Lebron-Colon, Marisabel

Meador, Michael

Miller, Sandi

Williams, Tiffany

NASA Technical Reports Server

National Aeronautics and Space Administration 
www.nasa.gov 
Polymer and Nano-Material Research in the 
Polymers Branch at NASA Glenn Research Center 
SERMACS 2011 
October 26th – 28th 
Richmond, VA 
 
Sandi Miller, Marisabel Lebrón-Colón, Tiffany Williams, 
and Michael Meador 
Polymers Branch 
Structures and Materials Division 
NASA Glenn Research Center 
Cleveland, OH. 44135 
1 
https://ntrs.nasa.gov/search.jsp?R=20150010359 2019-08-31T08:04:01+00:00Z
National Aeronautics and Space Administration 
www.nasa.gov 2 
Future Exploration Mission Requirements Cannot Be  
Met with Conventional Materials 
Satellites and rovers 
• Reduced mass and volume 
• Reduced power requirements 
• Increased capability, multifunctionality 
 Vehicles and habitats 
• Reduced mass 
• High strength 
• Thermal and radiation protection 
• Self-healing, self-diagnostic 
• Multifunctionality 
• Improved durability 
• Environmental resistance 
   (dust, atmosphere, radiation) 
 EVA Suits 
• Reduced mass 
• Increased functionality and mobility 
• Thermal and radiation protection 
• Environmental resistance 
National Aeronautics and Space Administration 
www.nasa.gov 
Characterization 
RXP Nanomaterials Research 
3 
Dispersion/Processing 
Functionalization 
Giannelis group-  
Cornell 
NASA 
Nanotechnology 
Gallery 
R
e
la
ti
v
e
 
In
te
n
s
it
y
 
2 Theta 
30B in API
resin
30B in PES1
Incorporation 
into Composite 
Structures 
Synthesis 
National Aeronautics and Space Administration 
www.nasa.gov 
Outline 
• Nanocomposites for Highly Loaded Structures 
 
• Nanocomposites for Cold Temperature Applications 
(cryogen storage) 
 
• Nanocomposites for High Temperature Applications 
(300oC) 
4 
National Aeronautics and Space Administration 
www.nasa.gov 
Composite Fan Blade 
5 
Goal: Enable Reduced Blade Thickness through Improved 
Composite Fracture Toughness and Interlaminar Strain 
Approach: 
1. Investigate the influence of a wide range of 
nanoparticles on epoxy toughness. 
2. Design materials to best utilize the various 
nanoparticles. 
National Aeronautics and Space Administration 
www.nasa.gov 
Composite Fan Blades 
Background 
6 
0
1000
2000
3000
4000
5000
0 10 20 30 40 50 60
Strain (%)
S
tr
e
s
s
 (
p
s
i)
Neat Resin 
2% clay 
2% clay- premixed 
5% clay 
5% clay- premixed 
Materials: 
o Tensile strength and ductility are improved when nano-  
     particles can align in the direction of applied load. 
o Pre-dispersion forces clay into the more mobile 
components  of the resin. 
NH2CHCH2
CH3
OCH2CH NH2
CH3
[ ]x
x = 2.6
Jeffamine D230 
Mn < 385
n
H2C CHCH2
O
O CH2CH OCH2CH
CH3
CH2
O
[ ]
Araldite DY3601 
Epon 826 
0
500
1000
1500
2000
2500
3000
3500
4000
4500
baseline 2% matrix 2%
preswell
5% matrix 5%
preswell
K
1
c
 M
P
a
*m
^
(1
/2
) 
2 7 12
R
e
la
ti
v
e
 I
n
te
n
s
it
y
 
