1. 1. Natural Materials, Bio derived Materials & Their Composites Derivation, Properties and Applications Dr. K. Padmanabhan Professor and Assistant Director School of Mechanical and Building Sciences VIT- University, Vellore-632014.
2. 2. 2 Mythology
3. 3. 3 Bottom up and Top down Philosophy
4. 4. 4 Contents History Natural Materials-The Basics Bio derived plastics Natural and bio derived fibres Chemical, Physical and Mechanical Properties Wood composites Myths Applications of natural composites
5. 5. 5 Indus Valley and Natural Composites Mud Composite Figurines and Sun Baked Mud Composite Bricks Were Produced by The Indus Valley People from 5000 BC It was not the Egyptians- A myth !
6. 6. 6 Kajal or Mai- the home made nanocarbon from castor oil ! Nanocarbon structures are present in the soot !
7. 7. 7 Natural Materials -The Basics
8. 8. 8
9. 9. 9 Sustainable Development Preventing rural exodus Using local labour forces Environmentally sound PROFITABLE for the growers as well as for the industry- a myth shattered ! Biogenics versus Non-biogenics ( i.e. Production from life processes. Like cotton or silk ) Green Product / Green Process Ecomenia (ecological + profitable)
10. 10. 10 Base Bio vs. Base Fossil 10
11. 11. 11 Triangulo de Campbell NF Must be Sustainable
12. 12. 12 External Forces Shaping the Natural Fibre Composites Industry
13. 13. 13 Why bio-based polymers and natural fibres? Environmental Advantages? Renewable raw material base Biodegradable Reduced fossil fuel and resource consumption Lower Greenhouse gas emissions Lower overall emissions and environmental impacts Energy recovery from incineration Economic advantages? (Short v/s Long run) Rising petroleum prices, technological progress and scale economies
14. 14. 14 Drivers of environmental superiority of NFRP Natural fiber production v/s glass fiber production emissions Higher fiber % (substitution of base polymer and GF with lower emission NF) Credits for carbon sequestration ( capture and storage of CO2 so that it is not let in to the atmosphere ) Higher N2O & eutrophication ( response of ecosystem due to the addition of natural or artificial substances ) due to cultivation
15. 15. 15 Other Benefits Carbon sequestration in hemp ~ 0.79kg CO2/kg fiber Energy recovery from fiber burning ~10 MJ/kg RENEWABLE/LOCAL Material base
16. 16. 16 GROWTH FACTORS Comparative weight reduction part for part Cheap filler / structural reinforcement Suitability for one-pass processing Relatively good impact performance Occupational health handling advantages Re-use of moulding offcuts Lack of toxic emissions Abundant supply Green credentials - sustainable resource with superior environmental balance Suitability for recycling processes COST REDUCTION
17. 17. 17 Advantages Lighter 30% less than current materials Biodegradable Low energy to manufacture Excellent energy absorption Replace current plastics and even steels Non-Toxic
18. 18. 18 Uses Car bodies Less weight = greater fuel economy Toys Luggage Building material Aerospace Medicine Agriculture Bicycles Consumer products
19. 19. 19 Bio-derived Thermoplastics and Thermosets
20. 20. 20 Bio polyethylene Biopolyethylene (also known as renewable polyethylene) is polyethylene made out of ethanol , which becomes ethylene after a dehydration process. It can be made from various feedstocks including sugar cane, sugar beet, and wheat grain. One of the main environmental benefits of this project will be the sequestration of roughly 2 kg of CO2 per kg of polyethylene produced, which comes from the CO2 absorbed by the sugar cane while growing, minus the CO2 emitted through the production process. Over 1.5 billion pounds of CO2 will be annually removed from the atmosphere. Dow and Toyota are making it !
21. 21. 21 Bio PLA, PHB and Polyester Bioplastics are plastics derived from renewable biomass sources, such as vegetable fats and oils, corn starch, pea starch or microbiota. Polylactic acid (PLA) is a transparent plastic produced from corn or dextrose. The biopolymer poly-3-hydroxybutyrate (PHB) is a polyester produced by certain bacteria processing glucose, corn starch or wastewater . Similar to PP. Polyester is also produced from potato starch.
