Graphene Polymer Nanocomposites Graphene Polymer · 2015-06-12 · National Aeronautics and Space...
Transcript of Graphene Polymer Nanocomposites Graphene Polymer · 2015-06-12 · National Aeronautics and Space...
National Aeronautics and Space Administration
Graphene Polymer Nanocomposites
Mitra Yoonessi
Graphene Polymer Nanocomposites
Thermal, Mechanical Properties, and Fracture Toughness of Surface Modified Graphene Epoxy
Nanocomposites
Nanocomposites
Eileen Boyd, Derek J. Quade, Daniel Scheiman
Ohi A I tit t Cl l d OHOhio Aerospace Institute, Cleveland, OHNASA Glenn Research Center, Cleveland, OH
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https://ntrs.nasa.gov/search.jsp?R=20150010367 2018-07-29T07:43:07+00:00Z
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Polymer Nano-Composites for Aerospace ApplicationsAerospace Applications
• GrapheneL d Sili t
Multi-Functional MaterialsReinforcements, Mechanical
t th i id t t
Conductive PolymersDC & AC Electrical - Permittivity –Stiffness / Ductility • Layered Silicates
• Carbon NT• Expanded Graphite• Carbon nanofibers• Magnetic nanoparticles
strength in a wide temperature range- Barrier - Toughness
y
g p• Organometallic physical
crosslink A two-seat F106B jet made 1,496 thunderstorm penetrations and got struck by lightning 714 times during NASA's eight-year Storm Hazards Research Program
SensorsStatic dischargeLightening strike
Smart Adaptive MaterialsActuation– Thermal, Magnetic, Electrical
year Storm Hazards Research Program. Credit: NASA
Lightening strikeActuators
Adaptive fan blade
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Adaptive fan bladeMorphing fan casing Blended wing body inletFlex. packagingSpace deployable structures
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Graphite and GrapheneGraphite:
Advantages: Naturally abundant materialAdvantages: Naturally abundant material, Low cost
Graphene - Mechanical peeling- CVD- Acid intercalation, thermal shock, sonication - Acid intercalation followed by high pressure, high temperature treatments
800
1000
u. 3.48ÅAb f600
800
a.u.
1598 71356.8
200
400
600
nten
sity
, a.
graphite
Absence of a sharp peak
200
400
600
an In
teni
sty,
a
2942.52693.3
1598.7
~ 9.2x 15.1 micron
G bandE2g
D banddefects
Graphene: •In-plane stiffness of 1,060 GPa Polymer nanocomposites,
optoelectronic applications;
20 30 400
In
2theta, degree
0 1000 2000 3000 40000R
am
Raman Shift, cm-1
700nm- 15 mic.Average of 3 mic.
•resistivity in the range of 50μΩ cm•98.7% transmission normal to the incident beam for the first layer, 2.3% reduction for the next layers in vacuum
•Thermal conductivity: ~ 3000 W/mK•Field effect mobility of 200 000 cm2/Vs1
optoelectronic applications; transparent conductors, field emission displays, supercapacitors, devices, emissive displays,
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Field effect mobility of 200 000 cm /Vs1micromechanical sensors, and future microprocessorsNovoselov, K.S., Geim, A.K., et al. Science Oct 22 (2004)
McAllister, M. J.; Prud’homme, R. K.; Aksay I. A. et al. Chem. Mater. 2007, 19, 4396- 4404.Schniepp, H. C.; Kudin, K. N.; Li J.-L.; Prud’homme, R. K.; Car, R.; Saville, D. A.; Aksay, I. A. ACS Nano 2008, 2, 2577-2584.Schniepp, H.C.; Aksay, I. A. et al. J. Phys. Chem. B, 2006, 110, 8535-8539.
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Graphene Surface and InterfaceTailored Interface •Compatibility with the polymer matrixTailored Interface Compatibility with the polymer matrix
•Improving dispersion •Load/stress transfer•Electron transfer•Thermal energy transport
Surface Characteritics:•SP2 hybridization for electron transport
van der Waal Interaction (aromatic structures)
Thermal energy transport
•Combination of sp3 and sp2 hybridization Covalent bonding; -OH, -COOH, -phenolic-OH, -epoxide
Covalent bonding
Grafting to
g
Grafting from
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Epoxy Graphene Nanocomposites-Reinforcement P l +Reinforcement Polymer+
Objectives:• To determine the effects of graphene addition and surface modification
on the thermal and dynamic modulus, fracture toughness of the low content graphene nanocomposites.
