Final Report Summary - NANOFRABS (Halogen Free Flame Retardant ABS nanocomposites for electric and electronic devices)
Executive Summary:
The European FP7 research project NANOFRABS has been successfully finished in August 2014. It has focused on developing a new more effective halogen free flame retardant for ABS compound by means of incorporation of nanofillers. Six technical work packages described below, shows the work done along the project:
WP1 Nanoparticles synthesis, functionalization and characterization (from month 1 to 12)
Nearly 40 nanofillers (organomodified montmorillonites, zirconium phosphates and layer double hidroxides between them) have been synthetized, functionalized and characterized. Once realized the chemical (FTIR, ATR-FTIR) and thermal (TGA, DSC..) characterization as well as morphological features (XRD), twenty of them have been selected to be added to the ABS matrix in order to get the respectively compounds (WP2)
WP2 Preparation and characterization of new flame retarded ABS formulations (from month 1 to 16)
Once properly functionalised nanoparticles (WP1) have been introduced in ABS formulations. Chemical characterization (by FTIR and ATR-FTIR), morphological investigation (SEM and TEM), mechanical(impact), rheological and fire properties of these ABS compounds modified with the new HFFR have been done. From the work done in this work package, two nanofillers have been selected for doing the final product validation (one montmorillonite based and the other one layer double hidroxide based)
WP3 Final product validation (from month 17 to 22)
Results obtained at lab scale have been confirmed and validated at large scale. Nanofillers, masterbatches, halogen free flame retardant ABS (HFFR-ABS) compounds and the injection of an Electric and Electronic device have been scaled up at PROLABIN &TEFARM, MASTERBATCH, SITRAPLAS and DASYC facilities respectively. During the scale up, optimal processing conditions have been evaluated. All the products have been characterized (thermal stability, nanoparticles dispersion, impact, viscosity and fire behaviour) and the MSDS and technical data sheets have been generated.
WP4 Recycling of new HFFR ABS products (from month 21 to 24)
In this work-package, the recyclability of the final HFFR-ABS compound has been studied by its re-processing (extrusion-injection) in four different cycles. Thermal stability, chemical structure, nanofiller dispersion, mechanical properties, color variation and fire properties have been evaluated.
WP5 Dissemination and use/exploitation (from month 1 to 24)
Dissemination of the work done along the project has been realized with: different ferias attendance, preparation of the project brochure, presentation of three posters in three international meetings (France, UK and Italy), the set up and update of the NANOFRABS project web page (www.nanofrabs.eu) the publication of a news in the Newsletter for non-halogen fire safety solutions. Phosphorous, Inorganic & Nitrogen Flame Retardant Association (PINFA), inclusion of the Project Results on the Partners’ Web Sites, usage of the communication and diffusion networks provided by the European Commission as well as other webpages.
A plan for exploitation of the results has been developed within the project.
WP6 Project management (from month 1 to 24)
In this work package, activities such as: technical and administrative assistance to project partners, organization of consortium meetings and meetings with the Commission and development of Technical and Financial progress reports have been done.
Project Context and Objectives:
The two years NANOFRABS project has been coordinated by TECNALIA and has been carried out jointly with the POLITECNICO DI TORINO UNIVERSITY (Italy) and four SME: a compounder, SITRAPLAS GMBH (Germany), a nanofiller producer, PROLABIN & TEFARM SRL (Italy), a polymer masterbatch manufacturer, MASTERBATCH SRL (Italy) and an Electric and Electronic devices injector, DASYC (Greece).
The Restriction of Hazardous Substances (RoHS) and waste electric and electronic equipment (WEEE) directives discouraged the use of halogenated flame retardants in electric and electronic devices. For this reason, effective non halogenated alternatives have to be developed. The project aims at developing new halogen free flame retardant (HFFR) for ABS (acrylonitrile-butadiene-styrene) compounds, which are widely use in the electric appliances sector, with good impact and fire properties.
NANOFRABS project aims at developing a new more effective halogen free flame retardant for ABS, by means of incorporation of nanoparticles. Moreover, halogenated FR acts the gas phase, resulting in a high smoke density and toxicity, while intumescent FR acts in the condensed phase, with dramatically lower smoke production.
The main goal is to develop a new halogen free flame retardant (HFFR) for actrylonitrile-butadiene-styrene copolymers (ABS), based on the synergic combination of phosphorus compounds, and nanofillers in order to obtain:
Target flame retardancy properties are as follows:
- UL94 V0 [IEC 60695-11-10]
- Glow Wire Flammability Index (GWFI) at 960°C [IEC 60695-2-12]
- Glow Wire Ignition Temperature (GWIT) at 725°C [IEC 60695-2-13]
- A decreasing (at least a 25 %) of the halogen free flame retardant dosage for ABS in order to obtain better mechanical and rheological properties without decreasing the fire behavior of the final product.
- New ABS products (telephone housings, audio and electrical housings, high performance toys, computers) easily recyclable and environmental friendly, with low toxicity of the gases and vapors evolved during combustion
In order to reach these improvements, nanofillers have been combined with phosphorous-based flame retardants, either a) by Physical Combination of flame retardants and nanofillers in proper mixtures (PC), b) by Chemical Combination of nanofillers with flame retardants (CC) or a variant of the b) combination: c) by Physical Combination of Chemical functionalized lamellas and flame retardants (PCC) to be dispersed in the polymer by melt blending.
Scientific objectives:
- To develop HFFR ABS nanocomposites using two approaches:
- Physical combination of commercial nanoparticles and fire retardants.
- Chemical combination of nanoparticles and fire retardant, grafting flame retardant groups as phosphates or melamine derivatives onto the nanoparticles
- Control of mechanical properties of fire retarded ABS. Nanoparticles affect both stiffness and impact resistance, acting on both the mechanical properties of the polymer and on the morphology of the polymer/FR blends. The incorporation of nanoparticles into the FR polymer has been carried out by melt blending
- To check the possibility to modify thermal degradation pathway of ABS by the addition of halogen free chemical additives, promoting charring as a side reaction during polymer decomposition, thus limiting production of hydrocarbons to feed the flame.
Industrial objectives:
- To obtain a high-tech halogen free flame retardant to be synergistically exploited with nanoparticles, leading to a new and competitive environmental friendly FR. This is a breakthrough from the current ABS technology, as no effective halogen-free solutions are currently available.
- To improve mechanical properties and ease of processing of ignifugated ABS compounds, through the reduction of FR additives compared to the state of the art of halogen-free ABS. In addition of the clear advantage of obtaining a halogen-free environmental-friendly ABS compound, advantage could arise in term of processability of the new FR solutions compared to the state of the art. To exploit nanotechnology, through the development and industrial upscaling of chemically modified lamellar inorganic nanoparticles as carriers of HFFR
- Ignifugated ABS with improved recyclability (15 % less energy required for processing), due to the improvement of the thermal stability of the ABS compound
Economical objectives:
- To develop new market areas for the nanotechnology
- To improve the competitiveness of SMEs belonging to different sectors: fire retardant, ABS compounder, end user, through the development of advanced and environmental friendly solutions for ABS fire retardancy
- To recover ABS market share lost with the new RoHS regulation
Social Objectives:
- This project allows sustainable development in the field of flame retardants. It increases the employment of non-hazardous materials and uses leading edge technologies developing more effective materials.
