Composites from renewable
resources
Natural fibre reinforcement
Biobased thermosets matrix
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1
Life cycle for fossil materials
CO2
Combustion
0 to 10 years
Plants
Renewable
resources
Fuels
Plastics
1 000 000 000 years
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Crude oil
2
Life cycle for biobased
materials
Combustion
CO2
0 to 100 years
0 to 10 years
Plants
Renewable
resources
Fuels
Plastics
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3
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
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4
Historical development
Conducting
polymerers
High-temp
polymers
NATURAL
ORIGIN
MATERIALS
Wood
Skin
Fibers
Straw-brick
Paper
10 000 bC
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Polyesters
PE
Nylon
Bakelit
Natural rubber
Fishbone glue
Linoleum
Celluloid
Linseed oil paints
0
1800
1900
PP
EpoxyPVC resins
PS
Biopolymers
Carbon
fibres
Glass fibres
SYNTHETIC
MAN MADE
MATERIALS
1950
2000
5
Ref: www.ars.usda.gov/is/pr/1998/980209.htm
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ENERGY CONSUMPTION DURING
COMPOSITE PRODUCT LIFE-TIME
1%
USE
MANUFACTURE
99%
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Environmental impact of
composites
1. 99 % of all product related energy is
consumed during use, only 0.5 %
during production
2. The environmental impact for
composites is reduced by their
durability, low weight, and energy
efficient processing
3. Composites are by ¨defintion¨
environmentally friendly materials!
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8
Wood – a biobased composite
50 m
50 m
Matrix: Lignin and
extractives
Reinforcement: Cellulose
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9
Wood – a anisotropic composite
Y
X
Delamination in X direction
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No delamination in Y direction
10
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
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DDR’s Trabant
contained natural fibres
11
Why natural fibers?
Renewable
Abundant
Cheap
Light weight
Biodegradable
Non-abrasive to
processing
equipment
• CO2 neutral when
incinerated
•
•
•
•
•
•
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• Flexible and though
• Can be incinerated
with energy
recovery
• Good mechanical
stiffness
• Good acoustic and
thermal insulating
properties
12
In nature occurring fibers:
Plant fibers
• Flax
• Hemp
• Kenaf
• Jute
• Ramie
• Sisal
• Banana
• Coconut
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Animal fibers
• Chicken feathers
• Hair
1000 plants can be used for
manufacturing industrially
usable fibers…..
13
Use of natural fibres in composites in
the German automotive production
Market study by nova-Institut,
Germany
20000
45 000 tons of plant fibre NFCs
36 000 tons of wood fibre NFCs
79 000 tons of cotton fibre NFCs
17200
18000
18000
15100
16000
12200
Quantity (t)
14000
Totally 160 000 tons composites of
which 88 000 tons natural fibres
12000
9600
10000
8000
6000
4000
4000
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
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2000
0
1996
1999
2000
2001
2002
2003
Total
4000
9600
12200
15100
17200
18000
Hemp
0
300
1200
1600
2200
2300
Exotic (Jute, Kenaf, etc.)
2000
2300
2000
5000
6000
6300
Flax
2000
7000
9000
8500
9000
9400
14
Use of natural fibres
North America 2000
Car parts
8%
Other 7%
Industry
10%
Totally
200 000 ton
(7 % of reinforcement and filler
market volumes)
700 000 ton 2005
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Construction
75%
15
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
1.4-1.5
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Production of plant fibers
Fibre
Price comp. to
glass (%)
Jute
18
Production
(1000 t)
3600
E-glass
100
1200
Flax
130
800
Sisal
21
500
Banana
40
100
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Data from 1993
17
Composition of different
cellulose based natural fibers
Cotton
Jute
Flax
Ramie
Sisal
Cellulose
82.7
64.4
64.1
68.6
65.8
Hemicellulose
5.7
12.0
16.7
13.1
12.0
Pectin
5.7
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
0.6
0.5
1.5
0.3
0.3
Water
10.0
10.0
10.0
10.06
10.0
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Ref.: Bledzki, Prog. Polym. Sci. 24 (1999) 221
18
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
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•
19
The cellulose polymer
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OH up
Cellulose
OH down
Cellobiose repeating unit (-Dglucose)
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
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Compatibilization
by maleic anhydride modified
polymers
Maleated polymer
O
H
HO
H
H
H
O
H
O
HO
O
H
O
HO
OH
H
OH
H
O
HO
OH
H
H
O
O
HO
O
O
HO
O
O
O
H
H
HO
Maleated polymer
HOOC
O
O
H
H
H
H
H
H
H
OH
H
beta-D-glucose
beta-D-glucose
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Flax
(Linum usitatissimum)
A bast fibre
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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
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World-wide cultivation area for flax fibres
Total area:
China:
France:
Belarus:
Russia:
the Netherlands:
Belgium:
Ukraine:
Lithuania:
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386 000 ha
132 500 ha
66 000 ha
40 000 ha
30 000 ha
16 300 ha
14 500 ha
9 300 ha
5 000 ha
Data from FAOSTAT 2000
25
Flax cultivation output kg/ha:
Raw flax
Rippled flax
Seeds
Long fiber
Short fiber
Total fiber
kg/ha
7950
6150
750
1560
290
1850
local variation
5 860 – 10 510
4 560 – 8 480
570 – 985
1 310 – 1 930
200 – 420
1 510 – 2 360
Data from Belgium cultivation tests 2002
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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
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Air-laid insulation
Scutching
Scutched fibre bundles
Short fibre tow
Flax fibre
processing cycle
Hackling
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Long
fibre line yarn
Spun yarns
Carding
Spinning
28
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:
1.
