Composites from renewable resources 25/04/2017 Composites from renewable resources Natural fibre reinforcement Biobased thermosets matrix MSK 20111107

Life cycle for fossil materials CO2 Combustion 0 to 10 years Plants Renewable resources Fuels Plastics 1 000 000 000 years MSK 20111107 Crude oil

Life cycle for biobased materials Combustion CO2 0 to 100 years 0 to 10 years Plants Renewable resources Fuels Plastics MSK 20111107

CARBON NEUTRAL A material which has no impact on total atmospheric CO2 levels The CO2 released due to incineration or decomposition is compensated by an equal amount of CO2 absorbed during photosynthesis for generating the biomass MSK 20111107

Historical development Conducting polymerers High-temp polymers Bio- polymers NATURAL ORIGIN MATERIALS Polyesters PE PP Nylon Epoxy- resins Carbon fibres PVC Bakelit Wood Skin Fibers Straw-brick Paper Natural rubber PS Glass fibres Fishbone glue Linoleum Celluloid Linseed oil paints SYNTHETIC MAN MADE MATERIALS 10 000 bC 1800 1900 1950 2000 MSK 20111107

Ref: www.ars.usda.gov/is/pr/1998/980209.htm MSK 20111107

ENERGY CONSUMPTION DURING COMPOSITE PRODUCT LIFE-TIME MSK 20111107

Environmental impact of composites 99 % of all product related energy is consumed during use, only 0.5 % during production The environmental impact for composites is reduced by their durability, low weight, and energy efficient processing Composites are by ¨defintion¨ environmentally friendly materials! MSK 20111107

Wood – a biobased composite Matrix: Lignin and extractives Reinforcement: Cellulose MSK 20111107

Wood – a anisotropic composite X Y No delamination in Y direction Delamination in X direction MSK 20111107

Natural fibres – possible reinforcements for composites 25/04/2017 Natural fibres – possible reinforcements for composites Cellulose fibrous polymers No new idea! Textiles, ropes, canvas and paper have been made from natural fibres since centuries Wool, flax and silk have a long tradition in textiles Crude oil bases fibres replaced natural fibres India and Brazil continued their use DDR’s Trabant contained natural fibres MSK 20111107

Why natural fibers? Renewable Abundant Cheap Light weight Biodegradable Non-abrasive to processing equipment CO2 neutral when incinerated Flexible and though Can be incinerated with energy recovery Good mechanical stiffness Good acoustic and thermal insulating properties MSK 20111107

In nature occurring fibers: 25/04/2017 In nature occurring fibers: Plant fibers Flax Hemp Kenaf Jute Ramie Sisal Banana Coconut Animal fibers Chicken feathers Hair 1000 plants can be used for manufacturing industrially usable fibers….. Kenaf: drought-resistant relative to hibiscus, which grows without extensive use of herbicides or pesticides up to 4.2 m/7 months. Hemp: non-narcotic form are used Flax: Cargill’s Durafibre and Durafill MSK 20111107

25/04/2017 Use of natural fibres in composites in the German automotive production Market study by nova-Institut, Germany 45 000 tons of plant fibre NFCs 36 000 tons of wood fibre NFCs 79 000 tons of cotton fibre NFCs Totally 160 000 tons composites of which 88 000 tons natural fibres About 16 kg natural fibres used per car in Germany Plant fibre market volume 15 million euro in automotive 65 % thermoplastic and 35 % thermoset matrices MSK 20111107

Use of natural fibres North America 2000 25/04/2017 Use of natural fibres North America 2000 Totally 200 000 ton (7 % of reinforcement and filler market volumes) 700 000 ton 2005 MSK 20111107

Fiber properties Fiber E-modulus (Gpa) Strength (Mpa) Strain (%) Length (mm) Diam. (m) Density (g/cm3) Glass 72 2000-3400 1.8-3.2 Cont. 10 2.56 Ramie 128 500-1000 1.2-4 60-250 10-80 1.4-1.5 Flax 45-100 600-1100 1.5-2.4 13-70 10-30 1.37 Sisal 19-32 490-760 2.2-2.9 1-8 10-40 1.45 Hemp 35 400 1.1-1.6 5-55 10-50 MSK 20111107

Production of plant fibers Fibre Price comp. to glass (%) Production (1000 t) Jute 18 3600 E-glass 100 1200 Flax 130 800 Sisal 21 500 Banana 40 Data from 1993 MSK 20111107

