LCM Processing and Characterization of CNT … Processing and Characterization of CNT Modified Fibre...

LCMProcessingandCharacterizationofCNTModifiedFibreReinforcedComposites.

M.UbaidUllahKhalid

/2 /

WHOAMI?

Graduation: B.ScPolymerEngineeringfromUniversityofEngineeringandTechnologyLahoreSession:2006to2010

Post Graduation: M.ScPolymerTechnologyfromHochschuleAalenandUniversittBayreuthSession2011to2013

Professional FibreCraftIndustriesAffiliation: FromAugust2010toFebruary2011

May2013topresent

CoreAreaofInterest:Thermosettingresinsbased FibreReinforcedcomposites

/3 /

WHATISFIBRECRAFTINDUSTRIES?Intro: Pioneerinthefieldofadvancedandhigh

performancecompositesinPakistan.

Founded: 1985

Where: Lahore Pakistan

Staff: >150skilled

Annualsales: Rs.230million

Customers: OilandGassectorChemicalprocessingindustryMarineindustryElectricalDistributionCompaniesDefenceorganizationsPowerPlantsSecurity Forces

OurBrandsOurBrands

/5 /

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.

WhatwillIdiscuss?

LCM Processing and Characterization of CNTModified Fibre Reinforced Composites.

WhatareCNTs?

InfluenceontheMechanicalPropertiesofNanocompositesandHybridComposites.

MechanismsoffailureinCNTmodifiedcomposites.

HowtoinsertCNTsintoHybridComposites.

HowtodeterminewhetherCNTsareequallydistributedinthecomposite.

Introduction

/8 /

DemandofComposites

Growthopportunitiesinglobalcompositeindustry,20122017;ChuckKazmierski,Lucintel(2012)

Annualincreaseof8.2%inthedemandof

composites.

Aerospace

Automobile

Wind energy

Construction

/9 /

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

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

/11 /

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

Stateoftheart

/12 /

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

/13 /







Matrix modification


CNT dispersion as an interlayer

StateoftheartIntegratingCNTsintoFRPs

/14 /







Matrix modification


Direct mixing of CNTs into the matrix or matrix modification

StateoftheartIntegratingCNTsintoFRPs

Liquidcompositemolding

/15 /

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)

Whatstheplan?

/16 /

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.

Approach

/17 /

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

Materialselection

Materials

DOW,LiquidEpoxyresins(Brochure)

DGEBA n=0.15,functionality =2

/18 /

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

Results(CNT/epoxynanocomposites)

/19 /

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.

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


/20 /

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

Micromechanicsmodellingapproach

/21 /

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


/22 /

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


/23 /

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.


/24 /


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.

Liquidcompositemolding

/25 /

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)

Processinghybridcomposites

/26 /

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.


/27 /

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

Overview

/28 /

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.

Results(Ramanspectroscopy)

/29 /

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

Results(Ramanspectroscopy)

/30 /

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

Results(Hybridcomposites)

/31 /

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


/32 /


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

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


/33 /

Interlaminarfracturetoughness(modeI)

ISO15024,CalculatedusingmodifiedcompliancecalibrationorMCC

Obervations: SlightimprovementinGIc. Enhancedfiberbridginginhybrid

composites.

40m

Hybrid composites

Fiber reinforced composites

40m

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


/34 /

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


/35 /

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.

Summary

/36 /

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.

Conclusions

/37 /

EffectivecharacterizationmethodsbasedonRamanspectroscopyandlengthdistributionanalysisweredeveloped.

Mechanicalandfracturemechanicalmechanismsinnano andhybridcompositeswereaprehended.

MicromechanicsmodelingwasdonetosignifytheroleofdifferentCNTstowardsreinforcementandthepotentialofCNTs.

/39 /

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!

/40 /

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!

LCM Processing and Characterization of CNT … Processing and Characterization of CNT Modified Fibre...

Documents

Transcript of LCM Processing and Characterization of CNT … Processing and Characterization of CNT Modified Fibre...