22. 22. 22 Genetically modifed bioplastics Genetically modified bioplastics Genetic modification (GM) is also a challenge for the bioplastics industry. None of the currently available bioplastics which can be considered first generation products require the use of GM crops, although GM corn is the standard feedstock. Looking further ahead, some of the second generation bioplastics manufacturing technologies under development employ the "plant factory" model, using genetically modified crops or genetically modified bacteria to optimise efficiency.
23. 23. 23 Epoxies from soybean oil Biobased Epoxy Resins from Epoxidized Soybean Oil (ESBO) Cured with Maleic Anhydride (MA). Epoxidized soybean oil (ESBO), obtained from a renewable resource was used in the production of thermoset resins. Samples of the ESBO were initially treated with maleic anhydride, equal mixture of catalyst (1,3- butanediol anhydrous and benzyldimethylamine) and the mixture was cured for 5h at different temperatures. After the curing process, the ratio between the ESBO and the anhydride (ratio EEW:AEW) was evaluated in terms of the different mechanical properties
24. 24. 24 Plastic from Badam Oil Plastics can be synthesized from badam oil ! Lot of research is going on in this sector ! Indians might take the lead !
25. 25. 25 Castor oil as plasticizer Castor oil derivatives are used as plasticizers in rigid plastics. Environmental fingerprinting and CO2 emissions can be reduced by replacing petroleum derived plasticizers with castor oil plasticizers. BASF a german company is working on this ! Used in toys, impact resistant plastics, hose pipes, medical aids.
26. 26. 26 Cashew Nut Shell Oil as Composite Matrix Material Cashew nut shell oil can be polymerized using acids, toluene as inhibitor and formaldehyde at 120 celsius. A tough and strong maroon coloured matrix !
27. 27. 27 Composition of CNSL
28. 28. 28 CNSL Matrix Material
29. 29. 29 Waste Bioplastic to Fuel When you have enough of bioplastic waste you can pyrolyse it and make bio plastic derived petrol, diesel kerosene and wax !!!
30. 30. 30 Natural and Bio-derived Fibres
31. 31. 31 CLASSIFICATION OF NATURAL FIBRESNATURAL FIBRES PLANT ANIMAL BAST LEAF SEEDS FRUIT GRASS Flax (Linum Usitatissimum) Hemp (Cannabis Sativa) Kenaf (Hibiscus Cannabinus) Jute (Corchorus Capsularis) Ramie (Boechmeria Nivea) Isora (Helicteres Isora) Ananas (Ananas Bracteatus) Sisal (Agave Sisalana) Abaca (Musa Textilis Nee) Curaua (Ananas Erectifolius) Cabuya (Furcraea Andina) Palm Opuntia (Opuntia Galapagos) Paja (Carludovica Palmata) Jukka (Yucca L) African Palm Chambira (Astrocaryum Chambira) Cotton (Gossypium) Coir (Cocos Nucifera) Kapok (Ceiba Pentandra) Soya (Glycine) Poplar (Populus Tremula) Calotropis (Calotropis Procera) Coir (Cocos Nucifera) Luffa (Luffa Aegyptiaca) Bamboo (Bambusa Shreb.) Totora (Scirpus Californicus) WOOLS AND HAIR SILK Sheep (Ovis Aries) Alpaca (Lama Pacos) Camel (Camelus Bactrianus) Natural (Bombyx Mori L) Spider Silk (Araneus Diadematus) Goat (Genus Capra) Horse (Equus Caballus) Rabbit (Oryctolagus Cuniculus) Vicuna (Lama Vicugna) MINERAL Asbestos Glass Mineral Wool Basalt Ceramic Aluminium Borate Silicate Carbon WOOD hardwood softwood
32. 32. 32 Natural Fibres: Taboa (Typha domingensis) Sisal Jute Fique Abaca Pineapple Curaua Banana Coir Pulp & Paper sludge Peanut shells and Rice Husk Aloe Vera Cotton and Silk 32 Newcomers: Piaava Imbira Caro
33. 33. 33 From plant to fibre Harvest (combining or pulling) Retting (dew-, wet-, stand- or enzyme-retting) enzymes (e.g. pectinase digests pectin binder) Decortication (scutching) Hammer mill Fluted rollers Willower Cleaning (removal of shive) Carding (brushing/combing to align fibres) product is known as sliver Spinning (twisting to bind the fibres) product is known as yarn or filaments
34. 34. 34 Chemical Composition of Some Vegetable Fibres
35. 35. 35 Main physical properties of cellulose based fibres compared with conventional synthetic fibres
36. 36. 36 COMPARABLE FIBRE CHARACTERISTICS . COMMON CHARACTERISTICS- PHYSICAL High tensile strength and tenacity Low extension High modulus of elasticity High coefficient of friction Excellent heat, sound, electrical insulation properties Biodegradable Combustible Feel and handle Less reactivity It is seen that some myths about natural composites are shattered here !
