lcm processing and characterization of cnt … processing and characterization of cnt modified fibre...
TRANSCRIPT
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LCMProcessingandCharacterizationofCNTModifiedFibreReinforcedComposites.
M.UbaidUllahKhalid
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WHOAMI?
Graduation: B.ScPolymerEngineeringfromUniversityofEngineeringandTechnologyLahoreSession:2006to2010
Post Graduation: M.ScPolymerTechnologyfromHochschuleAalenandUniversittBayreuthSession2011to2013
Professional FibreCraftIndustriesAffiliation: FromAugust2010toFebruary2011
May2013topresent
CoreAreaofInterest:Thermosettingresinsbased FibreReinforcedcomposites
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WHATISFIBRECRAFTINDUSTRIES?Intro: Pioneerinthefieldofadvancedandhigh
performancecompositesinPakistan.
Founded: 1985
Where: Lahore Pakistan
Staff: >150skilled
Annualsales: Rs.230million
Customers: OilandGassectorChemicalprocessingindustryMarineindustryElectricalDistributionCompaniesDefenceorganizationsPowerPlantsSecurity Forces
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OurBrandsOurBrands
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ProcessesandProducts
Processes ContactMolding Pultrusion(Pultron) Pulwinding SMC RollWraping FilamentWinding(McleanAnderson) VacuumInfusion RTM(PlastechUK) Extrusion(Leistritz) Thermoforming
FRP/GRPPipes
HumiditycontrolledHumiditycontrolledEnclosures/Containers
CoolingTowers
upto90,000voltsLadders,safe
upto90,000volts
DoubleHull
boats
DoubleHullUnsinkable
boats
FilamentFilamentwoundtanksupto100,000
liters
Fanblades
windmills
FanbladesforCoolingtowers/windmills
PortaCabins
CustomizedFRP/GRPfabricationsbasedoncustomersneedsand
requirements.
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WhatwillIdiscuss?
LCM Processing and Characterization of CNTModified Fibre Reinforced Composites.
WhatareCNTs?
InfluenceontheMechanicalPropertiesofNanocompositesandHybridComposites.
MechanismsoffailureinCNTmodifiedcomposites.
HowtoinsertCNTsintoHybridComposites.
HowtodeterminewhetherCNTsareequallydistributedinthecomposite.
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Introduction
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DemandofComposites
Growthopportunitiesinglobalcompositeindustry,20122017;ChuckKazmierski,Lucintel(2012)
Annualincreaseof8.2%inthedemandof
composites.
Aerospace
Automobile
Wind energy
Construction
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Anisotropyincompositeproperties
KimandKhan(2011),IJASS(12),115133RajoriaandJalili(2005),CompositeScienceandTechnology(65),20792093Yadamaetal.(2006),CompositesPartA(37),issue3,385392
Limitationsrelatedtocompositesproperties
In plane properties > Out of plane properties
Fatigue Damping Interlaminar properties Delamination characteristics
Matrix / interface dominatedfailure Delamination caused
under comrpression
Introduction
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ZBindingofinplanefibers
Stateoftheart
Improvingmatrixdominatedproperties
APMouritz(2004),JournalofMaterialsdesignandApplication,PartLFanetal.Composite:PartA39(2011)
/10 /
CNT as interlaminar reinforcement
Improving through thickness properties
Rubber modification
Thermoplastic toughening 3D fibers Z-binding Nanofillers
Carbon nanotubes
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CarbonNanotubes
Iijima,Nature(1991)Vol.354(6348),5658Demcyzketal.(2002),MatSci&EngA334(12):173178TohoTenaxEurope
Graphenesheetsrolledintoconcentriccylinders. SynthesizedbyIijimain1991.
Features: Outstandingspecificsurfacearea(~1300m2/g). Excellentelectrical(105107 S/m)andthermal(>3000W/mK)conductivities.
Properties of Carbon Nanotubes compared with other materials
Material Young's Modulus
[GPa]
Tensile Strength [GPa]
Elongation [%]
SWCNT 1054E - 5000T ~126T ~16E
MWCNT 800 950E ~150E -Carbon fiber ~430 ~5.3 1.5 - 2E-Glass Fiber ~73 ~2.2 ~3,5Epoxy ~3.5 0.08 1 - 10
Single walled and Multi walled CNTs
E- experimental result,T- theoretical results
Introduction
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Stateoftheart
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IntegratingCNTsintoFRPs
Bekyarovaetal.((2007)LangmunirVol.23,39704Jinetal.(2012)I&EC,Vol.51(13),49274933Lietal.(2009),CompositesPartA;Vol.40(12),20042012
DirectgrowthofCNTsonfibersurfaceandElectrophoresis
Manufacturing of 3D fibers
Direct growth of carbon nanotubes on fibers.
