Final Report Summary - FORBIOPLAST (Forest resource sustainability through bio-based-composite development)
Executive Summary:
The EC project FORBIOPLAST grant agreement no. 212239, selected by EC as a star project, started on the 1st July 2008. The research activity in FORBIOPLAST have been focused on the use of by-products from wood industry as raw materials for the production of composites with biodegradable and recycled polymers as well as for the production of hard and soft polyurethane foams by innovative sustainable synthetic processes with reduced energy consumption. The materials produced in the project are devoted to applications in automotive interior parts and in the packaging and agriculture fields.
The consortium coordinated by Prof. A Lazzeri of the University of Pisa had a very positive interaction among the members as attested by the regular reaching of the scheduled deadlines. The researchers: University of Pisa (UNIPI-Italy), University of Budapest (LPRT-Hungary), the Latvian State Institute of Wood Chemistry (IWC-Latvia), University of Almeria (UAL) and Fundacion CARTIF (CARTIF) (Spain), University of Bucharest (UASVM-Romania), Organic Waste Systems (OWS-Belgium-SME), Norconserv-Nofima A.S. (NORC-Norway-SME) constantly cooperated with the producer: PEMU Plastic Processing Co. (PEMU-Hungary-IND), RODAX (RODAX-SME) and Incerplast (INCP-SME) (Romania), Ritols Ltd. (RIT-Latvia-SME), and with the end users FIAT Research Centre (CRF-Italy-IND), Neochimiki (NEOC-IND) and Cosmetic (COS-SME) (Greece) with the inputs of Wiedeman (WIED-Germany-SME) a market expert in the exploitation of environmentally friendly materials.
Project Context and Objectives:
As reported in the Description of Work, the objectives of the FORBIOPLAST project were:
valorisation of forest resources for bio-based products production;
identification of the best ways for industrial exploitation of forest biomass at European scale;
production of polyurethanes from materials based on renewable resources;
development of improved technologies with regard to the present industrial synthesis of polyurethane and target of an industrial scale up of the process;
replacement of glass fibres and mineral fillers with wood derived fibres in automotive interior and exterior parts;
development of biodegradable polymer/wood derived fibre composites for application in the packaging, cosmetic and agriculture fields;
bio-valorization of FORBIOPLAST products after their use
eco-sustainability evaluated by LCA studies in the production chain of FORBIOPLAST products
Forest Resource Sustainability through Bio-based Composite Development (FORBIOPLAST), a Large Collaborative Project, coordinated by Professor Lazzeri, University of Pisa, supported by European Union (Grant Nr. 212239) within 7th Framework Programme, is aimed at valorization of forest biomass feedstock by development of bio-based composites and products. The project started in July 2008 and was concluded in June 2012.
In the first two years of the project, they were selected the wood fibres to be used for composites production. Raw fibres for composite production were acquired from La.So.Le (LS), Italy, as low cost fibres (type 200/150E) and Filtracele EFC 1000 (R), Germany, as more expensive but higher quality fibres. An accurate characterization was performed on both wood fibres including aspect ratio, density, chemical, physical and morphological analysis.
The extensive research activity on coupling of wood fibres with recycled polypropylene and biodegradable polymers achieved positive results which were reported in the relevant deliverables of WP4 and WP5.
It was organised an International Conference Bio-based Polymers and Composites with the abbreviation BiPoCo 2012. A website was launched (www.bipoco2012.hu) as the primary communication channel for the public. Two types of keynote presentations were selected: two focusing on the topic covered by the plenary lecture presented before them and three presenting the FP7-projects related to the conference (FORBIOPLAST, BIOSTRUCT and WOODY), having their own dedicated block in the scientific program. In all 94 oral lectures were presented and to extend the number of presentations two poster sessions were organized where topics were extended but harmonized with oral sessions. 110 poster presentations were selected to display. A poster-award was also announced and 6 posters were selected and rewarded by an international scientific jury. As the topic of three keynote presentations were about EC founded research projects, the conference emphasized the role of the European Commission in large scale international research projects. 8 oral and 18 poster presentations were presented by FORBIOPLAST partners and 30 from all the partners of the three projects disseminating the results and foreground knowledge obtained during the EC founded FP7 projects.
The FORBIOPLAST website is successfully online and will be kept running for next five years. Strong endeavors and the coherent collaboration within FORBIOPLAST, supported by European Union, lead to new knowledge and excellent results towards to be broadly introduced onto the market. For these reasons FORBIOPLAST is reported as a star project, and the consortium agreed to apply for FORBIOPLAST2, as demo action. This new proposal is focused on the exploitation of materials devoted to agriculture and packaging applications. Due to the stop of activity of partner INCP, the coordination of FORBIOLAST2, is proposed under a new partner, Tecnopack, a Spanish SME, specialised in the production of packaging materials and items produced by injection moulding, thus covering also production of pots and tomato yarns.
Project Results:
WP1: State of art Requirements and specification (WP Leader: 01-UNIPI) (sm1; em9)
WP1 was completed during the first year of activity in FORBIOPLAST. State of the Art Requirements Specification was performed from 1st Month to 9th Month. WP1 was divided in two tasks: Task 1.1 State of the art and Task 2.1 Market analysis on raw materials.
The objectives of WP1 were the following:
to study the state of the art of forest derived materials;
to study the technology for processing forest derived materials;
to identify technical requirements of FORBIOPLAST products for end users.
Relevant Deliverables: D1.1 State of the Art due to the 6th Month, and D1.2 Technical Specification for Targeted Products due to the 9th Month, were completed in scheduled time. A publishable part of D1.1 State of the Art was also prepared and loaded on the public area of the FORBIOPLAST website.
UNIPI coordinated the update of literature and patents on materials object of the FORBIOPLAST activity, this involved all the beneficiaries. The data on the characterization found in the literature have been relevant for the selection of the wood fibres performed in WP2. The analysis of the state of the art on polyurethanes, mainly performed by IWC, RIT, and UNIPI, considered both natural oils and methods for delignification of lignin to be later reacted to produce polyurethanes. Beneficiaries LPRT and UAL performed an update on modification of natural fibres by chemical and enzymatic pathways while LPRT reported a study on fibre properties and their effect on composite properties. It was also performed a screening of possible compatibilizers to be used for the production of composites materials.
Three main fields of applications were identified:
agriculture;
automotive;
packaging;
After internal discussion and considering information enclosed in D1.1 State of the art on forest materials and processing technologies, in order to focalize the efforts in agriculture and packaging field, these products were selected to be developed at prototype level: tomato yarn, trans planting pots, encapsulated fertilizers, cream jar, chemical container, trays, foams for transport of fish.
For tomato yarn elongation over 20% was suggested by INCP and by UASVM.
For other general packaging applications mechanical properties should be in the range: Modulus 350-450 MPa, Tensile Strength 53 MPa, Elongation 2.4-10%.
In the automotive sector car seat, insulation and spoiler were selected for development at prototype level.
Technical specifications for car seat based on recycled polypropylene (rPP) and wood fibres:
density: 0.95-1.15 g/cm3
flexural modulus:1.4-3.0 GPa
yield strain: greater than 2%
yield stress:greater than 25 MPa
impact strength: greater than 15 kJ/m2
Prototypes of the following products have been fully developed:
Foams - car seat, insulation panel, spoiler; supports for growth of enzymes, fish containers.
Composite based on biodegradable polymers - food tray, egg containers, creams jars, chemical containers, tomato yarn, pots, balcony pots, encapsulated fertilizer.
Composite based on recycled polypropylene car seat, chemical containers, cream jars, pots.
WP2: Collection and pre-treatment of forest materials (WP Leader: 05-CARTIF) (sm1; em24)
The objectives of WP2 were the following:
Identification of raw forest materials providers, availability, costs.
Characterisation of forest materials and fibres
Pre-treatment and pre-compounding of forest materials to get fibres and pellets for the production of bio-based foams and composites.
WP2 was completed in the second year of activity in FORBIOPLAST.
During the WP2 three main aspects: market, fibres characteristics and possible pre-treatments, have been studied with the objectives of exploring and identifying the raw material components for the FORBIOPLAST products, and evaluate providers and possible modifications in the production processes. Raw materials for the production of bio-based foams and composites were identified and their relevant technical data, providers and cost were reported in D2.1 European Market Analysis and Provider Identification to perform an appropriate choice of fibres. Fibre characterizations of several woods samples were carried out with the aim of detecting differences in the fibre properties between types of wood (softwood, hardwood and mixed wood) as well as possible affections after pelletizing treatments. Results were reported in D2.2 Report on forest materials characterization. The fibre pre-treatments carried out consisted of physical (fibres pelleting) and chemical (incorporation of specific additives), and the results related to them have been reported in D2.3 Report on forest materials pre-treatment.
The raw materials with forestry origin for producing the FORBIOPLAST products have very different characteristics and prices that can go from the 60 /t for wood residual fibres to 150.000/t for cellulose powder.
A detailed analysis has been done for different wood flour and fibres. Relating the chemical composition, it is very similar for all the wood flours analyzed in water content, lignin and holo-cellulose. Relating to the wax content the sample from oak and beech has a very high value which could make difficult the adhesion between this filler with the plastic matrix or the coupling agents. For this adhesion it is also better to have less wax content, and in this way fibre EFC 1000 Rettemaier is the best one, having more OH groups than the others. The materials selected, to be used in the project, according with these results have been the EFC 1000 Rettemaier fibres because of its high aspect ratio, and the La.So.Le 200/150 wood flour because of its price. The first one will be used as reference material to show the ideal point to reach the required characteristics for the materials developed, and the second one will be used for developing the FORBIOPLAST products in an economic industrial procedure system.
Main objectives were achieved for WP2, less quantity of chemical additives were required to obtain appropriate properties for the composites, and shorter pellets easier to be fed in the extruder were produced. Nevertheless it would be useful to improve further the pellets produced allowing their easier disintegration inside the extruder.
WP3: Developing bio-based polyurethane foams (WP Leader: 03-IWC) (sm3; em36)
Objectives of WP3 were the:
Laboratory synthesis of hydroxyl-containing esters through trans-esterification of tall oil and lignin containing compounds with polyvalent alcohols and alcanoamines; analysis of the synthesized esters;
Development of freon-free polyol systems suitable for long-term storage;
Development of polyurethane from lignin;
Detailed physico-mechanical investigation of polyurethane (PUR) and polyisocyanurate (PIR) foams. Accumulation of a full set of experimental data for different foams. Recommendations for improvement of performance
Production of Hard and soft polyurethane foams and scale up to industrial production for automotive components (T-node), bumper and packaging (fish box).
Soft foams were produced using different types of lignin. In an early attempt two different types of lignin were employed, one from kraft and one from soda process. Subsequently the soda lignin was subjected to hydroxypropilation process to make the OH group more easily accessible for the reaction with isocyanate. All the lignin were liquefied using an innovative microwave process which is less time and energy consuming than the traditional liquefaction process. Through this work liquefied lignin, with suitable chain extenders, was shown to be potential replacement to petroleum polyols for the production of flexible polyurethane foams. To increase the content of liquefied lignin in foam formulation, and ultimately achieving the goal of making still flexible foam with liquefied lignin, lowering the Tg of polyol phase was determined to be the most important issue.
In the attempt to produce flexible foams two type of chain extender were used in combination with liquefied ligin: polypropilenglycol triol and castor oil. The amount of lignin that was possible to introduce in the network varied from 6 to 13% and considering the renewable origin of the castor oil it is possible to state that in these samples the renewable content is more than 45%. The type of lignin did not influence greatly the structure and properties of the produced foams, hydroxypropylated lignin was easily dissolved in the liquefying agents and the characterizations of the foams produced with this material showed an intense phase mixing between liquefied lignin and chain extenders, higher than the unmodified lignin. For all the type of liquefied lignin, polypropylene glycol triol (PPG) was proven to be an effective chain extender. Samples with liquefied lignin and castor oil had phase mixed morphology and high glass transition temperature which was believed to be the factor giving rise to rigidity in those types of foams, these samples showed a density between 160-230 kg/m3 that is comparable with foams made with renewable resources, like palm or soy oil.