37. 37. 37 Natural Fibre Cross Section Confocal Laser Scanning Microscope (CLSM) images Non-uniform cross sections provide interesting interfacial properties and other mechanical properties
38. 38. 38 Jute (Corchorus) Corchorus capsularis. L. - white jute Corchorus olitorius L. - Tossa jute. second most common natural fibre, next to cotton, cultivated in the world grown in Bangladesh, Brazil, China, India, Indonesia
39. 39. 39 Kenaf Kenaf is an annual hibiscus plant ... a member of the mallow family, which includes the well-known crops of cotton and okra.
40. 40. 40 Kenaf (Hibiscus cannabinus L.) fibre plant native to east-central Africa. common wild plant of tropical and subtropical Africa and Asia grown for several thousand years for food and fibre unique combination of long bast and short core fibres two crops/year in Malaysia
41. 41. 41 Nettle (Urtica dioica) Nettles yield ~ 8-10 tonnesfibre/acre far stronger than cotton and is finer than other bast fibres such as hemp much more environmentally friendly fibre crop than cotton, which requires more irrigation and agrochemical input
42. 42. 42 Advantages of Hemp Hemp fibers have higher strength-to-weight ratios than steel and can also be considerably cheaper to manufacture Only traces of tetrahydrocannabinol
43. 43. 43 Banana Fibre The banana plant has long been a source of fibre for high quality textiles. The harvested fibre is boiled in lye to prepare fibres for yarn-making. These banana shoots produce fibers of varying degrees of softness, yielding yarns and textiles with differing qualities for specific uses. India is the worlds largest producer of Bananas Mercedes Benz uses banana fibre reinforced composites for the car interiors- it is myth that natural composites cant be used in high end applications !
44. 44. 44 Jute Fibre Jute is a long, soft, shiny vegetable fibre that can be spun into coarse, strong threads. It is produced from plants in the genus Corchorus. "Jute" is the name of the plant or fibre that is used to make burlap, Hessian or gunny cloth. Jute is one of the most affordable natural fibres and is second only to cotton in amount produced and variety of uses of vegetable fibres. Jute fibers are composed primarily of the plant materials cellulose and lignin. It falls into the bast fiber category (fibre collected from bast or skin of the plant) along with kenaf, industrial hemp, flax (linen), ramie, etc. The industrial term for jute fiber is raw jute. The fibers are off-white to brown, and 14 metres (313feet) long. Jute is also called "the golden fiber" for its color and high cash value. Bangaladesh and India are the largest producers of Jute. Continuous use of Jute however causes Byssniosis.
45. 45. 45 Cotton Fibre In 5000 BC indus valley people wore cotton fabric Cotton is a soft, fluffy staple fibre that grows in a boll, or protective capsule, around the seeds of cotton plants of the genus Gossypium. The fibre is almost pure cellulose. Under natural conditions, the cotton bolls will tend to increase the dispersion of the seeds. China and India are the largest producers of cotton Cotton exposure causes byssniosis a lung decease
46. 46. 46 Silk fibres Silk is a natural protein fibre, some forms of which can be woven into textiles. The protein fibre of silk is composed mainly of fibroin and produced by certain insect larvae to form cocoons. The best-known type of silk is obtained from the cocoons of the larvae of the mulberry silkworm Bombyx mori reared in captivity (sericulture). The shimmering appearance of silk is due to the triangular prism-like structure of the silk fibre, which allows silk cloth to refract incoming light at different angles, thus producing different colors. Some varieties of Thai and Chinese silks have ballistic resistance properties.