Electrophoresis Transfer printing
Powder dispersion or interleaf toughening
Dispersion of carbon nanotubes in the interlayers.
Matrix modification
Direct mixing of carbon nanotubes in the matrix.
Cloth plyTows of MWCNTCovered fibers
Ni2+ C2H2
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Bekyarovaetal.((2007)LangmunirVol.23,39704Jinetal.(2012)I&EC,Vol.51(13),49274933Lietal.(2009),CompositesPartA;Vol.40(12),20042012
Manufacturing of 3D fibers
Direct growth of carbon nanotubes on fibers.
Electrophoresis Transfer printing
Powder dispersion or interleaf toughening
Dispersion of carbon nanotubes in the interlayers.
Matrix modification
Direct mixing of carbon nanotubes in the matrix.
CNT dispersion as an interlayer
StateoftheartIntegratingCNTsintoFRPs
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Bekyarovaetal.((2007)LangmunirVol.23,39704Jinetal.(2012)I&EC,Vol.51(13),49274933Lietal.(2009),CompositesPartA;Vol.40(12),20042012
Manufacturing of 3D fibers
Direct growth of carbon nanotubes on fibers.
Electrophoresis Transfer printing
Powder dispersion or interleaf toughening
Dispersion of carbon nanotubes in the interlayers.
Matrix modification
Direct mixing of carbon nanotubes in the matrix.
Direct mixing of CNTs into the matrix or matrix modification
StateoftheartIntegratingCNTsintoFRPs
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Liquidcompositemolding
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IssuerelatedtoCNT/epoxyprocessing
Greenetal.Composites:PartA40(2009)14701475Romhanyetal.MaterialScienceForumVol.589(2008)169274
FiltrationofCNTsbythereinforcementfabric. ResultsinlocalvariationinCNTcontent.
CNTfiltrationvisibleonaglassfiberlaminateproducedusingRTM.
Intra tow filtration
Inter tow filtration Aim:Determination / Evaluation of carbon nanotubes filtration.Aim:Determination / Evaluation of carbon nanotubes filtration.
CNT/Polymer
Agglomerates
(Not to scale)
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Whatstheplan?
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Processingandcharacterizationofhybridcomposites
Manufacturing of hybrid composites. Processing method: Liquid composite molding
Development of effective physical characterization methods. Evaluation of filtration.
Determination ofmechanical properties. Role of carbon nanotubes on fracture mechanisms.
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Approach
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Projectbreakdown
Intrinsic properties of CNTs Electrical & Thermal conductivity Mechanical properties Distinct vibrational modes
Nano- / Hybrid compositesProcessing :Dispersion HomogeneityCharacterization : Physical
Based on intrinsic properties of CNTs
Mechanical Nanocomposites Hybrid composites
Carbon Nanotubes
Nanocomposites
200nmGlass fiber
Matrix
Hybrid composites
Processing&
Characterization
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Materialselection
Materials
DOW,LiquidEpoxyresins(Brochure)
DGEBA n=0.15,functionality =2
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Epoxy DER 331 (Resin) EC5430 (amine hardener)Matrix
BAYTUBES (Multi walled CNTs) with different surface functionalitiesCarbon nanotubes
E-Glass fiber fabric 701 g/m2 (Non woven unidirectional)
Layup [0]2s, [0]3sReinforcement
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Results(CNT/epoxynanocomposites)
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Flexuralproperties
DINENISO178Crossheadspeed2mm/min
Neatepoxy(top),CNT/epoxy(bottom)
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,80
20
40
60
80
100
120
140
160
180
Bending Strength
Bend
ingM
odul
us /
MPa
Bend
ing
Stre
ngth
/ M
Pa
Concentration / wt.%
0
400
800
1200
1600
2000
2400
2800
3200
3600
Bending Modulus
10 m
Significant improvement by just 0.1 wt.% CNT. Slight reduction after 0.5 wt.% due to tube-tube contacts. Clearly altered fracture surface.
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0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,00,0
0,2
0,4
0,6
0,8
1,0
1,2
Critical stress intensity factor Stiffness from Saxena and Hudak method
Concentration / wt.%
K Ic
/ MPa
m
0
600
1200
1800
2400
3000
3600
ESH
/ N
/mm
Results(CNT/epoxynanocomposites)
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Fracturetoughness
ISO13586,CTspecimenTestspeed:10mm/min,1NPreload
Remarks: Slightimprovementin
fracturetoughness. Materialinhomogeneities
affectingthetoughness. Stiffnessremained
unaffected.