2.
3.
4.
5.
Shorter retting time
Better fibre yield
Better fibre strength
Environmentally friendly process
Well-controlled and reproducible
method
6. Efficient method
7. Reduction of processing costs
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Photo: FinFlax Ltd
29
SEM surface analysis of enzyme and
field retted flax fibres
Field retted fibre, 1000X
Enzyme retted fibre, 1000X
Technical fibre, 50 – 100 m
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Kenaf (Hibiscus cannabis)
• Grows 4 m in 7 months
• Packaging materials,
paper, oil-absorbents
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Jute (Corchorus casularis)
• Short, inelastic fibres
• Carpet backing, sacks,
wall coverings, floor
coverings
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SISAL PLANTAGE
Photo by Kristiina Oksman
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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
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34
Palltruder®
Production of wood plastic omposites
K2004
Exhibition,
Düsseldorf
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www.pallmannpulverizers.com
35
Extrusion line for wood polymer
composite profiles
K2004
Exhibition,
Düsseldorf
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36
Construction materials
•
•
•
•
•
•
•
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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
37
Car parts from natural fibres
•
•
•
•
•
•
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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
38
TEXFLAX European project
Flax yarn
Flax fabrics
Flax fibre
Flax cultivation
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Composite product
Composite laminates
39
TEXFLAX Demonstrator prototypes
Sandwich
panel
Bicycle helmet
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Vacuum
infused lid
Flower pot
Water tank
40
Design and biocomposites
OLD CONCEPTS – NO DESIGN!
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NEW CONCEPTS – WITH DESIGN!
41
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
Electic guitar by Flaxwood
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www.kareline.fi
42
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
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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
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Biobased thermosets
Biobased thermoplastic polymers
(such as polylactic acid) are
commercially available, but have
minor importance in composites, so
they are not discussed here
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45
Biobased polymers: two strategies
1.
Polymers formed in biomass
during life cycles of green
plants, animals, bacteria and
fungi
•
•
2.
Natural polymers: proteins, chitin,
polyesters produced by bacteria,
lignin, carbohydrates …
Extraction, processing, reactive
modification is needed to obtain a
thermoset
Chemicals extracted from
biomass
•
•
•
Vegetable oils, lactic acid,
bioethanol,….
Many sources: grown crops, byproducts and waste from pulp and
paper, food production, municipal
waste streams,…
Thermoset polymers can be
synthesised, with varying biomass
content
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Silk
Bacterial PHB
Lactic acid from corn
46
Biothermosets are possible
to make from:
• Carbohydrates: sugars, starch,
cellulose
• Lignin
• Vegetable oils: linseed oil, soy oil,
olive oil, corn oil, palm oil
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Lignin structure
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TransFurans Chemicals BioRez
furanic resins
•
•
•
•
•
Furfural is obtained by
hydrolysis of
hemicellulose
10 wt-% of a plant
carbohydrate content
can be converted to
furfural
Annual production 450
000 tonnes 2004
(Wikipedia)
Furfural and furfuryl
alcohol can be reacted
with phenols to a
thermoset
Processing and
properties like
phenolic resins
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www.furan.com
49
Polylactide oligomer
thermoset
C=C group
• Branched lactic acid
oligomer terminated
with methacrylic groups
• Free radical
polymerisations with or
without reactive
solvents
• Developed by JVS
Polymers (Jukka
Seppälä)
• POLLIT, LAIT-X
products
• www.jvs-polymers.fi
J Appl Polym Sci 86 (2002) 3616
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Core
molecule
Lactide branch
50
Polylactide thermoset
synthesis
1. Formation of lactide
arm
2. Formation of
branched structure
3. Functionalisation to
get reactive
4. Crosslinking by free
radical
polymerisation
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Office chair demonstrator
• Natural fibres
• Non-wovens;
cellulose,
wool, flax
• Woven
fabrics; flax,
jute, hemp
• Thermosets
• POLLIT resin
• Cognis Tribest
• Processing
• Prepreg
• Compression
moulding
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Vegetable oils
• One of the oldest chemical raw materials still
used by humans in technical applications
• Plant oil annual consumption around 100
million tonnes in 2000
• Reactive double bonds in some oils: Linseed
oil: an old binder in paints
• Linoleum carpet 1860
• Curing by oxidative drying
