RESIDUALL Coordinator: Prof. Alcides Lopes Leao E-mail:
[email protected] 55(14)3811-7257 - BRAZIL
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Faculdade de Ciências Agronômicas Campus de Botucatu Brasil Coordinator: Prof. Alcides Lopes Leao E-mail:
[email protected] 55(14)3811-7257 - BRAZIL 2
unesp - Sao Paulo State University
Students:
- Undergraduate: 34,425 (5,800/yr.) - Graduate: 12,031 (2,000/yr) Professors: 3,350 (more than 85% work full time in teaching, research and extension services) Staff: 6,984 Campuses: 23 in 21 cities Laboratories: 1,900 Libraries: 30 Area Total: 62 million m2 Area of Construction: 733,000 m2 Budget 2008: USD 650 millions Graduate Programs: 174 graduate courses at Master and Doctorate levels divided into 101 Master and 73 Doctorate courses Undergraduate Programs: 168 undergraduate programs at bachelor's level in nearly every knowledge areas and 3 prepares students for 63 careers
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RESIDUALL Area: 800 m2 Equipments Available: - Twin and Single Screw Extruder – Coperion ZSK 25 - Blowing Machine 5 L – Pavan Zanetti - Injection Molding – Sandretto 65 t - Presses: Burkle 400 t and Omeco 100 t - Mechanical And Rheology Testing: EMIC (DL 3000) FTIR, Envirotron
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Processes Utilized in Composites at UNESP - Botucatu
Extrusion (profiles and pellets) – macro, micro and nano Injection molding Thermoforming BMC (partnership with private companies) SMC (partnership with private companies) RTM (partnership with private companies) LFRT – Long Fiber Reinforced Thermoplastics (profiles and railroad crossties) 5 5
Proverbs
“Technology is dominated by two types of people: those who understand what they manage, and those who manage what they do not understand” Putt’s Law
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International Year of Natural Fibers - 2009 FAO – Food and Agriculture Organization
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Searching
Key words: Natural Fiber; Polymer composite; Plastics Composite 2000-2005 Language: english
Rigail, 2005
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Where are the Technologies in FPC Fiber Plastics Composites 16
5
41
5 5 6 7
10
USA Germany India Japan Canadá Netherlands Italy Others
SciFnder
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Scientific and Technological Research? 50
50
45 40 35
35
30 25 20
15
15 10 5 0 Patents
Papers
Meetings
SciFnder 10
Which Natural Fibers are Used in Composites? Natural Fibers Bamboo Banana Hemp Coir Flax Jute Kenaf Sisal Pinneapple Curauá
No. Of Papers 8 6 38 18 46 37 28 30 4 4
SciFnder 11
Natural Fibers in South America Brazil is the biggest producer and consumer
Abaca – Ecuador Fique – Colombia, Ecuador Totora – Ecuador, Peru and Bolivia Flax – Argentina, Brazil PALF - Brazil Embira – Brazil Caroá – Brazil Bamboo - Brazil Phormium (imbira, New Zealand Flax) - Brazil Curaua – Brazil, Venezuela Kurowa (curaua) - Guiana Sugar cane bagasse – Brazil, Cuba and Colombia,
Sisal – Brazil, Cuba, Haiti México Buriti, Carnauba, Buriti, and Tucum – NE of Brazil (native palm trees Malva & Jute – Brazil Coir – Brazil Banana – Brazil Hemp – Chile Taboa (Typha) - Brazil Piteira – Brazil and Ecuador Tagua – Ecuador Jarina – Brazil (Vegetable ivory) Piaçava – Bahia, Brazil 12 12
Environmental Reflexion
Luiz Carlos 13 Dalben
ECOMENES (oikos-menes)
Extrativism – low pressure of natural resources Economics – high pressure; making money at any cost
Use natural resources based on an ecological intuition of non linear biological processes - SUSTAINABILITY eECOMENY Resulting Processes Of Low Environmental Impacts 14
For the Skepticals: The Proof of the Global Warming in our Planet
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Materials Cycle PRODUCTS Textiles, composites, agrochemicals, energy – 340 l ethanol/1ton straw
Biowaste Collection
Conversion
INTERMEDIATES COMPOST Biological Degradation Processing
CO2 H2O
10 ton Biomass collecting 2,5 ton CO2
Strach Celluloses, Agrochemicals, hemicelluloses, biopolimer Photosynthesis
Harvesting Extraction 10 to 20 tons dry mass /ha annualy
endothermic (capturing) 2,86 kJ/mol of glucose formed
RENEWABLE RAW MATERIALS
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CLASSIFICATION OF NATURAL FIBRES NATURAL FIBRES PLANT BAST
LEAF
SEEDS
FRUIT
GRASS
WOOD
Flax
Ananas
Cotton
Coir
Bamboo
(Linum Usitatissimum)
(Ananas Bracteatus)
(Gossypium)
(Cocos Nucifera)
(Bambusa Shreb.)