The target products of these systems are: different size and shape items, incl. car parts, such as spoilers, bumpers. The physical-mechanical characteristics are similar or better than conventional petrochemical foams and completely reach the industrial requirements of FORBIOPLAST Partners. Natural fibres are prospective filler for PUR foams; in this case the renewable material content (both tall oil and natural fibres) could reach 35% in end product. It must be taken into account the humidity of natural fibres, because the humidity decrease the density of PUR foams, with following decrease of physical mechanical properties. Only for high density foams (greater than 200kg/m3) there are improvements of mechanical properties of foams, if the fibre concentration is 3 6% by weight.
The optimum parameters for production of automotive parts were established and these results were transferred to activity in WP7.
Vegetable oils offers a variety of new structures in polyols, resulting in polyurethanes with new properties suitable for a range of applications, then it is normal to expect a dramatic increase in the use of renewable resources in the polyurethane field. The development of soft and hard foams resulted challenging tasks but some formulations were identified for the production of both soft and hard foams which meet the technical requirements of producer and end user and an industrial exploitation of these materials is envisaged. The addition of wood fibres in the PU foams was also a challenging task The activity in WP3 resulted particularly successful and the positive cooperation of RTDs and INDs involved in the WP has allowed the production of interesting prototypes at pilot scale and then on industrial scale. The objectives of the WP were achieved in scheduled time. Additional exploitation of the foams developed was found in application for growth of micro-organism in cooperation with Partner UAL, as bio-valorisation of FORBIOPLAST products, as reported in the activity of WP9. The PUR foam material usable for microorganism growing was object of a patent application by IWC, UAL, and UNIPI.
WP4: Physical, chemical and biological modification of wood fibres to improve compatibility in wood based composites. N (WP Leader: 02-LPRT) (sm3; em36)
Objectives of WP4 were:
To develop coupling technology for PP/wood composites, to select wood type, amount and type of coupling agent, recycled PP;
To select coupling agents for wood composites with biodegradable matrices adjusted to the chemical structure of the polymers;
To select a microbiological treatment for biological modification of wood;
To explore methods for the chemical modification of wood in order to improve its inherent strength and to reduce the water sensitivity of the composites;
To develop coupling technology for PU foam/wood composites.
Work progress in WP5: Production of composites based on recycled polypropylene filled with forest-derived fibres. (WP Leader: PEMU) (sm6; em42)
Objectives of WP5 were:
To develop a melt blending technology for recycled PP-wood composites with selected wood type, amount and types of coupling agent;
To make experimental production of PP-wood composites with forest-derived fibres according to the developed coupling technology at semi-industrial scale;
To define the proper compounding technology;
To produce compounds for the manufacturing of prototype(s);
The major achievements for WP 5 consisted of:
Investigation of the optimal recipe of wood flour filled rPP compounds
Selection of the suitable additives
Development of optimal compounding parameters
Production of suitable recipes
Tests of mechanical properties
Successful injection moulding trials
In the present WP, PEMU developed production technology for composites based on recycled polypropylene (rPP) loaded with forest-derived fibres and methods for their characterization. Participant UNIPI and Participant LPRT cooperated in structural, thermal and mechanical characterization of developed compounds.
Participant CRF followed the activity with inputs on technical requirements and as provider of rPP.
Revised specifications were (by Participant CRF):
Strain at Yield: greater than 2%
Yield Strength: greater than 25 MPa
Youngâ??s modulus:1.4 - 3 GPa
Density:0,95 - 1,15 g/cm3
Charpy impact strength: greater than 15 kJ/m2
The goal of WP5 was the melt blending of rPP-wood composites on laboratory, semi-industrial and industrial scale as well with forest - derived fibres according to the coupling technology developed in WP4. In this WP, PEMU selected raw materials, additives, coupling system, formulation and technological parameters for the targeted products in cooperation with Participant LPRT, and determined component properties and components of the rPP/wood composites. Different formulations were selected and processed from lower amount to higher amount of compounds for injection moulding tests. This cooperation was very important for PEMU which acquired new knowledge and improved the experience of its workers.
WP6: Production of composites based on biodegradable polymeric matrices filled with forest-derived fibres. (WPLeader: UNIPI) (sm6; em36)
Objectives of WP6 for were:
To produce films and composites based on biodegradable materials loaded with fibres and additive derived from forest resources on laboratory-scale;
To characterize produced items in terms of structural, thermal, mechanical, permeability properties;
To select best formulation to be promoted for trials at industrial scale.
Based on D1.1 State of the art, D1.2 Technical specifications for targeted products and D6.1 Report on laboratory scale production of composites based on forest derived materials and in collaboration with the project partners six targeted product were developed for agriculture and packaging applications:
Tomato yarn;
Biodegradable plant pot;
Food trays;
Egg containers;
Cosmetic package;
Chemical package.
WP7:Materials from forest resources for automotive applications. (WP Leader: CRF) (sm18; em45)
Objective of WP7 were:
To evaluate the use of lignin and other forest resources in the formulation of composites and foams for automotive applications with specific relevance to panels and structural parts for automobile interior.
To produce a car part prototype to verify the forming process and performance of materials based on forest resources (composites and foam).
To test the composites and foams according to the working standards in place for automobile components.
Objective of the WP is the study and evaluation of the use of lignin and other forest resources in the formulation of composites and foams for automotive applications with specific relevance to panels and structural parts for automobile interior.
They were evaluated and assessed the automotive prototypes parts produced using new bio based materials developed in FORBIOPLAST as described in D7.2a Report on the production of automotive parts based on forest derived materials. The scope was the demonstration that technically valid automotive parts can be produced using a percentage of bio materials improving the environmental impact as described in D10.3 Life cycle analysis based results on environmental burden and impact of the newly developed materials in automotive field and comparison with commercial products.
CRF developed a new concept of slim and ergonomic of a car seat bottom.
Computer simulation tool were used to assist the design procedure both for the part structural performances and process parameters of the injection moulding and permitted an optimisation of the part shape through an iterative process. Equipments for the production of the car seat by injection moulding were set-up by CRF. Before the final set-up of the mould, in conjunction with WP5, a series of sample sheets reproducing the main feature of the seat parts (different shaped ribs and holes, different thickness) were produced with the FORBIOPLAST composite material to verify the mouldability and possible problems. Thanks to this test it was possible also to find the best process parameters for the production of the car seat.
The first test after the production of the seat structure part was the dimensional stability. A measurements system detected a number of main points on the parts and compared with a 3% tolerance to the optimal design geometry. All the prototypes passed the test and their dimensions were compatible with the set tolerances. Then the prototypes were subjected to long thermal cycles according to the automotive standard conditions: no damage or deformation occurred on the parts after the thermal treatment. The parts were assembled with four screws in the side holes for the mounting of the structure on the full seat.
Materials developed in FORBIOPLAST from recycled PP and forest resources have been demonstrate to be suitable for the production of automotive parts, in particular a seat structure. All the final four materials are good with a different level of flexibility. Forest materials can be considerate an adequate form of resources in conjunction with plastic. An amount from 10% to 30% of natural resources is a reasonable value.
WP8 Materials by forest resource for agriculture and packaging applications (WP Leader: INCP) (sm18; em42)
Objectives of the WP were:
To produce at pilot- and industrial- scale films and composites based on biodegradable materials loaded with fibres and additives derived from forest resources,
To characterize the structure, thermal and mechanical properties, as well as permeability of the produced items.
To test produced prototype in packaging applications
To test produced prototype in open field tests
Formulations for the production of prototypes were defined in WP6 by Partners UNIPI, LPRT and PEMU. Characterization of developed materials in terms of structure, mechanical and thermal properties was performed by UNIPI and LPRT. Test of food trays for packaging in vacuum or in modified atmosphere were performed by RODAX, NORC and UASVM. Test of performance of tomato yarn were performed by Partner UAL and UASVM. Test on application of containers for chemicals and cosmetics were performed respectively by NEOC and COS.
Also UASVM tested flat and rounded yarns on tomato hybrid SIRIANA F1 for pallising and traditional yarns from PP and PVC, for comparison in the staking process. UASVM reported the best quality for formulations of flat yarns containing 15% of wood fibres La.So.Le. and 20% Rettenmaier, the staking procedure being realized in a proper way and stated for rounded yarns that the plants can be pallisate with an average degree of difficulty.
Low and tall shapes of pots produced with formulations based on PLA/Ecoflex/wood fibres were prepared and compounded by Partner UNIPI, LPRT and PEMU and were processed by INCP using injection moulding technology.
PEMU managed to manufacture some prototypes of the balcony flower boxes with formulations based on PLA, plasticizer and Rettenmaier fibre up to 40 wt%.
INCP encountered some difficulties in the production of pots by injection moulding using formulations based on PLA, ECOFLEX and wood fibres relating to flow of melted materials and filling of the mould.
Encapsulated fertilizer with very promising properties were prepared by LPRT from starch, wood and an industrial NKP compound (nitrogen, potassium, phosphorus). The work of LPRT was focused on improving the reproducibility in stick production, increase the nitrogen content and evaluate different wood reinforcement. The sticks produced are promising as slow release fertilizer.
The biodegradable fertilizers were tested by UASVM on the plants (Dianthus caryophyllus and Petunia hybrida). Before to organize the experiments, the fertilizers sticks were analysed for the following parameters: pH, N, P, K existent as total amount but also in soluble form. During the vegetation period, biometric they were made observations regarding growing and developments of plants, namely: height, roots length, number of shoots, number of flowers. Regarding the growth and developments of plants (height and number of shoots) all the fertilizers samples demonstrated a beneficial slow release process of the macro elements which determined a positive effect. At the same time didn`t noticed any negative deficiencies for any of the NPK elements in the tested plants.
Sensory profile consisted in touching smooth, touching familiar, visual natural looking, visual attractive, smell intensity, smell pleasant, all senses evaluation were used 20 volunteers with ages between 20 to 45 years. It is found that the prototype jars based on PP and Rettenmaier wood fibre had a strong smell of lignin which is a negative aspect for the general consumer and affects negatively the smell of the cream. Only the PHB with 20% Rettenmaier wood fibres seemed to be acceptable from the consumer tests for cosmetics packaging.
Chemicals packaging for industrial use consisting in three parts: body, lid and handle were produced by injection moulding by INCP. Several formulations from polypropylene/recycled propylene (rPP)/Rettenmaier/La.So.Le fibre were designed and compounded by LPRT and PEMU at 20 wt.% Rettenmaier/ La.So.Le fibres and respectively 30 wt.% Rettenmaier loading and at different PP: rPP ratios. Brown and black chemical containers having the size of 170x150 mm, thickness of 2.5 mm and capacity of 2 litres were obtained. Containers prepared from rPP and addition of virgin PP showed an improved processing than formulations based on just recycled polypropylene.
Chemical containers based on bio-composites have both economical and environmental advantages by replacing of amount of PP with rPP which is low cost, abundant, without affecting their mechanical performance.
Latvia's partners, Institute of Wood Chemistry (IWC-RTD) and Ritols Ltd. (RIT - SME) were involved on concept of fish boxes with thermal insulations. Thermal insulation material contains 29% of renewable raw material tall oil in ready foams. The processing of material is optimum and could be used on industrial foaming machines.
Food trays were produced by PEMU with PLA/Ecoflex in different ratios and Rettenmaier fibres. Different moulds were designed by PEMU for thermoforming lab scale trials of the food trays. Firstly PEMU produces thermoformed prototypes from pure PLA, then from PLA/Ecoflex in different mixing ratios of components and later from PLA/Ecoflex/Rettenmaier in different mixing ratios of components. PEMU tried to reduce the thickness of products, at the same time the price and the wood smell of prototypes, therefore were prepared trays with a sandwich structure in order to avoid the direct contact of wood fibres with food. The best performance was observed by RODAX, NORC and USAMV partners for prototypes produced as sandwich structure.
RODAX (SME Romania) tested the performance of food trays as following: sealing tests, seal strength tests, leakage tests, tray crash tests, package tests. RODAX manufactured the packaging equipments to make the sealing test of film over trays. Their characteristics regard the cutting and the sealing of the thermal assemblies respectively the hot cutting wire, hot sealing band or the aluminium heated plate with incorporated resistance. As film were used PLA, PLA/ECOFLEX and PP films. The best results for sealing and cutting have been obtained at temperature of 100 0C and 8 sec., at 140 °C and 150 °C for 4 sec. respectively 3 sec.
