National Aeronautics and Space Administration
Graphene Pol mer Nanocomposites forGraphene Polymer Nanocomposites forAerospace Applications
Mitra Yoonessi, James Gaier
Ohio Aerospace Instit te Cle eland OHOhio Aerospace Institute, Cleveland, OHNASA Glenn Research Center, Cleveland, OH
FACSS – Oct. 4th, Reno, NV
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https://ntrs.nasa.gov/search.jsp?R=20150010365 2020-06-24T08:34:57+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:Graphite:
Advantages: Naturally abundant material, Low cost
Graphene - Mechanical peelingp g- 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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National Aeronautics and Space AdministrationGraphene Polymer NanocompositesMultifunctional actuators
C d ti N it Polymer+
Polycarbonate Polyimide
Electrical PerformanceElectrical, thermal, mechanical And actuation performance
Conductive Nanocomposites
O C
CH3
CH3
N
O
O
ON
O
O
C
CH3
CH3
O O
n
• Solution mixing• Emulsion mixing
• Solution mixingDispersion via sonication
Epoxy- DC electrical conductivity- AC electrical conductivity
Dynamic mechanical analyzer
Reinforcement, toughness and thermal properties
- DC electrical properties-Mechanical properties,
modulus, Tg-Morphology:
• Emulsion mixing
Epoxy - Dynamic mechanical analyzer, modulus, Tg
- Morphology: - electron microscopy- SANS
electron microscopyEpon 826
• Solution mixing
D 230
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- Dynamic mechanical analyzer, modulus, Tg- Fracture toughness- TGA- Morphology; electron microscopy
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Electrical Percolation Low conductive nanoparticle concentration
Percolating the conductors
• Inherent conductivity of nanoparticle• Concentration
Increasing
• Concentration• Aspect ratio• Dispersion• Orientation
gC-nanoparticle concentration
Aggregation and Dispersion of ti lnanoparticles
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Conductive path Israelachvili Intermolecular Surface Forces, Academic Press, San Diego, Ed. 3, 2006
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Graphene Polycarbonate
Lexan 121, Mw = 26,301 g/mol, PDI=1.72
700nm- 15 mic.Average of 3 mic.
-Excellent thermal properties- Good mechanical properties- High impact strength and toughness- Good processability
~ 9.2x 15.1 micronc
tCCfDC )]/()[( 1 s
cDC )/(k/)( 10
Extended pair approximation model
0.01 0.23 S/cm
S/cm
0.51 S/cm
0.14 vol. %1E-5
1E-3
0.1
S/cm 0.55 vol. %
1.1 vol. %
2.2 vol. %
ωc 100
1000
1E-5
S/cm
25 oCT
1E-8
ondu
ctiv
ity
0.38 vol. %
-8
-6
-4
-2
0
D
C ,
S/cm
0.01 1 100 100001E-9
1E-7
',
Frequency, Hz
0.41 vol. %
ωcσωc= 1.1σDC
10
100
'/
DC
0
10-2 100 1021E-6145 oC
',
S
Frequency, Hz
25 CT
0.0 0.8 1.6 2.41E-14
C
, (Vol.%)Ch i ll difi d h PS it 0 1 l %
-3.6 -3.0 -2.4 -1.8 -1.2-10
-8
(c )/(1-c)
S-G PC series t = 4.18 + 0.26σf, =106.55 + 0.69 S/cm E-G PC series t = 4.04 + 0.58 σf = 106.39 + 1.32 S/cm
1E-5 1E-3 0.1 10 1000
1
c
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Chemically modified graphene PS nanocomposites 0.1 vol. % Conductivity of 0.001 S/cm at 1 vol.% •Stankovich, S.; Ruoff, R.S. et al. Graphene-Based Composite Materials. Nature 2006, 442, 282- 286.
Kilbride, B. E.; et al. J. Appl. Phy. 2002, 92, 4024-4030.
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Graphene PolycarbonateTunneling
1
Charge carrier can travel through the barrier insulating polymer gap, a distancelonger than the nanoparticle length
700
3.2x10-6 3.6x10-6 4.0x10-6 4.4x10-6
b
1E-3
0.1
0.01
0.1
1
, S/c
m
500
600
C
, Hz
ωc ~ σDCb
S-G-PC
3 5 4 0 4 5 5 0 5 5 6 0 6 51E-9
1E-7
1E-5
1E-4
1E-3D
C
3.5x10-5 4x10-5 4.5x10-5 5x10-55.5x10-5
400
b = 0.99 + 0.1E-G-PCb = 1.01 + 0.1
3.5 4.0 4.5 5.0 5.5 6.0 6.5
-1/3 DC, S/cmYoonessi, M.; Gaier, J. R. ACS Nano, 2010
www.nasa.gov 8Kilbride, B. E.; et al. J. Appl. Phy. 2002, 92, 4024-4030.
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Epoxy Graphene Nanocomposites-ReinforcementObj i Reinforcement
Epoxy: Epon 826
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.
