Book of Abstracts - COST Action FA0904

Transcription

Eco-sustainable Food
Packaging Based on
Polymer Nanomaterials
International Workshop
“Characterization, Mechanics and
Performance of Innovative Polymer
Nanomaterials for Food Packaging
Application”
Varna, Bulgaria,
September 24-25, 2013
Book of
Abstracts
Local organizing committee:
Prof. Rumiana Kotsilkova
Eng. Peter Todorov
Institute of Mechanics – BAS
COST Action FA0904 “Eco-sustainable Food Packaging based on
Polymer Nanomaterials” (2010-2014)
The main objective of this Action is to constitute an international scientific and
technological network on issues related to eco-sustainable polymer nanomaterials for
food packaging (PNFP).
The Action aims at exploiting the potentiality of polymer nanotechnology in the area
of food packaging treating in a complete way the demanding needs of the users, such
as health, environment, taste, cost and the specific requirements of the food industry.
The envisaged direction is to look at the complete life cycle of the PNFP by the
combined efforts of leading research and industrial groups. The Action will identify
the barriers (in research and technology, safety, standardisation, trained workforce
and technology transfer) that prevent a complete successful development of PNFP
and will indicate the strategies to proceed further.
Already 66 partners including 13 companies and coming from 33 countries have been
shown interest in the Action, including 28 COST Member Countries, 1 COST Near
Neighbor Country (Algeria) and
4 COST International Partner Countries (USA,
Canada, New Zealand and Brazil).
The Action is organized in 4 Working Groups :
•
WG1-Development of new safe PNFP;
•
WG2 Development of new processing technologies including modelling and
simulation;
•
WG3-Development of new strategies to identify any critical interaction of PNFP
with food;
•
WG4-Ethics, Standardization, Science-society dialogue.
Further information at:
www.cost.esf.org
1
International Workshop
COST Action FA0904
“Characterisation, Mechanics and Performance of Innovative Polymer
Nanomaterials for Food Packaging Application”
Varna, Bulgaria, September 24-25, 2013
Bulgarian Academy of Sciences, Institute of Mechanics, Open Laboratory for
Experimental Micro and Nano Mechanics, as a member of COST Action FA0904,
invites you to the International Workshop “Characterisation, Mechanics and
Performance of innovative polymer nanomaterials for food packaging
application”, under the COST FA0904 ”Eco-sustainable food packaging based on
polymer nanomaterials”
The workshop will be held at “Frederic Joliot-Curie” Hotel Congress Spa Complex
near Varna, Bulgaria, 24-25, 2013. It will be organized jointly with the 12th National
Congress on Theoretical and Applied Mechanics, 23-26 September 2013, “Sts.
Constantine and Helena”, Varna, Bulgaria. (http://nctam.imbm.bas.bg/index.php/nctam/12nctam)
Contact for the Workshop: cost.varna@gmail.com
The workshop will be related to Working Groups 1, 2 and 4 of the COST Action FA0904.
WG1 is responsible for the “Development and characterization of new safe PNFP”
selecting the constituents for development of improved / active / intelligent food
packaging polymer nano-materials, being effective in real applications.
WG2 is related to the “Development of new processing technologies including modelling
and simulation”.
WG4 deals with “Ethics, standardization and science-society dialog on PNFP”.
The following topics will be covered by the International Workshop in Varna:
1.
2.
3.
4.
5.
6.
Innovative PNFP compositions and processing technology;
Mechanics and rheology of nanomaterials – characterizations and modeling;
Improved properties of PNFP based on nanoscale and interfacial concept;
Structure at the hybrid interfaces and structure-property relationships;
Performance of PNFP at different processing and exploitation conditions;
Societal and environmental aspects of PNFP.
2
International Workshop, Varna, Bulgaria, 24-25 September, 2013
COST FA0904
CONFERENCE PROGRAM
TUESDAY, 24 September 2013: (Hall 5 - Hotel “Frederic Joliot-Curie”)
Time
Registration
08:00 09:00
09:00 09:10
Welcome & Introduction
09:10 12:40
SESSION 1: KEYNOTE LECTURES
09:10 09:30
Progresses and challenges of
COST ACTION FA0904
Prof Rumiana Kotsilkova
Prof. Vasil Kavardjikov
Chair: Prof Rumiana Kotsilkova
Dr. Clara Silvestre
09:30 10:10
Characterization of Nanostructured Polymeric
Materials
Prof Geoffrey Mitchell
10:10 10:50
Fully renewable high barrier nanostructured
biopolyester-based materials
Prof Jose M. Lagaron
M.J.Fabra, A.LopezRubio
10:50 11:20
11:20 12:00
12:00 12:40
Elaboration and manufacturing of
nanocomposite blown films using a bio-based
polymer: study of fracture behavior
The Question of Nanosafety: Some Hazards
and Recommendations
CDRsp, IPL, Portugal ;
CfAM, University of
Reading, UK
Novel Materials and
Nanotechnology Group.
IATA-CSIC, Valencia, Spain
Prof Patrick Ienny
M. Aloui-Dalibey,
A.-S Caro-Bretelle
Geoffrey Hunt,
Matt James
Centre des Matériaux des
mines d’Alès, Ales, France
St Mary's University
College, London, UK
Lunch
14:30 16:30
SESSION 2: INNOVATIVE PNFP and
CHARACTERISATION METHODOLOGIES
14:30 15:00
Functional nanofillers facilitate polymer
recycling
15:00 15:30
Poly(vinyl alcohol) composites and
nanocomposites for food packaging
Molecular probes for oxygen monitoring in
food packaging
16:30 18:30 POSTER SESSION (Coffee Bar – Hotel “Sirius”)
Chair: Prof Geoffrey Mitchell
Prof Marek Kozlowski
St. Frackowiak
Wroclaw University of
Technology, Poland
Prof Cornelia Vasile
E. Părpărită M. Baican
”Petru Poni” Institute of
Macromolecular
Chemistry, Iasi, Romania
Prof Isabel Coelhoso
REQUIMTE/CQFB,
Universidade Nova de
Lisboa, Portugal
S. Santoro, C. Portugal,
J. C. Lima, J. G. Crespo
Chair: Prof. Jose Maria Lagaron Cabello
Marilena Pezzuto
1
Properties characterization of In situ modified
biodegradable films from barley
2
Prediction of relaxation time spectrum of polymer
blends
3
Institute of Chemistry and
Technology of Polymers,
CNR, Pozzuoli, Naples, Italy
Coffee
12:40 14:30
15:30 16:00
Institute of Mechanics,
BAS, Sofia, Bulgaria
Rheological properties and characterization of hybrid
PP/MWCNT/Clay nanocomposites
Duraccio Donatella,
Gabriella Santagata, Razzaq
Hussam, Sossio Cimmino,
Clara Silvestre
Aneta VasiljevicSikaleska
F. Popovska-Pavlovska
Ivanka Petrova
E. Ivanov, R. Kotsilkova,
D. Duraccio, M. Pezzuto,
Institute of Chemistry
and Technology of
Polymers, Pozzuoli,
Naples, Italy
Integrated Business
Institute, Skopje, FYRM
3
COST FA0904
S. Cimmino, C. Silvestre
Tanja Radusin
4
Thermal degradation of bionanocomposites based on
PLA/silica nanoparticles
5
Aleksandra Kujundziski
Dielectric thermal analysis as a study technique for
D. Chamovska, T. Radusin,
the characterization of nanocomposite materials for
A. Marra, D. Duraccio, B.Pilic,
food packaging
B. Pilić, O. Bera, I. Ristić, A.
Novaković
C.Silvestre
Institute of Food
Technology, University
of Novi Sad, Serbia
International Balkan
University, Faculty of
Technical Sciences,
Skopje, FYRM
Romanian Academy,
‘‘P. Poni’’ Institute of
Macromolecular
6
DSC and rheological measurements of Epoxy/Clay/Au
nanocomposites
7
Recycling of PP hybrid bio-based composites useful in
food packaging by thermal treatment methods
8
Scratch and Nanoindentation Investigation of the
Mechanical Properties of Three-phase Polypropylene
Nanocomposites
I. Petrova, E. Ivanov,
V. Angelov, R.Kotsilkova,
C.Silvestre, S.Cimmino,
D. Duraccio, M.Pezzuto
9
Nano-indentation and AFM Investigation of Threephase Epoxy Nano-composites
V. Angelov, Y. Tsekov,
I. Petrova, E. Ivanov,
R. Kotsilkova
20:00
Verislav Angelov
E. Ivanov, R. Kotsilkova
Elena Parparita
A.Md. Uddin,
M.-T Nistor, C. Vasile
Yuliy Tsekov
Peter Todorov
Dinner
WEDNESDAY, 25 September 2013 (Hall 4 - Hotel “Frederic Joliot-Curie”)
09:00 12:30
SESSION 3: MECHANICS AND RHEOLOGY
Chair: Prof Patrick Ienny
Institute of Mechanics and its Activities in
European Research Area
Rheology of functional luminescent polymer
09:30 10:00
nanocomposites
Reinforcement of Silica/PDMS nanocomposites:
10:00 10:30
impact of charges functionalization on
mechanical properties
09:00 09:30
10:30 11:00
Relaxation properties of polymer systems
Prof. Vasil Kavardzhikov
Dr.Stanislaw Frackowiak
Marek Kozlowski
Dr. Anne-Sophie CaroBretelle, P. Ienny,
D. Mariot, F. Ganachaud
Prof. Frederika
Popovska-Pavlovska
A. Vasiljevic-Sikaleska
11:00 11:30
Ecole des Mines d’Alès,
Alès, France
Integrated Business
Institute, Skopje, FYRM
Coffee
Dr. Evgeni Ivanov
11:30 12:00
PP/MWCNT/OC Nanocomposites – Rheological
and Mechanical Properties
I. Petrova, R. Kotsilkova.
C. Silvestre, S. Cimmino,
D. Duraccio M. Pezzuto
12:00 12:30
Characterization by AFM and nanoindentation method of some stratified
nanocomposites destined to food packaging
Elena Pâslaru
12:30 14:30
Institute of MechanicsBAS, Sofia, Bulgaria
Wroclaw University of
Technology, Poland
Y. Tsekov,S. Munteanu,
R. Kotsilkova, C. Vasile
”Petru Poni” Institute of
Macromolecular
Lunch
4
COST FA0904
14:30 16:30
SESSION 4: PERFORMANCE OF PNFP
14:30 15:10
Biofilm formation on polyethylene by plastic
degrading bacteria (key note lecture)
Comparative performance of iPP based
15:10 15:40 nanocomposites versus multilayered material
for shelf-life of ready-to-eat meat products
15:40 16:10
The influence of oxide nanoparticles on the
thermal properties of polymer matrix
Spectroscopic characterization of
temperature-responsive polymers
New potential applications in food packaging
of the electrospinning / electrospraying
method used for polymer surface modification
and to obtain of nano(micro)structures from
16:40 17:10
antimicrobial agents as chitosan, silver and
various bioactive agents. I. Polylactic acid /
Silver NP/Vitamin E bio-nanocomposite fibers
with antibacterial and antioxidant activity.
16:10 16:40
Chair: Prof Isabel Coelhoso
Prof. Alex Sivan
Irit Gilan
Dr Zehra Ayhan
O. Estürk, B. Özcan,
D. Duraccio, C. Silvetre,
S. Cimmino
Dr Branka Pilić
O. Bera, M. Jovičić,
J. Pavličević, T. Radusin
Dr Lenka Hanykova
Bogdanel Munteanu
Z. Aytaç, T. Uyar,
C. Vasile
17:10 17:45
DISCUSSIONS AND CONCLUDING REMARKS
(Coffee Bar – Hotel “Sirius”)
17:45 18:00
Concluding Remarks and farewell
18:30
Ben Gurion University,
Beer Sheva, Israel
Mustafa Kemal
University, Hatay, Turkey
Faculty of Technology,
University of Novi Sad,
Serbia
Charles University,
Prague, Czech Republic
”Al. I. Cuza” University
Iasi, Faculty of Physics,
Iasi, Romania
Chair: Dr. Clara Silvestre
Dr. Marilena Pezzuto
Dinner
5
COST FA0904
ORAL PRESENTATIONS
6
COST FA0904
SESSION 1: KEYNOTE LECTURES
7
COST FA0904
Progresses And Challenges Of COST ACTION FA0904
Clara Silvestre
Institute of Chemistry and Technology of Polymers, Pozzuoli, Naples, Italy
E-mail: clara.silvestre@ictp.cnr.it
The progresses of the European Activity "COST ACTION FA0904 “Eco-sustainable Food
Packaging based on polymer nanomaterials" in term of scientific achievements, as well as
of promotion of new cooperation will be presented. In particular the details of synergy
realized with the Coordinated Research Project of the IAEA on the “Application of
Radiation Processing Technology in the Development of Advanced Packaging Materials
for Food Products” will be given. This synergy represents a new challenge to minimize
the huge and intolerable amount of food lost (∼40% total) between the points of
production and consumption and to ensure worldwide food safety, quality and quantity
as well as to facilitate international trade.
8
COST FA0904
Characterization Of Nanostructured Polymeric Materials
Geoffrey R Mitchell
CDRsp - Centre for Rapid and Sustainable Product Development
Polytechnic Institute of Leiria 2430-028 Portugal
and
Centre for Advanced Microscopy, University of Reading RG6 6AF UK
E-mail: g.r.mitchell@reading.ac.uk
The addition of small quantities of nanoparticles to conventional and sustainable
thermoplastics leads to property enhancements with considerable potential in many areas
of applications including food packaging, lightweight composites and high performance
materials. In the case of sustainable polymers the addition of nanoparticles may well
sufficiently enhance properties such that the portfolio of possible applications is greatly
increased.
The characterisation of such nanostructured polymers presents a number of challenges.
Foremost amongst these are the coupled challenges of the nanoscale of the particles and
the low fraction present in the polymer matrix. Very low fractions of nanoparticles are only
effective if the dispersion of the particles is good. This continues to be an issue in the
process engineering but of course bad dispersion is much easier to see than good
dispersion. In this presentation we show the merits of a combined scattering (neutron and
x-ray) and microscopy (SEM, TEM, AFM) approach. We explore this methodology using rod
like, plate like and spheroidal particles including metallic particles, plate-like and rod-like
clay dispersions and nanoscale particles based on carbon such as nanotubes and graphene
flakes. We describe the particular benefits of using an etching technique to reveal the
polymer morphology and the nanoparticles. We will draw on a range of material system,
many explored in partnership with other members of Napolynet. The value of adding
nanoscale particles is that the scale matches the scale of the structure in the polymer
matrix. Although this can lead to difficulties in separating the effects in scattering
experiments, the result in morphological studies means that both the nanoparticles and the
polymer morphology are revealed.
9
COST FA0904
Fully Renewable High Barrier Nanostructured BiopolyesterBased Materials
M.J. Fabra, A. Lopez-Rubio & J.M. Lagaron
Novel Materials and Nanotechnology Group, IATA-CSIC
Avda. Agustin Escardino 7, 46980 Paterna, Valencia, Spain.
E-mail: lagaron@iata.csic.es.
The use of biobased materials in packaging applications is becaming of great interest to
replace non-degradable petroleum based thermoplastics in order to tackle environmental
issues such as the reduction of the carbon footprint. One potential biopolymer to be
implemented in this application is the family of polyhydroxyalkanoates (PHA´s) that are
biosynthesized from a variety of microorganisms. In an effort to improve the barrier
properties of biopolyesters, the nanocomposites technology has been very often
considered (Lagaron, 2011). In this work PHA’s containing a poultry feather-derived
nanokeratin filler or bacterial cellulose nanowhiskers (BCNW) have been developed by
using a proprietary (Lagaron et al., 2010) blending process using the electrospinning
processing technique as a filler pre-dispersing method. Electrospinning is a physical
process used for the formation of ultrathin fibres by subjecting the polymer solution to
high electric fields. This technique relies on electrostatic forces to draw polymer solutions
or melts into ultrathin fibres, which can be deposited as fibrous mats for diverse
applications (Li & Xia, 2004). The important advantages of the electrospinning technique
are the production of very thin structures, in the order of few nanometers, with large
surface areas, ease of functionalization for various purposes, adhesive properties and ease
of processing. The possibility of generating high throughput large scale electrospun
productions via for instance multinozzle technologies combined with the simplicity of the
process makes this technique very attractive for relatively high volume applications.
On the other hand, it is also well- known that, one of the most important solutions to
provide high barrier in packaging applications is the proper design of multilayers.
Multilayer systems make use of tie layers to provide adhesion between non-compatible
layers. The development of renewable tie layers is still a largely standing issue in the
industry. A solution to this is the development of biopolyester-based multilayer films which
incorporate a self-adhesive high barrier protein or polysaccharide interlayer fabricated by
electrospinning coating. These developed films have shown excellent adhesion between the
biopolyester layers and presented considerably improved barrier properties with
minimum changes in mechanical and optical properties (Fabra, López-Rubio & Lagaron,
2013).
References:
1. Fabra, M.J.; López-Rubio, A. & Lagaron, J.M. Food Hydrocolloid 2013, 32(1), 106-114.
2. Lagaron, J. M.; Martinez-Sanz, M.; Lopez-Rubio, A. (2010) Patent Application P201030663.
3. Li, D. and Xia, Y. Adv. Materials 2004. 16(14), 1151-1170.
4. Lagaron, JM, Book Editor, Multinfunctional and Nanoreinforced Polymers for Food Packaging 2011,
Woodhead Publishing.
10
COST FA0904
Elaboration And Manufacturing Of Nanocomposite Blown Films
Using A Biobased Polymer: Study Of Fracture Behavior
Ienny Patricka, Aloui-Dalibey Madihab, Caro-Bretelle Anne-Sophiea
Advanced Polymer Materials, Centre des Matériaux des mines d’Alès, Ales, France
Polymers and Composites Technology & Mechanical Engineering Department, Ecole des Mines de
Douai, Douai, France,
E-mail : Patrick.Ienny@mines-ales.fr
a
b
To decrease the environmental impact of packaging on waste management, an alternative
consists in the use of biodegradable polymers. In this social context, the aim of this study
work is the development and the behavior analysis of blown nanocomposite films based on
polylactic acid (PLA). The use of the PLA is justified by its natural origin and by its good
physical properties. However, PLA presents some limits, in particular, its sensibility to the
thermal degradation, its difficult processabilty by extrusion-blowing. If its modification, by
branching and plasticization using additives, allows improving its manufacturing, the
reinforcement by nanoclays is necessary to increase the mechanical properties of the film.