Hemp
Sisal
Coir
Luffa
(Cannabis Sativa)
(Agave Sisalana)
(Cocos Nucifera)
(Luffa Aegyptiaca)
Kenaf
Abaca
Kapok
(Hibiscus Cannabinus)
(Musa Textilis Nee)
(Ceiba Pentandra)
Jute
Curaua
(Corchorus Capsularis)
(Ananas Erectifolius)
Ramie (Boechmeria Nivea)
Isora (Helicteres Isora)
MINERAL
ANIMAL
Totora (Scirpus Californicus)
hardwood
Sheep
Glass
(Ovis Aries)
softwood
Alpaca
Mineral Wool
(Lama Pacos)
Camel (Camelus Bactrianus)
Soya
Goat
(Glycine)
(Genus Capra)
Cabuya
Poplar
Horse
(Furcraea Andina)
(Populus Tremula)
(Equus Caballus)
Calotropis
Rabbit
Palm
Asbestos
WOOLS AND HAIR
(Oryctolagus Cuniculus)
(Calotropis Procera)
African Palm
Vicuna
Basalt
Ceramic
Aluminium
Borate
Silicate
(Lama Vicugna)
Chambira (Astrocaryum Chambira)
Carbon
SILK
Opuntia
Natural
(Opuntia Galapagos)
(Bombyx Mori L)
Paja
Spider Silk
(Carludovica Palmata)
(Araneus Diadematus)
Jukka (Yucca L)
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The increasing demand for natural and wood fibres
18 Source: UN 2006, AEO 2006, nova-Institut 2006
On a world basis, fiber demand of cotton, wool, silk and manmade fiber has decreased by 6.7% to 67.3 million tonnes, the steepest decline in history. The chart above shows the long-term inter-fiber competition. Since the beginning of the 1990’s, manmade fibers have been the most important fiber type in terms of volume. The average annual growth rate since 1980 for manmade fibers accounts for 3.9% for natural fibers it (*) Saurer Report „The Fiber Year 2008/ 2009” amounts to 1.9%. 19
All fiber types suffered from slowing demand. Small-scale fiber types like aramid and carbon fibers weathered the downturn not bad until the fourth quarter 2008. Although firm demand fell in aerospace, automotive, military and wind power they managed to stay on positive territory in terms of the growth rate. On the other hand, established fibers like polyester, polyamide, polypropylene and acrylic were down in volumes. The usage of cotton, wool and silk also decreased by 10.1 % to 25.2 million tonnes, manmade fibers fell by 4.5% to 42.2 million tonnes. The third section with kapok, ramie, flax, hemp, jute, sisal and coir is anticipated to (*)have stagnated at2009” 5.9 million Saurer Report „The Fiber Year 2008/ 20 tonnes.
Comparative Study of Carbon Sequestering for Biomass and Petroleum (Nafta) Fuel
Demand of Energy Carbon Net Emission
Natural Fibers 1000 kg 11,9 MJ/kg 70% Harvesting, processing, decortication, drying, ... 0,34 MJ/kg 0 kg in the NF
Total Emission of C Total Emission of CO2
18,1 kg 66,4 kg
Quantity Calorific Value Efficiency of Conversion Process
Petroleum 229 kg 42,7 MJ/kg 85% Extraction, transportation refining 10,9 MJ/kg 213,6 kg petroleum 279,2 kg 1023 kg
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Economical Aspects Development for prices of crude oil, standard thermoplast & natural fibres from Europe since 2003 220 % 200 % 180 % 160 % 140 % 120 %
Crude oil
Standard thermoplast
Jan. 2006
Jul. 2005
Jan. 2005
Jul. 2004
Jan. 2004
80 %
May 2003
100 %
Future trend: Fibres and Polymers based on renewable resources
Natural fibres (Bast) from Europe
(Karus, Ortmann, Otremba, Scheurer & Müssig 2006 .- adapted presentation)
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„Material Change“ Which materials will use the industry in the future? -
If mineral oil and gas will be more and more expensive, and in longer terms are running out ... What will happen to our energy and material supply? Energy supply has different alternatives: solar energy, wind energy, geothermie, biomass for electricity and heat, biofuels (biodiesel, ethanol, rape seed oil, BtL) ... nuclear energy. But the material supply has only a very few alternatives!!