Dispersion via sonicationEpoxy: Epon 826 Chemical and heat resistanceGood to excellent mechanical properties
g p p
Durability long term
Epoxy
Reinforcement, toughness and thermal properties
Good to excellent mechanical propertiesLow viscosity resinTransparent Excellent adhesion
Durability - long-term, High-temperature serviceBrittleness
p y• Solution mixing• Sonication• High shear mixing
J ff i D230 l th i ( i t i t d PPG)- Dynamic mechanical
analyzer, modulus, Tg- Fracture toughness- TGA
Jeffamine D230: a polyetheramine, (an amine terminated PPG)MW 230, X~ 2.5
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TGA- Morphology; electron
microscopy
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Epoxy Graphene Nanocomposites-Surface ModificationsSurface Modifications
Reduced graphene O- graphene
Reduced graphene sp2 hybridized
Highly oxygenated graphene,sp2, and sp3
Amino propyl polydimethyl siloxanegraphene, sp2, and sp3
2500 – 27000 g/mol
0.1
Si-O
ance
1256
10941006.5
788.4CH3, CH2
Si CH80
100
%
86%
320 oC
20000
25000
nts
C1s
CH3, CH2
Abs
orba
3302 2956
1562.5
1256
NH2
Si-CH3
20
40
60
Wei
ght,
%
5000
10000
15000
S2p
Inte
nsity
, cou
n
O1s
Cl2p
OKLL14 wt%
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4000 3000 2000 10000.0
Wave numbers, cm-1
3302 2956
0 100 200 300 400 500 600 700 800
20
Temperature, oC1200 1000 800 600 400 200 0
0
Binding Energy, eV
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XPS, O- Graphene SurfaceXPSA range of carbon oxygen moieties with 7% atomic oxygen (high resolution survey scans).
532.27 eV533.73 eV
OC=O, C-O, O-C-O
O1s binding energy: 532. 3 eVketone, ester, or acetate O1s binding energy: 533 73 eV
C1s: 285.07, 286.78, 289.2, 291.48, 294.19 eV
Bonding energies: ester, carboxylic, ether cabon hydroxyl carbon phenolic
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O1s binding energy: 533.73 eVadsorbed CO
Beamson G., Briggs D. High Res. XPS of Org. Polym.: the Sci. ESCA300 Database 1992
Wu, M.C.; Dong, S.Z.; Zhu, A.R. Surf. Sci. 1989, 216, 420
cabon, hydroxyl carbon, phenolichydroxyl, carbonate, ..
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XPS – Surface Modified
20000
30000
.u.
C1s
C1s O1s Si2p
79.1 14 6.9
Atomic percentage, %
3500
4000
4500
u.
Si-O-Si
532.2
10000
20000
OKLLInte
nsity
, a O1s
Si2P2000
2500
3000
3500
Inte
nsity
, a.
533.5
1200 1000 800 600 400 200 0
0
Si2PS2p
545 540 535 530 525 520
1000
1500
I
Bi di E VBinding Energy, eV
Binding Energy, eV
1000
1200
O-Si-O
u.
102.1
400
600
800
Inte
nsity
, a.u
www.nasa.gov 8Patel N. M., Dwight D. W., Hedrick J. L., Webster D. C., McGrath J. E. Macromolecules 21, 2689 (1988)
115 110 105 100 95 900
200
Binding Energy, eV
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Epoxy Graphene NanocompositesGlass Transition Temperaturep
Graphene loading 0.05 - 0.5 wt%
106.33
109.04108.19 107.68
mep
atur
e, o C
100
99.8
102.07
s tr
ansi
tion
tem
O-grapheneTg
0.0 0.1 0.2 0.3 0.4 0.5
Gla
ss
Graphene epoxy nanocomposites, wt%115
110109.54
108
105.58
108.04109.4
pera
ture
, o C
PDMS-
110
115
107.1
111.21109.78 109.2
mpe
ratu
re, o C
Reduced grapheneTg
100
105
99.83
rans
ition
tem PDMS
grapheneTg
105
99.8
105.7
rans
ition
tem
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0.0 0.1 0.2 0.3 0.4 0.5
100
Gla
ss tr
Graphene/epoxy nanocomposite, wt%0.0 0.1 0.2 0.3 0.4 0.5
100
Gla
ss tr
Graphene/epoxy nanocomposite, wt%
National Aeronautics and Space AdministrationEpoxy Graphene Nanocomposites-Reinforcements
28002629a
2400
26002370
2629
60 o C
), M
Pa
Graphene loading 0.05 - 0.5 wt%
1800
2000
2200
1639
1884
2099
Mod
ulus
(6O-graphene,Modulus @ 60C
0.0 0.1 0.2 0.3 0.4 0.51400
160015431639
Stor
age
Neat Epoxy
2400
270024642392
22452141 2183
o C),
MPa
Graphene epoxy nanocomposites, wt%
2400
2700 2625
23122223
2320
0 o C
), M
Pa
R d d
1500
1800
2100
1543
mod
ulus
(60
o1800
2100
21512223
ge M
odul
us (6
0 Reduced graphene,
Modulus @ 60C
PDMS-graphene,Modulus @ 60C
Neat Epoxy
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0.0 0.1 0.2 0.3 0.4 0.5
1200
Stor
age
PDMS-Graphene/epoxy nanocomposite, wt%0.0 0.1 0.2 0.3 0.4 0.5
1500
1543
Stor
ag
Graphene/epoxy nanocomposite, wt%
Neat Epoxy
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Epoxy Graphene NanocompositesFracture Toughnessg
Mode I Fracture ToughnessThe fracture toughness improved withLow graphene content, where further ddi i f h l d i
40
50 O-Graphene Epoxy
%
addition of graphene resulted in KIC deterioration.