Then, a surface treatment was realized on the surface of two different nanoclays
(montmorillonite and sepiolite) to improve the polymer / clay interaction. These clays
were incorporated into the polymer using a masterbatch via a direct melt intercalation
process by means of a co-rotating twin screw extruder. The dispersion level of the modified
clays was analyzed by rheology, XRD, MEB and MET. The dispersion analysis allowed us to
study the efficiency of the clay surface chemical treatments.
Finally, the mechanical properties of blown films based on modified PLA and nanoclays
have been optimized. The best formulation leading to the mechanical properties fixed by
the targeted application was fixed. The tear strength and the tenacity of various chosen
films have been studied using the Essential Work of Fracture method (EWF). Among the
existing normalized methods to analyze the strength of film, the EWF method leads to a
non-intrinsic mechanical property. In a first step the relevance of this method is studied via
the validation of hypotheses necessary for its application. Then, by considering a local
approach of the material behaviour, an energy-partitioning concept allows us to evaluate
intrinsic properties as the initiation and the propagation works of fracture; it is showed
that the improvement of the toughness by adding nano-particles is associated to the
increase of the initiation work.
11
COST FA0904
The Question Of Nanosafety:
Hazards And Recommendations
Geoffrey Hunt, Matt James
Centre for Bioethics & Emerging Technologies, St Mary’s University College, London, UK
E-mail: Geoffrey.Hunt@smuc.ac.uk
The question of the safety of manufactured nanomaterials (MNMs) – including polymer
matrices and coatings - is one of increasing urgency as these materials enter into a wider
and wider range of manufacturing processes, industrial and consumer goods and waste
management processes. Polymer production already has a history of unforeseen toxicity
consequences, and new polymers must learn from the past.
Our recent consensual reports of experts in the field of nanosafety – including toxicologists
- identified a number of priorities (Hunt et al 2012 and 2013). These are a general lack of
coherent, consistent and well-founded data, the need for realistic exposure scenarios,
better established dose–response relationships, improved extrapolation from in vitro to in
vivo findings, and the identification of the most relevant assessment parameters. In
particular, there is a need to understand the dynamics of biological-nanomaterial
interfaces, including an understanding of the behaviour of the protein corona that tends to
form around nanoparticles; to embark on long-term studies, and to gather information
about ageing, stability and reactivity. On the regulatory front the existing test guidelines
should continue to be fine-tuned for manufactured nanomaterials, and on the nanosafety
research front more advanced statistical and computational methods are required.
Although a good start has been made there exist very large gaps in understanding the
hazards and risks associated with: occupational health in the manufacturing process of
PNFP; leaching from new polymer nanomaterials for food packing (PNFP) into food or
drink; leaching from consumer misuse of PNFP; ageing, abrasion and release, as well as
degradation in the environment and the release of MNMs; entry into the food chain; the
design of PNFPs for recycling; toxic ‘adjuvants’ in manufacturing process of PNFPs
(congenors, catalysts, etc.).
References:
1. This presentation is derived from: Hunt,G., Lynch, I., Cassee, F., et al (2013) ‘Towards a Consensus
View on Understanding Nanomaterials Hazards and Managing Exposure: Knowledge Gaps and
Recommendations’,
Materials,
6:
1090-1117
(doi:
10.3390/ma6031090).
Open
access: www.mdpi.com/journals/materials. Also see: Hunt, G. & Riediker, M (2011) ‘Building Expert
Consensus on Uncertainty and Complexity in Nanomaterial Safety’, Nanotechnology Perceptions, Vol. 7
(July) 82-98.
12
COST FA0904
SESSION 2: INNOVATIVE PNFP and
CHARACTERISATION
13
COST FA0904
Functional Nanofillers Facilitate Plastics Recycling
Marek Kozlowski, Stanislaw Frackowiak
Wroclaw University of Technology, Faculty of Environment Engineering, Wroclaw, Poland
E-mail: marek.a.kozlowski@pwr.wroc.pl
Plastics waste recovery allows substantial savings of raw materials and energy, supports
also the environment protection. Annual demand for plastics in Europe reached 47 Mtonne
in 2011, of which packaging was the largest sector (ca. 40%). Packaging is a short life cycle
product, thus it has been dominating in plastic waste stream, that accounts to over 25
Mtonne/y. Recovery reached almost 60% in 2011, due to an increased efficiency of the
collection systems, sorting technologies and progress in the recovery methods. The recovery
options include recycling (mechanical, feedstock, organical) and energy recovery from
incineration. Currently recycling reaches 6.5 Mtonne, whereas energy recovery is over 8.5
Mtonne. However, recycled plastics have high commercial value only when the wastes have
been subjected to separation by a resin type prior to processing.
Biodegradable polymers are considered to be a promissing solution for packaging materials.
Such waste may be recycled either mechanically or organically, providing compost (when
degraded with the access of oxygen), or methane (if fermented in anaerobic conditions).
However, if biodegradable packaging end up in landfills, they generate greenhouse gases in
an uncontrolled manner, thus contributing to the atmosphere pollution and ozone layer
depletion. Considering that plastic waste disposal accounts to over 10 Mtonne, separation of
biodegradable fraction should bring about a reduction in the greenhouse gases emission.
Since the separation and classification of plastic waste is crucial for plastic waste recycling,
several sorting techniques based either on simple physico-chemical characteristics or more
sophisticated spectroscopic methods have been developed. The simplest technique is
manual sorting, which demands a sensitive and selective indicator for the visual
identification. Application of luminescent nanofillers for manufacturing polymer
nanocomposites used as indicators in packaging for sorting purposes has been presented.
Possible application for separation of petrochemical and bio-based polymers have been
proposed.
Acknowledgements:
The work was supported by Wroclaw Research Centre EIT+ within 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 (Operational Programme Innovative Economy, 1.1.2).
14
COST FA0904
Poly (Vinyl Alcohol) Composites And Nanocomposites For Food
Packaging
Cornelia Vasilea, Elena Părpărită, Mihaela Baicanb
a
Petru Poni” Institute of Macromolecular Chemistry, Physical Chemistry of Polymers Department, Iasi,
Romania;
b “Gr. T. Popa” Medicine and Pharmacy University, Iasi, Romania.
E-mail: cvasile@icmpp.ro
Polyvinyl alcohol (PVA) is a biodegradable synthetic polymer, innocuous, noncarcinogenic, has good biocompatibility and, excellent film-forming properties. PVA watersoluble film has good air barrier and resistance to oil. It could preserve food for longer time
and keep fresh. Because of the good biological activities of chitosan and PVA, a combination
of them may have beneficial effects on the biological characteristics of the mixed films1.
Polymer-layered silicate nanocomposites have attracted strong interest in today’s
materials research, due to the possible impressive enhancements of material properties,
comparatively with those of pure polymers.
Several starch / poly (vinylalcohol) / montmorillonite nanocomposites have been
subjected to surface modification by physical treatments such as dielectric barrier
discharge (DBD) exposure and coating with proteins or polysaccharides (chitosan) to
improve their biocompatibility. It has been established that the enhancement of the surface
characteristics depends on the type and concentration of incorporated nanoparticles as
well as on the treatment applied. Coupling of DBD exposure and coating techniques
appears to be highly efficient in creating antimicrobial and functional surfaces.
Freeze/thawing is another eco-friendly method to produce PVA–based materials, in
which repeated freezing and thawing cycles result in higher degree of crystallization of
PVA chains and produce a highly elastic hydrogel. As the number of cycles increases, the
percentage of crystalline regions within the hydrogel increases too; resulting in a stiffer
structure. Addition of chitosan and nanoclays in PVA composition superior physical,
mechanical and thermal characteristics and will improve the biocompatibility and will
impart to the materials antibacterial and antiacidic, antiinflamatory, antidiabetic
properties. Untreated and treated surfaces have been comparatively studied by contact
angle measurements, FT-IR spectroscopy, XRD and microscopy.
Acknowledgements:
Financial support from Romanian UEFISCDI through the bilateral collaborations Romania Greece
571/2012: Smart, Safe, Health-promoting, Green Food Packaging and Romania Slovenia 525/2012:
Functionalization of synthetic polymers for development of new antimicrobial packaging is gratefully
acknowledged
References:
1. Tripathi S., Mehrotra G.K., Dutta P.K., International J. Biological Macromolecules , 2009 45(4):372-6
15
COST FA0904
Molecular Probes For Oxygen Monitoring
In Food Packaging
S. Santoro, C. Portugal, J. C. Lima, J. G. Crespo, I. M. Coelhoso
REQUIMTE/CQFB, Dep. Química, FCT, Universidade Nova de Lisboa
2829-516 Caparica, Portugal
E-mai:l imrc@fct.unl.pt
The main cause of most food-spoilage is oxygen, since its presence allows a myriad of
aerobic food-spoiling microorganism to grow and thrive. Oxygen spoils also many foods
through the enzyme-catalysed reactions, destruction of ascorbic acid and the oxidation of a
wide range of flavours. For this reason, keeping the food in an atmosphere that is low in
oxygen concentration features strongly in most current, popular methods of food
packaging and storage. A major problem with food packaging is the lack of a simple,
inexpensive oxygen indicator to show that the package is intact and that oxygen level is not
significant [1,2].