- Improvement on citizen’s safety by reducing the risks caused by the fire in buildings (80 % of the mortal victims in a fire, is due to the smoke generation).
- To safeguard the human health and the environment, avoiding the release of toxic fire retardants
- An important job creation in countries as Greece, Italy and Spain, where the rate of unemployment due to the crisis is pronounced.
Environmental Objectives:
- Reduction of harmful (or potentially harmful) halogen fire retardants.
- Reduction of smoke and toxic gases generation (30% reduction in gas emission) in case of fire (comparing with conventional flame retardants)
- Increase of the protection human health and aids the environmentally-sound recovery and disposal of waste electrical and electronic equipment
- Facilitate the recycling of waste electric and electronic equipment (the main application of ABS products). Retention of 85 % of mechanical and/or fire properties after 3 subsequent extrusion processes.
Project Results:
The project has been organized according to the following Scheme: WP1: Nanoparticles synthesis, functionalization and characterization; WP2: Preparation and characterization of new flame retarded ABS formulations; WP3: Final product validation; WP4: Recycling of new HFFR ABS products; WP5: Dissemination and use/exploitation; WP6: Project Management
WP5 and WP6 are extended to the whole project. WP1 and WP2 finished at months 12 and 16 respectively. The duration of WP3 is from month 17 to 22 and WP4 started at month 21. The following actions were carried out along the project:
Management activities:
• Kick off meting (in Azpeitia), 6 and 9 month meetings (in Alessandria and Azpeitia respectively). Month 12 and First periodic report meetings in Brussels (Belgium) the 17th and 18th of September 2013 respectively, Month 20 meeting celebrated in San Sebastian (Spain) the 24th of April 2014 and the final project meeting that will take place the 16th of October in Perugia (Italy)
• Technical and administrative assistance to project partners
• Submission of the scheduled deliverables
Dissemination activities:
• Set up and up date of the project web page, “www.nanofrabs.eu”
• Presentation of three posters: in the FRPM 2013 (14th European Meeting on Fire Retardant Polymers), in the Fire retardant Technologies 2014 meeting (FRT 2014) celebrated at Preston (UK) and in the XXI Convegno Nazionale dell’Associazione Italiana di Scienca e Tecnologia delle Macromolecole (AIM 2014), celebrated in Torino.
• Presence in different sectorial fairs (FIP, Plastpol, Cosmoprof, Forum della Ricerca…)
• Elaboration NANOFRABS project brochure
• Evaluation of the project results exploitation and IPR
• Publication of news in the Newsletter for non-halogen fire safety solutions. Phosphorous, Inorganic & Nitrogen Flame Retardant Association (PINFA)
• Inclusion of the project results on the partners’ web wites.
• Usage of the communication and diffusion networks provided by the European Commission as well as other webpages.
RTD activities:
• Synthesis and functionalization of 38 different nanofillers (Layered Double Hydroxide (LDH), Zirconium Phosphate (ZrP) and Montmorillonites (MMT)) (WP1 task 1.1 and 1.2)
• Characterization of the synthetized and functionalized nanofillers (TGA, DTA, IR, X-Ray, P-NMR) (WP1 task 1.1 and 1.2)
• Fabrication and characterization (mechanical, thermal stability, dispersion and fire properties) of more than two hundred ABS compounds (WP2)
• Recyclability study. Characterization of the mechanical, impact, colour variation, thermal stability and fire behaviour of the ABS-HFFR final compound after being re-processed during different cycles.
Demonstration activities:
• Nanofiller (O-MMT and LDH-stearate) scale up at PROLABIN, Organicmodified-montmorillonite masterbatch fabrication at MASTERBATCH, ABS-HFFR compound fabrication at SITRAPLAS and a final Electric & Electronic device injection (smart electricity meter), at DASYC facilities. All the products have been characterized and the respectively technical data sheet and MSDS have been elaborated.
Covered challenges
NANOFRABS contributes to the advancement of knowledge related to technologies suitable for the environmentally-friendly large scale production of a halogen free flame retardant for ABS compounds based on innovative nanoparticles functionalization.
The following breakthroughs have been obtained from this project:
• The selective functionalisation of the nanofillers allows to drive the chemical reactions that lead to the formation of the char i.e. to design the final properties of the protective char
• Good dispersion of the modified LDH into the ABS matrix, promoting good mechanical properties when high flame retardant dosages are employed.
• The combination of a charring agent and the functionalized montmorillonite into the ABS formulation improves the char formation, leading to self-extinguishment of the burning material and getting a V0 classification following the UL94 standard
• The presence of the modified nanofillers inside the growing char increases its thermal properties.
• The profit from the barrier properties (to liquids and gases) of the developed formulation (reduction of migration of components, oxygen, toxic gases).
• Lower smoke toxicity, by the elimination/reduction of halogenated compound as well as taking advantage of lamellar structures of nanocomposites and their related gas barrier properties acting as smoke suppressant in case of fire by isolating as much as possible gas exit from underlying substrates creating a “tortuous path” for gas molecules.
The main results obtained in each work-package are:
WP1
- Between all the studied nanofillers, the organically modified montmorillonite, MMT-482 and the LDH-stearate have been the most successful ones. The extrapolation of both nanofillers fabrication conditions from the laboratory to the large scale has been studied.
WP2
- More than twenty different nanoparticles were used in combination with more than thirty different flame retardants, both commercial and of new conception ones (WP1).
- That work ended-up with two main formulations based on the two different nanoparticles: one montmorillonite-based (O-MMT synthetized by Tecnalia) and one MgAl based layer double hydroxide (LDH-modified fabricated by Prolabin) which have the best compromise between optimal flame retardant characteristics (in the first case) and good impact properties (in the second case).
- The formulation that reaches the fire target, V0 classification following the UL94 standard is: ABS+ charring agent+ flame retardant+ compatibilizer+ O-MMT. This formulation presents poor impact properties respect to the natural polymer although big efforts have been done with different compatibilizers in order to improve this lack.
- On the other hand, ABS+ flame retardant+ LDH-modified formulation presents good impact properties however the fire behavior is out of classification following the UL94 standard (near V1)
- Extrapolation of the developed ABS-HFFR compound fabrication parameters from laboratory scale to large scale has been studied.
- The use of superacids, ZnCl2, as char promoter shows good behavior at slow burn speed, TGA characterization. However, this effect is not observed when the speed of the flame is faster, as it is the case of UL94 standard.
WP3
- O-MMT and LDH-modified fabrication has been done at large scale at PROLABIN & TEFARM facilities.