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Weight of curauá composite relative to glass fiber composite (horizontal axis) vs. relative difference in ten different impact categories (vertical axis). A negative vertical value means that CU/PP is better than GF/PP – a positive value means the opposite (CU=Curauá / GF=Glass Fiber).
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100
Dark – curaua composite White – glass fibers composites
kg CO2 eq.
10
1
0.1
ife of -L
se En
d-
rU Ca
rt s Tr an
sit e m po Co
sp o
s
s er lym Po
Fi
be
rs
0.01
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LITERATURE Curauá Fibers in the Automobile Industry – a Sustainability Assessment Zah1, R Hischier1, A. L. Leão2, I. Braun3 Journal for Cleaner Production 1 Technology & Society Lab, Swiss Federal Laboratories for Materials Testing and Research (EMPA), Switzerland 2 UNESP, FCA, Campus Botucatu, SP, Brazil 3 Volkswagen AutoUni, Wolfsburg, Germany
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3D Fibres Created by Nature
Palm from Cuba
Galapagos Opuntia Cactus
Luffa (Luffa Aegyptiaca) 27
Heavy or Light?
Light weight materials?
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Concept inspired by nature
(ceramics, 2004)
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FROM PLANT TO FIBERS
Natural Fibers
Plant
Process
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FIBRE STRUCTURE GENERALLY COMPOSITE OF CELLULOSE, LIGNIN, AND CHEMICELLULOSE
Source: D.Kretschman Nature materials vol2, 2003
Fibers are themselves miniature composites formed from a „reinforcement” of cellulose, embedded in a „matrix” of lignin and other polysacharides
I-intercellular adhesive (e.g. lignin), S1-external side wall, S2-middle side wall, S3-internal side wall MFA microfibryl
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Technologies Involved - Other Aplications
Better utilization of the whole plant (ex.: nowadays, 95% are discarded for sisal and curauá plants); Non-traditional utilization of fibers and byproducts; Development of pharmaceuticals and contraceptives; Development of agrochemicals based on crop fibers byproducts; Animal feeding (goats, ovine and cattle) for milk and meat production; and Production of biogas from the exceeding mucilage – energy supply for the industrial plant. 33
The Role of Natural Fiber Technology in the Sustainable Development
Make possible changes in the productive process and the consumers that will result in lower agression to the environment and the work toward the sustainable development – “reduction” – controls the emission of efluents or wastes potentially toxics (ex.: car oil filters impregnated with phenolic resins, or MDF wastes) – “clean production” – technology development in the process que will result in reduction or elimination in the process or in the project que will reduce or eliminate the generation of residues or effluents (the curaua case) 34
Sustainable Development Growing X De velopment Development Sust ainable is worthless Sustainable Integration under environmental criteria toward the stratety and ecomomical practices in the organizations or corporations: fullfill the demands of continous growing and conserve the natural “capital” 35
Sustainable Development Dynamics • Sociopolitical considerations for attaining sustainable development ¾ Economic Business growth and efficiency ¾ Social Social justice Economic opportunity ¾ Environmental Conservation of natural resources Public health Levine, 2003
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Sustainable Development Social Justice
Environmental Sustainability
Sustainable Development
Economical Efficiency
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Exploration Paretto: Nobody gets the benefits unless SOMEBODY is hurt
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Viability
ECONOMICAL
R&D
ENVIRONMENTAL
Sustainable Development 39
Quality of Life
Environmental – preservation and conservation of the natural resources (Agenda 21) – wood replacement Social – Basic sanitation and schools (reduction of infant mortality and illiteracy rates) – non-qualified jobs – crop fibers regions are less developed Economical– direct jobs, creating economical alternatives to economical deprived areas. There are 13 chronical poverty areas in Brazil. Crop fibers are importtant alternatives
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Technologies Involved - Other Aplications
Better utilization of the whole plant (ex.: nowadays, 95% are discarded for sisal and curauá plants); Non-traditional utilization of fibers and byproducts; Development of pharmaceuticals and contraceptives; Development of agrochemicals based on crop fibers byproducts; Animal feeding (goats, ovine and cattle) for milk and meat production; and Production of biogas from the exceeding mucilage – energy supply for the industrial plant. 41
Social Advantages
