Carbon nanotubes and graphene nanoplatelets for multifor ... · composite fiber 3 Graphene3....
Transcript of Carbon nanotubes and graphene nanoplatelets for multifor ... · composite fiber 3 Graphene3....
Carbon nanotubes and graphenenanoplatelets for multi-functionalnanoplatelets for multi functional
composites
Dr. Aiping YuDepartment of Chemical EngineeringDepartment of Chemical Engineering
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Outline
1. Brief introduction to carbon nanotubes (CNTs) and graphene nanoplatelet
2 Single walled carbon nanotubes (SWNTs) Nylon 62. Single walled carbon nanotubes (SWNTs)- Nylon 6 composite fiber
3 Graphene epoxy composite3. Graphene-epoxy composite
4. CNTs/carbon fiber 3D matrix composite4. CNTs/carbon fiber 3D matrix composite
5. Work @ Sabic Innovative Plastics
6. Work @ UWIP
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Carbon nanotube & graphene nanoplatelet
1991-1993 2002-2005
:High mechanical strength and tensile modulus (Young’s modulus ~1TPa carbon fiber: 400-600 MPa conventional(Young s modulus 1TPa, carbon fiber: 400-600 MPa conventional
carbon fibers (200-800 GPa).Unique electrical properties (~1*105 S/cm )
Exceptional thermal conductivity (~3000 W/mK )
low density(~1.3-2g/ml) high aspect ratio (L/D~1000)y( g ) g ( )IP
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Synthesis of carbon nanotubesSynthesis of carbon nanotubes
Graphitecathode
C Ni-Y
Chemical vapor depositionArc-dischargeArc-dischargeIP
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Applying SWNTs & GNPs to polymersHigh mechanical properties
EMI shieldingAntistaticHigh mechanical properties
Against lighting strikeAgainst lighting strike
Nano-materials will bring revolution to industry
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Brief example-strongest polymer composite ever made
1.6
1.8
2.0 SWNT/PVA FiberSpider Silk
600
700
E
a
1.6
1.8
2.0 SWNT/PVA FiberSpider Silk
600
700
E
a
1.6
1.8
2.0 SWNT/PVA FiberSpider Silk
600
700
E
a
1.6
1.8
2.0 SWNT/PVA FiberSpider Silk
600
700
E
a
0 8
1.0
1.2
1.4
tress
(GP
a)
300
400
500
Energy Abso0 8
1.0
1.2
1.4
tress
(GP
a)
300
400
500
Energy Abso0 8
1.0
1.2
1.4
tress
(GP
a)
300
400
500
Energy Abso0 8
1.0
1.2
1.4
tress
(GP
a)
300
400
500
Energy Abso
0.2
0.4
0.6
0.8
True
St
100
200
orption (J/g)0.2
0.4
0.6
0.8
True
St
100
200
orption (J/g)0.2
0.4
0.6
0.8
True
St
100
200
orption (J/g)0.2
0.4
0.6
0.8
True
St
100
200
orption (J/g)0 10 20 30 40 50 60 70 80 90 100 110 120
0.0
Strain (%)
0
0 10 20 30 40 50 60 70 80 90 100 110 120
0.0
Strain (%)
0
0 10 20 30 40 50 60 70 80 90 100 110 120
0.0
Strain (%)
0
0 10 20 30 40 50 60 70 80 90 100 110 120
0.0
Strain (%)
0
Tensile strength matches spider silk and modulus (80 GPa) is much higher than spider silk
R. Baughman, 290,1310, Science, 2000
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N l 6/SWNT Ad d C itNylon 6/SWNT Advanced Composites--- mechanical/electrical enhancement
Yu,A. et at., J. of American Chemical Society 2005, 127, , y ,IPR 20
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Motivation and challengesMotivation and challenges
Nylon is a widely used thermoplastics owing to its good strength high elongation, excellent abrasion resistance, etcThere is need to improve the mechanical strength, toughness and electrical conductivityelectrical conductivity.