47. 47. 47 Silk fibre properties
48. 48. 48 Spider Silk Spider silk is sometimes stronger than silkworm silk. It may be 1.4 GPa in tensile strength compared to 500 MPa for the mulberry silkworm produced silk. It is a myth that natural fibres are weak !
49. 49. 49 Spider Silk
50. 50. 50 Wood: A natural, fiber-reinforced composite Cell walls: layered cellulose microfibrils (linear chains of glucose residues, degree of polymerization 5000 10000, 40-50 % w/w of dry wood depending on species), bound to matrix of hemicellulose and lignin
51. 51. 51 Cellulose Nanocrystals (I) Cellulose (linear chains of glucose residues), bound to matrix of lignin and hemicellulose, comprises 40-50 % w/w of dry wood Individual fibers have major dimensions ~ 1-3 mm, consisting of spirally wound layers of microfibrils bound to lignin-hemicellulose matrix; microfibrils contain crystalline domains of parallel cellulose chains; individual crystalline domains ~ 5-20 nm in diameter, ~ 1-2 m in length Nanocrystalline domains separable from amorphous regions by controlled acid hydrolysis (amorphous regions degrade more rapidly) Crystalline domain elastic modulus (longitudinal) ~ 150 GPa: compare martensitic steel ~ 200 GPa, carbon nanotubes ~ 103 GPa Suggests possible role for cellulose nanocrystals as a renewable, bio- based, low-density, reinforcing filler for polymer-based nanocomposites
52. 52. 52 Cellulose Nanocrystals (II) Cellulose microfibrils secreted by certain non-photosynthetic bacteria (e.g. Acetobacter xylinum), and form the mantle of sea- squirts (tunicates) (e.g. Ciona intestinalis) These highly pure forms are free from lignin/hemicelluloses; fermentation of glucose a possible microbial route to large-scale cellulose production. Adult sea-squirts Nanocrystalline cellulose whiskers, from acid hydrolysis of bacterial cellulose. Image courtesy of Profs. W.T. Winter and M. Roman, Dept. of Chemistry, SUNY-ESF, and Dept. of Wood Science and Forest Products at Virginia Tech.
53. 53. 53 Wood as a filler: Plastic Industrys Viewpoints Pros Low bulk density of wood flour vis-a vis plastics ( 0.5) Low specific gravity of wood Cons Low thermal stability of wood Tendency to absorb moisture
54. 54. 54 Technology Status Of WPCs Manufacture & Processing Wood Plastic Composites (WPC) are popular ! Two stage Process: Compounded pellets & shaping Commonly Used processing Techniques Sheets & profile extrusion Thermoforming Compression Molding Injection Molding New Trend In-Line Compounding & Processing
55. 55. 55 Application Benefits Improved dimensional stability - increased strength Lower processing temperatures - less energy used Increased heat deflection temperature - reduced thermal expansion Up to 30% reduced cycle time for injection moulded products - increased productivity Approximately 10 - 20% lower specific gravity - lighter products Reduced shrinkage - lower internal shear in pultrusion application Low volumetric cost
56. 56. 56 Biodegradability
57. 57. 57 Life cycLe of GReeN biodeGRadabLe pLastic mateRiaL
58. 58. 58 Applications
59. 59. 59 Cow Dung Composites
60. 60. 60 Bio plastic Tableware, Cutlery and Utensils
61. 61. 61 Totora Huros at Lake Titicaca
62. 62. 62 Silk Sarees
63. 63. 63 Footwear and Carpets
64. 64. 64 Agriculture and Medicine Bio derived fertilizers and organic farming Natural composites from organic farming Medicine capsule skin made from starch, cellulose and other edible products Bio derived peptides, proteins and drugs Bio derived polymers as insecticides and mosquito repellents Bio derived polymers as air fresheners, perfumes and cosmetics Nano bio polymers and composites
65. 65. 65 Wood Filled
66. 66. 66 Wood Filled PP Products
