A new natural reinforcement for polymer composite materials: … Vuure, AW.pdf · 2019-08-02 · A...
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A new natural reinforcement for polymer composite materials: Long Bamboo
fibres
Aart W. van Vuure, Lina Osorio, Eduardo Trujillo, Carlos Fuentes, Jan Ivens, Ignaas Verpoest
Department of Metallurgy and Materials Engineering,
Katholieke Universiteit Leuven
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First; what do we call polymer composite materials?
Fibre: reinforcement
Impregnate
Polymer: matrix
COMPOSITE
Consolidate
Light but weak
Light, stiff & strong
Light but stiff & strong!
• Long fibres give better mechanical properties
• Fibres typically Glass and Carbon
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Natural Fibres (and Bio-polymers): why?
3
Environmental reasons:
• Renewable resources
• Thermally recyclable, optionally biodegradable, CO2
neutral
• Natural fibres: Low energy consumption (low CO2 )
So: low “Carbon footprint”
0
20
40
60
80
100
120
140
lignocellulosicfibres
glass fibre carbon fibre
energy ( MJ/kg)
energy ( MJ/kg)mat
mat
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• Cost: often (potentially) low cost (not silk)
• Less abrasive
• Good specific mechanical properties (low density)
• Potential bio-compatibility for e.g. bio-medical applications
• Natural image, design aspects
• Others, like good acoustic & vibration damping, radar transparency, low CTE
Natural Fibres and Bio-polymers: why?
Specific tensile modulus E/rho (MJ/kg) for various fibres
0
20
40
60
80
100
120
140
Flax fibre Bamboofibre
Glass fibre Carbon fibre
Spec
ific
mod
ulus
(MJ/
kg)
Specific FLEXURAL modulus (E(1/3)/rho in N(1/3)m(7/3)/kg) for various fibres
0
0.5
1
1.5
2
2.5
3
3.5
4
Flax fibre Bamboofibre
Glass fibre Carbon fibreSpec
ific
bend
ing
mod
ulus
(N(1
/3)m
(7/3
)/kg)
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Good vibrational damping: Flax/Carbon hybrid bicycle frame
ISO2631:WholeBodyVibration
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Applications of bio-based composites; on the market
Museeuw/Lineo Flax-Carbonhybrid bike(JEC 2007);Prepregtechnology
Decathlon Artengo 820Flax/Carbon Fibre racket(prepreg Lineo)
Mixed NF – PPCar interiors
WoodPolymerComposites(WPC’s)e.g. deckings
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Applications of bio-based composites; prototypes
NPSP front-end train• flax-UP composite• vacuum injection• ~500 kg lighter than steelconstruction!
Toyota 1/X concept car (420 kg!):• Carbon Fibre frame• Roof of kenaf/ramie fibre composite
• heat and sound insulation• lightweight
Motive Kestrel electric vehicle•Launch 2012 in Canada?•Bio-based composite body
Prototype flax/PP (TU Delft)
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Natural Fibres, Quantities
Estimated annual production, in millions of tons:
Wood 1750
Steel 1000
Plastics/polymers 200
Composites (polymer) 5-10 mainly glass fibre composites
Glass fibre 2-4 (at 42% in composites)
Carbon fibre 0.050 (= 50,000 tons)
Synthetic fibres 30
Natural fibres 27 (large part cotton)
Flax fibres ~ 1.0
WPC 1.2
Plant fibre in composites 0.040 in automotive applications Europe
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Natural Fibres
PLANT / Lignocellulosic
FIBRES
Wood Stem/Bast
FlaxJute
HempKenafRamie
Leaf
SisalAbaca
PineappleBananaFique
HenequenPalm
Seed/Fruit
CottonCoconut
Grass
BambooRice
ANIMAL FIBRES (protein)
SoftwoodHardwood
SilkWool
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Main challenges for Bio-based Composites
1)
Fibre
properties:* Understanding structure (morphology) – mechanical property relationships
* Fibre off-axis properties: low transverse and shear properties
** Improve internal interface between elementary fibres
* Moisture sensitivity: Make fibres more hydrophobic? / seal them off (interface)
2) (Fibre) Processing• Extraction, yarn processing, preforming and prepregging
3) Fibre-matrix Interface:• Improving wetting and adhesion (surface energy matching)
4) Environmentally friendly matrices:* Biodegradable or Bio-based
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Bio-based Composites; Natural fibre properties; examples
Silk Composites have excellent falling weight impact performance!