The use of fluorophores as molecular probes is an attractive technology for non-invasive,
non-toxic and online detection of several parameters, such as temperature and oxygen
concentration [3]. A fluorophore is a fluorescent chemical compound that can re-emit light
upon light excitation. Optical sensors are prepared by dispersing fluorophores in a matrix
and are based on the measurement of one of the various parameters known in ﬂuorescence
that strongly depends from the environmental (i.e. intensity, lifetime and quenching) [4].
The aim of this work is the preparation of an intelligent food packaging material to give
information about the enclosed atmosphere; in particular to detect the oxygen level. The
novel food packaging materials were prepared by the dispersion of a molecular probe in
polymeric matrixes such as, polystyrene and poly 3-hydroxybutyrate-co-3hydroxyvalerate.
The response of the film to the oxygen concentration was evaluated by measurements of
fluorescence. The effects of the dispersion of the molecular probe on the barrier and
chemical-physical properties of the food-packaging materials were also evaluated.
References:
1.
2.
3.
4.
A. Mills, Chemical Society Reviews 34 (2005), 1003-1011.
M. E. Guynot, S. Marìn, V. Sachis, J. Ramos, Journal of Food Protection 66 (2003), 1864-1872.
C.-S. Chu, Y.-L. Lo, T.-W. Sung, P hotonic Sensors 3 (2011), 234–250.
Rharbi, A. Yekta, M. A. Winnik, Anal. Chem. 71 (1999), 5045-5053.
16
COST FA0904
SESSION 3: MECHANICS AND
RHEOLOGY
17
COST FA0904
Institute of Mechanics and its Activities in European Research
Area
Vasil Kavardjikov
Institute of Mechanics –BAS, Sofia, Bulgaria
E-mail: kavarj@imbm.bas.bg
The development of the colleaque of mechanics in Bulgaria Academy of Sciences (BAS)
since creation the Institute of Technical Mechanics in 1962 and his successor – Institute of
Mechanics & Bismechanics (in 1977) until 2010, when the Central Laboratory of
Physicochemical Mechanics was joined to the Institute of Mechanics (IMech) is revealed.
Six scientific directions are included in the Institutes’ actual structure: - Mechanics of
Multibody Systems, Solid Mechanics, Fluid Mechanics, Physicochemical Mechanics,
Biomechanics and Mathematical Modeling & Numerical Symulations. It is pointed out that
IMech is a multy profile scientific organization in which specialests with different basic
university education – mathematicians, physicists, mechanical, chemical, civil, electrical and
IT engineers, as wel as specialists in biomechanics are working. Young people are about
20% of them. This enables the Institute to work on a wide range of research and applied
projects in the field of mechanics.
Intrernational activities of researchers over the years that include join studies with
scientists from many institutions and universities in Europe, America and Asia illustrate
these capabilities. A special emphasis is placed on the current cooperative studies of IMech
scientists in the European Research Area. The modern experimental equipment at the
Institute and selected scientific results, as well as the publication activities of researchers are
presented also.
18
COST FA0904
Rheology Of Functional Luminescent Polymer Nanocomposites
Stanislaw Frackowiak, Marek Kozlowski
Wroclaw University of Technology, Wroclaw, Poland
E-mail: stanislaw.frackowiak@pwr.wroc.pl
Visible light emitting compounds consist of at least two materials, matrix and optically
excited activator (usually a metal with 2d or 4f electron configuration). The color and
emission time strongly depends on which activator was used. To minimize the influence of
external factors many researches are focused on implementing it into organic matrix, such
as polymers. Nanocomposites prepared by melt blending were investigated. Two different
luminescent fillers were used for composites preparation. Lutetium oxide activated with
Eu3+ which is a very promising phosphor for detection of ionizing radiation (especially for
medical imaging) and a phosphorous based filler exhibiting an after glow effect. For
polymer matrix polylactid acid (PLA), polycarbonate (PC) and poly (methyl methacrylate)
(PMMA) were investigated. To fully evaluate properties of obtained materials melt
rheology (Fig.1), tensile and UV-VIS transmittance tests were performed.
Fig.1. Melt viscosity of PLA composites filled with 10% of different phosphorous fillers
19
COST FA0904
Reinforcement Of Silica/PDMS Nanocomposites: Impact Of
Charges Functionalization On Mechanical Properties
Caro-Bretelle Anne-Sophie1, Ienny Patrick1, Mariot David1, Ganachaud François2
Advanced Polymer Materials, Ecole des Mines d’Alès, Alès, France
Charles Gerhardt Institute, UMR5253, ENSCM, Montpellier, France
E-mail: Anne-Sophie.Caro@mines-ales.fr
1
2
This study is focused on mechanical behavior of nanocomposites and especially on the
influence of mechanical load transition charge-matrix on global macroscopic properties. It
is now well known that traditional elastomer properties as Payne1 and Mullins2 effects are
closely related to microstructural conformation or interface charge/matrix property but
researchers are often unanimous on the origin of these phenomena3,4. The aim of this work
is to establish a link between chemical surface silica property (number of surface silanols
by NMR), matrix properties (molecular mass by swelling measurements) and Payne and
Mullins effect. Therefore a model composite is elaborated via extrusion/injection process
with a silica mass concentration of 40%. Some of the fillers are use after surface
modification with coupling or covering agents (with or without chemical link with matrix).
The microstructural state is first observed and analyzed by optical and MEB
measurements. We considered that observed change in microstructure composites is not
significant. The obtained results are:
• The amplitude of Payne effect is enhanced as the number of surface silanols increase
• The Mullins effect is maximized when the molecular mass between two reticulation
points is increased
• The ultimate stress is not really sensitive to surface treatment
• The ultimate strain behave as molecular mass.
References:
1. Kraus G.J. Apl. Polym. Sci. 1984;39:75-92
2. Mullins LJ. Rubber Res. 1947; 16:275–289
3. Maier PG et al. Kaut Gummi Kunstst. 1996;49:18-21
4. Cassagnau P et al. Polymer 2003;44(21):6607-6615
20
COST FA0904
Relaxation Properties Of Polymer Systems
Frederika Popovska-Pavlovska1, Aneta Vasiljevic-Sikaleska2
Integrated Business Institute, Skopje R. Macedonia
E-mail: f_popovska@t-home.mk
Complete rheological characterization, with special attention to relaxation
properties, of polymer systems under dynamic and steady state conditions in a molten and
solid state was performed. Dynamic experiments were carried out in the region of linear
viscoelasticy at small deformations of 1%. Some rheological characteristics were generated
using the correlation between dynamic and steady state properties, which was confirmed
to exist [1-3].
Using the non-linear regularization method [4] with data obtained from parallel plate
measurements and those generated the relaxation spectrum, F (θ ) , for a given system was
calculated. The polymer systems were five neat polymers, four binary mixtures with
different composition and concentration and one nanocomposite material based on
PVC/PEMA as a matrix with 5% montmorilonite nanoparticles [2,3,5,6].
The obtained results show that relaxation spectra of miscible mixtures lie between
neat polymers which is not the case with immiscible blends. The nanocomposite material
relaxation spectrum is also between neat polymers but higher than its matrix.
There is a good correspondence between functions experimentally determined and
those calculated [2,3,5].
As a whole, the interrelation among the set of functions used in the linear viscoelastic
theory and the existing correlation between dynamic and steady state properties enable to
calculate, or at least to predict, the other quantities under different stressing or straining
conditions if limited experimental viscoelastic data are known not only for pure polymer but
also for polymer mixtures and nanocomposite composed of polymer mixture and
nanoparticles.
Keywords: viscoelasticity, relaxation time spectrum, nonlinear regularization
References:
1. Vinogradov, G.V., Malkin, A.Y., Rheology of polymers, Mir Publishers, Moskow, 1980
2. Vasiljevic-Sikaleska, A., Flow induced microstructural changes in polymer blends, PhD Thesis, 2013
3. F.Popovska-Pavlovska, A.Trajkovska et al., Macromolecular Symposia, 149, (2000), 191
4. Malkin, A. Y., Int.J. Appl. Mech, Eng., 11, 2, (2006), 235
5. Vasiljevic-Sikaleska, A., Popovska-Pavlovska, P., Mat. Sc. and Eng., 40 (2012), 1
6. Vasiljevic-Shikaleska,A., Popovska-Pavlovska, F. et. al., J.Appl.Pol.Sc, 118, 3, (2010), 1320
21
COST FA0904
PP/MWCNT/OC Nanocomposites – Rheological And Mechanical
Properties
Evgeni Ivanov1, Ivanka Petrova1, Rumiana Kotsilkova1, Clara Silvestre2, Sossio
Cimmino2, Donatella Duraccio2, Marilena Pezzuto2
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,
E-mail: ivanov_evgeni@yahoo.com
1
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. Only few attempts have
been made to compare the mechanical properties of the conventional binary
nanocomposite to a ternary nanocomposite, which combines carbon nanotubes and
nanoclay as reinforcement in polypropylene matrix. In this study the effect of the MWCNTs
and organoclay combinations on the structure, rheological and mechanical properties of
the PP/MWCNT/OC nanocomposites is investigated and compared with those of the neat
polymer and the two-phase blends.
