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Extended shelf-life biopolymers for sustainable and multifunctional food packaging solutions

Final Report Summary - NANOBARRIER (Extended shelf-life biopolymers for sustainable and multifunctional food packaging solutions)

Executive Summary:
NanoBarrier – executive summary
The overall objective of NanoBarrier is to realize innovative and safe multifunctional packing solutions by developing a sustainable nanotechnology-based platform and integrate it into biomaterials in a safe and responsible manner.
The objectives of the development of the nanotechnology platform is to significantly improve barrier properties of the biomaterials in addition to ensure multifunctionality of the packaging by developing sensors to detect oxygen, mechanical rupture, temperature and pH changes.
Effective sensors and barrier promoters were developed for smart packages and their production was up-scaled to kg/day quantities. The barrier promoters are based on nanostructured fibrillar materials, organic and inorganic nanoparticles and oxygen scavengers. They considerably reduce the permeability of the food packaging (jars, bottles, trays) towards humidity and atmospheric oxygen. At the same time, smart stimuli responsive sensors can indicate the decay of the packed food resulted from either package damage or wrong storage conditions. The sensors can be in the form of nanoparticles or nanocapsules printed or painted on the food package or thermo-sensitive tags. The sensors irreversibly react on the pH changes and humidity inside package, resulting from the food decay, or temperature changes during improper storage.

Demonstrator development with preselected processing technology was based on PLA, PET and MFC (microfibrillated cellulose). A process was developed to spray coat two of the demonstrators. The demonstrator products, base materials and resulting improvements of oxygen barrier were:
- thermoformed multilayer films – PLA/MFC/PLA: 3 times lower oxygen transition rate (OTR) than the benchmark PE/PA/PE film
- Stretch blow moulded bottle – bio-PET: showed three times reduction of OTR compared to PET.
- Injection moulded jar – PLA and MFC: four times reduction in the OTR was achieved compared to PP
- Blown, multilayer film – PLA and MFC: 25 % reduced OTR rel. to PLA was achieved.
Safety and environmental aspects of all materials used in demonstrators were thoroughly evaluated. Evaluation of potential risks from nanosized materials in biomaterial packaging showed that all tested materials exhibit low toxicity evaluated in cell cultures. Significantly reduced CO₂ footprints compared to benchmarks. Proper waste management chain was defined for all demonstrator products.
NanoBarrier was represented at the Packaging And Converting Executive Forum (PACE) in Amsterdam in February 2016. This event was chosen as an adequate alternative for the 2nd open seminar which was planned from the beginning. On this event, project results were presented and attracted the attention of main actors within the packaging sector.

Project Context and Objectives:
NanoBarrier in a context

The scientific, economic and social basis for the proposed project:
Packaging can be described as a coordinated system of preparing goods for transport, warehousing, logistics, sale and end use. Packaging contains, protects, preserves, transports, informs, and sells. In food applications, packaging has been developed as protection against physical, chemical, biological and environmental factors, (e.g. heat, light, moisture, oxygen, microorganisms) in addition to aid consumers in using products, communicate, educate on the ingredients, nutritional contents and the materials used to provide the protection. Even though packaging has been successfully applied in a broad range on segments for decades, it possesses some inherent challenges, that through the increased awareness of and need to reduce environmental impact have become increasingly more relevant during the last years.

Challenges related to the diverse role of packaging and materials selection. There is a number of stakeholders involved that to a large extent are shaping innovation in product and process development. This is particularly strong within food, diary and beverage packaging;
• Customers demands for safe and convenient products.
• Manufacturers want lower costs combined with improved performance in the filling line and shipping chain.
• Retailers want great shelf appeal and containers that are easy to stock and handle.
• Product formulators want longer shelf life from containers, frequently requiring barrier properties for moisture, gas, oxygen, chemicals and other elements.
• Converters want faster production rates, designs that lend themselves to higher speed production and more repeatable, high quality capabilities.

In order to meet these diverse and to some extent conflicting specifications, packaging solution with poor environmental profile have been chosen. An example is the growing use of complex multi-layer/barrier solutions. The demand for EVOH was growing at a rate of at least 10% a year with 70% of that growth being in food packaging. Such solutions will to a large extent involve use of incompatible polymers and tie layers; which demands for complicated and expensive equipment. As the number of layers increases, so will also material consumption and cost. Improper compatibilization may lead to problems with delamination, increasing the percentage of rejects. Such solutions are difficult to recycle.

One of the main overall ideas of NanoBarrier is to develop new and innovative nanotechnology-based barrier promoters based on European R&D expertise and combine this with expertise in ecodesign to realize less complex barrier solutions and packaging designs with an overall sustainable profile in a product life perspective.

Challenges related to new materials opportunities and food safety/quality. The use of nanotechnology in packaging holds promise of new innovative materials formulations and solutions. However, only a few nano-aided packaging solutions have been developed and applied in Europe, where the development and implementation of nano-aided packaging is limited, due to uncertainties of customer acceptance, regulatory systems and food quality concerns.
• Consumer acceptance of the use of nanomaterials in food packaging is very important in the European market and will be greatly dependent on the demonstrated benefits and safety of the new packaging products. Uncertainty regarding long-term health and environment impacts, expectation of product cost increases and a lack of transparency of information from the industry are factors that dominate public fear.
• The regulatory system for food packaging is very complex, both legally and scientifically and not widely understood.
• With an increasing global customer base, food retailing is transforming. Food packaging requires longer shelf life along with monitoring food safety and quality based upon international standards. New solutions that contribute to consumer growth and acceptance of e.g. fish- and seafood in EU region are therefore desirable.

The overall idea in NanoBarrier is to combine European expertise in new and innovative nanotechnology-based with expertise on ecodesign to realize integration of novel nanostructures in packaging solutions in a safe and responsible manner.

Challenges related to end-of-life waste management of plastic product Approximately 4 per cent of the oil and gas production, a non-renewable resource, is used as feedstock for plastics. Furthermore, another 3–4% is expended to provide energy for their manufacture. A major fraction of plastic produced each year is used to make disposable items of packaging or other short-lived products that are discarded within a year of manufacture. Recycling is one important strategy for end-of-life waste management of plastic products. Directive 2008/98/CE of the European Parliament establishes that at least 30% of the plastic solid waste should be re-used or recycled, and in 2020, all solid waste streams should be diverted towards material recycling and energy or organic recovery to reduce landfill. There are, however, several challenges related to recycling;
• Most polymers are incompatible. This is both related to immiscibility at molecular level as well as different processing demands. The occurrence of PVC contaminant present in a PET recycle stream will degrade the recycled PET. Similar problems arise if PLA is introduced in the PET recycle stream.
• Different components involved. There is therefore limited recycling of multi-layer/multi-component articles because these result in contamination between polymer types. This also involves barrier materials, often consisting of several layers of inherent incompatible polymers.
• Quality degradation. It is often not technically feasible to add recovered plastic to virgin polymer without decreasing some quality attributes of the virgin plastic, such as colour, clarity or mechanical properties.
• Collection. Most post-consumer collection schemes are for rigid packaging. Flexible packaging tends to be difficult during the collection and sorting stages. Most material recovery facilities have difficulty handling flexible plastic packaging because of the different handling characteristics of rigid packaging. The low weight-to-volume ratio of films and plastic bags also makes it less economically viable to invest in collection and sorting facilities.

For paper- and board packaging the situation is better. It accounts for nearly three-quarters of all packaging materials recovered for recycling, amounting to almost 25 million tons.

One of the overall main ideas in NanoBarrier is to introduce biodegradable materials components and other solutions based on renewable resources in development of demonstrator concepts that could contribute to meet Directive 2008/98/CE.

The overall solution strategy in NanoBarrier
To meet the challenges described above and realize the expected impact listed in the present call, NanoBarrier will develop and integrate innovative and sustainable solutions at different design levels, using ecodesign principles. These three levels are

Component design; where an innovative and sustainable nanotechnology-based platform of barrier
promoters (oxygen- and moisture), sensor materials and process additives will be developed.
Materials integration and design; where the nanotechnology platform will be integrated with sustainable biomaterial formulations based on renewable resources in a safe and responsible manner through cost-efficient techniques, such as roll-to-roll nanocoating, thin-layer spray coating, extruder-based coating or compounding
Demonstrator design; where demonstrators/prototypes will be developed, showing a viable combination of technical, environmental and customer benefits.

The ecodesign principles will be based on early intervention in design at all design levels and integration of environmental parameters assessment (such as LCA) during product development.

Solution strategy related to Demonstrator Design
The demonstrators will be barrier-enhanced and multifunctional packaging products, based on renewable both biodegradable and recyclable solutions, addressing packaging sensitive segments of significant economic and social importance in EU. The planned demonstrators will be based on cost- and resource efficient (and existing) polymer processing routes, such as blow moulding, thermoforming, injection moulding and film blowing, as well as established board formation processes. The planned demonstrators will all be truly innovative, i.e. no similar products exist on the market today.

• Thermoformed 3-layer film for oxygen sensitive packaging, where the middle layer is a MFC film and the outer layer is moisture-enhanced PLA. Such a film could potentially have a broad application range, where the specific segment will be dependent on the actual performance obtained.
• Blow moulded oxygen sensitive bottles for food and beverage packaging. For these demonstrators, the barrier nanostructures will nominally be integrated with bio-PET by spray coating technology and sensors may be integrated by printing technology.
• Injection moulded oxygen sensitive jars for seafood packaging. Strict demands on barrier performance have been identified as defined in S&T objectives).
• Blown 3-layer films for flexible oxygen-sensitive packaging (e.g. meat). The barrier layer will be a middle layer PLA and microfibrillated cellulose (MFC). Outer layers are moisture-enhanced film grades of PLA.

S&T Objectives

To reach this overall S&T objective, objectives have been identified at all three design levels defined above; i) S&T objectives related to nanotechnology-based component design, ii) S&T objectives related to materials integration and design and iii) S&T objectives related to sustainable product design.

The first set of S&T objectives (O1.X) of NanoBarrier is related to development of novel biodegradable nanostructures that can bring desired enhanced barrier properties and multifunctionality in novel biopolymer formulations. This nanotechnology-based technology platform ensures multifunctionality of the package performance by combining barrier-promotion against humidity and oxygen with multisensory effect for the internal (oxygen, pH) and external (rupture, temperature) changes of the package environment.

