CNTs

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Introduction
Nanotechnology has emerged at the forefront of science and technology development. Carbon nanotubes (CNTs)
are major building blocks of this new technology. Due to their unique combination of electronic, thermal and
mechanical properties, the interest of the scientific community in potential applications of CNTs in composites,
electronics, computers, hydrogen storage, drug delivery, sensors, and many other areas has rapidly grown. Indeed,
NASA is developing materials using CNTs aiming for space applications, seeking to take advantage of their
superior stiffness and strength. It is strongly believed that carbon nanotube based composites could offer
strength/weight ratios beyond any material currently available.
An ideal carbon nanotube can be considered as a graphene sheet rolled-up to make a seamless cylinder with a
diameter as small as 0.4 nm, length of up to a few centimeters, and half of a fullerene molecule in each extremity
[1]. There are many types of carbon nanotubes, including single wall carbon nanotubes (SWCNTs), double wall
carbon nanotubes (DWCNTs), and multi wall carbon nanotubes (MWCNTs) (see Fig. 1). SWCNTs consist of a
single sheet of graphene forming a cylinder [2, 3]. DWCNTs consist of two such cylinders in a concentric
arrangement [4], whereas MWCNTs consist of an array of concentric cylinders that are positioned 0.35 nm distant
from each other [5].

Fig. 1 Schematic diagram of a single wall carbon nanotube (a), a multi wall carbon nanotube (b) and a double wall
carbon nanotube (c) (reproduced from [6]).

History of CNTs
Most reports on the literature attribute the discovery of hollow, nanometric-sized tubes composed of graphitic
carbon to the work of Iijima, published in 1991 [1], whereas the SWCNTs concept was first reported in 1993 in two
independent papers published by Nature, one by Iijima et al. [2] and the other by Bethune et al. [3]. However, a
much older paper, published by Oberlin et al. in 1976 [4], presents a Figure illustrating a nanotube, perhaps a
SWCNTs. The authors did not state that it was a nanotube structure and, due to magnification issues, the number of
walls could not be determined. Nevertheless, such a structure is now called a single- or double-wall carbon
nanotube [5].
The paper of Iijima in 1991 evidenced the possibility of growing CNTs without the need of a catalyst and boosted
research on MWCNTs [1], although the possibility of growing carbon filaments from the thermal decomposition of
gaseous hydrocarbon was first reported early before that, in 1889 [6]. In fact, the papers of Schzenberger et al. [7]
and Plabon [8] can be considered the earliest evidence of the growth of carbon nanotubes.

With the advent of the commercial transmission electron microscopes in 1939, significant progress towards the
characterization of carbon filaments was achieved. In 1952, Radushkevich et al. [9] published what is believed to be
the first transmission electron microscopy (TEM) image supporting the tubular nature of the nanometric-sized
carbon filaments. According to some authors, Radushkevich et al. should be credited for the breakthrough idea that
carbon filaments could be hollow and have a nanometric size, that is to say for the discovery of CNTs [10]. Having
said that, the paper published by Iijima in 1991 showing high resolution images of carbon nanotubes (see Fig. 1)
caused an unprecedented change in carbon science [1]. Eighteen years later, the number of publications related to
CNTs is still increasing exponentially.

Fig. 1. TEM micrographs of three MWCNTs consisting of five, two and seven concentric graphene shells
(reproduced from [1]).

Structure of CNTs
There are various ways of defining the structure of carbon nanotubes. One possibility is to consider that CNTs may
be obtained by rolling a graphene sheet in a specific direction,maintaining the circumference of the cross-section
[1]. Since the microscopic structure of the CNTs is closely related to graphene, the tubes are usually labeled in terms
of graphene lattice vectors. In addition, the reference to graphene allows the theoretical derivation of many
properties of carbon nanotubes.
The atomic structures of the carbon nanotubes may be described by the tube chirality, or helicity, defined by the
chiral vector, Ch, and the chiral angle . In Fig. 1, a graphene sheet with defined chiral vector and angle may be
seen. The chiral vector can be described in terms of the lattice translational indices (n,m) and the unit vectors a1 and
a2 (see Fig. 1), as shown in Eq. (1):
Ch=na1+ma2
(1)
where (n,m) are integers representing the number of steps along the zig-zag carbon bonds of the hexagonal lattice.

Fig. 1. Schematic diagram showing how a hexagonal sheet of graphite is 'rolled' to form a carbon nanotube.