2 Theta 
2% 30B in 100% E826 
2% 30B directly dispersed 
2% 30B in 100% DY3601 
2% 30B pre-dispersed 
O OCH2CHCH2 O
OH
OCH2CH CH2
O
CH2CHCH2
O
[ ]
n
Mn <700, n~1
Tensile 
Stress 
National Aeronautics and Space Administration 
www.nasa.gov 
Strain in Un-Toughened Epoxy-Clay 
Nanocomposites 
7 
0
10
20
30
40
50
60
70
80
0.00 2.00 4.00 6.00 8.00
S
tr
e
s
s
 (
M
P
a
) 
Strain (%) 
Clay in Curing 
Agent 
Clay in Epoxy 
Baseline Epoxy 
0
0.3
0.6
0.9
1.2
1.5
0.00 50.00
S
tr
e
s
s
 (
M
P
a
) 
Strain (%) 
Clay in Epoxy 
Clay in Curing 
Agent 
Baseline Epoxy 
Glassy at Room Temperature Rubbery at Room Temperature 
National Aeronautics and Space Administration 
www.nasa.gov 
Nanocomposites Based on Aerospace 
Grade Epoxies 
8 
0
1000
2000
3000
4000
5000
6000
7000
8000
0.000 0.010 0.020
S
tr
e
s
s
 (
p
s
i)
 
Vertical Strain (in/in) 
Clay Particles 
0
1000
2000
3000
4000
5000
6000
0.000 0.005 0.010 0.015
S
tr
e
s
s
 (
p
s
i)
 
Verticle Strain (in/in) 
CNF and Graphite 
Particles 
Neat resin, fails 
0.09 in/in 
Graphite particles were epoxy functionalized via solvent-
based wash.  CNF particles were not functionalized. 
No Clay 
Fracture surface of 
nano-reinforced 
samples indicate 
increased material 
toughness 
National Aeronautics and Space Administration 
www.nasa.gov 
Composite Structures 
9 
1. Epoxy Nanocomposite film laid up 
with between plies of base laminate.  
2. Autoclave cured using vendor 
recommended cure cycle 
3. Characterized for panel quality 
1. C-scan 
2. Acid Digestion 
3. Optical Microscopy 
4. Mechanical Testing 
Resin Interleave 
Resin Interleave 
Photomicrograph of SBS test coupon, 
[0]16 lay-up, along fiber direction 
R
e
la
ti
v
e
 I
n
te
n
s
it
y
 
2 Theta 
30B in API resin
Cloisite 30B
National Aeronautics and Space Administration 
www.nasa.gov 
Composite Testing: Thermal and Mechanical 
Testing Results 
10 
0
100
200
300
400
500
600
700
0 0.02 0.04 0.06 0.08
L
o
a
d
 (
lb
f)
 
Extension (in) 
Short Beam Shear 
Baseline Composite 
Resin Toughened Composite 
Nanoclay Toughened 
Composite 
100
1000
10000
100000
0 50 100 150 200 250 300
S
tr
e
s
s
 (
M
P
a
) 
Temperature (oC) 
DMA 
Resin Toughened Composite 
Nanoclay Toughened 
Composite 
Nanoclay interleave shows 
drop in short beam shear 
strength, but comparable or 
improved ductility  
Little difference in 
dynamic mechanical 
data. 
National Aeronautics and Space Administration 
www.nasa.gov 
Next Steps - Improved Nano-Incorporation 
• Need Better Dispersion 
– Do not have the facilities to handle 
this scale of dispersion. 
– Contract in place with Nanosperse 
to aid in dispersion 
 
• Exploring Alternative 
Mechanisms to Include 
Nanoparticles 
• Purchases in place with 
Nanocomp to incorporate  
 CNT sheets 
• Working with North Carolina  
 A&T University to electro-spin  
      PES for interleave material. 
 
 
 
 
 
 
 
  
 
11 
National Aeronautics and Space Administration 
www.nasa.gov 
Composite Tanks 
Goal: Reduce Permeation through Composite 
12 
03S02233-1009
ABL Tanks and Reuseable Launch Vehicles;
Composite Ducting
27
68
Metalic
Boss
Weight lbs.
175
104
Composite
Weight lbs.
79
103
Liner
Weight
lbs.
281
275
Tank
Weight
lbs.
19”d x
114”L
H2,N2
27”D x
81”L
H2O2
Tank
Conf.
Lbs.Reactant
 