Crop fibers can use as much as 5 people/hectare – from field to industry Possibilities of consortium (agroforestry) and use of byproducts and residues Cooperatives practices Local Culture – Artcrafts – keeps the local identity Sustainability of natural resources in the original region Fixation of the man in the local region (eg. North and Northeast region of Brazil) Drug crop alternative - cheaper than military alternative, mainly in Colombia 42
Natural Fibers Applications
Geotextiles – flexible mats made of bast or leaf fibers, with physical entanglement through carding or needle punching. These mats can be made of almost any gramature. These mats are applied in slopes, as slow release of fertilizer, agrochemicals or seed substrate; they enhance the soil structure. Can be used as well as under pavement in roads, to keep the separation betwenn different materials
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Natural Fibers Applications
Filters – Can be used as air filter elements, to remove particulates or even as substrate for reactions of chemicals added to the mats and chemicals that must be removed from the air. Absorbents – Utilization of lignocellulosics fibers to remover toxic metals, agrochemicals, colorantres, trace of chemical elements, purificatin of solvents and to remove oil from water in cities and roads. Per example is related that kenaf selectively absorbs oil spills in the ocean. 44
Natural Fibers Applications
Structural Composites – Composites developed to receive load, such as window rames, wall, roof, stairs, etc… In this case includes particleboad, veneer, and composits based on polyethylene and natural fibers extruded in profiles; Non-Structural Composites - Material not fitted to receive loads, not following any standards, therefore cheapter thant its counterparts
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Natural Fibers Applications
Molded Products – Follows the same geotextiles mats production with the addition of thermosetting or thermoplastics resins to hold the final shape of the molded parts. It has several applications, mainly in the packaging industry and structural non structural products; Packaging - Containers made of reinforced natural fibers suitable for transportation of fruits, greens and sacs for agricultural products. It can can for single use and be collapsed after its utilization aiming to reduce the volume in he to the prior shape or be grinded for the 46 recycling process; and
Tequila Production
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Discarded Fibers Destilation
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Economical Aspects Development for prices of crude oil, standard thermoplast & natural fibres from Europe since 2003 220 % 200 % 180 % 160 % 140 % 120 %
Crude oil
Standard thermoplast
Jan. 2006
Jul. 2005
Jan. 2005
Jul. 2004
Jan. 2004
80 %
May 2003
100 %
Future trend: Fibres and Polymers based on renewable resources
Natural fibres (Bast) from Europe
(Karus, Ortmann, Otremba, Scheurer & Müssig 2006 .- adapted presentation)
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Target Sectors in Brazil
Automotive Industry – 40,000 tons/year (23 kg/car in Europe and 13 kg/car in Brazil) – the Brazilian demand is about 8,000 tons/year Railroad crossties – replacement of solid wood and concrete crossties Civil Engineering – door frames, doors, window frames Geotextile – 100 millions m2 – 500.000 km roads & 50.000 km of railroads Furniture Industry – cabinets, back seats, profiles, etc.. Electro/Electronics – injection molded parts Packaging Industry – fruit box Pharmaceutical and veterinary industry (by-products from sisal, curauá and fique) 50
Application of Natural Fibers Composites Electronic components 10%
Marine 12% Construction 26%
Consumer products 8% Appliances Aerospace Miscellaneous 8% 4% 1%
Automotive 31%
Racz, 2005 51
Natural Fibers Applications
Geotextiles – flexible mats made of bast or leaf fibers, with physical entanglement through carding or needle punching. These mats can be made of almost any gramature. These mats are applied in slopes, as slow release of fertilizer, agrochemicals or seed substrate; they enhance the soil structure. Can be used as well as under pavement in roads, to keep the separation betwenn different materials
52
Natural Fibers Applications
Filters – Can be used as air filter elements, to remove particulates or even as substrate for reactions of chemicals added to the mats and chemicals that must be removed from the air. Absorbents – Utilization of lignocellulosics fibers to remover toxic metals, agrochemicals, colorantres, trace of chemical elements, purificatin of solvents and to remove oil from water in cities and roads. Per example is related that kenaf selectively absorbs oil spills in the ocean. 53
Natural Fibers Applications