The sensorial analysis of products stored in the developed FORBIOPLAST trays compared to standard commercial hydrocarbon-based plastic trays commonly used by the food industry were studied by NORC using modified atmosphere packaging of salmon. The FORBIOPLAST food tray could be used for packaging food preserving their own characteristic taste and odor. However sensitive foods will take up odor and taste from the wood fibres inside the tray. The tray must be further developed to hide the characteristic woody odor, as the tray is now it will have trouble complying with European food packaging directive and good manufacturing principle (GMP). This optimisation might be performed in a possible future demonstration project.
For the food trays experiments UASVM used packaging of fish and meat and stored at chilling temperature for 7-8 days and at frozen conditions storage for 3 months. After certain preservation period in refrigeration conditions (chilling or freezing) physic-chemical and microbiological analysis for fish and meat have been performed in order to establish the shelf life and also the food trays materials were analyzed. Thermal analysis (TGA, DSC, DMA), physical and mechanical analysis (density, compression) performed showed that neither the content nor storage conditions for food trays did not lead to any significant change occurred in the composition and structure of composites used in their manufacture. FTIR analysis did not reveal the existence of major changes in surface materials. The differences between samples in terms of specific heat (Cp), enthalpy of cold crystallization (Hc) and total melting enthalpy (Hm) measured by DSC are probably due to absorption of water during the time spent in contact with meat.
The promising FORBIOPLAST prototypes based on bio-polymers and bio-composites could be used in agricultural and packaging fields. Testing of prototypes performance demonstrated that some formulations have the same properties as the similar products presented on market, and in the same time they are superior to traditional products regarding the benefits on environment.
WP9 Biodeterioration, biodegradability and valorization of the developed materials (WP Leader: UAL) (sm15; em48)
Objectives of the period in the present WP were:
to study the biodegradability and compostability of the newly developed biobased products;
to evaluate ecotoxicity of newly developed products;
to explore processes for microbiological valorization of the packaging and agricultural produced material;
to evaluate the recyclability of the packaging and agricultural produced materials;
to determine biodeterioration of the developed materials for automotive applications
The biodegradation of the developed compounds was evaluated in a broad range of environments. Also the biodegradation of the basic Rettenmaier wood fibre, used in many applications within this project, was investigated. It was observed that the biodegradation under composting conditions and soil proceeded, but at low rate due to the lignin content. A previous bio-delignification process by treatment with ligninolytic fungi induced a positive effect on biodegradation rate.
Composites based on wood fibres (Rettenmaier) and biodegradable polymeric matrices such as PLA, PBAT (Ecoflex), starch and PHB were evaluated for biodegradation. These composites are suitable for compostable packaging and products (EN 13432). The PLA compounds also degraded under thermophilic, anaerobic conditions, but the rate was too low to yield complete degradation within industrial digestion process for treatment of waste. No complete biodegradation was observed for PLA/Ecoflex/Rettenmaier compounds at room temperature in compost, soil and water. This material is not suitable for home composting applications. The PLA component needs a certain temperature trigger (typically around 55°C) before the hydrolysis and biodegradation starts.
The starch/Rettenmaier compounds proved to be completely biodegradable in soil conditions. Together with the slow, but steady disintegration in soil the developed starch/Rettenmaier based fertilizer sticks are an environmental friendly fertilizer for flowers that promotes plant growth and flowering. This material also seems to stimulate biodiversity of soil microbial population, including those microorganisms involved in long-term maintenance of fertility (test still running). Because of this property the developed starch/Rettenmaier compounds may be used for bioremediation processes as biostimulants agents.
Three different approaches were attempted for materials valorization: Biogas production by anaerobic digestion, immobilization of microorganisms for ligninolytic enzymes production and production of single cell protein from materials hydrolysates.
The PLA based compounds were degraded under thermophilic, anaerobic conditions, but the rate was too low to yield complete degradation within industrial digestion process for treatment of waste. Products based on cellulose diacetate have the potential to be treated after their life-time in anaerobic digestion plants, yielding biogas for energy production.
Polyurethane (PU) rigid and soft foams were used as support for growth of microorganisms that produce ligninolytic enzymes, mainly laccase. In general enzyme production was enhanced when the fungus was immobilized in PUR foams with open cells structure and filled with wood fibres. Small size soft foams made of hydroxypropylated lignin and castor oil gave higher laccase production than those made of lignin and PPGtriol hydroxypropylated lignin or PPGTriol.
Production of single cell protein of the yeasts Pichia pastoris and Rhodotorula sp. to be used as additives in animal feed was attempted by hydrolysing several developed composites under different conditions. The highest quantity of yeast biomass was obtained for (PLA:Ecoflex 50:50):Rettenmaier 85:15 compound hydrolysed using H2SO4 and high temperature treatment.
The yarn prototypes based on PLA/Ecoflex/Rettenmaier blends were used to fasten different types of cultures in one cycle production. After crop, the plants together with the yarn were used to perform a semi-industrial-scale composting. Yarns were used to fasten cultures of melon, cucumber and tomato in greenhouses cultures and tomato in open field culture (as reported in WP8). The yarn made of (PLA:Ecoflex 20:80):Rettenmaier 70:30 was the most suitable to be composted at semi-industrial scale because besides of being the most adequate for field application it disintegrated after composting and the final compost was of high quality.
The materials developed for within this project developed polyurethane (PUR) with 20% rosin acid and recycled polypropylene with Rettenmaier fibres were quite resistant to biological degradation. PUR materials prepared for fish-box industry and automotive applications were highly resistant to microbial attack. Also polypropylene/wood composites for automotive applications and materials intended for chemical and cosmetic containers based on formulations containing PP and rPP with wood were heavily colonized by fungi but not impact on materials properties was evidenced. These characteristics are essential for long term outdoor applications such as insulation or automobile parts. In general the increase of wood content in materials favours the microbial colonization. All selected materials can be considered very durable from the point of view of susceptibility to microbial attack and biodeterioration.
WP 10: Life Cycle Analysis (WP Leader OWS) (sm 12, em 48)
Objectives of the present WP were:
To assess the hot spots in the production chain in order to make recommendation for future production of FORBIOPLAST materials.
To assess the environmental burden and impact originated from the life cycle of the packaging (comparison with commercial packaging) and automotive parts (comparison with actual car components).
An environmental assessment has been made by using the eco-indicator 99 (H) method on 5 different applications containing wood fibres:
Fertilizer sticks
Food trays
Tomato yarn
PHB pot
Automotive car pan
These materials have been chosen because of their different applications and compositions. The starting point in this assessment was the data inventory of the wood fibre production. This data inventory was based on a literature review, where it was assumed that the fibres are made from sawdust and afterwards transported to the production site in Germany. The production of sawdust, including the tree harvest steps seemed to be the most dominating step representing 46% of the total impact, mainly caused by land use, whilst energy use during further processing to fibres and transport to destination account for 29 and 25% respectively. Although it is expected that the used fibres in the studied application origin from sawdust, a sensitivity check was performed comparing the exact source of the wood biomass. From this analysis it can be concluded that the different types of wood chips found in the LCI database generally have a lower impact, especially concerning land use, compared to the used sawdust dataset. In some cases more fossils are used, but this impact seems to be low compared to the total impact of the wood fibres.
In general, adding wood fibres to plastic applications is an environmentally benign strategy. The overall environmental impact of the wood chips according to the eco-indicator 99 method is lower compared to any fossil or non fossil based material used in the studied materials, such as PE, PP, PVC, PS, PBAT, PHB, starch. Therefore, apart from material properties, it is clear that adding more wood is a good strategy to achieve a better environmental performance compared to reference products.
A large advantage of the materials produced in FORBIOPLAST is their biodegradability. This end of life scenario of the studied materials however, was too difficult to model with the current methodologies used in LCA. In the case of fertilizer sticks, tomato yarn and the PHB pot, the biodegradability is positive because of the fact that they often end up directly into the natural environment. It would be even possible to assign carbon credits because of the potential soil enrichment effect of these materials. At the other side, the direct emission of a non biodegradable plastic is impossible to assess because no sound fate/exposure/effect models of these materials exist for LCA. In the case of food trays, the interaction with nature is less direct. A scenario has been analysed where the PBAT/PLA/wood material is composted compared to the reference products which are incinerated. Even when implementing this end of life scenario, the life cycle impact of the FORBIOPLAST material is higher. A careful recycling of the fossil based materials would enhance this effect. Nevertheless, the biodegradable food tray may be preferred in cases where they are highly contaminated with organic matter or in cases where a direct contact with the environment can be expected (e.g. festivals).
The recycled materials reinforced with natural fibres show good technical performances, as well as significant environmental advantages, so as the LCA has been able to highlight. While the environmental impacts are quite similar for the use and end of life phases, the FORBIOPLAST solutions show remarkable advantages in the production phase mainly concerning the avoided burdens due to the polypropylene recycling and the use of vegetable fibres instead of the mineral ones. Thanks to benefits in using recycled material and wood fibres and to other improvements due to a logistic optimization (transports), the FORBIOPLAST solutions deserve to be considered as good alternatives to those currently used.
Potential Impact:
European citizens tend to have an increasing positive attitude towards buying and using green and renewable technologies, especially because they reduce the impact on the environment. In the future, more people are expected to follow this behavior because of the increased advertising and policies applied in this area so the market of green technologies seems to look very bright.
The results and the prototypes produced in FORBIOPLAST attest for the possible valorisation of forest biomass for the production of environmentally compatible materials to be applied in packaging, agriculture and automotives. These materials include composites based on biodegradable polymeric matrices, or recycled polypropylene with lignin or wood fibres and hard and soft polyurethane, eventually loaded with wood fibres produced by green synthesis from tall oils or lignin.
More than 50 million tons of lignin annually derive from different pulping processes, while the Kraft process takes the lion's share of 76%. Merely 1 million t of the lignin is under commercial use. Hence, FORBIOPLAST research treats lignin for various materials, such as PUR soft foams. As a by-product of the Kraft pulping process, tall oil is available for further industrial use. The total yield is estimated on 1,5 million tons per year. Tall oil is primarily utilized for developing bio-based rigid polyurethanes and composites in FORBIOPLAST project.
The main objectives of the European Commission concerning the automotive sector are: to strengthen the competitiveness of the Automotive Industry, To complete, adapt and simplify the Internal Market regulatory framework, to promote globalization of the technical regulatory framework through UNECE. In order to achieve these ambitious goals, legislation in the European Union is focused on sustainable automotive industry. With regard to 8-9 million tons of waste deriving from end of life vehicles in European Union, the (Directive 2000/53/EC - the 'ELV Directive') has been officially adopted by the European Parliament and the Council in September 2000.
FORBIOPLAST works with recycled materials as well as biopolymers and responds to depletion of fossil resources. For example, the world's crude oil reserves were estimated on 184 billion tons in 2009. Assuming that annual consumption may vary between 3.7 and 3.9 billion tons (as occurred between years 2003-2009) and no significant reserves will be discovered, the resource will be exhausted in less than 50 years. From a total demand of 52.5 million tons of plastics, 18% of this request was polypropylene in 2007. Considering the environmental issues of plastics in Europe (EU27/NO/CH), it has been reported that 50% of the plastics have been recovered either for materials (20,4%) or for generating energy (29,4%).Recycled polypropylene plays a crucial role in development of ecological automotive parts (seat system) within the project. As a further part of cars, in FORBIOPLAST a seat has been designed to be produced from fully ecological material (rPP/wood fibre). PP is a very important polymer in automotive industry and as it has been recorded, from a car in the range of 1100 kg, 130 kg are plastics. From the plastics 45 kg (more than 1/3) are PP. At European scale, it means 600.000 t. The potential amount of plastic composites in a seat system is estimated on 10 kg per car. Moreover, replacement of metal by plastic composite entails reduction of weight of the seat and the car. FORBIOPLAST research and development has generated composites which exhibit economic and ecological advantages and its potential in seats in European cars is estimated on 80.000 t.
Research and development within FORBIOPLAST in the packaging area has resulted in prototypes like food tray, egg container, fish box, cosmetic container and chemical container. The FORBIOPLAST project has developed the process of a new generation of packaging solutions using renewable and fully recyclable materials that also respond to the growing packaging market. The future for fibre-based packaging will require the re-engineering of the packaging value chain to deliver increased, capital efficiency, product innovation and more competitive packaging materials. The main trend in modern packaging is the utilization of the biodegradable materials which enable the protection of the environment in accordance with the European legislation.
