coelhoso, I. M., 2014, “Microbial polysaccharide based membranes: Current and future
applications”, J. Appl. Polymer Sci., 131, 40047.
3. Fucose-containing bacterial biopolymer, Inventors: Maria A. Reis, Rui Oliveira, Filomena Freitas, Vitor D. Alves. International
Publication Number WO 2011/073874 A2, June 2011.
4. Garcia, M. A., Pinotti, A., Zaritzky, N. E., 2006, Physicochemical, water vapor barrier and mechanical properties of corn starch and
chitosan composite films, Starch-Starke, 58, 453-463.
26
NANOCELLULOSE-BASED RENEWABLE PACKAGING MATERIALS
J. M. Lagaron, A. López-Rubio, M. J. Fabra, M. Martínez-Sanz
Novel Materials and Nanotechnology Group, IATA- Avda. Agustin Escardino 7, 46980 Paterna, Valencia, Spain
[email protected]
High throughput electrohydrodynamic processing also known as electrospinning and electrospraying has emerged as a
versatile plastic processing method to produce nanostructured materials. Currently, the processing technique can be
employed to develop novel nanocomposites with improved nanofiller dispersion and, thus, with better barrier and
mechanical performance. The first part of this study will show the development of an efficient strategy for the
incorporation of highly dispersed cellulose nanowhiskers (CNW) by melt compounding through the use of
electrohydrodynamic processing as a vehicle for the pre-incorporation of relatively high loadings of CNW.
On the other hand, untreated cellulose based paper is hydrophilic and low barrier to water and gases. In the second part
of this study, we will show the development of a new biobased multilayer paper containing several barrier layers
reinforced by cellulose nanowhiskers, which provide a tremendous enhancement in moisture, organic vapours and
oxygen barrier. The objective of this last study is to provide an alternative to aluminum in systems such as the Tetrapak
technology while retaining the excellent barrier properties provided by the metallized packaging paper.
27
A STUDY OF THE COMBINED EFFECTS OF PHBV-g-AM COMPATIBILIZER AND CLOISITE 30B ON
PHBV/PLA BLENDS
M. Kaci1, I. Zembouai1, A. Benhamida1, S. Bruzaud2, Y. M. Corre2, Y. Grohens2, J. M. Lopez-Cuesta3
Laboratoire des Matériaux Polymères Avancés, Université Abderrahmane Mira, Faculté de Technologie, Bejaia, Algeria.
(2)
Laboratoire d’Ingénierie des Matériaux de Bretagne, Université de Bretagne-Sud, Rue de Saint Maudé, Lorient, France.
(3)
Centre de Recherche C2MA, Ecole des Mines d’Alès, 6 avenue de Clavières, Alès Cedex, France.
[email protected] r
(1)
Introduction
Recently, much attention has been focused on nanocomposites based on polymer blends. The major part of the research
work has dealt with the effects of the nanoparticles on miscibility/compatibility and the microstructure of the polymer
blends. It is well established that the main parameters which can affect the role and performance of the nanoparticles
in polymer blends are their localization, their interactions with polymer components and the dispersion state in the
polymer matrix. In a recent paper, virgin blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and PLA were
prepared by melt mixing1. The study showed that PHBV/PLA blends form a biphasic system over the whole composition
range. Thus, to improve the properties of biodegradable polymers like PLA or PHBV, the elaboration of hybrid systems
based on nanoclays associated to the polymer blend strategy seems to be a promising solution. Therefore, the objective
of the paper was to examine the combined effects of organomodified montmorillonite, i.e. Cloisite 30B and PHBV-g-AM
compatibilizer on the PHBV/PLA blend morphology. The resulted changes in terms of thermal stability, mechanical
properties and rheological behavior were investigated.
Results and discussion
The morphological results through SEM analysis indicate that the addition of 3 wt. % of C30B to PHBV/PLA blends,
induces more deformed and less discernible dispersed phase as shown in Figure 1a. The morphology is rather
co-continuous. In Figure 1b, the fracture surface of PHBV/PLA 25/75 at a clay loading of 3 wt.% with PHBV-g-MA
compatibilizer reveals that the compatibilizer incorporation into the PHBV/PLA blend nanocomposites changes the
co-continuous to a dispersed-type morphology. This can be attributed to the reduction of interfacial tension of the
system due to increased interfacial interactions between the blend components and to the localization of the clay in the
blend as a result of the chemical linkage. The study shows also that the incorporation of C30B contributes to enhance the
thermal stability of PHBV, PLA and PHBV/PLA blends. Further, the samples based on PHBV/PLA/C30B nanocomposites
exhibit improved mechanical properties in terms of Young’s modulus, comparatively to PHBV/PLA blend, especially
when PHBV is previously compatibilized. Finally, the rheological measurements indicate a significant increase of the
complex viscosity, the storage and the loss modulus by the addition of C30B in the PHBV/PLA blend. This is particularly
noticeable when samples are submitted to low shear frequency. Moreover, this increase in the rheological response is
much more pronounced in the presence of the compatibilizer.
a
b
Figure 1. SEM micrographs of fractured surface of PHBV/PLA: 25/75 with 3 wt. % of C30B (a) and PHBV/PLA: 25/75 with 3 wt. %
of C30B and 5 wt. % of PHBV-g-MA compatibilizer (b). 2000X.
References
1. Zembouai, I..; Kaci, M.; Bruzaud, S.; Benhamida, A.; Corre, Y. M.; Grohens, Y. Polymer Testing 2013, 32, 842.
28
THE INFLUENCE OF PHYSICAL MODIFICATION ON THE PROPERTIES OF PLA FILMS AS “GREEN”
PACKAGING MATERIALS
B. Pilić1, A. Miletić1, I. Ristić1, T. Radusin2
(1)
(2)
University of Novi Sad, Faculty of Technology, Novi Sad, Serbia
University of Novi Sad, Institute of Food Technology, Novi Sad, Serbia
[email protected]
The basic function of the food packaging is to protect food from physical damage, to maintain freshness, to protect from
light gases and vapor. Packaging is also an important factor in the buying decision process, so it must be attractive in
activate visual stimulation. Packaging materials and technologies have been developed over the centuries, but today’s
demands are looking for new improvement and innovation. It is well known that synthetic conventional polymer
materials (made from fossil fuels) have a number of advantages as food packaging materials because of their
availability at relatively low cost, good mechanical, thermal, barrier properties and good processability. Recently,
growing environmental awareness has led to new packaging material trends: sustainability, eco-efficiency and
biodegradability. New demands have stimulated the researchers for developing and using biodegradable and biobased
materials as alternatives to conventional non-degradable polymers for food packaging. Up to now, broad application of
biodegradable and biobased polymers has been limited due to many problems which must be solved in the future. The
major problems are: performance, processability and cost.
One of the most promising biopolymer and already the most commercialized is polylactic acid (PLA). It is versatile
polymer recyclable and compostable, with high transparency, high molecular weight, good processability and water
solubility resistance. However, the low mechanical properites and quite expensive price limit its application.
The aim of this study was to modify tensile strength and to improve elongation at the break of PLA films by adding
plasticisers (such as castor or soy bean oil, poly(ethylene) glycol and dibutyl sebacate), silica nanoparticles and by
blending with elastomer (based on styrene-butadiene polymer), keeping the existing thermal properties of neat PLA. A
series of PLA films were prepared by solution casting method and melt mixing in HAAKE Rheometer mixer using three
types of commercial PLA in various combinations of additives. In the first series of films, silica nanoparticles in the neat
PLA were added. The second series of films were made only by addition of different type of plasticisers (10 wt.%) and
the third series was combination of neat PLA, silica nanoparticles and plasticisers (10 wt.%). Blending of PLA was done
by the elastomer in the content of 5, 10 and 20 wt.% and in their combination with nanosilica (1, 2, 5 wt.%). Several
techniques (DSC, Instron Testing, SEM,) were performed to experimentally characterize the influence of additives on
thermal, mechanical and morphological properties of the obtained films. A strong influence of the preparation method
and additives contents on thermal properties of the prepared films was observed. Glass transition temperatures of the
samples, prepared from solution casting methods, decreased with addition of plasticisers while the presence of silica
nanoparticles has not shown significantly changes in Tg values. The samples prepared by melt mixing method have
shown increasing of Tg values with increasing of silica contents. However, the presence of plasticisers and elastomer,
improved elastic properties of all prepared samples, causing increasing elongation at the break. Addition of nanosilica
caused decreasing of elongation at the break but increasing of tensile strength of PLA composites, resulting in tougher
materials.
References
1. Bradley, E. L.; Castle, L;. Chaudry, Q.; Trends in Food Science & Technology, 2011, 22, 604-610.
2. Silvestre, C.; Duraccio, D; Cimmino, S.; Progress in Polymer Science, 2011, 36,1766-1782.
3. Rasal, R.; Janorkar,A.; Hirt, D.; Progress in polymer science, 2010, 35, 338-356.
29
REINFORCEMENT OF POLYSACCHARIDE-BASED FILMS: EVALUATION OF PHYSIC-CHEMICAL
PROPERTIES
M. A. Cerqueira, A. A. Vicente
IBB – Institute for Biotechnology and Bioengineering, Centre for Biological Engineering, University of Minho, Campus de Gualtar,
Braga, Portugal.
[email protected]
Currently, mainly non-biodegradable petroleum-based synthetic polymers are used as packaging materials for foods,
because of their availability, low cost and functionality. However, biodegradable/edible films can be made from
polysaccharides, proteins, and lipids without the environmental issues of petroleum-based polymers and with the
additional advantage of being available from renewable sources or as by-products or waste-products from the food and
agriculture industries. Recently, improvements on properties of these films have been made by reinforcement of the
polymer matrix with other materials. Several materials (e.g. micro/nano clays, lipids and hemicelluloses) were studied
in order to show how they could be used to improve physico-chemical properties. Polysaccharide based-films (i.e.
chitosan, galactomannan and k-carragennan) were reinforced by the additon of Cloisite 30B, micro/nano clays, lipids
and hemicellulose wheat straw and their properties evaluated. Different concentrations of compounds were added to
polysaccharide-based films and barrier properties (water vapor permeability, WVP; CO2 and O2 permeabilities) and
mechanical properties (tensile strength, TS and elongation at break, EB) were determined. In some cases the film
structure was investigated by X-ray diffraction (XRD), scanning electron microscopy, Fourier transformed infrared and
thermal properties.
According to the nature of the added compounds different behaviours were observed on film properties. Results showed
that the incorporation of micro/nano clay or Cloisite 30B in the films significantly affected their mechanical and barrier
properties1,2. An increase of the micro/nano clay concentration caused a decrease of WVP and an increase of TS. However,
they showed different influences in O2 and CO2 permeabilities and EB (e.g. Cloisite 30B decreased permeabilities and
micro/nano clay did not influence this property). These differences could be explained by the size of the compounds
added and by the degree of exfoliation of compounds in the films (as shown by the XRD patterns of the films). When
adding corn oil to films a more hydrophobic structure was observed with the decrease of the affinity of film matrix to
water3. This change will enhance the WVP (i.e. lower values) of the films and change the mechanical properties. Also
different behaviours according to the type of polysaccharide used were observed, explained by the specific sorption sites
for water of both polysaccharide-based films (i.e. O-H groups or O-H and/or NH2 groups). Glass transition temperature
and crystallinity of the films gave the indication of changes on the structure of the films after the addition of corn oil.
Also the addition of hemicellulose influenced the properties of polysaccharide-based films decreasing water affinity of
the films (i.e. lower moisture content and WVP) and increasing their mechanical performance (higher TS and EB),
explained by the increase of the matrix crystallinity4. Also important to mention is the antimicrobial behaviour of
polysaccharide films with incorporation of Cloisite 30B that shows an inhibitory effect against L. monocytogenes2.
Polysaccharide-based films can be reinforced, and their properties enhanced, being compounds such as clays, lipids, and
hemicelluloses valuable alternatives for the improvement of polysaccharide-based films properties (water vapour
transmission, mechanical, thermal).
References
1. Casariego,A.; Souza,B.W.S.; Cerqueira,M.A.; Teixeira,J.A.; Cruz,L.; Díaz,R.; Vicente A.A. Food Hydrocolloids 2009, 23, 1895.
2. Martins,J.T.; Bourbon,A.I.; Pinheiro,A.C.; Souza,B.W.S., Cerqueira,M.A.; Vicente, A.A. Food and Bioprocess Technology: An
International Journal 2013, 6(8), 2081.
3. Cerqueira,M.A.; Souza,B.W.S.;Teixeira,J.A; Vicente,A.A Food Hydrocolloids, 2012, 27(1),175.
4. Ruiz,H.A.; Cerqueira,M.A.; Silva,H.D.; Rodríguez-Jasso,R.M.; Vicente,A.A.; Teixeira,J.A. Carbohydrate Polymers 2013, 92(2), 2154.
30
THERMAL CHARACTERIZATION OF HYDROGELS BASED ON ANHYDRIDE MODIFIED COLLAGEN
AND 2 - HYDROXYETHYL METHACRYLATE
D. Pamfil1, C. Schick2, C. Vasile1
(1)
“Petru Poni” Institute of Macromolecular Chemistry, Department of Physical Chemistry of Polymers, 41 A, Grigore Ghica Voda
Alley, 700487, Iasi, Romania
(2)
Institute of Physics, University of Rostock, Wismarsche Str. 43-45, 18051, Rostock, Germany
[email protected]
Introduction
The thermal properties of collagen-based materials in dried and hydrated state have been investigated by differential
scanning calorimetry (DSC). DSC allows measurement of the stability of the triple helical structure of collagen
molecules. The collagen - based materials were porous modified - collagens bearing vinyl groups were synthesized by
reaction with dimethyl maleic anhydride (DMA) or citraconic anhydride (CTA) and also semi-interpenetrated hydrogels
were obtained by free radical polymerization of both anhydride - modified collagens with 2-hydroxyethyl methacrylate
(HEMA) in the presence of ammonium persulfate (APS) and N, N, N’, N’-tetramethylethylenediamine (TEMED). The
denaturation temperature (Td), denaturation enthalpy and glass transition temperature have been determined. The
water states (free or bonded) in the hydrated samples were correlated with their swelling degree.
By chemical modification of collagen with anhydrides was registered an increasing in Td indicating an improvement in
thermal stability, this effect is caused by the formation of new intermolecular hydrogen bonds because of carboxyl
groups incorporation. Comparing the thermal behavior of the samples in dried and hydrated state was remarked that
the absence of water led to an increase in the Td water playing a plasticizing role. The hydrated crosslinked samples
shown the very slight signal assigned to the denaturation enthalpy. The samples denaturation is irreversible inasmuch
as the signal attributed to Td completely disappeared by reheating. It was observed that the hydrogel networks
formation leads to a decrease in the bonded water content (Table 1) and to an increase of free water content presumably
due to involvement of hydrophilic groups in the formation of polymer network. Also, the amount of free water is less in
the second heating meaning that after the first run a part of free water becomes bonded.
Table 1. The bonded water content in the hydrated collagen - based materials after heating
Abbreviation
name*
Coll
CTA5.6
CTA9.6
DMA8.2
DMA7.2
H CTA5.6
H CTA9.6
H DMA8.2
H DMA7.2
Bonded water
content [%]
49.6
49
51.2
51.8
54.3
34.9
32.9
35.6
32.6
*coll: pure collagen, CTA: collagen modified with citraconic anhydride, DMA: collagen modified with dimethyl maleic anhydride,
the number is corresponding to the substitution degree, H: hydrogels obtained from corresponding modified collagen and HEMA.
Conclusion
The hydrogels show a decrease in the calorimetric parameters values in respect with the uncrosslinked collagen
samples; also, by crosslinking the water binding capacity has decreased. The analysis of water states evidenced the
strong hydrophilic character of the collagen materials giving them the possibility to be used as biomaterials.
Acknowledgements
The authors acknowledge the financial supported by COST STSM Action FA0904 within the STSM programme in Institute of Physics,
University of Rostock laboratory.
31
CHALLENGES IN INVESTIGATING NANOPARTICLES AS ANTIMICROBIAL IN FOOD PACKAGING.
ZNO CASE STUDY
L. Deschênes1, T. Savard1, C. Lapointe1, D. Chabot2, R. Zareifard1, F. Saint-Germain1, J. Barrette1
(1)
Food Research and Development Centre, Agriculture & Agri-Food Canada, 3600 Casavant, Saint-Hyacinthe, Qc, Canada, J2S 8E3
Eastern Cereal and Oilseed Research Centre, Agriculture & Agri-Food Canada, 960 av Carling, Édifice K.W. Neatby, Ottawa, On,
Canada, K1A 0C6
[email protected]
(2)
Zinc oxide is known for its antimicrobial properties. Interestingly it is also used as food supplement in the food industry
and is generally accepted by the authorities as food additive. The development of nanotechnologies opens new
opportunities for the use of ZnO, particularly in active food packaging applications. Most of the antimicrobial studies
with ZnO nanoparticles has been carried out using convential methods (mainly broth dilutions followed by plate
counting). In such experiments, many confounded effects could impact the results: aggregation of nanoparticles,
coating of nanoparticles, dissolution of nanoparticles and so on (e.g. Figure 1). The present contribution aims in pointing
out critical parameters affecting the dispersion, stability and solubilization of ZnO nanoparticles in aqueous media and
from packaging materials in which they are integrated. In addition, the resistance of lactic bacteria, mainly from the
genus lactobacilli, to ZnO nanoparticles has been investigated. Apparently, all of the L. plantarum strains have shown a
high resistance level to ZnO, while L. rhamnosus was concentration sensitive. Moreover, ZnO nanoparticules seem to act
on the outer layer of the bacteria as illustrated in Figure 2. Further investigation is needed to determine the mechanism
of action for this phenomenon.
After mixing and 15 min sonication
After 24 h sedimentation
Figure 2. Impact of the presence of ZnO on bacterial EPS of Lactobacillus plantarum after 24h (0% (left) and 0.1% (right) w/w,
respectively)
32
PREPARATION AND CHARACTERIZATION OF SEVERAL POLYMER/ZINC OXIDE
MICROCOMPOSITES WITH ANTIBACTERIAL ACTIVITY
M. Verelst1, J. Dexpert-Ghys1, D. Duraccio2, C. Silvestre2, S. Cimmino2, M. Pezzuto2, A. Marra3, V. Ambrogi3
(1)
Centre d’Elaboration de Matériaux et d’Etudes Structurales, Université de Toulouse - UPS, 29 rue Jeanne Marvig, BP 94347,
31055 Toulouse, Cedex 4, France.
(2)
(3)
Universita` di Napoli ‘Federico II’, Dipartimento Di Ingegneria Dei Materiali E Della Produzione, Piazzale Tecchio, Napoli, Italy
[email protected]
In this study, we investigated the influence of ZnO particles obtained by spray pyrolysis and showing submicron
dimensions on the structure, morphology, thermal stability, photodegradation stability, mechanical and antibacterial
properties of isotactic polypropylene (iPP), polyamide 6 (PA6) and low density polyethylene (LDPE) composites
prepared by melt mixing. The results of the morphological analyses indicate that, despite the surface polarity mismatch
between polymers and ZnO, the extrusion process and the characteristics of the used particles lead to composites with
a fair distribution of particles. The addition of ZnO particles imparts significant improvements on the photodegradation
resistance to ultraviolet irradiation, which confirms that ZnO particles act as screens for this type of radiation. The
thermal stability is also improved and increases with the content of ZnO. All composites exhibit significant antibacterial
activity. This activity is dependent on exposure time and composition. The bacterial slaying capability of these
nanocomposites was found better when zinc oxide was dispersed in PA6, where the efficiency is similar to pure ZnO
particles.
References
C Silvestre, S Cimmino, M Pezzuto, A Marra, V Ambrogi, J Dexpert-Ghys, M Verelst, Sylvain Augier, Ida Roman and D Duraccio “
Preparation and characterization of isotacticpolypropylene/zinc oxide microcomposites with antibacterial activity” Polymer Journal
(2013) 00, 1–8
Droval, G., Aranberri, I., Bilbao, A., German, L., Verelst, M. & Dexpert-Ghys, J. “Antimicrobial activity of nanocomposites: poly(amide)
6 and low density poly(ethylene) filled with zinc oxide” . e-polymers 128 (2008).
