Novel Hybrid Composites for Defense

Applications
Marwan Al-Haik
ONR Award No# N000141210380

Annual ONR Department Review

Office of Naval Research, Washington DC
June, 2014
 Outline

• Hybrid composites based on Mixing CNTs within FRP

• Hybrid Composites based on Surface Grown CNTs

• Hybrid Composites based on Surface Grown ZnO

• Smart composites for in situ SHM,

• Conclusions

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 Objective

• This project aims at developing multifunctional, multiscale, 
lightweight hybrid carbon fiber/CNTs and carbon fiber/ZnO 
nanowire polymeric composites for naval structures. 

• The synthesis and characterization experiments will ensure 
excellent mechanical properties : strength, stiffness, damping, 
Impact resistance.

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 Technical Approach

• The novelty of the present approach for developing composite 
materials is growing CNTs and or ZnO nanowires on the surface 
of microscale carbon fibers at relatively  low temperatures. 

• The resulting microstructure will be added to epoxy matrices to 
produce the polymeric composites. 

• Through variations of process parameters and structural 
topologies, the properties of the hybrid composite materials 
could be tailored to specific needs. 

• The developed materials offer the combined advantages of the 
carbon fibers and CNTs and ZnO reinforced composites.

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 Hybrid Composites based on CNTs

Adding CNTs to matrix Grafting CNTs onto the surface Spinning /processing
of the carbon fibers continuous yarns from CNTs
arrays

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 Three-phase Composite:
Carbon Fiber/Epoxy/CNTs

• Fiber: PAN-based plain-woven carbon fabric in 3,000 filament count tows (HexTow AS2C supplied by
HEXCEL Inc.) Tensile strength 4,440 MPa, Modulus=221 GPa, Elongation at Failure =1.9% ). Vf=60%
• Matrix: Aeropoxy™, by PTM&W Industries, Inc. ( Strength=67.7 MPa, Modulus=2.88GPa, , Elongation at
Failure =1.9% )

• Short MWCNTs (0.5-2.0 microns) from Cheaptubes, Inc., with a purity of 95 wt% and an average
diameter of 8 nm.
• The MWCNTs accounted for 2.0% of the total weight of the matrix. The CNTs were dispersed/ sonicated
homogenized and shear mixed.
• Fabrication: Pressure assisted, hand layup, 5 laminates, cured at 60 C.
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 Composites based on Added MWCNTs

~ 1% 12%
<1 %

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 Composites based on Added MWCNTs:
Dynamical Mechanical Analysis (DMA)

Tan delta 26% improvements on average

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 Energy Absorption Composites
based on Added MWCNTs
1.27 cm alloyed steel ball-bearing with a weight of approximately 8.4 grams.

Avg. Speed 100-110 m/s

The trajectory captured through a high-speed camera at 30,000 frames per second.

9.0% 10.1%
21.3%

Absorbed impact and shear punch energies

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 Graphitic Structures by Design
(GSD)

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 Fiber’s Configurations

Description
Raw Raw fabric as received
HT Raw fabric exposed to GSD growth environment (no CNTs grown)
Ni+G Raw fabric with GSD grown CNTs (catalyst: 2 nm nickel film)
Ni+2G Ni+G sample where CNT growth duration was doubled to achieve longer CNTs

Ni+CPG Ni+G sample where the underlying nickel catalyst film formed a coarse checkerboard
pattern

Ni+FPG Ni+G sample where the underlying nickel catalyst film formed a fine checkerboard
pattern
SiO2 Raw fabric coated with a 75 nm SiO2 layer
SiO2+HT SiO2 sample exposed to GSD growth environment

SiO2+G Raw fabric coated with a 75 nm SiO2 film and subsequently a 2 nm nickel catalyst
film. CNTs were thereafter grown on top of the coated fibers.

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 Coarse Vs Fine Growth Patterns

CFG: (a) Thread size 400 µm, opening size 840 µm, and an open area of
46% and FPG:(b) thread size 76 µm, opening size 140 µm, and an open
area of 24%. Inset: mesh pattern showing the threads and open areas.

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 Samples; de-sized fibers

Normal Growth Patterned Extended

Growth Growth

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 Materials & Processing

• Fibers: Plain-weave un-sized SGP196 carbon fiber (IM7-GP) fabric

with 6000 filament counts in a tow. Strength=5,310 MPa,
Modulus=276GPa, Elongation at Failure =1.8% .

• Matrix: Aeropoxy™, by PTM&W Industries, Inc. Strength= 67.7

MPa, Modulus=2.88 GPa, Elongation at Failure =1.9%

• Avg. Grown MWCNTs (2.0 microns).

• The MWCNTs accounted for 0.05% of the total weight of the fiber.
• Fabrication: Pressure assisted, hand layup, 5 laminates, cured at 60
C.
• Vf=52%.