20
30Graphene Epoxy
se o
f KIC
,
PDMS-Graphene Epoxyf(x)PK maxIC
0
10
Incr
eas PDMS-Graphene Epoxyf(x)
WB KIC
Neat Epoxy
0.00 0.02 0.04 0.06 0.08 0.10Graphene, wt%
2
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3/2
21/2
x)-2x)(1+(1)2.7x+3.93x-x)(2.15-x(1-1.996x f(x)
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Epoxy Graphene NanocompositesThermal StabilityThermal Stability
400
390
395
T d, o C
O-graphene,
0.0 0.1 0.2 0.3 0.4 0.5
385
Graphene wt%
Neat Epoxy
405
410
415Graphene, wt%
395
400
o C
Reduced graphene,
390
395
400
T d, o C
385
390
395
T d, o
PDMS-graphene,
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0.0 0.1 0.2 0.3 0.4 0.5380
385
Graphene, wt%0.0 0.1 0.2 0.3 0.4 0.5
385
Graphene, wt%
Neat Epoxy
Neat Epoxy
National Aeronautics and Space AdministrationEpoxy Graphene Nanocomposites-Dispersionp
PDMS modified
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PDMS modified graphene in epoxy 0.05wt%
Reduced graphene in epoxy
O-graphene in epoxy
Good dispersion was obtained in all nanocomposites
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SEMFractured, O2 plasma treated surface of PDMS-Graphene epoxy nanocomposites
0.5 wt% PDMS-graphene Nanocomposites
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Concluding RemarksConcluding Remarks
• Low graphene content (0.05-0.5 wt%) graphene epoxy nanocomposites using reduced graphene O graphene and surface modified grapheneusing reduced graphene, O-graphene, and surface modified graphene were prepared by solution mixing.
• All nanocomposites exhibited improvements in glass transition temperature, modulus, thermal stability, and fracture toughness.
• TEM studies showed good dispersion of graphene in the epoxy resin matrixmatrix.
• SEM micrographs indicated crack generation and energy dissipative phenomena in the graphene nanocomposites compared to neat epoxy.
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Acknowledgements
•The NASA Aeronautics-Subsonic Fixed Wing Program: Contract NNC07BA13B
• Dr. Michael A. Meador, Agency Nanotechnology Lead, Polymer Branch Chief,NASA GRC
• Dr. Dave Kankam, NASA USRP program, NASA GRC• Dr. Rick Rogers, Dave Hull,Terry McCue, NASA/GRC• Professor Aksay, Princeton University,• Vorbeck Materials Inc., John Lettow ,
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NASA-University ProgramsGRC L d f th t h l
- NRA – Aeronautics - NASA inspire web site
GRC Lead for the agency nanotechnology
- NASA Graduate Student Researchers Program (GSRP)- http://fellowships.hq.nasa.gov/gsrp/nav/
NASA Undergraduate Student Research Program (USRP)- NASA Undergraduate Student Research Program (USRP)- http://usrp.usra.edu/
- NASA Experimental Program to Simulate Competitive Research (EPSCoR)
NASA Glenn Faculty Fellowship Program (NGFFP)- NASA Glenn Faculty Fellowship Program (NGFFP)- http://nbpo.grc.nasa.gov/university-affairs/ngffp/
- LERCIP Higher Education (College) – Undergraduate program
- Space Grant Consortium
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