O1.1 Develop new types of barrier-promoting and biodegradable nanostructures for incorporation/combination with biomaterials. The targeted barrier properties these nanostructures should deliver will depend on the actual demonstrators, being
➢ Oxygen-sensitive bottles and jars; A factor 10 improvement in oxygen barrier performance compared to commercially available MX-D6 polyamide should be reached, amounting to at least 0.3 cm3 mm/(m2 day atm) (for a 20µm film at 60% humidity). Moisture sensitivity comparable to MX-D6 polyamide should be obtained.
➢ 3-layer blown and thermoformed films; Comparable oxygen/moisture barrier to commercially available MX-D6 polyamide-based solutions for blown and thermoformed 3-layer solutions, amounting to 3 cm3 mm/(m2 day atm) (for a 20µm film at 60% humidity).
➢ Barrier-enhanced board; a water vapour barrier comparable to synthetic polymers such as PE.
O1.2 Develop and combine new types of biodegradable nanostructures for incorporation in boards.
O1.3 Develop new types of nanostructures capable of acting as multi-sensor materials, reacting upon the following stimuli; pH, temperature, mechanical rupture and oxygen.
O1.4 Document safe and robust strategies for upscaling of the nanotechnology platform, compatible with amounts and conditions present in pilot scale tests.
O1.5 Demonstrate compatibility with health & safety regulations and environmental recommendations for developed and proposed nanostructures in a perspective beyond product life time.

The second set of S&T objectives (O2.X) of NanoBarrier is related to integration of the biodegradable nanostructures in biomaterial formulation in a safe and responsible manner, using predominately coating approaches.
O2.1 Develop and validate innovative biopolymer formulations compatible with cost-efficient polymer processing routes; thermoforming, injection moulding, injection stretch blow moulding and film blowing.
O2.2 Demonstrate potential for improved performance of selected biopolymer formulations (in terms of barrier-, processing and mechanical properties) through chemical modification and/or cross linking reactions.
O2.3 Demonstrate targeted barrier-performance (O1.1) after lab-scale integration of selected nanostructures with biomaterials formulations.
o MFC and selected biopolymer formulations integrated into a 3-layer structure through roll-to-roll nanocoating or extruder coating.
o Integrating selected nanostructures with biomaterial formulations through spray coating formulations, showing a VOC <100g/kg solvent.
o Integrating hydroxyl-decorated organic nanoparticles with biopolymer formulations through compounding.
O2.4 Combine new types of biodegradable nanostructures in board formulations. In quantified terms, a 3D formability comparable with PP and/or PE should be obtained.
O2.5 Demonstrate targeted sensor functionality (O1.3) after integrating selected sensors in ink formulations for printing or in coating formulations.
O2.6 Demonstrate migration levels of nanostructures for all integration strategies comply with limits and
restrictions/specifications described in COMMISSION REGULATION (EU) No 10/2011.
O2.7 Demonstrate biodegradability of the integrated solutions in-line with EN13432.

The third set of S&T objectives (O3.X) of NanoBarrier is related to sustainable demonstrator design. Since more than 70% of the final environmental impacts, waste management processes, costs or functional requirements of the new products are determined already at the design step, these aspects should be taken into account at all steps in the packaging value chain.
O3.1 Develop innovative and sustainable demonstrators showing a combination of social, economical, environmental- and technical benefits in a value-chain perspective, in a time frame beyond product life time.
O3.2 Demonstrate targeted barrier-performance (O1.1) and sensor functionality (O1.3) of the demonstrators.
O3.3 Demonstrate migration levels of nanostructures for all demonstrators being compatible with
O3.4 Demonstrate robustness of proposed demonstrators in relation to existing waste management streams.
Project Results:
NanoBarrier main S&T results/foregrounds
Development of the nanotechnology platform

The overall objective of this work package (WP2) was to develop a biodegradable nanotechnology-based platform that could enable significant barrier-enhancement and ensure multifunctionality of the package by combining barrier-promotion with multisensors for the presence of oxygen, mechanic rupture, temperature and pH changes related to the package. The tailored nanotechnology components were supplied to the other WPs and integrated either as an additive during package fabrication, by printing or by coating.
To achieve the DoW objectives in sensors and barrier promoters areas, WP2 have the 3 Tasks including 8 Subtasks.
Task 2.1: Development and up-scaling of biodegradable barrier-promoting nanostructures.
The objective of Task 2.1 is to develop a family of barrier promoting nanostructures enabling significant increase in shelf-life of selected biopolymer packaging.
Subtask 2.1.1: Inorganic-organic hybrid polymers as barrier promoters.
The objective of Subtask 2.1.1 is to develop barrier formulations based on biodegradable inorganic-organic hybrid polymers with hydrolysable functional organic groups.
Subtask 2.1.2: Microfibrillated cellulose as barrier promoter.
The objective of Subtask 2.1.2 is to develop an oxygen barrier film with reduced sensitivity towards moisture.
Subtask 2.1.3: Oxygen and moisture scavenging technology.
The objective of Subtask 2.1.3 is to develop oxygen and/or moisture scavenging structures for sustainable materials.
Subtask 2.1.4: Hydroxyl-decorated organic nanoparticles as barrier promoters.
The objective of Subtask 2.1.4 is to develop, spherical or elongated, organic nanostructures, decorated with hydroxyl groups, which will provide barrier-promoting properties to packaging.

The objectives of the Task 2.1 and all sub-tasks were fully accomplished.
1. Synthesis procedures for the barrier material based on methyl salicylate modified inorganic-organic hybrid polymer and lactic acid modified inorganic-organic hybrid polymer were developed. The products were successfully up-scaled to 8 kg batches. The obtained barrier material is thermoplastic and can thus be directly compounded.
2. Biohybrid films were synthesized by combining microfibrillated cellulose (MFC) dispersions with vermiculite or montmorillonite nanoclay. The resulting hybrid films are flexible, strong and rather transparent. The oxygen barrier properties of the biohybrid films outperform that of pure nanocellulose films. The oxygen permeability of the hybrid films can be tuned by using nanoclays with different aspect ratio and by adjusting the amount of clay in the films. The incorporation of plasticizers; sorbitol and glycerol, to the MFC films significantly increased the strain-to-failure of the material.
3. Iron-based polymeric oxygen (moisture)-scavenging nanoparticles were obtained by emulsion polymerization of adequate monomers (maleic acid, N,N-dimethylacrylamide) and cross-linkers in the presence of Fe(II) ions. The final synthetic protocol involves the use of an Fe(II) source (FeSO4), monomers and crosslinkers, oil phase, emulsifier. 400 g of iron-based polymeric oxygen (moisture)-scavenging nanoparticles were supplied for the use in demonstrators.
UV-triggered organic oxygen scavenging nanoparticles were obtained by vinyl-functionalization of anthraquinone (the molecule with the oxygen scavenging efficiency) followed by copolymerization of the vinyl-modified anthraquinone during the synthesis of NPs through emulsion polymerization. 50 g of UV-triggered oxygen-scavenging nanoparticles were supplied for the use in demonstrators.
4. The protocol for the synthesis of hydroxyl-decorated spherical nanoparticles (HDNP) was developed and scaled-up for the production of larger quantities of unhydrolyzed, fully hydrolyzed nanoparticles and partially hydrolyzed ones. 150 g of HDNPs were supplied for the use in demonstrators.
More detailed information about the synthesis and up-scaling of barrier promoters can be found in submitted deliverables: D2.1 “Procedure for synthesis of barrier promoters based on inorganic-organic hybrid polymers” (M17); D2.2 “Procedure for synthesis of barrier promoters based on microfibrillated cellulose” (M17); D2.3 “Procedure for synthesis of oxygen and moisture scavengers” (M36); D2.4 “Procedure for synthesis of barrier promoters based on hydroxyl-decorated organic nanoparticles” (M17). Deliverable D2.6 “Cost-performance effective barrier promoters for demonstrator applications” (M29) analyses the starting prices for the barrier promoters, which are in the scale below 1 Euro per gram and have high capacity in the cost reduction considering higher manufacturing volumes on the industrial scale. Deliverable D2.7 “Upscaled technology for selected barrier promoters” (M36) provides information about procedures for up-scaling the production of barrier promoters for smart packages.
Task 2.2: Development and up-scaling of new intelligent sensor materials.
The objective of Subtask 2.2 is to develop new, cost-efficient and intelligent multisensor materials and indicators for packaging which will react upon defined stimuli: presence of oxygen, mechanic rupture, temperature and pH changes.
SubTask 2.2.1: Sensor development by encapsulation technology.
The objective of Subtask 2.2.1 is to develop new intelligent sensor materials based on encapsulation technology, which will react upon defined stimuli.
SubTask 2.2.2: Sensor development by ink formulations.
The objective of Subtask 2.2.2 is to develop ink formulations that respond with a visual change upon external stimuli.
SubTask 2.2.3: Sensor development by layered double hydroxides.
The objective of Subtask 2.2.3 is to synthesize and develop Layered Double Hydroxide nanosensors, by investigating how the LDH structure changes when humidity within the packages is present (qualitative detection) and pH varies (quantitative determination).
SubTask 2.2.4: Sensor development based on fixed sensing elements.
The objective of Subtask 2.2.4 is to develop new intelligent (multi)sensor materials through fixation of the sensing elements on the sensor platform.

The objectives of the Task 2.2 and all sub-tasks were fully accomplished.
1. Two different pH indicators; methyl red and bromocresol green (3:1 molar ratio) were incorporated into gel based capsule sensors to achieve high contrast signal at pH<4.5. Thermal sensitivity of the capsules was improved to 35 °C by decreasing molar weight of polymer gel components to 4-8 kDa. Mechanic stability of the sensors on the demonstrator surface was provided by electrostatic deposition of the monolayer of ionised polyglutamic acid on 1 µm or less sensor capsules. In SiO2-based sensors, bromophenol blue was encapsulated into mesoporous silica particles of 200 nm diameter. The feasibility of the up-scaled fabrication of the improved sensor elements enough for production >1000 sensors sensitive to changes in pH value or in surrounding temperature was demonstrated. Validation of the sensor application in demonstrators was done covering the inner side of 400 bottle caps (1 inch diameter, either plastic or Al) with sensor elements.
2. Time-temperature indicator (TTI) was developed basing on physical mechanism such as melting processes of compounds involved in multilayer systems with colour reactions (Maillard reaction, FeCl3-NaOH). Carboset® and polyamide were used as the final binders for TTi formulation. Developed TTi was implemented as a printable indicator on the package labels.
3. Several batches of layered double hydroxides (LDH) powders were prepared and up-scaled by calcination-rehydration procedure, whereas functionalized cellulose acetate films containing LDHs with sensing molecules were obtained via layer-by-layer assemly methodology. Prepared multilayer LDH sensors consist of cellulose acetate films with environmentally friendly polyelectrolytes chitosan and alginate, exfoliated LDHs and bromocresol green or rhodamine 6G as sensing species for providing sensor signal in lactic acid solution, which has pH value associated with meat spoilage. Approximately 5 kg of the LDH sensors were prepared for using in demonstrators.
4. The pH-responsive luminescent organic nanoparticles decorated with quinoline derivatives were prepared and optimized as a function of several structural parameters: chemical structure of quinoline derivative (simple quinoline or quinoline-pyridine unit), quinoline content (0.5% mole-2% mole), cross linking density and degree of hydrolysis of the luminescent nanoparticles (unhydrolyzed and 100% hydrolyzed). The synthetic procedure was scaled-up and 20 g of pH-sensoring fluorescent nanoparticles were available for further exploitation in demonstrators.
More detailed information about synthesis and up-scaling of sensors can be found in submitted deliverables: D2.8 “Procedure for synthesis of sensors based on encapsulation technology” (M17); D2.9 “Procedure for synthesis of sensors based on ink formulations” (M17); D2.10 “Procedure for synthesis of sensors based on layered double hydroxides” (M17); D2.11 “Procedure for synthesis of sensors based on fixed sensing elements” (M17). The final costs of sensors’ increment per package (D2.12 M29) depend on the (i) selected sensor technology, (ii) quantity of the sensor material per one package unit and (iii) processing costs. Current evaluation of the costs only showed the starting prices for the sensor elements in the scale 2 Euros and below per gram. Deliverable D2.13 “Upscaled fabrication technology for selected sensor components” (M36) provides information about procedures for up-scaling the production of sensors for smart packages. Deliverable D2.14 “Supply of the selected sensor components to the pilot plant fabrication of new multifunctional packages enough to fabricate 100 (1000) sensors” (M42) confirmed the feasibility of the sensor production on a pilot scale for smart packages.