Composition of different cellulose based natural fibers Cotton Jute Flax Ramie Sisal Cellulose 82.7 64.4 64.1 68.6 65.8 Hemi-cellulose 5.7 12.0 16.7 13.1 Pectin 0.2 1.8 1.9 0.8 Lignin - 11.8 2.0 0.6 9.9 Water sol. Subst. 1.0 1.1 3.9 5.5 1.2 Wax 0.5 1.5 0.3 Water 10.0 10.06 MSK 20111107 Ref.: Bledzki, Prog. Polym. Sci. 24 (1999) 221

Properties for natural fibres 25/04/2017 Properties for natural fibres Mechanical properties: Large variations among species, dependence on environment and geographical cultivation location, climate and age Chemical properties: Inhomogeneous and large variations, hydrophilic Physical structure: Complex and heterogeneous, different properties on different size levels Surface properties: Heterogeneous, hydrophilic, must be modified before processing MSK 20111107

The cellulose polymer MSK 20111107

Cellulose OH up OH down Cellobiose repeating unit (-D-glucose) 25/04/2017 OH up Cellulose OH down Cellobiose repeating unit (-D-glucose) The combination of -D-glucose make it possible to form long straight chains DP 9 000 – 15 000 MW = 10 000 – 150 000 5 - 7 m linear length in wood Hydrogen bonds MSK 20111107

Compatibilization by maleic anhydride modified polymers 25/04/2017 Compatibilization by maleic anhydride modified polymers MSK 20111107

Flax (Linum usitatissimum) - a slender stemmed plant with branches and flowers near the top - the stem is around 3 mm thick, and the plant can be up to 1 m high - flax is a bast fibre, with the fibers in bundles between the outer bark and the central, woody portion of the stem - the fiber bundles are as high as the plant is high A bast fibre MSK 20111107

Flax fibres can be made into non-wovens 30 % lighter than same stiffness glass fiber Traditionally used in textiles Industrial use as insulating material, and in automotive composites MSK 20111107

World-wide cultivation area for flax fibres 25/04/2017 World-wide cultivation area for flax fibres Total area: 386 000 ha China: 132 500 ha France: 66 000 ha Belarus: 40 000 ha Russia: 30 000 ha the Netherlands: 16 300 ha Belgium: 14 500 ha Ukraine: 9 300 ha Lithuania: 5 000 ha Flax fiber output/ha depends largely on geographic location: in western Europe it is possible to get 1800 kg fiber/ha, while in China and Russia it can be as low as 500 kg/ha <this corresponds to 1-2 % of annual worldwide volumes MSK 20111107 Data from FAOSTAT 2000

Flax cultivation output kg/ha: kg/ha local variation Raw flax 7950 5 860 – 10 510 Rippled flax 6150 4 560 – 8 480 Seeds 750 570 – 985 Long fiber 1560 1 310 – 1 930 Short fiber 290 200 – 420 Total fiber 1850 1 510 – 2 360 Data from Belgium cultivation tests 2002 MSK 20111107

Flax - from plant to fabric 25/04/2017 Flax - from plant to fabric A step-wise process: harvesting seed rippling drying retting scutching hackling carding drawing spinning weaving fabric treatment Seed rippling – traditional method Field retting Carding Spinning Weaving MSK 20111107

Flax fibre processing cycle Air-laid insulation Scutching 25/04/2017 Air-laid insulation Scutching Scutched fibre bundles Short fibre tow Flax fibre processing cycle Hackling Spun yarns MSK 20111107 Carding Long fibre line yarn Spinning

Biotechnical retting process Developed by Finflax Ltd, Finland Characteristics: Bioreactor retting vessel Closed system with recirculation and regeneration of retting liquor Pectinase and hemicellulose enzymes Easy to control (pH, temperature, O2) 12 - 24 hours processing time Benefits: Shorter retting time Better fibre yield Better fibre strength Environmentally friendly process Well-controlled and reproducible method Efficient method Reduction of processing costs A satisfactory batch-wise enzymatic-retting process shall be simple, fast, cheap, reproducible and easily adaptable to existing equipment. The main principles of Arctic Flax retting process are to fulfil these criteria as controlled as possible at industrial scale. Therefore, the retting liqueur consists of selected pattern of industrial pectinase enzymes either commercial or produced at FinFlax bioprocess department. This retting process is easily to be expanded, enables production automation having low operational costs. The whole process is closed minimizing unwanted microbial effects. It is easily controlled (pH, temperature, oxygen, organic acids, enzymatic activities etc.). The retting time can easily vary (12 - 24 hours) depending on the type of fibers to be retted or the quality of fibers needed in different technical applications.  Retting liquor consists of industrial enzymes and selected microbes producing enzymes  Main enzymes are pectinases and hemicelluloses  Bioreactor type of retting vessel with modular structure  Closed system; no unwanted microbial (enzymatic effects)  Recirculation and regeneration of retting liquor; removal of solids and other inhibitory materials  Controlled; pH, temperature, oxygen, organic acids, enzymatic activities Tailoring; retting process depending on raw material or requirements of fiber type and quality MSK 20111107 Photo: FinFlax Ltd