Highly hydrophobic surfaceg y y p
• Lack of functionality resulting chemical incompatibility with the polymer matrix and the self-aggregation of SWNTs into bundles due to van der Waals attractionvan der Waals attraction
• Homogeneous dispersion & SWNTs not pull out from polymerIP
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Strategy
Ensure efficient load transfer from the matrix to the fiber, the interfacial bonding between the polymer matrix and the carboninterfacial bonding between the polymer matrix and the carbon nanotubes is necessary to prevent fiber pull out
Controlled HNO3 treatment of SWNTs, brings –COOH to the end of SWNT
In-situ grafting PA6 chain to SWNT surface
Nylon matrixNylon matrix
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Step one: HNO3 treatment
1. SWNT surface hydrophilic2. Removed catalyst particles
Atomic Force Microscopy
40 AP-SWNT
0
20
al (m
V)
-40
-20 SWNTs-COOH
ta p
oten
tia
2 4 6 8 10-80
-60 AC
zet
2 4 6 8 10pH
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Step 2: In-situ grafting nylon 6 to SWNT
N H 2 (C H 2 ) 5 C O O HN H
O
O HO
in it ia to r S W N T sc a p ro la c ta m (m o n o m e r)
OH6,aminocaproic acid sonication, 80 oC
NH
Protonated monomer
H2N(CH2)5COO++ -
2. polymerization, 250 oC
H3N CHN C N
Hn
+ -250 oC
O
O
COO- nH2O Advantages:
OHO
+ H N CHN C N+ -
O
COO
No solvent PA6 grafted to SWNT
OH +
O H O
H3N C N C NHnO
COO
NH C N C NHn
-
OCOO
- nH2O
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Characterization of SWNTs with grafted Nylon 6
IR spectra samples prepared using different initiator concentrations
AFM of SWNT
0 0
different initiator concentrationsBefore
0.0
0.4
0.8
After
wt% initiator
1500 2500 3500
1640 cm-1 C=O group of the amide functionalityg p y1540 cm-1 combination of N-H bond C-N bond of the amide group
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In situ polymerization setup & fiber preparation
N2
Composite fibersComposite fibers
fiber spinneretLab reactor Cross-section IP
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Characterization of SWNTs-Nylon 6 composite
SEM TEMSEM
300 1.0
1.5
4 wt% SWNT in Nylon 61.51.0
Differential thermal analysis. Thermal decomposition T.
150
300
0.0
0.5
0.2
μg/M
in)
0
A
(μv)
0.50.2
0.0
0
150
wt% SWNT in Nylon 6
DTG
(μ
-4
DTA
420 440 4600
Temperature (oC)
150 200 250 300
Temperature (oC)
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Results of electrical conductivity
Samples @ 1wt % loading
Electrical conductivity@ 1wt % loading conductivity (S/cm)
PA6 graftedSWNT it
1.1E-6SWNT composite
Electrical conductivity data show:Th it i th ti t tiThe composites are in the anti-static range 1 wt % SWNT loading
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Mechanical properties of SWNTs-Nylon 6 composite
8 0
6 0
s (M
Pa) Pure N ylo n
0.1 wt% 0.2 wt%
%4 0
2 0
Stre
ss 0.5 wt% 1.0 wt% 1.5 wt%
0
4003 0020010 00 4003 0020010 00St ra in (% )
The PA6 grafted leads to 84 % increased tensile strength and 170%Young’s modulus (1.5 wt% loading)
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Modeling calculation of SWNTs-Nylon 6 compositeModeling calculation of SWNTs Nylon 6 compositeHalpin–Tsai modelIs widely used to predict the modulus of unidirectional or randomlyIs widely used to predict the modulus of unidirectional or randomly distributed filler-reinforced composites
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SummarySummary
The PA6 chains are found to be grafted to the SWNTs by aThe PA6 chains are found to be grafted to the SWNTs by a condensation reaction between the –COOH groups of the SWNTs and the terminal amino group of PA6
The grafted PA6 chains enhance the SWNT-nylon6 interfacial interaction and improve their compatibility, a homogeneous dispersion of the SWNTs in the nylon matrix
The Young’s modulus, tensile strength, and thermal stability of nylon 6 fibers are greatly improved by the incorporation of SWNTs via the process
p y
The composite is also anti-static in the pursued concentration rangeIPR 20
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Graphene/ Epoxy Resin Composites--- Thermal Interface Materials
Patent : US and WO patent: WO/2008/143692
Yu,A. ;Ramesh P. ;Itkis M.; Bekyarova E.; Haddon R., J. of Physical , ; ; ; y ; , yChemistry C 2007,111,7565-7569
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Composites: Thermal management in high density electronics
Source : Intel
With continued scaling of devices heat transport problems will most
Thermal interface material (TIM)
With continued scaling of devices, heat-transport problems will mostlikely be aggravated at all levels
