Contract Agreement: 604248 Website: http://www.fibralspec.net/
Coordinator: Prof. Dr. Constantinos Charitidis, National Technical University of Athens
Table 1 Consortium List.
No. Beneficiary name Short name Country
1 National Technical University of Athens NTUA GRE
2 Politecnico di Torino POLITO ITA
3 University of Birmingham UOB UK
4 Euromobilita S.R.O. EUMO CZ
5 Thales Research and Technology TRT FR
6 GlobalSafeGuard Ltd GSG UK
7 Open Source Management Ltd OSM UK
8 Anthony, Patrick & Murta Exportação AP&M POR
9 Frantsevich Institute for Problems of Materials Science IPMS UKR
10 CTM Ltd CTM UK
11 CB Yuzhnoye YUZ UKR
Contents
1 Summary ... 103 2 Background ... 103 3 Scientific and technological challenges ... 104 4 Major Outcomes to date ... 105
5 Expected Impact ... 106 6 Directory ... 107 7 Copyright ... 107
1 Summary
Project Duration: 48 months, Project Funding: 6,083,991.00 € FIBRALSPEC initiative addresses new technologies, which have a clear market potential and a strong impact and as such promotes European Union’s (EU) wide cooperation. FIBRALSPEC focuses on conducting innovative processes with streamlining and improved control through Unit for Continuous PAN-based carbon fiber Pilot Production. Testing of laminates and prepregs production based on the new developed carbon fibers followed by manufacturing of laminates/coupons and high- performance filament wound tubes.
The project also efforts on functionalization, mainly focused on cost reduction and improvement of mechanical and chemical properties of carbon fibers. During the life of project, novel carbon fiber precursors such as lignin are being developed. Life cycle assessment assists in possible commercial risks that are continuously estimated during the project and quantify/assess the environmental impact of the materials that will be used. As for recycling and used utility of recycled carbon fibers, new techniques
are applied to provide commercially-relevant products that are manufactured from waste carbon Fibers.
Keywords: Carbon Fibers, Novel Precursosrs, Surface Treatment, Oxidation, Life Cycle Analysis, Supercapacitors, Rapid Deployment Secure Emergency Shelter
2 Background
Carbon fibers (CFs) are one of the most important reinforcement materials used for composite manufacturing, as they combine an exceptional set of properties (low density, high stiffness etc.) that makes them ideal for high performance composites; usually CFs are combined with thermo set resin matrices, yet thermoplastic matrix composites have begun to increasingly appear. Even
though the industrial scale production of CFs started from the late 1960s/early to 1970s, due to several challenges in their manufacturing the production volume has not grown on par with the increasing demand; as a result, the price of the CFs based materials remains still high. Thus, there are still a lot of opportunities for improvement in this field, with the focus being on the precursor material used for carbonization and optimization of stabilization process.
Currently, the CFs precursors of choice are polyacrylonitrile (PAN) and pitch fibers; both of them originate from petroleum and as such they follow its price trends. There are several alternate possible precursors that have been proposed; the most significant is lignin, a natural polymer existing in all plants. Lignin is considered as a sustainable and renewable source, given that large amounts are separated as byproduct from wood during paper pulp production.
FibralSpec’s main motivations include :
• The improvement of production of carbon fibres from green precursors such as lignin and renewable resources
• The manufacturing of fibre reinforced composites via ecofriendly-production techniques
• The use of the reinforced composites in different applications, such as: flexible supercapacitors and Rapid Deployment Secure Emergency Shelters
• LCA and LCC analyses will quantify the green credentials of the reuse and recycling strategies from the start -precursor development-, till the carbon fibre waste.
3 Scientific and technological challenges
Many other polymers have been proposed as alternate carbon fibres precursors to PAN and pitch (e.g. polyvinylchloride, PVC), but none of them worked as good as these two materials and now they are abandoned. The properties of the carbon fibres (and especially their high mechanical strength and stiffness) are exploited through their composites (Carbon Fibre-Reinforced Composites, CFRC). However, the full exploitation of the outstanding carbon fibre properties has not yet been achieved.