In conclusion, the developed sensors are sensitive to the pH changes caused by food decay, increase of humidity inside the package caused by package damage and temperature changes caused by improper storage conditions. Barrier promoters and scavengers terminate permeability of the package for atmospheric oxygen and humidity.
Both organic and inorganic particles can work as sensors and barrier promoters. The selection of the sensor/barrier promoter depends on the target package material and processing technology. Barrier promoters are most sensitive to this because they have to be distributed thought the whole package. Sensors can be applied to the package on the post-processing step as a printed label or painted spot. Our calculations showed that the application of the sensor element on the plastic or Al bottle cap increases the price of the bottle (for yogurt, ketchup) by 0.1 Cent or lower.
Developed sensors and barrier promoters (as well as their synthetic methods) can be applied not only in the smart packages. They can be used in functional paints, concretes, sealants, medical equipment, etc. Interesting will be the use of external impact (e.g. light) to control barrier properties (e.g. light “on” – window is permeable for oxygen; light “off” – permeability is also “off”).
Integration of nanotechnology platform in biomaterial formulations
The overall objective for this WP (WP3) was a functional integration of the nanotechnology platform and biomaterial formulations in a safe and responsible manner. More specifically, this includes: (i) define and develop biodegradable biomaterials compatible with resource-efficient processing routes and nanostructures developed in WP2, (ii) develop and implement surface coating technologies enabling barrier enhancement and/or sensor technology on lab- as well as pilot scale level, (iii) development of biomaterial-nanostructure compounds, (iv) development of 3-layer barrier structures through roll-to-roll coating or extruder coating and (v) document feasibility to read off sensor signal on lab-scale formulations as well as pilot scale formulations.
The objectives for the particular Tasks were as follows:
Task 3.1: Biomaterial formulations. Relative objectives were to define and develop biomaterials and biomaterial formulations compatible with selected resource-efficient processing routes and applications. Develop and validate innovative biopolymer formulations compatible with cost-efficient polymer processing routes; thermoforming, injection moulding, extrusion blow moulding and film blowing. Demonstrate potential for improved performance of selected biopolymer formulations (in terms of barrier-, processing and mechanical properties) through chemical modification and/or cross linking reactions.
Task 3.2: Integration of barrier promotors and sensors in biopolymer formulations through compounding. Relative objectives were to develop compounds based on selected nanostructure technologies developed in WP2. Demonstrate targeted barrier-performance after lab-scale integration of selected nanostructures with biomaterials formulations.
Task 3.3: Integration of barrier promoters and selected sensors in biomaterials through development and application of thin-layer coatings. Relative objectives were to develop surface coating technology to realize barrier enhancement and/or sensor technology in the chosen biomaterial formulations
SubTask 3.3.1: Integration of hybrid polymers and selected sensors in biomaterials through liquid based coatings. Relative objectives were to develop liquid-based thin-layer coating with barrier performance and low VOC.
SubTask 3.3.2: Integration through in-situ formed water vapour barrier coatings on board Relative objectives were development and characterization of in situ-formed water-vapor, oxygen and VOC barrier coatings with paperboard using silica-based formulations enhanced by different barrier promoters.

Task 3.4: Integration of MFC and biopolymer formulations through roll-to-roll nanocoatings and extruder coatings Relative objectives were to enable a 3-layer barrier structure based on biopolymer formulations from Task 3.1-3.2 and MFC formulations from SubTask 2.1.2.
Task 3.5: Integration of sensor elements in biomaterial formulations through printing technology Relative objectives were to integrate selected sensors developed in WP2 in biomaterials formulations as a functional ink, to validate the applicability of sensors in different food packaging.
Task 3.6: Integration of formability promoters in board. Relative objectives were to integrate nanostructures developed in Task 2.3 in board formulations as formability promoter.
Task 3.7: Reading of the sensor signal. Relative objectives were to demonstrate the feasibility of reading of the sensor signal after its visual response on the packaging material surface.
Task 3.8: Structure-to-transport relationship. Relative objectives were to elucidate the relation between internal structure of the packaging material and barrier performance and provide numerical predictions of the effect of compounding on oxygen and moisture permeability thus saving on extensive and heuristic experimentation.

The main S&T results
Towards objectives of Task 3.1.
The basic requirements to the industrial materials and processes and a processing conditions window for the pre-selected series of biomaterials and biomaterial formulations have been defined. The commercial PLA from Nature Works and Biome was acquired and the grade Ingeo PLA 3052D (Nature Works) was tested to define the processing window for injection molding. The bio-PET has been required to use in the processing trials. Two natural and renewable biopolymers, soy-protein (SPI) and corn-starch (CS), and their processing to develop an optimal compounding for producing barrier films have been studied. A series of novel SPI-based films with improved moisture barrier properties have been developed via compounding and coating methods including different SPI-whey and SPI-xylan films. The silica coated SPI-xylan and SPI-whey films revealed the WVTR and tensile strength from 15 to 42% and from 65 to 116%, respectively. By using the sorbitol (SOR) instead of the gylcerol (GLY) as plasticizers (in the presence of water) for Soy-protein-isolate (SPI) films preparation by a compression molding, the WVTR and OTR properties are improved from 159±36 g min-1 m-2 to 13.5±4 g min-1 m-2 and from 8±0.5 cm3/m2d to 0.29±0.12 cm3/m2d, respectively, without significant changing of the tensile strength (7-6 MPa) and elasticity (80-64%). Pre-modified LDH and AMS nano-particles were incorporated into SPI films formulations and the barrier properties (WVTR and OTR) of newly produced films have been evaluated. The SPI-based films doped with 5% PEG-modified LDH showed deterioration of WVTR (ca 70%) and improvement of OTR (ca 30%), when compared to films doped with unmodified LDH.

Towards objectives of Task 3.2.
In the task Elastopoli worked with a twin screw compounding unit to incorporate hydroxyl decorated nanoparticles (HDNP’s) provided by FORTH and microfibrillated cellulose (MFC) provided by Borregaard. Both materials were incorporated to PLA polymer matrix and delivered to WP4 for processing the demonstrators. HDNP´s were compounded with a 26mm small twin screw extruder to masterbatch that could be further diluted to final compounds. This phase would improve dispersion in the final compound and save material for the first screening tests. A screening protocol was agreed upon with the following amounts of final compounds. The amount of HDNPs 100%HD did not allow making a full screening test. HDNPs 100%HD and PLA hand blended and compounded through a 26 mm twin screw extruder were HDNPs 50%HD and PLA extruded to a 9,1% masterbatch. The compounds were sent to ARGO for injection molding of jar lids. The lids will be used for screening of the barrier properties and assessing the right amounts of fillers needed for the demonstrator compounds. Also a small amount of samples was sent to FORTH for SEM analysis to improve simulation results. SINTEF will receive samples of the injection molded lids for their purposes. MFC were incorporated to PLA as barrier promoter. This was possible through a technology Elastopoli had developed already earlier for compounding wet cellulose fibres into polymer matrixes via devolatilization (DEVO) processing. The first compounding with the DEVO process was done with a stationary process. This means that the water removal stage was done on a stationary water removal wire belt. In the DEVO process the belt is usually moving but the pilot line needs to have an excess of 3 m3 of material to run it as a continuous process. Borregaard provided Elastopoli with 2% MFC water solution for the process. The DEVO process produced 10 kg of 50%MFC/50%PLA masterbatch with Ingeo 3052D PLA as the polymer matrix. Elastopoli has tested the DEVO method pre NanoBarrier with MFC and various polymers. The patent of the DEVO process is pending. Using the DEVO was not in the original plans of the project but Elastopoli used its background for the benefit of the project to come up with a viable technology that could produce pre-industrial amounts of compound when it became evident that upscaling the production HDNP’s was not possible to produce enough materials to manufacture the demonstrators.

Towards objectives of Task 3.3.1.

A series of new hybrid organic-inorganic hybrid polymers (OIHP) have been developed. Developed barrier hybrid materials have been applied as barrier promotors on card-board and on PLA using essentially organic solvent media. UV-curing of coatings was achieved using different UV-reactive reagents. Surface of the mesoporous silica sensor nanocontainers (NCs) was modified with ethyl adenine or polyethylene glycol for better compatibility of the liquid matrix components. OIHP materials were supplied to other partners from WP3 and for the demonstrators (i.e. PET bottles and multilayered films). The spray application coating have been developed on a pilot scale for the PET-based or multi-layered bottles and jars coatings using hybrid polymer formulations in organic solvents. The coating layer has a thickness layer between 10 and 15 µm. Coated bottles showed two fold improved OTR when compared to uncoated bottles. Original protocols were developed at DELTA for the oxygen permeation in plastic materials (OTR) allowing to put a large number of samples in test simultaneously.