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GNPs as fillers in epoxy matrix for TIMs
Thermal conductivity ofpolymer matrix: 0.2-0.4 W/mK
Requirements of TIMs:Thermal conductivity ≥ 2 W/mKLow thermal expansion
Conventional Particles: Using GNPs as filler
Low thermal expansion
SiO2, AlN, Ag
Ad f GNPAdvantages of GNPs • High thermal conductivity• High aspect ratio
L CTE
Disdvantages:Low aspect ratio • Low CTE
• Low density
Low aspect ratio high loading
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Schematic process to obtain GNPs
Natural graphite
IntercalationH2SO4/HNO3
Thermal shockExfoliated graphite
Physical processy pIP
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Microscopic observation of GNPs
(a) (b)
Optical Microscopic
800 oCC
Exfoliated graphite
400 oC
200 oCNatural graphite
0.5 mm5 mm
Scanning Electron MicroscopicIP
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AFM of GNPs
800 oC800 oC
Statistic size
L ~ 1.1 μm, t ~ 1.7 nm, AR = 200; 4 layer graphene (G4)
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GNP/epoxy composite
Epoxy: Diglycidyl ether of bisphenol A
Challenges: High loading nano-material dispersion
Epoxy: Diglycidyl ether of bisphenol A
H2C CH
CH
OO
CH3
O CH
CH
OH
CH
O
CH3
O CH
CH
CH2
O
H H2 CH3H2 H H2 CH3
H2 H
n
H2N NH2
CH3
Even in lab scale, mechanical stirring is not enough H2N NH2
CH2CH3CH3CH2
, g g
Curing agent: Diethyl-toluenediamineDiethyl-toluenediamine
Homogenizer:Shear mixing
Three roll mill
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Schematic show of the composite processSchematic show of the composite process
Shear mixing & sonicationin acetonein acetone
Shear mixing C li ki
Exfoliated graphite
Cross-linkingepoxy
Three-roll mill curing
GNP-Epoxy5 nm5 nm
p yCross section TEM image of GNP-Epoxy
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High resolution TEM of GNP in epoxy matrixg p y
1 nm
L ~ 1.1 μm, t ~ 1.7 nm, AR = 200; 4 layer graphene (G4)
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Thermal conductivity measurements:heat flow two thickness testingheat flow two thickness testing
Samplechamber
cooler
D i d di t ASTM C518 98
cooler
Designed according to ASTM C518-98From Lasercomp. Inc.
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Thermal conductivity of the GNP/epoxy composites
%)
7.0
)
Temperature dependence of
0.25 vol loading compositeThermal Conductivity vs GNP Ratio
3000
0.25 Vol6 44 W/ Knc
emen
t (%
0.2 Vol4.76 W/mK
T=30 oC
6.8
7.0
uctiv
ity (W
/mK
)
T-dependence of GNPs of 25 voL%
2000
6.44 W/mK
vity
Enh
an
6.4
6.6
Ther
mal
Con
du
1000
Con
duct
iv
20 30 40 50 60 70 80
6.4
Temperature (oC)
0.0 0.1 0.2 0.30
Ther
mal
GNP V l F ti H tGNP-Epoxy
Heat sink
GNP Vol Farction
• Linear increase of thermal conductivity with filler loading• Thermal conductivity up to (10 12 W/mK-40 Vol%)- suitable for electronic
Heat source
• Thermal conductivity up to (10.12 W/mK-40 Vol%)- suitable for electronic packaging, superior than conventional fillers• In the T range of computer run, performance is good
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Comparison of carbon fillers
600
700nt
(%)
500
600 10 wt % Loading
nhan
cem
e
CB- carbon black
300
400
uctiv
ity E
n GMP- graphite microplateletMWNT-Multi-Walled
Carbon NanotubesSWNT- Single-Walled
100
200
mal
Con
du Carbon NanotubesGNP- graphite nanoplatelet
CB GMP MWNT SWNT GNP0
100
Ther
m
• GNPs filler perform better than other carbon fillers• GNP shows: 130% enhancement / 1 vol.% – efficient filler
Whereas it is 20 30% for conventional fillersWhereas it is 20-30% for conventional fillersReason: High aspect ratio and rigid 2D structure of – High performance
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Modeling prediction & discrepancyModeling prediction & discrepancy
1. Inverse Rule of Mixtures15
mK
)
1. Inverse Rule of Mixtures
2. Nielsen’s model accounts for
1/K=Φ1/k1+ Φ2/k2
model
10GNPs-epoxy
duct
ivity
(w/m
121
1fc ABK
K Bφφ
+=
the geometry of the fillers
5
SWNT-epoxy
erm
al C
ond1
1E
p fK B
A k
ψφ−
= − SWNT epoxyTh
0 0.1 0.2 0.3 0.4
/ 1/
E
p
p
Kf KKf K AB
−+=
21
1 ( )f
p
m
m
f
φφ
ψ φ−
= +Experimental data are significantly lower thanmodeling prediction; Th d l d difi ti f t i lmφ The model needs modification for nanomaterials
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Summary of 2D-GNP/epoxy compositeSummary of 2D-GNP/epoxy composite
Thermal conductivity of GNP epoxy resin compositeThermal conductivity of GNP-epoxy resin composite is high up to 10.12 W/mK, which is excellent for thermal
interface material application.