The chiral angle , determining the degree of twisting" of the tube, is defined as the angle () between the vectors
Ch and a1, which varies in the 0o || 30o range. In terms of the integers (n,m), can be described by the set of
equations below [1]:

Based on the geometry of the carbon bonds around the circumference of the tube, there are two limiting cases,
corresponding to the achiral tubes, known as armchair ( = 30 o) and zig-zag ( = 0o), as shown in Fig. 2. In addition,
when 0o < || < 30o, the nanotube is called chiral. In terms of the chiral vector, a nanotube is armchair for (n,m) and
zigzag for (n,0).

Fig. 2. Schematic model of (a) an armchair nanotube, (b) a zig-zag nanotube, and (c) a chiral nanotube (reproduced
from [2]).
Once the inter-atomic spacing between carbon atoms is known, the nanotube diameter (d, in ) may be calculated
by Eq. below:

Production Methods
Carbon nanotubes can be synthesized using different methods. Amongst the most common arc discharge [1-5], laser
ablation [6], chemical vapor deposition (CVD) from hydrocarbons [7-11] and high pressure conversion of carbon
monoxide (HiPco) [12]. The production of CNTs with high purity and uniformity, low cost, and at a large scale is
still a major concern of the scientific community and the industry. In this section, the most important methods for
producing CNTs and some of the benefits and drawbacks of these processes will be briefly reviewed.

Arc Discharge
Arc discharge was the method used by Iijima in 1991 to prepare MWCNTs [13]. In this method, a DC arc plasma is
generated between two carbon electrodes under an inert atmosphere, as depicted in Fig. 1. As the anode is
consumed, a soft fibrous deposit containing carbon nanotubes and other carbon particles is formed on the cathode
[14,15]. To achieve SWCNTs, the electrodes are doped with a suitable catalyst, such as Ni-Co, Co-Y or Ni-Y [2,1517]. The tubes produced by this method are usually tangled and of varied length and diameter. However, the CNTs
are of high quality, with low incidence of defects.

Fig. 1. Schematic illustration of the arc-discharge method (reproduced from [5]).

Laser Ablation
Laser ablation was first used for the synthesis of fullerenes. In this method, a graphite target is vaporized by laser
irradiation under flowing inert atmosphere at temperatures near 1200 oC [18-20], as shown in Fig. 2. The laser
vaporization produces carbon species, which are swept by the owing gas and accumulate on a water-cooled
collector [21]. SWCNTs remarkably uniform in diameter can be produced when the graphite target is doped with a
small amount of transition metals such Ni and Co.

Fig. 2. Schematics of the laser ablation method (reproduced from [22]).

Chemical Vapor Deposition

Chemical vapor deposition (CVD) has been used to produce carbon filaments and fibers since the 1960s. In this
method, a carbon-containing gas is decomposed on a substrate in the presence of catalyst metal particles at high
temperatures ( 600 oC or higher) [23], as illustrated in Fig. 3. The lower temperatures used in this method reduce
production costs. In addition, the deposition of catalysts on the substrate allows the formation of novel structures.
However, CNTs made by this method generally have a very large amount of defects [24].

Fig. 3. Schematics of the CVD apparatus.

High Pressure Conversion of Carbon Monoxide (HiPco)

The method called high pressure conversion of carbon monoxide (HiPco) is employed to produce SWCNTs by
continuously flowing CO gas phase (i.e. the carbon feedstock) and Fe(CO) 5, the catalyst precursor [25], through a
heated reactor (see Fig. 4). The average diameter of HiPco SWCNTs is approximately 1.1 nm and the yield reaches
70 % [12, 26]. CNTs made by this method generally have an excellent structural integrity, although the production
rates are still relatively low.

Fig. 4. Layout of CO flow-tube reactor, showing the water-cooled injector and the `showerhead' mixer (reproduced
from [12]).

The carbon nanotube production methods described above are the most often cited in the literature. Nevertheless,
several adaptations of these methods and new tendencies in the production of carbon nanotubes are constantly
emerging, such as those reported in references [25-36].

Cost and Production

The CNTs production methods described previously show large differences with respect to achievable space-time
yield, amorphous carbon content and carbon purity [1]. The arc discharge and laser ablation methods usually
produce on the gram scale and are therefore, relatively expensive. Currently, the CVD method is believed to yield
large amounts at the lowest prices, although the nanotubes show more imperfections [2].
In 2006, the global production capacity of MWCNTs was higher than 300 tonnes. The Bayer company, for instance,
was operating with a nominal production capacity of 60 ton/year in 2007. In 2010 Bayer has opened the largest
carbon nanotube facility in the World, boasting annual capacity of 200 tonnes.
The 2009 overall SWCNTs production was estimated in the hundreds of kilograms worldwide, with a production
rate that could reach 50 g/h.
The expectation for the next 5-10 years is that the demand for CNTs will grow steadily, as long as cost/quality,
purity and production yield issues are overcome. The cost of carbon nanotubes has been changing considerably in
the past few years, being dependent on their purity and type as well as the supplier. The MWCNTs cost is usually
between US$ 0.5-100/g, while DWCNTs can be obtained for around US$ 10/g. The cost of SWCNTs also varies a
lot, usually between US$ 20-2000/g.

Health Issues
All materials pose some treat to health. Even water, the sustence of life, can be toxic. When too much water is
consumed, it causes an electrolyte imbalance leading to hypotonia, a condition in which a salt imbalance leads
quickly to death. Thus, a key aspect to understanding toxicity of materials is to know how much of a substance - the
dose - can cause harm [0].
The disseminated use of nano-based materials has raised debate on the toxicological and environmental aspects, for
instance the expected effects due to direct and indirect exposure to these materials. The concern about CNTs toxicity
originated from their structural resemblance to asbestos. Inhalation of asbestos fibers is known to induce asbestosis
(a progressive fibrotic disease of the lung), lung cancer, and malignant mesothelioma of the pleura [1-3]. This
carcinogenic silicate mineral has a fibrous form (like carbon nanofibers); consequently, size, aspect ratio, and
surface charge may all have an influence on toxicity [1, 4].
Since asbestos has a micro- instead of a nano-fiber form, direct comparison between these materials must be
exercised carefully. CNTs are nanoparticles and therefore potential harmful effects may arise from the combination
of high surface area and intrinsic surface toxicity [5]. Different from conventional larger materials, nanoparticles
(i.e. with at least one dimension under 100 nm) may be more toxic to the lung and even modify the structure of
proteins. Therefore, nanoparticles could activate inflammatory and immunological responses of the body and may
affect regular tissue function [5]. In fact, investigation of the pulmonary toxicity of SWCNTs in mice has concluded
that severe exposure to the inhalation of SWCNTs is a serious occupational health hazard [6].
In a recent study [7], Poland et al. showed that exposing the mesothelial lining of the body cavity of mice, as a
surrogate for the mesothelial lining of the chest cavity, to long multi walled carbon nanotubes results in asbestoslike, length-dependent, pathogenic behavior. This includes inflammation and the formation of lesions known as
granulomas. The results suggested the need for further research and great caution before introducing such products
into the market if long-term harm is to be avoided.
In another study [8], Ryman-Rasmussen et al. demonstrated that MWCNTs reach the subpleura in mice after a
single inhalation exposure of 30 mg m-3 for 6 h. The work suggests that minimizing inhalation of nanotubes during
handling is prudent until further long-term assessments are conducted.

It is currently known that nanoparticles may enter the human body via lungs and intestines (if ingested). Although
skin penetration is less evident, the likelihood that some nanoparticles may reach deep into the dermis can not be
discarded [1].
Thus, the toxic effects of nanoparticles are still not completely elucidated. Therefore, until an unequivocal toxicity
evaluation is available, CNTs should be considered a toxic material. Thus, direct contact with nanoparticles and
pollution of air in rooms must be avoided. The handling of nanoparticles also requires great care. Personal
protective equipment as overall, gloves, glasses and mask have to be worn. Nanoparticles should not be stored
and/or transported openly. Transfer or weighing should preferably be carried out in closed boxes, as glove-boxes,
and polluted surfaces must be cleaned with wet tissues. When a polymer encapsulates the CNTs, i.e. producing
nanocomposites, any harmful effect that may exist should be greatly reduced.

You may download Guides to Safe Handling CNTs at the links of interest page.