Structural Composites – Composites developed to receive load, such as window rames, wall, roof, stairs, etc… In this case includes particleboad, veneer, and composits based on polyethylene and natural fibers extruded in profiles; Non-Structural Composites - Material not fitted to receive loads, not following any standards, therefore cheapter thant its counterparts
54
Natural Fibers Applications
Molded Products – Follows the same geotextiles mats production with the addition of thermosetting or thermoplastics resins to hold the final shape of the molded parts. It has several applications, mainly in the packaging industry and structural non structural products; Packaging - Containers made of reinforced natural fibers suitable for transportation of fruits, greens and sacs for agricultural products. It can can for single use and be collapsed after its utilization aiming to reduce the volume in he to the prior shape or be grinded for the 55 recycling process; and
Natural Fibers Applications
Combination with other resources – Blends of natural fibers with other materials such as glass fiber, metals, plastics and other man-made materials. A metallic matrix offers mechanical and thermal resistance, mainly in the aerospace industry.
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Natural Fibers in South America Brazil is the biggest producer and consumer
Abaca – Ecuador Fique – Colombia, Ecuador Totora – Ecuador, Peru and Bolivia Flax – Argentina (?) Embira – Brazil Caroá – Brazil Bamboo - Brazil Phormium (imbira, New Zealand Flax) - Brazil Curauá – Brazil, Venezuela Kurowa (curaua) - Guiana Sugar cane bagasse – Brazil, Cuba and Colombia,
Sisal – Brazil, Cuba, Haiti México Buriti, Carnauba, Buriti, Piaçava and Tucum – Brazil (native palm trees Malva & Jute – Brazil Coir – Brazil Banana – Brazil Hemp – Chile Taboa – Brasil Pita or Piteria – Brazil and Ecuador ~Tagua – Ecuador Jarina – Brazil (Vegetable ivory) 57
¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾
Environmentalist pressure over more utilization of Natural Renewable Resources Better eficiency in converting raw-materials in products compared to other man-made fibers Products based on Life Cycle Analysis (ISO 14.000) National strategy to create rural jobs in economically deprived areas Good mechanical properties relations: Weight versus Resistance Composites/Ecomenes Recyclability Greenhouse Effect 58 Marketing – Lignocelullosics Composites = Low Tecnology
Advantages of Natural Fibre Reinforcement
Renewable source of rawmaterial. Excellent specific strength and high modulus. High flexural and tensile modulus - up to 5× base resin, high notched impact strength - up to 2× base resin Reduced density of products. Biodegradable. Lower price of polymer composites reinforced with natural fibres than those reinforced with glass fibre. Reduced tool wear. Safe manufacturing processes, no airborne glass particles, relief from occupational hazards. Reduced dermal and respiratory irritation. No emission of toxic fumes when subjected to heat and incineration. Most thermoplastic composites are recyclable. Possibility of recycling the cuttings and manufacturing wastages. Energetically recyclable. Racz, 2005 59
Advantages
Component Weight: Plant fibres have a max. density of 1.5 g/cm3 (that of Cellulose) Density curauá = 1.3g/cm3 Density Glass fibres = 2.5 g/cm3
Resulting in high specific strength and stiffness = low component weight Injection moulded ABS 4 door panels = 9 kg, same panels utilising NF’s = 5 kg for similar mechanical properties
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Limitations
Concerns over fibre consistency/quality Low impact strength (high concentration of fibre defects) Problem of storing raw material for extended time – Possibility of degradation, biological attack of fungi and mildew – Foul odor development
Fibres are hydrophilic UV resistance – similar to plastics Low surface hardness – Quinch-kinch Issues of bonding with polymers Previous 2 issues largely overcome by development of effective fibre surface treatments – MAPP Emission issues – fogging and odour Processing Temps – natural sugars caramelise between 150205ºC must keep below this level. Limits the number of applicable matrix polymers 61
History & The Automotive Sector
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History
3000 years ago first composite material made in ancient Egypt - clay/mud reinforced by straw to build walls
Development of other more durable construction materials such as metals, NF interest was lost
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History
Early 1930’s, Henry Ford walked into his Company’s research lab with a bag of chicken bones, dumped them on a desk and said, “See what you can do with these!” Tried cantaloupes, carrots, cornstalks, cabbages and onions Soybean stalks. In 1940, Soybean oil could be used to make high quality paint enamel and could be moulded into a fibre based plastic with 10 times the shockresistance of steel If the material had not required a long cure time and had associated moulding problems, we might be driving around in soybean fords today!!
