Carbon Nanotubes–Properties and Applications

-Marmik Prajapati (201801431)

Abstract

In the field of nanotechnology, Carbon Nanotube (CNT) is one of the unique inventions. It was
discovered in 1991, and since then it has been studied by many researchers around the world.
CNTs are rolled graphene with sp2 hybridisation. The essential aspects of CNTs are their
lightweight, small size with a high aspect ratio (can be as high as 1.32 million:1), and good
conducting characteristics, good tensile strength, which make them useful as fillers in different
materials such as polymers, metallic surfaces and ceramics. CNTs are also used in the field of
nanotechnology, nanomedicine, transistors, actuators, sensors, membranes, and capacitors.
There are various methods which can be used for the synthesis of CNTs, which includes Arc
discharge, CVD (chemical vaporise deposition) method, CCVD (Catalytic Chemical Vapour
Deposition) method, and Laser ablation. CNTs are classified into two types Single-Walled
Carbon Nanotubes (SWCNTs) and Multi-walled Carbon Nanotubes(MWCNTs). The present
article is focused on the synthesis, functionalisation, properties and applications of CNTs.

Carbon Nanotubes (CNTs)

CNTs are cylindrical nanostructured allotropes of carbon with diameters typically measured in
nanometres. They are also referred to as buckytubes, with unique properties that make them
potentially useful in a wide variety of applications. These include applications in nano-
electronics, optics, and materials applications. They were discovered independently by Lijima
and Ichihashi and Bethune et al. in carbon arc chambers similar to those used to produce
fullerenes. van der Waal forces held them together. Half a meter long CNTs have been created,
and it is being assumed that length could be infinite.

Structure of CNTs: CNTs, also known as tubular fullerenes, are cylindrical graphene sheets of
sp2 -bonded carbon atoms. In CNTs the graphene sheet is rolled upon itself to form different
allotropes of carbon, including graphite, fullerenes and CNTs

Type of CNTs: CNTs are categorised on the basis of numbers of tubes present in CNTs.

1. Single-walled CNTs (SWCNTs): It consists of a single layer of graphene rolled upon itself
with a diameter of 0.4 to 2.0 nm. Single-walled carbon nanotubes can be formed in
three different designs: Armchair, Chiral, and Zigzag. The design depends on the way the
graphene is wrapped into a cylinder. A single-walled nanotube's structure is represented
by a pair of indices (n,m) called the chiral vector. The structural design has a direct effect
on the nanotube's electrical properties. When n − m is a multiple of 3, then the
nanotube is described as "metallic" (highly conducting) otherwise, the nanotube is a
 semiconductor. The Armchair design is always metallic while other designs can make the
nanotube a semiconductor.

1. Multi-walled CNTs (MWNTs): There are two structural models of multi-walled

nanotubes. There are two models that can be used to describe the structures of multi-
walled nanotubes. In the Russian Doll model, sheets of graphite are arranged in
concentric cylinders, e.g., a (0,8) single-walled nanotube (SWNT) within a larger (0,17)
single-walled nanotube. In the Parchment model, a single sheet of graphite is rolled in
around itself, resembling a scroll of parchment or a rolled newspaper. Multi-walled
carbon nanotubes have similar properties to single-walled nanotubes, yet the outer
walls on multi-walled nanotubes can protect the inner carbon nanotubes from chemical
interactions with outside materials.

Synthesis

Meaningful progress in nanotechnology requires a thorough knowledge of carbon nanotube

structure, properties, and synthesis aspects. Carbon nanotubes (CNT) are generally produced
using five primary techniques: ARC discharge, laser ablation, chemical vapour deposition (CVD),
catalyst chemical vapour deposition (CCVD) and template-directed synthesis. Although
scientists are searching for more economical ways to produce these structures, nanotubes self-
assemble from the resulting carbon vapour in different ways. We can classify the synthesis
process into three types, Physical Processes, Chemical Processes, and Miscellaneous Processes.