Keywords: polypropylene, multiwall carbon nanotubes, organo-clay, ternary nanocomposites,
rheological properties, mechanical properties
Acknowledgments:
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.
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., et al., Journal of Applied Polymer Science, vol. 115 (6), 3576–3585, 2010.
22
COST FA0904
Characterization By AFM And Nano-Indentation Method Of
Some Stratified Nanocomposites Destined To Food Packaging
Elena Pâslarua, Yuliy Tsekovb, Silvestru B. Munteanuc, Rumiana Kotsilkovab,
Cornelia Vasilea
Petru Poni” Institute of Macromolecular Chemistry, Physical Chemistry of Polymers Department, Iasi,
Romania;
b Open Laboratory for Experimental Mechanics, Institute of Mechanics, Bulgarian Academy of Sciences,
Sofia, Bulgaria;
c “Al. I. Cuza” University, Faculty of Physics, Iasi, Romania.
E-mail: elena.paslaru@icmpp.ro
a
The investigation of surface properties of polymeric materials intended to be used in
food packaging applications is a key step for understanding the nature of interactions
between the package and food.
The stratified composites were obtained using two different substrates namely poly
(ethylene) (PE) and poly (lactic acid) (PLA). The PE was coated with a natural
polysaccharide (chitosan) by spreading method and onto PLA were deposited silver
particles and silver particles incorporated in PLA and chitosan matrices by electrospraying
/ electrospinnig. To improve the surface adhesion, the substrates were previously plasma
activated.
The surface morphology was evaluated by atomic force microscopy (AFM) and
scanning electron microscopy (SEM). Micro-adhesion and nano-indentation tests, and
contact angle titrations were also performed.
By these coatings the polymeric substrates surface properties were improved such as
micro-adhesion, nano-mechanics (hardness and Young’s modulus), contact angle and also
the obtained stratified composites presents pH-sensitivity and antibacterial activity. It was
also found a relationship between the surface morphology and nano-mechanical properties
of the polymeric material.
Acknowledgements:
The authors acknowledge the financial support given by COST Action FA0904 and UEFISCDI through
research projects.
References:
1. Somorjai G.A, Li Y. (2010) Introduction to Surface Chemistry and Catalysis (Wiley, Hoboken, NJ), 2nd
Ed.
23
COST FA0904
SESSION 4: PERFORMANCE OF PNFP
24
COST FA0904
Biofilm Formation On Polyethylene By Plastic Degrading
Bacteria
Alex Sivana, Irit Gilanb
Ben Gurion University, Beer Sheva, Israel
E-mail: sivan@bgu.ac.il
b Ben Gurion University, Beer Sheva, Israel
a
Polyethylene (PE) is the most abundant synthetic polymer and appears to be one of the
most inert plastic polymers. This promotes the continuous increase in PE waste worldwide
in the order of 60-80 million tons/year imposing grave environmental hazards. Since
plastics are also buoyant, an increasing load of plastic debris is being dispersed over long
distances, and when finally settle in sediments may persist for centuries. Recycling of the
plastic waste handles only a small percentage of the problem and therefore, gives rise to
the need for safe, appropriate ways to dispose of the plastic waste, which brought forth the
concept of biodegradation.
We have shown that unique bacteria are capable of growing and forming biofilms on PE.
Two of the major components of the extra cellular polymeric substance (EPS), i.e. DNA and
protein, were shown to increase the stability of the biofilm. The formation of biofilms
increase the biodegradation efficacy of PE by strain C208. Apparently, the bacterial
adhesion to the PE enables the microorganism to be in close contact with its substrate.
Characterization of the biofilm and revealing its composition may shed some light on its
mode of action and facilitate its use in biodegradation processes.
This study suggests that extracellular eDNA and proteins play multiple roles in structure
and function of the biofilm matrix and are, presumably, involved in detachment processes
via quorum-sensing mechanisms. Some of these proteins are probably extracellular
proteolytic enzymes operating within the matrix. This approach could be further utilized to
characterize other EPS polymers
25
COST FA0904
Comparative Performance Of Ipp Based Nanocomposites
Versus Multilayered Material For Shelf-Life Of Ready-To-Eat
Meat Products
Zehra Ayhan1*, Okan Estürk1, Birgül Özcan2, Donatella Duraccio3, Clara Silvetre3,
Sossio Cimmino3
1Mustafa
Kemal University Food Engineering Department Hatay Turkey
2Mustafa Kemal University Biology Department Hatay Turkey
3Istituto di Chimica Tecnologia dei Polimeri-CNR Pozzuoli Naples Italy
E-mail: *zehra.ayhan@gmail.com
The aim of this work was to compare performance of iPP based nanomaterials with
multilayer material for shelf life of ready to eat sliced salami. Nano-iPP film and activenano-iPP film were prepared with the addition of 1% of nanoclay, and with 1% nanoclay
plus 5% poly-β-pinene (PβP), respectively. Sliced salami was packaged using these
nanomaterials and multilayer material (PP/PA/EVOH/PE) under air, vacuum and active
MAP conditions (50% CO 2 -50% N 2 ) and cold stored at 4°C. Packaged products were
monitored for physical (color, L* value-brightness and a* value-redness), chemical (lipid
oxidation as TBARs), microbial (total aerobic bacteria) and sensory properties (taste)
during storage period of 90 days. In general, L* values of vacuum applications were tended
to be lower than that of air and MAP applications for all tested materials. However, a* value
indicating redness decreased notably in all applications during increased storage, possibly
due to formation of brown color pigments caused by oxidation. Overall the product color
was preserved best by the multilayered material under vacuum and high CO 2 -MAP
applications. TBARS values indicating lipid oxidation of all vacuum applications were lower
than that of air and MAP applications. High TBARS values were possibly due to high oxygen
concentration of MAP applications leading to increased lipid oxidation. The PβP containing
material was more effective on bacteria than yeast and molds and no bacterial growth was
observed under vacuum during 75 days of storage. The total bacterial load under vacuum
of all tested materials was 1-2 log CFU g−1 less than that of MAP applications at the end of
the storage. The product taste was acceptable for 75 days of storage for multilayer material
under both vacuum and high CO 2 -MAP.This period was limited to 50 days for both
nanomaterials under vacuum and 30 days for the nanomaterials using air and high CO 2 MAP due to visible mold growth on the product surface. In conclusion, physical, chemical,
microbial and sensory quality of the products were best preserved in vacuum and high CO 2
applications using multilayer material with the product shelf-life of 75 days. The shelf-life
of the sliced salami was 50 days for nanomaterial containing PβP under vacuum; however,
it was limited to 30 days under high CO 2 -MAP application.
Acknowledgements:
This work was supported by TUBİTAK-COST project (111O333), COST ACTION FA0904 and the
Commission of Scientific Research Projects of Mustafa Kemal University (1105 Y 0112).
26
COST FA0904
The Influence Of Oxide Nanoparticles On The Thermal
Properties Of Polymer Matrix
Branka Pilića, Oskar Beraa, Mirjana Jovičića, Jelena Pavličevića, Tanja Radusinb
aFaculty
of Technology, University of Novi Sad, 21000 Novi Sad,
Bulevar cara Lazara 1, Serbia
bInstitute of food technology, University of Novi Sad, 21000 Novi Sad,
E-mail: brapi@uns.ac.rs
It is well known that the incorporation of nanoparticles in polymer matrix has a significant
impact on the properties of nanocomposites. One of the properties of a polymer which can
be profoundly affected by nanoparticles is the glass transition temperature, Tg.
Investigation of the glass transition of nanocomposites can lead to different results
depending on the materials involved and the method of mixing the nanoparticles with
polymer matrix. The influence of the nanoparticles in polymer composites on Tg is
controversial since Tg of nanocomposites depends on a variety of factors. In some cases
polymer nanocomposites show an increase of the Tg but in other cases a decrease in Tg is
observed. A series of polymer nanocomposites based on polystyrene, poly(methyl
methacrylate), poly(lactic acid) with different type and content of oxide nanoparticles
(silica, titania, alumina) were prepared. The influence of polymer chemical structure,
method of preparation, filler size, filler loading, dispersion conditions on Tg obtained by
differential scanning calorimetry (DSC) was reported.