Neatepoxy(left),CNT/epoxy(middle&right)
10 m 100 m 5 m
Agglomerates
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Micromechanicsmodellingapproach
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Thostenson&ChouJ.Phys.D:Appl.Phys.36(2003)573582
Thostenson and Chou Modification for random orientation of CNTs
NomenclatureENC Stiffness of nanocompositeENT Stiffness of nanotubeEm Stiffness of matrixt Thickness of graphite layerNT Nanotube contentAR Aspect ratiol Length of nanotubed Diameter of nanotube
Halpin Tsai for parallel orientation of
glass fiber
Thostenson and Chou for parallel
orientation of CNTs
Thostenson and Chou for random
orientation of CNTs
Halpin Tsai for random orientation of
glass fiber
Modification by Thostenson & Chouregarding the eff.geometry of CNTs
),,,,,,( NTNTmNC tdlAREEfE
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Results(CNT/epoxynanocomposites)
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Micromechanicsmodelling PotentialofCNTs
Thostenson&Chou(2003),JournalofPhysics,Vol.36,Iss.5
0 400 800 1200 1600 2000 2400 2800 32000
10
20
30
40
50
60
70
80
CNT Length / nm
SWCNT
DWCNT
MWCNT
CNT diameter
0.7 nm
1 nm
2 nm
4 nm
10 - 21 nm
Drawback:The models do not consider: Agglomeration Tube-tube contacts CNT straightness
Diameter plays a more important role than the aspect ratio and smaller
diameter tubes have higher reinforcement capability.
For CNT content of 0.5 wt.%.
0 100 200 300 400 500 6000
5
10
15
20
25
30
35
40
Aspect Ratio
CNT diameter1 nm
2 nm
4 nm
10 - 21 nm
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Results(CNT/epoxynanocomposites)
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Dynamicmechanicalanalysis
TorsionRectangular,Temp=150oCto170oC,T=3K/min,Strainamplitude=0.1%ResultsaveragedforthreesamplesRajoriaetal.(2005)CompSciTechVol.65(14):20792093
-120 -90 -60 -30 0 30 60 90 120 150
G' /
Pa
Neat epoxy
106
107
108
109
1010
fCNT/epoxy (0.5 wt.%)
Temperature / C
fCNT/epoxy (1.0 wt.%)
G" /
Pa
Stick-slip Mechanism
Enhanced loss modulus due to stick slip mechanism.Energy lost due to interfacial friction.
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Results(CNT/epoxynanocomposites)
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Dynamicmechanicalanalysis
TorsionRectangular,Temp=150oCto170oC,T=3K/min,Strainamplitude=0.1%Differencecalculatedat25CResultsaveragedforthreesamples
-120 -90 -60 -30 0 30 60 90 120 150
G' /
Pa
Neat epoxy
5,0x108
1,0x109
1,5x109
2,0x109
2,5x109
3,0x109
CNT/epoxy (0.5 wt.%)
Temperature / C
CNT/epoxy (1.0 wt.%)
-20 0 20 40 60 80 100 120
2,0x107
4,0x107
6,0x107
8,0x107
1,0x108
1,2x108
1,4x108
G" /
Pa
Temperature / C
Neat epoxy CNT/epoxy (0.5 wt.%) CNT/epoxy (1.0 wt.%)
CNT content G improvement G Improvement0.5 wt.% 6 % 6 %1.0 wt.% 16 % 30 %
Values on a linear scale to highlight the differences.
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Liquidcompositemolding
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IssuerelatedtoCNT/epoxyprocessing
Greenetal.Composites:PartA40(2009)14701475Romhanyetal.MaterialScienceForumVol.589(2008)169274
FiltrationofCNTsbythereinforcementfabric. ResultsinlocalvariationinCNTcontent.
CNTfiltrationvisibleonaglassfiberlaminateproducedusingRTM.
Intra tow filtration
Inter tow filtration Aim:Determination / Evaluation of carbon nanotubes filtration.Aim:Determination / Evaluation of carbon nanotubes filtration.
CNT/Polymer
Agglomerates
(Not to scale)
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Processinghybridcomposites
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Lengthdistributionanalysis(Strategy)
Conc.ofCNTs0.1g/literSolvent:Tetrahydrofuran(THF)
Resin Injection Point
Resin Injection Point
VacuumVacuum
THF + Uncured CNT/Epoxy
THF + Uncured CNT/Epoxy
Length of carbon nanotubes was measured using the TEM micrographs.