Towards objectives of Task 3.3.2.
A new method to improve the barrier properties of paper board employing roll-to-roll application technique for the in situ-formed coatings using a series of silica-based formulations (totally more than 30 formulations) with water vapor, oxygen and VOCs barrier promoters have been developed. The detailed description of the procedure for optimized silica-based formulations to integrate water vapor barrier coatings on board by roll-to-roll coating is presented in Deliveries 3.5. The coatings were exhaustively characterized and their water vapor, oxygen and formaldehyde barrier properties have been evaluated.
The roll-to-roll coating industrial paperboard samples with a silica nanocoating comprising of TEOS_APTES_LDHs formulation (2-3 g/m2) or modified xylan films (4-5 g/m2) reduces water vapour transmission rate in 76% and 90%, respectively, and reduces the oxygen transmission rate in ca 70% and 99.95%, respectively, when compared to parent uncoated paper board. The incorporation of molybdovanadophosphates (PMo11V and PMo10V2) in silica formulation containing aminopropyl moieties (TEOS_APTES) didn’t change the water barrier properties when compared to silica base formulation (TEOS_APTES), but provided much better results for O2 barrier property (74% decrease in JO2) and demonstrated the barrier properties for formaldehyde.
Towards objectives of Task 3.4.
A completely novel and technical benign roll-to-roll process for producing large-scale, thin and dense films based on microfibrillated cellulose (MFC) has been developed. The films have excellent oxygen barrier properties and exhibit high-strength properties. A pilot-scale extrusion unit was used for extrusion coating of polylactic acid (PLA) on both sides of the MFC films, forming a three-layered structured film. The three-layered films possessed high oxygen barrier properties in combination with high-strength properties and strain-to-failure, which fulfilled the first set of S&T objectives of Nanobarrier (O1.1). The incorporation of plasticizers; glycerol and sorbitol, to the MFC films significantly increased the strain-to-failure of the material. The addition of 20% glycerol resulted in an increase of the strain-to-failure of more than 100% compared with a pure MFC film. Interestingly, the oxygen permeability of the films was unaffected by the amount of added sorbitol. The oxygen permeability was significantly increased with the amount of glycerol. The E-modulus of the sorbitol-plasticized MFC films decreased significantly with an increased temperature, indicating thermoforming properties of the material. A vacuum thermoforming technique has been developed to fabricate trays of the three-layered structured films. The multilayers consists of PLA, semicrystalline or amorphous, had a midlayer of a transparent MFC film. The oxygen barrier properties of the three-layered structured films were three times better than the benchmark PE/PA/PE.

Towards objectives of Task 3.5.
At the beginning of this Task 3.5 different printing techniques and time-temperature systems were considered to develop and test the printed ink-based sensors (SubTask 2.2.2) in order to select the most cost efficient solution and to achieve the less interference in the nanobased material processing. Printing methods and systems were applied and tested on external layer of packaging material with the purpose of achieving a more accurate response of the indicator against unsuitable temperature changes. Procedure for integration of sensors through printing technology is presented in Deliverable 3.7. Moreover, several physical characterization tests and study of colour response were addressed in parallel to validate printed time-temperature indicators (TTIs). Studies of TTi’s coatings stability were performed. Finally, drawdrons of the final TTI formulation was applied in demonstrator’s materials and sent to NANOBARRIER partners for validation.

Towards objectives of Task 3.6.
SCA, SINTEF and Borregaard developed a thermoformed 3D board for production of 3D-shaped packaging such as food trays. The concept included the two steps of first preparing a planar board substrate and then thermoforming it into 3D-shaped articles. A summary on material and process requirements are given in Deliverable 3.1. Material formulations for thermoformed 3D board were developed in Task 3.6. The strategy was to add a formability promoter to the board in order to improve the extensibility. The investigated formability promoters comprised of a set of seven inorganic-organic hybrid polymers, synthesized in Task 2.3 and two grades of microfibrillated cellulose (MFC). A procedure for incorporating the formability promoters in board was reported in Deliverable 3.8. The components were added in the form of polymer-MFC complexes, which solved the problem of fixing the nano-sized polymers in the board. The effect of the formability promoters was evaluated for board handsheets containing up to 135 kg/ton of complexes. Tensile testing at thermoforming temperature showed that strain at break increased from 2.5% to 3.7%, which was deemed too low for the application. A competitive substrate for thermoforming would require a strain of at least 20%, more preferably above 50%. After sharing the results, the consortium decided to stop further development of thermoformed board.

Towards objectives of Task 3.7.
UoL and PLA groups carried out work towards characterization and improvement of sensor signals from prototypes with two main aims: (i) improving stability of the sensor activity and signal and (ii) test sensors in conditions more relevant for demonstration conditions, such as in the presence of lactic acid, which is one among well-known products associated with food degradation. Additionally, mechanic and chemical stability of the polymer capsule based sensors deposited on Al and plastic caps (prototypes) was evaluated and the adhesion properties were improved. 200 plastic caps and 200 Al foil caps were modified by deposition of either pH-sensitive hydrogel capsule based sensors or temperature-sensitive hydrogel capsule sensors. The high-contrast optical signal (red colour) was achieved at pH <4. (typical pH level of food degradation products) The temperature sensors showed irreversible disappearance of the yellow colour for the caps stored at the temperature above 32 C for more than 5 minutes. The measurements of the sensor signal were also performed in presence of lactic acid by UV-Vis spectrophotometry. Moreover, prototypes of the fluorescent sensor from FOR and optical LbL assembled sensor from UAVR were evaluated. Significant results are:
-polymer gel based capsule sensors with improved adhesion to the bottle caps were developed and evaluated;
-stable, high-contrast optical signals were achieved from polymer gel based capsule sensors responsive to pH changes (below 4.5) and temperature changes (above 32 C);
-LbL assembled sensor from UAVR demonstrated effective signal at pH below 3.5.

Towards objectives of Task 3.8.
Through sophisticated simulations it was found that, for the same volume fraction and transport properties of the nanoparticles, their shape and orientation relevant to the gas transport direction play a decisive role in the hybrid membrane transport properties, rendering them effective or not barriers. Membrane permeability was found to be strongly affected by the fillers volume fraction, by the fillers shape and orientation in the membrane, and by the fillers permeability, as well. Solubility effects were found significant. However, its influence was compressed in the case of membranes with fillers that act as strong barriers, i.e. their permeability was very small compared to the polymer permeability. It was also found that poor polymer-filler affinity can result in increased membrane permeability, destroying the barrier effect of the fillers. In fact, the existence of a non-selective void interphase between filler and matrix allows rapid bypass of the filler, which may lead to permeability increase compared to the neat polymer permeability in the case of small diffusing molecules.

Demonstrator products
This work package (WP4) concentrated on realizing the developments of NanoBarrier project to actual products that would represent the need of packaging industry broadly. Four major thermoplastic processes, thermoforming, blow molding, injection molding and extrusion were all represented in the processes. The demonstrators were thermoformed multilayer film, blown molded bottle, injection molded jar and multilayer blown film. The aim was to find the best possible process parameters for the given products and barrier promoters created by the partners in the project.
All demonstrators were successful in running the materials in the process used commercially by the industry and showed that the new developments could be added as a drop-in-replacement to the existing processes. All the demonstrators showed improved barrier properties. Thermoformed multilayer film exceeded the set targets for barrier properties. Blown molded bottle and injection molded jar were very close to a commercial level. 3-layer blown film showed an unforeseen process where MFC could be extruded into an extremely this mid-layer but further developments in both polymers and MFC/PLA compound are needed for commercial level barrier properties.

Thermoformed multilayer film
Thermoformed multilayer film is used typically for packaging foods like meat slices, cheese and sausages. They require barrier properties for oxygen to keep the food from spoiling too fast and water vapour barrier to keep to moisture in the packaging. These products are usually sold in grocery shops and they predominantly end in mixed municipal waste.
The motivation of this demonstrator was to produce a biodegradable package that would have the same or better barrier properties as the existing commercial solutions but would be bio-degradable. This way the package would degrade in the municipal waste.
In thermoformed multilayer film the barrier functionality came from a uniform MFC film in a mid-layer of a PLA/MFC/PLA structure. Sorbitol was used to give the MFC structure more flexibility without compromising the barrier properties of the end product.
The structure was achieved by a coating lamination process that was run at Tampere University of technology in Finland.

Thermoforming trials
The preform sheet that was produced with extrusion coating lamination process was used in thermoforming trials with a mould described below.
The first trials were made with a on sided mould that is assisted with a vacuum from underneath. The elongation properties of the mid-layer MFC film were not sufficient for the 15mm drawing with 10° drawing angle. As a result the ruptures were seen in the mid-layer because the biggest elongation stress is in the side wall.
With the incorporation of a two sided mould the results were very good. The creasing in the edges of the product was smoothened out and the cracking of the mid layer MFC film could be controlled. The demonstrator was run with two materials non- and semi-transparent films.
Barrier properties
The benchmark for the oxygen permeability for new developments was a commercial polyamide MX-D6 3 cm3 mm/(m2 day atm) (for a 20µm film at 60% humidity). With the structure of PLA/MFC/PLA having 10% sorbitol as plasticizer value of 0.24 cm3 mm/m2 day atm (for a 20µm film at 60% humidity) was measured. This meets target set by the project.
Integration of sensors
Demonstrator 1 was also chosen to test the pH sensor and how it could be integrated to the packages. Due to uncertainty of in safety issues it was decided that the sensor was glues outside the package. The likely industrial application of sensor could be for example a sticker that was designed to be glued on PLA based package surface.
Blow Moulded Bottles
The petrochemical PET is produced today from two main monomers, Mono- or Di-Ethylene-Glycol (MEG or DEG), and Terephthalic Acid (TPA). The Bio Base PET (or BioPET) is produced with Mono- or Di-Ethylene-Glycol coming from renewable resources and is present in the BioPET in a ratio of 30%. M&G as one of the most important players of the PET Market is trying to find a solution for the production of bioTPA and in a very close future 100% BioPET will be available.
For the 3rd Demonstrator it was consider that the most sustainable solution will be in consequence a solution that can be integrated in the BioPET produced today by M&G under the commercial name Cleartuf MAX B
The Oxygen barrier performance of a PET bottle alone is not adequate for commercial use. In this demonstrator various techniques to improve this were tested. Under the scope of the NanoBarrier Project the following materials were tested using the existing Injection Molding tools at Logoplaste Innovation Labs to produce the preforms:
- Layered double hydroxides (LDHs) produced by Aveiro University
- Titanium Oxonitride Nanoparticles (TiNO) produced by PlasmaChem GmbH
- Hybrid Polymer in a PETG compounding provided by SINTEF
- Oxygen scavenger provided by FORTH
- Hybrid Polymer Coating provided by DELTA
The use of Titanium Oxonitride Nanoparticles is an excellent achievement for the Blowing Technology of PET, as it reduces the amount of energy consumption when compared with the benchmark.

1. The existing technologies at Injection Stretch Blow Molding can be used to produce preforms and bottles with the different solutions tested under the NanoBarrier Project but the following considerations are important:
a. Materials in the powder form need to be compounded with compatible carriers with the PET matrix in order to facilitate their incorporation using the existing dossing systems for solids and liquids.
b. In order to warranty a better homogeneity of the mix and a good level of dispersion the compounding is the preferable to be compatible with the PET matrix providing more stable compounds without the formation of agglomerates that will difficult the processability of the material and modify the properties in the final packaging.
c. As observed, all materials/additives used affect the process ability, increasing the melt viscosity of the PET, due to the higher concentration of particles in suspension and/or due to the non-miscibility of the materials. In consequence, the process conditions at injection and as well at the blowing process were affected. Also, in some cases, the production of preforms and bottles were not possible or in other cases their properties change drastically.
2. The use of LDH SH can be an alternative of passive barrier if a better level of dispersion is achieved in order to add higher concentrations able to be oriented in the BioPET matrix.
3. Titanium Oxonitride Nanoparticles (TiNO) when added to BioPET can provide energy savings to achieve the same preform temperature profile at ISBM process.
4. The Hybrid Polymer did not show an improvement in oxygen barrier performance when blended with the BioPET and PETG. However, better results were achieved when the Hybrid Polymer was applied by Spray coating in a Monolayer BioPET bottle. The results showed a barrier improvement factor of tree compared to a Monolayer BioPET bottle
5. An Iron base Oxygen scavenger is still under development by FORTH and due to its low temperature resistance will need to be applied by spray coating in Monolayer BioPET bottles.