Key words: polystyrene, poly(methyl methacrylate),
nanoparticles, glass transition temperature Tg
poly (lactic acid), silica, titania, alumina,
27
COST FA0904
Spectroscopic Characterization Of Temperature-Responsive
Polymers
Lenka Hanykova
Charles University in Prague, Faculty of Mathematics and Physics,
V Holesovickach 2,
Prague 8, Czech Republic
It is now well established that acrylamide (AAm)-based hydrogels and hydrogels of some
other polymers undergo a volume phase transition (collapse) induced by a small change in
external parameters like solvent composition, temperature, pH etc. It is also well known
that AAm-based polymers and other polymers with amphiphilic character in aqueous
solutions exhibit a lower critical solution temperature (LCST). They are soluble at low
temperatures, but heating above the LCST results in phase separation which. On the
molecular level, both phase separation in solutions and similar volume phase transition
(collapse) in crosslinked hydrogels are assumed to be a macroscopic manifestation of a
coil-globule transition. Stimuli-responsive hydrogels that undergo abrupt changes in
volume have potential applications in the creation of “smart” material systems (actuators.
sensors, switching devices etc). The fact that LCST of thermoresponsive AAm-based
polymers can be adjusted by copolymerization or using additives near to human body
temperature (37 °C) makes them viable as drug release systems. They can be also used in
column packing materials for temperature-responsive liquid chromatography. A similarity
to the LCST behaviour of elastin-like polypeptides and to thermal denaturation of proteins
in aqueous solution also makes them interesting from an academic point of view.
We combined NMR spectroscopy with other physical methods to characterize structures
and interactions in aqueous solutions and gels of series of responsive multicomponent
polymer systems with various architecture. Information how the architecture of the
polymer system affects the phase-separated globular structures on various level was
obtained. This includes information on the sizes and shape of these structures, on the
fraction of monomeric units directly involved in these structures, on changes in hydrogen
bonding of specific funtional groups, on changes in the arrangement and order of water
molecules as well as on changes in the dynamics both of polymer segments and water
molecules due to the phase transition.
28
COST FA0904
New Potential Applications In Food Packaging Of The
Electrospinning / Electrospraying Method Used For Polymer
Surface Modification And To Obtain Of Nano(Micro)Structures
From Antimicrobial Agents As Chitosan, Silver And Various
Bioactive Agents. I. Polylactic Acid / Silver NP / Vitamin E
Bionanocomposite Fibers With Antibacterial And Antioxidant
Activity
Bogdanel Silvestru Munteanua, Zeynep Aytaçb, Tamer Uyarb, Cornelia Vasilec
”Al. I. Cuza” University Iasi, Faculty of Physics, 11 Carol I bvd, Iasi, Romania
UNAM – Institute of Materials Science and Nanotechnology, Bilkent University, Ankara 06800, Turkey
c Romanian Academy, “P.Poni” Institute of Macromolecular Chemistry, 41A Grigore Ghica Voda Alley,
700487, Iasi, Romania
E-mail: msbogdanel18@yahoo.com
a
b
The antibacterial properties of silver nanoparticles were
combined with the antioxidant activity of Vitamin E by
incorporation of these two components into the PLA
nanofibers. The obtained nanofibers were characterized
by SEM, TEM – Fig.1, XRD. The antioxidant activity of the
incorporated Vitamin E was evaluated. The released
amount of silver ions from the water immersed fibers was
determined by Inductively Coupled Plasma-Mass
Spectrometry (ICP-MS). It has been established that the
content of silver in nanofibres remains approximately
constant even after 12 days of immersion in deionized
water, from which it can be concluded that the
antimicrobial properties of the fibers are preserved after
immersion in water. It has been established that vitamin
E imparts an efficient antioxidant activity to PLA
nanofibres.
Figure 1: TEM image of
PLA/AG/Vitamin E nanofiber.
29
COST FA0904
POSTERS
30
COST FA0904
Properties characterization of In situ modified biodegradable
films from barley
Marilena Pezzuto a, Duraccio Donatella a Gabriella Santagata a, Razzaq Hussam b,
Sossio Cimmino a and Clara Silvestre a
Institute of Chemistry and Technology of Polymers, Pozzuoli, Naples, Italy
b The New Zealand for Plant and Food Research (PFR), Lincoln- Canterbury, New Zealand
E-mail: marilena.pezzuto@ictp.cnr.it
a
Advances in developing biodegradable plastics for coating and packaging are progressing
at fast pace and successful products are being manufactured and marketed nowadays(1).
The principal raw material for the majority of these products is starch(2-3). Recently other
kinds of non starch polysaccarides have been introduced; β-glucan derived by barley is one
of these. The aim of this study is to correlate the structure and the morphology of films of
barley β-glucan, obtained by solvent casting with the thermal, mechanical and barrier
properties in dependence on of β-glucan extraction conditions.
References:
1) T.I. Shkvarkina et al.: "Modified starches as improvers of bread quality", & KHLEBOPEK.
Konditer. Prom-ST. 1975, (6), 15-18, Chemical abstracts, vol. 83, no. 15, 13th October 1975,
page 390, abstract no. 130218b, Columbus, Ohio, US.
2) S. Chattopadhyay, R. S. Singhal, P. R. Kulkarni, Carbohydrate Polymers, 34, 4, 1997, 203–
212.
3) P.J. Meikle , N.J. Hoogenraad, I. Bonig, A. E. Clarke and Bruce A. Stone, The Plant Journal, 5, 1 ,
1-9, 1994).
31
COST FA0904
Prediction Of Relaxation Time Spectrum Of Polymer Blends
Aneta Vasiljevic-Sikaleska1, Frederika Popovska-Pavlovska2
Integrated Business Institute, Skopje, R. Macedonia
E-mail: aneta@fbe.edu.mk
In order to predict viscoelastic properties of real polymeric materials in a wide
range of deformation relaxation time spectrum was used.
Neat polymers (PVC, PMMA, PEMA, PBMA and PP) and their binary mixtures, with
PVC as matrix, were prepared by melt blending in a brabender mixer.
Rheological characterization of samples, under steady state shear or oscillatory
shear, within the linear viscoelasticity region, was carried out by different techniques and
methods. [1]
⋅
The functions of storage modulus, G ' (ω ) , loss modulus, G" (ω ) , shear viscosity, η (γ )
and dynamic viscosity, η ' (ω ) , were obtained. The relaxation time spectrum F (θ ) was
calculated based on experimentally determined G ' (ω ) and G" (ω ) dependencies. [2,3]
Effects of both, the nature and the concentration of the second polymer constituent,
on viscoelastic properties were studied thoroughly.
The comparison of all rheological functions shows that samples behave as shear
thinning fluids obeying the power law. Materials with increased storage and loss moduli
are obtained when PVC is blended with PMMA and PEMA, where as in the case of
immiscible PVC/PBMA and PVC/PP mixtures the rheological functions are below those of
neat PVC. Generally, the observed changes are more pronounced when the concentration of
the second polymer constituent is increased up to 30% wt.[3]
Concerning the relaxation properties, it was noticed that mixtures have longer
relaxation times compared to neat PVC, which was also confirmed with the values of
relaxation times determined experimentally as reciprocal frequency at the cross-point
between G ' (ω ) and G" (ω ) curves[4]. As the concentration of the second constituent was
increased the cross-point shifts toward lower frequencies i.e. longer relaxation times.
Summarizing, although relaxation time spectrum is impossible to be directly
measured it can be evaluated on the basis of experimental data (like dynamic moduli
functions, creep etc.) and used for modelling other material functions (such as the
relaxation modulus, shear viscosity, steady-state compliance and others) having in mind
the correlation between dynamic and steady state properties, which was confirmed to
exist.
References:
1. Vasiljevic-Sikaleska, A.,Flow induced microstructural changes in polymer blends, PhD Thesis, 2013
2. Malkin, A. Y., Int.J. Appl. Mech, Eng., 11, 2 (2006), 235-243
3. Malkin, A., Y., Masalova, I., Rheol Acta, 40, (2001), 261
4. Vega, J. F., et al., J. Rheol., 48, 3, 2004, 663-678
32
COST FA0904
Rheological Properties And Characterization Of
PP/MWCNT/Clay Hybrid Nanocomposites
I. Petrovaa, E. Ivanova, R. Kotsilkovaa, D. Duracciob,
M. Pezzutob, S. Cimminob, C. Silvestreb,
a
OLEM, Institute of Mechanics, Bulgarian Academy of Sciences, Sofia, Bulgaria
b Institute of Chemistry and Technology of Polymers, CNR, Pozzuoli, Italy
E-mail: ivanka.petrova@yahoo.com
In this study, the rheological control for estimation of the degree of clay exfoliation
and carbon nanotube dispersion in polypropylene was studied. The nanocomposite
hybrids were processed by extrusion processing of the PP/Clay and the PP/MWCNT
masterbatches with polypropylene in different proportions to produce three-phase
nanocomposites with an interesting combination of properties.
The rheology method will be used for control of the dispersion quality of the clay
nano-layers and carbon nanotubes and their combination in the polypropylene matrix. The
degree of nanofiller dispersion in polymer matrices will be determined using experimental
data from the low amplitude oscillatory shear combined with rheological models.
Acknowledgements: The study was partially supported by the COST FA0904
References:
1. Kotsilkova R. Thermoset nanocomposites for engineering applications. Smithers Rapra Technology,
Shawbury, Shrewsbury, UK-USA, 344, 2007.
2. Kotsilkova R, Ivanov E, Krusteva E, Silvestre C, Cimmino S, Duraccio D. Evolution of Rheology,
Structure and Properties around the Rheological Flocculation and Percolation Thresholds in Polymer
Nanocomposites. Chapter In: “Ecosustainable Polymer Nanomaterials For Food Packaging” (Silvestre
C, Cimmino S, Eds), Taylor & Francis Books, Inc (2012) pp.55-87 (in press).