Cosmetic is a very important industry sector in Europe. Following a market study of Global Insight, the European market size of cosmetics and toiletries was 63.5 billion in 2006. That means about the value of the combined market size of USA (38.2 billion) and Japan (23,7 billion). The Chinese market was valued with 8.2 billion in 2006. Cosmetic packaging should grow 4.2% per year to reach $24 billion (PIRA, 2012). North America has the largest share at 66% followed by Europe at 63%. The largest categories using rigid plastics are hair care, bath and shower, facial skincare and deodorants. Cosmetic containers which includes cosmetic compacts and lipstick and mascara cases, is growing at 3% a year but in Asia Pacific, Latin America and the Middle East and Africa it is expected to grow at 5-6% a year to 2014. The top performing rigid plastic pack is expected to be plastic jars growing at 5% a year (http://www.rexam.com/files/pdf/packaging_unwrapped_2011.pdf). It is suppose that the innovative FORBIOPLAST cosmetic container can replace around 10% of packaging in cosmetics. FORBIOPLAST research and development in the cosmetic packaging area and its outcomes offer bio-based and sustainable solutions for cosmetics industries. The advantages of properties which could be promoted within the FORBIOPLAST cosmetic container are the followings: ease of moulding into complex shapes, rigid enough, impact toughness, abrasion resistance and chemical resistance that reduces scalping and permeation of valuable ingredients, a superior barrier against oxygen, fragrance and contamination, the chemical and aroma barrier properties keep volatile and valuable ingredients inside the package where they belong, making sure product value and quality reach the consumer intact, anti-static properties, 100% eco friendly, unique design, gloss surface, easy to print with high-quality graphics to increase the visibility and the attractiveness of the package, and cost-efficient decorative effects, best price with top quality.FORBIOPLAST has produced an environmentally friendly cream jar based on traditional polymers and natural fibres while commonly PP, PE and PET is used for that purpose. Like any new product, packaging materials products resulted from FORBIOPLAST project require special promotion supported by adequate advertising and improved functional qualities. Demands in cosmetic container applications will be supported by growth in production, as well as by expansion in all age population body and beauty care segments, which comprise many of the most intensive consumers of cosmetics. Traditional 200ml jars from PP are sold in the range from 0.18 -0.40 per piece. The container produced in FORBIOPLAST could be competitive in terms of price and environmental issues.
Toward 2014 the growth of chemical container demand in the world will increase with 2.9% and will be driven by performance advantages over alternative packaging media, which will stimulate ongoing opportunities in a broad range of applications. It is expected that 15% from total chemical packaging can be replaced with FORBIOPLAST products. Certainly, the incorporation of a percentage of recycled polypropylene in the formulation has a positive cost impact and helps to re-use polypropylene. Price of polypropylene versus price of polyethylene is not expected to make a big difference since both are widely used plastics. The mixture of recycled polypropylene with pure polypropylene without affecting the mechanical properties will offer a price advantage as well as the incorporation of up to 30% of wood fibres in the formulations.
The main advantages of the FORBIOPLAST tomato yarn comparative with tomato yarn based on traditional petrochemical products are: It is derived from sustainable resource; Help in preserving non-renewable resources like petroleum, natural gas and coal; Toxic free; Compostable; Environmental protection; Best suited for short shelf life products; Low barriers of oxygen/water vapours transfer.
Advantages of FORBIOPLAST pots compared with traditional pots are: Compostable;
Can be planted directly in the soil, saving time if based on polymers degradable is soil such as polyhydroxybutyrate; Eliminating stress to planting to induce the earlier production, achieving a savings in terms of manual labor; Reducing waste since the pots decompose in the soil; Easier application; Labor force concentrated in a smaller area; Ability to manage growing conditions, less climatic risk; Smaller area needed for the same production numbers; Greater success rate in comparison to traditional bare root.
As a further product devoted to the agricultural market segment, an encapsulated fertilizer with a bio-based and biodegradable coating is created within the project.
The global market for coated fertilizers shows tremendous growing rates and this type of fertilizer is more and more applied in major agriculture crops like cereals and potatoes. Among the advantages of these fertilizers are a possible reduction of fertilizer application quantity and full nutrient supply for plants under plastic cover.
The Common Agricultural Policy is also integrating environmental concerns as a most sensitive objective and it aims to head off the risks of environmental degradation and enhancing the sustainability of agro-ecosystems. Around half the EU's land is farmed and farming is important for the EU's natural environment, so, farming and nature influence each other. Inappropriate agricultural practices and land use can have an adverse impact on natural resources, like pollution of soil, water and air, fragmentation of habitats and loss of wildlife. The Common Agricultural Policy (CAP) has identified and set three priority areas for action to protect and enhance the EU's rural heritage which can be achieved through solutions given by biocomposite materials: biodiversity and the preservation and development of 'natural' farming and forestry systems, and traditional agricultural landscapes; water management and use; dealing with climate change. FORBIOPLAST Project helps reaching these policies by aiming the valorisation of forest resources for the production of bio-based products with the additional contribution to solve the problems related to materials produced by petro-derived resource, to waste disposal, to the use of energy consumption and polluting chemical pathways and to the use of hazardous substances. The project helps in meeting the European agriculture policies: CAP. The main topic of the research activity will be focused on the use of wood and paper mill by-products as raw materials for the production of polyurethane foams by an innovative sustainable synthetic process with reduced energy consumption. Efforts were devoted to the promotion of the use of wood derived fibres in the agriculture sector (mulching, greenhouse, tomato clips, different types of pots and yarns etc) as in FORBIOPLAST Project, 2012.
Polyurethanes (PUR), often described as the most versatile plastics materials, are produced with remarkable share from bio-based feedstock (tall oil and lignin) within FORBIPOLAST research towards end uses in automotive acoustic insulation, spoilers and packaging such as fish transport boxes (Hard PUR). Lignin-based Soft PUR can be applied e.g. in furniture industry as the biggest consumer of PUR in Europe (2005) as well as in automotive sector. Opposed to bio-based polyols from vegetable oils already introduced onto the market, FORBIOPLAST polyols are generated from waste material of pulp industry and their raw materials are commonly not grown on agriculture crop areas. Positive impact are expected from the exploitation of hard polyurethane produced by tall oils since tall oil is prospective raw material for polyol production for polyurethane foams. A spoiler, partly deriving from renewable resources has been produced by partner PEMU. As it is emphasized, the properties and the price of this automotive part which is primarily devoted to sports- and luxury cars, are comparable to traditional crude oil based materials. Following appraisals, Green PUR could achieve 300.000 t for spoilers.
New efficient methods of processing and new materials are generated as a result of the activities undertaken within the project. Saving raw materials and reducing costs for manufacturing and logistics will supply competitive products and secure employment. Energy consumption and effects of greenhouse gas emissions will be reduced by the exploitation of the new materials and commodities. Due to the new technologies customers benefits will be the availability of items with improved quality and lower prices related to environmentally friendly waste disposal. Renewable resources are continually renewed by the cycle of nature and are considered to be practically inexhaustible.
The research activity performed in the project had a significant impact on the RTDs performers in terms of increased knowledge, new contact, positive cooperation and experience acquired in working with industries. Problems from the perspectives of the industrial users and producers were evaluated, and with these impressions the RTDs were able to attend the necessities required by the local industries. FORBIOPLAST research and development lead to gaining new knowledge in the area of biopolymers and biocomposites and provides new options for promotion of bio-based materials and products. Furthermore, due to conduction of market analysis, new market opportunities for innovative composites were identified.
The end users were very satisfied if the results and of the positive cooperation with the RTDs and producers. The use of biodegradable packaging for cosmetics is in its infancy. Poor barrier properties, higher price and low general public awareness are the major reasons for the limited use of biodegradable packaging in cosmetics. Partner Cosmetic (COS) had the opportunity to get an inside industry knowledge of the biodegradable packaging. The dissemination of FORBIOPLAST results to Cosmetic's customers has stirred conversations about the potential use of biodegradable packaging in this industry sector. COS is offering formulation and production services to other companies. It is to the company's advantage to offer the best advice to its customers especially the ones that have more green products. 1 billion $ world market for plastic cosmetic containers by injection moulding and 8 million is the corresponding Greek market. The above numbers are estimates based on the assumption that the cosmetics packaging produced by injection moulding corresponds to the 1/7 of the total. One fifth of the above could be replaced by the type of packaging developed in FORBIOPLAST. If biodegradable packaging becomes more widely-used, it is possible that the green certification bodies such as ICEA or Ecocert may require its use for providing the green label to cosmetic products. It is very likely that such a development will give more value to biodegradable packaging and raise general public awareness. The participation of COS to a large European consortium involving academic experts in the area has also been very beneficial towards improving the company's image and reinforcing its R&D profile, both within Greece and abroad. It has at the same time provided the basis for future research activity in the company in the area of biodegradable packaging or packaging materials in general. The industrial manufacturers could be some of the major plastic container producers in Greece e.g. Supremeplast, Argo and abroad e.g. Bormiolli, PET Power, M and H etc. The end user can be companies that have green marketing claims e.g. Korres, Macrovita, Apivita sold mainly in pharmacies and brands like Olivelia, Kalliston, Ollivelenic etc. sold in the touristic shops of Greece.
It was organised an International Conference Bio-based Polymers and Composites with the abbreviation BiPoCo 2012. The organiser was partner 02-LPRT but main milestones were discussed with the project coordinator UNIPI. A website was launched (http://www.bipoco2012.hu) program was carefully composed; four types of presentations were selected: Plenary lectures, Keynote lectures, Oral presentations, Poster presentations. Invited speakers were selected to cover the scope of the conference. Internationally well know authorities presented the latest work of their fields on the highest level:
Lars Berglund (KTH Royal Institute of Technology, Sweden) Biocomposites from small building blocks learning from plant structures; Claudia Crestini (University of Rome, Italy) Cellulosic composites from low to high tech versions; Ramani Narayan (Michigan State University, USA) The promise of bioplastics understanding the value proposition for biobased and biodegradable-compostable plastics; Balazs Imre (Budapest University of Technology and Economics ) Biopolymer blends: miscibility, compatibility, performance. Two types of keynote presentations were selected: two focusing on the topic covered by the plenary lecture presented before them and three presenting the FP7-projects related to the conference (FORBIOPLAST, BIOSTRUCT and WOODY), having their own dedicated block in the scientific program. In all 94 oral lectures were presented and to extend the number of presentations two poster sessions were organized where topics were extended but harmonized with oral sessions. 110 poster presentations were selected to display. A poster-award was also announced and 6 posters were selected and rewarded by an international scientific jury. As the topic of three keynote presentations were about EC founded research projects, the conference emphasized the role of the European Commission in large scale international research projects. 8 oral and 18 poster presentations were presented by FORBIOPLAST partners and 30 from all the partners of the three projects disseminating the results and foreground knowledge obtained during the EC founded FP7 projects.
CRF main interest for the products developed in FORBIOPLAST relies in the possibility to use the new eco-friendly materials based on wood fibers and plastics from post- consumer recycling and polyurethane formulations by lignin materials in automotive applications. The materials have been technically evaluated by CRF and demonstrated a good solution for semi -structural automotive parts and from the economic aspect they are also a cost effective solution. CRF also through its company Magneti Marelli - Plastic Components is interested to further strength its environmental sustainability approach also through the use of materials such as those developed in FORBIOPLAST.
Time scale for exploitation of FORBIOPLAST materials in automotive production is predicted between 2015 and 2020.
A part the specific materials and demonstrators developed by CRF for automotive, FORBIOPLAST project allowed CRF to get experience in bioplastics. Such materials were developed in FORBIOPLAST for agricultural and packaging applications, but they could be even employed with minor modifications in the future in automotive field. And this road will be investigated by CRF in future European projects (i.e. EU BRIGIT project).
PEMU is strongly interested to the industrialization of the materials developed in FORBIOPLAST, in particular for composites produced with recycled polypropylene and production of polyurethane for automotive applications. As well as CRF, PEMU feels the need for minor optimization of the production process. Also for PEMU the exploitation of FORBIOPLAST materials in automotive production is predicted between 2015 and 2020. CRF and PEMU consider the production of the car seat, and of the spoiler enough advanced, and the performances already meeting CRF requirements. These two partners considered not justifiable to go to a demo action for materials devoted to automotive applications.
