Production / Synthesis of CNTs

Techniques have been developed to produce nanotubes in sizeable quantities, including arc
discharge, laser ablation, and chemical vapor deposition (CVD).
Most of these processes take place in vacuum or with process gases.
CVD growth of CNTs can occur in vacuum or at atmospheric pressure.
Large quantities of nanotubes can be synthesized by these methods; advances in catalysis and
continuous growth processes are making CNTs more commercially viable.
1.Arc discharge
The arc discharge was the first available method for the production of both MWNTs and SWNTs .
It is worth noting that this technique has been in use for a long time for the production of carbon
fibers and that it is very probable that nanotubes were observed before 1991 but not recognized as
such.
An arc is struck between two graphite electrodes in a gas atmosphere. MWNTs produced by arc
discharge are long and straight tubes closed at both ends with graphitic walls running parallel to the
tube axis.
Iijima et al. and Bethune et al. reported in 1993 that an arc discharge with a cathode containing
metal catalysts (such as cobalt, iron or nickel) mixed to graphite powder results in a deposit
containing SWNTs.
SWNTs are usually assembled in ropes but some single tubes can also be found in the deposits.
The yield for this method is up to 30% by weight and it produces both single- and multi-walled
nanotubes with lengths of up to 50 micrometers with few structural defects


2. Laser ablation
This process was developed by Dr. Richard Smalley and co-workers at Rice University, who at the
time of the discovery of carbon nanotubes, were blasting metals with a laser to produce various
metal molecules. When they heard of the existence of nanotubes they replaced the metals with
graphite to create multi-walled carbon nanotubes.
Later that year the team used a composite of graphite and metal catalyst particles (the best yield
was from a cobalt and nickel mixture) to synthesize single-walled carbon nanotubes
In the laser ablation process, a pulsed laser vaporizes a graphite target in a high-temperature
reactor while an inert gas is bled into the chamber.
Nanotubes develop on the cooler surfaces of the reactor as the vaporized carbon condenses. A
water-cooled surface may be included in the system to collect the nanotubes.
The laser ablation method yields around 70% and produces primarily single-walled carbon
nanotubes with a controllable diameter determined by the reaction temperature. However, it is
more expensive than either arc discharge or chemical vapor deposition.


3.Chemical vapor deposition (CVD)
During CVD, a substrate is prepared with a layer of metal catalyst particles, most commonly nickel,
cobalt, iron, or a combination.
The metal nanoparticles can also be produced by other ways, including reduction of oxides or
oxides solid solutions.
The diameters of the nanotubes that are to be grown are related to the size of the metal particles.
This can be controlled by patterned (or masked) deposition of the metal, annealing, or by plasma
etching of a metal layer.
The substrate is heated to approximately 700C.
To initiate the growth of nanotubes, two gases are bled into the reactor: a process gas (such
as ammonia, nitrogen or hydrogen) and a carbon-containing gas (such
as acetylene, ethylene, ethanol or methane).
Nanotubes grow at the sites of the metal catalyst; the carbon-containing gas is broken apart at the
surface of the catalyst particle, and the carbon is transported to the edges of the particle, where it
forms the nanotubes.
This mechanism is still being studied. The catalyst particles can stay at the tips of the growing
nanotube during the growth process, or remain at the nanotube base, depending on the adhesion
between the catalyst particle and the substrate.
Thermal catalytic decomposition of hydrocarbon has become an active area of research and can be
a promising route for the bulk production of CNTs.
Fluidised bed reactor is the most widely used reactor for CNT preparation.

Properties of CNTs
1.Strength
Carbon nanotubes are the strongest and stiffest materials yet discovered in terms of tensile
strength and elastic modulus respectively.
This strength results from the covalent sp
2
bonds formed between the individual carbon atoms.
In 2000, a multi-walled carbon nanotube was tested to have a tensile strength of
63 gigapascals(GPa).