Epoxy: Epon 826 Low viscosity resinTransparent Jeffamine D230: a polyetheramine, (an amine terminated PPG)MW 230 X 2 5
MW 230, X~ 2.5
2500 – 27000 g/mol
Reduced graphene sp2 hybridized
Highly oxygenated graphene,sp2, and sp3
Amino propyl polydimethyl siloxane graphene,sp2, and sp3
0.1
Si O 1006 5788.4
CH3, CH2
100 320 oC25000 C1sSi-O
Abs
orba
nce
1562.5
1256
10941006.5
NH2
Si-CH3
60
80
Wei
ght,
%
86%
10000
15000
20000
nsity
, cou
nts
O1sOKLL
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4000 3000 2000 10000.0
CH3, CH2
Wave numbers, cm-1
3302 2956
0 100 200 300 400 500 600 700 800
20
40
W
Temperature, oC1200 1000 800 600 400 200 0
0
5000
S2p
Inte
n
Binding Energy, eV
Cl2p
OKLL
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Epoxy Graphene NanocompositesGraphene loading 0 05 0 5 wt%Graphene loading 0.05 - 0.5 wt%
108
111
ratu
re, o C
108
110
atur
e, o C
108
110
prat
ure,
o C
102
105
108
ansi
tion
tem
per
Reduced grapheneTg
102
104
106
tran
sitio
n te
mep
102
104
106
tran
sitio
n te
mep
O-grapheneTg
PDMS-grapheneTg
0.0 0.1 0.2 0.3 0.4 0.5
99
Gla
ss tr
a
Graphene/epoxy nanocomposite, wt%0.0 0.1 0.2 0.3 0.4 0.5
100Gla
ss
Graphene epoxy nanocomposites, wt%
0.0 0.1 0.2 0.3 0.4 0.5
100
Gla
ss t
PDMS-Graphene/epoxy nanocomposite, wt%
Neat EpoxyNeat Epoxy Neat Epoxy
2100
2400
0 o C
), M
Pa
2400
2600
2800
60 o C
), M
Pa
2400
2700
(60
o C),
MPa
1200
1500
1800
age
mod
ulus
(60
1800
2000
2200
ge M
odul
us (6
1800
2100
orag
e M
odul
us
Reduced graphene,Modulus @ 60C O-graphene,
Modulus @ 60C
PDMS-graphene,Modulus @ 60C
N t E Neat Epoxy
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0.0 0.1 0.2 0.3 0.4 0.5
1200
Stor
aPDMS-Graphene/epoxy nanocomposite, wt%0.0 0.1 0.2 0.3 0.4 0.5
1400
1600
Stor
ag
Graphene epoxy nanocomposites, wt%
0.0 0.1 0.2 0.3 0.4 0.5
1500Sto
Graphene/epoxy nanocomposite, wt%
Neat EpoxyNeat Epoxy
Neat Epoxy
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Epoxy Graphene Nanocomposites50P
30
40
50 O-Graphene Epoxy
KIC
, %
f(x)WB
P K maxIC
E-(1 G
22
ICicK)
10
20
30Graphene Epoxy
crea
se o
f K
PDMS-Graphene Epoxy
3/2
21/2
x)-2x)(1+(1)2.7x+3.93x-x)(2.15-x(1-1.996x f(x)
0.00 0.02 0.04 0.06 0.08 0.10
0Inc
Graphene, wt%
Neat Epoxy
405
410
415
395
400
395
400
o C
Graphene, wt%
Reduced graphene,
390
395
400
405
T d, o C
385
390
395
T d, o C
385
390
T d,
PDMS-graphene,O-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%0.0 0.1 0.2 0.3 0.4 0.5
Graphene, wt%
Neat EpoxyNeat 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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Polyimide Graphene Nanocomposites Aromatic polyimide: low color flexibility high T high thermal PMR 15
2 Polyimide, thermal stability >500 oC, Tg > 200 oC, flexible and semi-transparent.
Aromatic polyimide: low color, flexibility, high Tg, high thermal stability, and radiation resistance.1
PMR-15GRCAfter burner
Thermal imidization: - Mixing and dissolving equi-molar ratio diamine in anhydrous-NMP under dry N2 followed by addition
f d h d id d ti i f 24h i fl d i d lof dry anhydride and stirring for 24h in flame dried vessels.- Then, increasing the temperature ~230 oC (NMP reflux) for 3h and precipitating in methanol and drying
Solvent casting+ Polyimide
solutionsonication
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1Qu,L., Connell, J.W., Sun, Y.-P., Macromolecules, 2004, 37, 6055-6060.2Lebron-Colon, M. Meador, M. A., Gaier, J. R., Sola, F., Scheiman, D.A., McCorkle, L.S. ACS Applied Materials and Interfaces, 2010, 2 ,3 , 669–676 .