List of Websites:
http://www.forbioplast.eu
Lazzeri Andrea, University of Pisa, Department of Chemical Engineering, Industrial Chemistry, and Materials Science, Via Diotisalvi 1, 56126, Pisa, Tel 00390502217807, a.lazzeri@ing.unipi.i
The EC project FORBIOPLAST grant agreement no. 212239, selected by EC as a star project, started on the 1st July 2008. The research activity in FORBIOPLAST have been focused on the use of by-products from wood industry as raw materials for the production of composites with biodegradable and recycled polymers as well as for the production of hard and soft polyurethane foams by innovative sustainable synthetic processes with reduced energy consumption. The materials produced in the project are devoted to applications in automotive interior parts and in the packaging and agriculture fields.
The consortium coordinated by Prof. A Lazzeri of the University of Pisa had a very positive interaction among the members as attested by the regular reaching of the scheduled deadlines. The researchers: University of Pisa (UNIPI-Italy), University of Budapest (LPRT-Hungary), the Latvian State Institute of Wood Chemistry (IWC-Latvia), University of Almeria (UAL) and Fundacion CARTIF (CARTIF) (Spain), University of Bucharest (UASVM-Romania), Organic Waste Systems (OWS-Belgium-SME), Norconserv-Nofima A.S. (NORC-Norway-SME) constantly cooperated with the producer: PEMU Plastic Processing Co. (PEMU-Hungary-IND), RODAX (RODAX-SME) and Incerplast (INCP-SME) (Romania), Ritols Ltd. (RIT-Latvia-SME), and with the end users FIAT Research Centre (CRF-Italy-IND), Neochimiki (NEOC-IND) and Cosmetic (COS-SME) (Greece) with the inputs of Wiedeman (WIED-Germany-SME) a market expert in the exploitation of environmentally friendly materials.
Project Context and Objectives:
As reported in the Description of Work, the objectives of the FORBIOPLAST project were:
valorisation of forest resources for bio-based products production;
identification of the best ways for industrial exploitation of forest biomass at European scale;
production of polyurethanes from materials based on renewable resources;
development of improved technologies with regard to the present industrial synthesis of polyurethane and target of an industrial scale up of the process;
replacement of glass fibres and mineral fillers with wood derived fibres in automotive interior and exterior parts;
development of biodegradable polymer/wood derived fibre composites for application in the packaging, cosmetic and agriculture fields;
bio-valorization of FORBIOPLAST products after their use
eco-sustainability evaluated by LCA studies in the production chain of FORBIOPLAST products
Forest Resource Sustainability through Bio-based Composite Development (FORBIOPLAST), a Large Collaborative Project, coordinated by Professor Lazzeri, University of Pisa, supported by European Union (Grant Nr. 212239) within 7th Framework Programme, is aimed at valorization of forest biomass feedstock by development of bio-based composites and products. The project started in July 2008 and was concluded in June 2012.
In the first two years of the project, they were selected the wood fibres to be used for composites production. Raw fibres for composite production were acquired from La.So.Le (LS), Italy, as low cost fibres (type 200/150E) and Filtracele EFC 1000 (R), Germany, as more expensive but higher quality fibres. An accurate characterization was performed on both wood fibres including aspect ratio, density, chemical, physical and morphological analysis.
The extensive research activity on coupling of wood fibres with recycled polypropylene and biodegradable polymers achieved positive results which were reported in the relevant deliverables of WP4 and WP5.
It was organised an International Conference Bio-based Polymers and Composites with the abbreviation BiPoCo 2012. A website was launched (www.bipoco2012.hu) as the primary communication channel for the public. Two types of keynote presentations were selected: two focusing on the topic covered by the plenary lecture presented before them and three presenting the FP7-projects related to the conference (FORBIOPLAST, BIOSTRUCT and WOODY), having their own dedicated block in the scientific program. In all 94 oral lectures were presented and to extend the number of presentations two poster sessions were organized where topics were extended but harmonized with oral sessions. 110 poster presentations were selected to display. A poster-award was also announced and 6 posters were selected and rewarded by an international scientific jury. As the topic of three keynote presentations were about EC founded research projects, the conference emphasized the role of the European Commission in large scale international research projects. 8 oral and 18 poster presentations were presented by FORBIOPLAST partners and 30 from all the partners of the three projects disseminating the results and foreground knowledge obtained during the EC founded FP7 projects.
The FORBIOPLAST website is successfully online and will be kept running for next five years. Strong endeavors and the coherent collaboration within FORBIOPLAST, supported by European Union, lead to new knowledge and excellent results towards to be broadly introduced onto the market. For these reasons FORBIOPLAST is reported as a star project, and the consortium agreed to apply for FORBIOPLAST2, as demo action. This new proposal is focused on the exploitation of materials devoted to agriculture and packaging applications. Due to the stop of activity of partner INCP, the coordination of FORBIOLAST2, is proposed under a new partner, Tecnopack, a Spanish SME, specialised in the production of packaging materials and items produced by injection moulding, thus covering also production of pots and tomato yarns.
Project Results:
WP1: State of art Requirements and specification (WP Leader: 01-UNIPI) (sm1; em9)
WP1 was completed during the first year of activity in FORBIOPLAST. State of the Art Requirements Specification was performed from 1st Month to 9th Month. WP1 was divided in two tasks: Task 1.1 State of the art and Task 2.1 Market analysis on raw materials.
The objectives of WP1 were the following:
to study the state of the art of forest derived materials;
to study the technology for processing forest derived materials;
to identify technical requirements of FORBIOPLAST products for end users.
Relevant Deliverables: D1.1 State of the Art due to the 6th Month, and D1.2 Technical Specification for Targeted Products due to the 9th Month, were completed in scheduled time. A publishable part of D1.1 State of the Art was also prepared and loaded on the public area of the FORBIOPLAST website.
UNIPI coordinated the update of literature and patents on materials object of the FORBIOPLAST activity, this involved all the beneficiaries. The data on the characterization found in the literature have been relevant for the selection of the wood fibres performed in WP2. The analysis of the state of the art on polyurethanes, mainly performed by IWC, RIT, and UNIPI, considered both natural oils and methods for delignification of lignin to be later reacted to produce polyurethanes. Beneficiaries LPRT and UAL performed an update on modification of natural fibres by chemical and enzymatic pathways while LPRT reported a study on fibre properties and their effect on composite properties. It was also performed a screening of possible compatibilizers to be used for the production of composites materials.
Three main fields of applications were identified:
agriculture;
automotive;
packaging;
After internal discussion and considering information enclosed in D1.1 State of the art on forest materials and processing technologies, in order to focalize the efforts in agriculture and packaging field, these products were selected to be developed at prototype level: tomato yarn, trans planting pots, encapsulated fertilizers, cream jar, chemical container, trays, foams for transport of fish.
For tomato yarn elongation over 20% was suggested by INCP and by UASVM.
For other general packaging applications mechanical properties should be in the range: Modulus 350-450 MPa, Tensile Strength 53 MPa, Elongation 2.4-10%.
In the automotive sector car seat, insulation and spoiler were selected for development at prototype level.
Technical specifications for car seat based on recycled polypropylene (rPP) and wood fibres:
density: 0.95-1.15 g/cm3
flexural modulus:1.4-3.0 GPa
yield strain: greater than 2%
yield stress:greater than 25 MPa
impact strength: greater than 15 kJ/m2
Prototypes of the following products have been fully developed:
Foams - car seat, insulation panel, spoiler; supports for growth of enzymes, fish containers.
Composite based on biodegradable polymers - food tray, egg containers, creams jars, chemical containers, tomato yarn, pots, balcony pots, encapsulated fertilizer.
Composite based on recycled polypropylene car seat, chemical containers, cream jars, pots.
WP2: Collection and pre-treatment of forest materials (WP Leader: 05-CARTIF) (sm1; em24)
The objectives of WP2 were the following:
Identification of raw forest materials providers, availability, costs.
Characterisation of forest materials and fibres
Pre-treatment and pre-compounding of forest materials to get fibres and pellets for the production of bio-based foams and composites.
WP2 was completed in the second year of activity in FORBIOPLAST.
During the WP2 three main aspects: market, fibres characteristics and possible pre-treatments, have been studied with the objectives of exploring and identifying the raw material components for the FORBIOPLAST products, and evaluate providers and possible modifications in the production processes. Raw materials for the production of bio-based foams and composites were identified and their relevant technical data, providers and cost were reported in D2.1 European Market Analysis and Provider Identification to perform an appropriate choice of fibres. Fibre characterizations of several woods samples were carried out with the aim of detecting differences in the fibre properties between types of wood (softwood, hardwood and mixed wood) as well as possible affections after pelletizing treatments. Results were reported in D2.2 Report on forest materials characterization. The fibre pre-treatments carried out consisted of physical (fibres pelleting) and chemical (incorporation of specific additives), and the results related to them have been reported in D2.3 Report on forest materials pre-treatment.
The raw materials with forestry origin for producing the FORBIOPLAST products have very different characteristics and prices that can go from the 60 /t for wood residual fibres to 150.000/t for cellulose powder.
A detailed analysis has been done for different wood flour and fibres. Relating the chemical composition, it is very similar for all the wood flours analyzed in water content, lignin and holo-cellulose. Relating to the wax content the sample from oak and beech has a very high value which could make difficult the adhesion between this filler with the plastic matrix or the coupling agents. For this adhesion it is also better to have less wax content, and in this way fibre EFC 1000 Rettemaier is the best one, having more OH groups than the others. The materials selected, to be used in the project, according with these results have been the EFC 1000 Rettemaier fibres because of its high aspect ratio, and the La.So.Le 200/150 wood flour because of its price. The first one will be used as reference material to show the ideal point to reach the required characteristics for the materials developed, and the second one will be used for developing the FORBIOPLAST products in an economic industrial procedure system.
Main objectives were achieved for WP2, less quantity of chemical additives were required to obtain appropriate properties for the composites, and shorter pellets easier to be fed in the extruder were produced. Nevertheless it would be useful to improve further the pellets produced allowing their easier disintegration inside the extruder.
WP3: Developing bio-based polyurethane foams (WP Leader: 03-IWC) (sm3; em36)
Objectives of WP3 were the:
Laboratory synthesis of hydroxyl-containing esters through trans-esterification of tall oil and lignin containing compounds with polyvalent alcohols and alcanoamines; analysis of the synthesized esters;
Development of freon-free polyol systems suitable for long-term storage;
Development of polyurethane from lignin;
Detailed physico-mechanical investigation of polyurethane (PUR) and polyisocyanurate (PIR) foams. Accumulation of a full set of experimental data for different foams. Recommendations for improvement of performance
Production of Hard and soft polyurethane foams and scale up to industrial production for automotive components (T-node), bumper and packaging (fish box).
Soft foams were produced using different types of lignin. In an early attempt two different types of lignin were employed, one from kraft and one from soda process. Subsequently the soda lignin was subjected to hydroxypropilation process to make the OH group more easily accessible for the reaction with isocyanate. All the lignin were liquefied using an innovative microwave process which is less time and energy consuming than the traditional liquefaction process. Through this work liquefied lignin, with suitable chain extenders, was shown to be potential replacement to petroleum polyols for the production of flexible polyurethane foams. To increase the content of liquefied lignin in foam formulation, and ultimately achieving the goal of making still flexible foam with liquefied lignin, lowering the Tg of polyol phase was determined to be the most important issue.
In the attempt to produce flexible foams two type of chain extender were used in combination with liquefied ligin: polypropilenglycol triol and castor oil. The amount of lignin that was possible to introduce in the network varied from 6 to 13% and considering the renewable origin of the castor oil it is possible to state that in these samples the renewable content is more than 45%. The type of lignin did not influence greatly the structure and properties of the produced foams, hydroxypropylated lignin was easily dissolved in the liquefying agents and the characterizations of the foams produced with this material showed an intense phase mixing between liquefied lignin and chain extenders, higher than the unmodified lignin. For all the type of liquefied lignin, polypropylene glycol triol (PPG) was proven to be an effective chain extender. Samples with liquefied lignin and castor oil had phase mixed morphology and high glass transition temperature which was believed to be the factor giving rise to rigidity in those types of foams, these samples showed a density between 160-230 kg/m3 that is comparable with foams made with renewable resources, like palm or soy oil.
The target products of these systems are: different size and shape items, incl. car parts, such as spoilers, bumpers. The physical-mechanical characteristics are similar or better than conventional petrochemical foams and completely reach the industrial requirements of FORBIOPLAST Partners. Natural fibres are prospective filler for PUR foams; in this case the renewable material content (both tall oil and natural fibres) could reach 35% in end product. It must be taken into account the humidity of natural fibres, because the humidity decrease the density of PUR foams, with following decrease of physical mechanical properties. Only for high density foams (greater than 200kg/m3) there are improvements of mechanical properties of foams, if the fibre concentration is 3 6% by weight.