33
PRODUCTION TECHNOLOGIES OF ANTIMICROBIAL
SILVER-CONTAINING PACKAGING MATERIALS
R. Rutkaite, P. P. Danilovas, A. Zemaitaitis
Kaunas University of Technology, Department of Polymer Chemistry and Technology, Radvilenu plentas 19, Kaunas LT-50254,
Lithuania
[email protected]
Introduction
Antimicrobial materials can give major benefits in areas of healthcare and packaging by helping to minimize the
persistence and spread of microbes. Nowadays, silver-based antimicrobials capture much attention not only because of
the non-toxicity of the active Ag+ to human cells, but mainly because of being a long lasting biocide with high
temperature stability and low volatility. Moreover, as an antimicrobial agent it can be incorporated into the carriers in
order to get continuous and controlled release of the active agent in an environmentally-friendly manner and to keep it
active over a long period of time. In this work we explore different ways to obtain new antimicrobial silver-containing
environmentally friendly polymer materials, their applications in food packaging and in water purification or air
disinfection systems, as well as convenient production technologies.
Cellulose acetate (CA) has been used as the matrix for the immobilization of silver (Ag) and Ag-containing inorganic or
organic nano-, microparticles. Composites containing antimicrobial additives were prepared in two different ways:
microfibers were formed from CA spinning solution in acetone by using dry spinning technique and CA nanofibers – by
using electrospinning technique. Antimicrobial additives were prepared by mixing silver nitrate with respective carriers.
In this way CA nano- or microfiber materials with silver were produced. Non-woven silver-containing CA fabric was used
to produce the seals for drinking water bottles, meanwhile, non-woven CA fabric with carbon-Ag microparticles was
employed in production of antibacterial air filters to be used in drinking water dispensers (see Figure 1).
The other production technology is based on applying of coating film containing silver containing carriers on flexible
packaging by using flexographic printing. The coating composition was comprised inorganic antibacterial agent
(transparent mesh structure glass, carrying silver ions) and film forming material. The different amount of the aqueous
coating material was applied on the polyolefin packaging films by varying the density and coverage area of the coating.
The alternative packaging film production technology was developed by introducing silver containing antibacterial
agent into low density polyethylene extrusion mixture.
The antibacterial properties of all types of packaging materials were assessed. Prepared samples possessed an excellent
antibacterial activity against tested organisms. The developed water storage and flexible packaging materials could be
used for protection of water and food against bacterial contamination and growth.
Antibacterial seal
from non-woven fabric
Conventional
seal
from PE
CA fibers
CA fibers with antibacterial
particles
Figure 1. Antibacterial products for water storage:
(i) seal for drinking water bottle;
(ii) air filters for drinking water dispensers.
Acknowledgements
The authors are grateful to the Research Council of Lithuania and NMA under the Ministry of Agriculture for financial support of the
project MT 1131.
34
ANTIBACTERIAL MEMBRANES BASED ON POLYURETHANE AND BIOLOGICAL POLYMERS
B.S. Munteanu1, D. Macocinschi2, E. Paslaru2, R. P. Dumitriu2, G.E. Hitruc2, C. Vasile2
(2)
(1)
Al.I. Cuza” University, Faculty of Physics, Iasi, Romania.
“Petru Poni” Institute of Macromolecular Chemistry, Iasi, Romania.
[email protected]
Introduction
Polyurethanes (PU) are versatile materials used in many applications1. As biomaterials they can be used because of high
biocompatibility, chemical structure similar to that of proteins and elastomer characteristics2. Polyurethane mixed with
biological molecules (hydrolyzed collagen, elastin, chondroitin sulphate (CS) and hyaluronic acid (HA)) allowed cell
attachment and growth over the culture period and did not interfere with morphological and functional characteristics
of the cells evidencing a high biocompatibility3. By incorporation of silver nanoparticles into polyurethane/natural
compounds-based composites is intended to obtain nanomaterials with antibacterial properties.
Polyurethane/biological polymer membranes (hydrolyzed collagen, elastin, chondroitin sulphate (CS) and hyaluronic
acid (HA)) with and without Silver Nanoparticles were obtained by two different methods: solvent casting the
Polyurethane/ biological polymers/Ag formulations or by electrospinning/electrospraying of the formulations onto
pure PU membrane in order to modify the surface properties of the PU. The prepared composites membranes were
analyzed by different investigation methods such as: contact angle measurements, Attenuated Total Reflection-Fourier
Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (SEM-EDX), Atomic Force Microscopy,
antimicrobial and cell viability tests. Rheological measurements were also performed on to evidence the influence of
the biological polymer and Silver Nanoparticles on electrospinnability. For solutions based on PU with different silver
NPs contents in DMF, the viscosity and dynamic moduli increased with the silver content. ATR-FTIR spectra revealed the
presence of biological components in the solvent-casted membranes and interactions between components. The
method used for obtaining the PU membranes has a strong influence on surface morphology which further affects the
surface wettability. The AFM images show that the homogeneity of the pure PU solvent-casted membrane changes due
to the addition of natural compounds and silver nanoparticles. The solvent-casted membranes have a granular structure
which converts into a ”donut”-like morphology by silver addition while the electrospun/electrosprayed membranes
have a structure of particles interconnected by fibers. Cell viability tests showed the strong dependence on the silver
concentration, an optimum amount of 0.1-0.2 % being established to achieve a balance between cell viability and
antimicrobial properties.
Conclusion
Polyurethane/Biological polymers/Silver Nanoparticles membranes were obtained by solvent casting or
electrospinning/electrospraying. It has established the dependence of the morphology, rheological properties,
biocompatibility and antimicrobial properties on the silver content.
Acknowledgements
The authors acknowledge the financial support given by Romanian UEFISCDI through research project BIONANOMED No. 164/2012
and to COST Action FA0904.
References
1. Lee, M.; Hong, S.C.; Lee, S.W. Polymer Engineering & Science 2007, 47, 439.
2. Macocinschi, D.; Filip D.; Vlad, S. Biomaterials Applications for Nanomedicine, www.intechopen.com.
3. Moldovan, L.; Craciunescu, O.; Zarnescu, O.; Macocinschi, D.; Bojin, D. Journal of Optoelectronics and Advanced Materials 2008, 10,
942.
35
EVALUATION OF A MONO-COMPONENT AND A MULTI-COMPONENT HERBAL EXTRACT AS
CANDIDATES FOR ANTIMICROBIAL PACKAGING OF FRESH RETAIL MEAT
P. Del Serrone1, M. Nicoletti2
(1)
Consiglio per la Ricerca e la sperimentazione in Agricoltura CRA, Centro di Ricerca Produzioni Carni e Miglioramento Genetico
CRA PCM, Via Salaria 31 00015 Monterotondo, Rome Italy
(2)
Department of Environmental Biology, Sapienza University of Rome, Piazz.le Aldo Moro 5 00161 Rome, Italy
[email protected]
Introduction
Limitations of the use of antimicrobials include inactivation of compounds on contact with the meat surface or
dispersion of compounds from the surface into the meat mass. Incorporation of bactericidal compounds into meat
products may result in their partial alteration by muscle components knew to significantly affect the efficacy of the
antimicrobial substances and their release. So, physicochemical characteristics of muscle could alter the activity of
antimicrobials. Furthermore, the antimicrobial activity and chemical stability of incorporated active substances could be
influenced also by water activity of the meat. The evaluation of biological activity is necessary for screening new
antimicrobials of vegetal origin. It is here reported the antimicrobial activity (AA) of two Plant Derived Extracts (PDEs)
evaluated by the broth meat model system for their potential as candidates for antimicrobial packaging.1
Materials and Methods
Two PDEs: a hydroalcoholic extract of garlic (Allium cepa L.) bulbs (GBE); and a hydroalcoholic multi extracts (1:1:1) of
laurel (Laurus nobilis L.) berries, roots of marshmallow (Althaea officinalis L.) and lavender (Lavandula angustifolia L.)
flowers (LMLE) and the meat spoilage bacteria: Escherichia coli, Brochothrix thermosphacta, Carnobacterium spp.,
Lactobacillus curvatus, Lactobacillus sakei and Leuconostoc spp. were considered in the experiment. These bacterial
strains were isolated in a previous study and then maintained in Microbank™ vials at -70°C.2 The AA of PDEs was
evaluated according the broth model meat system. It consists in three steps: growth inhibition (IZ) on appropriate solid
medium using disk diffusion method with 100 μg PDEs; percent of growth reduction (GR) in liquid medium using broth
macrodilution method at lower PDEs concentration (1:10-1:100,000) and detection of the survived bacterial cells in
experimentally inoculated packaged beef meat after treatment with PDEs simulating an abusive refrigerated storage at
10°C. The presence of viable cells of all bacteria tested were checked in beef meat samples experimentally inoculated
and treated with PDEs, distilled water, ciprofloxacin and Tween® 80 at 2, 4, 6. 8. 10, 12 days after treatments. They were
detected using either microbiological official methods or direct and nested PCR with species specific primer pairs,
reaction mixture and amplification conditions as reported in literature, and propidium monoazide dye. Water, Tween®
80 and Ciprofloxacin were considered as controls.
Results
PDEs showed AA against all microorganisms tested in different amounts. The AA as growth IZ (mm) varies significantly
(p≥0.05) respect the controls activity. The bacterial growth reduction (%GR) varies also significantly (p≥0.05) in
function of the concentration of PDEs considered. The highest percentage of bacterial GR in appropriate liquid medium
was obtained with 1 μg concentration of GBE and 10 μg of LMLE. The bacteria experimentally inoculated (1 ml of
bacterial suspension for each bacteria) in minced vacuum-packed and treated with 1 μg of GBE and 10 μg of LMLE were
detected up to 4th day and 6th day respectively after treatment. The microbiological detection and counts of
microorganisms by official methods were according with the molecular biology detection methodologies. Amplicons of
the expected size were obtained for all bacteria tested.
Conclusions
The results show that both PDEs should be considered as potential biopreservatives for fresh retail meat. These results
match with those obtained in a previous study accomplished for evaluating the AA of Neem (Azadirachta indica A. Juss)
Cake Extract2. The methodology was confirmed useful for screening phytocomplexes as new antimicrobials.
References
1. Del Serrone, P.; Nicoletti, M. Int. J. Environ. Res. Public Health 2013, 10, 3282-3295.
2. Del Serrone, P.; Saccares, S.; Saccani, G. 2007 Proceedings 3rd CIGR Naples, Italy 24-26 September 2007, AIDIC. 257.
3. Del Serrone, P.; Nicoletti, M. Pharmacologyonline 2013 30 (3): 148-152.
36
CRITICAL INTERACTIONS BETWEEN PALLADIUM BASED OXYGEN SCAVENGER AND THE FOOD
S. Yildirim, B. Hasler, N. Renke
Institute of Food and Beverage Innovation, Zurich University of Applied Sciences, Waedenswil, Switzerland
[email protected]
Introduction
Palladium catalysis the oxidation of hydrogen in the presence of oxygen. In a previous work, palladium was coated on a
film using magnetron sputtering technology and the oxygen scavenging activities were tested1. Palladium coating was
optimized, influence of different packaging materials on the oxygen scavenging activities have been elucidated.
Test of oxygen scavenging films with different food systems showed that the oxygen scavenging activities are
significantly reduced and in some cases it is even deactivated in the presence of the food. Storage of oxygen scavenging
films in the presence of wine, coffee beans, grains of corn, sauerkraut and onion resulted in deactivation of the oxygen
scavenging films within 5 to 10 minutes (Figure 1).
1.2
Coffee beans
Grain of corn
Sauerkraut
Onion
Oxygen Concentration [%]
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0
5
10
15
20
25
30
35
40
Time [min]
Figure 1. Deactivation of oxygen scavenging catalyst in the presence of different food systems
It has been shown that sulphur compounds may lead a significant degradation of performance of palladium based
catalysts2. Therefore, the influence of different suphur compounds such as thiols, dimethyl sulfide (DMS) and sulphur
dioxide (SO2) on the oxygen scavenging activity of palladium based oxygen scavenger films were tested. Such sulphur
compounds found naturally in tested foods. Ethanetiol, and Furfrylthiol resulted in a very fast deactivation of the
catalyst at concentrations above 0.1 mmol/L. Propanthiol and DMS had a similar effect at concentration above 0.01
mmol/L. Concentrations of 1 μmol/L of thiols and DMS did not have a significant effect on the oxygen scavenging
activity of the films. Wine containing 30 mg free SO2 also deactivated the catalyst whereas SO2 free wine did not show
any significant influence on the activity.
Conclusions
Palladium based oxygen scavengers were deactivated in the presence of foods containing sulphur compounds. Oxygen
scavenging activity tests with solutions containing pure sulphur compounds showed that the deactivation can be due
to the presence of such compounds in the food systems. Deactivation is dependent on the concentration of sulphur
compounds in the system.
References
1. Yildirim S., Lohwasser W., Gsell V. Renke N., “Development of Palladium Based Oxygen Scavenging Film for Food Packaging”, in
18th IAPRI World Packaging Conference, DEStech Publications, Inc., Lancaster, ISBN No. 978-1-60595-084-6, 2012.
2. Bartholomew, C. H., Agrawal, P.K., Katzer, J.R., “Sulphur Poisining of Metals”, Advances in Catalysis, Volume 31, 135-242, 1982.
37
INFLUENTIAL FACTORS OF BISPHENOL A LEACHING FROM POLYCARBONATE CONTAINERS
INTO DRINKING WATER: A SIMULATION STUDY
S. Gaengler, K. C. Makris
Cyprus International Institute for Environmental and Public Health in association with Harvard School of Public Health, Cyprus
University of Technology, Limassol Cyprus
[email protected]
[email protected]
Introduction
Bisphenol A (BPA) is a high production volume chemical that has raised public concerns due to its widespread
occurrence in the environment and in human biospecimen and its links to various health outcomes (e.g. reproductive
and developmental effects)1. The main route of human exposures to BPA is through ingestion. BPA is used in various
food packaging materials, such as polycarbonate (PC), epoxy resins, can linings2 and recycled cardboard3. Mineral water
dispensers found in public places and homes use PC bottles to package the potable water. These containers are exposed
to various environmental and handling conditions, such as industrial cleaning between uses, and storage under
fluctuating environmental conditions such as air temperature or sunlight4. Occasionally, in household settings these 19L
PC bottles are also used to package tap water that often contains residual disinfectant (chlorine). BPA readily reacts with
chlorine and forms chlorinated derivatives, which also have endocrine disrupting activity5. Thus, the following
experiments were conducted using both mineral and tap water.
Objective
We investigated the leaching behavior of BPA from PC- bottles into water under the exposure to varying temperatures,
number of reuse cycles and UV-light irradiation.
Methods
The PC bottles were exposed to different combinations of temperature (4-45 °C), reuses cycles (0-51 times) and
UVA-light (0-8h), set with the central composite design. The samples will be analyzed with limited storage time at
-80°C, using gas chromatography coupled with triple quadrupole mass spectrometer. The tap water will be analyzed for
chlorinated BPA congeners, as well.
Results
Anticipated results will reveal information on the leaching behavior of BPA under the influence of the three tested
variables. The main and interaction terms of each tested variable on the magnitude of leached BPA and its chlorinated
BPA derivatives will be assessed. The findings of this study will reveal the storage and handling precautions that should
be followed to minimize consumer’s exposures to BPA and chlorinated BPA, and therefore their related health risk.
References
1. Vandenberg, L. N.; Maffini, M. V; Sonnenschein, C.; et al. Bisphenol-A and the Great Divide: a Review of Controversies in the Field
of Endocrine Disruption. Endocr. Rev. 2009, 30, 75–95.
2. Von Goetz, N.; Wormuth, M.; Scheringer, M.; Hungerbühler, K. Bisphenol a: How the Most Relevant Exposure Sources Contribute
to Total Consumer Exposure. Risk Anal. 2010, 30, 473–87.
3. Suciu, N. a; Tiberto, F.; Vasileiadis, S.; et al., M. Recycled Paper-Paperboard for Food Contact Materials: Contaminants Suspected
and Migration into Foods and Food Simulant. Food Chem. 2013, 141, 4146–51.
4. Makris, K. C.; Andra, S. S.; Jia, A; et al. Association Between Water Consumption from Polycarbonate Containers and Bisphenol A
Intake During Harsh Environmental Conditions in Summer. Environ. Sci. Technol. 2013, 47, 3333–43.
5. Gallard, H.; Leclercq, A.; Croué, J.-P. Chlorination of Bisphenol A: Kinetics and by-Products Formation. Chemosphere 2004, 56,
465–73.
38
PLASTICIZATION OF PLA WITH ESTERIFIED OLIGO-PLA
2
M. Avella , V. Ambrogi1, R. Avolio2, R. Castaldo2, M. Cocca2, E. Di Pace2, M. E. Errico2, G. Gentile2
(1)
Department of Chemical, Materials and Industrial Production Engineering, University of Naples “Federico II”
(2)
Institute of Chemistry and Technology of Polymers (ICTP – CNR)
[email protected]
During last years a number of high and low MW additives have been employed to increase the ductility of polylactic acid
(PLA), however in many cases the plasticization effect was not stable during time due to phase separation and/or
physical aging1. In the present study, two hydroxyl (A) or carboxyl (B) end-capped oligomeric esters of lactic acid were
tested as plasticizers for PLA. Blends containing from 10 to 25% of A or B were prepared in the melt by using a batch
mixer and the effects on chemico-physical as well as mechanical properties of PLA as a function of aging were
investigated.
The miscibility of blends and its stability with aging time was assessed by SEM, DSC and DMTA, that showed the absence
of phase separation. Both esters lowered the glass transition of the PLA, showing a plasticizing effect; the extent of Tg
depression is in good agreement with the prediction of the empirical Fox equation2. Regarding mechanical properties,
a sharp transition from brittle to ductile behavior was observed above 20 wt% content of both plasticizers, with
maximum elongation above 400%. At the same time, the modulus (E) and tensile strength (σ) decreased while the
impact toughness remained almost unchanged. Finally, oxygen and water permeability slightly increased with both
oligomer content. Table 1 resumes some mechanical and calorimetric results for the most promising composition.
Table 1. Main results of mechanical and calorimetric analyses
As prepared
Plasticizer
E(Mpa)
20 % A
20 % B
2200
565
640
σ(MPa)*
60
12
13
8 weeks aging
ε(%)
Tg(°C)
E(Mpa)
σ(MPa)
5
430
480
60
35
34
2250
1422
1605
68
34
41
ε(%)
5
180
140
Tg(°C)
64
38
32
Also total migration test were carried out using food simulants, according to the European Standard EN 1186-1:2002,
revealing the compliance of the 20% A blend with current UE regulation for food contact plastics.
Sample
PLA
20 % A
20 % B
Table 2. Total migration results
Simulant
Total migration (mg/dm2)
Water
3 wt% acetic acid
Water
3 wt% acetic acid
Water
3 wt% acetic acid
0
0
6
7
17
18
Future developments will be focused on the combination of plasticizers with calcium carbonate nanoparticles, aiming
to further improve barrier and mechanical properties.
References
1. Rasal,R.M.; Janorkar,A.V.; Hirt,D.E. Prog. Polym. Sci. 2010, 35, 338.
2. Fox, T.G.; Bull. Am. Phys. Soc. 1956, 1, 123-128.
--------------------------------------------------------* For ductile samples (20 % A and 20% B) the peak stress before necking and plastic deformation (i.e. yield stress) is reported, as is
it more readily compared with the peak stress of PLA that shows a fragile behaviour.
39
SINGLE PARTICLE-ICP-MS AND ASYMMETRIC FLOW FIELD FLOW
FRACTIONATION-UV-MALS-ICP-MS FOR THE ANALYTICAL DETERMINATION OF INORGANIC
NANOPARTICLES RELEASED FROM POLYMER NANOMATERIALS FOR FOOD PACKAGING
F. Aureli, M. D’Amato, A. Raggi, F. Cubadda
Istituto Superiore di Sanità, Dept. Food Safety and Veterinary Public Health. Viale Regina Elena 299, 00161 Rome, Italy
[email protected]
Eco-sustainable Polymer Nanomaterials for Food Packaging (PNFP) have great prospects as novel tools with improved
mechanical, barrier and antimicrobial properties for the preservation and distribution of high quality and safe food.