CNT/epoxy dissolved into THF.
Two samples; before injection and after injection.
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Results(CNT/epoxynanocomposites)
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LengthdistributionanalysisTotalnanotubescount>400
0 200 400 600 800 1000 1200 1400 16000,000,020,040,060,080,100,120,140,16
Before Injection
Norm
aliz
ed F
requ
ency
0,00,20,40,60,81,01,21,41,6
Com
mul
ativ
e no
rmal
ized
freq
uenc
y
0 200 400 600 800 1000 1200 1400 16000,000,020,040,060,080,100,120,140,16
Nanotube Length Class / nm
After Injection
0,00,20,40,60,81,01,21,41,6
No evidence of filtration was observed.
Only the filtration based on CNT length
was evaluated.
TEM micrograph
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Overview
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Ramanspectroscopy
Dresselhausetal.Philosophicaltransaction(2004)Vol.36220652098
D-Band is associated to non-graphitic rings.
D is an overtone of D-band.
D-bandG-band
D-band
Radial breathing modesare more promienent inSWCNTs.
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Results(Ramanspectroscopy)
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RamanspectroscopyofCNT/epoxynanocomposite
Dresselhausetal.Philosophicaltransaction(2004)Vol.36220652098
400 800 1200 1600 2000 2400 2800 3200 3600 4000
0
25
50
75
100
125 Spectrum of MWCNT/epoxy
Ram
an in
tens
ity
Wavenumber / cm-1
~1330 cm-1 (D-band)~1590 cm-1 (G-band)
~2660 cm-1 (D'-band)(overtone D-band)
~3065 cm-1Aromatic stretch
~1610 cm-1
aromatic ring stretch
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Results(Ramanspectroscopy)
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Calibrationcurve
Ramanspectroscopycandetectconcentrationdifferencesmorepreciselythanothertechniquese.g.TGA,FTIR,thermalandelectricalconductivity.
400 800 1200 1600 2000 2400 2800 3200 3600 40000
20
40
60
80
100
120
140
160
180
Ram
an in
tens
ity
Wavenumber / cm-1
0.5 wt.% CNT 0.05 wt.% CNT
D-Band from CNTs
Aromatic band
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,90,0
0,4
0,8
1,2
1,6
CNT Content / wt.%
Band
ratio
: int
.~26
60cm
-1 /
int.~
3050
cm-1
Equation y = 2.18 * x
ConfocalRamanmicroscope(objective10x)Linearpolarizedlazer(HeNe=632.8nm)10measurementsaveragedforonespectrum
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Results(Hybridcomposites)
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CNTcontentinhybridcomposites
ConfocalRamanmicroscope(objective10x)Linearpolarizedlazer(HeNe=632.8nm)10measurementsaveragedforonespectrum
Slight tendency of filtration along the resin flow path.
0 4 8 12 16 200,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
1,6
Band
ratio
: int
.~26
60cm
-1 /
int.~
3050
cm-1
Matrix flow length / cm
0,0
0,2
0,4
0,6
CNT
con
tent
/ w
t.%
Equation y = 1.01 - 0.01*x
Flow
pat
h0
cm --
------
-18
cm
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Results(Hybridcomposites)
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Dynamicmechanicalanalysis
TorsionRectangular,Temp=150oCto170oC,T=3K/min,Strainamplitude=0.1%ResultsaveragedforthreesamplesKhanetal.(2011)CompSci&Tech,Vol.71,14861494
CNTcontentofonly0.5wt.%showingremarkableimprovementinhybridcomposites.
Improvementindampingwhichisimportantforfatiguelifeofcomposites.
108
109
1010
Hybrid composite
-100 -50 0 50 100 150
Fiber reinforced composite
G' /
Pa
Temperature / oC
13 % increase
15 % increase
-150 -100 -50 0 50 100 150 200106
107
108
109
G" /
Pa
Temperature / oC
Hybrid composite
21 % increase
Fiber reinforced composite
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0 5 10 15 20 25 30 35 40 45 50 550
200
400
600
800
1000
1200
1400
1600
1800
GIc /
J/m
2
Crack Propagation Length / mm
CNT Modified Composite
Unmodified Composite
F
Results(Hybridcomposites)
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Interlaminarfracturetoughness(modeI)
ISO15024,CalculatedusingmodifiedcompliancecalibrationorMCC
Obervations: SlightimprovementinGIc. Enhancedfiberbridginginhybrid
composites.