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 Composites based on Surface
Grown CNTs On-axis Results

4.2%
3.3% 12.0 11.0
11.0
1.7%
0.9%
0.3% Ref 1.7
Ref -3.0 -2.0
-1.0% -1.6 -5.8
-2.1%
-11.0

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 Composites based on Surface Grown
CNTs On-axis results, cont.

37% 35%

22%
16.0%
8.6%
7.2%
3.3% 3.1 %

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 Composites based on Surface
Grown CNTs:
Off-axis Results

19.0%
16.0% 16.0% 5.0%
Ref -1.0% 1.0%
-4.0% -10.0%
12.0%
-17.0%
7.0% 7.0% 6.0%
Ref
-5.0% -48.0%

-20%

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 Composites based on Surface Grown
CNTs: DMA

56% improvements on average

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 Impact Delaminated Cross
Sections and Absorbed Energy

R HT

Ni+G Ni+FPG

SiO2+HT SiO2+G

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 Composites based on ZnO over Carbon
Fibers

Mixture of zinc acetate

hexahydrate Zn(O2CCH3)2(H2O)2
and Hexamethylenetetramine
(HMTA) (CH2)6N4

The solution is left in a

convection oven at 85°C, and
then the pre-sputtered fabric is
immersed in the solution for 4
hours.

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 Materials

Fibers: PAN-based plain-woven carbon

fabric (AS2C supplied by Hexcel Inc.) with
3k bundles. Strength=4,500 MPa, ,
modulus=231 GPa, elongation to
failure=1.8%

Matrix: Epon 815C (resin) and Epikure

3282 (curing agent) supplied by Miller-
Stephenson Chemical Company, Inc.
Tensile strength= 75 MPa tensile
elongation= 6.5%.
Fibers wt increase=0.7% after ZnO growth

4-layers. Pressure assisted hand lay-up,

cured at 60°C for 4 hours and post cured in
the oven for 2 hours at 100°C.

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 ZnO/Carbon Composites
DMA Results

ZnO NWs increase the internal friction and hence the damping (50%)

but reduces slightly (7%) the structure storage modulus

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 ZnO over Carbon Fibers:

On-Axis results Off-Axis results

20% increase in tensile strength 25% increase in tensile strength

7% increase in Young’s modulus 7% increase in Young’s modulus

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 Interlaminar Shear Strength

87% improvement in ILSS when growing ZnO NWs on CF’s surface

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 Stress Relaxation

Neat ZnO

Patterned CNTs
HT

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 Stress Relaxation
25°C  Neat p‐CNT ZnO  HT
20%  1.059342 0.668275 0.866573  0.868584
40%  1.766245 1.362406 2.04619  2.058689
60% 3.556796 2.151806 3.748239  4.263741
80%  4.814638 3.398118 4.509082  5.696185
45°C 
20% 1.913202 1.434373 1.449862 1.607032
40% 2.652005 2.15709 2.877453 2.651244
60% 4.229969 3.285414 5.273846 4.595969
80% 5.713981 4.837782 7.102321 6.950715
65°C   
20%  2.296914 1.905199 1.807146  2.47688
40% 4.361795 2.736171 3.02819  3.883592
60%  5.715676 3.568918 5.250491  5.103873
80%  5.990284 5.236189 6.766621 7.542014
85°C
20% 4.026611 2.836245 3.690051 4.097273
40%  6.227166 3.52668 4.203568 7.090168
60% 7.896453 4.845896 8.975187  9.289945
80%  9.385748 5.924324 9.584136  12.39058
  Normilized percentage of stress reduction after 15 min
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 Creep

ZnO
Neat

HT P-CNTs

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 Creep
25ºC  Neat  p‐CNT  ZnO  HT 
20% 0.919422 0.857499 0.648315  0.933761
40% 2.225635 1.241896 1.867918  1.21874
60% 3.7728 1.827361 1.989878  1.934219
80% 3.84889 2.330033 2.894952  4.46265
45ºC 
20% 1.440493 0.888466
1.253448 0.94134
40% 2.224122 1.718059
2.793999 1.27461
60% 3.797141 2.440607
3.004075 2.572607
80% 5.756212 2.531594
3.879388  4.677467
65ºC   
20% 1.540948 1.080037 1.510925  2.511946
40% 2.534919 1.73595 2.40563  2.87518
60% 4.416993 2.520087 3.122578  2.9775
80% 5.857956 2.96887 3.484015 5.059704
85ºC
20% 2.098429 1.084969 1.915418 2.552874
40% 3.005857 1.903627 3.014345  2.880296
60% 5.540986 2.934348 3.260833  4.51741
80% 6.164843 3.304224 4.462463  5.402474
 
Normilized percentage of creep after 15 mins

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 Smart Composites with In-situ
Structural Health Monitoring

Proposed Solution
Need for a structural health monitoring (SHM)
Problem
system that can detect delamination at the early
Structures made of fiber
stages.
reinforced plastics (FRPs) are
exposed to interlaminar Zinc oxide (ZnO) piezoelectric nanowires for
delamination that SHM can increase inspection area for less
compromises the structural money than leading technology; PZTs. It also
stability and results in can strengthen the composite.
catastrophic failure.