The optimum parameters for production of automotive parts were established and these results were transferred to activity in WP7.
Vegetable oils offers a variety of new structures in polyols, resulting in polyurethanes with new properties suitable for a range of applications, then it is normal to expect a dramatic increase in the use of renewable resources in the polyurethane field. The development of soft and hard foams resulted challenging tasks but some formulations were identified for the production of both soft and hard foams which meet the technical requirements of producer and end user and an industrial exploitation of these materials is envisaged. The addition of wood fibres in the PU foams was also a challenging task The activity in WP3 resulted particularly successful and the positive cooperation of RTDs and INDs involved in the WP has allowed the production of interesting prototypes at pilot scale and then on industrial scale. The objectives of the WP were achieved in scheduled time. Additional exploitation of the foams developed was found in application for growth of micro-organism in cooperation with Partner UAL, as bio-valorisation of FORBIOPLAST products, as reported in the activity of WP9. The PUR foam material usable for microorganism growing was object of a patent application by IWC, UAL, and UNIPI.
WP4: Physical, chemical and biological modification of wood fibres to improve compatibility in wood based composites. N (WP Leader: 02-LPRT) (sm3; em36)
Objectives of WP4 were:
To develop coupling technology for PP/wood composites, to select wood type, amount and type of coupling agent, recycled PP;
To select coupling agents for wood composites with biodegradable matrices adjusted to the chemical structure of the polymers;
To select a microbiological treatment for biological modification of wood;
To explore methods for the chemical modification of wood in order to improve its inherent strength and to reduce the water sensitivity of the composites;
To develop coupling technology for PU foam/wood composites.
Work progress in WP5: Production of composites based on recycled polypropylene filled with forest-derived fibres. (WP Leader: PEMU) (sm6; em42)
Objectives of WP5 were:
To develop a melt blending technology for recycled PP-wood composites with selected wood type, amount and types of coupling agent;
To make experimental production of PP-wood composites with forest-derived fibres according to the developed coupling technology at semi-industrial scale;
To define the proper compounding technology;
To produce compounds for the manufacturing of prototype(s);
The major achievements for WP 5 consisted of:
Investigation of the optimal recipe of wood flour filled rPP compounds
Selection of the suitable additives
Development of optimal compounding parameters
Production of suitable recipes
Tests of mechanical properties
Successful injection moulding trials
In the present WP, PEMU developed production technology for composites based on recycled polypropylene (rPP) loaded with forest-derived fibres and methods for their characterization. Participant UNIPI and Participant LPRT cooperated in structural, thermal and mechanical characterization of developed compounds.
Participant CRF followed the activity with inputs on technical requirements and as provider of rPP.
Revised specifications were (by Participant CRF):
Strain at Yield: greater than 2%
Yield Strength: greater than 25 MPa
Youngâ??s modulus:1.4 - 3 GPa
Density:0,95 - 1,15 g/cm3
Charpy impact strength: greater than 15 kJ/m2
The goal of WP5 was the melt blending of rPP-wood composites on laboratory, semi-industrial and industrial scale as well with forest - derived fibres according to the coupling technology developed in WP4. In this WP, PEMU selected raw materials, additives, coupling system, formulation and technological parameters for the targeted products in cooperation with Participant LPRT, and determined component properties and components of the rPP/wood composites. Different formulations were selected and processed from lower amount to higher amount of compounds for injection moulding tests. This cooperation was very important for PEMU which acquired new knowledge and improved the experience of its workers.
WP6: Production of composites based on biodegradable polymeric matrices filled with forest-derived fibres. (WPLeader: UNIPI) (sm6; em36)
Objectives of WP6 for were:
To produce films and composites based on biodegradable materials loaded with fibres and additive derived from forest resources on laboratory-scale;
To characterize produced items in terms of structural, thermal, mechanical, permeability properties;
To select best formulation to be promoted for trials at industrial scale.
Based on D1.1 State of the art, D1.2 Technical specifications for targeted products and D6.1 Report on laboratory scale production of composites based on forest derived materials and in collaboration with the project partners six targeted product were developed for agriculture and packaging applications:
Tomato yarn;
Biodegradable plant pot;
Food trays;
Egg containers;
Cosmetic package;
Chemical package.
WP7:Materials from forest resources for automotive applications. (WP Leader: CRF) (sm18; em45)
Objective of WP7 were:
To evaluate the use of lignin and other forest resources in the formulation of composites and foams for automotive applications with specific relevance to panels and structural parts for automobile interior.
To produce a car part prototype to verify the forming process and performance of materials based on forest resources (composites and foam).
To test the composites and foams according to the working standards in place for automobile components.
Objective of the WP is the study and evaluation of the use of lignin and other forest resources in the formulation of composites and foams for automotive applications with specific relevance to panels and structural parts for automobile interior.
They were evaluated and assessed the automotive prototypes parts produced using new bio based materials developed in FORBIOPLAST as described in D7.2a Report on the production of automotive parts based on forest derived materials. The scope was the demonstration that technically valid automotive parts can be produced using a percentage of bio materials improving the environmental impact as described in D10.3 Life cycle analysis based results on environmental burden and impact of the newly developed materials in automotive field and comparison with commercial products.
CRF developed a new concept of slim and ergonomic of a car seat bottom.
Computer simulation tool were used to assist the design procedure both for the part structural performances and process parameters of the injection moulding and permitted an optimisation of the part shape through an iterative process. Equipments for the production of the car seat by injection moulding were set-up by CRF. Before the final set-up of the mould, in conjunction with WP5, a series of sample sheets reproducing the main feature of the seat parts (different shaped ribs and holes, different thickness) were produced with the FORBIOPLAST composite material to verify the mouldability and possible problems. Thanks to this test it was possible also to find the best process parameters for the production of the car seat.
The first test after the production of the seat structure part was the dimensional stability. A measurements system detected a number of main points on the parts and compared with a 3% tolerance to the optimal design geometry. All the prototypes passed the test and their dimensions were compatible with the set tolerances. Then the prototypes were subjected to long thermal cycles according to the automotive standard conditions: no damage or deformation occurred on the parts after the thermal treatment. The parts were assembled with four screws in the side holes for the mounting of the structure on the full seat.
Materials developed in FORBIOPLAST from recycled PP and forest resources have been demonstrate to be suitable for the production of automotive parts, in particular a seat structure. All the final four materials are good with a different level of flexibility. Forest materials can be considerate an adequate form of resources in conjunction with plastic. An amount from 10% to 30% of natural resources is a reasonable value.
WP8 Materials by forest resource for agriculture and packaging applications (WP Leader: INCP) (sm18; em42)
Objectives of the WP were:
To produce at pilot- and industrial- scale films and composites based on biodegradable materials loaded with fibres and additives derived from forest resources,
To characterize the structure, thermal and mechanical properties, as well as permeability of the produced items.
To test produced prototype in packaging applications
To test produced prototype in open field tests
Formulations for the production of prototypes were defined in WP6 by Partners UNIPI, LPRT and PEMU. Characterization of developed materials in terms of structure, mechanical and thermal properties was performed by UNIPI and LPRT. Test of food trays for packaging in vacuum or in modified atmosphere were performed by RODAX, NORC and UASVM. Test of performance of tomato yarn were performed by Partner UAL and UASVM. Test on application of containers for chemicals and cosmetics were performed respectively by NEOC and COS.
Also UASVM tested flat and rounded yarns on tomato hybrid SIRIANA F1 for pallising and traditional yarns from PP and PVC, for comparison in the staking process. UASVM reported the best quality for formulations of flat yarns containing 15% of wood fibres La.So.Le. and 20% Rettenmaier, the staking procedure being realized in a proper way and stated for rounded yarns that the plants can be pallisate with an average degree of difficulty.
Low and tall shapes of pots produced with formulations based on PLA/Ecoflex/wood fibres were prepared and compounded by Partner UNIPI, LPRT and PEMU and were processed by INCP using injection moulding technology.
PEMU managed to manufacture some prototypes of the balcony flower boxes with formulations based on PLA, plasticizer and Rettenmaier fibre up to 40 wt%.
INCP encountered some difficulties in the production of pots by injection moulding using formulations based on PLA, ECOFLEX and wood fibres relating to flow of melted materials and filling of the mould.
Encapsulated fertilizer with very promising properties were prepared by LPRT from starch, wood and an industrial NKP compound (nitrogen, potassium, phosphorus). The work of LPRT was focused on improving the reproducibility in stick production, increase the nitrogen content and evaluate different wood reinforcement. The sticks produced are promising as slow release fertilizer.
The biodegradable fertilizers were tested by UASVM on the plants (Dianthus caryophyllus and Petunia hybrida). Before to organize the experiments, the fertilizers sticks were analysed for the following parameters: pH, N, P, K existent as total amount but also in soluble form. During the vegetation period, biometric they were made observations regarding growing and developments of plants, namely: height, roots length, number of shoots, number of flowers. Regarding the growth and developments of plants (height and number of shoots) all the fertilizers samples demonstrated a beneficial slow release process of the macro elements which determined a positive effect. At the same time didn`t noticed any negative deficiencies for any of the NPK elements in the tested plants.
Sensory profile consisted in touching smooth, touching familiar, visual natural looking, visual attractive, smell intensity, smell pleasant, all senses evaluation were used 20 volunteers with ages between 20 to 45 years. It is found that the prototype jars based on PP and Rettenmaier wood fibre had a strong smell of lignin which is a negative aspect for the general consumer and affects negatively the smell of the cream. Only the PHB with 20% Rettenmaier wood fibres seemed to be acceptable from the consumer tests for cosmetics packaging.
Chemicals packaging for industrial use consisting in three parts: body, lid and handle were produced by injection moulding by INCP. Several formulations from polypropylene/recycled propylene (rPP)/Rettenmaier/La.So.Le fibre were designed and compounded by LPRT and PEMU at 20 wt.% Rettenmaier/ La.So.Le fibres and respectively 30 wt.% Rettenmaier loading and at different PP: rPP ratios. Brown and black chemical containers having the size of 170x150 mm, thickness of 2.5 mm and capacity of 2 litres were obtained. Containers prepared from rPP and addition of virgin PP showed an improved processing than formulations based on just recycled polypropylene.
Chemical containers based on bio-composites have both economical and environmental advantages by replacing of amount of PP with rPP which is low cost, abundant, without affecting their mechanical performance.
Latvia's partners, Institute of Wood Chemistry (IWC-RTD) and Ritols Ltd. (RIT - SME) were involved on concept of fish boxes with thermal insulations. Thermal insulation material contains 29% of renewable raw material tall oil in ready foams. The processing of material is optimum and could be used on industrial foaming machines.
Food trays were produced by PEMU with PLA/Ecoflex in different ratios and Rettenmaier fibres. Different moulds were designed by PEMU for thermoforming lab scale trials of the food trays. Firstly PEMU produces thermoformed prototypes from pure PLA, then from PLA/Ecoflex in different mixing ratios of components and later from PLA/Ecoflex/Rettenmaier in different mixing ratios of components. PEMU tried to reduce the thickness of products, at the same time the price and the wood smell of prototypes, therefore were prepared trays with a sandwich structure in order to avoid the direct contact of wood fibres with food. The best performance was observed by RODAX, NORC and USAMV partners for prototypes produced as sandwich structure.
RODAX (SME Romania) tested the performance of food trays as following: sealing tests, seal strength tests, leakage tests, tray crash tests, package tests. RODAX manufactured the packaging equipments to make the sealing test of film over trays. Their characteristics regard the cutting and the sealing of the thermal assemblies respectively the hot cutting wire, hot sealing band or the aluminium heated plate with incorporated resistance. As film were used PLA, PLA/ECOFLEX and PP films. The best results for sealing and cutting have been obtained at temperature of 100 0C and 8 sec., at 140 °C and 150 °C for 4 sec. respectively 3 sec.
The sensorial analysis of products stored in the developed FORBIOPLAST trays compared to standard commercial hydrocarbon-based plastic trays commonly used by the food industry were studied by NORC using modified atmosphere packaging of salmon. The FORBIOPLAST food tray could be used for packaging food preserving their own characteristic taste and odor. However sensitive foods will take up odor and taste from the wood fibres inside the tray. The tray must be further developed to hide the characteristic woody odor, as the tray is now it will have trouble complying with European food packaging directive and good manufacturing principle (GMP). This optimisation might be performed in a possible future demonstration project.