Injection molded jars
Injection molded jars are widely being used in various packaging that are sensitive for permeable oxygen water vapor transmission. Typical package that was also demonstrated during the project was an injection molded jar for crab meat.
The approach was to incorporate barrier promoter both to the injection molded material and also use new spray coating techniques developed at Delta engineering to further increase the barrier properties of the packaging.

Both addition of MFC and coating of virgin PLA improved the barrier properties by 38-39%. When the two techniques were combined the improvement was 58%. The result is very close to an industrial solution and with small development of both techniques it is likely that commercial level barrier properties can be achieved.
3-layer blown film
Multilayer blown films are widely used in packaging industry to pack various fresh products including fresh meat. The conventional packaging is predominantly using multilayer polyethylene films where a mid-layer is constructed of a barrier polymer like polyamide. As with other household plastic packages when they have been used they end up in the municipal waste stream and to dumping grounds. It would be beneficial for the environment is the packages used would be biodegradable. The demonstrator aimed to achieve a biodegradable multilayer blown film with barrier enhanced mid-layer.
A compound of 5% and 10% MFC compounded into PLA was used as the modified mid-layer for blown film application.
The materials were compounded at Elastopoli, dried and extruded into a 3-layer film shown above. The materials were dried prior to processing due to the sensitivity of PLA to moisture. The process itself did not require any special tooling but due to the hydroscopic nature of all the components a drying system is required for industrial scale production.
There are still some noticeable development needed in the blown film extrusion graded of PLA. Although they work very well in the extrusion blowing the surface of the polymers seem to be too brittle when it cools down. Also the surface had too high friction for the roll-up mechanism to work properly.

At the end a 20 micron mid-layer with 5% MFC was produced. The film improved the barrier properties by 25% but it was still far from the desired properties that are needed for fresh meat packaging. With reference to thermoformed multilayer film and injection molded jar that uses the same material combinations it can be concluded that with the thickness of the mid layer and the MFC consistency in it the targeted properties cannot be reached. The process itself worked fine and with developments in the polymers and ability to increase the MFC content in the future it is possible to create a biodegradable structure that has adequate level of barrier properties for packaging meat and other fresh products. For other products requiring less barrier performance the results achieved may already be adequate.

Spray coating and OTR measurements
Delta Engineering built a spray coating unit for bottles and jars for the project. This facilitated many of the nanomaterials that were crated during the project. Delta Engineering designed the solution for the spraying and adjusted the robot programs as well as spray parameters such as viscosity, temperature, rotation speed, amount of solution and atomizing air. The unit has shown its capability by producing repeatable results with thickness between 10 and 15 µm.

Demonstrator safety analysis
This work package (WP5) consisted of two tasks: migration control (5.1) and risk identification assessed by cell toxicity experiments (5.2).

SubTask 5.1.1&2 [Migration control of nano-structured materials incorporated biopolymer packaging, Migration control of printing inks applied on the non-food-contact surface of biopolymer packaging]
Characterization of each of the materials (a) proposed within the works of NanoBarrier (b) used in the bio-polymer formulations and (c) the final NanoBarrier-enhanced multifunctional demonstrators was performed. In order to establish migration control of nano-structured materials appropriate methodologies were developed. The methodologies involved building of calibration curves for the various components that were expected to migrate to food-staff. The calibration curves correlated the intensity of selected peaks appearing in the UV-Vis or Surface Enhanced Raman spectra with the known concentration for each species of interest dissolved/suspended in various food simulants. From these calibration curves the limits of detection and limits of quantification were extracted.
Investigation of the possibility to apply SERS for the identification and quantification of migrating species (mostly sensors as well as some of the polymeric fragments) was fulfilled. In addition, actions were undertaken regarding the optimization of SERS experimental process in order to achieve best performance (detection limits and reproducibility) on the components of interest.
The submersion method was applied for the case of biopolymer formulations. Pre-weighted pieces (with known dimensions) of the formulations were immersed in food simulants and were subjected to migration tests. The migration tests were performed within glassy vessels placed in a shaking incubator maintaining constant temperature (40oC) for a period of 10-30 days. Portion of the food simulant was regularly removed in order to perform laboratory measurements and was subsequently transferred back to the vessel. The measurements involved UV-Vis absorption and SERS for the identification and quantification of the NPs as well as Dynamic Light Scattering (DLS) for the extraction of the size distribution of particles in the food simulant. The food simulants used were 3D water, 10%, 20%, 50% EtOH solutions and 3% acetic acid solutions. A summary of the results from the biopolymer formulations are given below:
1. Appropriate calibration curves were constructed for UV-Vis and SERS techniques in order to quantify the migrating species
2. In most of the cases nanoparticles incorporated in the polymer matrices were not found to migrate in the food simulants apart maybe from TiNO. For the latter more intensive experiments are required both for identification and quantification.
3. Particles were detected in the food simulants in most cases that PLA, MFC or inorganic/organic hybrid polymers were used for the migration tests.
4. Very low detection limits were obtained only for some of the sensors as well as fragments from the hybrid polymers.
The methodologies followed for the study of migration of species into food simulants into biopolymer formulations were adapted for the study of migration from the final demonstrators. For the case of demonstrators specifically designed migration cells, according to EU standards and regulations, were used. The submersion method was thus more controlled since the surface area of the demonstrators which was in contact with the food simulant is known with satisfactory precision. The food simulant volume is also better controlled.
The cells were meticulously cleaned before the migration experiments. In addition the demonstrator parts were rinsed thoroughly with the food simulant before the test in order to discard any particles that could interfere with our measurements. The cells were subsequently put in the shaking incubator at stable temperature (40oC) for a period of ten days. Portion of the food simulant was carefully removed after some days and transferred to the measurement area (UV-Vis and DLS) in order to be checked with respect to migrating species. This portion was then put back in the cell after the measurements.

A summary of the conclusions derived from the migration tests on the demonstrators is given below (more details are given in deliverables 5.2 and 5.4):
Demonstrator 1 – thermoformed multilayer film
The PLA based biopolymer is actually a blend consisting of 70% Fkur PLA BioFlex F 6510 and 30% Fkur PLA Fkur A 2243. The barrier promoter is a mixture of NFC and sorbitol. No sensors and no scavengers involved.The packaging material is specified for meat food and is a tri-layered film consisting of the PLA based biopolymer film in the outer layers and the barrier promoter in the middle layer.
Typical food simulants (meat food): 10% and 50% EtOH solutions and the 3% acetic acid solution
Migrating species after 10 days of migration test:
50% EtOH: Terephthalic species belonging to the structure of the biopolymer (concentration ~2.5 μg/ml in an experiment involving single side use of a 120 mm in diameter migration cell with 200 ml food simulant. That is ~4.4 μg migrating to the food simulant per 1 cm2 of film).
10% EtOH: Terephthalic species belonging to the structure of the biopolymer (concentration ~0.25 μg/ml in an experiment involving single side use of a 60 mm in diameter migration cell with 50 ml food simulant. That is ~0.22 μg migrating to the food simulant per 1 cm2 of film).
3% Acetic acid: Terephthalic species belonging to the structure of the biopolymer (concentration not trustful, however estimated to be similar to the 10% EtOH case).
Notes: The structure of the film is altered after the migration tests. The visually inspected alterations were studied by μRaman, FTIR, XRD and DSC. The results correlate well with the species found in the food simulants during the migration test. Slight modification of polymer MW of the side that is in contact with the food simulant is indicated by DSC. The overall H2O and O2 transport properties of the tri-layered film are not altered after the migration test (i.e. after structural alterations) at least within the error bar offered by the technique used
Demonstrator 3 – blow moulded bottle
The biopolymer is BioPET (few samples contained PETG in 10% proportion with bioPET). The Barrier promoters used are (a) Funzio-nano (hybrid polymer from SINTEF) either spray coated or blended, (b) LDH SH (from Aveiro) blended. Scavengers: produced in FORTH, blended. No sensors were involved. The packaging material is specified for Beverages & sauces and is a blown film.
Typical food simulants (sauces):
The 50% EtOH and the 3% acetic acid solutions. 3D water was also studied (for the DLS experiments). 2D with SDS was studied for the case of scavengers.
Migrating species after 10 days of migration test: 50% EtOH: Nothing observed for the case of bioPET spray-coated with Funzio-nano. Nothing observed for the case of bioPET blended with scavengers.
3% Acetic acid: Nothing observed in the bioPET blended with LDH-SH.
3D water: Nothing observed for the case of bioPET blended with LDH-SH or Funzio-sano.
3D water with SDS: Nothing observed for the case of bioPET blended with scavenger.
Notes: DLS results indicate the migration of nanoparticle in the 3D water food simulant especially in the case of Funzio-nano blend and the LDH blend (with the highest concentration). However the development of the particles as a function of migration time is not significant a fact that suggests that the particles observed have migrated to the food simulant by desorption.
Demonstrator 4 – injection moulded jar
The biopolymer is PLA. The barrier promoter is spray-coated Funzio-nano. NFC was also served as a secondary barrier promoter blended with PLA. The packaging material is specified for sea-food.
Typical food simulants (sea food):
10% and 20% EtOH solutions and the 3% acetic acid solution
Migrating species after 10 days of migration test:
20% EtOH: Salicylic acid species belonging to the structure of the hybrid polymer/Funzio-nano (varying concentrations from ~0.32 μg/ml to ~11 μg/ml different experiments involving single side use of a 30 mm in diameter migration cell with 10 ml food simulant. That is ~0.5 μg to 15.6 μg migrating to the food simulant per 1 cm2 of film).
3D water: Salicylic acid species belonging to the structure of the hybrid polymer/Funzio-nano slightly visible peaks after 10 days of migration test
Notes: A number of experiments were repeated for verification of the migration of the Funzio-nano migration into the food simulants. Due to the fact that there exist strong deviations of the migrated quantities in each experiment, there exists a possibility for the inner walls of the jars to have been spray-coated by the Funzio-nano barrier promoter. This statement is supported by the lack of detection of migrating species when the Funzio-nano is either spray-coated on or is blended with bioPET.
Demonstrator 5 – blown film
The biopolymer is PLA. The barrier promoter is a mixture of NFC and sorbitol (5% in total blended with PLA). No sensors and no scavengers involved. TTI sensor was applied and was studied in D5.4. The packaging material is specified for meat food and is a blown tri-layered film consisting of PLA film in the outer layers and the barrier promoter in the middle layer.
Typical food simulants:
10% and 50% EtOH solutions and the 3% acetic acid solution
Migrating species after 10 days of migration test:
50% EtOH: Nothing observed for the case of PLA tri-layered film. Unspecified species (UV-Vis absorption at ~280 nm) migrate progressively with time for the case of PLA/NFC/PLA tri-layered film.
3% Acetic acid: Unspecified species (UV-Vis absorption at ~280 nm) migrate progressively with time for the case of PLA/NFC/PLA tri-layered film. Their concentration is less than half the one observed in the 50% EtOH food simulant.
3D water: DLS experiments indicate the existence of nanoparticles with size roughly 80 and 500 nm whose scattering intensity increases with time of incubation.
Notes: No migrating species from TTI sensor were detected. Components of the film (NFC and sorbitol) were not received. For detailed study of the migrating species all components involved in the film formation should be thoroughly studied. With respect to the TTI sensor ee have developed a useful methodology for the detection of ascorbic acid incorporated in printed inks that may migrate into food simulants from the food packaging materials. The methodology deals with the possible instability of ascorbic acid and attempts to transform any resulting species in stable oxidation ones that can be detected easily with UV-Vis.
Additional toxicological experiments were performed on the food simulants collected from the migration cells after the completion of the 10 days period migration tests applied on the demonstrators. The information extracted from the supplementary experiments was considered valuable since the results evaluate the direct effect of the possible existence of migrating species in the food simulants to the living cells. All toxicological tests applied on the food simulants after the migration tests indicated that within the examined concentration range all the materials tested exhibit low toxicity with respect to the control food simulants for each case.
For the last months an additional Task was approved and consequently added in the framework of WP5. The Task covered the end-users migration tests and in brief the specific Task consisted of a series of experiments:
- Migration measurements of bottles and jars (10 days at 40oC) filled with appropriate food simulants and an additional end-users product filled with real food (ketchup).
- Final migration solutions were studied with several techniques.
- Migration solutions were subjected to toxicity tests (to identify and evaluate potential risks and fate) including.
Subtask 5.1.3. Migration modelling and experiments: Results/foregrounds
The effect of crystallinity ratio on the diffusion coefficient using EMT approximation was investigated using CFD simulations in one and two dimensions, and validated with experimental results. Three-dimensional studies have also been performed, and secondary crystallization effects have been investigated.
The effect of the crystallinity ratio on the migratability of 5 nm nanoparticles for 1 year in PLA was investigated using CFD simulations, for several key operating temperatures. The migratabilities increase with decreasing crystallinity and increasing operating temperatures, in accord with experimental observations. In similar structures, i.e. semi-crystalline PLA of ordered anisotropy, the temporal evolution of the apparent diffusion coefficient of 5 nm nanoparticles was also studied during this period with CFD calculations, and shown to depend on the crystallinity. More general conclusions for the crystallinity effect on the membrane migratability were also drawn using non-ordered (random) anisotropy.
The rate of particles that enter the food after migration in the interior of the polymer was found to have significant effect on the migration of nanoparticles over a wide range of nanoparticle diffusivities.