67. 67. 67 Foaming Expands Possibilities For Wood Fibre / PP Composites Sea coral foams, natural rubber foams and sea sponges are the naturally occurring flexible and rigid foams
68. 68. 68 Foaming Expands Possibilities For wood Fibre / PP Composites A bio resin derived foam can be used in aerospace, automobiles , damping & insulation applications
69. 69. 69 PVC / Wood Composites
70. 70. 70 A Bamboo Bicycle
71. 71. 71 Ford Soybean FRP Car of 1940s Picture shows Henry Ford I trying to break The Soybean with a sledgehammer, rather unsuccessfully. Soybean was made of steel tubular frame and 14 panels containing phenolic resin and natural fibres. It was worlds first car with an FRP body courtesy Ford Motors
72. 72. Today Europe is ahead of North America in its use of natural fibre composites in automotive applications by approximately 5 years. The global vision of the bio-economy foresees an annual revenue growth for biofuels of 15%, biochemicals 12%and biomaterials 14% for the year 2010,and by 2030 the biomaterials projected growth is 25%. Mercedes-Benz automobiles have more than 30 parts made of natural fibres
73. 73. 73 AUTOMOTIVE MOULDING PROCESSES COMPRESSION MOULDING Bast Fibres (jute, flax, hemp, sisal, kenaf) or ground woodchip / wood flour with binder eg Fibrit, Woodstock, LoPreFin, EXPRESS, Cofibre Thermoplastic - fibre & polymer (PP) co-mingled or Thermoset - fibre mat with resin impregnation Processes - hot platen compression, RTM, SCRIMP etc Substrate usually needle felt nonwoven
74. 74. 74 AUTOMOTIVE MOULDING PROCESSES INJECTION MOULDING Wood flour or short-staple natural fibre with PP as granulate eg Coexil (wood) Processes - co-injection, co-extrusion, LP backmould Not in commercial use yet for natural fibre Challenges exist when FRP manufacturing techniques are employed for NCs !
75. 75. 75 AUTOMOTIVE APPLICATIONS A. MATURE PRODUCTS Weight (kg) Front door liners 1.2 - 1.8 Rear door liners 0.8 - 1.5 Boot liners 1.5 - 2.5 Parcel shelves up to 2.0 B. DEVELOPING PRODUCTS Seat backs 1.6 - 2.0 Sunroof sliders up to 0.4 NVH material min 0.5 Headliners avge 2.5 Floorpan substrate NK C. NEW PRODUCTS Hard interior components 8 - 12 ?? (dashboards, consoles, A/C pillars) Some exterior components (spoilers, trim)???
76. 76. 76 Weight Reduction Component Study NFRP component Base component Auto side panel Wotzel et al 820 g (hemp- epoxy) 1125g (ABS) Auto insulation Schmidt 2.6 kg (hemp-PP) 3.5kg (GF-PP) Transport Pallet Corbiere 11.77kg (CR-PP) 15kg (GF-PP)
77. 77. 77 Example - Door panel made from sisal/Polyurethane
78. 78. 78 Example dashboard support made of 30% sisal fibre reinforced polypropylene
79. 79. 79 Polypropylene Developments Wood Filled Repol PP for Door Trims
80. 80. 80 Self Reinforced Natural Composites The same material as the fibre and the pulp matrix The fibre matrix-interface is interesting Weight and cost savings Interesting Properties ! Bio derived self reinforced polyethylene from sugar cane
81. 81. 81 Positive Hybrid Effect Synergy in Properties Cellulosic Interfaces Silane and Other Interfaces Shear to Tensile Strength Ratios Fracture Behaviour Crack tip blunting, Fracture energy Underlying Mechanisms
82. 82. 82 The future ? Extracting fibre without damage Effective coupling agents cellulose chemistry instead of silanes Environmental durability barriers to prevent moisture absorption sterilize fibres to prevent biodeterioration to improve fatigue life Natural composites for durable use and short term use Chemical process and cost considerations Aircraft interiors applications !
83. 83. 83 Aircraft Interiors So natural composites are destined to fly high !
84. 84. 84 The Rig Veda There were impregnations, There were powers, There was energy below, There was impulse above -Rig Veda, Existence, 10.129.5 Krishi Mandala