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History
1939-45 WWII – shortage of Aluminium in England, led to the use of flax fibres impregnated with phenolic resin to form fuselage skins of spitfires – “Gordon-Aerolite” 1942 Henry Ford – prototype hemp fibre composite car – did not enter production due to economic limitations at that time
Trabant (1950-90) first production car to be built from NF’s – Cotton within a Polyester matrix
Only in the last 15-20 years have NFC’s seen renewed interest 65
Erfurt 2005
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Route to the Automotive Market Fibre Producer Curaua
Non-woven mat maker Can be Tier 1
Tier 1 supplier
Car Manufacturer 67
Automotive Market
To the natural fibre producer the automotive market is attractive – Model platform life is minimum 5 years – 7-8 years – Gives credibility to the material – High quality high quantity demand
Most important processes: Compression Moulding and Injection moulding
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Driving Force Government Legislation
Recycling concerns being driven by EU regulations [EU directive Article 7 on end of life vehicle disposal] Recovery Wt %
Recycling Wt %
Jan 1st 2005
85
80
Jan 1st 2015
95
85
Pressure on manufacturers to consider environmental impact of products at all stages of their life cycle including the ultimate disposal 69
World Potential
58m vehicles produced yearly Max natural fibre consumption 50:50 natural:synthetic ~800,000 tonnes/year If each vehicle used every possible application of NF’s available today Brazil – potential of 3 million cars year
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“The most environmentally friendly thing that you can do for a car that burns gasoline is to make lighter bodies”
Henry Ford
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Advantages to using Natural Fibres in the Auto Industry Reduction in weight between 12-30% (primary importance) Reduction in cost (secondary importance) Renewable and sustainable plant fibre resources Recyclable Abundant supply, accessible to car manufacture areas
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Injection Moulding
Injection moulded composites reinforced by short natural fibres Short fibres (4-6mm) + PP in single/twin extruder to produce granulate for injection moulding Examples exterior
apps – spoilers and fenders interior apps – “hard” items - dash and instrument panels speakers holders (Audi A6)
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Materials Composition for Model Gol 44
45 40 35
31.5
30
25.4
25
20.8 19
20 14.1
15
11.9 9.7
10 5
25.9
9
6.9 3.9
0
Percent by Weight
PUR ABS RUBB FELT PA PE PVC PP PES ASPHALT GLASS OTHERS
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List of Automotive Parts Based on Natural Fibers Composites
Volkswagen: back of seats, doorpanels, trunkpanels (Golf, Passat, Variant, Bora, Gol) Audi: back of seats, sidepanels, trunkcovering, speakers holders (A2, A4, Avant, A6, A6 Avant, A8) BMW: doorpanels, headliners, trunk floorpanel (Serie 3, 5 and 7) Daimler Chrysler: doorpanles, business tables, padding-pillars reinforcing, dashboard parts (Class A, C, E and S) 75
List of Automotive Parts Based on Natural Fibers Composites
Opel: headliners, doorpanels, dashboard parts (Astra, Vectra, Zafira) Peugeot: back of seats, trunkcoverings (406-607) Renault: rear shelf (Clio, Twingo)
Mercedes Benz trucks: front sections for the trucks. HSK
LS 1938, internal engine cover, insulation for the engine, sun-blades, interior insulation and bumper. HPN L 1622 internal insulation; wheel box; roof; and back cover.
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Plant Fibre Utilisation per vehicle (Brazil – 13 kg)
Front door liners: 1.2-1.8 kg Rear door liners: 0.8-1.5 kg Boot liners: 1.5-2.5 kg Parcel Shelves:
