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CNT composites for aerospace applications

Article  in  Journal of Experimental Nanoscience · September 2007

DOI: 10.1080/17458080701376348

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Stefano Bellucci C. Balasubramanian

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 CNT Composites for Aerospace Applications
S Bellucci1, C Balasubramanian1,2, P Borin1,3, F Micciulla1,3, G Rinaldi4
1
INFN-Laboratori Nazionali di Frascati, Via E. Fermi 40, 00044 Frascati, Italy
2
Department of Environmental, Occupational and Social Medicine, University of Rome Tor
Vergata, Via Montpellier 1, I-00133 Rome, Italy
3
University of Rome "La Sapienza", Department of Aerospace and Astronautics Engineering Via
Eudossiana 18, 00184 Roma, Italy
4
University of Rome "La Sapienza", Department of Chemical Engineering and Materials, Via
Eudossiana 18, 00184 Roma, Italy
bellucci@lnf.infn.it, bala@lnf.infn.it, borin@pd.astro.it, starfederico@inwind.it,
gilberto.rinaldi@ingchim.ing.uniroma1.it

ABSTRACT on whether it is SWNT or MWNT. Of the two types

SWNT is better suited for mechanical applications.
Carbon nanotubes were synthesized by thermal arc
plasma process after optimization of the synthesis Owing to their exceptional morphological
parameters. These samples were then analysed by characteristics, electric, thermal and mechanical, carbon
Scanning and Transmission electron microscopes (SEM nanotubes yield a material particularly promising as
and TEM), in order to establish the morphology of the reinforcement in the composite materials with metallic
nanostructures. Atomic Force Microscopy (AFM) and matrixes, ceramics and polymers.
Electron diffraction studies were also carried out before The key factor in preparing a good composite
using the sample for the composite material preparation. rests on good dispersion of the nanotubes, the control of
Composites of epoxy resin with curing agent as well as a the bonding between nanotubes and matrix, the density of
mixture of graphite and carbon nanotubes were prepared the composite material [2]. Besides, the type of nanotubes
with varying proportions of the mixture. The electrical (SWNT, MWNT) the synthesis mode (arc discharge,
resistivity of the material was studied under varying laser, CVD) etc are important variables since they
pressure and voltage conditions. Preliminary results of determine the perfection of the structure and the reactivity
these studies present interesting features which are of the surface.
reported here.
2. EXPERIMENT
1. INTRODUCTION
Carbon nanotubes were synthesized in a DC arc
The study of nanotubes has advanced plasma system in helium atmosphere at a pressure of 600
tremendously in a relatively short span since its first torr. Arc was struck between two electrodes consisting of
discovery in 1991 by Iijima [1]. The properties of these a high purity graphite rod and a block of graphite. The
nanostructures are so unique and enhanced that it is discharge is typically carried out at a voltage of 20V and a
finding applications in various spheres of life – right from current in the range of 80 – 100 A. Some amount of the
bio-medical to optical and to space applications [2-12]. evaporated carbon condenses on the tip of the cathode,
Essentially two families of carbon nanotubes forming a slag-like hard deposit. The deposit essentially
exist: SWNT or (single wall nanotubes), that are in the cathode consists of bundles of carbon nanotubes
constituted by only one rectilinear tubular unity and the mixed with small quantity of amorphous carbon.
other MWNT (multi wall nanotubes}, that are constituted The as-synthesised samples were characterized
by a series of coaxial SWNT. Though generally both the by means of SEM, TEM and AFM. Figures 1 and 2 show
types have high aspect ratio, high tensile strength, low SEM images.
mass density, etc. the actual values could vary depending

NSTI-Nanotech 2006, www.nsti.org, ISBN 0-9767985-6-5 Vol. 1, 2006 129

 Fig.1 : SEM images of CNT with arc discharge. Fig. 2: SEM image of CNT which shows straight and
long nanotubes

2.1 Nanotubes Composites resistivity behavior, has not been investigated yet. In the
present work, we fill up this gap, in the part concerning
Due to the unique properties of carbon nanotubes the electrical transport properties.
they are being widely studied as a constituent of
composite material. CNT based composite materials are The composite was made by manually mixing
increasingly being considered for mechanical, electrical the micron sized (particle size ~ 20 microns) graphite
and space applications. Even studies on biosensor powder in the resin+curing agent. Care was taken to avoid
composites based on functionalized nanotubes and air bubbles in the mixture. The experiments were
nanoparticles are reported [9-12]. They are also being performed in two stages : Initially two types of resin with
studied for the suitability and applications in aerospace curing agents were used to find the one most suitable for
and aeronautical fields. A prospective application in the earlier defined applications. In the second stage this
aerospace that we are studying is the improvement of resin was mixed along with the CNT to study the change/
electrical properties of composites made from carbon enhancement of the electrical property.
nanotubes and epoxy resin [13-15]. To start with it was
decided to mix the epoxy resin with graphite. The purpose In order to comply with the standard
was to make a light, thin and mechanically strong specification of the U.S. military authorities, we tested the
composite material to cover electric circuits against electrical properties of the composite materials, making
external electromagnetic interference. This is very use of “Y” shaped electrical circuits having two parallel
important for air and space crafts. lines as the tail of the “Y” with 1 mm gap between them
and a length of about 2.5 cms. The circuits were made on
The epoxy resin that was used is a commercial a PC base with silver print and the two arms of the “Y”
Shell product Epon 828. Two types of curing agent were were connected to the picoammeter and the high voltage
used along with the resin; mainly A1 curing agent and supply. The composite mixtures were spread, like thin
PAP8 agent. Also some of the resin+curing agent samples films, on the circuit and electrical resistance tests were
were mixed with 20 wt% of graphite and these were used carried out using Keithley 6485 Picoammeter with short
for the analysis of the electrical resistivity studies. We circuit protection.
stress that the first curing agent possesses polar groups in The current through the sample was recorded for
its chemical composition, whereas the second agent three different applied DC voltages, namely – 200, 500
contains benzene groups. As a consequence, the and 1000 V. The resistance and the resistivity were then
mechanical properties of composites where the PAP8 calculated. The experiment was repeated under three
agent has been used turn out to be improved [16]. different pressures – atmospheric, 10-2 and 10-6 mbar. The
However, the stability of the mechanical properties, under low pressure measurements gave indirectly the effect of
varying pressure conditions, as well as the corresponding moisture on the resistivity values of the samples. The

130 NSTI-Nanotech 2006, www.nsti.org, ISBN 0-9767985-6-5 Vol. 1, 2006

plots in figures 3, 4, 5 and 6 show the resistivity vs agent the resistivity changes marginally more with
applied voltages for various samples under varying increasing voltage.
voltage and pressure conditions. Notice that the resistivity data were collected
with the same samples at two different times of the year
3. RESULTS AND DISCUSSION (i.e. July 2005 and September 2005), in order to have a
rough estimate of the influence of climatic and
environmental conditions on their performance. It
A. Studies with resin and graphite appears, from a preliminary analysis of our data, that the
Analysing the data it is observed that the stability of composites employing PAP8 agent is
resistivity of samples with curing agent A1 is found to be jeopardized by the addition of graphite. In the case of
a few times lower than the samples with curing agent composites with A1 curing agent the behavior is quite
PAP8. It is important to note that the absolute change in opposite, i.e. the stability of the material increases as
resistivity is less over a wide voltage range of 200 to 1000 graphitic additions are included. This seems to favor the
volts for the sample with A1 curing agent (as seen from use of A1 curing agent from the point of view of the
figures 3 & 4), whereas for the sample with PAP8 curing optimization of the aerospace applications sought for.

Fig. 3: Plot of resistivity vs. voltage for the sample Fig. 4: Plot of resistivity vs. voltage for the sample
Resin+A1 with no graphite added Resin + A1+graphite added.

Fig. 5: Plot of resistivity vs. voltage for the sample Fig. 6: Plot of resistivity vs. voltage for the sample
Resin + PAP8 Resin + PAP8 + graphite added

NSTI-Nanotech 2006, www.nsti.org, ISBN 0-9767985-6-5 Vol. 1, 2006 131

 3.1 Variation of resistivity with about 3 to 5 times.
pressure/humidity These above results when considered in totality
It is expected that when the ambient pressure is gives a broad spectrum wherein we find that the resin +
decreased while doing the resistivity measurements the A1 curing agent + graphite seems to be an ideal candidate
humidity also gets decreased resulting in higher resistivity for applications in various pressure ranges as well as
values. The resisitivity values for all the samples show voltage ranges. The Resin + A1 + graphite has the lowest
some variation when done in atmosphere as compared to changes in the resistivity values for voltages from 200 to
when done in low pressure. However, this variation gets 1000 V and also for a pressure difference of atmospheric
reduced when graphite is added to the resin. to 10-6 mbar
From the plots above we observe that, for the
first sample (i.e. sample with curing agent A1 – figures 3 B. Studies of Resin with CNTs
and 4), when we work in different pressure conditions, the
resistance changes very little Instead in the second Resistivity measurements were performed for
sample, the resistance undergoes remarkable variations composites with A1 resin in combination with carbon
when we work in different pressure and humidity nanotubes (shown in Fig. 1). Composites were made
conditions, as seen in (figures 5 and 6). This feature might replacing graphite with CNTs. The quantity of CNTs
constitute a drawback for the use of the corresponding added was 0.5 wt% of the resin mixture. Figure 7 shows
curing agent PAP8 for composite devices working under the plot of resistivity vs. voltage for this sample. As can
standard aerospace conditions, where the values of the be observed the resistivity values changes drastically with
pressure can undergo substantial variations. the addition of a small quantity of CNTs. The Resin A1
with no graphite or CNT has a resistivity in the range of
3.2 Variation of resistivity with graphite few tens of M ohms (u 105) /cm3 whereas when 0.5 wt%
addition of CNT is added the resistivity reduces by a factor of 103
to values ranging from 0.01 to 0.04 Mohms (u105)/cm3.
Also when these values are compared with the composite
It is observed that the resistivity change is very
of resin A1 with graphite (refer Fig. 4), we observe that
large – near about 3 orders of magnitude when 20%
the resistivity 20 wt% of graphite is ten times higher than
graphite is added to the resin + A1 curing agent, whereas
the addition of a small fraction of CNT.
for the PAP8 curing agent the increase in resistivity due to
addition of graphite is comparatively only marginal, of

Fig. 7 : Plot of resistivity vs voltage for composites of Resin A1 with CNT 4. CONCLUSIONS

Resistivity studies were performed on

the composite material made from a resin with
different curing agents (namely A1 and PAP8).
Comparison was also made of composite of
graphite against composites made from carbon
nanotubes. The results of these studies present
interesting features which are useful in choosing
the ideal composition and ratio of the composite
material for use in shielding of electrical circuits
of space vehicles from radiations of the outer
space.
We can deduce that the PAP8 curing
agent is very sensitive to the humidity variations
over a long time period and cannot optimize the
performance of the circuits. Instead the A1
curing agent in combination with 20 wt%
graphite microparticles is not very sensitive to these variations and makes the behaviour of an electrical circuit more
stable.
The same resing A1 when combined with carbon nanotubes, in place of graphite powder, yielded resistivity
values which were orders of magnitude better than either with plain resin or with large quantity of graphite powder.

132 NSTI-Nanotech 2006, www.nsti.org, ISBN 0-9767985-6-5 Vol. 1, 2006

 REFERENCES
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[2] Ahn C H et al. 2004 Springer Handbook of Nanotechnology, Bharat Bhushan Editor.
[3] S. Bellucci, Phys. Stat. Sol. (c) 2, 34 (2005).
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NSTI-Nanotech 2006, www.nsti.org, ISBN 0-9767985-6-5 Vol. 1, 2006 133

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