This is mainly due to the inherently inert and smooth surface of carbon fibres, which does not permit a strong anchoring of the matrix onto the surface of the fibres; thus, the fibres are not loaded with the stress that they can carry, but with a smaller load which is defined by the winkle out of the fibres from the matrix (pull out effect)1. Moreover, a class of materials with similar structure that have been commercialized are the polyimides (which also have high char yield), but these belong to the
“engineering polymers” class and are quite expensive materials, thus they are not considered as carbon fibre precursors.
Nevertheless, the potential to improve the quality and the effectiveness of the PAN-based carbon fibre processes should not be underestimated. So, apart from developing novel precursors, there are also other still open research fields on PAN precursors which are as important, in both production procedures as well as in
1Morgan, P.; Carbon fibres and their composites, Taylor & Francis, Boca Raton, 2005, p. 65-324, 501-550.
composites manufacturing. New carbon fibre precursor need to have at least as good properties and be as cost-effective as PAN.
Furthermore, carbonaceous nanomaterials are widely used as electrodes materials for supercapacitor applications, because of their high specific surface area and high electrical conductivity.
Among carbonaceous nanomaterials, activated carbon are widely used in commercial supercapacitors and several scientific works have reported the properties of CNTs, graphene, onion like carbons for electrode materials. Carbon NanoFibres (CNFs) have been less described although presenting a lot of interesting physical properties like high specific surface, high electrical conductivity and low cost. CNFs are a carbonaceous material of interest for the development of supercapacitors devices as a standalone materials or in combination with others nanomaterials.
CNFs are also a promising nanomaterial for the development of pseudocapacitors after chemical modification and grafting of electroactive organic or inorganic materials.
Medium technology – large scale: Rapid Deployment Secure Emergency Shelter (RDSES)
The existing concept “Rapid Deployment Secure Emergency Shelter-FibreGlass” (RDSES-FG) which is designed and developed by applying traditional composite manufacturing techniques is be extended; employing the use of carbon fibre, the unit mass will be reduced while at the same time increasing rigidity, durability and end user usability, resulting in Rapid Deployment Secure Emergency Shelter Carbon Fibre (RDSES-CF).
Figure 1. Rapid Deployment Secure Emergency Shelter (RDSES) The unit will be formed of a bottom unit and a top unit, internal sleeping platforms and a door unit. The idea behind this project is that top and bottom units would be a common part, with the aim of reducing manufacturing costs. The units and all other components can be stacked / nested inside each other.
Figure 2.Unique unit and stacking ability to facilitate transportation
After more than 5 decades of research, carbon fibres and their composites have reached maturity and they are currently not just a
‘high-end’ costly solution for low rate production, but represent a growing industry with a multitude of applications. Their success is due to their high strength-to-weight ratio and to the fact that in composites they exhibit a combination of valuable properties that may provide a solution in complex problems of materials science and technology. In 2013 carbon fiber demand was abound 46,500 tons, with expected growth rate of around 12.5 % for the following years. Some of their most important applications are in the sports and leisure industry with articles for many sports (tennis racquets, golf clubs, bicycles etc.), in the aerospace industry (the newest and largest commercial airplanes, Boeing 787 and Airbus A380, demonstrate a large part of their airframe built using carbon fibre composites) and for the blades used in wind turbines2,3. The state of the art precursor (in terms of production volume) is polyacrylonitrile (PAN) fibres; PAN-based carbon fibres represent more than 70 % of the total carbon fibre (CF) production4. A point to note here is the supply and availability of carbon fibres in the future where there is the need for EU States to be independent of the current supply chain. Moreover, there is also a need to consider for ‘green’ CF precursor which do not derived from petroleum. Other important precursor materials are pitches of various forms like petroleum-, coal tar- or mesophase- pitch.
4 Major Outcomes to date
The use of lignin makes the material carbon-neutral (CO-emission vice). More importantly, the energy needed for making CF from lignin is reported to be only 10% of making PAN-based CF (which typically is 270MJ/kg). Hence, energy efficiency (allowing low price for customers) in combination of non-use of fossils provide a route for a sustainable carbon fibre feed-stock (importance of recycled CF). Again the energy needed for reclaiming the used CF from CFRP-composites (Recycled CF) is only 10% of that needed for making new fibres. This in combination with the fact that the mechanical properties of the recycled CF are practically unaffected opens a route for cheap, sustainable, R-CFRP materials.
