Graphene Polymer Nanocomposites Graphene Polymer · 2015-06-12 · National Aeronautics and Space Administration Graphene Polymer Nanocomposites Mitra Yoonessi Graphene Polymer [email protected]

National Aeronautics and Space Administration

Graphene Polymer Nanocomposites

Mitra Yoonessi

Graphene Polymer Nanocomposites

[email protected]

Thermal, Mechanical Properties, and Fracture Toughness of Surface Modified Graphene Epoxy

Nanocomposites

[email protected]

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

www.nasa.gov 1

https://ntrs.nasa.gov/search.jsp?R=20150010367 2018-07-29T07:43:07+00:00Z


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

www.nasa.gov 2

Adaptive fan bladeMorphing fan casing Blended wing body inletFlex. packagingSpace deployable structures


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,

www.nasa.gov 33

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.


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

www.nasa.gov 4


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

www.nasa.gov 5

TGA- Morphology; electron

microscopy


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%

www.nasa.gov 6

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


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

www.nasa.gov 7

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, ..


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


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

www.nasa.gov 9

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

www.nasa.gov 10

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


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

www.nasa.gov 11

3/2

21/2

x)-2x)(1+(1)2.7x+3.93x-x)(2.15-x(1-1.996x f(x)


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,

www.nasa.gov 12

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

www.nasa.gov 13

PDMS modified graphene in epoxy 0.05wt%

Reduced graphene in epoxy

O-graphene in epoxy

Good dispersion was obtained in all nanocomposites


SEMFractured, O2 plasma treated surface of PDMS-Graphene epoxy nanocomposites

0.5 wt% PDMS-graphene Nanocomposites

www.nasa.gov 14


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.

www.nasa.gov 15


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 ,

www.nasa.gov 16


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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Documents

Graphene Polymer Nanocomposites Graphene Polymer · 2015-06-12 · National Aeronautics and Space Administration Graphene Polymer Nanocomposites Mitra Yoonessi Graphene Polymer [email protected]