JOINT (TRANSNATIONAL) R&D SCHEME FOR ENVIRONMENTAL BIODEGRADABLE POLYMERS

JOINT (TRANSNATIONAL) R&D SCHEME FOR ENVIRONMENTAL BIODEGRADABLE POLYMERS

Innovative value chain development for sustainable plastics in Central Europe Work Package 3 Developing a roadmap for action – from science to innovation in the value chain

January 2013

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Introduction Over the past few years, the PLASTiCE Consortium has been involved in basic and applied research at the different stages of the environmental biodegradable plastics value chain. While each R&D institution is theoretically capable of delivering most research services, in practice, each institution is specialised in specific R&D activities. To better meet the needs of the biodegradable polymer and plastics producers in Central Europe and to enhance the development of new market applications, the PLASTiCE Consortium developed a joint (transnational) R&D scheme for environmental biodegradable polymer materials.

Thanks to the cooperation between seven R&D institutions from four countries, the joint R&D scheme offers tailor-made solutions for the companies in Central Europe that are involved in bringing new environmentally biodegradable polymer applications to market.

For further information on cooperating with the PLASTiCE Consortium, please contact your local R&D institution.

For Italy, Austria

University of Bologna, Department of Chemistry Ciamician’ (PP8) Mariastella Scandola, Professor, head of the Polymer Science Group +39 051 20 99 577/+39 051 20 99 456 mariastella.scandola@unibo.it

For Czech Republic, Slovak Republic

Polymer Institute of the Slovak Academy of Sciences (PP5) Ivan Chodak, Senior scientist, Professor +421 2 3229 4340 / +421 2 5477 5923 upolchiv@savba.sk Slovak University of Technology in Bratislava (PP6) Dušan Bakoš, Professor +421 903 238191, +421 2 5932 5439/ +421 2 5249 5381 dusan.bakos@stuba.sk

For Slovenia, Balkan States

National Institute of Chemistry (LP) Laboratory for Polymer Chemistry and Technology Andrej Kržan, Senior research associate +386 8 205 45 01 / +386 1 47 60 300 andrej.krzan@ki.si Centre of Excellence Polymer Materials and Technologies (PP11) Urska Kropf, Researcher +386 4 42 58 400 urska.kropf@polieko.si

For Poland, Baltic States

Polish Academy of Sciences, Centre of Polymer and Carbon Materials (PP12) Marek Kowalczuk, Head of the Biodegradable Materials Department +48 32 271 60 77/+48 32 271 29 69 cchpmk@poczta.ck.gliwice.pl Polish Packaging Research and Development Centre (PP13) Hanna Żakowska, Deputy Director for Research +48 22 842 20 11 ext. 18 ekopack@cobro.org.pl

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Contacts

National Institute of Chemistry, Laboratory for Polymer Chemistry and Technology (LP) Contact person: Andrej Kržan Function: senior research associate Tel./fax: +386 8 20 54 501 / +386 1 47 60 300 E-mail: andrej.krzan@ki.si Scientific personnel involved in R&D on biodegradable plastics : Professor: 1 Doctor: 3 Other scientific personnel: Infrastructure Laboratory for Polymer Chemistry and Technology Main equipment: FTIR, DMA, SEC, SEC-MALS, extruder, injection moulding Infrastructural centre NIC Main equipment: NMR, AFM, TEM, computer simulation

Polymer Institute of the Slovak Academy of Sciences (PP5) Contact person: Ivan Chodak Function: senior scientist, professor Tel./fax: +421 2 3229 4340 / +421 2 5477 5923 E-mail: upolchiv@savba.sk Scientific personnel involved in R&D on biodegradable plastics : Professor: 1 Doctor: 1 Other scientific personnel: 3 Infrastructure Department of Composite Materials Main equipment: Basic equipment for processing (laboratory mixer, extruder, mini-extruder), Advanced equipment for the characterisation of physical properties (mechanical properties, DSC, XRD, DMTA, XPS, dielectric spectroscopy, FTIR, nanoindenter, oscillating rheometer, tensometer), Equipment for modification of plastics – atmospheric plasma generator

