Synthesis of Carbon NanoTube

By Carbon Arc Discharge Method

 Carbon NanoTubes
• Allotropes of carbon.
• Applications :
 nanotechnology
 electronics
 optics
 biomedical
 other fields of
materials science.
• Efficient conductor of heat
• Limited by their potential
toxicity.
 Methods of Synthesis
• 3 Major Routes :
i. Arc Discharge
ii. Laser Ablation
iii. Chemical Vapor Deposition
Carbon Arc Discharge Method
 Working Principle
• The carbon arc discharge method, initially used for producing
C60 fullerenes
• Simple and easy
• In the arc discharge, a vapor is created by an arc vaporization
between two carbon rods(electrodes) placed end to end,
separated by approximately 1mm, with or without catalyst.
• Typically, the anode is a long rod approximately 6 mm in
diameter and the cathode a much shorter rod 9 mm in diameter
• Process is carried out in an enclosure that is usually filled with
inert gas (helium, argon).
• Low pressure process: between 50 and 700 mbar.

• A direct current of 50 to 100 A driven by approximately 20 V

creates a high temperature discharge between the two electrodes
2000-3000 °C.

• The discharge vaporises one of the carbon rods and forms a

small rod shaped deposit on the other rod.

• CNTs Can be found in the carbon soot of graphite electrodes

during an arc discharge involving high current.

• This process yields CNTs with lengths up to 50 microns

• The Nanotubes created using this method are usually short
tubes with diameters ranging from 0.6 to 1.4 nm for single
walled and 10 nm outerdiameter multi-walled nanotubes.

• Efficient cooling of the cathode has been shown to be

essential in producing good quality nanotubes.

• Producing nanotubes in high yield depends on the uniformity

of the plasma arc and the temperature of the deposit form
on the carbon electrode

• It produces a mixture of components and requires separating

nanotubes from the soot and the catalytic metals present in the
crude product.
 SWNTs
• Anode is doped with metal catalyst, such as Fe, Co, Ni, Y or
Mo.
• The quantity and quality of the nanotubes obtained depend on
various parameters such as the metal concentration, inert gas
pressure, kind of gas, the current and system geometry.
• Diameter : 1.2 to 1.4 nm
• Advantage: The diameter can slightly be controlled by
changing thermal transfer and diffusion. This is achieved by
changing:
o Inert gas :-Ar with lower thermal conductivity and
diffusion coefficient gives lower diameter SWNTs
 o Anode to cathode distance(Optical plasma control) :- The
ACD is adjusted in order to obtain strong visible vortices
around the cathode. This enhances anode vaporisation,
which improves nanotubes formation
o Catalyst :- Mixture of Co and Mo in high concentrations
results in the diameter range of 0.6-1.2nm

• Improvement in the oxidation resistance is obtained for

SWNTs :- arc-discharge method using a bowl-like cathode
• Disadvantage: Product contains a lot of metal catalyst and
defects.Its purification is hard to perform
 MWNTs
• If both electrodes are graphite, the main product will be MWNTs.
• A lot of side products are formed such as fullerenes, amorphous
carbon, and some graphite sheets.
• inner diameter : 1-3 nm and an outer diameter : 10nm
• Because no catalyst is involved in this process, there is no need for a
heavy acidic purification step.
• The MWNT can be synthesised with a low amount of defects
• For more pure MWNTs:
– Magnetic field synthesis
– Plasma rotating arc discharge
– Synthesis in liquid nitrogen
 SYNTHESIS METHOD
• Arc–evaporation apparatus is maintained inside a vacuum chamber.
• Electrodes – graphite rods.
• Gap distance- 1-2 mm.
• Ensures stable current density and anode consumption rate. The chamber
is first evacuated by diffusion pump.
• Then rarefied ambient gas is introduced.
• Next a dc arc is applied between two graphite rods.
• The anode is consumed.
• Part of the evaporated anode carbon is deposited on the top of the cathode
(CATHODE DEPOSIT).
• In case of SWNT a catalyst is used at the anode (COMPOSITE ANODE).
 Optical image of the Cathode deposit

A – top of cathode.
B – a deposit having columnar texture.
C – top of cathode deposit facing the anode.
D – graphite layers.
d – thickness of the deposited. (reported to be 6mm)
SEM micrographs of top of cathode deposit