- The new ABS-HFFR compound fabrication has been done at SITRAPLAS facilities from the formulation developed at WP2
- An Electric & Electronic device (smart electricity meter) has been injected at DASYC facilities. Even if three different pieces of the smart electricity meter have been obtained, problems during the injection of these pieces (due to the poor impact properties of the compound) have been produced.
- All the products obtained during the scale up have been characterized following the quality standard of each company. Technical and safety data sheets have been obtained (except for the injected ones)
WP4
- The ABS-HFFR compound fabricated at SITRAPLAS facilities has been repro-cessed several times by extrusion and injection cycles in order to know how many times a material can be reprocessed before losing its applicability in the required application.
- After each reprocessing step, test specimens have been prepared by injection. Variation in the thermal stability, mechanical, impact, colour and fire properties has been evaluated.
- A noticeable change in the color of the ABS-HFFR compound has been appreciated after the third cycle; joint with a slight reduction of the mechanical properties and not uniform fire performance in UL94 test. Meanwhile, thermal stability remains constant with the re-processing cycles.
Potential Impact:
The project results will lead to the different impacts addressed below.
Scientific objectives:
- An ABS-HFFR nanocomposite with a V0 classification (at 3.2 mm thickness) following the UL94 standard has been developed by physical combination of an organically modified montmorillonite and a fire retardant (APP). The charring agent has been also added to the formulation as char promoter and with the aim of improve the nanofiller dispersion in the polymeric matrix.
- The new ABS-HFFR compound has a Glow Wire Ignition Temperature value, GWIT, higher than the halogenated one (675 versus 725 °C), achieving the same value for the Glow Wire Flammability Index.
Environmental objectives:
- Reduction of smoke and toxic gases generation in case of fire (in comparation with halogenated ABS). Following are the reduction results (%)
CO emission (Kg/Kg): 46, Smoke Darkness (m2/Kg): 54, Total smoke production (m2): 63, Smoke production rate (m2/s): 88
- Facilitate the recycling of waste electric and electronic equipment (the main application of ABS products). Retention of 85 % of mechanical and/or fire properties after 3 subsequent extrusion processes has been achieved.
Mechanical properties
Variation of (%) Original 1st cycle 2nd cycle 3rd cycle 4th cycle
Notched impact (KJ/m2) 2,26 + 27% + 32% + 23% + 9%
Young Modulus (MPa) 1982 + 3% + 9% +4% 0%
Tensile strength (mm/mm) 26 - 2% -2% -12% 0%
Fire properties
There is a slight decrease of the fire classification related with the UL94 standard after the 3rd reprocessing cycle. A slight increase of the heat release rate peak (cone calorimeter behavior) can also be observed after the fourth re-processing cycle, possible due to the loss of flame retardancy effect of the flame retardant system with the reprocessing cycles (due to the partial degradation of the flame retardant).
Original 1st cycle 2nd cycle 3rd cycle 4th cycle
UL94 classification V0 V0 V0/V1 V0/N.C. V0/V1
Variation of (%) Original 4th cycle
Ignition time (s) 57 + 5.3
HRRpeak (KW/m2) 208 + 20
Where “+” symbol means properties increase and “–“, decrease.
Socio-economic and industrial objectives
- A new ignifugated ABS compound with a good recyclability has been achieved. The new halogen free flame retardant ABS compound can be re-processed three times without suffer drastically changes in mechanical, impact, fire or color properties. A slight variation of color and the fire behavior can be observed after the third re-processing cycle.
DIFFUSION OF THE PROJECT
Dissemination material
Dissemination of knowledge has being carried out in two different levels internal and external. All participants in the project have been responsible for the dissemination of results, both from industrial companies and from RTD centres.
Within the consortium partners:
All the information generated on the project is spreading among all the partners that constitute the Consortium in order to improve their know-how. TECNALIA is the responsible for an optimum circulation of this information to the partners. Project results and the information associated has been elaborated and distributed between the partners. Special effort of dissemination has been made in the internal meetings held in Alexandría in month 6 (February the 14th), Month 9 (6th of June) in San Sebastián, Month 12 (September the 17th) in Brussels, Month 20 (April the 24th) in San Sebastián and final meeting that will be carried out the next October 2014 in PROLABIN facilities (Perugia).
Specific effort has been done by RTD performers in order to transmit the synthesis procedures and processing conditions developed at laboratory scale: This has been critical for the correct up-scaling of the different developed products. Special attention has been paid to the transmission of:
Synthesis protocol for the nanoparticles up-scale. Detailed information has been supplied to PROLABIN & TEFARM by TECNALIA:
- Synthesis of O-MMT.
Processing conditions for the up-scaling of different masterbatches. Detailed information supplied to MASTERBATCH by POLITO:
- Masterbatch charring agent + MMT
- Masterbatch ABS + LDH + Compatibilizer
Processing conditions for the up-scaling of compounds. Detailed information supplied to SITRAPLAS by POLITO:
- Compounding: ABS+charring agent+MMT+APP+Compatibilizer.
Processing conditions for the up-scaling of injection process. Detailed information supplied to DASYC by POLITO and TECNALIA.
Outside of the consortium partners:
Include the activities carried out by partners, in order to achieve a proper dissemination of the results to the whole European industry as well as to European research organizations. Dissemination of the project results is being done in different sectors and coordinated by PROLABIN and TECNALIA.
Initial effort is focus on the dissemination of project concept. The webpage of the project was used as one of the principle dissemination tool (www.nanofrabs.eu). The aim of this webpage is to offer information about the project, including objectives, structure and partners, to everyone around the world).
This web page is being the main NanoFRABS foreground dissemination tool and is being continuously updated. On the other hand each partner has included NanoFRABS project news in their own webpages. Other webpages have been used in order to do dissemination such as: facebook, nanobasque, nanowerk, nantopaint..
Publications:
- A project brochure has been prepared
- The consortium has presented a poster in the congress “Fire retardant Technologies 2014 (FRT2014)” held in Preston, University of Central Lancashire, (14th-17th April 2014). Additionally a publication in the congress proceedings was admitted.
- The consortium has presented a poster in the 14th European meeting on fire retardancy and protection of materials (FRPM13) conference held in Lille (30th June- 4th July 2013). Additionally a publication in the congress proceedings was admitted.
- The consortium has presented a proceeding in the XXI Convegno Nazionale dell’Associazione Italiana di Scienza e Tecnologia delle Macrololecole (AIM). Torino (Italy), 14-19 Settembre 2014.
- Phosphorous, Inorganic & Nitrogen Flame Retardant Association (PINFA). Newsletter for non-halogen fire safety solutions.
http://www.pinfa.org/documents/Media/Newsletter/pinfa_newsletter_issue_no29_may-2013.pdf
Publishable results
Publishable results are being disseminated by partners though the NanoFRABS web page.
According to the DOW, there have been submitted some public deliverables to the commission.