Patent: WO 2007-110758 (with Hermès)
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MatricesClassification of matrices:
* Thermoplastic (TP) and thermoset resins (TS)
• Research on renewable matrices is relatively recent, especially for bio-thermosets
Examples of polymers Natural polymers:(renewable)
BIO-BASED
polymers (renewable feedstock, synthesized!):
“Synthetic” petroleum based polymers
Biodegradable Lignin PLAPHA, PHBStarch
PBSPCLPVA
Non-biodegradable Cashew nut shell resin (CSNL)
Furan resinVegetable oil -PUR (polyol)AESOEthanol based PESome nylons (PA-11)
Most well-known polymers:* PP, PE, nylons, etc.* Epoxy, UP
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Bio-based Composites; Developing environmentally friendly matrices
Development of renewable gluten based bio-polymers:
• Improvement of toughness & rheology
• Patent on thiol-based modifiers (WO 2004/029135)
• So far 50% improvement in strength and strain to failure (approaching epoxy)
Gluten
ResinBio-based
Polymer or CompositeMaterial
Controlled-releaseNitrogenFertilizer
Wheat
agriculture
Starch
industrialprocessing
recycling
chemical or(bio)catalyticmodification
polymerprocessing
Compost
composting
Thiol-terminated star-branched modifiers:Crosslinking + phase separation?
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Fibre processing research; Effect of twist on FLAX UD-composite stiffness (CELC)
-
35 % !!
Back-calculatedfibre stiffness(matrix=epoxy)
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Bio-based Composites; Fibre
processing
80‐100%
~50% !
Research in cooperation with CELC
Combined effect of twist and crimp on composite modulus
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Bio-based Composites; Paper honeycomb panels
Applications of ‘Torhex’ cardboard honeycombs; sandwich panels with NF composite skins
www.econcore.com
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Large Projects at SLC - BioComposites
•Cornet Nature Wins (with Centexbel and ITA Aachen)
Thermoplastic bio‐composites, flax/hemp + PLA
•
Mixed yarns & textiles / non‐wovens
•
Consolidation and thermoforming
•TIS Change2Bio (with VKC and Centexbel)“Renewable polymers – important element to develop the bio‐economy”
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Bamboo Fibre Composites
Culm with vascular bundles Technical
fibre(s)
• Bamboo fibres have excellent
mechanical properties
• Specific properties comparable to glass fibre
• Bamboo can grow to 20 m in 6 months
• Can fix 50-60 tons of C/ha.year
• Challenge is to extract technical fibres
Elementary fibres
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Bamboo Fibre processing
150
250
350
450
550
650
750
850
0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0
Extraction method
Stre
ngth
(MPa
)
Mechanical(rolling mill machine)
Chemical extraction(in some cases
mechanical process is required)
Steam explosion
Mechanical process(in some cases chemical process is required)
KULeuven process
Loop test
Bamboo Fibre
Extraction
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Bamboo Fibre properties
Single fibre tensile tests;
Corrected for system compliance
* E(extrapolated) ~ 44 GPa
New developments: * use of Digital Image Correlation (camera extensometer)
* Fibre bundle tests (dry + impregnated)
* Study of off-axis properties
E-modulus as f(1/test length), Single bamboo fibre testing
05
1015202530354045
0.00 0.05 0.10 0.15 0.20 0.251/test length (1/mm)
E-m
odul
us (G
Pa)
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Bamboo Fibre morphology (Lina Osorio)
4
3
Bamboo wallLiese, W., 1998Vascular bundleFibre
bundle
Bamboo culm Cross section
Elementary fibres
Vascular bundles have higher concentration towards the outside of the culm
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Bamboo Fibre morphology
Most elementary fibres seem to havea simple 2 layer structure
Next: Measurement of off-axis properties (tests on composites)
Primary layer with 90° orientation;from fracture surface
Secondary layer with 0° orientation;After etching away primary layer
5 μm5 μm5 μm
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Continuous UD prepreg
Discontinuous UD prepreg
Discontinuity of the fibre
Length of internodes
(± 25 cm)
Node
Internode
Bamboo fibre process development(Eduardo Trujillo)
Problem statement
UD prepreg with discontinuous fibres; continuous process?