5% clay in 
epoxy matrix 
lead to a 
70% 
reduction in 
helium leak 
rate 
compared to 
the baseline 
tank.   
0.00E+00
1.00E-07
2.00E-07
3.00E-07
4.00E-07
5.00E-07
6.00E-07
7.00E-07
8.00E-07
0 500 1000 1500 2000
H
e
li
u
m
 (
m
b
a
r.
l/
s
) 
Time (s) 
0% clay, pristine 
2% and 5% clay, 
pristine 
5% clay, cycled 
2% clay, cycled 
0% clay, cycled 
Permeability of epoxy/clay (no carbon fiber).   
o The majority of this effort has focused on 
clay nanoparticles. 
o Reduced material permeability following 
nanoclay dispersion is well documented. 
o Expected that the platelet structure of clay 
contributes to the improved barrier 
performance. 
Clay layer dispersion and alignment, with 
respect to the permeation direction, greatly 
influence the barrier performance of the matrix 
Bharadwaj, R.K. Macromolecules 2001, 34, 9189 
National Aeronautics and Space Administration 
www.nasa.gov 
High Temperature Polymer Nanocomposites 
Goal: Improve High Temperature Durability of Matrix Resin 
13 
+
NH3
NH2
+
H3N
CH2H2N N
O
O
H2N CH2 (CH2)10 CH3
PMR-15 
processing 
temperature 
Elevated PMR-15 
processing temperatures 
led to development of 
unique nanoclay modifier. 
MDA-C12 
co-ion 
exchange 
National Aeronautics and Space Administration 
www.nasa.gov 
Thermal and Physical Properties of PMR-15/Clay 
Nanocomposites 
14 
5.6
6
6.4
6.8
7.2
7.6
8
1000 hours (288
o
C)
P
e
rc
e
n
t 
W
e
ig
h
t 
L
o
s
s
0% silicate
1% silicate
3% silicate
5% silicate
7% silicate
Oxygen Permeability of Carbon Fiber Composites
5400
5500
5600
5700
5800
5900
6000
6100
6200
O
x
y
g
e
n
 T
r
a
n
s
m
is
s
io
n
 R
a
t
e
 
(
c
c
/m
2
/d
a
y
)
Carbon Fiber Neat Carbon Fiber Clay
Silicate PGV- 
(MDA-C12) 
PGV-
C12 
0% 335 335 
1% 336 337 
3% 340 326 
5% 337 321 
7% 338 311 
•  Glass transition temperature was maintained      
   with increased clay loading. 
•  Weight loss with thermal aging reduced with  
   increased clay loading. 
•  Oxygen permeation through nanocomposite     
   reduced compared to baseline material. 
 
National Aeronautics and Space Administration 
www.nasa.gov 
0
0.5
1
1.5
2
2.5
PMR-15
composite
0.5 wt%
graphite
0.5 wt%
CNF
0.25
wt%CNF,
0.25 wt%
graphite
%
 W
e
ig
h
t 
L
o
s
s
 (
5
0
0
 h
o
u
rs
) 
15 
Neat Resin 
0.5 wt% CNF 
High Temperature Polymer Nanocomposites 
CNF dispersion 
results in weight loss 
comparable to clay 
National Aeronautics and Space Administration 
www.nasa.gov 
Carbon Nanotube Efforts- Focus on Functionalization 
16 
16 
SWCNTs Non-Covalent Functionalization  
 
N
O
H
NO
O
N
O
H
NO
O
N
O
H
NO
O
N
O
H
NO
O
N
O
H
NO
O
Schematic illustration of the 
SWCNTs/Pyrene complex  
 85 
 90 
 95 
 100 
%
T
 
 85 
 90 
 95 
 100 
%
T
 
 60 
 70 
 80 
 90 
 100 
%
T
 
 600     800     1000    1200    1400    1600    1800    2000   
cm-1 
(a) SWCNTs 
(b)SWCNTs/Pyrene 
(c) Pyrene 
Pyrene derivative  
0
20
40
60
80
100
0 200 400 600 800 1000
Temperature (ºC)
W
e
ig
h
t 
(%
)
 a
b
c
(a) SWCNTs 
(b) SWCNTs/Pyrene 
(c)  Pyrene 
National Aeronautics and Space Administration 
www.nasa.gov 17 
17 
 