(For illustration, this translates into the ability to endure tension of a weight equivalent to 6422 kg
on a cable with cross-section of 1 mm
2
.)
Further studies, conducted in 2008, revealed that individual CNT shells have strengths of up to ~100
GPa, which is in good agreement with quantum/atomistic models.


Since carbon nanotubes have a low density for a solid of 1.3 to 1.4 g/cm
3
,its specific strength of up
to 48,000 kNmkg
1
is the best of known materials, compared to high-carbon steel's 154 kNmkg
1
.
2.Hardness
Standard single-walled carbon nanotubes can withstand a pressure up to 24GPa without
deformation. They then undergo a transformation to superhard phase nanotubes. Maximum
pressures measured using current experimental techniques are around 55GPa. However, these new
superhard phase nanotubes collapse at an even higher, albeit unknown, pressure.
The bulk modulus of superhard phase nanotubes is 462 to 546 GPa, even higher than that of
diamond(420 GPa for single diamond crystal).
3.Kinetic properties
Multi-walled nanotubes are multiple concentric nanotubes precisely nested within one another.
These exhibit a striking telescoping property whereby an inner nanotube core may slide, almost
without friction, within its outer nanotube shell, thus creating an atomically perfect linear or
rotational bearing.
This is one of the first true examples of molecular nanotechnology, the precise positioning of atoms
to create useful machines.
Already, this property has been utilized to create the world's smallest rotational motor.
4.Electrical properties
Band structures computed using tight binding approximation for (6,0) CNT (zigzag, metallic) (10,2)
CNT (semiconducting) and (10,10) CNT (armchair, metallic).
Because of the symmetry and unique electronic structure of graphene, the structure of a nanotube
strongly affects its electrical properties. For a given (n,m) nanotube, if n = m, the nanotube is
metallic; if n m is a multiple of 3, then the nanotube is semiconducting 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.
However, this rule has exceptions, because curvature effects in small diameter carbon nanotubes
can strongly influence electrical properties.
Thus, a (5,0) SWCNT that should be semiconducting in fact is metallic according to the calculations.
Likewise, vice versa-- zigzag and chiral SWCNTs with small diameters that should be metallic have
finite gap (armchair nanotubes remain metallic).