Slovak University of Technology in Bratislava (PP6) Contact person: Dušan Bakoš Function: professor Tel./fax: +421 903 238191 /+421 2 5249 5381 E-mail: dusan.bakos@stuba.si Scientific personnel involved in R&D on biodegradable plastics : Professor: 2 Doctor: 4 Other scientific personnel: 5

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Infrastructure Centre for applied research of environmentally friendly polymer materials Main equipment: Twin-screw extruder,Mixer Laboratory of plastics processing Main equipment: Laboratory twin-screw extruder, Brabender Laboratory of rheology Main equipment: Oscillating rheometer. Capillary rheometer Testing laboratory Main equipment: Air-conditioned laboratory, Mechanical and thermal properties, Electron microscopy

University of Bologna, Department of Chemistry ‘G. Ciamician’ (PP8) Contact person: Mariastella Scandola Function: Professor, head of the Polymer Science Group Tel./fax: +39 051 20 99 577/+39 051 20 99 456 E-mail: mariastella.scandola@unibo.it Scientific personnel involved in R&D on biodegradable plastics : Professor: 2 Doctor: 2 Other scientific personnel: 4 Infrastructure Polymer Science Lab Main equipment: GPC Instrument, Differential scanning calorimeter; Thermogravimetric analyser; Dynamic mechanical analyser; Dielectric analyser; Polarised optical microscope with a hot stage and digital acquisition; Wide angle X-ray diffractometer equipped with an Anton-Paar TTK 450 heating device; Scanning electron microscope; Infrared spectrometer; UV-Vis spectrometer; Dynamometer; Contact angle; Atomic force microscope Nanoscope 3D; Electrospinning facility (with humidity and temperature control); Miniature mixing-injection moulding machine; Laboratory press; Spin coater; Temperature-controlled shaking bath; Vacuum oven

Center of Excellence Polymer Materials and Technologies (PP11) Contact person: Urška Kropf Function: researcher Tel./fax: +386 3 42 58 400 E-mail: urska.kropf@polieko.si Scientific personnel involved in R&D on biodegradable plastics : Professor: Doctor: 6 Other scientific personnel: 1 Infrastructure Centre of Excellence for Polymer Materials and Technologies laboratory Main equipment: MALDI-TOF-TOF MS; TGA; DSC; Reaction calorimeter; Pilot plant ultrasound processor; Laboratory mini-extruder Respirometric analyser for polymer biodegradation measurement; PoliMaT Laboratory elemental analyser C, N, H, S, O; Upgraded SIMS mass spectrometer; Adsorption porosimeter; UV system for polymerisation; Upgraded HECUS System-3 to S3-MICROpix; Model Free Kinetics software & UV set; Laboratory spray dryer; Laboratory mixer reactor; DSC measuring cell; Laboratory high pressure reactor; Apparatus for particle size determination in water; Laboratory shear mixer for powders; GPC/SEC instrument; Lyophilizator; Mass spectrometer (MS); Near infrared (NIR) spectrometer; Electrospinning device; Friction/peel tester; Upgraded injection moulding machine; Sputtering device for gold and carbon coating; Auxiliaries and accessories for AFM; Pilot scale electrospinning device

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Polish Academy of Sciences, Centre of Polymer and Carbon Materials (PP12) Contact person: Marek Kowalczuk Function: Head of the Biodegradable Materials Department Tel./fax: +48 32 271 60 77/+48 32 271 29 69 E-mail: cchpmk@poczta.ck.gliwice.pl Scientific personnel involved in R&D on biodegradable plastics : Professor: 3 Doctor: 5 Other scientific personnel: 6 Infrastructure Biodegradable Materials laboratory Main equipment: Micro-Oxymax; Instron model 4204, Mettler Toledo TGA/DSC STARe; ESI-MS; GPC; MiniLab II, MiniJet II; Mass spectrometer LCMS-IT-TOF, FTIR Analytical laboratory Main equipment: NMR spectroscopy

