Composite materials based on Carbon Nanotubes for aerospace

applications
S. Belluccia*, C. Balasubramaniana, F. Mancia b, M. Marchettic, M. Regic, F. Tombolinia
a
INFN-Laboratori Nazionali di Frascati, Via E. Fermi 40, 00044 Frascati, Italy
b
C.S.M. Centro Sviluppo Materiali, Via di Castel Romano 100, 00128 Roma , Italy
c
University of Rome La Sapienza, Department of Aeronautics and Astronautics Engineering
Via Eudossiana 18, 00184 Roma, Italy
ABSTRACT
Electrical and mechanical properties of composite materials based on Carbon Nanotubes are considered for aerospace
applications. Nanostructured materials gained great importance in the past decade, owing to their wide ranging potential
applications in many areas, e.g. mechanical, structural, sensor, biomedical, electronics. Of particular interest are carbon
nanotubes, which can be used as a main constituent of composite materials with exceptional mechanical and electrical
properties, very suitable for aerospace applications, also due to their light weight, mechanical strength and flexibility. We
present results obtained recently in our laboratories concerning the electrical and mechanical properties (including resilience
measurement, stress analysis, conductivity) of carbon nanotubes we synthesized by arc discharge and other techniques,
embedded in a polymer matrix.
Keywords: Carbon Nanotubes, Composite materials, Mechanical properties, Aerospace structuress, Anisogrid lattices

1.

INTRODUCTION

Carbon nanotubes (CNTs) can be distinguished into: single wall nanotubes (SWNTs), i.e. a cylinder with only one external
wall; multi wall nanotubes (MWNTs), made of multiple coaxial cylinders. The SWNT parameters are the diameter and the
chiral vector (n,m) or helicity, i.e. the graphite rollup direction wth respect to the cylinder axis. On the other hand, a MWNT
is made of coaxial SWNTs. The main properties of CNTs are: mechanical properties; conductivity; gas adsorbtion and
capillarity; field emission (FE); fluorescence.
The mechanical resistence of CNTs is due to one of the strongest bonds in nature, i.e. the C-C sp3 one. Their flexibility
allows one to bend CNTs repeatedly up to 90 without breaking or damaging them. The exceptional mechanical properties
of CNTs find two different applications: the strengthening of fibers in high-performance composite materials, replacing
standard C fibers, kevlar, glass fibers; the probes for scanning tunneling microscopes.
Owing to their extreme properties, CNTs yield suitable candidates for aerospace applications, such as CNT-based electron
field emitters and composite materials for extremal conditions (aerospace environment, large temperature and pressure
gradients, radiation etc.). Their high structural perfection, lightweight and chemical inertness may be ideal for spacecraft
atmosphere re-entering applications.

2.

CARBON NANOTUBES LIFECYCLE: PHASES AND REQUIREMENTS

CNTs can be synthesized by different methods (see e.g. [1-4]), including arc discharge, laser vaporization, chemical vapour
deposition (CVD). The latter yields the most important technique for potential industrial applications (see Table 1).
One needs to implement purification techniques, as synthesized CNTs are always contaminated by unwanted elements, such
as: other forms of Carbon; metallic particles from the catalyst; substrate granules (for CVD). The role of defects in CNTs
consists essentially in increasing the range of application of their properties (similarly to what happens for doping in
semiconductors). Defects can be induced by various methods, e.g. high energy ion bombardment, high thermal processes.
Defects are useful in many applications, as they can be used to functionalize the NTs and change their properties
considerably. Defect induced property enhancement can be observed in connection with the mechanical properties of CNTs.
Changes in stiffness are observed, i.e. the stiffness decreases with the unavoidable topological defects (intrinsically forming
in the synthesis process) and increases with functionalization (on the defect sites); defect generation and growth are
observed during the plastic deformation and fracture of NTs; composite properties can be improved with chemical bonding
between matrix and NT.
Table 1

Lifecycle of CNTs.

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NTS LIFECYCLE
MANUFACTURING TECHNOLOGICAL PROCESS
PLANNING AND
SYNTHESIS

CHARACTERIZATION

FUNCTIONALIZATION

Requirements :
Choice and use of the
procedure, chemical
composition of the material
and the substrate for the
selected application
Methods :

Requirements :
Define and measure the
properties of the deposited
NTs
Methods :

Requirements:
Post-syntesis treatment of
the NTs, for aligning the
achieved properties with
the expected ones
Methods :

Inert Gas Phase

condensation

Plasma Synthesis (CVD,

Arc discharge)

Laser ablation
Laser Pyrolysis
Sol-gel Synthesis
Electrochem. etching
Ball milling

SEM
TEM
Raman spectroscopy
AFM
STM
FTIR
XRD
Particle Channeling

3.

APPLICATIONS

Requirements:
Manufacturing of Prototypes of
the selected applicative driver,
to be forwarded to the industrial
and the production phases
Methods :
Diverse, depending on the
specific selected application
Main Applications

Ion-Beam Bombardment
UV Laser Light Irradiation
Chemical Purification
Biological and space research
Use of e.m. fields
Micro/nanostructured films, for
Patterning
X-ray sources and gas
discharge tubes.
Interaction sample Vacuum technology, sensors,
substrate (AFM)
Note: Some techniques
can be applied during
deposition, for achieving
adequate properties

electro- medical devices

Applications in radiotherapy.

MATERIALS AND SYNTHESIS CRITERIA

Our DC arc plasma, struck between two graphite rods technique yields high quantity of CNTs. We completed recently a
thermal CVD, useful for patterned substrate and large area deposition. SWNTs and MWNTs are obtained in our laboratories
under varying synthesis conditions, using different parameters e.g. the plasma current, thermal gradients. The samples are
studied with electron microscopy (Fig. 1, coll. CNR-IFN, Rome, Italy) for determining optimal conditions for maximum
yield of CNTs (in relation to amorphous material, onion-like strutures, nanoparticles and so on) [5-7].

High-yield raw material:

cathodic deposit obtained by a
arc-discharge technique, (SEM
imaging in coll. with CNRIFN, Roma).

Fig. 1

122

SEM image of a nanotube carpet

synthesized at INFN -LNF with a
different arc-discharge setup, (SEM
imaging in coll. with CNR-IFN, Roma).

SEM images of CNTs synthesized at INFN-LNF.

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Concerning the characterization of INFN-LNF CNTs, a morphological analysis of our samples by SEM, TEM, AFM, STM
yields ratio and dimensions of the CNTs. SEM images show that the ratio of NTs is very high (more than 70%). SWNTs
have an average diameter 1.3 nm and a length of several microns. They exist in bundles of 20 40 nm transverse size.
MWNTs have a wide range of diameter (20 60 nm). Through AFM studies of our samples we evaluated, for different
types of substrate, the friction coefficient of the nanotube with the substrate surface. Contact mode AFM was used for the
imaging under a constant force (coll. IMM-CSIC Madrid, Spain ). The nanotube samples were initially dispersed in
isopropyl alcohol and sonicated for a few hours. Drops of this were then suspended on three different substrates, namely
highly oriented pyrolithic graphite (HOPG), Silicon wafer and Mica sheet (Fig. 2).

H
O
P
G

m
i
c
a

600nm

600nm

600nm
Si

Fig. 2 AFM images of CNT on (a) HOPG (b) Mica and (c) Silicon surface
The adhesion of nanotubes was found to be highest for HOPG, as compared to mica and silicon (where the nanotubes got
displaced easily by the AFM tip). Also it was observed that the nanotubes got laterally compressed on a HOPG surface (due
to Van der Waals interaction of the nanotubes with the substrate) to a ratio of 0.5. For mica and silicon there was lateral
elongation of the order of nearly 3 times , indicating that the interaction of the tube with tip was far greater than the
interaction of the tube surface with substrate. From such results we can say e.g. that mica and silicon can be used for
nanomechanics and HOPG for applications where strong bonding of nanotubes to substrates is required.

4.

DISPERSION TEST OF NANOMETRIC PARTICLES IN AN EPOXY RESIN MATRIX

In the manufacturing of nanostructured composite materials [8], the primary step is the definition of a procedure necessary
to obtain an homogeneous dispersion of a nanometric particles in the polymeric matrix (epoxy resin). The mechanical
behaviour of this new kind of composite material is related to the interface between the resin and the nanoparticles
(chemical characterization, adhesion problems, etc.). The materials employed in manufacturing composite samples are:
commercial epoxy resin
curing agent: developed by Chemical Department of La Sapienza University Rome
nanometric graphite powder with carbon nanotubes
graphite powder granulometry 20 m.
Fig. 3 (left) shows an examples of the specimens produced (dimension: 10x10x120 mm) with a different percentage of
embedded nanoparticles (0%, 10% and 20% in wt) [9-11].

Fig. 3 Specimens for mechanical tests (left); Optical analysis of composite sample (right)
The following curing process were adopted:
room temperature curing x 24 hrs
furnace curing 80 C x 3 hrs.
Dynamic tests where performed obtaining the following preliminary results:
1. the reduction of powder granulometry increases the impact resistance properties
2. a good surface finishing improves the mechanical properties.
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Fig. 3 (right) shows the fracture surface of a sample containing 20 % of nanoparticles. The pre-crack length is 2 mm. A
brittle behaviour of crack propagation is evidenced. With the SEM characterizations it is possible to understand the fracturemechanic composite behaviour. Fig. 4 shows the SEM images of the samples containing 10% or 20% of powders. In the
area A (crack initiation) and B (propagation) there is no presence of preferentialdirections of crack propagation.

Fig. 4 SEM analysis of fracture surface of composite specimen:10% powder addition (left); 20% addition (center and right)
Instead, in the sample containing 20% powder, preferential directions of crack propagations are observed (Fig. 4 center,
zones A,B, C and D). The presence of a preferential direction is due to the non-uniformity of powders dispersion in the
matrix and to the curing process. With another SEM investigation, it is possible to observe a fracture lines change direction
in correspondence of cavities (or voids). In Fig. 4 right, two fracture lines (A & B) are deviated by the presence of a void
(see points C & D), and are stopped in point E. The next step is to apply this new composite material to the aerospace
structures. The anisogrid lattice (Fig. 5) is a particular structure configuration characterized by helicoidal rib (resistant to the
compression load), and circumferential rib (to ensure stability against local and global buckling).