sonication
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Polyimide Graphene Nanocomposites Addition of graphene resulted in
it i f t ith t
0.1
10
cm
tCCfDC )]/()[( 1
0.92 S/cm0.036%
2000
MPa
composite reinforcement without adverse effect on the Tg
1E 9
1E-7
1E-5
1E-3
ctiv
ity, S
/c
3
-2
-1
0
DC
), S/
cm 1500 150 oC
Mod
ulus
, M
50 oC
1E-15
1E-13
1E-11
1E-9
Con
du
-2.6 -2.4 -2.2 -2.0 -1.8 -1.6 -1.4-5
-4
-3
Log
(
Log (CC)
t= 3.79
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
1000
Stor
age
240
250
C
0 1 2 3 4 51E 15
Graphene vol. % Graphene wt%
210
220
230
T g, o CT g
, oC
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0.0 0.5 1.0 1.5 2.0 2.5200
210
Graphene vol %Graphene, vol.% 14
Flexible films at 2wt% with 200 micron thickness
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Dispersion of graphene in polyimideTEMTEM
C d ti th10
10 micron
1.1 vol.%Conductive path
0.025 vol.%10 micron
1E-7
1E-5
1E-3
0.1
tivity
, S/c
m
1E-15
1E-13
1E-11
1E-9
Con
duct
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0 1 2 3 4 51E 15
Graphene vol. %200 nm 500 nm
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Reinforcement: O-Graphene Surface ModificationsModifications
-Covalent bonding of imide moieties using grafting to method-Provide compatibility with the polyimide resin matrixGenerate steric hindrance and promote dispersion-Generate steric hindrance and promote dispersion
P-amino phenyl trimethoxy silane
3,3',4,4'-Biphenyl tetracarboxylicdianhydride (s-BPDA)
2,2'-Dimethyl-4,4'-diaminobiphenyl (m-Tolidine)
3 units were on the surface: 23 units were on the surface: 2 anhydride and 1 diamine After 2 months
80
100Imide modified graphene
O- graphene
280 oC
72%984 oC
40
60
Wei
ght,
%
g p
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O-grapheneGraphene with rigid surface modifierGraphene with flexible surface modiier
0 200 400 600 800 10000
20
Temperature, oC
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Covalent Functionalization of imide structure to Graphene
Surface Modification of Graphene with Rigid Imides
Covalent Functionalization of imide structure to Graphene
0 060.070.080.090.10
y
0.020.030.040.050.06
Inte
nsity 3430
OH, NH2
2917.82853
CH2, CH3
Si-O1094
17241656
1572
imide arbonylamid carbonyl
1368
imide C-N
4500 4000 3500 3000 2500 2000 1500 1000 5000.000.01
Wavenumber, cm-1
28531775
1572
0.06
0.08
0.10
y
amid carbonyl1566
1248
0.02
0.041345
imide C-N-C
Inte
nsity
3430OH, NH2
2917.82853
CH2, CH3
Si-O1081
imide arbonyl imide C-N
1720
1771
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4000 3000 2000 1000 0
0.00
Wavenumber, cm-1
Mw 1058.28 g/mol: 3 unit
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Surface Imidized Graphene Polyimide NanocompositesPolyimide Nanocomposites
Addition of graphene with rigid surface imide moieties resulted in increase in modulus and Tg
1600
1700
s@ 1
50 o C
, MPa
230
235
of G
raph
ene
o C
1 wt%
1400
1500
tora
ge m
oduo
us
225
8.5 oCansi
tion
Tem
p.
Poly
imid
e, o
17.1 oC
-0.25 0.00 0.25 0.50 0.75 1.00 1.25
1200
1300
Dyn
amic
St
G h i ht t %
0.1 0.2 0.3 0.4 0.5
2208.5 C
Gla
ss T
ra
Graphene weight Percent, %Graphene weight percent, %
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Conclusions
• Incorporation of reduced graphene in the both polycarbonate and polyimide resulted in superior electrical conductivity along with reinforcement with none or insignificant adverse effect on the glass transition temperature.
• The plateau electrical conductivity of graphene polyimide nanocomposite• The plateau electrical conductivity of graphene polyimide nanocompositereached to 0.92 S/cm with a critical percolation of 0.036 vol. fraction.
• Low graphene content (0.05-0.5 wt%) graphene epoxy nanocompositesexhibited improvements in glass transition temperature, modulus, thermal stability, and fracture toughness.
• Graphene surface characteristics is the key for the target propertyGraphene surface characteristics is the key for the target property enhancement in all three resin matrices.
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Acknowledgements•The NASA Aeronautics-Subsonic Fixed Wing Program: Contract NNC07BA13B
• Dr. Michael A. Meador, Nanotechnology Lead, Polymer Branch Chief,NASA GRCNASA GRC
• Dr. Dave Kankam, NASA USRP program, NASA GRC• Dr. Kathy Chuang, NASA GRC• Dr. Marisabel Lebron-Colon, NASA GRC
Daniel Scheiman ASRC/NASA GRC• Daniel Scheiman, ASRC/NASA-GRC• Matthew Dittler, USRP student• Eileen Boyd, USRP student• Ying Shi, Graduate assistant, University of Akron
Dr Rick Rogers Dave Hull Derek Quade Terry McCue NASA/GRC• Dr. Rick Rogers, Dave Hull, Derek Quade, 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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