Polish Packaging Research and Development Centre (PP13) Contact person: Hanna Ĺťakowska Function: Deputy Director for Research Tel./fax: +48 22 842 20 11 ext. 18 E-mail: ekopack@cobro.org.pl Scientific personnel involved in R&D on biodegradable plastics : Professor: 2 Doctor: 1 Other scientific personnel: 4 Infrastructure CBiR Main equipment: LCA station, Program SimaPro 7, Station for compostability testing Laboratory for Packaging Materials and Consumer Packaging Testing Main equipment: Equipment for research on application properties

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Complementarity The PLASTiCE Consortium offers R&D services related to the polymer materials PLA and PHA, as well as starch-based materials, etc., according to the specific needs of the industry.

The following table gives an overview of the specialisation areas consortium partners.

Area of research

PLA PHA Starch-based materials

of the

Other materials

Characterisation of polymers on the market, including: composition and molecular structure solid-state properties

PP5, PP6, PP12

PP5, PP6, PP12

PP8, PP5, PP6, PP11

PP8, PP5, PP11

Modification of polymer properties using chemical routes, including: modification (with polymer modifiers)

PP5, PP11, PP12

PP5, PP11,PP12

PP11, PP12

PP11, PP12

functional polymers

Modification of polymer properties using physical routes, including: modification with additives

PP5, PP6, PP11 PP5, PP6, PP11, PP12

PP5, PP6, PP11 PP5, PP6, PP11, PP12

PP5, PP6, PP11

PP5, PP6, PP11

rheology, processing parameters

PP5, PP6, PP11

PP5, PP6, PP11

homogenisation (using internal mixers, single screw extruder, twin screw extruder)

PP5, PP6, PP11

PP5, PP6, PP11

films

PP6, PP11*, PP12

PP6, PP11*, PP12

rigid packing

PP6, PP11*, PP12

PP6, PP11*, PP12

flexible packaging

PP6, PP12

PP6, PP12

mulch films

PP6, PP12

PP6, PP12

polymer blends polymer composites, including nanocomposites

Processing, including:

Industrial production, including:

foamed materials

PP5

PP5

coated materials

PP11*, PP12

PP11*, PP12

Application properties of polymer products, including: aging properties of polymer materials

LP, PP5, PP12, PP13

LP, PP5, PP12, PP13

barrier properties of polymer materials (gas permeation)

PP5, PP12, PP13

PP5, PP12, PP13

PP5, PP6, PP8, PP11, PP12, PP13

PP5, PP6, PP8, PP11, PP12, PP13

PP13

PP13

thermo-mechanical properties of polymer materials durability and shelf-life properties (food contact, according to the European Directive EU 10/2011)

Biodegradation and compostability testing (according to EN, ASTM and ISO), including: under laboratory conditions

PP6*, PP11, PP12, PP13

PP6*, PP11, PP12, PP13

PP12

PP12

at municipal and industrial aerobic composting facilities

*: In cooperation with partners

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Area of research services

Description of the research activities

Characterisation of polymers on the market Solid-state physical properties (thermal, mechanical, structural, morphological) Analysis of the thermal stability (degradation temperature) of single- or multi-component materials (by thermogravimetric analysis, from RT to 900 °C in an inert atmosphere or air)

3 working days (single sample) 1-2 weeks (up to 10 samples)

Analysis of the thermal stability and mass spectrometry of volatiles (by TGA-MS, from RT to 900°C in an inert atmosphere)

3 working days (single sample) 1-2 weeks (up to 10 samples)

Analysis of thermal transitions (glass transition, crystallisation and melting, with determination of the transition temperatures and of the respective specific heat increments, crystallisation and melting enthalpies, by differential scanning calorimetry, T-range of -100°C-250°C, cooling with liquid Nitrogen), 2 scans per sample