Task 5.2: Cell viability assays & cellular uptake of nanomaterials, Oxidative stress & Cell cycle, Cell morphological evaluations & genotoxicity testing, In vitro digestion studies
An extensive study, applied to all materials used in demonstrator products has been carried out.
NPs based on PVAc demonstrated dose dependent impact to cells viability. K29, 38% hydrolyzed NPs show the least impact to the cells and can be considered as non-toxic The other PVAc based NPs are slightly toxic and have a 50 % reduction of cells proliferation at concentrations of 200 to 500 µg/ml which is any way too high for the realistic conditions.
Calcined and commercial hydrotalcite from the University of Aveiro (UAVR) were dissolved in 1 M hydrochloric acid, diluted with buffer and cell culture medium and added to the growing cells. Both materials in this state demonstrated the low toxicity. It was show previously that the calcined hydrotalcite dispersed in a buffer has demonstrated the moderate toxicity in the wide range of concentration (from 10 to 1000 µg/ml). Commercial hydrotalcite does not mix with buffer and its toxicity in the native state could not be evaluated.
Mesopurous silica (unloaded) and quantum dots dispersed in serum demonstrate low cytotoxicity in the studied concentration range. In opposite, the silica particles loaded with quantum dots are cytotoxic with viability of 50 % at about 50 µg/ml.
The possible explanation for this behavior is that toxicity of Mesoporous silica depends on the purification rate. The cetyltrimethylammonium chloride (CTAC) serves as a template during silica preparation and is removed by washing with tetra ammonium chloride solution. QD- loaded mesoporous silica grows in the presence of CTAC and QDS, and is purified using the same procedure. Most probably, the QD-loaded mesopourous silica samples contain excessive CTAC which adsorbs to quantum dots via hydrophobic interactions and cannot be removed by a standard purification procedure.
Titanium oxonitride (TiNO) nanoparticles as well as the extracts from PET and PET/TiNO composites show low cytotoxicity in the whole studied concentration range (1 to 1000 µg/ml).
SubTask 5.2.2.: Oxidative stress & Cell cycle
The initiation of inflammation response is one of the most important adverse effects after exposure to a toxic agent. Nanoparticles/nanomaterials were evaluated for their cytotoxicity in terms of oxidative stress (ROS generation, induction of immune response) and their effect on the cell cycle. The release of pro-inflammatory cytokines (IL-6, IL-8) by A-549 cells treated with the tested materials was evaluated in terms of inflammatory response by the enzyme linked immunosorbent assay (ELISA) in cell culture supernatants, after 24h incubation with the tested materials. The ROS generation plays an important protective and functional role in the immune system. Oxidative stress occurs in cells when the generation of ROS overwhelms the cells’ natural antioxidant defenses. Cells were exposed to certain concentrations of tested substances, were loaded with fluorescent dye and fluorescence intensity was measured.
SubTask 5.2.3.: Cell morphological evaluations & genotoxicity testing
Toxicity related with oxidative stress was examined in terms of cell morphological evaluation and genotoxicity. In order to examine any possible adverse effects on cell cytoskeleton and cell morphology caused by nanoparticles/nanomaterials were classified. For this reason, cells were labeled with anti α-tubulin antibody and phalloidin dye against F-actin, characteristic structural components of cell microtubules network, depicting microtubule properties such as stability and structure. Moreover, detection of DNA damage is conducted via comet assay, following treatment of blood cells with nanoparticles, encapsulation of cells in an agarose suspension, electrophoresis of lysed cells and staining the DNA to determine the extent of DNA damage. Finally, the hemolytic potential of red blood cells upon exposure to nanoparticles was also assessed, measuring the amount of hemoglobin released. After the preparation of an erythrocyte suspension from fresh blood of healthy human donors, bold cells were treated with the tested samples and the amount of hemoglobin released into the supernatant was determined spectrophotometrically.
SubTask 5.2.4.: In vitro digestion studies
In cases where the nanomaterials persists in the food/feed matrix and before starting in vivo toxicity, studies including the transformation and stability of the nanomaterials in gastric fluids were investigated. The effect of the gastric conditions on the studied materials was simulated by incubating the formulations in simulated gastrointestinal fluids for 4 h in 37oC. A measurement for absorbance at 450nm was taken for the samples before the simulated gastric fluids (pH 1.2 pepsin 0.32% w/v) were added in order to exclude the potential absorbance from them alone. Nanoparticles digestion in gastric fluid was determined by the measurement of each sample supernatant absorbance in 450nm.
The conclusions derived from the toxicological tests is that all materials tested showed low toxicity.

Sustainable product design
The sustainability aspects of NanoBarrier demonstrator products have been the topic of the work package WP6. This work was divided in three blocks: life cycle assessment, ecodesign and waste management.
The objective of the Life cycle assessment in NanoBarrier was to identify and prevent the environmental impacts associated to the products and demonstrators developed. The work carried out in this area is subsequently described.
The objective of the ecodesign was to guide the development of the demonstrator by taking into account environmental, technical and economic considerations. The work carried out in this area is subsequently described.
The objective of the waste management activities in was to guarantee that the development of products and demonstrators is aligned with current recycling, composting and valorization technologies.
The main outline of the work in this area with main conclusion are:
Life cycle data collection and life cycle description
✓ Life Cycle Definition and Description including and describing the initial LCA diagrams for the four demonstrators was described.

Environmental assessment by LCA
✓ Life cycle questionnaires of the four demonstrators
✓ Life cycle models of the four demonstrators
✓ Information collected to update the life cycle models for the four demonstrators
✓ Results showed reduced environmental impact in most of the impact categories

Demonstrators ecodesign
✓ Execution of an ecodesign workshop in which the methodology to integrate environmental criteria during packaging development have been explained to the partners. The documents derived from this workshop are: program of the workshop, presentation for each phase of the workshop, documentation required to carry on the example of application. This workshop was carried out in the first project period.
✓ Formation of the four ecodesign groups which will carry out this activity during the project.
✓ Execution of the first ecodesign step (Ecodesign planning).
✓ 1st report on ecodesign integration in demonstrators.
✓ Execution of the second ecodesign step (Initial Environmental Impact Analysis).
✓ 2nd report on ecodesign integration in demonstrators.
✓ Execution of the third ecodesign step (Actions for environmental improvement).
✓ Preparation of the material to carry out the following steps of ecodesign (development of concepts, design, action plan and final evaluation).
✓ Ecodesigned demonstrators with a significantly reduced Carbon footprint compared to benchmarks

Waste management chain
✓ Analysis of the waste management options in Europe of the future packaging demonstrators.
✓ Definition of the waste management guidelines associated to the packaging demonstrators.
✓ Recycling trials. Description of the initial methodology to experimentally identify and prevent the valorization constraints associated to the packaging demonstrators.
✓ Initial overview of the spectra of conventional and biobased, coated and uncoated plastics have been prepared (PET and PLA) to conclude on compatibility with spectroscopic sorting systems.
✓ The conclusion is that the demonstrators are compatible with existing waste management systems (composting or recycling).

Potential Impact:
Potential impacts of NanoBarrier.
The expected final result will be sustainable packaging solutions with improved barrier properties and integrated sensor elements to ensure food safety. The project will contribute to competitive advantage of these food segments of high economical importance for EU-region, i.e. the sustainable barrier packaging systems will strengthen the position of the EU-region in these markets that are very packaging-sensitive. There are significant market perspectives for both raw material producers and plastic converters.
NanoBarrier will develop several demonstrators which if successful will contribute to a low-carbon economy. Life cycle analysis indicate that bioplastics could enable a CO2 saving of 30-80% compared to conventional plastics. This does not, however, apply generally, but depends on the product and application. Demonstrator development in NanoBarrier was therefore closely linked with ecodesign methodology and sustainability evaluation to ensure solutions compatible with the whole packaging value chain. The demonstrators were realized on existing resource-efficient processing equipment, ensuring viable solutions for the packaging business, i.e. the realization will not depend on heavy investment of processing equipment.