Delamination

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 Smart Composites with In-situ
Structural Health Monitoring
• We built a composite beam that incorporates ZnO nanowires  with a 250  m  
cupper layer acting as electrode.
• Mechanical vibrations were  imposed using electrodynamic shaker. The tip 
displacement of the piezoelectric composite beam was measured with a laser 
vibrometer sensor.
• The dynamic properties of the fabricated beam were characterized. The open 
circuit voltage was examined at the resonant frequency (f= 43.2 Hz) of the device. 

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 Smart Composites with In-situ
Structural Health Monitoring
• We induced both surface damage and delamination damage (separately) 
and measured the change in the electrical impedance of the beam.
• Clearly, there is a noticeable change in impedance (it always decreases) 
with the presence of damage.

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 Why not, ZnO NW+ MWCNTs?

ZnO-CNT-G: Carbon fibers undergone sputtering and then soaked in a solution

containing Zn2+ cations in DI water for 4 hrs at 85 ºC to grow ZnO nanorods and
then are coated with 2 nm of Ni layer and then undergone CNT growth process
for 1 hr at 550 ºC to grow CNTs on top of ZnO nanorods.

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 Conclusions

• Growing CNTs directly yields improvements on the on on‐axis 
and off‐axis strengths and moduli. It also improves the impact 
resistance and damping.  
• Maximum improvements on both on‐axis and off axis tensile is 
through patterned growth of CNTs. 
• Growing CNTs on carbon fibers also enhances Viscoelastic 
performance( creep compliance).
• ZnO NWs improve the damping within the CFRP structure.
• ZnO NWs growth increases interlaminar properties of CFRPs and 
relaxation and creep resistance.
• Growing ZnO also can provide ins‐situ SHM capabilities of large 
structures.
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 Publications
(Aug 2013-Aug 2014
Published/accepted
1. M. Safdrai** and M. Al‐Haik. Synergistic electrical and thermal transport properties of hybrid polymeric nanocomposites 
based on carbon nanotubes and graphite nanoplatelets. Carbon, 64: 111‐121 (2013).
2. M. Tehrani, A.Y. Boroujeni**, C.C. Luhrs, J. Phillips and M. Al‐Haik. Hybrid composites based on carbon fibers/carbon 
nanofilament reinforcement. Materials,7, 4182‐4195 (2014).
3. A.Y. Boroujeni**, M. Tehrani, A.J. Nelson**, M.S. Al‐Haik. Hybrid Carbon Nanotube‐Carbon Fiber Composites with Improved 
In‐Plane Mechanical Properties Composites. Composites Part B: Engineering,66: 475‐483 (2014).
4. N. Masghouni** and M. Al‐Haik. Quasistatic and dynamic mechanical characterization of a woven carbon fiber‐‐zinc oxide 
nanowires‐‐epoxy composite. Polymer Composites, published online: 3 JUL 2014, DOI: 10.1002/pc.23129 (2014).
5. A. Alipour Skandani **, A.Y. Boroujeni**, R. Kalhor **, S.W. Case and M. Al‐Haik. Viscoelastic behavior of epoxy/carbon 
fiber/zno nano‐rods hybrid composites. Polymer Composites, published online: 18 JUN 2014, DOI: 10.1002/pc.23106 (2014).
6. N. Masghouni** and M. Al‐Haik. Computational Molecular Dynamics Study of Hybrid Composite Incorporating ZnO 
Nanowire. Journal of Computational and Theoretical Nanoscience, In press (2014). 
Under review
1. A.Y. Boroujeni**, M. Tehrani, , M.S. Al‐Haik. Impact damage assessment of hybrid carbon nanotube/carbon fiber reinforced 
polymer composites. Polymer Composites (2014).
2. N. Masghouni**. J. Burton*, M. Philen and M. Al‐Haik. Investigating the energy harvesting capabilities of a hybrid 
multifunctional zno nws/cfrp composite device. Nano Energy, under review (2014).
3. A.Y. Boroujeni**, M. Tehrani, M. Manteghi, Z. Zhou, M. Al‐Haik, Electromagnetic shielding effectiveness of a hybrid carbon 
nanotube/glass fiber reinforced polymer composite, ASME Journal of Materials Science & Engineering, submitted (2014).
Other Publications
• Two provisional patents (Dec 2013, Feb 2014)
• Two PhD dissertations: Amir Alipour Skandani, Aug 2014), Nejib Masghouni ( May 2014)
• 10 Conference proceedings/presentations (ASME, MRS,..)

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