2-4 weeks (depending on the number of samples)

Evaluation of mechanical properties at room temperature (elastic modulus, stress and strain at yield and break, by tensile testing with statistical analysis of the results for a minimum of 8 specimens)

2-5 weeks (depending on the number of samples)

Determination of the viscoelastic relaxations (by dynamic mechanical analysis in single- or multi-frequency mode, T-range of 150°C-250°C ) Structural analysis of the crystal phase (by wide angle X-ray powder diffraction) Product the client receives Area of research services

Description of the research activities

Product the client receives

Estimated service delivery time

3-4 weeks 2 weeks

Report on the physical properties of the analysed polymers Estimated service delivery time

Characterisation of polymers on the market Composition and molecular structure Determination of the solid-state properties using infrared spectroscopy (FTIR, Fourier Transform Infrared spectrometer)

1-2 weeks

Characterisation of the material solubility and determination of the polymer percentage in the plastic (chemical analysis)

1-3 weeks

Characterisation of the polymer in the plastic by NMR (nuclear magnetic resonance) spectroscopy

1-3 weeks

Evaluation of the polymer molecular weight using the GPC technique (gel permeation chromatography)

1-3 weeks

Analysis of the additives using the mass spectrometer LCMS-IT-TOF (hybrid mass spectrometer with the ability of an ion trap and with the resolution and mass accuracy of a tandem mass spectrometer)

1-3 weeks

Characterisation of biodegradable copolyesters (PHA) using sequencing and the tandem mass spectrometer ESI-MSn (electrospray “soft” ionisation with multistep mass spectrometry)

1-3 weeks

Report on the polymer molecular structure and characterisation of the additives in plastics

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Area of research services

Description of the research activities

Modification of polymer properties using chemical routes, including:  Modification (with polymer modifiers)  Functional polymers

Estimated service delivery time

Synthesis of chemical modifiers

1 month - 2 years

Determination of the physical properties of polymeric materials Modification of polymers to achieve specific properties: crosslinking of polymers for better solvent resistance

3 days - 2 weeks

Modification of polymers to achieve specific properties: increased polymer surface polarity for better printability or adhesion, increased thermal and oxidation stability

Product the client receives

Standard commercial polymers possessing certain properties

Area of research services

Modification of polymer properties using physical routes, including:  Modification with additives  Polymer blends  Polymer composites including nanocomposites

Description of the research activities

Product the client receives

Area of research services

Description of the research activities

Product the client receives

1 month - 2 years 1 month - 2 years

Estimated service delivery time

Modification of the properties of a particular polymer by adding low-molecular additives, e.g., plasticisers, chain extenders, stabilisers, or by blending with small quantities of another polymer to achieve the desired properties

1 month - 2 years (or longer)

Blending two polymers over their full concentration range, desired properties are achieved by modification of the interface and compatibilisation of the components

1 month - 2 years (or longer)

Preparation of composites based on a polymeric matrix with tailored properties via modification of the interface

1 month - 2 years (or longer)

Report on alternatives for the compatibilisation of various biodegradable polymer blends

Processing, including:  Rheology, processing parameters  Homogenisation (using internal mixers, single screw extruders, twin screw extruders)

Estimated service delivery time

Selection of the most promising blends of BDPs for application purposes, proposals for areas of application

1 day-3 months

Determination of the processing parameters of the materials

1-4 weeks

Report on the processing parameters of selected biodegradable polymers, recommended general processing methods, including processing equipment and typical processing parameters

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Area of research services

Description of the research activities

Product the client receives

Area of research services

Industrial production (research on the industrial processing properties), including:  Production of films  Production of rigid packing  Production of flexible packaging  Production of mulch films  Production of foamed materials