40m
Hybrid composites
Fiber reinforced composites
40m
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0 5 10 15 20 25 30 35 40 45 50 550
200
400
600
800
1000
1200
1400
1600
1800
GIc /
J/m
2
Crack Propagation Length / mm
CNT Modified Composite
Unmodified Composite
F
Results(Hybridcomposites)
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Interlaminarfracturetoughness(modeI)
ISO15024,CalculatedusingmodifiedcompliancecalibrationorMCC
Obervations: SlightimprovementinGIc. Enhancedfiberbridginginhybrid
composites.
Hybrid composites
200nm
Slightly enhanced matrix toughness and unaffected fiber/matrix interface
Glass fiber
Matrix with CNTs
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Results(Hybridcomposites)
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ModeII,ILSSandTensile90o
DIN65563(modeII),DINENISO5275(Tensile90o),DINENISO14130(ILSS)
Fiber reinforced composites Hybrid composites0
10
20
30
40
50
60
70
80
ILSS
and
Ten
sile
Stre
ngth
90o
/ M
Pa ILSS Tensile 90o
GIIc
0
600
1200
1800
2400
3000
3600
4200
4800
GIIc
/ J/
m2
Fiber reinforced composites
Hybrid composites
20m
20m
Observations: Noimprovementinfiber/matrixinterface. Absenceofhacklesonfracturesurfaceinhybrid
composites.
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Summary
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MechanicalcharacterizationMaterial Approach/Aim Testing methods
Nanocomposites
Understanding of the mechanisms.
Modelled using the micromechanics modelling for CNT reinforced nanocomposites.
Fracture toughness Flexural testing Tensile testing DMA
Hybrid composites Evaluation of mechanical properties. Understanding of the mechanisms.
Tensile (0 and 90) mode I and II interlaminar
fracture toughness ILSS Compression testing DMA
ILSS and mode II
mode I
Tensile testing
Good understanding of mechanical and fracture mechanical mechanisms in nano- and hybrid composites was developed.
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Conclusions
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EffectivecharacterizationmethodsbasedonRamanspectroscopyandlengthdistributionanalysisweredeveloped.
Mechanicalandfracturemechanicalmechanismsinnano andhybridcompositeswereaprehended.
MicromechanicsmodelingwasdonetosignifytheroleofdifferentCNTstowardsreinforcementandthepotentialofCNTs.
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LiteratureoverviewofCNT/epoxynanocomposites
Gojnyetal.CompSciTech(2005)Vol.6523002313Martoneetal.CompSciTech(2011)Vol.7111171123
Criticalissues: Surfacefunctionality Dispersion Aspectratio Agglomeration
Gojny et al. 20050,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
0.5
wt.%
MW
CN
T- N
H2
0.5
wt.%
MW
CN
T- N
H2
0.5
wt.%
MW
CN
T
0.5
wt.%
MW
CN
T- N
H2
0.5
wt.%
MW
CN
T
Norm
aliz
ed V
alue
Tensile Modulus Tensile Strength Fracture Toughness
Whatothersdid!
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LiteratureoverviewofCNT/epoxynanocomposites
Gojnyetal.CompSciTech(2005)Vol.6523002313Martoneetal.CompSciTech(2011)Vol.7111171123
Rule of mixture :
Effective modulus of reinforcement :
fmfc EEE 1..
f
mcm
EEEE
TheoreticalmodulusofCNTs
E G
Pa
CNT content / vol.%
No systematicity in the literature.
Whatothersdid!
-
Inam et al.
2010
Wichmann e
t al. 2006
Godara et a
l. 2009
Seyhan et a
l. 2008
Romhany et
al. 2009
Warrier et a
l. 2010
Karapappas
et al. 2009
Tsantzalis e
t al. 2007
Sadeghian e
t al. 2006
Yokozeki et
al. 2007
Davis et al.
2011
Veedu et al.
2006
Khan and K
im, 2011
Garcia et al.
2008a0,0
0,5
1,0
1,5
2,0
2,5
3,0
1.0
0.5
0.50.3
MW
CN
T tr
ansf
er p
rintin
g
Buc
ky P
aper
2 w
t.% M
WC
NT
grow
n on
SiC
fabr
ic
Nor
mal
ized
GIc a
nd G
IIc
GIc GIIc
0.1 0.3
0.5
0.1
1.0 5.0
0.5
XD-C
NT
/41 /
LiteratureoverviewofCNTmodifiedFRPs
XDCNT:amixtureofSWCNTs,DWCNTsandMWCNTsCNTcontentinwt.%
DWCNT MWCNT CNF
No direct correlation between the CNT content and property modification exists.
Whathappenedearlier!