33
COST FA0904
Thermal Degradation Of Bionanocomposites Based On
PLA/Silica Nanoparticles
Tanja Radusina, Branka Pilićb, Oskar Berab, Ivan Ristićb, Aleksandra Novakovića
aInstitute
of food technology, University of Novi Sad, 21000 Novi Sad,
bFaculty of Technology, University of Novi Sad, 21000 Novi Sad,
E-mail: tanja.radusin@fins.uns.ac.rs
Poly (lactic acid) (PLA) has recieved more attention due to its biocompatibility,
biodegradability and thermoplastic processibility. However PLA has very poor thermal
stability and its highly sensitive to heat. Addition of silica nanoparticles in PLA polymer
matrix can improve thermal stability and change the thermal degradation model due to
specific nanoparticle performances. The aim of this research was to determine the
influence of different silica content on degradation kinetics of neat polymer. Neat PLA and
PLA films with 0.2, 0.5, 1 and 3 wt % of nanosilica were prepared by solution casting
method in chloroform. Thermo gravimetric analysis was performed on the TG analysis
device 701 LECO. Analyses were performed in defined temperature range from 25 to
600°C. Samples were subjected to thermo gravimetric analysis (TGA) in an inert
atmosphere of nitrogen with different heating rates (3, 5, 10 and 20°C/min)
respectively. To calculate the kinetic parameters of the degradation of the nonisothermal DTG curves, different models based on the assumption that the reaction rate for
a given level of conversion depends only on the temperature (Ozawa-FlynnWall (OFW), Kissinger Akahira-Sunose (KSA) and Friedman (FR)) were used. The kinetic
study of thermal decomposition enabled the prediction of PLA nanocomposites life-time.
Activation energy and life time values showed the increase for addition of silica
nanoparticles up to 0.5%, and decrease for higher load of silica content (1 and 3%) taking
in consideration that the lowest value was for neat PLA. This result is pointing that the
addition of only small amount of silica nanoparticles can have positive influence on thermal
stability of polymer matrix. For higher silica content this influence is not so intense, but
also has improvement compared to neat PLA.
Key words: Poly (lactic acid) (PLA), silica nanoparticles, thermal stability, lifetime
34
COST FA0904
Dielectric Thermal Analysis As A Study Technique For The
Characterization Of Nanocomposite Materials
For Food Packaging
Aleksandra Porjazoska Kujundziski1, Dragica
Chamovska2, Tanja Radusin3, Antonella Marra4, Donatella
Duraccio4, Branka Pilic5, Clara Silvestre4
1International
Balkan University, Faculty of Technical Sciences,
“Tasko Karadza” 11A, Skopje, R.Macedonia,
E-mail: aporjazoska@ibu.edu.mk
2Ss. Cyril and Methodius University, Faculty of Technology and Metallurgy,
“Rugjer Boshkovic” 16, Skopje, R.Macedonia
3University of Novi Sad, Institute of food technology, Bulevar cara Lazara 1, Novi Sad, Serbia
4Istituto di Chimica e Technologia dei Polimeri (ICTP)-CRN, Via Campi Flegrei 34, Pozzuoli, Italy
5University of Novi Sad, Faculty of Technology, Bulevara cara Lazara 1, Novi Sad, Serbia
Except the various restrictions in the application of conventional polymer packaging
materials for food, such as weak mechanical properties, questionable barrier properties;
uncertain optical properties, etc., their origin from nonrenewable sources and their
environment impact after the disposal, should be taken into consideration. Therefore the
introduction of biodegradable polymers in the food packaging industry is in the focus of
scientific interest. Due to a high mechanical strength and excellent processing capabilities,
one of the biopolymers that attracts particular attention is poly(lactic acid) (PLA). But, the
low toughness and big brittleness restricts its application. Some of the strategies applied to
upgrade mechanical properties, thermal stability, barrier properties, or optic features of
PLA is an introduction of nanofillers into the polymer matrix. Nanoscaled fillers, in which at
least one dimension is between 1 and 100 nm, involved in a polymer matrix, create big
interfaces with the matrix leading to their superior effect on the characteristics of the
nanosystem in respect to their microscaled counterpart. Along with the silica particles
(SiO 2 ) which are very light, featured with good thermal stability, high modulus and
strength, and low cost, titanium dioxide (TiO 2 ) draws a big importance in the application as
nanofiller. Namely, TiO 2 owns very good chemical reactivity, excellent photostability, it is
biocompatible, environmental friendly, and strong antimicrobial properties. In this study
an effort was made to recognize the possibilities of the application of dielectric thermal
analysis (DETA) in characterization of PLA/SiO 2 and PLA/TiO 2 nanocomposites for food
packaging applications. The dielectric properties of our interest, representing the polymer
behavior in the electric field, as, dielectric permittivity (ε’), dielectric loss (ε”), and phase
lag (tg δ), are associated to the chemical composition and structure of the polymer i.e. its
dipole moments, the temperature, the frequency and the voltage of the applied a.c.
electrical field.
Key words: DETA, poly(lactic acid), silica, titanium dioxide, food packaging
35
COST FA0904
DSC And Rheological Measurements Of Epoxy/Clay/Au
Nanocomposites
V. Angelov, E. Ivanov, R. Kotsilkova
OLEM, Institute of Mechanics, Bulgarian Academy of Sciences, Sofia, Bulgaria
E-mail: verislav@abv.bg , v.angelov@imbm.bas.bg
DSC technique measures the heat flow into or from a sample as it is heated, cooled
and/or held isothermally. For thermosetting resins, the technique provides valuable
information on glass transition temperatures (Tg), onset of cure, heat of cure, maximum
rate of cure, completion of cure and degree of cure. As the epoxy resin sits at room
temperature, it undergoes physical aging. Therefore the consequences of the 2nd and 3rd
Laws of Thermodynamics (entropy effects) cause the molecules to relax over time. When
the sample is heated during a DSC experiment, the time scale of the molecular motions are
very long in comparison to the time scale of the DSC experiment, and a large overshoot is
observed during Tg.
AR-G2 RHEOMETER & DMTA is instrument used to characterize the rheological
properties of materials, typically fluids that are melts or solution (wide viscosity range).
This instrument imposes a specific stress field or deformation to the fluid, and monitor the
resultant deformation or stress
The aim of this poster is to present some results from instrumental techniques (DSC
and AR-G2 RHEOMETER & DMTA) for investigation of two and three phase Epoxy/Clay/Au
nanocomposites prepared by “in-situ” polymerization. These techniques are very useful for
determining degree of cure, post curing temperature of thermosetting resins and degree of
dispersion of nanofillers in epoxy resin. This information is very important to achieve good
mechanical properties of the final nanocomposites.
Acknowledgements:
The study was partially supported by the project COST Action FA 0904. Also express my gratitude to
Assistant Professor Valeri Tzvetkov and Eng. Evelina Simeonova-Ivanova for joint work.
36
COST FA0904
Recycling Of PP Hybrid Bio-Based Composites Useful In Food
Packaging By Thermal Treatment Methods
Parparita Elenaa, Md. Uddin Azharb, Nistor Manuela-Tatianaa, Vasile Corneliaa
a
Romanian Academy, ‘‘P. Poni’’ Institute of Macromolecular Chemistry, Department of Physical
Chemistry of Polymers, Iasi, Romania
b Department of Energy and Materials, Okayama University, Okayama, Japan,
E-mail: elena.parparita@icmpp.ro
Because in the recent years, many developed countries are dealing with serious
sustainability problems, especially concerning energy needs and waste handling, it has
been focused more attention to recycling. Plastic wastes are of great importance due to the
increase of their production in recent years and waste plastics are also valuable source of
materials and energy when utilized properly. Biomass has lately attracted considerable
attention as a source of clean fuel, energy, and chemicals. Pyrolysis and gasification are
technologies aimed to convert carbonaceous materials such as coal, biomass, and waste
plastics into liquid and gaseous fuel, respectively. In this study composites based on
polypropylene and different types of lignocellulosic materials (wood: eucalyptus globulus
and Norway spruce; grasses: energy grass; crops: brassica rapa, and crops by-products:
pine cones) as fillers have been studied. The thermal/co-pyrolysis behavior of the
polypropylene/biomass waste composites has been investigated by thermogravimetry
(TG)/infrared spectrometry/mass spectrometry (MS) coupled methods. The volatile
compounds resulting during the thermal degradation were studied by in situ vapor phase
FT-IR spectroscopy and mass spectrometry techniques under a controlled
temperature/time program. The polypropylene/biomass waste composites were also
undergone to steam gasification in a dual-bed micro-reactor in a two-stage process for the
production of fuel gases. Gasification experiments were carried out at different gasification
temperatures, in absence and presence of Fe 2 O 3 /CeO 2 catalyst. The gases produced during
steam gasification were mainly H 2 , CO, CO 2 , CH 4, and some light-hydrocarbons. The
catalyst increases the synthesis gas and hydrogen amounts. The maximum hydrogen yield
was around 752 cc/g sample for steam gasification and 1300 cc/g sample for catalytic
gasification.