Within the framework of FibralSpec the main achievements include:
•
A prototype of advanced flexible supercapacitor based on CNFs for next generation energy storage devices has been delivered (Fig. 3).•
Concerning on fiber spinning process a prototype of Operational Mechano Electro spinner has been designed tested and delivered during the previous period (Fig.4).The software has also been developed and the maintenance manual has been delivered as well. This software controls the flow of each component in a full time closed loop model. After the precursor spinning
2Azarova, M.T.; Kazakov, M.E., Fibre Chemistry, 42 (2011), 271-277.
3Ishikawa, T.;, Advanced Polymer Science, 178 (2005), 109-112.
4Vaidya, U.K.; Chawla, K.K.;, International Materials Reviews, 53 (2008), 185-218.
stage thermal treatment follows in order to form carbon fibers.
•
Novel bio-based precursor materials have been melt spun by blending lignin with various polymeres (PLA, HDPE, PP) (Fig.5) in order to reduce the precursor cost, improve the mechanical properties and find new applications of lignin ; for the time being it is an undervalued product and moreover to create a sustainable, renewable bio-based material (reducing the cost of the carbon fibre precursor is feasible through the use of side product from cellulosic ethanol and paper industries).•
Concerning the stabilization procedure the fully automated continuous line has been tested on several different profiles and after several modifications finally setted (Fig. 6).Figure 3. Electrode fabricated using the dynamic spray-gun method and composed of mixtures of graphene/graphite and CNTs
Figure 4. Operational Mechano Electro Spinner
Figure 5. Melt spinning of lignin with polymers
Figure 6. Continuous Stabilization line
One of the important industrial problems is the production of complex geometrical shapes including the dual curvature ones.
Together with the method of winding, the production method based on prepreg manufacturing is very useful for aerospace industry. Prepregs are obtained by means of binder (epoxy and other resins) impregnating CF textile yarns preliminary produced on textile machines. One of the main features of carbon textile production is the processing of high strength and high modulus fibers with enhanced brittleness. During the yarn formation, it is necessary to exclude small bend radius. For these purposes it is possible to combine CF from PAN fibers situated without bends with more technological CF form HC-fibers. The last ones can form for example knitted loops around high strength CF from PAN-fibers. Furthermore, if another filaments are used (glasses, metals, kevlar, basalt) they form loops around CF from PAN-fibers. Carbon and textiles in composites lead to increase shear characteristics and transverse (relative to CF direction) strength.
5 Expected Impact
The expected impacts listed in the work program
The technology has clear market potential and will have a strong impact on the economic prospects the SME participants via two routes:
• The industrial partners will use the technology directly in their own manufacturing operations and/or directly in the services they provide.
• The industrial partners will market the technology through process licensing to other manufacturing organisations (via product type, market area, geographical region).
The FIBRALSPEC proposal well addresses all the impacts listed in the work programme of the Call. The project aims in increase of competitive power of European CF sector and especially that of the industrial partners. Industrial partners are more sensitive in the conditions of growing competitiveness because of the limited resources and access to modern RTD facilities.
Benefits for the involved SMEs and downstream producers The existing concept “Rapid Deployment Secure Emergency Shelter- fibreglass” (RDSES-FG) designed and developed applying
traditional composite manufacturing techniques will be extended through FIBRALSPEC by employing the use of carbon fibre, reducing the unit mass while at the same time increasing rigidity, durability and end user usability, resulting in Rapid Deployment Secure Emergency Shelter carbon fibre (RDSES-CF). The current RDSES-FG unit concept and all of its components weigh in at 500 kg. The target is to reduce the current design weight by 60% to approx. 200kg per RDSES-CF unit. A reduction of wall thickness by 50% from 60mm to 30mm would reduce mass per unit. This would allow greater numbers of stacked/nested units to be transported per shipment, therefore making significant gains in transport efficiency. An increase in components ability to resist damage would reduce the maintenance required during and after installation. Any increase in component rigidity would allow more efficient on-site installation. Less flexing would reduce the requirement for time consuming site preparation / ground levelling. As these RDSES-CF units will be sited in circumstances that may not have the use of lifting equipment, the target of 200kg reduces the amount of on-site manpower / manual handling required for unit assembly. Additionally, the use of carbon fibre would greatly assist in the end-of-life recycling. The shelter design could be made out of GRP sandwich; using strips of the new carbon fibre to stiffen the GRP panels will have significant impact for a carbon/glass combination where the structure is inflated from a packed state (deployable structure which can be parachuted to the disaster area and then inflated).