SEM surface analysis of enzyme and field retted flax fibres Field retted fibre, 1000X Enzyme retted fibre, 1000X Technical fibre, 50 – 100 m MSK 20111107

Kenaf (Hibiscus cannabis) 25/04/2017 Kenaf (Hibiscus cannabis) Grows 4 m in 7 months Packaging materials, paper, oil-absorbents Kenaf: drought-resistant relative to hibiscus, which grows without extensive use of herbicides or pesticides up to 4.2 m/7 months. Hemp: non-narcotic form are used Flax: Cargill’s Durafibre and Durafill MSK 20111107

Jute (Corchorus casularis) 25/04/2017 Jute (Corchorus casularis) Short, inelastic fibres Carpet backing, sacks, wall coverings, floor coverings MSK 20111107

SISAL PLANTAGE Photo by Kristiina Oksman MSK 20111107

Wood fibre reinforced thermoplastics 25/04/2017 Wood fibre reinforced thermoplastics Wood polymer composites (WPC) Wood fibres are used as a filler or reinforcement Compounding by extrusion Processing as thermoplastics 10 – 70 w-% fibre content PP, PE, PS, ABS, recycled thermoplastics MSK 20111107

Palltruder® Production of wood plastic omposites 25/04/2017 Palltruder® Production of wood plastic omposites K2004 Exhibition, Düsseldorf MSK 20111107 www.pallmannpulverizers.com

Extrusion line for wood polymer composite profiles 25/04/2017 Extrusion line for wood polymer composite profiles K2004 Exhibition, Düsseldorf MSK 20111107

Construction materials 25/04/2017 Construction materials 50 % growth in the US Easy maintenance Compared to impregnated wood less toxic Processed as wood A wood-like surface finish Can be colored with pigments ¨A plastic¨ surface feeling and out-look MSK 20111107

Car parts from natural fibres 25/04/2017 Mainly non-structural components for interior Flax, hemp, kenaf Reinforcement in non-woven form or chopped short fibres Processing by compression moulding EU directive End-of-Life Vehicle (ELV) demands that 85 % of car weight must be recycled, 10 % can be incinerated and only 5 % can be land-filled Plant fibres are 30-40 % of lower weight than glass fibres MSK 20111107

TEXFLAX European project Flax fabrics Flax yarn Flax fibre Flax cultivation Composite laminates Composite product MSK 20111107

TEXFLAX Demonstrator prototypes Sandwich panel Bicycle helmet Flower pot Vacuum infused lid MSK 20111107 Water tank

Design and biocomposites 25/04/2017 Design and biocomposites OLD CONCEPTS – NO DESIGN! NEW CONCEPTS – WITH DESIGN! MSK 20111107

Kareline Ltd, Finland Wood composite compounds 25/04/2017 Kareline Ltd, Finland Wood composite compounds Window frame by Allplast Bleached softwood pulp + polypropylene 50 wt-% fibre content Injection molding and extrusion molding Design aspects considered www.kareline.fi Electic guitar by Flaxwood MSK 20111107

Necessary developments: 25/04/2017 Necessary developments: Fibre processing techniques into usable forms Dust and microorganism in plants can be health hazards Hydrophilicity of natural fibers causes water sensitivity (rotting and swelling) Matrix incompatibility causes poor mechanical properties Seasonal variability in plant properties Better understanding about mechanical properties and structure Temperature stability (processability and recycling) Burning smell and odours while processing at high temperatures Cellulose degrades at 300 C, which is near the processing at 190-250 C. MSK 20111107

Natural fibre reinforcements The environmental impact of the natural fibre reinforcements must be evaluated, and all steps must be considered Cultivation: pesticides, fertilizers, erosion, farming equipment,… Processing: fibre extraction, spinning and weaving Disposal: end-of-life treatment During use: durability in the composite MSK 20111107