Besides their technical efficacy, i.e. improved properties for use as food contact materials, PNFP must be evaluated in
terms of absence of any negative impact on the safety or the quality of food. From the point of view of food safety, a
critical issue is the potential for contamination of the food by chemical migration from the polymer. In particular,
migration of inorganic, insoluble nanoparticles into the food matrix is of concern. Even though there is still a lack of
understanding of the hazard posed by ingestion of nanomaterials, inorganic nanoparticles that are potentially
bio-persistent are considered of high concern [1]. In order to exclude risks for human health, preventing exposure
appears to be the solution of choice. This means that any unwanted migration has to be avoided and this has to be
proved by means of analytical methods capable to detect and quantify inorganic nanoparticles in simulants and food.
State-of-the-art mass spectrometric techniques for the analytical determination of inorganic nanoparticles in
dispersion and (after proper sample extraction) in complex matrices have recently become available [2]. Being based on
atomic mass spectrometric, they are element-specific (i.e. provide information on chemical identity) and have the
potential to measure size, size distribution, number and mass concentration of particles. Single particle inductively
coupled plasma mass spectrometry (sp-ICP-MS) is based on time resolved analysis of very diluted nanoparticle
dispersions using short dwell times (≤10 ms). Each particle gives rise to a signal spike clearly distinguishable from
random background noise and, by means of appropriate algorithms, signal frequency distributions are converted into
size frequency distributions. In principle, the signal arising from ionic (i.e. soluble) forms of the element constituting the
particles, if any, can be distinguished from that due to the presence of the particles themselves. Therefore, this is a
particle-specific technique with sizing capability, presently having limitations mainly in the size detection limits
(depending on the element they can vary from ca. 10 to several tens nm). Another powerful technique is asymmetric
flow field flow fractionation, which provides separation of particles according to their size, combined on-line with
optical detectors for size determination (MALS, DLS, UV) and elemental detection and quantification by ICP-MS. With
AF4-(UV-MALS)-ICP-MS particles having diameters down to 1 nm can be determined with the additional advantage of
multi-detector capability.
Using these techniques our laboratory participated in the first interlaboratory study on sp-ICP-MS determination of Ag
particles in aqueous and ethanol dispersions and in the second interlaboratory study on sp-ICP-MS determination of Ag
particles in chicken tissue, both organized by RIKILT and the European Commission (JRC-Geel), as well as in the first
interlaboratory study on AF4-ICP-MS on determination of Ag particles organized by the European Commission
(JRC-Ispra).
References
1. Cubadda F. 2013. EFSA and national activities on safety assessment of nanomaterials in the food sector. In: NanotechItaly2013,
Quality in the Food Value Chain.
2. Aureli F., D’Amato M., Raggi A., Cubadda F. 2013. Analytical detection of engineered inorganic nanomaterials in food at ISS. In:
NanotechITALY 2013, Quality in the Food Value Chain.
40
EVALUATION OF SUITABILITY OF SOME BIOMATERIALS FOR FRESH FOOD CASE STUDY:
BIOMATERIALS FOR FRESH PRODUCTS
M. K. Pettersen1, S. Bardet2, J. N. Nilsen3, S. B. Fredriksen3
(1)
Nofima Mat AS, Osloveien 1, N-1430 Aas, Norway
(2)
INSFA Agrocampus, 35002 Rennes, France
(3)
Norner Innovation, N-3960 Stathelle, Norway
[email protected]
The important function of the packaging is to protect and maintain the food quality through the entire value chain, and
reduction of food waste is of great importance. Biopolymers are mainly used for packaging of fruits and vegetables due
to the shorter shelf life and respiration and humidity requirements of such foods. Evaluation of the potential for use of
biomaterials fillets for fresh salmon was performed. Polylactic acid (PLA) and starch based materials were compared to
traditional materials (high density polyethylene (HDPE) and amorphous polyester (APET)/ polyethylene (PE)). Pre-rigor
farmed salmon, packed within 36 hours after slaughtering, were stored in modified atmosphere consisting of 60% CO2
and 40% N2 in bags made of PLA or starch or 600ml trays made of HDPE or APET/PE. The fish filets were stored at 4ºC
for 14 days and the evaluation of suitability of different packaging materials was evaluated by monitoring the bacterial
growth and off-odour after 5, 7, 9 and 14 days of storage. Included in the experiment were also measurements of
properties and characteristics of biomaterials, such as content of copolymers and additive, processability and barrier
properties.
41
WATER SORPTION AND DIELECTRIC STUDY OF CHITOSAN FILMS WITH VARIOUS DEGREES OF
DEACETYLATION
C. Pandis1,2, M.A. Gámiz-González2, C. Chatzimanolis-Moustakas1, A. Vidaurre2,3, J.L. Gómez Ribelles2,3, A.
Kyritsis1
(1)
(2)
Physics Department, National Technical University of Athens, Greece
Centro de Biomateriales e Ingeniería Tisular, Universitat Politècnica de València, Spain
(3)
Ciber en Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), Spain
[email protected]
Introduction
Chitosan is a biodegradable biocompatible polymer derived from natural renewable resources with a great potential for
a wide range of applications including edible films and coatings for food packaging[1]. Furthermore, chitosan presents
antimicrobial activity, non-toxicity, versatile chemical and physical properties together with excellent film forming
ability. Thus, chitosan based films have proven to be very effective in food preservation. The presence of amino group in
chitosan provides major functionality towards biotechnological needs, particularly, in food applications[2]. The
concentration of the amino groups depends on the deacetylation degree (DD) of chitosan which in turn dictates many
of its properties. In this work the water sorption properties both from vapor and liquid water together with the dielectric
properties in a wide frequency and temperature range of chitosan films as a function of the DD are studied.
Materials preparation
Chitosan was dissolved in acetic acid 1% (w/v) while different amounts of acetic anhydride, mixed with methanol were
added to the chitosan solution to obtain, after neutralization, a powder of chitosan with different degree of
deacetylation. 1H-NMR was used to characterize the DD of the samples. Chitosan films were obtained by solvent casting.
Results and discussion
The obtained thin films present a DD ranging from 59% to 85% The equilibrium vapor water sorption isotherms of the
prepared films were acquired at room temperature for relative humidities (RH) ranging from 5% up 95% by means of a
vapor sorption analyzer. The diffusion coefficient of water was also evaluated from dynamic vapor sorption
measurements. Furthermore, sorption from liquid water was determined by immersion into water using gravimetric
technique. The films with various DD present similar water sorption isotherms irrespective of the deacetylation degree
with a water gain of about 42% at 95%RH. On the contrary, sorption from liquid water depends on DD with the films
with the lower DD absorbing 560% of water on a dry basis. The above is discussed in terms of alterations in swelling
behavior due to the different degree of crystallinity as determined by X-Ray diffraction studies.
The dielectric response of both dried and wet films was obtained by means of dielectric relaxation spectroscopy (DRS)
from -150 oC to 100 oC at a frequency range from 10-2 Hz to 106 Hz. The well known secondary dielectric relaxation
mechanism found in all polysaccharides was observed at low temperatures (-130 oC to -10 oC). The shape of the above
mechanism was dependent on water content but not on the deacetylation degree of chitosan indicating its water
related origin. The techniques used in this work provide valuable information on the study of the water-chitosan
interactions as a function of the deacetylation degree which is of fundamental importance for the understanding of the
structure and properties of chitosan for food and biotechnological applications.
Acknowledgement
The research project is implemented within the framework of the Action «Supporting Postdoctoral Researchers» of the Operational
Program "Education and Lifelong Learning" (Action’s Beneficiary: General Secretariat for Research and Technology), and is
co-financed by the European Social Fund (ESF) and the Greek State. MAGG, AV and JLGR would like to thank Spanish MICINN (Grant
no: MAT2010-21611-C03-01) for providing financial support to this project and MAGG the BES-2011-044740 grant.
References
1. Elsabee,M.Z.; Abdou,E.S. Chitosan based edible films and coatings: A review, Materials Science and Engineering C 2013, 33 1819.
2. Dutta,PK.; Tripathi,S.; Mehrotra,GK.; Dutta,J. Perspectives for chitosan based antimicrobial films in food applications, Food
Chemistry 2009, 114, 1173.
42
CONTRASTING NANOCOMPOSITES AND NANOSTRUCTURED POLYMERS FOR SAFE AND
EFFECTIVE FOOD PACKAGING
G. Mitchell, A. Tojeira
Centre for Rapid and Sustainable Product Development, Institute Polytechnic Leiria, Marinha Grande Portugal
[email protected]
Introduction
It was food packaging that made the development of self-service stores and subsequently supermarkets a practical
proposition. The packing provides physical and barrier protection for the food content and offers security to the
consumer. Plastics have proved to be particular suited to meetings the many demands in the design of food packaging.
A key required is a defined permeability for gases and water. We can limit the permeability in the polymer film by
dispersing platelike nanoparticles such as those based on clay. These can increase the tortuosity of the pathways for
gases. Of course this approach is most effective if the particles are well dispersed and the planes of the particles are
aligned parallel to the film surface. These are challenging requirements and we have explored if controlling the polymer
microstructure alone is sufficient to achieve the same result.
Approach
We show that the many requirements of high performance packaging coupled to the need for recycling and enhanced
sustainability can be meet by the use of polymer films with controlled morphology. By this we mean the controlled
distribution and orientation of structural elements such as crystalline lamellae, glassy domains or heavily cross-linked
regions which will significantly impact on the permeability of gases through the film. We find that the techniques for
achieving this are not dissimiliar to those required for the preparation of polymer based nanocomposites. We present
examples where the required morphology can be achieved and discuss the limitations which are intrinisic to such
processes.
Summary
We show that the requirements for the succesful preparation of polymer nanocomposites are essentially the same as
reuired for the preparation of polymeric materials with a defined nanostructure. We demonstrate that the
nanostructured polymers offers several crucial advantages with respect to nanocomposites.
Acknowledgements
This work was performed within the framework of the COST Action FA0904. In Part the experimental work was performed at The
European Synchrotron Research Facility in Grenoble and at the STFC Diamond Light Source and we thank the beamline scientists for
their involvement with the experiments. The microscopy studies were performed at the Centre for Advanced Microscopy at the
University of Reading.
43
CRYSTAL NUCLEATION IN POLY(EPSILON-CAPROLACTONE) - MULTIWALLED CARBON
NANOTUBE COMPOSITES
C. Schick, E. Zhuravlev
University of Rostock, Institute of Physics, Wismarsche Str. 43-45, 18051 Rostock, Germany
[email protected]
The nucleation efficiency of multi-wall carbon nano-tubes (MWCNT) in poly(ε-caprolactone) (PCL), as an example, was
tested for a wide range of temperatures and cooling rates and compared to the efficiency of homogeneously formed
nuclei. The temperature range below the maximum of crystallization rate is generally not accessible for non-isothermal
cooling experiments because the sample becomes amorphous at the needed cooling rates. Isothermal experiments
after fast quenches extend the temperature range down to and below the glass transition. The employed differential
fast scanning calorimeter (DFSC) allows cooling at rates up to 100,000 K/s and precise adjustment and control of
isothermal conditions in the time range from 10-4 to 104 s and longer. As shown in previous work, heterogeneous
crystal nucleation dominates at low supercooling, revealing a significant dependence of crystallization rate on MWCNT
concentration. Nevertheless, no saturation of the nucleation activity at a MWCNT loading of 0.2 to 0.5 wt% as seen in
slow DSC experiments was observed at the much higher cooling rates employed here. At high supercooling, where
homogeneous nucleation is prevalent, the addition of MWCNT does not enhance neither reduce the crystallization rate.
At the temperature of maximum homogeneous nucleation rate, formation of homogeneous nuclei always dominates
crystallization.
100
DSC
0.01K/s
heating at 5,000 K/s
Overall latent heat
6hcc+6hm
6h in J/g
50
0
-10
0 wt%
MWCNT content:
0.2 wt%
0.5 wt%
1 wt%
6hcc
2 wt%
-30
Cold crystallization5 wt%
-20
100
1000
10000
Figure 6. Overall latent heat on heating, and cold
crystallization enthalpy (for clarity scales are different),
as function of previous cooling rate measured for pure
PCL and PCL with different concentration of MWCNT. The
star shows the heat of fusion after crystallization at 1
K/min (0.016 K/s), measured in conventional DSC, which
is within the determination error the same for all
samples.
100000
Cooling rate in K/s
References
E. Zhuravlev, W. A., Pötschke P, Androsch R, Schmelzer JWP, Schick C
Kinetics of nucleation and crystallization of poly( -caprolactone) – multiwalled carbon nanotube composites
European Polymer Journal, 2014, accepted.
E. Zhuravlev, J.W.P. Schmelzer, B. Wunderlich, C. Schick,
Kinetics of nucleation and crystallization in poly(epsilon caprolactone) (PCL)
Polymer, 52 (2011) 1983-1997.
44
FOOD PACKAGING BASED ON NANOPOROUS-CRYSTALLINE POLYMERS
G. Guerra1, A. R. Albunia1, C. Daniel1, P. Rizzo1, L. Di Maio1, M. Galimberti2
(1)
(2)
Nano Active Film S.r.l., Spin-off Company of the University of Salerno
Department of Chemistry, Materials and Chemical Engineering, Politecnico di Milano, Via Mancinelli 7, 20131 Milano, Italy
[email protected]
The contribution is devoted to thermoplastic materials including nanoporous-crystalline phases,1-4 which are obtained
from co-crystalline host-guest phases by suitable guest extraction procedures (e.g., by carbon dioxide in supercritical
conditions). These nanoporous-crystalline phases are able to absorb guest molecules also from very dilute solutions
and have been till now obtained only for two commercial polymers: syndiotactic polystyrene (s-PS)1,2 and
poly(2,6-dimethyl-1,4-phenylene)oxide (PPO)3.
As for gas sorption, of particular economic relevance is the removal of ethylene5 and carbon dioxide6 from the packaging
environment of fruit and vegetables. Indeed, it is well known that the post-harvest life and quality of many fruits,
vegetables and flowers are negatively affected by the presence of carbon dioxide and seriously shortened by exposure
to trace amounts (also few ppb) of ethylene. For this purpose active packaging have been realized by adding zeolites,
silica or activated carbon to commercial polypropylene or polyethylene packaging films.
s-PS films presenting its nanoporous host δ phase exhibit a large ethylene uptake, which is associated with the
formation of a co-crystalline phase with ethylene guest molecules, oriented nearly perpendicular to the crystalline
polymer helices.5 The ethylene uptake from the nanoporous-crystalline film is much higher than for the amorphous film
and also much higher than for an industrial isotactic-polypropylene film containing large amounts (up to 25 wt%) of
silica.5
As already observed for other guest molecules of s-PS, the ethylene diffusivity in the host nanoporous crystalline phase
is markedly reduced with respect to the diffusivity in the corresponding glassy amorphous phases. In addition, ethylene
diffusivity can be further reduced by suitable selection of the uniplanar orientation (a// c// or a// c ) of the host
crystalline phase.5
Hence, the δ-nanoporous crystalline phase of s-PS presents high ethylene solubility and low ethylene diffusivity (which
can be also controlled by the orientation of the crystalline phase), associated with negligible water uptake. These
features, combined with good chemical and mechanical properties, make polymeric films presenting the δ-nanoporous
crystalline phase suitable candidates for produce packaging.5
Recent industrial developments in this field will be presented.
References
1. De Rosa, C.; Guerra, G.; Petraccone, V.; Dirozzi, B. Macromolecules 1997, 30, 4147.
2. Petraccone, V.; Ruiz de Ballesteros, O.; Tarallo, O., Rizzo, P.; Guerra, G. Chem. Mater. 2008, 20, 3663.
3. Daniel, C.; Longo, S.; Fasano, G.; Vitillo, J.G.; Guerra, G. Chem. Mater. 2011, 23, 3195.
4. Guerra, G.; Daniel, C.; Rizzo, P.; Tarallo, O. J.Polym.Sci.Polym.Phys.Ed. 2012, 50, 305.
5. Albunia, A.R.; Minacci, T.; Guerra, G. J.Mater.Chem. 2008, 18, 1046.
6. Annunziata, L.; Albunia, A. R.; Venditto, V.; Mensitieri, G.; Guerra, G. Macromolecules 2006, 39, 9166.
45
INTELLIGENT PACKING TO SUPPORT SUPPLY CHAIN FOOD TRACEABILITY
F. Marandino, L. Magliulo
Penelope Spa - Via Cervantes de Saavedra M., 55 - 80133 Napoli
[email protected]
[email protected]
Food safety is a top priority for consumers and the food industry. The attention paid by the media to food safety and
possible food quality problems, the globalization of the international marketplaces, the ever increasing risks associated
with liability, the growing complexity of the supply chains all represent strong drivers of traceability. Eventually, safety
and security represent the two most important drivers in the food industry as dramatic recalls have frequently been
reported around the world.
According to EU law, food and feed businesses - whether they are producers, processors or importers - must make sure
that all foodstuffs, animal feed and feed ingredients can be traced right through the food chain, from “farm- to-fork”.
Each business must be able to identify its suppliers and which businesses it supplied in a one-step-up, one-step-down
approach.
Progress in ICT technologies and the emerging of Internet of Things (IoT) make possible to create tools to support
traceability at supply chain level. In this scenario an active role can be played by intelligent packaging (IP).
Unlike active packaging, whose role is to interact with the food and with the environment within the pack to help
extend shelf life and ensure safety, the tern IP was coined to describe packaging designed to monitor the pack
environment and the condition of the food and then communicate information about food quality and safety.
This is the crucial point, if IP communicates information about the quality and safety of food, when it is integrated into
a tracking system it can be an active component capable to release critical information for traceability of food and to
support the detailed reconstruction of the history of a product. It’s clear that the creation of an extensive system for
traceability, which also includes information from IP, must possess architectural features to ensure the ubiquity of access
points to data, a shared infrastructure by all systems in the supply chain, the ability, for the different systems, to use
resources according to specific requirements (scalability). In short, a cloud computing infrastructure.
ValueGo is an architectural framework that provides such characteristics. It is basically a system that collects data from
several components: smart package devices, sensors, databases, farming/processing/logistics/retail applications in the
food supply chain to realise a complete traceability along the chain.
Data acquired at the various stages of the food supply chain is aggregated and shared in a cloud infrastructure and make
available as vertical (for own business) and horizontal (for the whole supply chain business) views. A specific horizontal
view is generated for consumer that, simply using a smartphone, is addressed to a web page describing the product
being considered for purchase
Developed in an open source environment, ValueGo technology features two distinctive elements active or passive tags
and domain ontologies. A semantic database implements the application domain ontology. Through the use of
ontologies, the concepts related to any business or product domain can be shared in multiple application environments,
and domain-specific knowledge can be further enriched.
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processing
Figure 1. Framework for integrated supply chain.
The basic concept of the system is that: everything in the chain put data in the cloud, the cloud returns aggregated
information profiled for different uses.
46
CHARACTERIZATION OF POLYETHYLENE TEREPHTHALATE BASED HYBRID NANOCOMPOSITES
R. Merijs Meri1, J. Zicans1, T. Ivanova1, R. Berzina1, G. Japins1, V. Kokars2
(1)
Riga Technical University, Faculty of Materials Science and Applied Chemistry, Institute of Polymer Materials, Latvia
(2)
Riga Technical University, Faculty of Materials Science and Applied Chemistry, Chair of Chemistry, Latvia
[email protected]
Polyethylene terephthalate (PET) is one of the basic materials in plastic packaging. In the meantime packaging makes
nearly 40% from the whole plastics demand in the EU market. Considering short life cycle of plastic packaging, it leaves
tremendous influence on the waste generation. Hence plastic packaging recycling issues are of very high importance. In
2010 European recycling levels for plastic packaging reached almost 33% thereby reducing plastic packaging life-cycle
energy demand by 24% and greenhouse gas emissions by 27%1. Taking into the account conditions of the ambitious
vision “Zero Plastics to Landfill by 2020”2 and by considering waste as a resource, benefits from plastic packaging
recycling should be noticeably greater. Consequently it is worth to consider plastic recyclates as a versatile and valuable
future raw material option for developing of many innovative products.
This research is devoted to evaluation of recycled bottle-grade polyethylene terephthalate (RPET) as a potential source
for development of advanced nanocomposites. RPET has been supplied by the main post-consumer soft-drink bottle
re-processor in Latvia – JSC “PET Baltija”. Neat and organically modified montmorillonite clays (MMT and OMMT
respectively) from Laviosa Chimica Mineraria S.P.A. as well as various laboratory synthesized liquid crystalline modifiers
(LCM) have been used as modifiers. Polymer hybrid composites have been obtained by melt mixing of RPET with
nanoclay (1 to 5 wt. %) and LCM (1 to 5 wt. %) by using twin screw extruder. Mechanical, rheological, barrier and
structural characteristics of RPET/LCM/MMT and RPET/LCM/OMMT hybrid composites have been characterized by means
of rotational rheometry, dynamic mechanical thermal analysis, thermogravimetric analysis, tensile stress-strain testing,
instrumented impact strength testing, water vapour sorption analysis, differential scanning calorimetry and electron
microscopy.
It has been shown that purposeful selection of the modifying additives (LCM, MMT, OMMT) allows increase modulus3-4,
strength3-4, creep resistance3, thermal stability4 and other exploitation characteristics of the investigated RPET
composites. It is worth mentioning that results of the investigations testify that simultaneous addition of LCM and
either MMT or OMMT synergistically affect Young’s modulus and yield strength of the hybrid RPET nanocomposites.
Certain improvements of barrier characteristics are also observed along with rising LCM and OMMT content in the
polymer matrix. Besides it has been observed that addition of LCM considerably improve processability of RPET by
increasing viscosity of the material. The change of these properties has been justified by the corresponding change of
calorimetric features and morphology of the investigated composites.
References
1. http://www.plasticseurope.org/use-of-plastics/packaging.aspx
2. http://www.plasticseurope.org/plasticssustainability/zero-plastics-to-landfill.aspx
3. Merijs Meri,R.; Zicans,J.; Maksimovs,R.; Ivanova,T.; Kalnins,M.; Berzina,R.; Japins,G. Composite Structures (submitted)
4. Merijs Meri,R.; Zicans,J.; IvanovaT.; Berzina,R.; Japins,G.; Locs,J. Key Engineering Materials 2013, 527, 44.
47
THE CONVERGENCE OF NEW FOODTECHNOLOGIES: SOCIAL & ETHICAL ISSUES
G. Hunt
Centre for Bioethics & Emerging Technologies, St Mary’s University College, London TW1 4SX
[email protected]
Nanotechnology is already transforming the food and drink manufacturing and distribution process in terms of new or
enhanced...
1. food and drink content design and manufacturing, such as taste and colour
2. enhanced and novel forms of packaging, such as new polymer films and coatings
3. distribution such as labelling and tracing
4. storage, enhancing shelf life at all stages from transport through to retail
5. recycling and waste disposal, in accordance with cost-cutting and compliance with new consumer and environmental
protection regulations
6. prevention of contamination at all stages
These technologies are not only responses to the economic factors of competition and cost-cutting but also more
recently to: crises of food and water shortage; factors associated with climate change, such as crop failure and new crop
disease patterns; increased and burgeoning world population; the energy crisis, such as oil prices affecting
manufacturing costs and polymer design
An example of a developing technology is the use of irradiation, which is the process of exposing food to ionizing
radiation in order to disinfest, sterilise or preserve food. Others include ‘High temperature, short processing’ methods,
and ‘process optimisation’ methods.
This presentation reviews the chaging food demand and supply situation in the content of economic, social and
environmental crises and how various food technologies can converge to solve some of the associated problems. For
example, there is the question of bringing together polymer nanomaterial design and irradiation techniques.
The above dramatic changes are taking place in the context of the recently growing question of the social acceptance of
food technologies. The complexity, rate of change and uncertainties involved pose issues for consumers. There are
difficult questions of perception of benefits over risks, consumer attitudes based on habit, familiarity and attitude, and
the popular cultural background which is rich with values about food, preparation of food and food-related health
issues.
References
Olsen, N. V., Grunert, K.G., & Anne-Mette, S. (2010). Consumer acceptance of high-pressure processing and pulsed-electric field: a
review. Trends in Food Science & Technology, 21(446-472)
48
ECO-SUSTAINABLE PLASTIC FOOD CONTACT MATERIALS USING NANOMATERIALS - FROM
DEVELOPMENT TO FINAL PRODUCT
E. J. Hoekstra
Joint Research Centre of the European Commission
[email protected]
Introduction
Innovation in science and technology plays a key role in the success of developing eco-sustainable materials for food
packaging. Reduction of the use of resources, better recyclable or biodegradable materials and reduction of food waste
are important objectives to achieve. These objectives are covered by several pieces of legislation and strategies which
may influence the success of eco-sustainable food contact materials and their final placement on the EU market. In
addition to food safety requirements materials and articles also need to comply with product safety and waste
requirements. Implications of safety requirements are paramount for new substances that may not yet be regulated
under existing measures. This presentation will give an overview and insight in these requirements. Examples will be
given to illustrate the combination of various potential aspects shown below.
Directive general product safety
Regulation good manufacturing practice FCM
Framework Regulation FCM
Product safety
Regulation plastic FCM
Eco-sustainable
plastic FCM
Waste
Food safety
Regulation food additives / enzymes / flavourings
Directive packaging and packaging waste
49
Regulation active / intelligent FCM
Regulation biocidies
BIODEGRADATION OF PLA AND PLA COMPOSITES
M. Kwiatkowska, M. Kozlowski
Faculty of Environmental Engineering Wroclaw University of Technology, Poland
[email protected]
[email protected]
The use of long-lasting polymers for short lived applications is not highly desirable because of the depletion of fossil
and non renewable feedstocks. Thus, there is an increasing demand for biodegradable packaging materials, which could
be easily renewable. The key matter for the twenty-first century is the usage of biopolymers for packaging materials.
That solution allows to eliminate issues related with waste disposal, i.e.: landfilling and sorting. The unique adventage
of the biopolymers is their compostability. As a green food and compostable packaging material poly(lactic acid) (PLA)
stands the growing alternative for fresh food packaging market (thermoformed containers). Currently PLA is widely
used as a polymer for short shelf life products: lamination films, drinking cups, overwraps and blister packages.
Degradation of PLA depends on several factors. The major is L-lactide content and the initial crystallinity of the
packaging material, the others are: temperature, humidity, and pH of the compost pile1-3.
Biodegradability of (D,L) PLA NW2002D and PLA/flax composite in compost was evaluated by means of the amount of
CO2 evoluted with time. As reference materials cellulose and polyethylene were used. PLA and PLA composite exhibited
a biodegradation rate comparable to that of cellulose.
o ute CO2 g
70
1
60
2
50
3
4
40
30
20
10
10 20 30 40 50 60 70
80 90 100 110 120 130 140 150 160 170 180 190
Time
ays
Fig. 1. Progress of biodegradation as measured with carbon dioxide amount
The research was supported by Wroclaw Research Center EIT+ under the project ‘The Application of Nanotechnology in Advanced
Materials’— NanoMat (POIG.01.01.02-02-002/08) co-financed by the European Regional Development Fund (Innovative Economy
Operational Programme 1.1.2).
References
1. Kale G., Auras R., Singh S.P., J. Polym. Env., 2006, 14, 317-334.
2. Funabashi M., Ninomiya F., Kunioka M., J. Polym. Env., 2007, 15, 245-250.
3. Copinet A., Bertrand C., Longieras A., J. Polym. Env., 2003, 11, 169-179.
50
FAO GLOBAL INITIATIVE ON FOOD LOSS AND WASTE REDUCTION – SAVE FOOD
R. Van Otterdijk
Food and Agriculture Organization of the United Nations, Vva delle Terme di Caracalla, Rome,Italy
[email protected]
Food losses and waste levels are high and depend on specific conditions. Food losses refer to the decrease in edible food
mass available for human consumption throughout the different segments of the supply chain. In addition to
quantitative losses, food products can also face a deterioration of quality, leading to a loss of economic and nutritional
value. Food losses resulting from decisions to discard food that still has value to others are also called “food waste”. Food
waste is most often associated with the behaviour of retailers, the food service sector and high income consumers but
food waste and losses take place all along food supply chains.
Accurate estimations of the magnitude of losses and waste are still lacking, particularly in develop-ing countries.
Nevertheless, there is no doubt that the levels of food loss and waste remain unac-ceptably high. Recent studies
commissioned by FAO estimated yearly global quantitative food loss-es and waste at roughly 30% for cereals, 40-50%
for root crops, fruits & vegetables, 20% for oilseeds, meat and dairy, and 30% for fish.
The impacts of food losses and waste are multi-faceted, affecting people’s food and nutrition securi-ty, the environment
and the availability of natural resources (land, water, energy), the economy and the distribution of economic benefits
among actors in the food supply chains.
Interventions by food chain actors are required to reduce food losses and waste. The private sector needs to engage in
better production planning aligned with markets, promoting resource-efficient production and processing practices,
improving preservation and packing technologies, improving transportation and logistics management. The public
sector on the other hand needs to support sup-ply chain interventions by creating a policy and institutional enabling
environment and a better in-vestment climate, support product and process innovation, organize capacity
development, under-take awareness raising and advocacy campaigns, and build partnerships and alliances.
As part of its public role FAO has launched the Global Initiative on Food Loss and Waste Reduc-tion, which is based on
four pillars: i) collaboration and coordination of world-wide initiatives on food loss and waste reduction; ii) awareness
raising on the impact of, and solutions for food loss and waste; iii) research and policy, strategy and programme
development for food loss and waste reduction; iv) support to investment programmes and projects, implemented by
private and public sectors.
References
1. FAO 2011 – Global Food Losses and Food Waste
2. FAO 2011 – Appropriate Food Packaging Solutions for Developing Countries.
51
ITALY-CANADA RELATIONS IN SCIENCE AND TECHNOLOGY
E. Fiore1-2
(1)
(2)
Ministero degli Affari Esteri (MAE)
Consiglio Nazionale delle Ricerche (CNR) – Istituto di Chimica e Tecnologia dei Polimeri (ICTP)
[email protected]
[email protected]
Emanuele Fiore, Scientific Attaché at the Italian Embassy in Canada. Technologist at the Institute of Chemistry and
Technology of Polymer (ICTP) of the Italian National Research Council (CNR) .
International bilateral cooperation between Italy and Canada in scientific research and technology innovation is one of
the priorities of Italy’s foreign policy, in order to ensure, through Italian know-how, the country’s competitive abilities
and the development of advanced production industries.
Another aim was to increase awareness of the Canadian and Italian scientific communities, with a view to promoting
innovation development at the international level and further enhancing bilateral cooperation between Italian and
Canadian research centres and universities in a European context.
Science and Technology and Economic relations between Italy and Canada have been consolidated during the last years.
Even not representing one of our first trading partners, also because of the “distance”, trade with Canada has reached an
interesting level. In terms of export towards Canada, Italy represents the eighth trading partner, with a market share of
1.23% in 2013, (+ 11.2 % compared to the previous year). The main sectors of interchange are industrial machineries,
the Agri-Food and manufactured goods. There are also broad prospects in aviation; in the pharmaceutical sector; in
chemistry and new technologies. Regarding the interchange from Canada to Italy, we are the twelfth Country partner,
52
within a ranking largely dominated by United States whose market absorbs more than two-thirds of the Canadian
exports. Italy imports from Canada above all raw materials and tools for aerospace. From the point of view of the direct
investments’ flow, although there has been in the last years a growth in both directions, there are considerable margins
of increase, especially if the respective national legislations will be able to satisfy the needs of the foreign investor.
Italian companies operating in Canada have the support of the diplomatic-consular network, which strives to give
information and technical support, as well as constantly monitoring the Canadian market and report possible business
opportunities. The gap between the two Countries on the investments EXPENSE/GDP is about 0.6% more for the
Canadian system, a significant figure because the presence of the investments in SME and R&S is very important due to
the strong value in exports, today around 1.2 billion Canadian dollars in 2010 ( Statistics Canada), with an
unemployment rate of 6% and with a presence of about 97 Universities at high international rating and over 118.000
operators of research and more than 82.000 researchers in the following Canadian institutions: National Research
Council (NRC), Genoma Canada, Industry Canada, Canada Foundation for Innovation (CFI), Federal Partners in
Technology Transfer (FPTT), Natural Sciences and Engineering Research Council of Canada (NSERC), Social Sciences and
Humanities Research Council of Canada (SSHRC), ERA-CAN, Canada Space Agency (CSA), Environment Canada,
Innovation Canada.
On the contrary the Italian system of research is represented by 123.000 operators of research and more than 65.000
researchers and on international level it is present with about 10.400 scientific jobs in 2012 and about 1016 scientific
jobs for 1100 researchers in Italy, with a presence of about 81 Universities with a several works cited of 27% and a
percentage of 10% of programs approved by the Seventh Framework Programme of Research of European Union (EU) in
all the priorities-actions.
The Canadian centres of excellence involved as partners include the following institutions: University of British
Columbia, Institut National de la Recherche Scientifique (INRS) Energie, Materiaux et Commincations, National Research
Council (NRC) of Canada-Insitute for Diagnostics (NRC-IMS), Canadian Energius Center for Advanced
Nanotechnology-ECAM. The sectors at the heart of the intense activity of scientific and technological cooperation
between the two countries are the ones of physics, biochemistry and nanotechnologies.
The main key sectors Italy-Canada are:
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and Natural Sciences and Engineering Research Council (NSERC).
References
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'JPSF&"òBUBUP-i5FDIOPMPHZ5SBOTGFS"O*OUFSOBUJPOBM0QFO4ZTUFN.PEFMow&EJ[JPOJ4DJFOUJöDIF*UBMJBOF&4*
53
PREPARATION OF NEW FOOD PACKAGING MATERIALS BY RADIATION-INITIATED REACTIONS
AND RELEVANT IAEA SUPPORT TO MEMBER STATES INSTITUTIONS
A. Safrany, S. Sabharwal, M. Venkatesh
International Atomic Energy Agency, Vienna International Centre, P.B.100, A-1400 Vienna, Austria
[email protected]
The prepared convenience food sector has become a significant part of the economy and/or is evolving in many
developed and developing countries. Packaging technology underpins the development of this sector and ensures food
quality and safety. Radiation processing could provide attractive options for the food packaging industry worldwide.
Radiation technology enables the development of new polymeric materials (modified natural polymers and
nanocomposites), new packaging technologies (surface irradiation) and new dye printing methods (e.g. high gloss,
abrasion and chemical resistant finish produced without volatile chemicals), which can be both sustainable and
environmentally friendly. In addition, the irradiation of prepackaged food requires radiation tolerant packaging that
retains the necessary properties to prevent post treatment contamination.
There is an opportunity for furthering development through collaboration between radiation chemists, material
scientists, food irradiation specialists and food safety specialists to examine the complete life-cycle of food packaging
and encourage the development of novel and environmentally friendly food packaging technologies. In order to
facilitate the coordination between the different stakeholders, the IAEA has organized consultancy meetings, training
courses, and workshops. Two on-going coordinated research projects (CRP) are aimed at supporting Member States to
develop methodologies and protocols for radiation curable nano-composites from natural polymers; biodegradable
packaging materials based on bio-sourced materials; new methods to modify surface characteristic of nano-sized
materials to enhance polymer fillers interaction; to address the effects of ionizing radiations on commercially relevant
polymers in contact with foods; and the influence of radiation on functional properties of emerging polymer packaging
and coatings formulations along with the safety and suitability in food packaging.
Acknowledgements
This presentation will describe ways radiation technology could be used for synthesis and modification of polymer materials as well
as the achievements under present activities of the IAEA and plans for future supports for fostering development and application of
advanced packaging for food products in developing Member States.
54
COST ACTION MP1206 ON ELECTROSPINNING NANOFIBERS
E. Kny
Chair of Cost Action MP1206, Kemyk, Austria
[email protected]
Electrospinning, an electro-hydrodynamic process is a versatile and promising platform technology for the production
of electrospun nanofibrous materials consisting of a great variety of polymers and polymer composites. This platform
process can provide bio- or oil based polymer nanofibrous materials to be used for innovative biomedical devices or for
many diverse other application fields like in food packaging. The COST Action will cover scientific breakthroughs and
innovations in the electrospinning process itself, nanofibrous materials and nanofibrous composite advancements and
the post treatment processing of electrospun materials. Besides applications in biomedical and technical fields health,
societal and environmental issues are considered as well.
The main aim of this recently started COST Action MP1206 entitled "Electrospun Nano-Fibres for Bio Inspired Composite
Materials and Innovative Industrial Applications" is to form a European multidisciplinary knowledge platform on
electrospinning of nanofibres to facilitate their rapid development and applications. In particular, this platform will help
to promote cooperation between researchers from different scientific disciplines, efficiently exchanging ideas and
strategies in order to lead developments in science, technology and innovative applications of electrospun nanofibres
and corresponding materials.
One of the many promising application areas of electrospun nanofibres and materials is their use for food packaging
applications. The presentation will further give an up to date overview about the different, very innovative application
approaches in the field of food packaging.
55
NEW FEATURES IN FOOD PACKAGING SECTOR: ITALIAN RESEARCH UPDATING
M. P. T. Cattaneo
Consiglio per la Ricerca e la sperimentazione in Agricoltura, CRA-IAA, Milano, Italy
[email protected]
Introduction
Food packaging carries out the well-known and established functions of containment, protection and handling
facilitation of the food packaged inside. With the passing of time, new functions have arisen, mostly derived from the
needs of the always changing society. Therefore, the packaging has currently an important hedonistic function,
basically related on the driving force of marketing.1 Further, has to be mentioned the communicative function of
packaging, often times defined as the ‘silent seller’. Recently, new functionalities have been ascribed to the packaging,
due to a new vision of the package itself. Indeed, it appears a passive component no longer, being nowadays considered
as an active part of the environment/packaging/food system. In other words, it is now able to interact both with the
external environment as well as with the food inside, taking advantage of its privileged intermediate position. New
solutions take into account new concepts of smart, active and/or eco-friendly food packaging materials. Fast methods
able for classifying, sorting, and identifying the quality and the stability characteristics associated to the different
materials are requested along the food chain in order to validated their properties. This paper reports latest developing
opportunities, tested inside Italian research projects, potentially helpful in suggesting new features in this field.
Two different approaches have been used in developing new packaging solutions: i) the use of a natural antioxidant and
antimicrobial component as “active compound” for the preparation of a new active-packaging material; ii) the
assessment of an eco-friendly packaging based on the use of a transparent film, in agreement with a low
environmental impact. Both the solutions are testing in order to satisfy the needs of industry and consumers about the
availability on the market of safe products with a prolonged shelf life, and a good total quality. Particular attention is
focused in founding trasversal approaches, able to be potentially applied to several food chains.
Active packaging: Since 2010, a demonstration project, funded by the Italian Ministry of the Economic Development, is
running with the aim to find out a new and straightforward application for the Italian propolis, especially in a always
increasing field like that of “active food packaging”. The product/commodity can be properly defined a “controlled
release active packaging system”. In particular, the release will take place thanks to the direct contact with the food,
whose misture content will represent the trigger enabling the release of the actives. When cellulosic polymers (paper)
have to be used, the following drawing are considered: i) propolis, as hydro-alcoholic solution; ii) flexible cellulosic
substrate, where the propolis will be incorporated.
Eco-friendly packaging: A second demonstration project, funded by the Italian Ministry of the Agriculture in 2011, is in
progress with the aim to assess a new series of biodegradable films to be used as coatings for food preservation. The
flexibility of the new materials could allow their use for several and differentiated uses from field to market, and not
only for food sector. All developing solutions start from industry demand in order to solve some preservation problems.
Monitoring food packaging quality: In order to evaluate the potential use of the experimental food packaging materials,
some scheduled steps about its characterization and stability have to be necessarly made in a fast and reliable way. Near
infrared (NIR) technology, in terms of transmitted or reflected spectra of electromagnetic waves ranging from 800 to
2500 nm, has shown a great potential in all facets of material assessment (for example, polymer, textile, pharmacy,
petrochemical, etc.). Preliminary results about the NIR perfomances in monitoring food packaging properties will be
presented.
Conclusion
Final results of the cited research projects will be available at the end of 2014 for dissemination and knowledge transfer,
and they could constitute an helpful set of information for implementing the competitivity of Italian and European
SMEs.
Acknowledgements
Funding Ministries and all partners cooperating in reaching the specific objectives of the reported researches.
References
1. Piergiovanni, L.; Limbo, S. Packaging Technology and Science 2004, 17, 155.
56
A FORESIGHT PERSPECTIVE TO THE ROLE OF PACKAGING IN THE SUSTAINABILITY OF FOOD
AND ENVIRONMENT
C. Bartolucci, A. M. Paci, F. Tampieri
CNR, Gruppo Foresight S&T Internazionale
[email protected]
The National Research Council (CNR) and the Trieste Area Science Park Consortium (AREA), with the support of the
Ministry of Education, University and Research (MIUR), launched the Science and Technology Foresight Project (STFP) to
strengthen the development of new technologies in the medium to long term to deal with important problems related
to health, food, environment and energy. This initiative is motivated by the need to develop new strategic directions.
A key aspect of the project is the involvement of scientists and experts from academia, government and the private
sector. This method differs from others traditionally used by foresight institutions/bodies because it allows each expert
involved to make his or her knowledge available to others, in a reciprocal way, developing a systemic, collective and
integrated vision, essential in dealing with complexity. To this end, STFP has developed a web-platform
(http://www.foresight.cnr.it) to facilitate the interaction among the participants. The web-platform represents the
operational infrastructure of the collective network of STFP, and will enhance knowledge sharing between different
competences. A series of “face-to-face” workshops, each of them with its own focus on different, but correlated,
sub-topics are being organized. Participants in the workshops will be able to share knowledge, to identify gaps in
knowledge, to point out obstacles, to identify needs for more and better education as well as for more funding, and to
outline market potential and social acceptability for activities and products.
Within the topic Food, we identified “Sustainability” as the main challenge and “Nanotechnology” as the key enabling
technology. In particular in food packaging nanomaterials play already an important role and many problems can be
addressed through innovation in this sector (see Table 1). Benefits would result from further development regarding
intelligent and active packaging and a better synergism with other converging or emerging technologies would be
advisable in particular because of the important role it plays in the environmental impact. Furthermore the
consideration of packaging as an integral part of the food chain needs to be encouraged.
Table 1. Challenges that can be addressed through the application of nano-materials in the food sector
Bio-Economy, Security
Health
Safety
Packaging
- Better food chain
Control of Waste Environmental
management/surveillance through:
Impact through:
Distribution
- Match durability with product shelf life
- Biodegradable packaging
Storage
-Tracking
- Intelligent Traceability for environment
- Better food chain management
- Bacterial/Spoilage detection
- Longer shelf life
The introduction of nanomaterials, especially in the food sector, is accompanied by reluctance since it is difficult to
evaluate their hazard on the environment and human health. The development of appropriate analytical methods,
allowing for the characterization and quantification of NMs and NPs within a life cycle framework, is of primary
importance. It would allow for the toxicological evaluation necessary for the development of intelligent hazard
strategies for risk assessment and subsequent strategies for risk reduction.
Social acceptance is key to the adoption of a new technology. Consumers should recognize a real benefit in innovation
and not just a market driven strategy. New forms of packaging, including packaging with interactive labeling, could
provide a good starting point for the introduction of nanomaterials. However it is mandatory that Consumer Trust be
gained through better information, transparency and willingness to communicate with stakeholders and the public.
Acknowledgements
The authors would like to thank E. Andreta, G. Einaudi and S. Taylor for their support.
57
NANOTECHNOLOGY IN ITALY AND THE ROLE OF NANOTEC IT
A. Porcari, E. Mantovani
Center for Nanotechnologies and KETs, Italian Association for Industrial Research (AIRI/Nanotec IT)
[email protected]
Research into nanotechnology in Italy is wide-ranging and of high quality. Competences, cooperation, funding and
business have grown in the past years, and nanotechnology related activities are present in all major university and
public research institutions dealing with science, as well as in leading industry and high tech SMEs. Investment in the
field are both public, coming from different sources (EU, national and regional), and private. The growing public and
private efforts of the recent years have helped to develop several key initiatives, such as regional cluster and reference
centres on nanotech, as well as a consolidated industrial base.
As emphasised by the study on the Priority Technologies for the Italian Industry that AIRI publishes on a regular basis,
the particular sectors of the Italian economy in which nanotechnology plays, either already or soon, an important role
include: Chemistry & Materials; Electronics & ICT; Pharma & Bio Industrial applications; Manufacting; Transport;
Aeronautics and Space; Food and Food Packaging, Textile and Clothing, and other “Made in Italy” sectors.
The spectrum of R&D activities is ample, covering most of the fields of research related to nanotechnologies, with not
much difference when industry and public research are compared.
This commitment has already been translated in the production of nanomaterials and nano-related products, some of
them already surfacing on the market.
AIRI/Nanotec IT is the national focal point for nanotecnologies and a large part of the organizations involved in this field
are amongst its members.
The Association is active at international and national level, organizing and participating to projects, working groups,
multistakeholder dialogues and conferences. Promote industrial Research and Innovation and enhance co-operation
between the private and public sector in Italy. Responsible Research and Innovation is one of the main duty of the
Association.
References
1. Tecnologie Prioritarie per l’Industria Italiana: Innovazioni per il prossimo futuro, Associazione Italiana per la Ricerca Industriale
(AIRI), December 2012.
2. Key Enabling Technologies:their role in the priority technologies for the Italian industry,AIRI, April 2013.
3. NanotechItaly 2013 Conference: Key Enabling Technologies for Responsible Innovation.
58
POSTERS
SMART CITY
L. Affatato
[email protected]
Introduction
The quantity of information which is produced by the interaction of several sensing systems is achieving unthinkable
levels today. Thanks to several kinds of sensors, it is possible to measure and see in real time the conditions of every
aspect of the city. By analysing in an effective way this enormous data’s amount, we will be able to take more focused
and smarter decisions, on different time scales, about the management and the optimal planning of ecosystem of the
city.
The Institute of Chemistry and Technology of the Polymers (ICTP-CNR) is involved on the ORCHESTRA project1 financed
by MIUR (Organization of Cultural Heritage for Smart Tourism and Realtime Accessibility) with University of Naples
Federico II (LUPT, DSF, DEA, DDS), IBM, Autostrade Tech, Lauro and other institutes of the National Research Council
(IRAT, ICAR, IMCB).
The activity of the project is focused on methodologies for the design of a bidding system which starts from the most
recent scientific knowledge on the subject, in particular on the development of a technological solutions system. Those
solutions are oriented to the valorisation of the material and immaterial culture heritage, of Historical centre of Naples
for tourist, visitors and citizens, by respecting the principles of sustainable mobility and eco-compatibility for the waste
field.
After a comparison between the several best practices in Europe on the smart waste system, the partners involved on
the project , are going to determine the most effective collection solutions and to evaluate their potential in terms of
reduction the environmental impact (consumption monitoring, and generation of refuse from tourist streams in the
“zero waste” viewpoint). The study, in the first time, was concentrated on the differentiation between different types of
plastic items used by visitors (residents/tourists) and traders. PET containers and HDPE containers were analyzed. With
the support of sensors it will be able to receive in real time information on right use of waste in order to prevent any
problem and to plan corrective actions. The activities carried out by consortium will put into a technology platform with
the aim to achieve a smart city.
Conclusion
The impact of the whole project on the city, it will stimulate territorial marketing actions that will be able to help drive
sustainable economic growth, through the creation of new enterprises and organizations that will provide directly and
indirectly services related to the chain of the “tourism industry”.
References
1. PON04a2_00348_ORganization of Cultural HEritage for Smart Tourism and Real-time Accessibility. (OR.C.HE.S.T.R.A.).
62
MORPHOLOGY AND MECHANICAL PROPERTIES OF POLYAMIDE 11/OMMT NANOCOMPOSITES
PREPARED BY MELT MIXING
A. Benhamida1,2, M. Kaci1, W. W. Focke2
(1)
Laboratory of Advanced Polymer Materials, University of Bejaia (Algeria)
(2)
Institute of Applied Materials, University of Pretoria (South Africa)
[email protected]
In recent years, polymer/clay nanocomposites have attracted great interest from researchers since they frequently
exhibit unexpected hybrid properties synergistically derived from the two components. Compared to their
“micro-counterparts” and the pristine polymer matrix, polymer/clay nanocomposites exhibit improved tensile strengths
and moduli, decreased thermal expansion coefficients, decreased gas permeabilities, increased swelling resistances,
enhanced ion conductivities and reduced flammabilies1.
Organoclay has been incorporated into a variety of polymeric matrices successfully by in situ polymerization, melt or
solution blending2.
The polymer/clay nanocomposites have found wider applications in automotive industry, packaging, aerospace, and
some commercial products are now available in the market, such as nylon 6 and polypropylene based nanomaterials.
Recently, Nylon 11 (polyamide 11) has attracted much attention as one of the promising engineering plastics, which can
be produced from renewable resources. Because of its excellent piezoelectric behaviour and good cryogenic and low
moisture sorption properties, PA11 is widely used in industrial fields from automotive to offshore oilfield applications.
Many efforts have been made to improve its mechanical properties, ferroelectric, and piezoelectric property or to reduce
its yield cost3.
In this study, we have used organically modified montmorillonite clays to improve mechanical and dynamic mechanical
properties of PA11.
It is also well known that the chemical structure of the polymer affects its interaction with both the clay surface and the
organic modifier which influences exfoliation during melt processing.
In this work, the relevant nanocomposites were prepared by melt blending using a twin screw extruder. Three different
commercially organo-modified montmorillonite were used. The main difference is the chemical structure of the
surfactant used to modify the montmorillonite. The effects of different nanofillers on the morphology, mechanical and
dynamic mechanical properties of PA11 have been investigated using TEM, XRD, tensile tests and DMA analysis.
The XRD analysis showed an exfoliated structure with the addition of 5% of organoclay within PA11, observed by
monitoring the absence of the 001 basal reflections. TEM pictures revealed a good dispersion of the organoclay into the
polymer matrix, more pronounced in the case of Cloisite 30B. The tensile tests and dynamic mechanical spectra showed
a significant increase of the modulus for all nanocomposites compared to the neat polymer.
References
1. Zhang, Q., Yu, M., Fu, Q. Polymer International 2004, 53(12), 1941.
2. He, X., Yang, J., Zhu, L., Wang, B., Sun, G., Lv, P., Phang, I. Y. Journal of Applied Polymer Science 2006, 102(1), 542.
3. Zhang, Y., Wang, B., Hu, G. Journal of Applied Polymer Science 2012, 123, 273.
63
INCORPORATION OF NANOHYDROGELS IN POLYSACCHARIDE-BASED FILMS: EFFECT ON
PHYSIC-CHEMICAL PROPERTIES
A. I. Bourbon, L. C. Maciel, M. J. Costa, M. A. Cerqueira, A. A. Vicente
IBB – Institute for Biotechnology and Bioengineering, Centre of Biological Engineering, Universidade do Minho, Campus de
Gualtar, 4710-057 Braga, Portugal
[email protected]
Edible films based on renewable materials have received great attention as potential packaging materials, mainly
because such biodegradable films are considered to be a promising solution to environmental issues. Edible films can be
used to: improve food quality, enhance sensory properties and increase the shelf life of various food products.
Carboxylmethylcellulose (CMC) is an anionic polysaccharide, derivates from cellulose and is widely used to improve
products and processing properties in several applications (e.g. food, cosmetic, and pharmaceutical industry). Besides
acting as a protective barrier, edible films can be used as carrier of bioactive compounds, enhancing the functional
properties of the food product promoting their health benefits. In this work, CMC-based films containing protein
nanohydrogels (composed by lactoferrin (Lf) and Glycomacropeptide (GMP) with a hydrodynamic diameter around 170
nm) were produced and their mechanical, barrier properties (water vapour, oxygen and carbon dioxide permeabilities)
and watter afinity (moisture, solubility and contact angle) were evaluated. The addition of Lf-GMP nanohydrogels to
CMC-based films influenced their tensile strength and the elongation-at-break. The incorporation of Lf-GMP
nanohydrogels also lead to a decrease of (p<0.05) gas permeability (water vapor permeability (from 8.33 x 10-11 ± 2.48
x 10-12 to 6.38 x 10-12 ± 2.30 x 10-12 for CMC edible films without and with nanohydrogels, respectively) and oxygen (from
2.41 x 10-13 ± 9.57 x 10-14 to 1.47 x 10-13 ± 5.83 x 10-14 for CMC edible films without and with nanohydrogels,
respectively) and carbon dioxide (from 1.27 x 10-13 ± 2.84 x 10-14 to 8.63 x 10-14 ± 3.86 x 10-15 for CMC edible films
without and with nanohydrogels, respectively) permeability). Scanning electronic microscopy allowed to visualize the
morphological structure of the films, mainly the homogeneous distribution of the nanohydrogels in the film matrix
(Figure 1). The addition of protein-based nanohydrogels also affects the hydrophobicity of CMC films: incorporation of
Lf-GMP nanohydrogels significantly increases moisture content (from 16.80 ± 1.71 to 22.10 ± 4% (w/w) for CMC edible
films without and with nanohydrogels, respectively), decrease the solubility (from 66.81 ± 5.88 to 53.01 ± 4% (w/w)
for CMC edible films without and with nanohydrogels, respectively) and increase the contact angle (from 45.36 ± 2.98
to 82.76 ± 2.85 ° for CMC edible films without and with nanohydrogels, respectively). Results showed that it is possible
to incorporate protein-based nanohydrogels in edible films; this work contributes to the establishment of an approach
to optimize edible films after the addition of nanostructures promoting new and enhanced functionalities of packaging
materials.
A)
B)
Figure 1. Morphology of CMC edible films: A) without nanohydrogels and B) with Lf-GMP nanohydrogels.
64
EFFECT OF DBD PLASMA TREATMENT ON PROPERTIES OF POLY(ETHYLENE TEREPHTHALATE)
FOILS
A. Choukourov, A. Kuzminova, A. Shelemin, O. Kylián, J. Hanuš, H. Biederman
Charles University in Prague, Faculty of Mathematics and Physics, Department of Macromolecular Physics, V Holešovičkách 2, 180
00 Prague, Czech Republic
[email protected]
Poly(ethylene terephthalate) (PET) is a material widely used in food packaging industry due to its advantageous bulk
properties such as optical transparency, relatively high thermal stability and resistance, high strength-to-weight ratio,
flexibility or barrier properties. However, the use of PET is hampered by its low surface energy which can lead, for
instance, to poor printability or low adhesion between PET and a subsequent functional coating. Because of this, it is
favorable to increase the surface energy of PET foils. Among various strategies that were developed for surface
modification of polymeric materials, atmospheric plasma treatment represents highly attractive option, as the
technique is easy to implement, cost effective and in general environmentally friendly. Plasma based technologies are
moreover typically low temperature processes and, since plasma affects only the outermost layers of a treated object,
their bulk properties remain unchanged during and after the treatment. Although plasma treatment was traditionally
performed in low pressure discharges, there is evident growing interest in plasmas operated at atmospheric pressure
and especially using air plasma. This is mainly due to the possible decrease of the costs of the process both in terms of
capital investments (operation of atmospheric plasma does not require an expensive vacuum equipment) and running
costs (if ambient air is used as a working gas).
In this study, we investigate the influence of dielectric barrier discharge (DBD) operated at 30 W in air on chemical
structure, surface energy, morphology and mechanical properties of 50 μm thick PET foils (Goodfellow). It is shown that
even short plasma treatment lasting for 0.5 s causes a dramatic increase of surface energy, mainly of its polar
component, as measured by a sessile droplet method. This is consistent with the results of XPS measurements that
indicated the increase of the concentration of polar groups on the PET surface after the plasma treatment. However, it
was found that prolongation of the plasma treatment has no further effect on the chemical composition, surface free
energy and wettability of the surface (Fig.1).
In contrast, DBD treatment time was found to influence morphology and mechanical properties of the PET foils. Related
to the surface morphology, AFM analysis showed appearance of randomly distributed bumps on the PET surface, whose
sizes increased with the treatment time (Fig.1). This is accompanied by gradual increase of surface roughness from
about 1 nm for the untreated foil up to 8 nm for the PET foil treated for 30 s by the DBD plasma. The plasma duration had
also effect on mechanical properties of the foil surfaces measured by nano-dynamic mechanical analysis. Complex
modulus was found to increase with treatment time to a value almost 4 times higher than the one for the untreated foil.
This increase is most likely related to increased cross-linking in the outer layers of PET.
Figure 1. Water droplets (top) and 2x10 μm AFM scans of PET foils treated by DBD plasma
Acknowledgement
This work was supported by grants COST FA0904 and COST CZ grant LD11032.
65
PROJECT EUREKA - COMPOUNDING WITH ALIMENTARY ADDITIVES FOR LAYERS WITH
ANTIMICROBIAL AND ANTIOXIDANT PROPERTIES – PILOT PHASYS
D. Constantinescu
SC ICEFS COM SRL, Romania
[email protected]
The poster relates with EUREKA project describe the compound polymer-based polypropylene (PP) and/or polyetilene
of low density (LDPE) with additives such as chitosan activated , 1076 Irganox , carnauba wax and E vitamin .
The compounds obtained on the basis of polypropylene (PP) and/or low density polyethylene (LDPE) and additives
(chitosan activated freeze-dried, Irganox 1076, carnauba wax and vitamin E) confer on the product properties and
multiple functionalities such as antimicrobial agent bioactive principles.
The compounds and/or films obtained were characterized by determination of induction period of oxidation and by
determining the degree of inhibition of the growth of micro-organisms like Listeria monocytogenes, Escherichia coli
and Salmonella enteritidis, settling material showing good antimicrobial properties and assets.
Products with special properties, antimicrobial, inhibiting a 100% increase, both gramm positive, and gram negative
and all at once may be a bioactive principles by the qualities of the vitamin E so that they can be used in various branches
of the food industry, pharmaceuticals and textiles.
66
COMBINED EFFECT OF CELLULOSE NANOCRYSTALS EXTRACTED FROM PHORMIUM TENAX
LEAVES AND LIMONENE ON THE PROPERTIES OF PLA FILMS
E. Fortunati1, D.Puglia1, F. Luzi1, F. Dominici1, C. Santulli2, L. Torre1, J. M. Kenny1,3
(1)
(2)
Materials Engineering Center, UdR INSTM, University of Perugia, Strada Pentima Bassa, 4, Italy
Università degli Studi di Camerino Scuola di Architettura e Design (SAD), Viale della Rimembranza - Ascoli Piceno - Italy
(3)
Institute of Polymer Science and Technology, CSIC, Calle Juan De La Cierva, 3, 28028 Madrid, Spain
[email protected]
Several biodegradable polymers have been investigated during the last few decades as alternatives to non-degradable
polymers currently used in film production with particular attention to the packaging sector. In particular, poly(lactic
acid) (PLA) is becoming increasingly popular as a biodegradable engineering plastic owing to its high mechanical
strength and easy processability compared to other biopolymers1,2. However, its high brittleness limits PLA uses in
flexible films and sheets2. In order to improve PLA performance, PLA can be plasticized: nevertheless, the selection of
plasticizers is limited by the requirements of biodegradability and good miscibility with the matrix. Recent studies have
been conducted on the use of limonene as new novel monomer, the main component of citrus oils and one of most
important contributors to citrus of orange peel oil.
In the rpesent work, multifunctional poly(lactic acid) (PLA) bio-nanocomposite films modified with limonene as
plasticizer and reinforced with cellulose nanocrystals (CNC) extracted from Phormium tenax leaves have been prepared
by using a twin-screw microextruder and characterized (Figure 1). The extraction of cellulose, by a first chemical
treatment and a subsequent sulphuric acid hydrolysis process, was successfully carried out. Binary and ternary films
containing the plasticizer (20 %wt) and/or the CNC (1 and 3 %wt of CNC) were produced and characterized in terms of
morphological, thermal, mechanical, wettability and transparency properties. The effect of CNC content and the
combination with the specific plasticizer on the structural properties of PLA films was deeply investigated.
Disintegration study was also carried out under simulated composting conditions in a laboratory-scale test at 58ºC, 50
% of humidity and in aerobic conditions. The addition of limonene into the PLA matrix decreases as expected the glass
transition temperature of the films, and affects the mechanical properties of the films with an evident increase of the
plastic response of the PLA. The disintegration tests performed in composting conditions demonstrated that the
presence of both plasticizer and CNC can alter the degradation rate of developed PLA-based formulations. These results
suggested the promising use of these new bio-nanocomposites in active food packaging in relation to the
environmental concern.