UD bamboo fibre-polypropylene tape
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Technical fibre ~100 – 200 μm
Elementary fibre ~10 μmWith micro/nano fibrils:
Microstructure Surface
Chemical composition
Topography
Wetting
vapour
liquid
Micro balanc
e
F (μN)
R
Fibre
and matrix
Molecular kinetic theory
Equilibrium contact angle
SEC theories
Owens/Wendt
Dsv
Psvsv
Acid/base
cos1, iiL =)θ+(γ
)(2 ,,, SiLSiL
LWS
LWiL
Adhesion Improvement
Approaches:1. Make a good match
with untreated fibre:
Polyvinylidene fluoride (PVDF)
2. Treat the surface to get a good match:
Chitosan layer, Silanes
Interface Characterization
Streaming Potential
Micromechanical test: Pull-out tests
Flexural test: Transverse
3 point bending test
X-ray photoelectronspectroscopy (XPS)
AFM
Profilometer
Primary wall: 90°
orientation
Secondary wall: 0°
orientation
Understanding and improving the fibre-matrix interface;a combined physical-chemical-mechanical approach(Carlos Fuentes)
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Bamboo fibre surface analysis
0
10
20
30
40
50
60
70
80
0.0 0.2 0.4 0.6 0.8 1.0
C1/C (%)
O/C
O/C vs C1/C
Non‐autoclave treated bamboo
Autoclave treated bamboo
Theoretical Cellulose
Theoretical milled wood Lignin
Protobind 1000 Granit Lignin
Cellulose
Lignin
Measured Lignin
XPS results; courtesy C. DuPont, UCL
Extracted bamboo fibre surface seems to be covered with lignin
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Interface studies; Bamboo fibre composites
Bamboo fibre UD composites
R2 = 0.6963
0
5
10
15
20
25
40 45 50 55 60 65 70 75 80
Work of physical adhesion (mJ/m2)
Tran
sver
se 3
PB
str
engt
h (M
Pa)
Matrix: PP and PVDF (+ some treatments)
Results of Surface Energy Component matching; Effect of Physical Adhesion in thermoplastic composites
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Addition of chemical adhesion
Transverse 3 point bending strength for UD Bamboo-epoxy
15
20
25
30
35
40
45
0 1 2 3 4 5 6Alkali treatment (%) (20 min)
T3PB
(MPa
)
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Work of Adhesion versus Interface strength for coir composites
Chemical bonding dominant Physical adhesion
U = Untreated
T = Alkali treated
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Bio-based Composites; Fibre properties
Flax fibre property improvement* Fibre Treatment to Reduce Direct and Indirect Moisture Uptake
* Fibre Treatment to Improve internal fibre strength
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Bamboo Fibre Composite performance
COMPOSITE longitudinal flexural tests
Efficiency factor = measured property / theoretical property based on fibre properties
.... ..
Force
..
Efficiency factors in longitudinal flexural test
0
10
20
30
40
50
60
70
80
90
100
Efficiency factor strength Efficiency factor modulus
Effic
ienc
y fa
ctor
(%)
PPPVDFepoxy
+ Transverse 3 PB strength values
15 MPa
15 MPa23 MPa
33 MPa23 MPa
33 MPa
30
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Moisture resistance Bamboo fibres Moisture uptake of bamboo fibre at 23oC (from dry
condition)
02468
1012141618
0 20 40 60 80 100
Environmental relative humidity (%)
Moi
stur
e up
take
(wt%
)
Fibre moisture uptake,
Absorption isotherm
Moisture uptake is intermediate to literature data for (solid) lignin and cellulose
Diffusion coefficient [m2/sec]
Bamboo 1.04 x 10-10
Flax 1.25 x 10-8
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Moisture effects on Bamboo fibres
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Thermal degradation Bamboo fibre composites
Single fibres: Degradation starts around 170°C in normal atmosphere
Flexural strength and failure strain for UD bamboo fibre/thermoplastic composites at different processing
temperatures
020406080
100120140160180200220
0 0.5 1 1.5 2 2.5 3
Strain at maximum strength (%)
Stre
ngth
(MPa
)
PP/BF 175°C
PP/BF 185°C
MAPP/BF 170°C
MAPP/BF 180°c
.... ..
Force
..
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Concluding (Bamboo Fibre Composites)
• A promising fibre extraction process was developed for Bamboo Fibres• Next processing development is cleaning, stretching, aligning and prepregging• Most elementary fibres have predominantly 0 degree nanofibril orientation, combined
with an outer wrap of 90 degrees• Extracted bamboo fibre seems covered by lignin• Surface energy component matching allows improving physical adhesion; so far good
results with PVDF• There is a clear correlation between interface strength and UD longitudinal strength• Efficiency factors for epoxy reach 95% for modulus and 80% for strength• Moisture uptake is as expected intermediate to solid cellulose and lignin• Fibre strength and modulus are hardly affected by moisture; strain to failure is
affected (plasticisation)
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Thanks for your attention!
JEC 2012 Tradeshow in Paris: KU Leuven - SLC booth
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CompositesWeek@Leuven16-20 September 2013
The Composite Materials Groupof the Department of Metallurgy and Materials Engineering (MTM) of the
Katholieke
Universiteit
Leuven
(Belgium)cordially invites you to the
Three one-day symposia
on : •nano-engineered composites,
•designing with composites •bio-based composites
+the TEXCOMP 11
conference on textile composites
www.mtm.kuleuven.be/Onderzoek/Composites/Composietenwww.texcomp10.com