• Chemical modification (epoxidation)
increases reactivity
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Plant oils are triglycerides
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Fatty acids
Linear saturated or unsaturated acids
O
OH
Stearic acid - a C18 saturated fatty acid
O
OH
Linoelic acid – a C18 unsaturated fatty acid
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Plant oil composition is varying in different plants:
Typically 14 to 22 carbons in length and 0 to 3
unsaturated double bonds per fatty arm
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Epoxidation of soy-oil
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20111107
Ref: Chemtech
1999
57
A triglyceride is a ester of glycerol
and fatty acids
Fatty acid
O
O
O
O
O
O
Glycerol
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Esterbond
58
Reactive sites in the triglyceride can be
functionalized into a cross-linking site
The allylic carbons
O
O
O
O
O
O
The ester groups
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The double bonds
59
University of Borås development:
Resins based on soybean oil
Methacrylate group
O
O
O
O
O
2
3
OH
3
3
O
O
3
O
O
O
O
O
O
3
3
O
2
O
OH
O
O
O
O
O
O
O
O
O
O
O
O
7
OH
O
O
O
7
Methacrylic anhydride modified soybean oil
Methacrylated soybean oil
O
O
O
O
O
O
O
O
O
2
3
O
3
3
O
O
O
O
O
O
7
O
Acetate group
O
Acetic anhydride modified soybean oil
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Henry Fords soybean car
Description:
• Presented August 13, 1941
• 14 plastic panels
• 35 % weight saving compared to
steel cars at that time
• Soybean resin, hemp, flax, ramie
or soy bean fiber, phenolic resin
Motivation:
• Utilise agricultural products in
industrial products
• Safer car with plastic panels due
to toughness
• Shortage of metals
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Source: www.thehenryford.org
61
Green racing car concept from
University of Warwick, UK
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Ashland ENVIREZ® resins
• Soy bean oil based thermoset,
ethanol containing
• Peroxide curing
• Developed for John Deere
farming machines
• Biobased content: 12 wt-% -to
21 wt-%, will be increased
• Can be processed by all
common methods; lamination,
infusion, SMC/BMC, casting,
pultrusion
• Available in Europe and US
Campion Marine, Canada
www.campionboats.com
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Glycerin is a potential chemical feedstock
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AMROY EUROPE OY EpoBiox
• Biobased epoxyresin
• Phenols from pulp
processing are converted
to Bisphenol A (not food
biomass!)
• Epichlorhydrine made
from plant oil glycerol
• 50 to 90 wt-% biobased
content
• Different viscosity
grades available
• 4000 tonnes production
capacity in Finland
• www.amroy.fi
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DSM Palapreg ECO P 55-01
• An vinyl ester resin (?)
• 55 % of the raw
material from bio
sources
• SMC and BMC
applications
(automotive)
• Low shrink, equal
mechanical performance
compared to oil based
resins in the application
www.dsm.com
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O
CH3
O
O
O
O
+
HO
CH3
CH3
CH3
CH3
O
O
O
OH
OH
O
O
O
CH3
CH3
67
ASTM D6866: BIOBASED CONTENT IN A MATERIAL
• Biobased content: the fraction biobased carbon (14C) of the
total organic carbon content
• In atmosphere the CO2 carbon is both isotopes 12C and 14C
• Half life of 14C is 5730 years
• Fossil feed stock will not contain any 14C isotope
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Challenges for biomass based
composites
RAW MATERIAL SOURCE
-Fibre
- Bioresin
PROPERTIES &
PERFORMANCE
-Fibre
- Bioresin
-Composite
-End product
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PRODUCTION
-Fibre production
- Bioresin production
-Composite production
-End product production
MARKETING & SALE
-Product performance
-Customer expectations
-Govermental directives
-Public opinion
69
BIOMASS
FOOD
-Agricultural
-Animal production
-Fish production
-Wild animal hunting
Produced by photosynthesis
Very large annual production
Clean, effecient, high capacity,
complex chemicals
INDUSTRIAL
USE
-Pulp&paper
-Textiles
-Building material
-Natural chemicals &
Resins
-Fuel
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ECOLOGICAL
USE
-Preservation of
ecosystems
and wild life
-Needed for keeping
climate balance
RECREATIONAL
USE
-Tourism
-National parks
70
Genetic modification?
• For tailoring plants to produce
industrially usable raw materials
• Ex: starch from potatoes, regulation
of oil types in oil plants
• Consumer concerns and green
movement are critical
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71
Necessary developments:
• Fibre processing techniques into technical
reinforcements
• 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
MSK 20111107
72
Biobased composites questions:
• A chemical processing is often necessary
• Plant genetic modification can be necessary
• Environmental effect must be evaluated by
life cycle analysis
• Should the agricultural area be used for
food or raw material production?
• Today's highly effective agriculture affects
the environment
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