An introduction to bio resin based natural fibre composites and their applications

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
Mythology

3. 3
Bottom up and
Top down Philosophy

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
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
Kajal or Mai- the home made
nanocarbon from castor oil !
Nanocarbon structures are present in the soot !

7. 7
Natural Materials
-The Basics

8. 8

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
Base Bio vs. Base Fossil
10

11. 11
Triangulo de
Campbell
NF Must be Sustainable

12. 12
External Forces Shaping the Natural
Fibre Composites Industry

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
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
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
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
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
Uses
• Car bodies
• Less weight = greater fuel economy
• Toys
• Luggage
• Building material
• Aerospace
• Medicine
• Agriculture
• Bicycles
• Consumer products

19. 19
Bio-derived
Thermoplastics and
Thermosets

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
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
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
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 5 h 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
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
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
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
Composition of CNSL

28. 28
CNSL Matrix Material

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
Natural and
Bio-derived Fibres

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
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:
Piaçava
Imbira
Caroá

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
Chemical Composition of Some
Vegetable Fibres

35. 35
Main physical properties of cellulose based fibres
compared with conventional synthetic fibres

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
Natural Fibre Cross Section
Confocal Laser Scanning
Microscope (CLSM) images
Non-uniform cross sections
provide interesting interfacial
properties and other mechanical
properties

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
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
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
Nettle (Urtica dioica)
• Nettles yield ~ 8-10 tonnes fibre/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
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
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 world’s largest producer of
Bananas
• Mercedes Benz uses banana fibre
reinforced composites for the car interiors-
it is myth that natural composites can’t be
used in high end applications !

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 1–4 metres (3–13 feet)
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
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
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
Silk fibre properties

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
Spider Silk

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
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 µm 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
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
Wood as a filler: Plastic
Industry’s
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
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
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
Biodegradability

57. 57
Life cycLe of ‘GReeN’
biodeGRadabLe pLastic
mateRiaL

58. 58
Applications

59. 59
Cow Dung Composites

60. 60
Bio plastic Tableware,
Cutlery and Utensils

61. 61
Totora – Huros at Lake Titicaca

62. 62
Silk Sarees

63. 63
Footwear and Carpets

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
Wood
Filled

66. 66
Wood Filled PP Products

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
Foaming Expands
Possibilities For wood Fibre /
PP Composites
A bio resin derived foam
can be used in aerospace,
automobiles , damping &
insulation applications

69. 69
PVC / Wood Composites

70. 70
A Bamboo Bicycle

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 world’s first car with an FRP body –
courtesy Ford Motors

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
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
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
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
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
Example - Door panel made from sisal/Polyurethane

78. 78
Example
dashboard support made of 30%
sisal fibre reinforced polypropylene

79. 79
Polypropylene Developments
Wood Filled Repol PP
for Door Trims

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
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
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
Aircraft Interiors
So natural composites are destined to fly high !

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