Estimated service delivery time

Laboratory scale production of films: research on processing and blending, production of master batches (mini twin screw extruder (MiniLab II) combined with the injection moulding machine (Mini Jet II) HAAKE, using the force feeder, continuous extrusion with very small volumes, mini-injection moulding machine enables production of specimens for material testing, the rheological properties can simultaneously be recorded)

1 - 2 weeks

Laboratory scale production of flexible packaging

1 - 2 weeks

Support of pilot production on-site

1 day - 6 weeks

Controlling the mechanical properties of the product during the production process: mechanical property measurements, Instron model 4204 tensile tester

1 - 2 weeks

Controlling the molecular properties of the product during the production process

1 - 2 weeks

Report on the polymer stability with respect to the packaging content Testing of the application properties of polymer products (packaging materials and packaging), including:  Aging properties of polymer materials  Barrier properties of polymer materials (gas permeation)  Thermo-mechanical properties of polymer materials  Durability properties testing of packaging for food contact (food contact, according to the European Directive EU 10/2011) Xenotest method used to determine the material behaviour in natural conditions Determination of total organic carbon and biobased content in polymer materials Testing the permeability of water vapour, oxygen and carbon dioxide

Description of the research activities

4 months* 1 month* 2 weeks*

Determination of tensile properties (stress at break, elongation at break, modulus of elasticity, etc.)

2 weeks*

Determination of tear resistance

2 weeks*

Determination of impact resistance using the free-falling dart method

2 weeks*

Sealing properties (max load at break, sealing resistance, etc.)

2 weeks*

Hot-tack seal testing

2 weeks*

DSC (scanning calorimetry) and FTIR (infrared spectroscopy)

1 week*

Sensory analysis

Product the client receives

Estimated service delivery time

1-1.5 months*

Overall and specific migration testing of low-molecular 2 months* substances into foodstuffs Testing of the monomer contents in plastic materials and of the 1 month* emission of volatile substances Investigation of bioplastic (biodegradable/biobased) materials to determine their properties. Report and analysis on the properties of the polymer materials useful for packaging applications.

*Average delivery time, including preparation, testing and reporting; times can vary based on the actual laboratory queue

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Area of research services

Description of the research activities

Biodegradation and compostability testing (according to EN, ASTM and ISO), including:  Under laboratory conditions  At municipal and industrial aerobic composting facilities

Estimated service delivery time

Degradation and compostability testing under laboratory conditions: preliminary tests of biodegradation on the packaging material using simulated composting conditions in a laboratory-scale test according to EN 14806: 2010

4 months

Degradation and compostability testing under laboratory conditions: hydrolytic degradation test in water or a buffer solution (degradation tests of biodegradable polymers in simple aging media to predict the behaviour of the polymers)

From a few weeks to 6 months, depending on the type of materials and the standard

Degradation and compostability testing under laboratory conditions: laboratory degradation in compost using a respirometry test (Respirometer Micro-Oxymax S/N 110315 Columbus Instruments for measuring CO2 in laboratory conditions according to PN-EN ISO 14855-1:2009 Determination of the ultimate aerobic biodegradability of plastic materials under controlled composting conditions - Method by analysis of evolved carbon dioxide - Part 2: Gravimetric measurement of carbon dioxide evolved in a laboratory-scale test)

From a few weeks to 6 months, depending on the type of materials and the standard

(Bio)degradation and compostability testing at composting facilities (tests of biodegradable material in an industrial composting pile or a KNEER container composting system)

From a few weeks to 6 months, depending on the type of materials and the standard

Certification of compostable goods associated with possibly marking the packaging "compostable" (in cooperation with DIN CERTCO, Germany) Product the client receives

2 - 4 months

Report on the behaviour of the new polymeric materials during the (bio)degradation tests Certificate

This document was prepared within the Work Package 3 of the project Innovative Value Chain Development for Sustainable Plastics in Central Europe (PLASTiCE), co-financed under the Central Europe Programme by European Regional Development Fund.

March 2013

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