In theory, metallic nanotubes can carry an electric current density of 4 10
9
A/cm
2
, 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.
Multiwalled carbon nanotubes with interconnected inner shells show superconductivity with a
relatively high transition temperature T
c
= 12 K.
In contrast, the T
c
value is an order of magnitude lower for ropes of single-walled carbon
nanotubes or for MWNTs with usual, non-interconnected shells
5.Optical properties
Within materials science, the optical properties of carbon nanotubes refer specifically to
the absorption, photoluminescence, and Raman spectroscopy of carbon nanotubes. Spectroscopic
methods offer the possibility of quick and non-destructive characterization of relatively large
amounts ofcarbon nanotubes.
There is a strong demand for such characterization from the industrial point of view: numerous
parameters of the nanotube synthesiscan be changed, intentionally or unintentionally, to alter the
nanotube quality.
As shown below, optical absorption, photoluminescence and Raman spectroscopies allow quick
and reliable characterization of this "nanotube quality" in terms of non-tubular carbon content,
structure (chirality) of the produced nanotubes, and structural defects.
Those features determine nearly any other properties such as optical, mechanical, and electrical
properties.
Applications of carbon nanotubes
1.Energy: Because of large surface area main applications are for electrical energy storage particularly as
hydrogen storage medium, as fuel component, in gas diffusion layers, charge storage devices in batteries
etc.
2. Conductive or reinforced plastics: Electromagnetic interference/ Radio frequency interference shielding
components, coatings for enclosures, gaskets and other uses such as electrostatic dissipation, antistatic
materials, transparent conductive coatings and radar-absorbing materials. By loading insulation plastic with
(CNTs), they have been added into side mirror plastics of automobiles.
3.Field emission property is used in field emission flat panel displays in flat screen televisions and computer
monitors, others include low- voltage cold-cathode lighting sources, lightning arrestors and electron
microscope sources.
4) Molecular electronics and in electronic circuits at nanoscale dimensions CNTs become ideal candidates for
the connections in such molecular electronics. They have been demonstrated as switches themselves. Also
CNT based non-volatile random access memory for PC's have been in use. CNT based transistors are being
developed now.
5) Thermal materials: To move heat from one place to another anisotropic thermal
conductivity of CNTs are used in chips, ri bbons of CNTs and aligned structures.
Composites with CNTs have been shown to dramatically increase their bulk thermal
conductivity, even at very small loadings. Those features determine nearly any other
properties such as opti cal, mechanical, and el ectrical properties.
Appl ications of carbon nanotubes
1.Energy: Because of l arge surface area main appl ications are for electrical energy
storage particularly as hydrogen storage medi um, as fuel component, in gas diffusion
layers, charge storage devices in batteries etc.
2. Conductive or reinforced plastics: Electromagnetic interference/ Radio frequency
interference shiel ding components, coatings for enclosures, gaskets and other uses
such as electrostatic di ssipation, antistatic materials, transparent conductive coatings
and radar-absorbing materials. By loading insul ation plastic with (CNTs), they have
been added into si de mirror plastics of automobiles.
3.Field emission property is used i n fiel d emission flat panel displays i n flat screen
televisions and computer monitors, others incl ude low- voltage cold-cathode li ghting
sources, lightni ng arrestors and electron microscope sources.
4) Molecular electronics and i n electronic circuits at nanoscale dimensions CNTs
become ideal candidates for the connections i n such molecular electronics. They have
been demonstrated as switches themselves. Also CNT based non-volatile random
access memory for PC's have been in use. CNT based transistors are being developed
now.
5) Thermal materials: To move heat from one place to another anisotropic thermal
conductivity of CNTs are used in chips, ri bbons of CNTs and aligned structures.
Composites with CNTs have been shown to dramatically increase their bulk thermal
conductivity, even at very small loadings.
6) Structural composites: The mechanical properties such as stiffness, toughness and
strength of CNTs are used in advanced composites requi ring hi gh valves.
7) Fibres and fabrics: CNT added super-strong fibres have been applied in body and
vehicle armor, transmission line cables, woven fabrics and stain-resistant textiles.
8) Catalyst support: SWCNTs have enormously high surface area and are capable of
attaching any chemical species to their si dewal ls and therefore become unique
catalyst supports. These include cerium oxide, plati num, gold, pall adi um,
molybdenum, nickel and iri dium nonoparticles.
9) Air, water and gas fil tration: CNT based air and water fi ltration devices are used to
block smallest particles and to kill most bacteria, by making use of MWNTs.
10) Biomedical appl ications: Research is j ust underway. Cel ls have been shown to
grow on CNTs, so they have no toxic effects, and hence can be used as coatings for
prosthetics and surgical implants and as vascular stents and neuron growth and
regeneration. DNAcan be bonded to CNTs whi ch can be inserted into a cell, which has
potential appli cation i n gene therapy.
11) Ceramics: A ceramic material reinforced with CNTs becomes far tougher than
conventional ceramics, conducts electricity and heat and also acts as a thermal
barrier, hence used in coating turbine blades. More stronger material can be made
with CNTs mixed al umi num oxide and niobi um metal which has more electrical
conductivity and toughness which is used in thermal barrier coatings.
12) Consumer goods : CNT reinforced plastic packaging is used to keep food fresh for
long periods, for making tennis rackets, baseball bats and bicycle components
stronger. CNT reinforced plastic beer bottles keep it cool for longer periods of time.
13) Air crafts: Because of tensile strength, l ight weight and flexi ble nature CNTs are
used in ultra-li ght structural material s for wings of advanced ai r craft and space
problem to make them stronger and more energy efficient.