Del. No Deliverable / Milestone name WP No. Nature Dissemination level Delivery Date (month) PM Lead Beneficiary
D2.1 Sample (5 Kg) of HFFR system 1, where HFFR is obtained by physical combination 2 P PU* 6 16 MASTERBATCH
D2.3 Sample (5 Kg) of HFFR system 2, where HFFR is obtained by physical combination of APP and nanopartic 2 P PU* 12 16 MASTERBATCH
D3.1 Sample (10 Kg) of new HFFR ABS compound 3 P PU* 19 10 SITRAPLAS
D3.3 Optimized HFFR system and new HFFR ABS compound description: Technical and Safety Data Sheet 3 R PU* 22 19 POLITECNICO DI TORINO
D5.1 Project website 5 O PU 3 1 TECNALIA
D5.2 Project summary report 5 O PU 2 7 PROLABIN & TEFARM
* Samples of those deliverables are public. Some of the information included in the deliverable has been treated as confidential.
Assistance to sectorial fairs and meetings
The attendance and participation in National and International fairs will enhance the finding of potential customers, increasing market opportunities. In the table below the attended event by NanoFRABS project partners is shown.
Masterbatch:
FIP in Lyon (France), June 2014, Plastpol in Kyelce (Poland), May 2014. K fair in Düsseldorf, Germany, October 2013.
Prolabin:
Forum della Borsa della Ricerca, May 2014. Cosmoprof worlwide Italy, April 2014. Circolly della conoscenza Italy, december 2013. International conference Nanotech Italy, November 2013. Fare rete per l’ambiente, Italy, October 2013
Sitraplas:
UL International TTC GmbH UL Seminar (Germany), April 2014. Fire resistance in plastic conference, Germany, November 2013. K fair in Düsseldorf, Germany, October 2013.
Polito
Fire retardant technologies 2014 (FRT 2014), UK, April 2014. Fire resistance in plastic conference Germany, November 2013. 14th European meeting on fire retardancy and protection of materials (FRPM13), France June 2013. XXI Convegno Nazionale dell’Associazione Italiana di Scienza e Tecnologia delle Macrololecole (AIM), Italy, september 2014
Tecnalia
Fire retardant technologies 2014 (FRT 2014), UK, April 2014. Construmat, Spain, May 2013.
EXPLOITATION OF THE RESULTS
Modified montmorillonites have shown interesting results in terms of flame retardant performance in ABS. However, the exploitation of the new Halogen Free Flame Retardant system (HFFR) based on nanotechnology (nanofillers functionalized with flame retardant groups) in ABS is pending on the improvement of ABS compounds properties. The loss of mechanical resistance of ABS (Impact) when a large amount of filler is added (over 25 % including flame retardants, nanoparticles and charring agents), do not allow the generalised use of this product in injection processes. Therefore, additional R&D effort is required in order to spread the use of this compound..
Overcoming the necessary improvement required for ABS, which can be addressed in a future project, basic rules for the economic exploitation of the main results of the project has been defined by the partners: The agreements are related to the following family products:
Nanoparticles synthesis and modification:
PROLABIN have 100 % ownership in this project result and is considering apply for patent protection. SITRAPLAS is interested in using this technology if some of the problems that remain in the ABS compounds are solved, mainly the loss of mechanical properties (impact) of HFFR compound compared with the standard ABS. In that case, SITRAPLAS will be interested in having a licensing agreement. It will have the possibility to use the new synthesised and functionalized nanoparticles for the fabrication of HFFR ABS compounds. MASTERBATCH S.r.l will have a licensing agreement in order to prepare FR masterbatches including LDH and modified montmorillonites. Both companies have to sign a specific agreement with PROLABIN.
Potential customers
APPLICATION Share (%)
Masterbatch sectors 80
Compounders 20
MARKET Share (%)
Italy 30
Germany 25
Spain 10
Other 35
New HFFR ABS compounds:
SITRAPLAS have the ownership in this project result. DASYC might have a licensing agreement and it will have the possibility to use the new HFFR ABS compounds in order to get, by injection, the end product (electrical and electronic devices). It has to sign a specific agreement with the owner (SITRAPLAS). MASTERBATCH and PROLABIN will have advantageous relationships with SITRAPLAS, in order to be the single providers of flame retardant masterbatches and functionalizer nanofillers respectively.
Potential customers
Obtaining final product (electric/electronic devices):
DASYC have the ownership of this project result. SITRAPLAS will have preferred relationships and favourable terms of sales with DASYC as HFFR ABS compound supplier for a period of time (in agreement with DASYC). MASTERBATCH and PROLABIN have the final product properties knowledge, needed in order to be sure that their products work well and can be commercialized.
MARKET Share (%)
Greek 20
Germany 35
Italy 10
Other 35
Potential customers
POTENTIAL CUSTOMERS
Bosch-Siemens Home Appliances (BSH)
Demka
Vibracoustic GmbH
Vodafone
Festo KG
Recycling study:
The ownership of this project result is distributed among the partners MASTERBATCH, PROLABIN, SITRAPLAS and DASYC.
As previously explained, impact properties have been a critical parameter in ABS compounds and it is an unresolved issue. Considering this situation, the exploitation strategy is outlined below. This strategy will be launched under the responsibility of the Exploitation manager (PROLABIN).
Next Steps.
During the following years, additional R&D effort is required in order to improve general properties of HFFRABS compounds (impact properties). Once this improvement is achieved the following steps will be carried out:
Samples of the new Halogen Free Flame Retardant (HFFR), based on nanotechnology, will be produced to demonstrate the potential of the new product to future customers and end users: ABS resin producers, ABS compounders and electric/electronic devices manufacturers. The dissemination activities, as well as the different networks to which the Consortium members belong will be used to try to widespread present the new product to potential users. First sales will be carried out. The new HFFR will compete directly with commercial flame retardant as: APP (ammonium polyphosphate), others.
In order to assure the competitiveness of the new solutions, the cost for the new ABS compound has been analysed
Typical ABS halogen based compound has a cost of 3,8 €/kg. Therefore, a cost of 4,7 €/kg that is calculated for the new Halogen Free ABS compound seems to be reasonable for the commercialisation of this product.
Finally, the good performance of modified montmorillonite in the charring agent and the demonstrated effect in fire retardance opens the possibility of exploitation of this nanoparticle as nanofiller for other thermoplastics different from ABS and that are no so drastically affected by the loading of fillers, namely. PA, PET, PBT….. . Additional R&D effort in this field is planned for the future.