NanoBarrier impacts
NanoBarrier was planned to contribute to the main goal of Theme NMP as it to develop the necessary competence to realize innovative, sustainable and safe nanomaterials and incorporation of those into biomaterial-based packaging to enable safe, added-value food packaging solutions in several important food sectors. NanoBarrier also contributes to reinforce the scientific and technological base several SMEs and larger enterprises through an effective integration of nanotechnology, materials science and design and at the same time, supporting sustainable production and consumption. NanoBarrier focuses on the call listed in the work programme as “NMP-2011.1.1-1 Smart and multifunctional packaging concepts using nanotechnology”.
NanoBarrier will contribute to the following listed impacts in the call:
i). To demonstrate the viability and benefits of smart and multifunctional packaging concepts capable of enhancing environmental sustainability of packaging business and contributing to low-carbon economy.
Viability and benefits
The viability and benefits of the smart and multifunctional packaging concepts developed in the NanoBarrier project are related to;
• Traditionally barrier solutions often involve multilayer solutions constituting incompatible polymers. There is therefore a need for tie layers which demands for complicated and expensive equipment. As the number of layers increase, so will also the material costs increase. Improper compatibilization may lead to delamination problems, increasing the percentage of rejects. Some existing products contain more than ten layers thus demanding substantial investments in equipment. Technological complications could be considerable. NanoBarrier will work with packaging demonstrator concepts involving simpler barrier solutions where barrier- and sensor performance is predominantly introduced through coatings and/or printing technologies. This also means that potentially more actors will be able to enter the market – thereby strengthening the viability. As examples, the multifunctional jars planned in NanoBarrier will be a monolayer solution, which is much simpler for a technological point of view compared to multi-layer solutions. A simpler design will in general also be related to more cost- and energy efficient production processes.
A further benefit that will enhance viability through simpler design is within blow moulding. The significant amount of end caps/scrap occurring during production is hard to re-enter into the production line when multi-layer barrier solutions are used. However, this will be omitted through simpler solutions where the barrier layer is introduced through a coating approach. Therefore, more in-house scarp is expected to be re-used with bottle demonstrators proposed in NanoBarrier.
A third benefit that will enhance viability through simpler design is compatibility with existing waste streams. As an example, the planned development of 3D formed board will replace todays` solutions where parts of the packaging is polymer based and parts of the packaging is fibre-based. Solutions that fit mono streams are desired, and NanoBarrier will contribute towards such a development.
• Viability and benefits due to continuously increased attention by the ever more environmental-conscious European customers and focus on health risk due to food spoilage. NanoBarrier will develop demonstrators that specifically address these aspects, through use of sustainable materials from renewable resources and solution concepts with built-in sensors for customer safety and enhanced barrier performance.
• The concepts and solutions in NanoBarrier will be developed to be compatible with the major existing processing methods within conventional plastic processing; thermoforming, injection moulding, blow moulding and film blowing. This increase probability for industrial up-take and implementation.
• The planned coating solutions in NanoBarrier for bottles and jars are based on spray coating, a methodology that today is to a large extent automated in industry. This approach is therefore cost-efficient which increase the viability and potential for market penetration.
• As described in section 2.3.5 the industrial consortium is well balanced between SMEs, which have the flexibility to enter smaller scale niche productions with added-value products, and large multi-national actors having large market impact, with large volume capacities. This balance and variety also contributes to increase the viability of the planned concepts.
Contribution to low-carbon economy
NanoBarrier will develop several demonstrators based on use of barrier promoters and sensors integrated in biopolymer formulations in a safe and responsible manner. Life cycle analysis indicate that bioplastics could enable a CO2 saving of 30-80% compared to conventional plastics but this depends on the product and application. Demonstrator development in NanoBarrier will therefore be closely linked with ecodesign methodology and sustainability evaluation to ensure solutions compatible with the whole packaging value chain. The demonstrators were realized not depending on heavy investment of processing equipment.

ii) To meet the demands on packaging recyclability and raw material based on renewable sources.
NanoBarrier contribution: The project aimed to develop a nanotechnology-based technology platform for barrier-enhanced and multifunctional food packaging solutions. There are several aspects that contribute towards this expected impact;
• The concepts and solutions in NanoBarrier are based on biodegradable or recyclable materials and components. Actions and activities were planned to understand and secure minimum impact on present waste streams. The influence of planned biodegradable solutions on existing plastic waste streams was explored. Separation of the biodegradable solutions through spectroscopic methods was explored. This technology can be used to avoid contamination of given waste streams or, if found a viable alternative, separate the biopolymer in a fraction for recycling. Furthermore, the biodegradable solutions in NanoBarrier will apply thin layer coating technology that also contribute to minimize potential negative effects on waste streams. Furthermore, there will be solutions in NanoBarrier, e.g. the board, being directly compatible with existing recycle streams.
• At all levels in NanoBarrier, materials based on renewable resources will be applied. Examples are the various biopolymers that will be applied, the fibre-based board that will be formed, microfibrillated cellulose (MFC) used as barrier films, scavengers and additive technology based on renewable resources and hybrid polymers where all major components are based on renewable resources.

iii) To promote the creation of markets for products and processes utilising smart and multifunctional packaging concepts, thus boosting the competitiveness of the European packaging industry and contributing to growth and jobs.

NanoBarrier will enable several sustainable demonstrators based on smart- and multifunctional packaging concepts in a range of important food markets where the prospects are set for significant growth, contributing to business and jobs. The project will contribute to competitive advantage of these food segments of high economical importance for EU-region, i.e. the sustainable barrier packaging systems will strengthen the position of the EU-region in these markets that are very packaging-sensitive. There are significant market perspectives for both raw material producers and plastic converters. This will be discussed below.

NanoBarrier has addressed all three packaging sectors; i.e. rigid- and flexible plastics and boards that in summary constituted 71% of the global packaging market in 2012.

Market perspectives for board
The paperboard sector is mainly considered in conjunction with the paper industry. The annual production of paper used for packaging applications is of the order 45 million tonnes (2015) according to data from CEPI, the Confederation of European Paper Industries. Hence the packaging sector is of major importance for the industry. Two key market trends relate to sustainability, i.e. minimising the use of fibre material and additives such as fossil based barriers, and product safety. Here the results from NanoBarrier are expected to pave the way for new innovative product concepts combining a sustainable packaging solution with a long and safe shelf life. The market outlook for such solutions is very positive once they can be made at a reasonable cost. In such cases rapid changes can be foreseen since the market request is already there.

Market perspectives for flexible plastic packaging
The global flexible packaging market was projected to a reach of $210 billion in 2015 accounting for 22 % of the world total. Flexible plastics has been the largest and fastest growing materials for flexible packaging. Europe remains one of the world’s largest and most sophisticated flexible packaging markets. Further growth in plastic film is expected to be particularly strong in food applications, such as meat, seafood, fresh food and frozen food. Flexible barrier films that preserve product freshness are gaining market share. Another important factor is that biodegradable, sustainable and recyclable flexible packaging materials are gaining favour as retailers and brand owners seek to improve the environmental footprint of their packaging.
NanoBarrier will develop demonstrators based on sustainable multifunctional barrier-enhanced and flexible plastic film, both from film blowing and thermoforming, where meat packaging is one important target segment. Demand for meat and poultry packaging increased by 3.5 percent annually to $9.2 billion in 2013 in US. Similar trends are seen on the European arena, driven by an expansion in meat and poultry production and the continuing shift to case-ready packaging by many retailers. Such packaging typically employs higher cost trays and high barrier films, thus boosting value gains. These products, typically using more packaging relative to volume, will continue to be favoured by consumers. Growth will be driven by favourable prospects for high barrier film and pouches. High barrier film demand will be aided by the rising percentage of meat in case-ready packaging, which requires value-added materials to extend shelf life and otherwise protect the contents during shipping and handling.

Market perspectives for rigid plastic packaging
Global rigid plastic packaging consumption amounted to 30.7 million tones in 2009 and is forecast to grow to reach 37.1 million tones in 2014. In Europe this had a value of $44.6 billion in 2009, was expected to grow to $ 51.6 billion in 2014. An important trend is that stringent recycling targets are putting pressure on packaging suppliers to collect and recycle waste packaging. There is growing public pressure to reduce excessive packaging as consumers become more aware of how packaging has an impact on the environment. Packagers are responding to these concerns in a number of different ways. These include a greater recycled content for the plastics packaging, continued light weighting of plastic packaging, and adopting polymers that are either biodegradable or recyclable derived from sustainable resources.

The blow moulded bottles market is presently largely driven by developments in the mineral water and household chemicals markets, where plastic bottles account for more than 90% of the packaging used. An important driver is that glass is believed to have reached its limits in terms of light-weighting, and there is growing doubt among the brand owners about its ability to evolve with market needs. The growing emphasis on the carbon footprint of packaging supply and end of life management will therefore give a competitive advantage for plastic packaging. Research from Applied Market Information suggests that the latent potential for PET barrier bottles in beer, wine, and milk is equivalent to the current size of the carbonated soft drinks (CSD) market for PET bottles in Europe. PET bottle consumption was 3 million tons in 2014 with a resin recycling rate of 57.2 %. In particular, beer represents a market of significant long-term potential for plastic bottles, which today is dominated by aluminium cans and clear and coloured glass. Important markets trends are believed to be more barrier plastic bottles, inclusion of time – temperature indicators and secondary packaging from renewable/biodegradable polymers. In general, the blow moulding industry is moving toward multi-layer and barrier applications. Other opportunities are expected to emerge in food markets, where plastic bottles have yet to make a major impact.
NanoBarrier will develop demonstrators based on sustainable multifunctional barrier-enhanced injection stretch blow moulding bottles for oxygen-sensitive segments, e.g. juice, beer, ketchup. As described above, there is a significant market perspective in e.g. beer bottles. Furthermore, the European fruit beverage consumption was 11 billion litres in 2013. There is a demand for organic, natural and sustainable products, which directly relates to consumers concern about health, and immunity. In fact, Europe consumes 40% of all orange juice produced in the world.
NanoBarrier furthermore aims to develop barrier-enhanced and multifunctional solutions for seafood packaging (e.g. crab). Although the health benefits of fish and seafood are known and documented, consumers often resist buying fresh seafood due to short shelf life. New barrier-enhanced packaging can remedy that problem. Being highly susceptible to oxidation and degradation, seafood is often treated with thermal processing methods such as cooling, ice (which requires special drainage and handling processes to avoid pathogenic contamination) or vacuum-packing. Meat, poultry and seafood applications are predicted to increase 4.2 percent annually aided by rising production volumes and a perception of them as economical protein sources, as well as ongoing growing demand from the foodservice sector.