Figure 1. Electrospinning process (Nanospider™ technology, 2013
References
1. Fortunati, E., Armentano, I., Zhou, Q., Iannoni, A., Saino, E., Visai, L., Berglund, L.A., Kenny. J.M. Carboydrate Polymer, 2012, 87,
1596.
2. Auras, R., Harte, B., Selke, S. Macromolecular Bioscience, 2004, 4, 835.
67
FABRICATION AND CHARACTERIZATION OF a-C:H/Cu NANOCOMPOSITES PREPARED BY
PECVD COMBINED WITH GAS AGGREGATION SOURCE
J. Hanuš, T. Steinhartová, A. Choukourov, J. Kousal, O. Kylián, H. Biederman
Charles University in Prague, Faculty of Mathematics and Physics, Department of Macromolecular Physics, V Holešovičkách 2, 180
00 Prague, Czech Republic
[email protected]
Due to their hardness and tribological properties, amorphous hydrocarbon (a-C:H) films are nowadays widely used as
protective coatings in many applications in machinery and automotive industry. Moreover it was shown in our previous
work that a-C:H coatings with the thickness of several tens of nanometers exhibit also excellent barrier properties for
gases [1] which makes them suitable for use in food packaging industry. From the point of view of the recent demands
on packaging materials, highly interesting is also possibility to combine a-C:H films with metallic nanoparticles. These
nanocomposites may be used for instance as functional antibacterial barrier layer on common polymeric packaging
foils.
In the present work we study the possibility to incorporate copper nanoparticles into a-C:H and evaluation of chemical
composition, morphology, optical and mechanical properties of such materials. The a-C:H matrix was deposited in a
mixture of Ar and organic precursor (n-hexane). The substrates were placed on water cooled planar electrode connected
to the RF power supply. This arrangement enables to control the energy of positive ions impinging on the substrate
surface during deposition and thus also mechanical and barrier properties of deposited films.
Gas aggregation cluster source (GAS) was used for the deposition of Cu nanoparticles (NPs). This source, which is
described in detail in [2], consisted of a 3-inch, DC driven, planar magnetron equipped with Cu target. The magnetron
was placed into a water cooled gas aggregation chamber ended by an exit cone with an orifice of 2 mm in diameter. The
entire assembly of the magnetron and the gas aggregation chamber was attached on the main deposition chamber. The
direction of beam of NPs was normal to the substrate.
It was found that during simultaneous deposition of a-C:H matrix and copper NPs no Cu NPs reached the substrate. To
overcome this, it was necessary to pulse RF discharge. Two different strategies were tested for deposition of a-C:H/Cu
nanocomposites. First, the NPs were deposited at constant operational parameters in GAS, i.e. with constant flux of Cu
NPs leaving the gas aggregation source, while RF duty cycle was changed. In the second case the parameters for matrix
deposition were kept constant, but the magnetron current in the GAS was varied form 50 mA up to 300 mA, which led
to substantial increase of efficiency of production of Cu nanoparticles.
It was found that in both cases Cu NPs were incorporated in a-C:H matrix as witnessed by SEM, AFM and XPS analysis of
the samples. All prepared films exhibit anomalous absorption with the maxima at about 600 nm. The intensity of this
anomalous absorption peak increased with increasing amount of Cu NPs in the nanocomposites. Finally, it was found
that amount of incorporated Cu NPs causes also changes of the mechanical properties of the coatings.
Acknowledgement
This work was supported by grants COST FA0904 and COST CZ grant LD11032.
References
1. O. Polonskyi, O. Kylián, M. Petr, A. Choukourov, J. Hanuš, H. Biederman, Thin Solid Films 540 (2013) 65-68.
2. O. Polonskyi, P. Solař, O. Kylián, M. Drábik, A. Artemenkoa, J. Kousal, J. Hanuš, J. Pešička, I. Matolínová, E. Kolíbalová, D. Slavínská,
H. Biedermana, Thin Solid Films 520 (2012) 4155–4162.
68
POLYPROPYLENE COMPOSITES BASED ON MWCNT AND ORGANOCLAY
E. Ivanov1, I. Petrova1, R. Kotsilkova1, C. Silvestre2, S. Cimmino2, D. Duraccio2, M. Pezzuto2
(1)
Open Laboratory for Experimental Mechanics of Micro & Nanomaterials (OLEM), Institute of Mechanics, Bulgarian Academy of
Sciences, Acad. G. Bonchev Street, Block 1, 1113 Sofia, Bulgaria
(2)
Institute of Chemistry and Technology of Polymers, CNR, Via Campi Flegrei 34 Olivetti, 80078 Pozzuoli (NA), Italy
[email protected]
Introduction
Carbon nanotubes (CNTs) have attracted a large interest due to their extraordinary and unique properties. However,
hybrid materials that combine two nanofillers particles in a polymer matrix are seldom researched. Researchers
reported on extraordinary property enhancement in the case of hybrid nanocomposites incorporating two different
nanophases. Based on the above mentioned, the goal of this investigation is to study the effect of clay particles on the
behavior of PP/CNT composites.
It was found that the pure PP shows a Newtonian behavior at low frequencies with respect to its viscosity whereas the
filled samples exhibit a significant increase in melt viscosity with decreasing frequency. With increasing the MWCNT
content the viscosity values increase further. The remarkable shift in the shape of the dynamic viscosity plots from pure
PP to the composite with 1 wt% MWCNT clearly indicates that a transition from the liquid-like to solid-like behavior has
taken place and the systems after 1 wt% MWCNT can be regarded as rheologically percolated. The SEM observations of
the filled nanocomposites are presented in order to confirm these results. Generally, the addition of nanotubes in the
investigated concentration range up to 3wt% enhances the thermal stability of iPP in air atmosphere. Importantly, a
significant improvement of thermal properties appears at the low filler content of 0.5%, where the TGA curves of
iPP/MWCNT composites are shifted significantly toward higher temperatures (with 39 oC), as compared with iPP.
Further increase of the nanotube amount (up to 3 wt%) shifted the curves with 65 oC. The addition of 0.5% and 3%
nanotubes in the iPP/MWCNT/Cloisite30B has shifted the TGA curves of iPP by 30 and 68 oC toward higher temperatures
in air atmospheres, respectively. Small addition of MWCNTs results in a significant improvement of the nanomechanical
properties. This effect is more pronounced for the three-phase samples where the improvement of the hardness and
elastic modulus is of about 26 % and 52 %, respectively.
Conclusion
In general, rheologically determined percolation threshold could provide preliminary prediction on the effectiveness of
the nanotube content, where the improvement of the mechanical properties of nanocomposites may be expected. Two
main aspects are considered to be dominant for the mechanical and thermal properties improvement of the
as-prepared iPP composites, when the nanotube content increases: (i) the flocculated structure, which is formed by
interconnected nanotubes and incorporated iPP matrix; and (ii) the homogeneity of the composites. Based on the
significant improvement of thermal and hardness properties at very low nanotube contents, the
iPP/MWCNT/Cloisite30B composites have a high potential for application as a reinforced and lightweight plastics for
packaging and other engineering applications.
Acknowledgements
This work was financially supported by the COST FA0904 grant given to Dr. E. Ivanov for a research visit at Institute of Chemistry and
Technology of Polymers (ICTP), CNR, Pozzuoli (NA), Italy and CfAM, University of Reading (Prof. G. Mitchell).
References
1. Kotsilkova R, Ivanov E, Krusteva E, Silvestre C, Cimmino S, and Duraccio D. Evolution of Rheology, Structure and Properties around
the Rheological Flocculation and Percolation Thresholds in Polymer Nanocomposites. Chapter 3 In: “Ecosustainable Polymer
Nanomaterials For Food Packaging. Innovative Solutions, Characterization Needs, Safety and Environmental Issues” (Silvestre C,
Cimmino S, Eds), ISBN: 978-90-04-20737-0, Taylor & Francis Group, LLC (2013) pp.55-86.
2. Kotsilkova, R., E. Ivanov, E. Krusteva, C. Silvestre, S. Cimmino, D. Duraccio. Isotactic polypropylene composites reinforced with
multiwall carbon nanotubes, part 2. Thermal and mechanical properties related to the structure. Journal of Applied Polymer
Science, vol. 115 (6), 2010, 3576–3585.
69
STRUCTURE AND PROPERTIES OF ZINC OXIDE CONTAINING POLYMER NANOCOMPOSITES
T. Ivanova1, A. Grigalovica1, R. Merijs Meri1, J. Zicans1, J. Grabis2
(1)
Riga Technical University, Faculty of Materials Science and Applied Chemistry, Institute of Polymer Materials, Latvia
(2)
Riga Technical University, Institute of Inorganic Chemistry, Latvia
[email protected]
Polyoxymethylene (POM) is one of the most important engineering polymers having wide usability in automotive
(engine part, interior and exterior elements), electronics (home appliances, power supply goods and other) and “living
material” (food/beverage packaging, kitchenware, consumer goods etc) sectors, because of good balance between
mechanical and chemical properties. However, range of POM applications is limited due to its insufficient ductility,
thermal stability and formaldehyde release. Consequently these are the main addressed issues, when modifying POM.
POM has been effectively toughened by modification with thermoplastic elastomers and rubbers (polyurethane,
thermoplastic olefine copolymer, ethylene–methacrylic acid copolymer, ethylene propylene diene terpolymer etc)1-4,
while thermal stability of POM has been raised by modification with both organic (biphenol monoacrylate,
poly(ethylene-co-methyl acrylate), poly(styrene-co-butadiene-co-styrene) copolymers etc)5 and inorganic
(montmorillonite clays, zinc oxide, carbon nanotubes etc) additives6-8.
In the current research the effects of simultaneous addition of ethylene-octene copolymers (EOC) with varying α-octene
contents (17 and 38 %), as well as plasma synthesized zinc oxide (ZnO)9 on the structure and exploitation behaviour of
low- and high viscosity commercial POM grades are investigated. POM nanocomposites with EOC (10, 30, 50 EOC wt. %)
and ZnO (2 and 5 wt. %) have been obtained by using two roll mill at 170 oC. Compounding has been continued 7 min
after the introduction of ZnO in the polymer blend melt. ZnO nanofiller with purity of 99.7% represented plate- and
whisker-like particles with the corresponding side lengths of 20–100 nm and diameters of ~20 nm. Mechanical,
thermogravimetric, calorimetric and sorption characteristics of POM/EOC/ZnO nanocomposites have been investigated.
Results show that impact strength and water vapour barrier characteristics of the investigated POM matrix
nanocomposites increase along with growing elastomer content. Addition of ZnO, in its turn, contributes to the
improvements in modulus and strength of the investigated nanocomposites. Modification of POM with either EOC or
ZnO, allows increasing thermal stability of POM, thus diminishing also formaldehyde release. Improvements in the
above mentioned characteristics have been attributed to the anisometric nature of the nanofiller as well as its influence
on the structure perfection of the polymer matrix.
References
1. Gao,X.; Qu,C.; Fu Q. Polymer International 2004, 53, 1666.
2. Uthaman,R.N.; Pandurangan,A; Majeed S.S.M.A. Journal of Polymer Research 2007,14, 441.
3. Wang,X.;Cui,X. European Polymer Journal 2005, 41, 871.
4. Uthaman,R.N.; Pandurangan,A.; Majeed,S.S.M.A. Polymer Engineering&Science 2007, 47, 934.
5. Wang,Q. Journal of Applied Polymer Science 2011, 121, 376.
6. Wacharawichanant,S.; Sahapaibounkit,P.; Saeueng,U. Advanced Materials Research 2012, 488-489, 82.
7. Wacharawichanant,S.; Thongyai,S.; Phutthaphan,A.; Eiamsam-anga,C. Polymer Testing 2008, 27, 971.
8. Yu,N.; He,L.H.; Ren,Y.Y.; Xu,Q. Polymer 2011, 52, 472.
9. Grigalovica,A.; Merijs Meri, R.; Zicans,J.; Ivanova,T.; Grabis, J. IOP Conference Series: Materials Science&Engineering 2013, 49,
012004
70
CERIUM OXIDE NANOPARTICLES IN LEXAN POLYCARBONATE: NEW FILMS COMPOSITE
PROSPECTIVE FOR FOOD CONTAINER
C. Larosa1,2, R. Eggenhöffner2
(1)
(2)
Department of Chemical and Process Engineering, University of Genoa, street Opera Pia, 15, 16145 Genoa, Italy
Department of Surgery Science and Integrate Diagnostic, University of Genoa, street Rosanna Benzi, 30, 16132, Genoa, Italy
[email protected]
Introduction
Nano crystalline cerium oxide particles (CeO2) have been extensively studied due to its remarkable absorption spectra in
the u.v range. Cerium oxide has potential uses in many applications, such as UV-blockers and filters, with high refractive
index1,2,3 and anti-scratch properties. Cerium oxide is also currently used for doped polycarbonate PC, variety Lexan 121R
and in order to increase the cover in the u.v range spectra. The aim of this work is to increase the optical cover of the
amorphous polycarbonate films by using a blending method4 without changing the amorphous state of polycarbonate
to crystalline. Polycarbonate and ceria nanoparticles are mixed by using a common apolar solvent: dichloroetilene.
Preliminary results in dry films don't show aggregation of cerium oxide and the DSC profile remark the absence of
crystalline domain. The wettability of these films is also investigated.
Results
Cerium oxide in powder has been characterized by light scattering and the average size has dimensions of 28 nm and it
is used to dope PC pellets. A yellow powder, supply from Sigma Aldrich company, was dispersed in apolar solvent and
sonicate for 10 minute at room temperature. Preliminary results have been acquired by spectrophotometric absorption
of this films doped with ceria nanoparticles, in a spectra range between 200 to 750 nm. The thickness of the films
obtained from a solution of PC, doped with ceria, after evaporation of the solvent, is included in a range between 0.185
and 0.094 mm. DSC analysis of 10 mg of samples with different ratio of ceria NPs/PC doped don't show a significant
change of the transition temperature Tg from the value of 145°C.
Discussion
Experimental condition such as temperature, concentration and speed of solvent evaporation have a strong influence in
the final optical properties of the film. Films, obtained by blending method, have a considerable major cover in the u.v
range of the spectra in concentration of 1-2 % W/V. If the thickness of the film during the preparation achieve a
threshold limit value of 0.5 mm the solvent remain entrapped inside the composite and the film change colour from
transparent to white opache materials with micro-crack and micro-voids.
Conclusion
Thermodynamic conditions have a strong effect on the final properties of the films composite ceria/PC.
Acknowledgement
The group of biophysics from University of Genoa is grateful for the collaboration and visit with the Institute of polymer of Riga,
Latvia with your held director Ing. Jānis Zicāns and Remo's group.
Reference
1. Hua Gu, Mark D. Soucek. Chem. Mater. 2007, 19, 1103-1110
2. Krogman. K, Druffel T., Sunkara M., Nanotechnology 16, 2005, S338–S343
3. Tsunekawa, S.; Fukuda, T.; Kasuya, A., J. Appl. Phys. 2000, 87, 1318.
4. Larosa C. , Enrico S., Eggenhöffner R., Nicolini C., Materials 2009, 2, 1193-1204
71
DIFFUSION OF DIFFERENT MOLECULAR WEIGHT PROTEINS THROUGH POLY
Ε-CAPROLACTONE FILMS WITH ENCAPSULATED TRYPSIN
A. J. Martins1, A. I. Bourbon1, A. A. Vicente1, J. A. Lopes da Silva2, C. Rocha3
(1)
Institute for Biotechnology and Bioengineering, Centre of Biological Engineering, University of Minho, Braga, Portugal
(2)
QOPNA, Department of Chemistry, University of Aveiro, Portugal
(3)
REQUIMTE, Department of Chemical Engineering, Faculty of Engineering, University of Porto, Porto, Portugal
[email protected]
The ability to promote nanoencapsulation within nanofibrous films for food packaging enables the possibility to have a
double functionality: protection and bioactive compound dispensing. Aiming at a possible smart packaging material
application, nanofibrous films from with encapsulated trypsin (PCL+tryp) were studied. Films’ properties, structure and
morphology were characterized using Differential Scanning Calorimetry (DSC), Termogravimetric Analysis (TGA),
Swelling Degree (SD), mechanical properties evaluation and Scanning Electron Microscopy (SEM). This work also
focused in the diffusion properties of PCL+tryp films. The solutes chosen for transport mechanism evaluation were
bovine serum albumin (66.5 kDa), lysozyme (14.7 kDa) and lactoferrin (80 kDa). PCL+tryp films showed a reduction of
average pore size in the range of 30% to 40%, and an average pore diameter of 1/3 of the size when compared to simple
PCL film without encapsulation; hence the former were less permeable to larger molecules at some point (e.g.
lactoferrin). The most appropriate mathematical model, which accounts for both Fickian diffusion and relaxation of
polymer1 was selected from literature and fitted to the experimental data using non-linear regression, in order to
understand which mechanisms were responsible for the diffusion of the different proteins thru the films. Results have
shown that with the increase of protein molecular weight (Mw), the amount of protein migration by relaxation of the
polymer increases as well. However Kf (Fickian rate constant) is reduced, which is possibly related with the difficulty of
migration for larger molecules. Figure 1 shows the adhesion of lactoferrin molecules to PCL nanofibers; after a diffusion
test. Figure 1 also shows the higher compactness of the PCL+tryp film. This work allowed developing a PCL+tryp active
film with good mechanical and chemical properties.
Figure 1- SEM images of PCL and PCL+tryp films. A- Lactoferrin fouling presented in the PCL nanofibers surface B- Transversal cut
of PCL+tryp film
References
1. Berens, A. R., & Hopfenberg, H. B. (1978). Diffusion and relaxation in glassy polymer powders. 2. Separation of diffusion and
relaxation parameters. Polymer, 19(5), 489-496.
72
EFFECT OF LAYERED NANOMATERIALS AND NANOFIBERS ON MECHANICAL AND BARRIER
PROPERTIES OF BIOBASED POLYMER COMPOSITES
R. B. Padamati, T. Woods, M. Rajendrian
School of Physics and CRANN, Trinity College Dublin, Ireland
[email protected]
The continued use of polymers such as PET and HDPE for polymer packaging materials has resulted in landfill problems
due to poor recycling and slow degradation rates of these petrochemical polymers. The recent upsurge in
bio-degradable polymer to counteract this problems has led to continued research in such materials. Few such
polymers suitable for pacakaging applications is Polyhydroxybutyrate and Polylactic acid produced from renewable
resources. Available in powder or pellet form from a number of commercial suppliers the continued potential use for
this polymers in plastic packaging materials depends on improvements in its mechanical and oxygen barrier properties.
The aim of our research is to use additives such as nanofibers, nanoadditives (boron nitride, graphene, Nanoclays and
MOS2) at loading levels from 0.02 % to 3% loading levels to improve these properties.
73
LACTOFERRIN-COATED POLY(LACTIC ACID)
E. Paslaru1, G. E. Hitruc1, E. G. Ioanid1, A. Vesel2, G. Pricope3, C. Vasile1
(1)
“Petru Poni” Institute of Macromolecular Chemistry, Iasi, Romania
(2)
Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia
(3)
Veterinary Laboratory and Food Safety, Food Safety Department, Iasi, Romania
[email protected]
Introduction
Plasma treatment technologies are likely to be the most useful commercial techniques for controlled surface
functionalization of a broad range of polymers1. Lactoferrin is a multiple bioactive glycoprotein that is involved in
several physiological functions, including: regulation of iron absorption in the bowel; immune response; antioxidant,
anti carcinogenic and anti-inflammatory properties; and protection against microbial infection, recommend it for
utilization in obtaining new bioactive materials with different characteristics for human, animals and materials
protection against microorganism attack2.
The intrinsec surface properties of poly (lactic acid) films were modified by radiofrequency plasma treatment and
lactoferrin immobilization. To optimize the surface functionalization conditions of PLA a variation of the discharge
parameters were performed. Were used two discharge gases, nitrogen and air. The plasma exposure time for poly (lactic
acid) films was varied and the wettability and weight loss by water contact angle measurements and high-precision
gravimetric measurements, respectively were evaluated. The water contact angle of the PLA surfaces decreases by
increasing the N2 plasma exposure time, the surface wetting being enhanced. By increasing the plasma exposure time
it can be also observed a direct proportional mass loss. Comparing the nitrogen and air plasma it can be noticed that the
plasma generated in nitrogen atmosphere is more efficient in terms of improving wetting properties. Typical chemical
compositions of the native, nitrogen plasma treated and lactofferin coated PLA surfaces were characterized using
surface-sensitive XPS measurements. After nitrogen plasma exposure of PLA substrate in the XPS survey spectra an
emission signal assigned to nitrogen atom is recorded, which does not appear in the XPS spectra of native PLA. After
lactoferrin coating, the nitrogen atomic percentage increases even more, the highest content being found for lactoferrin
immobilized onto PLA surface using coupling agents (EDC+NHS). ATR-FTIR spectroscopy confirms the results obtained
from XPS. Surface topoghraphy was evaluated by atomic force microscopy (AFM) and was observed that both plasma
treatment and lactoferrin immobilization influences the PLA surface features.