Cost effective production: Graphite $50/Kg
Hi h t fill ffi i i i id 2D fillHighest filler efficiency using rigid 2D fillers
32
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3 D Multi-functional Composites
Biaxial Weave
Triaxial Weave
Knit Multiaxial Multilayer Warp Knit
3-D Cylindrical C
3-D Braiding 3-D Orthogonal Angle-Interlock CConstruction Fabric Construction
T. W. Chou and F. Ko, Textile Structural Composites, Elsevier Sci., Amsterdam, 1988
B i 787 D li it t i l f h lf f th t t tiBoeing 787 Dreamliner: composite materials for half of the parts, next generationAirplane material is not metal, will be carbon fiber matrix
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Motivation and Objectivej
Matrix rich region
Crack
T W Ch F K
Carbon fiber – Kelvar –Polymer composite
T. W. Chou, F. Ko, Textile Structural Composites, 1988
Motivation:Matrix rich regions form defect in the carbon fiber - polymer compositeC ki d f il ll t t d t f th d f t itCracking and failure usually start and propagate from these defect sites
Approach:Carbon nanotube to reinforce matrix regions and void the defect in compositeIncrease the carbon fiber – polymer interfacial interaction and load transferc ease t e ca bo be po y e te ac a te act o a d oad t a s e
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Multi-Scale Composite
Bridging the scale from Bridging the scale from NanoNanoto Macroto Macro 10 μm
Epoxy Matrixto Macroto Macro
1 μm
CarbonFiber
NanocompositeNanocomposite
100 nmCarbon Nanotubes
1Zig-ZagArmchairAtomic Interactions 1 nm
g gAtomic Interactionsr0
Stretching 0θ
Bending
Torsionvan der Waals
1 Å
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Strategy
1 mm As-Received Fiber
500 nm
8 µm
500 nm
55CNT reinforcement increases the interfacial interaction and 5 nm5 nmCNT reinforcement increases the interfacial interaction and the loading transfer and can avoid fiber pull-out
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CVD Deposition of CNTs on Carbon Fiber/Fabricsp
d iti f i (F ) f l ti th f CNT
FeCl3
-deposition of iron (Fe) for selective growth of CNTs
FeCl3
Carbon fiber3
FeCl3H2
Carbon FiberFe
Fe
Iron-coatedcarbon fibers
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SEM of Carbon Fibers Coated with CVD-grown CNTs
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Epoxy resin system
EPON 862 – EPI‐Cure W Curing Agent (Resolution Performance Products Inc )(Resolution Performance Products, Inc.)
Bisphenol-F Epichlorohydrin Epoxy
Aromatic Diamine (diethyltoluenediamine)
Amine hydrogen equivalent wt (AHEW) 43-46
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Vacuum assisted infusion
Peel Ply
Distribution Media
Vacuum Bag Resin Inlet
Peel Ply
Distribution Media
Vacuum Bag Resin Inlet
Tool
Layers of Gl F b i
Nanotube-Coated C b Fib B dl
Peel Ply
Vacuum Outlet
Tool
Layers of Gl F b i
Nanotube-Coated C b Fib B dl
Peel Ply
Vacuum Outlet
Glass Fabric Carbon Fiber BundlesGlass Fabric Carbon Fiber Bundles
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SEM observation of the compositep
C b fibCarbon fiber
Carbon fiber
CNTsIPR 20
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Electrical conductivity enhancement
Both in-plane and out-plane electrical conductivity increased about17 % @ 0.5 wt% CNTs loading
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Mechanical properties enhancementMechanical properties enhancement
Flexural strength and stiffness of Shear strength of CF/epoxy composites Flexural strength and stiffness of CF/epoxy composites with and without CNTs were slightly improved.
with and without CNT was enhanced at 35% (loadings of 0.2 and 0.5 wt %).IP
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Summary
• CNTs had been deposited on carbon fiber surface
• Both in-plane and out-plane electrical conductivity increased about 17 %
• Flexural strength and stiffness were slightly improved and shear strength of the carbon fiber epoxy was enhanced at 35% with 0.5 wt % of CNTs. IP
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My work in SABIC Innovative Plastics
Ai i YAiping Yu IPR 20
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M k @ t lMy work @ uwaterloo
Supercapacitors
CompositesIPR 20
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My work @ uwaterlooSupecapacitor: a new energy storage device
y @
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My work @ uwaterlooHigh loading multi-functional graphene/polycarbonate composite
SEM
Cross-section
Infiltration with polycarbonate SandwishM ltil it
Infiltration with polycarbonate
Hot press
SandwishMultilayer composite
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R t bli ti f hRecent publications of graphene
1600
mbe
r Papers published in allgraphene field
60
mbe
r Papers published in polymer composite area
1200
icat
ion
num graphene field
30
45
icat
ion
num
400
800
urna
l Pub
li
15
urna
l Pub
li
2005 2006 2007 2008 2009 20100
Jo
Year2005 2006 2007 2008 2009 2010
0Jo
YearYear Year
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Welcome collaborations and suggestions for applying carbon nanotubes and graphene to polymer composites
Thanks a lot for your attentionThanks a lot for your attentionIP
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