Fig. 5 Anisogrid lattice structures

With the assigned values of the radius (R) and height ( H) of a cylindrical structure, of the applied external compression load
(W) and of the employed material, it is possible to calculate the ribs dimensions (Fig. 5) with the Vasiliev model [12],
satisfying the following three requirements:
Minimum mass of the element
Static resistance
Local and global buckling stability.
The Vasiliev model is only a preliminary design. A FEM analysis is always requested (Fig. 6, left). A MATLAB programs
was developed to evaluate the dimensions of the anisogrid element, when a set of the structures characteristic dimensions
are given (radius R, height H and the applied load W). With the Vasilev model it is possible to calculate the variation of the
geometry of the anisogrid element, when radius R and height H of the structure are simultaneously varied (see in Fig. 6,
center, the plot 3D of the mass structure vs. R and H). This is a important application for the launchers design.

Fig. 6 FEM analysis (left); Structure Mass Mvs Radius R and Length H (center); Dynamic analysis (right)
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It is necessary to verify that, in correspondence of structure calculated dimension (with the Vasiliev Model), the applied
load is exactly the buckling load (unitary eigenvalue). Different kinds of load and constraints distributions have been
studied. An eigenvalue 0.98 was reached, thanks to the following configuration:
The load is uniformly distributed on all the nodes of the FEM model
The basement of the structure is constrained against translation
All the remaining nodes of FEM model are constrained against rotation.
The 0.98 eigenvalue demonstrates that, with the above loads and constraints configuration, the buckling stability in the
minimum mass (Vasiliev model) is verified. With the same configuration it is possible to satisfy the static resistance
condition. Also a dynamic analysis of the element has been performed (Fig. 6, right). This analysis is important for the
integration of a space system (for example a satellite) inside a launcher. The Vasiliev model is useful, in order to evaluate
the mass reduction of the structure, when different materials (for typical aerospace applications) are used.
In particular: a) aluminium alloy Al 2024, b) composite epoxy resin carbon fibres reinforced (Hs/Ep), c) composite epoxy
resin reinforced by carbon fibres and by a dispersion of carbon nanotubes, 5% by weight. The Vasiliev Theory is applied on
a cylindrical anisogrid lattice geometry (radius R =1.5 m, height H = 4 m, applied load W = 3 MN) (Table 2).

Table 2 Structure Mass calculated for different materials

Table 2 shows how the use of CNTs , with the given particular geometric configuration (anisogrid), yields the possibility to
design a very advanced aerospace structure. The validation of the structure requires the following steps :
preliminary design numerical FEM analysis prototype design
prototype manufacturing
final test.
After a computerised calculation and verification by FEM analysis, a flat prototype of anisogrid lattice structure was
produced. The final target is the realization of a full scale anisogrid cylindrical prototype.
After a preliminary design (Fig. 7, left, dimensions: 21x17 cm), the mould was prepared (Fig. 7, center) by traditional
mechanical tooling. For the manufacturing of the prototype the following materials are used:
epoxy resin
curing agent (Triaethylentetramin)
glass fibres (12000 per single filament)
nanometric powder (graphite) + carbon nanotubes,
with the curing process below
room temperature (21 C) curing x 24 hours
furnace curing at 80 C x 3 hrs.

Fig. 7 Structure preliminary design (left); Mould (center); Flat anisogrid lattice prototype (right)
Fig. 7 (right) shows the produced prototype after some preliminary and successful mechanical tests (vibration and tension
applied loads). For a future industrialization in the anisogrid elements manufacturing, a CAD design was performed (see
Fig. 8, left ), necessary to realization (with the rapid prototyping technology) of a positive simulacra (Fig. 8, right). The
negative mould was obtained in Si resin (Fig. 9).

Fig. 8 CAD design of the anisogrid lattice flat element (left); Rapid prototyping positive mould (center);
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Fig. 9 Negative silicon mould and the relative flat anisogrid prototype manufactured
For the cylindrical geometry the same procedure is necessary (Fig. 10).

Fig. 10 Cylindrical anisogrid element manufacturing procedure

5.

CONCLUSIONS

The addition of carbon nanotubes in a composite material (epoxy fibre reinforced polymers) improves the mechanical
properties. In particular, the increase of the Young Modulus offers the possibility to further reduce the mass of the structure
in correspondence of the same mechanical properties and performance. Besides, with the innovative design of anisogrid
lattice structures (manufactured with composite materials containing carbon nanotubes), it is possible to obtain a strong
overall mass reduction of the structural component, maintaining the stability requirements.

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*bellucci@lnf.infn.it; phone 39 06 9403-2888 (or -8222); fax 39 06 9403-2427 (or -2716)

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