Conclusions
The chemical immobilization of lactoferin onto PLA surface is more efficient than the simple physical adsorption.
Lactoferrin coating induces the modification of the PLA antimicrobial properties improving also the biocompatibility
characteristics.
Acknowledgements
The authors acknowledge the financial support given by IAEA through research project No. 17689 and to COST FA0904 Action.
References
1. Steven,M.D.; Hotchkiss,J.H. In: Novel food packaging techniques, Raija Ahvenainen (Ed.), Woodhead Publishing Limited,
Cambridge, England, 2003, pp. 71-103.
2. García-Montoya,I.A.; Cendón,T.S.; Arévalo-Gallegos,S.; Rascón-Cruz,Q. Biochimica et Biophysica Acta (BBA) - General Subjects
2012, 1820, 226.
74
THE USE OF PLASTICIZERS AS COUPLING AGENTS IN PREPARATION OF PLA-BASED
NANOCOMPOSITES
E. Passaglia1,4, R. Spiniello1, C. De Monte1, F. Cicogna1, S. Coiai1, W. Oberhauser2, A. Lazzeri1,3,4, P. Cinelli4, I.
Anguillesi3, S. Fiori5, J.Gomez6
(1)
CNR-ICCOM UOS Pisa, Pisa, Italy
CNR-ICCOM, Sesto Fiorentino, Firenze, Italy
(3)
UNIPI, Pisa, Italy
(4)
INSTM, Firenze, Italy
(5)
Condensia Química S.A.C, Barcelona (Spain)
(6)
AVANZARE Innovacion Tecnologica S.L. C, La Rioja (Spain)
[email protected]
(2)
PLA is a biobased-material particularly attractive due to its optical and thermal properties, and it is considered a
challenging candidate for the replacement of oil-based polymers. However, the large scale application of PLA is limited
due to its poor mechanical properties, poor thermal resistance, low gas and vapor barrier1. In this context,
nanocomposite materials offer a new and promising prospective since they exhibit significant changes of physical
properties even in the presence of small amounts (i.e. less than 3%) of nanosized fillers. The dispersion of nanofillers in
a polymer matrix is generally achieved by tuning the interfacial properties through the chemical filler modification and
the use of suitable coupling agents. In this work poly(lactic acid) (PLA) nanocomposites were prepared via melt
blending with different nanofillers previously dispersed in low molecular weight polyesters which were generally used
as plasticizers. The ultimate aim was to improve both mechanical features and dispersion/distribution of the filler.
Low MW polymers based on adipic acid and propylen glycol (GLYPLAST® 206/3NL) and low MW D/L-lactic acid polymers
(GLYPLAST OLAs) were mixed with organophilic layered nanofillers (montmorillonite and/or bentonite modified with
different types of surfactants), graphene and nanofibers and these masterbatches were dispersed in the molten PLA
matrix. The morphological features and the thermomechanical properties were investigated by XRD, SEM, DMTA and
TGA analysis. The collected results compared with blank experiments showed a good dispersion level and an
improvement of thermal stability depending mainly on the nanofillers amount and on their physicochemical
characteristics.
Acknowledgement
This research is funded by the “DIBBIOPACK” Collaborative Project of Seventh Framework Programme Grant Agreement no: 280676.
References
1. L. T. Lim, R. Auras, M. Rubino. Prog. Polym. Sci. 2008, 33, 820-852.
75
STUDY OF THE EFFECT OF IONIZING RADIATION ON THE PROPERTIES OF RANDOM
POLYPROPYLENE NANOCOMPOSITES FOR FOOD PACKAGING APPLICATIONS
M. Pezzuto1, S. Cimmino1, D. Duraccio1, A. Marra1, M. Perrotti1, V. Ambrogi2, D. S. Pillai3, C. Silvestre1
(1)
(2)
University of Federico II, Naples, Italy
(3)
National Center for Electron Beam Research, Texas A&M University
[email protected]
In the last decades, the use of polymers as food packaging materials has increased enormously due to their advantages
over other traditional materials.1,2 Polymer packaging provides many properties including strength and stiffness, barrier
to oxygen and moisture. In order to ensure food safety, reduce post harvest losses and facilitate international trade,
recently radiation technologies are always more often applied by the food industry.
The decontamination of food by ionizing radiation is a safe, efficient, environmentally clean and energy efficient
process.3
In the field of packaging, films of isotactic polypropylene (iPP), polypropylene random copolymers (PPR), metallocene
polypropylene (mPP) hold a prominent position because of their transparency, brilliance, low specific weight, chemical
inertness and good processability. Unfortunately, polypropylenes, as other polyolefins, is characterized by low barrier
properties, in particular oxygen, which results in poor protection of the packaged food.4 To overcome this drawback the
incorporations a few percent of commercial nanoparticles, in particular modified montmorillonite (MMT) in a polymeric
matrix, can lead to several improvements as a decrease in the package permeability to gas and aroma, and an extended
shelf life for the food.4,5
The objective of this research was to study the changes of the structure and properties of composite films formed by a
polypropylene random copolymer6 (PPR3221 from Total Petrochemicals) and motmorillonite (Cloisite 15A from
Rockwood) due to electron irradiation with electrons accelerated in an electric field. The e-beam had a fixed dose rate
of approximately 103Gy/second.
The results indicated that the improvement of the thermal stability and in some tensile parameters of the film could be
related to the formation of crosslinks in the polymer matrix probabily due the irradiation process. Moreover, the
improvement in thermal stability is probably due to a physical barrier effect of the silicate layers. The morphological
analysis revealed the presence of some eroded regions on the irradiated surfaces. The number of these regions
decreased by increasing the clay content indicating that the silicate layers could act as barrier for the irradiation process.
The presence of clay in the polymer matrix and the irradiation process did not induce any change in the values of the
oxygen permeability.
Acknowledgement
The research leading to these results has received support from COST Action FA0904, IAEA’s Coordinated Research Project (CRP).
References
1. Silvestre, C.; Cimmino, S.Eds, "Eco-sustainable polymer nanomaterials for food packaging” Taylor and Francis Press -2013.
2. Silvestre, C., D. Duraccio, S.Cimmino, Food packaging based on polymer nanomaterials, Progress in Polymer Science 2011, 36,
1766–1782.
3. Farkas, J. International Journal of Food Microbiology 1998, 44, 189.
4. Duraccio, D.; Silvestre, C.; Pezzuto, M.; Cimmino, S. and Marra, A. Polypropylene and Polyethylene based nanocomposites for food
packaging applications, in Ecosustainable Polymer Nanomaterials for Food Packaging, Eds C. Silvestre, S. Cimmino, Taylor & Francis
Group, 2013 ISBN: 978-90-04-20737-0.
5. Cimmino, S.; Silvestre, C.; Duraccio, D.; Pezzuto, M.; "Effect of hydrocarbon resin on the morphology and mechanical properties of
isotactic polypropylene/clay composites , Journal of Applied Polymer Science, 2011, 119 1135–1143.
6. Silvestre, C.; Cimmino, S.; Triolo, R.;" Structure, morphology, and crystallization of a random ethylene–propylene copolymer
Journal of Polymer Science Part B: Polymer Physics 2003, 41, 413–500.
76
Κ-CARRAGEENAN/CHITOSAN NANOLAYERED COATING AS A VEHICLE FOR INCORPORATION OF
BIOACTIVE COMPOUNDS
A. C. Pinheiro1, M. A. Coimbra2, A. A. Vicente1
(1)
IBB – Institute for Biotechnology and Bioengineering, Centre of Biological Engineering, University of Minho, Campus de Gualtar,
4710-057 Braga, Portugal
(2)
Chemistry Department, University of Aveiro, 3810-193 Aveiro, Portugal
[email protected]
Introduction
Nanotechnology holds a great potential to generate very innovative solutions for food industry and packaging is one of
the many areas that can benefit from this new technology. Layer-by-layer (LbL) assembly is based on the alternating
deposition of oppositely charged polyelectrolytes and can be applied to produce nanolayered coatings, which can be
specially engineered to incorporate and allow the controlled release of bioactive compounds. Nanolayered coatings
have promising applications in food systems such as fresh-cut fruits and vegetables or cheese, however for these
applications to be possible, biofunctionality and the use of non-toxic materials are the most fundamental conditions to
be met. Therefore, natural polyelectrolytes such as chitosan (cationic polysaccharide with antimicrobial activity) and
κ-carrageenan (sulphated anionic polysaccharide with good film forming properties) are competitive candidates as
materials for the formation of nanolayered coatings.
In this work a nanolayered coating was prepared by LbL deposition of κ-carrageenan and chitosan onto
aminolyzed/charged polyethylene terephthalate (PET) and the coating was characterized in terms of its permeabilities
and surface properties. In order to evaluate the ability of this nanolayered coating to act as a vehicle for bioactive
compounds incorporation, the model compound methylene blue (MB) was incorporated and its loading and release
behaviour was evaluated.
The nanolayered coating composed of three κ-carrageenan and two chitosan layers has been successfully assembled on
PET substrate, as confirmed by the increase of absorbance, changes in the contact angle and SEM. The
κ-carrageenan/chitosan nanolayered coating exhibits exhibit good gas barrier properties (WVP = (0.020 ± 0.002) × 10
−11
g.m−1.s−1.Pa and O2P = (0.043 ± 0.027) × 10−14 g.m−1.s−1.Pa).
MB was successfully incorporated on the κ-carrageenan/chitosan nanolayered coating (Figure 1a) and the results of
fitting the Linear Superimposition Model (LSM) to the experimental data of MB release suggest an anomalous
behaviour, with one main polymer relaxation (Figure 1b). The effects of layer position, temperature and pH on MB
release were evaluated and different results were observed depending on the position of MB incorporated on the
nanolayered coating or the pH and temperature of the medium.
a
b
Figure 1: SEM images of the κ-carrageenan/chitosan nanolayered coating incorporating MB (a); example of Fick’s (Eq. 1) and LSM
(Eq. 2) description of MB release from the 4th at pH=2 (inserts show the detail of the model fitting).
Conclusions
The developed biodegradable nanolayered coating is a promising delivery system for application in food products, as a
strategy for shelf-life extension.
Acknowledgements
The author Ana C. Pinheiro was recipient of fellowship from the Fundação para a Ciência e Tecnologia (FCT, Portugal) through grant
SFRH/BD/48120/2008.
77
A CONTRIBUTION TO THE RHEOLOGICAL AND RELAXATION PROPERTIES OF POLYMER
NANOCOMPOSITE MATERIALS
F. Popovska-Pavlovska1, A. V. Sikaleska1, C. Silvestre2, S. Cimmino2, D. Duraccio2, M. Kozlowski3, S.
Frackowiak3, J. Macyszyn3, A. Iwanczuk3
(1)
(2
Integrated Business Institute, Skopje, R. Macedonia
(3)
Wroclaw University of Technology, Wroclaw, Poland
[email protected]
The viscous and relaxing behaviour of polymeric materials is of primary concern in polymer processing operations. In
that regard the rheological and relaxation properties of neat thermoplastic polymers, their binary blends and
nanocomposite materials with polymer blend as a matrix, in a molten and solid state, were subject to a thorough
investigation using different experimental techniques and calculation methods. The obtained results are briefly
reviewed in this article.
Following the three steps for material functions evaluation1: specified stress field (simple shear and dynamic oscillatory
flow), rheological model (linear viscoelasticity) and experimental technique (parallel plate rheometer), analytical
expressions for , , G'(ω), G"(ω) and η* (ω) were found. Both, the pseudoplastic character of the viscous behavior and
the viscoelasticity do not change regardless the material is a neat polymer, blend or nanocomposite. But, the numerical
values of these material functions are strongly influenced by the material structure, many physical characteristics
(pressure, time, flow geometry) and particularly by the mode of mixing and temperature. When polymer blends are
concerned these functions vary significantly with the blend composition (micro and macrostructure), degree of
dispersion of the components in blends and the mode of their distribution (interfacial characteristics). The previously
mentioned findings were also followed and confirmed by SEM micrographs. Great morphological changes and in some
cases flow induced microstructures during flow were noticed affecting strongly the rheological behavior and hence
materials ultimate properties. The results in a solid state showed that all samples exhibit visoelastic behavior and the
components of the complex modulus, G’ and G”, characterize the properties of a linear viscoelastic material. When
nanocomposite is concerned the elasticity decreases. These results correspond to those obtained in a molten state.2,3
There is a correlation, confirmed with our experimental results, between functions characterizing steady state
rheological properties and the functions describing the dynamic properties as an inherent property of viscoelastic
materials1,2,3. This feature was used to generate dynamic rheological data for the nanocomposite.
The relaxation properties are presented in terms of a continuous relaxation time spectrum which was calculated with
the aid of a computer program by employing the NLREG method and experimentally measured G'(ω) and G"(ω) data.
The calculated relaxation spectra showed that big differences exist among them especially when spectral functions of
neat polymers are considered. Most likely it is due to different molecular characteristics because the relaxation spectrum
reflects molecular movements of macromolecules.
The concept of a relaxation spectrum for treating viscoelastic behaviour of polymeric materials is a very promising and
powerful tool because enables complete rheological characterization of polymer (neat, blend and nanocomposite)
melts with limited but representative data, which is especially important for nanocomposites where we face with lack
of data. Hence, the relaxation spectrum may be used as a master curve because includes many information about
molecular parameters and allows finding the stress-strain relationship in an arbitrarily wide range of deformation
conditions. Therefore, it presents a fundamental input in achieving products with desired specific properties by
designing the process as a whole using advanced computational procedures of modeling, simulation and optimization
instead of trial and error.
Keywords
material functions, viscoelasticity, relaxation properties, NLREG method
References
1. Vinogradov, G.V., Malkin, A.Y., Rheology of polymers, Mir Publishers, Moskow, 1980
2. Vasiljevic-Sikaleska, A., Popovska-Pavlovska, P., Mat. Sc. and Eng., 40 (2012), 1
3. Popovska-Pavlovska, F. Vasiljevic-Shikaleska,A., International workshop, COST FA0904, September 2013, Varna
78
DEVELOPMENT OF NEW PLA/SILICA NANO COMPOSITES WITH POTENTIAL USE FOR
PACKAGING OF FRESH MEAT
T. Radusin1, B. Pilić2, P. Ikonić1, V. Tomović1, A. Novaković1, L. Šarić1 ,T. Tasić1
(1)
Institute of food technology, University of Novi Sad, Bul. Cara Lazara 1, 21000 Novi Sad, Serbia
(2)
Faculty of technology, University of Novi Sad, Bul. Cara Lazara 1, 21000 Novi Sad, Serbia
[email protected]
Introduction
The development of alternative biodegradable packaging has been the subject of research and development in recent
times, particularly with regard to renewable alternatives to traditionally oil derived plastics. Currently poly (lactic acid)
(PLA) is used in food packaging application only for short shelf-life products. The goal of this work was to investigate the
potentials of PLA/silica nanocomposites for food packaging application, especially packaging of fresh meat as one of the
most sensitive foodstuff.
Materials and Methods
The PLA used in this study was provided from Esun, China. The nano silica (AEROSIL®R812) was kindly supplied by Evonik
(Hanau, Germany), and was hydrophobic, modified with hexametyldisilazan (HMDS) with specific area of 260±30
m2g-1and average particle size 7 nm. Neat PLA and PLA composites with 0.2, 1, 3 wt. % of nano silica were prepared by
casting film technique on twin screw extrusion. Selected cuts of pork M. longisimus dorsi were packed under vacuum in
selected films (polyethylene film as control, neat PLA and PLA with 0.2, 1 and 3 wt. % of nano silica). The shelf-life
characterisation was conducted during selected time line (0, 4, 7, 9 and 11 days) by several techniques as sensory
evaluation and standard physicochemical and microbiological analysis.
Spherical nanoparticles had very good dispersion in prepared films. Incorporation of nanoscale silica particles into PLA
matrix shows the improvement in tensile strength for addition of only 0.2% concentration of nanosilica. The results
obtained during determinaton of technological (pH, color, water holding capacity), microbiological (total viable count,
lactic acid bacteria, Enterobacteriaceae, E. coli) and sensory quality (color) of meat showed no statistically significant
differences (P> 0.05) in relation to type of film (convencional PE film vs. PLA with 0.2, 1 and 3 wt. % of nano silica) used
for packaging.
Conclusions
Based on the obtained results in this research it can be concluded that there is great potential for use of PLA/nano
composites in packaging of fresh pork meat, but more attention needs to be directed on developing a methodology of
materials production in industrial environment. The technique that was used in this study can be a good starting point
for potential industrial application of the new PLA/silica nano composites for packaging of fresh pork meat.
Acknowledgements
This work is a result of the research within the project III46001 financed by the Ministry of Education and Science, Republic of Serbia
and support of COST action FA0904
79
EFFECT OF IONIZING RADIATION ON NANOCOMPOSITES BASED ON POLYLACTIC
ACID/MONTMORILLONITE COMPOSITE FILMS
M. Salvatore1, S. Cimmino1, D. Duraccio1, A. Marra1, M. Pezzuto1, V. Ambrogi2, D. S. Pillai3, C. Silvestre1
(1)
(2)
Università di Napoli ‘Federico II’, Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale (DICMaPI),
Piazzale Tecchio 80, Napoli, Italy
(3)
National Center for Electron Beam Research, Texas A&M University
[email protected]
The aim of this study is dual: to develop new films based on Polylactic Acid/Montmorillonite (PLA/MMT) with improved
properties for applications in the food packaging industry and then to examine the effect of electron-beam (e-beam)
radiation on the structural, morphological, mechanical, thermal and barrier properties of these nanocomposites. PLA
based composites with 1, 3 and 5wt% of MMT were prepared in a twin screw extruder and then filmed by a calender.
All nanocomposites were irradiated with electron beam; one set at radiation doses of 1 kGy and another at 10 kGy. The
effects of MMT addition and of e-beam radiation on the properties of the polylactic acid were assessed. For all
compositions good distribution and dispersion of MMT in the PLA and also orientation and intercalation of MMT were
obtained. All nanocomposites showed an increase of the mechanical and oxygen-barrier properties compared to neat
PLA. The e-beam radiation caused increase of the crystallinity, formation of crosslink, increase of the glass-transition
temperatures (Tg) and enhancement of the yield values in the stress-strain curves for all nanocomposites. This study
demonstrates that PLA/MMT films are suitable materials for irradiation of pre-packed food at the doses analyzed in this
work.
References
1. Krikorian, V.; Pochan, D. J. "Poly (L-lactic acid)/layered silicate nanocomposite:fabrication, characterization, and properties".
Chem. Mater., 2003, 15, 4317-4324.
2. Pillai, S.D.; L. A. Braby, and C. B. Lavergne. Electron beam technology for food irradiation. International Review of Food Science
and Technology 2005, 96-101.
3. Silvestre,C.; Duraccio, D.; Cimmino, D. Food packaging based on polymer nanomaterials, Progress in Polymer Science 2011, 36,
1766–1782.
4. Duraccio, D.; Silvestre, C.; Pezzuto, M.; Cimmino, S. and Marra, A. "Polypropylene and Polyethylene based nanocomposites for food
packaging applications", in Ecosustainable Polymer Nanomaterials for Food Packaging, Eds C. Silvestre, S. Cimmino, Taylor & Francis
Group, 2013 ISBN: 978-90-04-20737-0.
5. Tran Minh Quynh, Hiroshi Mitomo, Naogutsu Nagasawa, Yuki Wada, Fumio Yoshii, Masao Tamada "Properties of crosslinked
polylactides (PLLA & PDLA) by radiation and its biodegradability" European Polymer Journal 2007, 43 1779–1785.