List of Websites:
For further information regarding the project, please visit the web-page: www.nanofrabs.eu or contact the project co-ordinator from (Tecnalia): sara.villanueva@tecnalia.com
The contacts from the different partners of the project are:
Politecnico di Torino, Polito: Dr. Alberto Fina, alberto.fina@polito.it
Masterbatch: Domenico Anderlini, domenico.anderlini@masterbatch.it
Prolabin & Tefarm: Dr. Roberto Spogli, roberto.spogli@prolabintefarm.com
Sitraplas, Ibrahim Assebban, Ibrahim.asseban@sitraplas.com
Dasyc, George Lianos, g.lianos@dasyc.gr
The European FP7 research project NANOFRABS has been successfully finished in August 2014. It has focused on developing a new more effective halogen free flame retardant for ABS compound by means of incorporation of nanofillers. Six technical work packages described below, shows the work done along the project:
WP1 Nanoparticles synthesis, functionalization and characterization (from month 1 to 12)
Nearly 40 nanofillers (organomodified montmorillonites, zirconium phosphates and layer double hidroxides between them) have been synthetized, functionalized and characterized. Once realized the chemical (FTIR, ATR-FTIR) and thermal (TGA, DSC..) characterization as well as morphological features (XRD), twenty of them have been selected to be added to the ABS matrix in order to get the respectively compounds (WP2)
WP2 Preparation and characterization of new flame retarded ABS formulations (from month 1 to 16)
Once properly functionalised nanoparticles (WP1) have been introduced in ABS formulations. Chemical characterization (by FTIR and ATR-FTIR), morphological investigation (SEM and TEM), mechanical(impact), rheological and fire properties of these ABS compounds modified with the new HFFR have been done. From the work done in this work package, two nanofillers have been selected for doing the final product validation (one montmorillonite based and the other one layer double hidroxide based)
WP3 Final product validation (from month 17 to 22)
Results obtained at lab scale have been confirmed and validated at large scale. Nanofillers, masterbatches, halogen free flame retardant ABS (HFFR-ABS) compounds and the injection of an Electric and Electronic device have been scaled up at PROLABIN &TEFARM, MASTERBATCH, SITRAPLAS and DASYC facilities respectively. During the scale up, optimal processing conditions have been evaluated. All the products have been characterized (thermal stability, nanoparticles dispersion, impact, viscosity and fire behaviour) and the MSDS and technical data sheets have been generated.
WP4 Recycling of new HFFR ABS products (from month 21 to 24)
In this work-package, the recyclability of the final HFFR-ABS compound has been studied by its re-processing (extrusion-injection) in four different cycles. Thermal stability, chemical structure, nanofiller dispersion, mechanical properties, color variation and fire properties have been evaluated.
WP5 Dissemination and use/exploitation (from month 1 to 24)
Dissemination of the work done along the project has been realized with: different ferias attendance, preparation of the project brochure, presentation of three posters in three international meetings (France, UK and Italy), the set up and update of the NANOFRABS project web page (www.nanofrabs.eu) the publication of a news in the Newsletter for non-halogen fire safety solutions. Phosphorous, Inorganic & Nitrogen Flame Retardant Association (PINFA), inclusion of the Project Results on the Partners’ Web Sites, usage of the communication and diffusion networks provided by the European Commission as well as other webpages.
A plan for exploitation of the results has been developed within the project.
WP6 Project management (from month 1 to 24)
In this work package, activities such as: technical and administrative assistance to project partners, organization of consortium meetings and meetings with the Commission and development of Technical and Financial progress reports have been done.
Project Context and Objectives:
The two years NANOFRABS project has been coordinated by TECNALIA and has been carried out jointly with the POLITECNICO DI TORINO UNIVERSITY (Italy) and four SME: a compounder, SITRAPLAS GMBH (Germany), a nanofiller producer, PROLABIN & TEFARM SRL (Italy), a polymer masterbatch manufacturer, MASTERBATCH SRL (Italy) and an Electric and Electronic devices injector, DASYC (Greece).
The Restriction of Hazardous Substances (RoHS) and waste electric and electronic equipment (WEEE) directives discouraged the use of halogenated flame retardants in electric and electronic devices. For this reason, effective non halogenated alternatives have to be developed. The project aims at developing new halogen free flame retardant (HFFR) for ABS (acrylonitrile-butadiene-styrene) compounds, which are widely use in the electric appliances sector, with good impact and fire properties.
NANOFRABS project aims at developing a new more effective halogen free flame retardant for ABS, by means of incorporation of nanoparticles. Moreover, halogenated FR acts the gas phase, resulting in a high smoke density and toxicity, while intumescent FR acts in the condensed phase, with dramatically lower smoke production.
The main goal is to develop a new halogen free flame retardant (HFFR) for actrylonitrile-butadiene-styrene copolymers (ABS), based on the synergic combination of phosphorus compounds, and nanofillers in order to obtain:
Target flame retardancy properties are as follows:
- UL94 V0 [IEC 60695-11-10]
- Glow Wire Flammability Index (GWFI) at 960°C [IEC 60695-2-12]
- Glow Wire Ignition Temperature (GWIT) at 725°C [IEC 60695-2-13]
- A decreasing (at least a 25 %) of the halogen free flame retardant dosage for ABS in order to obtain better mechanical and rheological properties without decreasing the fire behavior of the final product.
- New ABS products (telephone housings, audio and electrical housings, high performance toys, computers) easily recyclable and environmental friendly, with low toxicity of the gases and vapors evolved during combustion
In order to reach these improvements, nanofillers have been combined with phosphorous-based flame retardants, either a) by Physical Combination of flame retardants and nanofillers in proper mixtures (PC), b) by Chemical Combination of nanofillers with flame retardants (CC) or a variant of the b) combination: c) by Physical Combination of Chemical functionalized lamellas and flame retardants (PCC) to be dispersed in the polymer by melt blending.
Scientific objectives:
- To develop HFFR ABS nanocomposites using two approaches:
- Physical combination of commercial nanoparticles and fire retardants.
- Chemical combination of nanoparticles and fire retardant, grafting flame retardant groups as phosphates or melamine derivatives onto the nanoparticles
- Control of mechanical properties of fire retarded ABS. Nanoparticles affect both stiffness and impact resistance, acting on both the mechanical properties of the polymer and on the morphology of the polymer/FR blends. The incorporation of nanoparticles into the FR polymer has been carried out by melt blending
- To check the possibility to modify thermal degradation pathway of ABS by the addition of halogen free chemical additives, promoting charring as a side reaction during polymer decomposition, thus limiting production of hydrocarbons to feed the flame.
Industrial objectives:
- To obtain a high-tech halogen free flame retardant to be synergistically exploited with nanoparticles, leading to a new and competitive environmental friendly FR. This is a breakthrough from the current ABS technology, as no effective halogen-free solutions are currently available.
- To improve mechanical properties and ease of processing of ignifugated ABS compounds, through the reduction of FR additives compared to the state of the art of halogen-free ABS. In addition of the clear advantage of obtaining a halogen-free environmental-friendly ABS compound, advantage could arise in term of processability of the new FR solutions compared to the state of the art. To exploit nanotechnology, through the development and industrial upscaling of chemically modified lamellar inorganic nanoparticles as carriers of HFFR
- Ignifugated ABS with improved recyclability (15 % less energy required for processing), due to the improvement of the thermal stability of the ABS compound
Economical objectives:
- To develop new market areas for the nanotechnology
- To improve the competitiveness of SMEs belonging to different sectors: fire retardant, ABS compounder, end user, through the development of advanced and environmental friendly solutions for ABS fire retardancy
- To recover ABS market share lost with the new RoHS regulation
Social Objectives:
- This project allows sustainable development in the field of flame retardants. It increases the employment of non-hazardous materials and uses leading edge technologies developing more effective materials.