Physical Processes:

Arc discharge: Arc discharge is a well-known method for CNT synthesis. However, it is difficult
to control the morphology of CNTs, such as length, diameter, and the number of layers. The
carbon needles, ranging from 4 to 30 nm in diameter and up to 1 mm in length, were grown on
the negative end of the carbon electrode used for the direct current (DC) arc-discharge
evaporation of carbon. During the process, Lijima used a pressurised chamber filled with a gas
mixture of 10 Torr methane and 40 Torr argon. Two vertical thin electrodes were installed in
the centre of the chamber (Figure 1). The lower electrode (cathode) contained a small piece of
iron in a shallow dip made purposefully to hold iron. The arc was generated by running a DC
current of 200A at 20V between the electrodes. The use of the three components, namely
argon, iron and methane, was critical for the synthesis of SWNT. Carbon soot produced as a
result of arc-discharge settled and nanotubes grew on the iron catalysts contained in the
negative cathode.

Laser Ablation:

In the laser ablation process, a pulsed laser is made to strike at graphite target in a high-
temperature reactor in the presence of inert gas such as helium which vaporises a graphite
target. The nanotubes develop on the cooler surfaces of the reactor, as the vaporised carbon
condenses. A water-cooled surface is also included in the most practical systems to collect the
nanotubes (Figure 2).

Chemical Processes

Chemical Vapor Deposition: This method is capable of controlling growth directions on a

substrate and synthesising a large quantity of carbon nanotubes. In this process a mixture of
hydrocarbon gas (ethylene, methane or acetylene) and a process gas (ammonia, nitrogen,
hydrogen) is made to react in a reaction chamber on a heated metal substrate at a temperature
of around 700˚C - 900˚C, at atmospheric pressures. CNTs formed as a result of decomposition of
hydrocarbon gas and deposit and grow on the metal catalyst (substrate). The catalysts particle
can stay at the bottom or top of growing carbon nanotube. The use of the catalyst and
preparation of the substrate is one of the most important factors in CVD, as this substrate will
define the nature and type of carbon nanotubes formed. The common substrate material is
silicon, but glass and alumina are also used. The catalysts are metal nanoparticles, like Fe, Co
and Ni, which can be deposited on substrates by means of electron beam evaporation, physical
sputtering or solution deposition. The nanotube diameter depends on the catalyst particle size;
therefore, the catalyst deposition technique should be chosen carefully to yield the desired
result.

Liquid electrolysis method: In 2015, researchers in the George Washington University

discovered a new pathway to synthesise MWCNTs by electrolysis of molten carbonates. The
mechanism is similar to CVD. Some metal ions were reduced to a metal form and attached on
the cathode as the nucleation point for the growing of CNTs. The reaction on the cathode is
LiCO3 -> Li2O + CNTs + O2. The formed lithium oxide can in-situ absorb carbon dioxide (if
present) and form lithium carbonate, as shown in the equation. Li2O + CO2 -> Li2CO3 Thus the
net reaction is CO2 -> CNTs + O2. In other words, the reactant is only greenhouse gas of carbon
dioxide, while the product is high valued CNTs.