6. Kai-Lai G. Ho and Anthony L. Pometto III "Effects of Electron-Beam Irradiation and Ultraviolet Light (365 nm) on Polylactic Acid
Plastic Films", Journal of Environmental Polymer Degradation 1999, 7, 93-100.
Acknowledgement
The research leading to these results has received support from COST Action FA0904, IAEA’s Coordinated Research Project (CRP)
F22063 and Italy/Quebec joint project n. PGR01085.
80
DEVELOPMENT AND RADIATION PROCESSING OF POLYCAPROLACTONE/CHITOSAN (PCL/CS)
BLEND FOR ACTIVE FOOD PACKAGING
A. E. Swilem1, H. A. Abd El-Rehim2
(1)
(2)
Department of Chemistry, Faculty of Science, Ain Shams University, Abbassia, Cairo 11566, Egypt
Department of Polymers, National Center for Radiation Research and Technology, Nasr City, Cairo 11371, Egypt
[email protected]
Alternative to classical packaging that offer only passive protective function, more dynamic and functional “active
packaging” systems have been developed to fulfill other necessary requests. The term active packaging describes mainly
food packaging that interacts chemically or biologically with its contents or head space to extend shelf-life. It can
protect the food products from various environmental conditions, such as oxygen, moisture, microorganisms, light and
temperature. Moreover, there is an interest in biodegradable packaging to reduce the environmental risks caused by the
other non-biodegradable one. In this connection, chitosan (CS) which has antimicrobial and antioxidant properties was
incorporated into the biodegradable polycaprolactone (PCL) base polymer to obtain active packaging material.
Due to the poor compatibility between PCL and CS, trials were made to develop a method to enhance the dispersion of
CS in PCL and to obtain relatively homogenous PCL/CS films. It was found that the dispersion of CS in PCL can be
improved by using acetic acid cosolvent and low molecular weight CS. Therefore, CS (high viscosity) solution was
prepared at concentration of 5 % in 1% acetic acid solution and exposed to different radiation doses (10, 20, 30, and 40
kGy) in order to obtain different molecular weights of CS. Then the required amounts of CS powder and PCL granules
were mixed with a little of glacial acetic acid and warmed at 60 °C for 5 min with good stirring to obtain a homogenous
viscous blend. After drying, the PCL/CS films were prepared hot pressing in a compression molding machine operated at
100 °C for 1 min.
It was shown from the FTIR spectra of PCL, CS, and PCL/CS that there is no interaction between CS and PCL. In additon,
the use of acetic acid at these conditions does not alter the structure of PCL. Incorporation of CS into PCL decreases
generally both the tensile strength and elongation of PCL at break. However, the mechanical properties of the PCL/CS
films that prepared from irradiated CS at 5 wt% were better if compared with those prepared from non-irradiated CS.
Moreover, there was no a significant difference in the mechanical properties of the PCL/CS films that prepared from CS
irradiated with different doses (10-40 kGy). The effect of CS content (from 0-10 wt %) on the mechanical properties of
the prepared PCL/CS films was also studied. As the CS content increases, both the tensile strength and elongation at
break decrease. It was noted also that the yellow coloration of the prepared PCL/CS films increases as with the
irradiation dose and content of CS.
In conclusion, CS can be incorborated into PCL after irradiation at 10 kGy and at 1-3 wt % in order to maintain the
mechanical properties of PCL and reduce the yellow coloration of CS. Moreover, the preparation method should be
modified to obtain more homogenous films. Extra characterization and evaluation of the antioxidant and antimicrobial
capacities of the developed PCL/CS films will be carried out. In addition, the effect of ionizing radiation on the emerging
films will be studied.
81
STUDY OF THERMAL PROPERTIES AND HEAT-INDUCED DENATURATION OF HYBRID
HYDROGELS BASED COLLAGEN
C. Vasile1, M.T. Nistor1, D. Pamfil1, C. Schick2
(1)
Romanian Academy, “P.Poni” Institute of Macromolecular Chemistry, Iasi, Romania
(2)
University of RöstockAffiliation
[email protected]
Introduction
The sensitivity of collagen in the manufacture step of biomaterials and other products such as sensitivity to acidic or
basic environments, changes in temperature or presence of radiation, enzymes, and so on, has led to interest in its
chemical modification and thus to improve the physicochemical and biological properties. The most common and
effective treatment is chemical crosslinking of peptide chain. The efficiency of crosslinking procedures on thermal
behaviour of protein have been studied on gels, sponges and collagen films using different types of crosslinkers. In
addition to improved enzymatic resistance, swelling ability, rheological properties, the cross-linking agents can
enhance the thermal stability of modified collagen. Under thermal stimulus, the transition of collagen from native to
denatured state is a cooperative phenomenon with significant uptake of heat, observable on DSC curve as an
endothermic peak. The thermal transition is responsible by the rupture of intermolecular hydrogen bonds and
appearance of unfolding triple helix. Transition to amorphous state of peptide chain occurs with changes in protein
conformation and certainly of physical properties. These processes are stamped on calorimetric behaviour by variation
of thermal characteristics and enthalpy.
The hybrid hydrogels have been prepared by crosslinked the poly(N-isopropyl acrylamide) with diethylene glycol
diacrylate on collagen membrane loaded with inorganic nanoparticles. Semi-interpenetrated polymeric support
fabricated by insertion of poly(N-isopropyl acrylamide-co-diethylene glycol diacrylate) onto collagen without
nanoclays was used as reference for all nanocomposites hydrogels. The study underlines the effect of natural nanoclays
- Dellite® HPS (purified montmorillonite) (HPS) compared with chemically modified montmorillonite nanoparticles,
respectively chemically modified with dimethyl dihydrogenated tallow ammonium - Dellite® 67G (G) or methyl
dehydrogenated tallow ammonium - Cloisite® 93A (C) and hydroxyapatite (HA) nanoparticles on the thermal behaviour
of hybrid hydrogels. DSC investigations in hydrated state of hydrogels were performed in -50 °C to 110 °C temperature
range and in the dehydrated state between 0 °C and 150 °C or 220 °C. Inorganic nanoparticle intercalation into
polymeric material cause changes in thermal behavior, noticeable as consecutive endothermic processes. This
modification is justified by the ability of clay nanoparticles to maintain and transfer parts of internal energy
accumulated during the thermal process to polymeric support. Additional, for the multi-hybrid hydrogels, the presence
of hydroxyapatite and montmorillonite nanoparticles in the polymeric matrix results in hastening of calorimetric
processes. Thus, the presence of inorganic materials reflects in increasing of internal energy amount as a result of
interposition of inorganic materials between the polymeric sheets thereby inhibiting the heat transfer.
References
1. Nistor MT, Chiriac AP, Vasile C, et al. Synthesis of hydrogel based on poly(NIPAM) inserted into collagen sponge. Colloids Surf B
Biointerfaces 2011; 87(2): 382–390.
2. Manuela T Nistor, Cornelia Vasile, Aurica P Chiriac, Liliana Tartau, Biocompatibility, biodegradability, and drug carrier ability of
hybrid collagen-based hydrogel nanocomposites, Journal of Bioactive and Compatible Polymers, DOI: 10.1177/0883911513509021,
28(7), 2013]
82
PLA NANOCOMPOSITES AS POTENTIAL ANTIMICROBIAL MATERIALS
2
C. Vasile , R. Darie1, G. M. Pricope2, A. Sdrobis1, E. Paslaru1, G. E. Hitruc1, A. Baklavaridis3, I. Zuburtikudis3
(1)
Romanian Academy, “P.Poni” Institute of Macromolecular Chemistry, Iasi, Romania
Veterinary Laboratory and the Food Safety, Food Safety Department, Iasi, Romania
(3)
Western Macedonia University of Applied Sciences T.E.I. of Western Macedonia, Kozani, Greece
[email protected]
(2)
Introduction
Poly(lactic acid) (PLA) is produced from renewable resources and approved by the Food and Drug Administration for
medical use. Because of these “green” features combined with its benign degradation behavior, PLA is considered as a
potential packaging material in many fields. Biomedical uses of PLA have been widespread, which include
bioabsorbable surgical sutures and implants, controlled drug delivery, and tissue culture. The principal drawbacks of
polylactide in terms of applications in packaging or biomedical field are its poor thermal and mechanical resistance,
limited barrier properties, solvent resistance, and flame retardance which are often not enough for end use. In order to
improve PLA properties, different layered silicate nanoclays are added as montmorillonites without or with organic
modifiers.
It is well-known that the clays are the greatest natural healer available. The scientists have proved antibacterial
properties of clays. Rhim, Hong, Park, and Ng (2006) reported that some nanocomposite films prepared with a certain
organically modified nanoclay had a strong antimicrobial function against both Gram-positive and Gram-negative
bacteria. They postulated that the antimicrobial function of nanocomposite films could be attributed to the quaternary
ammonium groups of organically modified clays which disrupts the bacterial cell membranes and causes the cell to lyse.
This study investigates the effect of the hydrophibicity of nanoclay on the mechanical, thermal properties and
morphology as well as antimicrobial activity of the PLA-based composite films.
Several nanocomposites with PLA matrix and 3 wt% of different nanoclays have been obtained by melt processing in a
Brabender plastograph with the mixer blades counter-rotating at 60 rpm for 10 minutes, processing temperature being
of 175 °C. It was considered the following order of increased hydrophylicity: 67G < C 15A < C 20A < C 93A < C30B <
HPS. By XRD it has been established that mainly exfoliated nanocomposites are obtained. Both mechanical, thermal,
barrier and surface properties (Fig. 1) of PLA nanocomposites are controlled by hydrophobicity of the nanoclay. The
antimicrobial activity is manifested only by highly hydrophilic nanoclay – Table 1.
Fig.1. Variation of the contact ange with water
nanocomposite composition
Table 1: ESCHERICHIA COLI growth inhibited by PLA/nanoclay
composites
C o n ta c t a n g le , d e g re e s
90
Proba
80
PLA
PLA / CLOISITE 93 A
PLA / CLOISITE 30 B
PLA / HPS
70
60
UFC /
0,1ml 24h
84
68
58
44
UFC /
0,1ml 48h
6
22
7
9
% Inhibition % Inhibition
24h
48h
34.88
52.71
47.29
82.95
55.04
94.57
65.89
93.02
A
PL
A/
H
PS
B
30
93
A/
C
PL
A/
C
20
A/
C
PL
PL
A
A
G
15
A/
67
A/
C
PL
PL
PL
A
50
Conclusions
All obtained nanocomposites showed superior properties in respect with PLA; the enhancements is dependent on clay
hydrophobicity so the properties can be controlled by this clay characteristic.
Acknowledgements
This work is financially supported by UEFISCDI through the BIONANOMED project 164/2012.
References
1. Rhim J.W.; Mohanty K.A.; Singh S.P.; Ng P.K.W. J. Appl. Polym. Sci., 2006, 101, 3736–3742.
83
ELECTROSPUN NANOFIBERS AS A FOOD CONTACT LAYER FOR IRON BASED OXYGEN
SCAVENGING FILMS
S. Yildirim1, C. Jeannette1, N. Renke1, C. Adlhart2
(1)
(2)
Institute of Food and Beverage Innovation, Zurich University of Applied Sciences, Waedenswil, Switzerland
Institute of Chemistry and Biological Chemistry, Zurich University of Applied Sciences, Waedenswil, Switzerland
[email protected]
Introduction
Oxygen present in the headspace of a food packaging may result in oxidation of the product and therefore affect the
sensorial properties of food, change its color or cause nutritional losses [1]. To overcome such oxidation problems
oxygen scavengers can be used. Oxygen scavenging rate of such active films is a critical factor. To be able to effectively
prevent the oxidation, such scavengers should remove the oxygen faster than the oxidation rate of the product. Iron
based oxygen scavengers are well developed and integrated into the packaging film [2]. They require a food contact
layer to overcome the migration of iron into the product. This reduces the oxygen scavenging rates of the active films
since oxygen and water have to first diffuse through the food contact layer before they react with the iron integrated in
the film. Electrospun nanofibers have the potential to be used as a food contact layer for such oxygen scavenging
systems. They have a pore size below 100 nm and the transport properties of liquid, moisture and gasses can be tailored
individually by selecting processing parameters and the materials.
In this study we coated two different iron based oxygen scavenger films; 2600 (PE/PE+Fe) and 5100 (EVA/PE+Fe) with
polyacrylonitrile (PAN) using a nanospider (LAB 200, Elmarco) (Figure1). Additionally, PE/PE+Fe/PE films and non
coated films were used as control. Samples were placed in a tray and packaded with 1% of oxygen and 95% relative
humidity in the package and stored at 23°C for 35 days. Oxygen content in the package were fallowed during the
storage.
Figure 1. Electrospinning process (Nanospider™ technology, 2013)
Non-coated 2600 and 5100 films showed oxygen scavenging rates of 26 and 34 ml/(m2×d), repsectively. Coating with
PAN did not effected the oxygen scavenging rates significantly. On the other hand laminating 2600 films with PE as a
food contact layer reduced the oxygen scavenging rates to 14 ml/(m2×d).
References
1. Rebertson, G.L. ed. Food Packaging and Shelf Life. 2010, CRC Press Taylor and Francis Group: Boca Raton. 388.
84
PARTICIPANTS
Lorena Affatato
Institute of Chemistry and Technology of Polymers,
(ICTP-CNR), Italy
[email protected]
Luigi Ambrosio
Department of Chemical Science & Materials Technology, CNR, Italy
[email protected]
Annarita Appetito
National Research Council (CNR), Italy
[email protected]
Ilaria Armetano
University of Perugia, Italy
[email protected]
Federica Aureli
Istituto Superiore di Sanità, Italy
[email protected]
Maurizio Avella
[email protected]
Zehra Ayhan
Mustafa Kemal University, Turkey
[email protected]
Cecilia Bartolucci
[email protected]
Aida Benhamida
University A. Mira of Bejaia, Algeria
[email protected]
Hynek Biederman
Charles University in Prague, Czech Republic
[email protected]
Isabel Bourbon
Universidade do Minho,Portugal
[email protected]
Cosimo Carfagna
[email protected]
Tiziana Maria P. Cattaneo
Consiglio per la Ricerca e la Sperimentazione in Agricoltura, Italy
[email protected]
Miguel Cerqueira
Universidade do Minho,Portugal
[email protected]
Andrei Choukourov
[email protected]
Sossio Cimmino
(ICTP-CNR), Italy
[email protected]
Isabel Coelhoso
Universidade Nova de Lisboa, Portugal
[email protected]
Doina Constantinescu
SC ICEFS COM SRL, Romania
[email protected]
Pasquale De Luca
(ICTP-CNR), Italy
[email protected]
Paola Del Serrone
Consiglio per la Ricerca e la Sperimentazione in Agricoltura,
CRA, Italy
[email protected]
Louise Deschênes
Agriculture & Agri-Food, Canada
[email protected]
Maria Laura Di Lorenzo
(ICTP-CNR), Italy
[email protected]
Emilia Di Pace
(ICTP-CNR), Italy
[email protected]
Donatella Duraccio
(ICTP-CNR), Italy
[email protected]
Anna Esposito
(ICTP-CNR), Italy
[email protected]
Vittorio Fattori
Food & Agriculture Organization- UN, Italy
[email protected]
Ana Rita Ferreira
Universidade Nova de Lisboa, Portugal
[email protected]
Emanuele Fiore
Embassy of Italy, Canada
[email protected]
Elena Fortunati
[email protected]
Stephanie Gaengler
Cyprus University of Technology, Cyprus
[email protected]
Gaetano Guerra
Nano Active Film S.r.l., Spin-off Company of the University
of Salerno, Italy
[email protected]
Jan Hanuš
[email protected]
Eddo Hoekstra
Joint Research Centre of the European Commission, Italy
[email protected]
Elisabetta Lupotto
Consiglio per la Ricerca e la sperimentazione in Agricoltura CRA
[email protected]
Francesca Luzi
[email protected]
Francesco Marandino
Penelope SpA, Italy
[email protected]
Geoffrey Hunt
St Mary’s University College, UK
[email protected]
Antonella Marra
(ICTP-CNR), Italy
[email protected]
Evgeni Ivanov
Bulgarian Academy of Sciences, Bulgaria
[email protected]
Artur Martins
University of Minho, Portugal
[email protected]
Tatjana Ivanova
Riga Technical University, Latvia
Remo Merijs Meri
[email protected]
Mustapha Kaci
University A. Mira of Bejaia, Algeria
[email protected]
Josè Kenny
[email protected]
Erich Kny
Kemyk, Austria
[email protected]
Rumiana Kotsilkova
Bulgarian Academy of Sciences, Bulgaria
[email protected]
Marek Kozlowski
Wroclaw University of Technology, Poland
[email protected]
Marlena Kwiatkowska
Wroclaw University of Technology, Poland
[email protected]
Apostolos Kyritsis
National Technical University of Athens, Greece
[email protected]
José María Lagaron
Spanish Council for Scientific Research (CSIC), Spain
[email protected]
Claudio Larosa
University of Genoa, Italy
[email protected]
Francesco Loreto
Department of Biology, Agriculture & Food Science,CNR,Italy
[email protected]
Geoffrey Mitchell
Institute Polytechnic Leiria, Portugal
[email protected]
Bogdanel Silvestru Munteanu
AL.I. Cuza University,Romania
[email protected]
Augusta Maria Paci
National Research Council, Italy
[email protected]
Ramesh Babu Padamati
Trinity College, Ireland
[email protected]
Daniela Pamfil
Petru Poni Institute of Macromolecular Chemistry, Romania
[email protected]
Christos Pandis
National Technical University of Athens, Greece
[email protected]
Elena Paslaru
Petru Poni Institute of Macromolecular Chemistry, Romania
[email protected]
Elisa Passaglia
Istituto di Chimica dei Composti Organo Metallici, CNR, Italy
[email protected]
Kvalvåg Marit Pettersen
NOFIMA, Norway
[email protected]
Marilena Pezzuto
(ICTP-CNR), Italy
[email protected]
Branka Pilic
University of Novi Sad, Serbia
[email protected]
Ioanna Stavridou
COST Science Officer Food and Agriculture Domain, Belgium
[email protected]
Ana Cristina Pinheiro
University of Minho, Portugal
[email protected]
Amhed Swilem
Ain Shams University, Cairo, Egypt
[email protected]
Frederika Popovska-Pavlovska
Integrated Business Institute, R.Macedonia
[email protected]
Mikko Tuominen
SP Technical Research Institute of Sweden, Sweden
[email protected]
Andrea Porcari
Center for Nanotechnologies and KETs, Italian Association for
Industrial Research (AIRI/Nanotec IT), Italy
[email protected]
Mika Vähä-Nissi
VTT Technical Research Centre of Finland, Finland
[email protected]
Francesca Proia
[email protected]
Debora Puglia
[email protected]
Tanja Radusin
University of Novi Sad, Serbia
[email protected]
Annamaria Randazzo
National Research Council, Italy
[email protected]
Ramune Rutkaite
Kaunas University of Technology, Lithuania
[email protected]
Agnes Safrany
International Atomic Energy Agency, Austria
[email protected]
Marcella Salvatore
(ICTP-CNR), Italy
[email protected]
Christoph Schick
University of Rostock, Germany
[email protected]
Gustaaf Schoukens
Ghent University, Belgium
[email protected]
Clara Silvestre
(ICTP-CNR), Italy
[email protected]
Alex Sivan
Ben Gurion University of the Negev, Israel
[email protected]
Arantzazu Valdés García
[email protected]
Robert Van Otterdijk
Food & Agriculture Organization- UN, Italy
[email protected]
Cornelia Vasile
“P.Poni” Institute of Macromolecular Chemistry, Romania
[email protected]
Rimantas Venskutonis
[email protected]
Marc Verelst
Université Paul Sabatier Toulouse III and CNRS, France
[email protected]
Selcuk Yildirim
Zurich University of Applied Sciences, Switzerland
[email protected]
Ilmars Zalite
[email protected]
Algirdas Zemaitaitis
[email protected]
Janis Zicans
[email protected]
Ioannis Zuburtikudis
Technological Education Institute (T.E.I.) of Western
Macedonia, Greece
[email protected]
Final Conference
Cost Action FA0904
26 - 28 February, Sala Marconi - CNR - Piazzale A. Moro, 7 - ROME - ITALY

“Eco-sustainable Food Packaging Based on Polymer Nanomaterials”

Transcription

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