N
O
H
NO
O
N
O
H
NO
O
N
O
H
NO
O
N
O
H
NO
O
N
O
H
NO
O
SWCNTs 
complex 
SWCNTs 
Complexes form stable colloidal dispersion in polar 
solvents –enables production of homogeneous polymer films.  
SWCNTs Non-Covalent Functionalization  
SWCNTs, wt%
0.0 0.2 0.4 1.5 3.5 5.5
T
e
n
si
le
 S
tr
e
n
g
th
, 
M
P
a
0
20
40
60
80
100
120
140
160
180
F-SWCNTs
SWCNTs
Agglomeration of SWCNTs is 
clearly visible in the SEM image 
of the SWCNT nanocomposite 
film.  
The addition of 3.5 wt% SWCNT/complexes 
increased the tensile strength of the polyimide 
from 61.4 to 129 MPa; higher loading levels led 
to embrittlement and lower tensile strengths 
National Aeronautics and Space Administration 
www.nasa.gov 18 
Carbon Nanotubes Functionalization – PMC Peer Review 18 
• The oxygen content of the SWCNTs (i.e., photo-oxidation, acid treatment) has been 
studied by X-ray photoelectron spectroscopy (XPS). 
• Photo-oxidation adds nearly 2X the oxygen to the SWNTs than acid treatment alone. 
Results: Photo-Oxidation of SWCNTs   
520530540550560570
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
Oxygen Region
Binding Energy (eV)
N
o
rm
a
liz
e
d
 I
n
te
n
s
it
y
(3)
(2)
(1) 1 2 3
O
xy
g
e
n
 A
to
m
ic
 %
0
2
4
6
8
10
12
14
1.6
6.7
11.3
(1) Photo-oxidized SWCNTs without sensitizer
(2) Acid Treated SWCNTs
(3) Photo-oxidized SWCNTs with sensitizer
(a) Overlay of oxygen peaks from the survey scan after normalizing the carbon peaks.  
(b) Oxygen concentration of SWCNTs oxidized by photo-oxidation (with and without sensitizer) 
and by acid treatment. 
                                   ( a)                                ( b ) 
National Aeronautics and Space Administration 
www.nasa.gov 19 
Carbon Nanotubes Functionalization – PMC Peer Review 19 
 70 
 75 
 80 
 85 
 90 
 95 
 100 
%
T
 
 70 
 75 
 80 
 85 
 90 
 95 
 100 
%
T
 
 1000    1500    2000    2500    3000    3500    4000   
Wavenumbers (cm-1) 
a 
b C-O-C -O-C=O 
OH-C=O O-HCO 
FT-IR: (a) SWCNTs and (b) photo-oxidized SWCNTs. 
280285290295
0
2000
4000
6000
8000
10000
SWNT’s Photo-oxidized w/sensitizer
Carbon Curve Fitting
Binding Energy (eV)
c/
s
C
-C
C
-O
O
-C
=
O
C
=
O
XPS: Curve-fitting of the carbon region of the photo-
oxidized SWCNTs with RB. 
. 
• XPS is sensitive to matrix effects and is able to provide both oxidation and chemical 
state information about the elements detected.   
• An overlay of all of the carbon regions after normalization revealed the presence of a 
shoulder on the main carbon peak (284.8 eV) of the photo-oxidized 
• Peaks at 286.3 eV, 287.9 eV, and 289.3 eV are indicative of C-O, C=O, and O-C=O, 
respectively. 
• Analytical characterizations by FT-IR also confirmed the presence of oxygen groups. 
Results: Photo-Oxidation of SWCNTs   
National Aeronautics and Space Administration 
www.nasa.gov 
Additional Nanomaterials Efforts 
• Magnetic nanoparticle synthesis and dispersion 
• Nanoparticle influence on shape memory polymer 
• Nanoparticle modified carbon fibers 
• Boron Carbide Nanotube materials (radiation shielding) 
• Graphene nanocomposites for improved electrical 
conductivity. 
20 


Polymer and Nano-Material Research in the Polymers Branch at NASA Glenn Research Center

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