For the food trays experiments UASVM used packaging of fish and meat and stored at chilling temperature for 7-8 days and at frozen conditions storage for 3 months. After certain preservation period in refrigeration conditions (chilling or freezing) physic-chemical and microbiological analysis for fish and meat have been performed in order to establish the shelf life and also the food trays materials were analyzed. Thermal analysis (TGA, DSC, DMA), physical and mechanical analysis (density, compression) performed showed that neither the content nor storage conditions for food trays did not lead to any significant change occurred in the composition and structure of composites used in their manufacture. FTIR analysis did not reveal the existence of major changes in surface materials. The differences between samples in terms of specific heat (Cp), enthalpy of cold crystallization (Hc) and total melting enthalpy (Hm) measured by DSC are probably due to absorption of water during the time spent in contact with meat.
The promising FORBIOPLAST prototypes based on bio-polymers and bio-composites could be used in agricultural and packaging fields. Testing of prototypes performance demonstrated that some formulations have the same properties as the similar products presented on market, and in the same time they are superior to traditional products regarding the benefits on environment.
WP9 Biodeterioration, biodegradability and valorization of the developed materials (WP Leader: UAL) (sm15; em48)
Objectives of the period in the present WP were:
to study the biodegradability and compostability of the newly developed biobased products;
to evaluate ecotoxicity of newly developed products;
to explore processes for microbiological valorization of the packaging and agricultural produced material;
to evaluate the recyclability of the packaging and agricultural produced materials;
to determine biodeterioration of the developed materials for automotive applications
The biodegradation of the developed compounds was evaluated in a broad range of environments. Also the biodegradation of the basic Rettenmaier wood fibre, used in many applications within this project, was investigated. It was observed that the biodegradation under composting conditions and soil proceeded, but at low rate due to the lignin content. A previous bio-delignification process by treatment with ligninolytic fungi induced a positive effect on biodegradation rate.
Composites based on wood fibres (Rettenmaier) and biodegradable polymeric matrices such as PLA, PBAT (Ecoflex), starch and PHB were evaluated for biodegradation. These composites are suitable for compostable packaging and products (EN 13432). The PLA compounds also degraded under thermophilic, anaerobic conditions, but the rate was too low to yield complete degradation within industrial digestion process for treatment of waste. No complete biodegradation was observed for PLA/Ecoflex/Rettenmaier compounds at room temperature in compost, soil and water. This material is not suitable for home composting applications. The PLA component needs a certain temperature trigger (typically around 55°C) before the hydrolysis and biodegradation starts.
The starch/Rettenmaier compounds proved to be completely biodegradable in soil conditions. Together with the slow, but steady disintegration in soil the developed starch/Rettenmaier based fertilizer sticks are an environmental friendly fertilizer for flowers that promotes plant growth and flowering. This material also seems to stimulate biodiversity of soil microbial population, including those microorganisms involved in long-term maintenance of fertility (test still running). Because of this property the developed starch/Rettenmaier compounds may be used for bioremediation processes as biostimulants agents.
Three different approaches were attempted for materials valorization: Biogas production by anaerobic digestion, immobilization of microorganisms for ligninolytic enzymes production and production of single cell protein from materials hydrolysates.
The PLA based compounds were degraded under thermophilic, anaerobic conditions, but the rate was too low to yield complete degradation within industrial digestion process for treatment of waste. Products based on cellulose diacetate have the potential to be treated after their life-time in anaerobic digestion plants, yielding biogas for energy production.
Polyurethane (PU) rigid and soft foams were used as support for growth of microorganisms that produce ligninolytic enzymes, mainly laccase. In general enzyme production was enhanced when the fungus was immobilized in PUR foams with open cells structure and filled with wood fibres. Small size soft foams made of hydroxypropylated lignin and castor oil gave higher laccase production than those made of lignin and PPGtriol hydroxypropylated lignin or PPGTriol.
Production of single cell protein of the yeasts Pichia pastoris and Rhodotorula sp. to be used as additives in animal feed was attempted by hydrolysing several developed composites under different conditions. The highest quantity of yeast biomass was obtained for (PLA:Ecoflex 50:50):Rettenmaier 85:15 compound hydrolysed using H2SO4 and high temperature treatment.
The yarn prototypes based on PLA/Ecoflex/Rettenmaier blends were used to fasten different types of cultures in one cycle production. After crop, the plants together with the yarn were used to perform a semi-industrial-scale composting. Yarns were used to fasten cultures of melon, cucumber and tomato in greenhouses cultures and tomato in open field culture (as reported in WP8). The yarn made of (PLA:Ecoflex 20:80):Rettenmaier 70:30 was the most suitable to be composted at semi-industrial scale because besides of being the most adequate for field application it disintegrated after composting and the final compost was of high quality.
The materials developed for within this project developed polyurethane (PUR) with 20% rosin acid and recycled polypropylene with Rettenmaier fibres were quite resistant to biological degradation. PUR materials prepared for fish-box industry and automotive applications were highly resistant to microbial attack. Also polypropylene/wood composites for automotive applications and materials intended for chemical and cosmetic containers based on formulations containing PP and rPP with wood were heavily colonized by fungi but not impact on materials properties was evidenced. These characteristics are essential for long term outdoor applications such as insulation or automobile parts. In general the increase of wood content in materials favours the microbial colonization. All selected materials can be considered very durable from the point of view of susceptibility to microbial attack and biodeterioration.
WP 10: Life Cycle Analysis (WP Leader OWS) (sm 12, em 48)
Objectives of the present WP were:
To assess the hot spots in the production chain in order to make recommendation for future production of FORBIOPLAST materials.
To assess the environmental burden and impact originated from the life cycle of the packaging (comparison with commercial packaging) and automotive parts (comparison with actual car components).
An environmental assessment has been made by using the eco-indicator 99 (H) method on 5 different applications containing wood fibres:
Fertilizer sticks
Food trays
Tomato yarn
PHB pot
Automotive car pan
These materials have been chosen because of their different applications and compositions. The starting point in this assessment was the data inventory of the wood fibre production. This data inventory was based on a literature review, where it was assumed that the fibres are made from sawdust and afterwards transported to the production site in Germany. The production of sawdust, including the tree harvest steps seemed to be the most dominating step representing 46% of the total impact, mainly caused by land use, whilst energy use during further processing to fibres and transport to destination account for 29 and 25% respectively. Although it is expected that the used fibres in the studied application origin from sawdust, a sensitivity check was performed comparing the exact source of the wood biomass. From this analysis it can be concluded that the different types of wood chips found in the LCI database generally have a lower impact, especially concerning land use, compared to the used sawdust dataset. In some cases more fossils are used, but this impact seems to be low compared to the total impact of the wood fibres.
In general, adding wood fibres to plastic applications is an environmentally benign strategy. The overall environmental impact of the wood chips according to the eco-indicator 99 method is lower compared to any fossil or non fossil based material used in the studied materials, such as PE, PP, PVC, PS, PBAT, PHB, starch. Therefore, apart from material properties, it is clear that adding more wood is a good strategy to achieve a better environmental performance compared to reference products.
A large advantage of the materials produced in FORBIOPLAST is their biodegradability. This end of life scenario of the studied materials however, was too difficult to model with the current methodologies used in LCA. In the case of fertilizer sticks, tomato yarn and the PHB pot, the biodegradability is positive because of the fact that they often end up directly into the natural environment. It would be even possible to assign carbon credits because of the potential soil enrichment effect of these materials. At the other side, the direct emission of a non biodegradable plastic is impossible to assess because no sound fate/exposure/effect models of these materials exist for LCA. In the case of food trays, the interaction with nature is less direct. A scenario has been analysed where the PBAT/PLA/wood material is composted compared to the reference products which are incinerated. Even when implementing this end of life scenario, the life cycle impact of the FORBIOPLAST material is higher. A careful recycling of the fossil based materials would enhance this effect. Nevertheless, the biodegradable food tray may be preferred in cases where they are highly contaminated with organic matter or in cases where a direct contact with the environment can be expected (e.g. festivals).
The recycled materials reinforced with natural fibres show good technical performances, as well as significant environmental advantages, so as the LCA has been able to highlight. While the environmental impacts are quite similar for the use and end of life phases, the FORBIOPLAST solutions show remarkable advantages in the production phase mainly concerning the avoided burdens due to the polypropylene recycling and the use of vegetable fibres instead of the mineral ones. Thanks to benefits in using recycled material and wood fibres and to other improvements due to a logistic optimization (transports), the FORBIOPLAST solutions deserve to be considered as good alternatives to those currently used.
Potential Impact:
European citizens tend to have an increasing positive attitude towards buying and using green and renewable technologies, especially because they reduce the impact on the environment. In the future, more people are expected to follow this behavior because of the increased advertising and policies applied in this area so the market of green technologies seems to look very bright.
The results and the prototypes produced in FORBIOPLAST attest for the possible valorisation of forest biomass for the production of environmentally compatible materials to be applied in packaging, agriculture and automotives. These materials include composites based on biodegradable polymeric matrices, or recycled polypropylene with lignin or wood fibres and hard and soft polyurethane, eventually loaded with wood fibres produced by green synthesis from tall oils or lignin.
More than 50 million tons of lignin annually derive from different pulping processes, while the Kraft process takes the lion's share of 76%. Merely 1 million t of the lignin is under commercial use. Hence, FORBIOPLAST research treats lignin for various materials, such as PUR soft foams. As a by-product of the Kraft pulping process, tall oil is available for further industrial use. The total yield is estimated on 1,5 million tons per year. Tall oil is primarily utilized for developing bio-based rigid polyurethanes and composites in FORBIOPLAST project.
The main objectives of the European Commission concerning the automotive sector are: to strengthen the competitiveness of the Automotive Industry, To complete, adapt and simplify the Internal Market regulatory framework, to promote globalization of the technical regulatory framework through UNECE. In order to achieve these ambitious goals, legislation in the European Union is focused on sustainable automotive industry. With regard to 8-9 million tons of waste deriving from end of life vehicles in European Union, the (Directive 2000/53/EC - the 'ELV Directive') has been officially adopted by the European Parliament and the Council in September 2000.
FORBIOPLAST works with recycled materials as well as biopolymers and responds to depletion of fossil resources. For example, the world's crude oil reserves were estimated on 184 billion tons in 2009. Assuming that annual consumption may vary between 3.7 and 3.9 billion tons (as occurred between years 2003-2009) and no significant reserves will be discovered, the resource will be exhausted in less than 50 years. From a total demand of 52.5 million tons of plastics, 18% of this request was polypropylene in 2007. Considering the environmental issues of plastics in Europe (EU27/NO/CH), it has been reported that 50% of the plastics have been recovered either for materials (20,4%) or for generating energy (29,4%).Recycled polypropylene plays a crucial role in development of ecological automotive parts (seat system) within the project. As a further part of cars, in FORBIOPLAST a seat has been designed to be produced from fully ecological material (rPP/wood fibre). PP is a very important polymer in automotive industry and as it has been recorded, from a car in the range of 1100 kg, 130 kg are plastics. From the plastics 45 kg (more than 1/3) are PP. At European scale, it means 600.000 t. The potential amount of plastic composites in a seat system is estimated on 10 kg per car. Moreover, replacement of metal by plastic composite entails reduction of weight of the seat and the car. FORBIOPLAST research and development has generated composites which exhibit economic and ecological advantages and its potential in seats in European cars is estimated on 80.000 t.
Research and development within FORBIOPLAST in the packaging area has resulted in prototypes like food tray, egg container, fish box, cosmetic container and chemical container. The FORBIOPLAST project has developed the process of a new generation of packaging solutions using renewable and fully recyclable materials that also respond to the growing packaging market. The future for fibre-based packaging will require the re-engineering of the packaging value chain to deliver increased, capital efficiency, product innovation and more competitive packaging materials. The main trend in modern packaging is the utilization of the biodegradable materials which enable the protection of the environment in accordance with the European legislation.