Market perspectives for additive and nanomaterials producers
The global market for functional additives and barrier coatings used in plastic packaging is forecast to reach $3.7 billion in 2018. PVC coatings, followed by metallized coatings and EVOH have had the major market share.
NanoBarrier will work entirely by bio-based materials. In Europe, 50% of the biopolymers are used in packaging applications. In 2013 the biopolymer production is set to be 900 000 tons giving 450 000 tons within packaging. If an additives level of 5% is assumed, this will represent 25 000 tons of additives, a significant market for actors willing to promote and enter the biopolymer-based packaging market. This is highly relevant figures for several of the companies in NanoBarrier as Borregaard and PlasmaChem. Furthermore. Active technology represents the largest share of the market, and will continue to do so. Among active technologies, oxygen scavenger, moisture absorbers and barrier packaging represent more than 80% of the current market.

A final comment is made on market perspectives related to quantum dots (QD). The market of QD was estimated to 1 Billion US$ by 2013. The biggest problem so far, which may influence development of this market upon introduction of regulations on toxic products – is the employment of cadmium as one of the QDs components. This also hinders the employment of QDs in the products, where their concentration should be high (current regulations permit the use of Cd at max. 0.01% from weight of a homogeneous phase). These all limitations can be successfully overcome if Cd-free quantum dots with comparable characteristics can be synthesized. ZnO, as is targeted in NanoBarrier, is a good candidate. Other areas of potential use of such QDs include: lightning applications, medical diagnostics and photovoltaic applications.

Provide tangible benefits to consumers in terms of improved performance, safety and security of products and management of domestic waste.
NanoBarrier contribution:

Benefits to consumers through improved performance
The main benefits to the customers will be packaging showing a combination of desired performances
• Solutions with reduced environmental footprint, in-line with the environmental-conscious European customer. Materials based on renewable resources.
• Built-in sensors for increased customer safety (see also below)
• Design that prevents nanomaterials to come in direct contact with food (see also below)
• Shelf-life according to expectations.

Benefits to consumers through safety and security of products
It has been claimed that nanoparticles and/or nanostructured materials (particularly in the form of nanotubes that resemble asbestos) may be harmful to the human health because they do not degrade. However, so far very little is scientifically known about this issue. It should be noticed that e.g. silicates (that is going to be used in NanoBarrier) have been used for nearly one century in applications such as foundry, detergency, paper, and ceramics without any provable harmful effects. In this particular case, the starting material constitutes micron-sized particles (aggregates) due to an extreme affinity between individual particles, so at this stage there is no release of single particles to the environment. At synthesis and processing conditions, the nanostructured materials (also to be used in the present project) are typically handled in closed systems.

A further important health and safety aspect in the NanoBarrier project is the design of barrier- and sensor solutions, to avoid unwanted food contact, i.e. to take advantage of nanotechnology solutions but at the same time minimizing the potential for interaction between the nanostructured materials and the food. In NanoBarrier, sensors and barrier solutions involving use of nanostructured materials are i) either confined to the outside of the packaging, either within a coating, or applied through printing technologies, or ii) confined as a separate barrier layer as the middle layer in a 3-layer structure. Therefore, no solutions where nanomaterials come in direct contact with food will be applied. In addition, only components approved for food contact will be used in designing the barrier- and sensor materials.

NanoBarrier will e.g. provide innovative sensor concepts through nanocapsules that allows for monitoring and release upon unwanted pH gradients. This will work as a sensor to monitor food spoilage, which is a major concern for the consumers. As an example, there has been concern due to tendency of fish and seafood for rancidity and texture softening. Enzymatic and chemical reactions are usually responsible of the initial loss of freshness attributes whereas microbial activity is responsible for the overall spoilage, determining product shelf-life. Therefore, the potential positive health impact of fish consumption is depressed due to growing customers’ scepticism and quality concern. An integrated sensor system that could release e.g. dyes (that could be monitored) upon spoilage, will therefore contribute to customers safety. NanoBarrier will therefore represent a sustainable approach to further ensure consumer growth and acceptance of e.g. fish- and seafood in EU region, taking customer safety into account.

In the NanoBarrier project, health and safety issues will be closely monitored during the whole project period, and to secure the necessary attention, competence and integration of health and safety, a separate WP has been designed (WP5) to properly address this. Migration tests will be performed in relation to all potential solutions. In addition cytotoxicity of nanoparticles will be assessed by cell proliferation and cell viability assays. Activities will also address fate of nanostructures beyond packaging lifetime. NanoBarrier will therefore promote and secure industrial up-take of novel solutions based on nanotechnology, in a safe and responsible manner.
Benefits to consumers through management of domestic waste
The NanoBarrier project will introduce demonstrator solutions that are believed to be compatible with present domestic waste systems, i.e. the waste system will not be more complicated or expensive for the customers

Need for a European approach.
The food packaging market is increasingly in the hands of multinational companies. There is a global competition between USA, Asian and European multinational companies. Hence, any incentive programme would best be handled at the European level for better efficiency and co-ordination. In NanoBarrier, all partners have participated to trans-national R&D initiatives and projects. New break-through insights in nanoparticle technology developed at single institutes and companies that normally do not interact, are brought together to foster the development and dissemination of new barrier-enhanced and multifunctional design. The diverse knowledge necessary to realise this needs a European approach. The proposed consortium is the best possible solutions to address these needs since the different partners complement each other perfectly, covering all the required S&T fields and the value-chain ideally. None of the individual partners would be able to succeed in developing the proposed technology alone and within a short time. For the reliable achievement of the ambitious NanoBarrier objectives a European project approach is required. The synergic and complement collaboration between universities, institutes and industries of different European countries allows a fruitful networking for the effective and efficient accomplishment of the project goals, rather than a national technology program. A national project, being limited to a local choice of the partners, might not always have the best "players" for achieving the defined objectives.
The interest in sustainable, nano-aided and safe packaging solutions is growing worldwide, since developments in this field could provide society with innovative and cost efficient products in combination with increased customer-safety. In order for Europe to be competitive in this area, it is necessary to join forces, competence and facilities.
In general, most member states in the EU region have SME specific support actions, however they tend not to promote trans-national cooperation which is becoming increasingly important for SMEs aiming to internationalise their activities. Therefore, the NanoBarrier initiative, which has central SME partners from different EU-countries, need to be raised to an EU-level.

Assumptions/external factors necessary to bring about the impacts
The following assumptions/external factors have been made to bring about these impacts;

Future growth and price competitiveness for bioplastics
The expected impact is dependent of a further growth and a positive price development of bioplastics as compared to traditional plastics. The overall cost of demonstrators will be dependent on the biopolymer price and therefore the viability of the demonstrators will rely on a proper cost-performance development of the biopolymers. The present price level is in general regarded too high for biopolymer-based solutions to be fully competitive in the food- and beverage packaging market. PET had in Feb 2011 a general price level of 1.3 €/kg, compared to PLA that ranged from 1.3-1.9 €/kg, PHA that ranged from 3.7-4.5 €/kg and starch-based materials from 2.3-3.4 €/kg. Polyolefin prices, PE and PP, have varied around 1.2 €/kg and for a relevant barrier material as EVOH the price has been in the range 5-6 €/kg over the last years. However, by 2020, global bioplastic packaging demand is forecast to reach 2 million tonnes, with an aggregate growth rate of 21% between 2015 and 2020, and 18.3% in the period 2015-2020. In general, it is furthermore claimed that using a full cradle to grave approach that not only looks at financial cost and processability of the material, but also the cost for disposal and incineration will make the price difference smaller when compared to conventional material.

End-of-life handling
Due to the present low volume of biopolymers and since conventional recycling facilities are not designed to accommodate bioplastics, there is at present a risk of contamination of such plants. In the medium-to longer terms, dedicated plants for bioplastics will therefore be required. Furthermore, as e.g. bioplastic-based injection moulded products are realized, products having wall thickness on the mm-scale will start to appear, rather than films and application in the µm scale. This will probably require attention in the composting lines, and also the current composting directives are based on thin applications.

Comparing new sustainable packaging to existing solutions we have taken the environmental impact of the solutions into account. A candidate measure is the global-warming potential (GWP) which is a relative measure of how much heat a greenhouse gas traps in the atmosphere. Comparing PLA to glass, which is relevant for Argo's injection moulded jar, glass has twice the GWP compared to PLA.

Main dissemination activities and exploitation of results
From project start, a public website was established:
Most of the dissemination activity during the project period has been as conference presentations. In all 15 oral or poster presentations have been given at different conferences.
Partners have published 4 articles in scientific journals during the same period. More scientific publications have been announced for the period after the end of the project as one during project execution has focused on meeting project goals on component production and demonstrator properties.
Popular dissemination of results has taken form as press releases, an article in Food Production Daily, project description in Logoplaste's information folder to customers.
The 1st open seminar was organized on October 1st 2014 in collaboration with another EU FP7-project - Dibbiopack, and funded within the same call as NanoBarrier. Two other projects contributed with posters in the seminar; ECLIPSE and OLI-PHA. On this occasion results from NanoBarrier was displayed through seven oral or poster presentations.
Rather than inviting participant for a 2nd open seminar, it was decided to participate in the PACE conference in Amsterdam February 9-11 2016. In this way one assured the presence of main actors from both the packaging the industry and the food sector. On this occasion, NanoBarrier was presented by an oral presentation to the full audience, a booth with project posters and demonstrator products in addition to two round-table open discussions that attracted considerable attention. Several contacts were made for possible follow-up of NanoBarrier results.

Exploitation of results
As background for exploitation of project results, an Exploitation Strategy Seminar (ESS) was arranged in Stockholm on 27th of March 2014.
By then, we already had produced a preliminary exploitation plan presented as a deliverable report to the Commission.
Together, this formed the basis for the final exploitation plan in NanoBarrier which was presented at the end of the project.

The final exploitation plan points to several categories of exploitable results are expected within the framework of the NanoBarrier project:
•Exploitation through demonstrators
4 demonstrators have been developed within NanoBarrier.
− Thermoformed multilayer film
− Blow moulded bottle
− Injection moulded jar
− Blown film

•Exploitation through barrier promoters
5 groups of barrier promoters are planned within NanoBarrier;
− Inorganic-organic hybrid polymers
− Microfibrillated cellulose
− Oxygen scavengers
− Hydroxyl-decorated organic nanoparticles
− Silica-based formulations

•Exploitation through sensors
4 groups of sensors are planned within NanoBarrier;
− Nanocapsules
− Ink-based sensors
− Layered double hydroxides
− Hydroxyl-decorated nanoparticles with fixed sensing elements

•Other exploitable results
− Waste management
− Life cycle assessment
− Polymer processing
− MFC based compounds using devolatilization technology

List of Websites:

Dr. Åge Larsen
SINTEF Materials and Chemistry
Tel: +47 98 28 39 35
Fax: +47 73 59 33 50