Mechanical Properties
Following simulations and experimental findings, carbon nanotubes have been recognized as one of the strongest
materials available [1, 2]. It has been long known that graphite has an in-plane modulus of 1.06 TPa [3] and, due to
their carbon-carbon sp2 bonding, CNTs are expected to show similar stiffness [4]. As a consequence, numerous
studies have focused on the viability of using CNTs as reinforcement to obtain strong light-weight materials [5, 6].
Despite obvious experimental difficulties, there have been many experimental reports on the mechanical properties
of carbon nanotubes. In 1997, Wong et al. performed the first direct measurement [7], the Young's modulus of arcgrown MWCNTs, aided by an atomic force microscope (AFM). An average value of 1.28 0.59 TPa was obtained.
Furthermore, the first strength measurement was also carried out, and an average bending strength of 14 GPa was
obtained. Two years later, using a similar method, Salvetat et al. obtained an average modulus of 810 410 GPa for
MWCNTs [8] and, for SWCNTs, 1 TPa [9]. Other techniques, such as micro-Raman spectroscopy, have also been
used to evaluate the mechanical properties of CNTs [10]. Perhaps the ultimate measurements have been carried out
by Yu et al. in 2000, who used a mechanical loading stage operating inside a scanning electron microscope to
perform the first in situ tensile testing of individual MWCNTs and ropes of SWCNTs [11], as shown in Fig. 1.

Fig. 1. SEM images showing: (a) Tensile loaded carbon nanotube rope between an AFM tip and a SWCNTs "paper"

sample, (b) Close-up view showing the extremity of the nanotube rope attached to the AFM tip, and (c) Rope
rupture for higher loading (reproduced from [12]).

For SWCNTs, tensile strength ranging from 13 to 52 GPa and Young's modulus between 320 and 1470 GPa were
reported. Regarding MWCNTs, the strength of the outer shell ranged from 11 to 63 GPa, modulus ranged from 270
to 950 GPa and a fracture strain of up to 12 % was obtained [13].
Theoretical studies have also addressed the mechanical properties of CNTs [13-17], some showing agreement with
the experimental observations [18-20]. It is worth noting that [21] SWCNTs display inter-tube slippage within
bundles and, due to their weak interlayer bonding, MWCNTs are inefficient in transferring load to their inner shells.
In fact, it should be pointed out here that the production of similar CNTs samples is a challenge and that their
characterization is not well established yet. Indeed, only recently a standard characterization was proposed, even
though only SWCNTs were covered [22].

Transport Properties
The unique electrical properties of carbon nanotubes are in a large extent derived from their 1-D character and the
peculiar electronic structure of graphite [1]. Graphite is considered to be a semi-metal but, it has been shown that,
depending on the chiral vector, Ch, related to the integers (n,m), CNTs may be either metallic or semiconducting
[2,3]. A CNT is metallic when n = m or m and n have values such that |m-n| = 3i, where i is an integer. In all the
other cases the nanotubes are semiconducting. On average, approximately 1/3 of SWCNTs are metallic and 2/3
semiconductor [4]. In general, MWCNTs are quite often found to be one-dimensional conductors with a high
electrical conductivity [5]. Their metallic properties are due to their multiple-shell structure consisting of tubes with
various electrical properties, where additional electronic coupling between shells takes place.
In a 1-D conductor, electrons can travel only forward or backward. Under these circumstances, only back-scattering
can lead to electrical resistance. As a consequence, CNTs display a very low resistance. In addition, they can carry
the highest current density of any known material, measured as high as 10 9 A/cm2 [6,7]. Experimental results
showed that the conductivity for metallic SWCNTs was between 10 5 to 106 S/m, and about 10 S/m for
semiconducting tubes [3]. The conductivity of bundles of SWCNTs have been found to be in the order of 10 4-106
S/m [5,8,9]. For MWCNTs, the conductivity of individual tubes has been reported to range between 20 and 210 7
S/m [10]. The effect of length, temperature and defects on the electrical conductivity of CNTs has also been studied
[11-15].
Prior to carbon nanotubes, diamond was the best known thermal conductor. CNTs have been shown to have a
thermal conductivity at least twice that of diamond [16,17]. Thermal conductivity is a key factor for heat
dissipation. Heat can be transported in a solid by phonons, which are quantized sound waves. In CNTs the specific
heat and thermal conductivity are determined primary by phonons.
Theoretical calculations suggest that the thermal conductivity for individual SWCNTs could be as high as 6000
W/mK in the axial direction but has very small values in the radial direction [18-20]. Experimental values for
MWCNTs higher than 3000 W/mK were already presented [21]. In addition, CNTs are thermally stable up to 2800
o
C in vacuum.