- Improvement on citizen’s safety by reducing the risks caused by the fire in buildings (80 % of the mortal victims in a fire, is due to the smoke generation).
- To safeguard the human health and the environment, avoiding the release of toxic fire retardants
- An important job creation in countries as Greece, Italy and Spain, where the rate of unemployment due to the crisis is pronounced.
Environmental Objectives:
- Reduction of harmful (or potentially harmful) halogen fire retardants.
- Reduction of smoke and toxic gases generation (30% reduction in gas emission) in case of fire (comparing with conventional flame retardants)
- Increase of the protection human health and aids the environmentally-sound recovery and disposal of waste electrical and electronic equipment
- Facilitate the recycling of waste electric and electronic equipment (the main application of ABS products). Retention of 85 % of mechanical and/or fire properties after 3 subsequent extrusion processes.
Project Results:
The project has been organized according to the following Scheme: WP1: Nanoparticles synthesis, functionalization and characterization; WP2: Preparation and characterization of new flame retarded ABS formulations; WP3: Final product validation; WP4: Recycling of new HFFR ABS products; WP5: Dissemination and use/exploitation; WP6: Project Management
WP5 and WP6 are extended to the whole project. WP1 and WP2 finished at months 12 and 16 respectively. The duration of WP3 is from month 17 to 22 and WP4 started at month 21. The following actions were carried out along the project:
Management activities:
• Kick off meting (in Azpeitia), 6 and 9 month meetings (in Alessandria and Azpeitia respectively). Month 12 and First periodic report meetings in Brussels (Belgium) the 17th and 18th of September 2013 respectively, Month 20 meeting celebrated in San Sebastian (Spain) the 24th of April 2014 and the final project meeting that will take place the 16th of October in Perugia (Italy)
• Technical and administrative assistance to project partners
• Submission of the scheduled deliverables
Dissemination activities:
• Set up and up date of the project web page, “www.nanofrabs.eu”
• Presentation of three posters: in the FRPM 2013 (14th European Meeting on Fire Retardant Polymers), in the Fire retardant Technologies 2014 meeting (FRT 2014) celebrated at Preston (UK) and in the XXI Convegno Nazionale dell’Associazione Italiana di Scienca e Tecnologia delle Macromolecole (AIM 2014), celebrated in Torino.
• Presence in different sectorial fairs (FIP, Plastpol, Cosmoprof, Forum della Ricerca…)
• Elaboration NANOFRABS project brochure
• Evaluation of the project results exploitation and IPR
• Publication of news in the Newsletter for non-halogen fire safety solutions. Phosphorous, Inorganic & Nitrogen Flame Retardant Association (PINFA)
• Inclusion of the project results on the partners’ web wites.
• Usage of the communication and diffusion networks provided by the European Commission as well as other webpages.
RTD activities:
• Synthesis and functionalization of 38 different nanofillers (Layered Double Hydroxide (LDH), Zirconium Phosphate (ZrP) and Montmorillonites (MMT)) (WP1 task 1.1 and 1.2)
• Characterization of the synthetized and functionalized nanofillers (TGA, DTA, IR, X-Ray, P-NMR) (WP1 task 1.1 and 1.2)
• Fabrication and characterization (mechanical, thermal stability, dispersion and fire properties) of more than two hundred ABS compounds (WP2)
• Recyclability study. Characterization of the mechanical, impact, colour variation, thermal stability and fire behaviour of the ABS-HFFR final compound after being re-processed during different cycles.
Demonstration activities:
• Nanofiller (O-MMT and LDH-stearate) scale up at PROLABIN, Organicmodified-montmorillonite masterbatch fabrication at MASTERBATCH, ABS-HFFR compound fabrication at SITRAPLAS and a final Electric & Electronic device injection (smart electricity meter), at DASYC facilities. All the products have been characterized and the respectively technical data sheet and MSDS have been elaborated.
Covered challenges
NANOFRABS contributes to the advancement of knowledge related to technologies suitable for the environmentally-friendly large scale production of a halogen free flame retardant for ABS compounds based on innovative nanoparticles functionalization.
The following breakthroughs have been obtained from this project:
• The selective functionalisation of the nanofillers allows to drive the chemical reactions that lead to the formation of the char i.e. to design the final properties of the protective char
• Good dispersion of the modified LDH into the ABS matrix, promoting good mechanical properties when high flame retardant dosages are employed.
• The combination of a charring agent and the functionalized montmorillonite into the ABS formulation improves the char formation, leading to self-extinguishment of the burning material and getting a V0 classification following the UL94 standard
• The presence of the modified nanofillers inside the growing char increases its thermal properties.
• The profit from the barrier properties (to liquids and gases) of the developed formulation (reduction of migration of components, oxygen, toxic gases).
• Lower smoke toxicity, by the elimination/reduction of halogenated compound as well as taking advantage of lamellar structures of nanocomposites and their related gas barrier properties acting as smoke suppressant in case of fire by isolating as much as possible gas exit from underlying substrates creating a “tortuous path” for gas molecules.
The main results obtained in each work-package are:
WP1
- Between all the studied nanofillers, the organically modified montmorillonite, MMT-482 and the LDH-stearate have been the most successful ones. The extrapolation of both nanofillers fabrication conditions from the laboratory to the large scale has been studied.
WP2
- More than twenty different nanoparticles were used in combination with more than thirty different flame retardants, both commercial and of new conception ones (WP1).
- That work ended-up with two main formulations based on the two different nanoparticles: one montmorillonite-based (O-MMT synthetized by Tecnalia) and one MgAl based layer double hydroxide (LDH-modified fabricated by Prolabin) which have the best compromise between optimal flame retardant characteristics (in the first case) and good impact properties (in the second case).
- The formulation that reaches the fire target, V0 classification following the UL94 standard is: ABS+ charring agent+ flame retardant+ compatibilizer+ O-MMT. This formulation presents poor impact properties respect to the natural polymer although big efforts have been done with different compatibilizers in order to improve this lack.
- On the other hand, ABS+ flame retardant+ LDH-modified formulation presents good impact properties however the fire behavior is out of classification following the UL94 standard (near V1)
- Extrapolation of the developed ABS-HFFR compound fabrication parameters from laboratory scale to large scale has been studied.
- The use of superacids, ZnCl2, as char promoter shows good behavior at slow burn speed, TGA characterization. However, this effect is not observed when the speed of the flame is faster, as it is the case of UL94 standard.
WP3
- O-MMT and LDH-modified fabrication has been done at large scale at PROLABIN & TEFARM facilities.