Fig a : before purification Fig b : after purification

Fig a : SEM micrograph of
purified SWNT

Fig b : TEM micrograph of

purified SWNT
 FACTORS
• Atmosphere.
Different atmosphere influence the morphology of
CNT
He, CH4, H2, Ar, ethanol, acetone, hexane, NH3.
Production of MWNT is more in organic
atmosphere (ethanol, acetone and hexane).
NH3- a high efficient method.
H2- high crystalline MWNTs.
SEM micrographs

(e) air
Contd...
• Arc discharge.
DC arc discharge
o Commonly used method.
o MWNTs are deposited at the cathode.
AC arc discharge
o MWNTs are deposited on the reaction wall.
o Mass production of SWNTs are possible.
 TEM image of a CNT

AC ARC DISCHARGE
•Atmosphere – He. DC ARC DISCHARGE
•Pressure -140 torr. •Atmosphere – He.
•Voltage – 20-30V, Current – 700A •Pressure -500 torr.
•Voltage – 18-30V, Current – 40 to 80A
Contd.....
• Catalysts.
Fe catalysts (Ijima and Ichihashi).
Co catalysts (IBM group).
Magnetic metal catalyst- cotton like soot in the
chamber.
Metal catalysts –Pd, Ag, Pt, Co-Ni, Fe-Ni, Co-Cu,
Ni-Cu, Ni-Ti, Fe-No, Y-Ni alloy, etc.
Mo – increase the yield of soot
SWNTs using Fe catalysts

SWNTs using Co catalysts

Fig (a):Ni catalysts

Fig (b):Pd catalysts
Fig (c):Pt catalysts
• Purification of CNT
Acidic and thermal treatment.
Annealing.
Oxidation.
Filtration.
Ultrasonication.
IR irradiation.

Fig a : before purification Fig b : after purification

 Synthesis of SWNTs
The anode has to be doped with metal catalyst, such as Fe,
Co, Ni, Y or Mo
The quantity and quality of the nanotubes obtained depend
on various parameters such as the metal concentration, inert
gas pressure, kind of gas, the current and system geometry
The most common problems with SWNT synthesis are that
the product contains a lot of metal catalyst, SWNTs have
defects and purification is hard to perform
Ways to improve the process of arc discharge are :
(a) Inert Gas environment
(b) Optical plasma control and catalyst
(c) Improvement of oxidation resistance
 Synthesis of MWNTs
•If both electrodes are graphite, the main product
will be MWNTs.
•But a lot of side products are formed such as
fullerenes, amorphous carbon, and some graphite
sheets.
•Purifying the MWNTs means loss of structure and
disorders the walls.
•Because no catalyst is involved in this process,
there is no need for a heavy acidic purification
step. This means, the MWNT, can be synthesized
with a low amount of defects.
• Improvement can be achieved by
(a) Synthesis in liquid nitrogen
(b) Magnetic field synthesis
(C)Plasma rotating arc discharge
 Synthesis in Liquid Nitrogen
•Economical route to highly
crystalline MWNTs

• Mass production is possible

• Low pressure and expensive

inert gasses are not needed

•The content of the MWNTs

can be as high as 70 % of the
reaction product.
 Magnetic Field Synthesis
• Synthesis of MWNTs in
a magnetic field gives
defect-free and high
purity MWNTs
•In this case, the arc
discharge synthesis was
controlled by a
magnetic field around
the arc plasma
•Extremely pure
graphite rods (purity >
99.999 %) were used as
electrodes.
• Highly pure MWNTs
 Plasma Rotating Arc
Discharge
• The centrifugal force
caused by the rotation
generates turbulence and
accelerates the carbon
vapor perpendicular to
the anode. In addition,
the rotation distributes
the micro discharges
uniformly and generates a
stable plasma
• As a result it increases
the plasma volume and
raises the plasma
temperature
• High yield obtained with
 Advantages
• Involves an easy step

• High quality SWNTs can be collected

• Narrower tubes are obtained compared with laser ablation

• Large scale production of CNTs

• Economical way of synthesis

• Crystalline CNTs are produced

 Disadvantages
• High yield of MWCNTs are difficult

• The nanotubes produced contain more impurities compared to

other methods. More defects are observed in CNTs

• The consistency of the shape, wall, and lengths of the tubes are
somewhat random

• Purification processes required

• High temperature required

Thank You