Acknowledgements:
Financial support from Romanian UEFISCDI through the bilateral collaborations Romania Greece
571/2012: Smart, Safe, Health-promoting, Green Food Packaging and Romania Slovenia 525/2012:
Functionalization of synthetic polymers for development of new antimicrobial packaging is gratefully
acknowledged
37
COST FA0904
Scratch and Nanoindentation Investigation of the Mechanical
Properties of Three-phase Polypropylene Nanocomposites
Yuliy Tsekov1, Ivanka Petrova1, Evgeni Ivanov1, Verislav Angelov1, Rumiana
Kotsilkova1, Clara Silvestre2, Sossio Cimmino2, Donatella Duraccio2,
Marilena 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.
E-mail: yu.tsekov@imbm.bas.bg
2 Institute of Chemistry and Technology of Polymers, CNR, Via Campi Flegrei 34 Olivetti,
80078 Pozzuoli (NA), Italy.
The carried out mechanical investigations on the prepared by our team, in cooperation with
our colleagues from CNR, Italy, three-phase polypropylene nanocomposites give
comprehensive information about the micro- and nanomechanical properties and provide
information for better understanding the extent of reinforcement via nanoparticles.
The prepared nanocomposites have Polypropylene as matrix material and incorporate
organic clay (Cloisite 30B) and MWCNT fillers. The investigation and the following
comparison and analyses of the experimental results give good overview of the changes in
scratch coefficient of friction, hardness and elastic moduli exhibited with variation of the
fillers concentrations and presence.
These results can serve as a solid base for conducting additional experiments, improvement
of material design parameters and further research in order to create material suitable for
food packaging applications, which meets all European standards and regulations.
Furthermore a material, which is competitive to the conventional polymer materials we use
today.
Acknowledgments:
This work was carried out with the support of the COST FA0904 project.
38
COST FA0904
Nano-indentation and AFM Investigation of Three-phase Epoxy
Nano-composites
Peter Todorov, Verislav Angelov, Yuliy Tsekov, Ivanka Petrova, Evgeni Ivanov,
Rumiana Kotsilkova
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.
E-mail: pv_todorov@abv.bg
The mechanical and topological investigations, carried out by our team, on the prepared
three-phase epoxy nanocomposites give detailed information about the nano-mechanical
properties and good topological and phase separation, also parameters detection.
The nanocomposites prepared include epoxy as a matrix material and incorporate organic
clay Cloisite 30B and gold nanoparticles as fillers. The investigation and the subsequent
comparison and analyses of the experimental results give a good overview of the changes
in hardness, elastic moduli and inter-phase connections exhibited with variation of the
fillers’ concentrations.
The obtained results give a good understanding for inter-phase relation between the epoxy
matrix and the incorporated fillers and serve as a solid base for further investigation.
Acknowledgments:
This work was carried out with the support of the COST FA0904 project.
39
COST FA0904
COST ACTION FA0904 “Eco-sustainable Food Packagingbased on Polymer Nanomaterials”
INTERNATIONAL WORKSHOP
Characterization, Mechanics and Performance of Innovative Polymer Nanomaterials for
Food Packaging Application
24-25 September 2013, Varna, Bulgaria
DELEGATES
№
Name
1
ANGELOV, Verislav
2
AYHAN, Zehra
3
CARO-BRETELLE,
Anne-Sophie
4
CIMMINO, Sossio
5
COELHOSO, Isabel
6
FRACKOWIAK,
Stanislaw
7
HANYKOVA, Lenka
Affiliation
OLEM, Institute of Mechanics,
Bulgarian Academy of Sciences, Sofia
Mustafa Kemal University Food
Engineering Department, Hatay
Ecole des Mines d’Alès, Ales
Istituto di Chimica e Tecnologia dei
Polimeri, CNR, Pozzuoli (NA)
REQUIMTE/CQFB,FCT,Universidade
Nova de Lisboa, Lisbon
Country
E-mail
Bulgaria
verislav@abv.bg
Turkey
zehra.ayhan@gmail.com
France
Anne-Sophie.Caro@mines-ales.fr
Italy
sossio.cimmino@ictp.cnr.it
Portugal
imrc@fct.unl.pt
stanislaw.frackowiak@pwr.wroc.pl
Wroclaw University of Technology
Poland
Charles University in Prague, Faculty of
Mathematics, Prague
Centre des Matériaux des mines
d’Alès, Ales
Czech
Republic
Lenka.Hanykova@seznam.cz
France
Patrick.Ienny@mines-ales.fr
8
IENNY, Patrick
9
IVANOV, Evgeni
Bulgaria
ivanov_evgeni@yahoo.com
10
JAMES, Mattew
St Mary’s University College, London
UK
jamesm@smuc.ac.uk
11
KAVARDJIKOV, Vasil
Bulgaria
kavarj@imbm.bas.bg
12
KOTSILKOVA,
Rumiana
Bulgaria
kotsilkova@yahoo.com
13
KOZLOWSKI, Marek
14
LAGARON, Jose
Maria
15
MITCHELL, Geoffrey
16
MUNTEANU,
Bogdanel
17
PARPARITA, Elena
18
PÂSLARU, Elena
Wroclaw University of Technology,
Wroclaw
Novel Materials and Nanotechnology
Group, IATA-CSIC, Paterna, Valencia
CDRsp, IPL, Lisbon
CfAM, University of Reading, UK
”Al. I. Cuza” University Iasi, Faculty of
Physics, Iasi
‘‘P. Poni’’ Institute of Macromolecular
Chemistry, Iasi
‘‘P. Poni’’ Institute of Macromolecular
Chemistry, Iasi
Poland
marek.a.kozlowski@pwr.wroc.pl
Spain
lagaron@iata.csic.es
Portugal/
UK
geoffrey.mitchell@ipleiria.pt
Romania
msbogdanel18@yahoo.com
Romania
elena.parparita@icmpp.ro
Romania
elena.paslaru@icmpp.ro
40
COST FA0904
19
PETROVA, Ivanka
20
PEZZUTO, Marilena
21
PILIĆ, Branka
22
23
POPOVSKAPAVLOVSKA,
Frederika
KUJUNDZISKIPORJAZOSKA,
Aleksandra
Istituto di Chimica e Tecnologia
dei Polimeri, CNR, Pozzuoli (NA)
Faculty of Technology, University of
Novi Sad, Novi Sad
Bulgaria
ivanka.petrova@yahoo.com
Italy
marilena.pezzuto@ictp.cnr.it
Serbia
brapi@uns.ac.rs
Integrated Business Institute, Skopje
FYRMace
donia
f_popovska@t-home.mk
International Balkan University, Skopje
FYRMace
donia
aporjazoska@ibu.edu.mk
Serbia
tanja.radusin@fins.uns.ac.rs
Italy
clara.silvestre@ictp.cnr.it
Israel
sivan@bgu.ac.il
Institute of food technology,
University of Novi Sad, Novi Sad
Istituto di Chimica e Tecnologia dei
Polimeri, CNR, Pozzuoli (NA)
Department of Biotechnology
Engineering, Ben-Gurion University of
The Negev, Beer Sheva
24
RADUSIN, Tanja
25
SILVESTRE, Clara
26
SIVAN, Alex
27
STAVSIDOU, Ioanna
COST office, Brussels
Belgium
ioanna.stavridou@cost.eu
28
TODOROV, Peter
Bulgaria
pv_todorov@abv.bg
29
TSEKOV, Yuliy
Bulgaria
yu.tsekov@imbm.bas.bg
30
VAHA-NISSI, Mika
VTT, Helsinki
Finland
Mika.Vaha-Nissi@vtt.fi
31
VASILE, Cornelia
Romania
cvasile@icmpp.ro
32
VASILJEVICSIKALESKA, Aneta
Romanian Academy, ‘‘P. Poni’’
Institute of Macromolеcular
Chemistry, Iasi
FYRMace
donia
aneta@fbe.edu.mk
Integrated Business Institute, Skopje
40
ADMINISTRATIVE CONTACTS
COST Action FA0904 Chair
Dr Clara Silvestre
Istituto di Chimica e Tecnologia dei Polimeri (ICTP)
Consiglio Nazionale delle Ricerche (CNR)
Via Campi Flegrei 34 -Comprensorio Olivetti
80078 Pozzuoli (NA) - Italy
Tel: + 39 081 8675067
Fax: + 39 081 8675230
Email: silvestre@ictp.cnr.it / clarasilvestre@yahoo.it
Local Organiser and COST FA0904 Vice Chair
Prof. Rumiana Kotsilkova
Head of Department Physico Chemical Mechanics
Eng. Peter Todorov
Institute of Mechanics
Bulgarian Academy of Sciences
Acad. G. Bonchev Street, Block 4
1113 Sofia, Bulgaria
Tel: +359 2 979 6462 Fax: +359 2 870 74 98
E-mails: kotsilkova@yahoo.com / cost.varna@gmail.com
COST FA0904 Grant Holder (at CNR, Italy)
Dr Sossio Cimmino
Istituto di Chimica e Tecnologia dei Polimeri (ICTP)
Consiglio Nazionale delle Ricerche (CNR)
Via Campi Flegrei 34 Olivetti
80078 Pozzuoli (NA) Italy
Tel: +39 081 867 5068
Fax:+39 081 867 5230
Email: ictp_cnr.cimmino@yahoo.it / cimmino@ictp.cnr.it
41

Book of Abstracts - COST Action FA0904

Transcription

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