Economic impact
Supercapacitors technology is being developed through this project and this fact creates huge economical potentials as well because this market looks promising with opportunities in transportation, electronics and energy industry The knowledge gained from this project could ceate qualified personell, decrease unemployment and contribute to EU’s economy. Another aim of this project is to enhance competitiveness and the exports of European industry by defining new international standards in CFs field. The increase of employment of high qualified personnel is also expected.
Environmental impacts
The replacement of less environmental friendly technologies will occur with more intelligent systems. Material waste losses will be reduced due to reliability and in service performance of components and reduced corrosion activity. Safer working conditions will also be ensured and carbon dioxide emissions will be limited due to savings in materials.
Social Impact
Within the area of Humanitanan aid the issue of protection of vulnerable people in disasters worldwide is critical. RDSES design and manufacturing process also could develop onsite manufacture right in the heart of the affected territories using containerized factories. This will allow a suitable programme of production using local labour, local resources were available and therefore stimulating local economic activity.
6 Directory
Table 1 Directory of people involved in this project.
First Name Last Name Affiliation Address e-mail
Costas Charitidis NATIONAL TECHNICAL
UNIVERSITY OF ATHENS Heroon Polytechniou Street 9
15780 Athens - GREECE charitidis@chemeng.ntua.gr Alberto Tagliaferro POLITECNICO DI TORINO Corso Duca degli Abruzzi 24
10129 Torino - ITALY alberto.tagliaferro@polito.it
Hanshan Dong THE UNIVERSITY OF
BIRMINGHAM Edgbaston
B15 2TTBirmingham - UNITED KINGDOM
H.DONG.20@bham.ac.uk
Ales Loncaric Euromobilita s.r.o. Taborska922
29301Mlada Boleslav - CZECH REPUBLIC
ales@euromobilita.com
Paolo Bondavalli THALES SA Rue de Villiers45
92200 Neuilly Sur Seine - FRANCE paolo.bondavalli@thalesgroup.com
Glen Monaghan GLOBAL SAFEGUARD LTD Todburn Moor FarmCottages2
NE65 8RXLonghorsley Morpeth Northumberland - UNITED KINGDOM
glen@globalsafeguard.com
Emmanuel Sofianopoulos OPEN SOURCE
MANAGEMENT LIMITED COWLEY ROAD
CB4 0WSCambridge - UNITED KINGDOM
emmanuel@osm.eu.com
Guy Simmonds ANTHONY, PATRICK &
MURTA-EXPORTACAO LDA Sitio Da Falfeira EN 120
8601 903Lagos - PORTUGAL simmonds.guy@gmail.com
Iryna Belan FRANTSEVICH INSTITUTE
FOR PROBLEMS OF MATERIALS SCIENCE OF NATIONAL ACADEMY OF SCIENCE OF UKRAINE
Krzhyzhanovsky Street 3
03142 Kiev- Ukraine belanira@bk.ru
Ruth Wootton C.T.M. EQUIPMENT
LIMITED Whaley Road Zenith Park
Unit E
S75 1HTBarnsley South Yorkshire - UNITED KINGDOM
ruth@ctmukltd.com
Irina Husharova YUZHNOYE DESIGN OFFICE
NAMED AFTER MIKHAIL YANGEL
Krivorozhskaya 3
49008Dniepropetrovsk - Ukraine space@yuzhnoye.com
7 Copyright
© 2017, NATIONAL TECHNICAL UNIVERSITY OF ATHENS, 9Heroon Polytechniou Street, 15780 Athens - GREECE on behalf of the FIBRALSPEC consortium.
FIBRALSPEC is a Large Integrating Collaborative project under the European Commission's 7th Framework Programme.
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