- The new ABS-HFFR compound fabrication has been done at SITRAPLAS facilities from the formulation developed at WP2
- An Electric & Electronic device (smart electricity meter) has been injected at DASYC facilities. Even if three different pieces of the smart electricity meter have been obtained, problems during the injection of these pieces (due to the poor impact properties of the compound) have been produced.
- All the products obtained during the scale up have been characterized following the quality standard of each company. Technical and safety data sheets have been obtained (except for the injected ones)
WP4
- The ABS-HFFR compound fabricated at SITRAPLAS facilities has been repro-cessed several times by extrusion and injection cycles in order to know how many times a material can be reprocessed before losing its applicability in the required application.
- After each reprocessing step, test specimens have been prepared by injection. Variation in the thermal stability, mechanical, impact, colour and fire properties has been evaluated.
- A noticeable change in the color of the ABS-HFFR compound has been appreciated after the third cycle; joint with a slight reduction of the mechanical properties and not uniform fire performance in UL94 test. Meanwhile, thermal stability remains constant with the re-processing cycles.
Potential Impact:
The project results will lead to the different impacts addressed below.
Scientific objectives:
- An ABS-HFFR nanocomposite with a V0 classification (at 3.2 mm thickness) following the UL94 standard has been developed by physical combination of an organically modified montmorillonite and a fire retardant (APP). The charring agent has been also added to the formulation as char promoter and with the aim of improve the nanofiller dispersion in the polymeric matrix.
- The new ABS-HFFR compound has a Glow Wire Ignition Temperature value, GWIT, higher than the halogenated one (675 versus 725 °C), achieving the same value for the Glow Wire Flammability Index.
Environmental objectives:
- Reduction of smoke and toxic gases generation in case of fire (in comparation with halogenated ABS). Following are the reduction results (%)
CO emission (Kg/Kg): 46, Smoke Darkness (m2/Kg): 54, Total smoke production (m2): 63, Smoke production rate (m2/s): 88
- Facilitate the recycling of waste electric and electronic equipment (the main application of ABS products). Retention of 85 % of mechanical and/or fire properties after 3 subsequent extrusion processes has been achieved.
Mechanical properties
Variation of (%) Original 1st cycle 2nd cycle 3rd cycle 4th cycle
Notched impact (KJ/m2) 2,26 + 27% + 32% + 23% + 9%
Young Modulus (MPa) 1982 + 3% + 9% +4% 0%
Tensile strength (mm/mm) 26 - 2% -2% -12% 0%
Fire properties
There is a slight decrease of the fire classification related with the UL94 standard after the 3rd reprocessing cycle. A slight increase of the heat release rate peak (cone calorimeter behavior) can also be observed after the fourth re-processing cycle, possible due to the loss of flame retardancy effect of the flame retardant system with the reprocessing cycles (due to the partial degradation of the flame retardant).
Original 1st cycle 2nd cycle 3rd cycle 4th cycle
UL94 classification V0 V0 V0/V1 V0/N.C. V0/V1
Variation of (%) Original 4th cycle
Ignition time (s) 57 + 5.3
HRRpeak (KW/m2) 208 + 20
Where “+” symbol means properties increase and “–“, decrease.
Socio-economic and industrial objectives
- A new ignifugated ABS compound with a good recyclability has been achieved. The new halogen free flame retardant ABS compound can be re-processed three times without suffer drastically changes in mechanical, impact, fire or color properties. A slight variation of color and the fire behavior can be observed after the third re-processing cycle.
DIFFUSION OF THE PROJECT
Dissemination material
Dissemination of knowledge has being carried out in two different levels internal and external. All participants in the project have been responsible for the dissemination of results, both from industrial companies and from RTD centres.
Within the consortium partners:
All the information generated on the project is spreading among all the partners that constitute the Consortium in order to improve their know-how. TECNALIA is the responsible for an optimum circulation of this information to the partners. Project results and the information associated has been elaborated and distributed between the partners. Special effort of dissemination has been made in the internal meetings held in Alexandría in month 6 (February the 14th), Month 9 (6th of June) in San Sebastián, Month 12 (September the 17th) in Brussels, Month 20 (April the 24th) in San Sebastián and final meeting that will be carried out the next October 2014 in PROLABIN facilities (Perugia).
Specific effort has been done by RTD performers in order to transmit the synthesis procedures and processing conditions developed at laboratory scale: This has been critical for the correct up-scaling of the different developed products. Special attention has been paid to the transmission of:
Synthesis protocol for the nanoparticles up-scale. Detailed information has been supplied to PROLABIN & TEFARM by TECNALIA:
- Synthesis of O-MMT.
Processing conditions for the up-scaling of different masterbatches. Detailed information supplied to MASTERBATCH by POLITO:
- Masterbatch charring agent + MMT
- Masterbatch ABS + LDH + Compatibilizer
Processing conditions for the up-scaling of compounds. Detailed information supplied to SITRAPLAS by POLITO:
- Compounding: ABS+charring agent+MMT+APP+Compatibilizer.
Processing conditions for the up-scaling of injection process. Detailed information supplied to DASYC by POLITO and TECNALIA.
Outside of the consortium partners:
Include the activities carried out by partners, in order to achieve a proper dissemination of the results to the whole European industry as well as to European research organizations. Dissemination of the project results is being done in different sectors and coordinated by PROLABIN and TECNALIA.
Initial effort is focus on the dissemination of project concept. The webpage of the project was used as one of the principle dissemination tool (www.nanofrabs.eu). The aim of this webpage is to offer information about the project, including objectives, structure and partners, to everyone around the world).
This web page is being the main NanoFRABS foreground dissemination tool and is being continuously updated. On the other hand each partner has included NanoFRABS project news in their own webpages. Other webpages have been used in order to do dissemination such as: facebook, nanobasque, nanowerk, nantopaint..
Publications:
- A project brochure has been prepared
- The consortium has presented a poster in the congress “Fire retardant Technologies 2014 (FRT2014)” held in Preston, University of Central Lancashire, (14th-17th April 2014). Additionally a publication in the congress proceedings was admitted.
- The consortium has presented a poster in the 14th European meeting on fire retardancy and protection of materials (FRPM13) conference held in Lille (30th June- 4th July 2013). Additionally a publication in the congress proceedings was admitted.
- The consortium has presented a proceeding in the XXI Convegno Nazionale dell’Associazione Italiana di Scienza e Tecnologia delle Macrololecole (AIM). Torino (Italy), 14-19 Settembre 2014.
- Phosphorous, Inorganic & Nitrogen Flame Retardant Association (PINFA). Newsletter for non-halogen fire safety solutions.
http://www.pinfa.org/documents/Media/Newsletter/pinfa_newsletter_issue_no29_may-2013.pdf
Publishable results
Publishable results are being disseminated by partners though the NanoFRABS web page.
According to the DOW, there have been submitted some public deliverables to the commission.