Cosmetic is a very important industry sector in Europe. Following a market study of Global Insight, the European market size of cosmetics and toiletries was 63.5 billion in 2006. That means about the value of the combined market size of USA (38.2 billion) and Japan (23,7 billion). The Chinese market was valued with 8.2 billion in 2006. Cosmetic packaging should grow 4.2% per year to reach $24 billion (PIRA, 2012). North America has the largest share at 66% followed by Europe at 63%. The largest categories using rigid plastics are hair care, bath and shower, facial skincare and deodorants. Cosmetic containers which includes cosmetic compacts and lipstick and mascara cases, is growing at 3% a year but in Asia Pacific, Latin America and the Middle East and Africa it is expected to grow at 5-6% a year to 2014. The top performing rigid plastic pack is expected to be plastic jars growing at 5% a year (http://www.rexam.com/files/pdf/packaging_unwrapped_2011.pdf). It is suppose that the innovative FORBIOPLAST cosmetic container can replace around 10% of packaging in cosmetics. FORBIOPLAST research and development in the cosmetic packaging area and its outcomes offer bio-based and sustainable solutions for cosmetics industries. The advantages of properties which could be promoted within the FORBIOPLAST cosmetic container are the followings: ease of moulding into complex shapes, rigid enough, impact toughness, abrasion resistance and chemical resistance that reduces scalping and permeation of valuable ingredients, a superior barrier against oxygen, fragrance and contamination, the chemical and aroma barrier properties keep volatile and valuable ingredients inside the package where they belong, making sure product value and quality reach the consumer intact, anti-static properties, 100% eco friendly, unique design, gloss surface, easy to print with high-quality graphics to increase the visibility and the attractiveness of the package, and cost-efficient decorative effects, best price with top quality.FORBIOPLAST has produced an environmentally friendly cream jar based on traditional polymers and natural fibres while commonly PP, PE and PET is used for that purpose. Like any new product, packaging materials products resulted from FORBIOPLAST project require special promotion supported by adequate advertising and improved functional qualities. Demands in cosmetic container applications will be supported by growth in production, as well as by expansion in all age population body and beauty care segments, which comprise many of the most intensive consumers of cosmetics. Traditional 200ml jars from PP are sold in the range from 0.18 -0.40 per piece. The container produced in FORBIOPLAST could be competitive in terms of price and environmental issues.
Toward 2014 the growth of chemical container demand in the world will increase with 2.9% and will be driven by performance advantages over alternative packaging media, which will stimulate ongoing opportunities in a broad range of applications. It is expected that 15% from total chemical packaging can be replaced with FORBIOPLAST products. Certainly, the incorporation of a percentage of recycled polypropylene in the formulation has a positive cost impact and helps to re-use polypropylene. Price of polypropylene versus price of polyethylene is not expected to make a big difference since both are widely used plastics. The mixture of recycled polypropylene with pure polypropylene without affecting the mechanical properties will offer a price advantage as well as the incorporation of up to 30% of wood fibres in the formulations.
The main advantages of the FORBIOPLAST tomato yarn comparative with tomato yarn based on traditional petrochemical products are: It is derived from sustainable resource; Help in preserving non-renewable resources like petroleum, natural gas and coal; Toxic free; Compostable; Environmental protection; Best suited for short shelf life products; Low barriers of oxygen/water vapours transfer.
Advantages of FORBIOPLAST pots compared with traditional pots are: Compostable;
Can be planted directly in the soil, saving time if based on polymers degradable is soil such as polyhydroxybutyrate; Eliminating stress to planting to induce the earlier production, achieving a savings in terms of manual labor; Reducing waste since the pots decompose in the soil; Easier application; Labor force concentrated in a smaller area; Ability to manage growing conditions, less climatic risk; Smaller area needed for the same production numbers; Greater success rate in comparison to traditional bare root.
As a further product devoted to the agricultural market segment, an encapsulated fertilizer with a bio-based and biodegradable coating is created within the project.
The global market for coated fertilizers shows tremendous growing rates and this type of fertilizer is more and more applied in major agriculture crops like cereals and potatoes. Among the advantages of these fertilizers are a possible reduction of fertilizer application quantity and full nutrient supply for plants under plastic cover.
The Common Agricultural Policy is also integrating environmental concerns as a most sensitive objective and it aims to head off the risks of environmental degradation and enhancing the sustainability of agro-ecosystems. Around half the EU's land is farmed and farming is important for the EU's natural environment, so, farming and nature influence each other. Inappropriate agricultural practices and land use can have an adverse impact on natural resources, like pollution of soil, water and air, fragmentation of habitats and loss of wildlife. The Common Agricultural Policy (CAP) has identified and set three priority areas for action to protect and enhance the EU's rural heritage which can be achieved through solutions given by biocomposite materials: biodiversity and the preservation and development of 'natural' farming and forestry systems, and traditional agricultural landscapes; water management and use; dealing with climate change. FORBIOPLAST Project helps reaching these policies by aiming the valorisation of forest resources for the production of bio-based products with the additional contribution to solve the problems related to materials produced by petro-derived resource, to waste disposal, to the use of energy consumption and polluting chemical pathways and to the use of hazardous substances. The project helps in meeting the European agriculture policies: CAP. The main topic of the research activity will be focused on the use of wood and paper mill by-products as raw materials for the production of polyurethane foams by an innovative sustainable synthetic process with reduced energy consumption. Efforts were devoted to the promotion of the use of wood derived fibres in the agriculture sector (mulching, greenhouse, tomato clips, different types of pots and yarns etc) as in FORBIOPLAST Project, 2012.
Polyurethanes (PUR), often described as the most versatile plastics materials, are produced with remarkable share from bio-based feedstock (tall oil and lignin) within FORBIPOLAST research towards end uses in automotive acoustic insulation, spoilers and packaging such as fish transport boxes (Hard PUR). Lignin-based Soft PUR can be applied e.g. in furniture industry as the biggest consumer of PUR in Europe (2005) as well as in automotive sector. Opposed to bio-based polyols from vegetable oils already introduced onto the market, FORBIOPLAST polyols are generated from waste material of pulp industry and their raw materials are commonly not grown on agriculture crop areas. Positive impact are expected from the exploitation of hard polyurethane produced by tall oils since tall oil is prospective raw material for polyol production for polyurethane foams. A spoiler, partly deriving from renewable resources has been produced by partner PEMU. As it is emphasized, the properties and the price of this automotive part which is primarily devoted to sports- and luxury cars, are comparable to traditional crude oil based materials. Following appraisals, Green PUR could achieve 300.000 t for spoilers.
New efficient methods of processing and new materials are generated as a result of the activities undertaken within the project. Saving raw materials and reducing costs for manufacturing and logistics will supply competitive products and secure employment. Energy consumption and effects of greenhouse gas emissions will be reduced by the exploitation of the new materials and commodities. Due to the new technologies customers benefits will be the availability of items with improved quality and lower prices related to environmentally friendly waste disposal. Renewable resources are continually renewed by the cycle of nature and are considered to be practically inexhaustible.
The research activity performed in the project had a significant impact on the RTDs performers in terms of increased knowledge, new contact, positive cooperation and experience acquired in working with industries. Problems from the perspectives of the industrial users and producers were evaluated, and with these impressions the RTDs were able to attend the necessities required by the local industries. FORBIOPLAST research and development lead to gaining new knowledge in the area of biopolymers and biocomposites and provides new options for promotion of bio-based materials and products. Furthermore, due to conduction of market analysis, new market opportunities for innovative composites were identified.
The end users were very satisfied if the results and of the positive cooperation with the RTDs and producers. The use of biodegradable packaging for cosmetics is in its infancy. Poor barrier properties, higher price and low general public awareness are the major reasons for the limited use of biodegradable packaging in cosmetics. Partner Cosmetic (COS) had the opportunity to get an inside industry knowledge of the biodegradable packaging. The dissemination of FORBIOPLAST results to Cosmetic's customers has stirred conversations about the potential use of biodegradable packaging in this industry sector. COS is offering formulation and production services to other companies. It is to the company's advantage to offer the best advice to its customers especially the ones that have more green products. 1 billion $ world market for plastic cosmetic containers by injection moulding and 8 million is the corresponding Greek market. The above numbers are estimates based on the assumption that the cosmetics packaging produced by injection moulding corresponds to the 1/7 of the total. One fifth of the above could be replaced by the type of packaging developed in FORBIOPLAST. If biodegradable packaging becomes more widely-used, it is possible that the green certification bodies such as ICEA or Ecocert may require its use for providing the green label to cosmetic products. It is very likely that such a development will give more value to biodegradable packaging and raise general public awareness. The participation of COS to a large European consortium involving academic experts in the area has also been very beneficial towards improving the company's image and reinforcing its R&D profile, both within Greece and abroad. It has at the same time provided the basis for future research activity in the company in the area of biodegradable packaging or packaging materials in general. The industrial manufacturers could be some of the major plastic container producers in Greece e.g. Supremeplast, Argo and abroad e.g. Bormiolli, PET Power, M and H etc. The end user can be companies that have green marketing claims e.g. Korres, Macrovita, Apivita sold mainly in pharmacies and brands like Olivelia, Kalliston, Ollivelenic etc. sold in the touristic shops of Greece.
It was organised an International Conference Bio-based Polymers and Composites with the abbreviation BiPoCo 2012. The organiser was partner 02-LPRT but main milestones were discussed with the project coordinator UNIPI. A website was launched (http://www.bipoco2012.hu) program was carefully composed; four types of presentations were selected: Plenary lectures, Keynote lectures, Oral presentations, Poster presentations. Invited speakers were selected to cover the scope of the conference. Internationally well know authorities presented the latest work of their fields on the highest level:
Lars Berglund (KTH Royal Institute of Technology, Sweden) Biocomposites from small building blocks learning from plant structures; Claudia Crestini (University of Rome, Italy) Cellulosic composites from low to high tech versions; Ramani Narayan (Michigan State University, USA) The promise of bioplastics understanding the value proposition for biobased and biodegradable-compostable plastics; Balazs Imre (Budapest University of Technology and Economics ) Biopolymer blends: miscibility, compatibility, performance. Two types of keynote presentations were selected: two focusing on the topic covered by the plenary lecture presented before them and three presenting the FP7-projects related to the conference (FORBIOPLAST, BIOSTRUCT and WOODY), having their own dedicated block in the scientific program. In all 94 oral lectures were presented and to extend the number of presentations two poster sessions were organized where topics were extended but harmonized with oral sessions. 110 poster presentations were selected to display. A poster-award was also announced and 6 posters were selected and rewarded by an international scientific jury. As the topic of three keynote presentations were about EC founded research projects, the conference emphasized the role of the European Commission in large scale international research projects. 8 oral and 18 poster presentations were presented by FORBIOPLAST partners and 30 from all the partners of the three projects disseminating the results and foreground knowledge obtained during the EC founded FP7 projects.
CRF main interest for the products developed in FORBIOPLAST relies in the possibility to use the new eco-friendly materials based on wood fibers and plastics from post- consumer recycling and polyurethane formulations by lignin materials in automotive applications. The materials have been technically evaluated by CRF and demonstrated a good solution for semi -structural automotive parts and from the economic aspect they are also a cost effective solution. CRF also through its company Magneti Marelli - Plastic Components is interested to further strength its environmental sustainability approach also through the use of materials such as those developed in FORBIOPLAST.
Time scale for exploitation of FORBIOPLAST materials in automotive production is predicted between 2015 and 2020.
A part the specific materials and demonstrators developed by CRF for automotive, FORBIOPLAST project allowed CRF to get experience in bioplastics. Such materials were developed in FORBIOPLAST for agricultural and packaging applications, but they could be even employed with minor modifications in the future in automotive field. And this road will be investigated by CRF in future European projects (i.e. EU BRIGIT project).
PEMU is strongly interested to the industrialization of the materials developed in FORBIOPLAST, in particular for composites produced with recycled polypropylene and production of polyurethane for automotive applications. As well as CRF, PEMU feels the need for minor optimization of the production process. Also for PEMU the exploitation of FORBIOPLAST materials in automotive production is predicted between 2015 and 2020. CRF and PEMU consider the production of the car seat, and of the spoiler enough advanced, and the performances already meeting CRF requirements. These two partners considered not justifiable to go to a demo action for materials devoted to automotive applications.
List of Websites:
http://www.forbioplast.eu
Lazzeri Andrea, University of Pisa, Department of Chemical Engineering, Industrial Chemistry, and Materials Science, Via Diotisalvi 1, 56126, Pisa, Tel 00390502217807, a.lazzeri@ing.unipi.i