Properties

CNTs reportedly have extremely high surface areas, large aspect ratios, and remarkably high
mechanical strength. The tensile strength of CNTs is 100 times greater than that of steel, and
the electrical and thermal conductivities approach those of copper. These unique properties
make CNTs good candidates as fillers in different polymers and ceramics to realise desirable
consumer products. It has also been predicted that CNT-based field-effect transistors (FETs) will
soon supplant their silicon-based analog counterparts. CNTs are also good incorporating agents
due to their unique electrical, mechanical and thermal properties.
1. Electronic nature of CNTs: CNTs show electrical properties in chiral forms. The
geometric differences such as defects, chirality, different diameters and the degree of
crystallinity of the tubular structure greatly influence the electronic properties of CNTs.
CNTs are either metallic or semiconducting along the tubular axis. For a given (n,m)
nanotube, if n = m, the nanotube is metallic; if n − m is a multiple of 3 and n ≠ m and nm
≠ 0, then the nanotube is quasi-metallic with a very small band gap, otherwise the
nanotube is a moderate semiconductor. Thus, all armchair (n = m) nanotubes are
metallic, and nanotubes (6,4), (9,1), etc. are semiconducting. Considering the bonding of
the carbon atoms in CNTs are arranged in a hexagonal lattice, each carbon atom is
covalently bonded to three neighbour carbons via sp2 molecular orbitals. Thus, the
fourth valence electron remains free in each unit, and these free electrons are
delocalised over all atoms and contribute to the electrical nature of CNTs. Thus, CNTs
can be conducting or semi-conducting types depending on the type of chirality. Carbon
nanotubes are not semimetallic because the degenerate point (the point where the π
[bonding] band meets the π* [anti-bonding] band, at which the energy goes to zero) is
slightly shifted away from the K point in the Brillouin zone because of the curvature of
the tube surface, causing hybridisation between the σ* and π* anti-bonding bands,
modifying the band dispersion. The rule regarding metallic versus semiconductor
behaviour has exceptions because curvature effects in small-diameter tubes can
strongly influence electrical properties. Thus, a (5,0) SWCNT that should be
semiconducting in fact is metallic according to the calculations. In theory, metallic
nanotubes can carry an electric current density of 4 × 109 A/cm2, which is more than
1,000 times greater than those of metals such as copper, where for copper
interconnects, current densities are limited by electromigration. Because of its
nanoscale cross-section, electrons propagate only along the tube's axis. As a result,
carbon nanotubes are frequently referred to as one-dimensional conductors. The
maximum electrical conductance of a single-walled carbon nanotube is 2G0, where G0 =
2e 2 /h is the conductance of a single ballistic quantum channel.
2. Mechanical properties of CNTs: CNTs are very strong materials as per tensile strength
and elastic modulus. The Young's modulus ranges from 270 to 950 GPa, while the tensile
strength is also very high, in the range of 11–63 GPa. This strength results from the
covalent sp2 bonds formed between the individual carbon atoms. Further studies, such
as one conducted in 2008, revealed that individual CNT shells have strengths of up to
≈100 gigapascals, which is in agreement with quantum/atomistic models. Carbon
nanotubes have a low density for a solid of 1.3 to 1.4 g/cm3, its specific strength of up
to 48,000 kN·m·kg−1 is the best of known materials, compared to high-carbon steel's
154 kN·m·kg−1. CNTs are not nearly as strong under compression. Because of their
hollow structure and high aspect ratio, they tend to undergo buckling when placed
under compressive, torsional, or bending stress. The first transmission electron
microscope observation of radial elasticity suggested that even the van der Waals forces
can deform two adjacent nanotubes. Later, nanoindentations with atomic force
microscope were performed by several groups to quantitatively measure radial elasticity
of multi-walled carbon nanotubes and tapping/contact mode atomic force microscopy
was also performed on single-walled carbon nanotubes. Radial direction elasticity of
 CNTs is important, especially for carbon nanotube composites where the embedded
tubes are subjected to large deformation in the transverse direction under the applied
load on the composite structure. Standards single-walled carbon nanotubes can
withstand a pressure up to 25 GPa without [plastic/permanent] deformation. CNTs are
superhydrophobic having a contact angle over 160o.
3. Thermal properties of CNTs: Measurements show that an individual SWNT has a room-
temperature thermal conductivity along its axis of about 3500 W·m−1 ·K−1; compare
this to copper, a metal well known for its good thermal conductivity, which transmits
385 W·m−1 ·K−1. An individual SWNT has a room-temperature thermal conductivity
lateral to its axis (in the radial direction) of about 1.52 W·m−1 ·K−1, which is nearly as
thermally conductive as soil. The thermal conductivity of individual MWNTs and found it
to be 3,000 W/K (higher than that of graphite) at room temperature. There are several
factors which influence the thermal properties such as the number of phonon-active
modes, the length of the free path for the phonons, and boundary surface scattering.
These properties also depend on the atomic arrangement, the diameter and length of
the tubes, the number of structural defects and the morphology, as well as the presence
of impurities in the CNTs.
4. Optical properties of CNTs: Carbon nanotubes have useful absorption,
photoluminescence (fluorescence), and Raman spectroscopy properties. Spectroscopic
methods offer the possibility of quick and non-destructive characterisation of relatively
large amounts of carbon nanotubes.

Applications of CNTs

Nanotechnology is one of the latest and the most developed technologies, presenting many
advantages and benefits for new materials with significantly improved properties.
Nanotechnology can be used in different applications in various fields, including nanomedicine,
energy, the environment, and in sensors.

1. CNTs as fillers: The use of CNTs as fillers in different materials to form nanocomposites
is one of the most developed fields in nanotechnology. The main idea for incorporating
CNTs into different polymeric and other materials is to improve the properties of these
materials. By doing so, the mechanical, electrical and thermal properties are enhanced
to almost an ideal range.
2. CNTs as Transistors:
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