Del. No Deliverable / Milestone name WP No. Nature Dissemination level Delivery Date (month) PM Lead Beneficiary
D2.1 Sample (5 Kg) of HFFR system 1, where HFFR is obtained by physical combination 2 P PU* 6 16 MASTERBATCH
D2.3 Sample (5 Kg) of HFFR system 2, where HFFR is obtained by physical combination of APP and nanopartic 2 P PU* 12 16 MASTERBATCH
D3.1 Sample (10 Kg) of new HFFR ABS compound 3 P PU* 19 10 SITRAPLAS
D3.3 Optimized HFFR system and new HFFR ABS compound description: Technical and Safety Data Sheet 3 R PU* 22 19 POLITECNICO DI TORINO
D5.1 Project website 5 O PU 3 1 TECNALIA
D5.2 Project summary report 5 O PU 2 7 PROLABIN & TEFARM
* Samples of those deliverables are public. Some of the information included in the deliverable has been treated as confidential.
Assistance to sectorial fairs and meetings
The attendance and participation in National and International fairs will enhance the finding of potential customers, increasing market opportunities. In the table below the attended event by NanoFRABS project partners is shown.
Masterbatch:
FIP in Lyon (France), June 2014, Plastpol in Kyelce (Poland), May 2014. K fair in Düsseldorf, Germany, October 2013.
Prolabin:
Forum della Borsa della Ricerca, May 2014. Cosmoprof worlwide Italy, April 2014. Circolly della conoscenza Italy, december 2013. International conference Nanotech Italy, November 2013. Fare rete per l’ambiente, Italy, October 2013
Sitraplas:
UL International TTC GmbH UL Seminar (Germany), April 2014. Fire resistance in plastic conference, Germany, November 2013. K fair in Düsseldorf, Germany, October 2013.
Polito
Fire retardant technologies 2014 (FRT 2014), UK, April 2014. Fire resistance in plastic conference Germany, November 2013. 14th European meeting on fire retardancy and protection of materials (FRPM13), France June 2013. XXI Convegno Nazionale dell’Associazione Italiana di Scienza e Tecnologia delle Macrololecole (AIM), Italy, september 2014
Tecnalia
Fire retardant technologies 2014 (FRT 2014), UK, April 2014. Construmat, Spain, May 2013.
EXPLOITATION OF THE RESULTS
Modified montmorillonites have shown interesting results in terms of flame retardant performance in ABS. However, the exploitation of the new Halogen Free Flame Retardant system (HFFR) based on nanotechnology (nanofillers functionalized with flame retardant groups) in ABS is pending on the improvement of ABS compounds properties. The loss of mechanical resistance of ABS (Impact) when a large amount of filler is added (over 25 % including flame retardants, nanoparticles and charring agents), do not allow the generalised use of this product in injection processes. Therefore, additional R&D effort is required in order to spread the use of this compound..
Overcoming the necessary improvement required for ABS, which can be addressed in a future project, basic rules for the economic exploitation of the main results of the project has been defined by the partners: The agreements are related to the following family products:
Nanoparticles synthesis and modification:
PROLABIN have 100 % ownership in this project result and is considering apply for patent protection. SITRAPLAS is interested in using this technology if some of the problems that remain in the ABS compounds are solved, mainly the loss of mechanical properties (impact) of HFFR compound compared with the standard ABS. In that case, SITRAPLAS will be interested in having a licensing agreement. It will have the possibility to use the new synthesised and functionalized nanoparticles for the fabrication of HFFR ABS compounds. MASTERBATCH S.r.l will have a licensing agreement in order to prepare FR masterbatches including LDH and modified montmorillonites. Both companies have to sign a specific agreement with PROLABIN.
Potential customers
APPLICATION Share (%)
Masterbatch sectors 80
Compounders 20
MARKET Share (%)
Italy 30
Germany 25
Spain 10
Other 35
New HFFR ABS compounds:
SITRAPLAS have the ownership in this project result. DASYC might have a licensing agreement and it will have the possibility to use the new HFFR ABS compounds in order to get, by injection, the end product (electrical and electronic devices). It has to sign a specific agreement with the owner (SITRAPLAS). MASTERBATCH and PROLABIN will have advantageous relationships with SITRAPLAS, in order to be the single providers of flame retardant masterbatches and functionalizer nanofillers respectively.
Potential customers
Obtaining final product (electric/electronic devices):
DASYC have the ownership of this project result. SITRAPLAS will have preferred relationships and favourable terms of sales with DASYC as HFFR ABS compound supplier for a period of time (in agreement with DASYC). MASTERBATCH and PROLABIN have the final product properties knowledge, needed in order to be sure that their products work well and can be commercialized.
MARKET Share (%)
Greek 20
Germany 35
Italy 10
Other 35
Potential customers
POTENTIAL CUSTOMERS
Bosch-Siemens Home Appliances (BSH)
Demka
Vibracoustic GmbH
Vodafone
Festo KG
Recycling study:
The ownership of this project result is distributed among the partners MASTERBATCH, PROLABIN, SITRAPLAS and DASYC.
As previously explained, impact properties have been a critical parameter in ABS compounds and it is an unresolved issue. Considering this situation, the exploitation strategy is outlined below. This strategy will be launched under the responsibility of the Exploitation manager (PROLABIN).
Next Steps.
During the following years, additional R&D effort is required in order to improve general properties of HFFRABS compounds (impact properties). Once this improvement is achieved the following steps will be carried out:
Samples of the new Halogen Free Flame Retardant (HFFR), based on nanotechnology, will be produced to demonstrate the potential of the new product to future customers and end users: ABS resin producers, ABS compounders and electric/electronic devices manufacturers. The dissemination activities, as well as the different networks to which the Consortium members belong will be used to try to widespread present the new product to potential users. First sales will be carried out. The new HFFR will compete directly with commercial flame retardant as: APP (ammonium polyphosphate), others.
In order to assure the competitiveness of the new solutions, the cost for the new ABS compound has been analysed
Typical ABS halogen based compound has a cost of 3,8 €/kg. Therefore, a cost of 4,7 €/kg that is calculated for the new Halogen Free ABS compound seems to be reasonable for the commercialisation of this product.
Finally, the good performance of modified montmorillonite in the charring agent and the demonstrated effect in fire retardance opens the possibility of exploitation of this nanoparticle as nanofiller for other thermoplastics different from ABS and that are no so drastically affected by the loading of fillers, namely. PA, PET, PBT….. . Additional R&D effort in this field is planned for the future.
List of Websites:
For further information regarding the project, please visit the web-page: www.nanofrabs.eu or contact the project co-ordinator from (Tecnalia): sara.villanueva@tecnalia.com
The contacts from the different partners of the project are:
Politecnico di Torino, Polito: Dr. Alberto Fina, alberto.fina@polito.it
Masterbatch: Domenico Anderlini, domenico.anderlini@masterbatch.it
Prolabin & Tefarm: Dr. Roberto Spogli, roberto.spogli@prolabintefarm.com
Sitraplas, Ibrahim Assebban, Ibrahim.asseban@sitraplas.com
Dasyc, George Lianos, g.lianos@dasyc.gr