CARBON NANOMATERIALS

Carbon has a great affinity for bonding with other small atoms,
including other carbon atoms, and it is capable of forming multiple
stable covalent bonds with such atoms. Because of these properties,
carbon is known to form nearly ten million different compounds, the
large majority of all chemical compounds.

Carbon compounds form the basics of all life on Earth. Most forms of
carbon are comparatively un-reactive under normal conditions. It
does not react with sulphuric acid, hydrochloric acid, chlorine or any
alkalis. At elevated temperatures carbon reacts with oxygen to form
carbon oxides, and will reduce such metal oxides as iron oxides to the
metal.
ALLOTROPES OF CARBON AND THEIR STRUCTURES
• But, buckyball or C60 fullerene and carbon nanotubes in 1991 by Iijima,
two more allotropes of carbon were added to the list.

• They are closed hollow cages consisting of carbon atoms interconnected

in pentagonal and hexagonal rings. Spherical fullerenes are also called
buckyballs, and
• cylindrical ones are called carbon nanotubes or buckytubes.
 CARBON NANOTUBES (CNT)
CNT: Rolling-up a graphene sheet to form a tube
TYPES OF CARBON NANOTUBES AND THEIR STRUCTURE
Carbon nanotubes can be broadly classified into two types:
• (a) single-walled carbon nanotubes (SWCNTs) and
• (b) multi-walled carbon nanotubes (MWCNTs).

1. Single - walled nanotubes (SWNTs)

• SWNTs consist of one tube of graphite.
• It is having a diameter of 2 nm and a
length of 100 m (10-4 m).
• SWNTs are very important, because they
exhibit important electrical properties.
• It is an excellent conductor.
Single walled nanotubes (SWCNTs) are classified according to the rolling
direction (orientation of the hexagon lattice) as armchair, zigzag, and chiral.
(a) Arm-chair structures: The lines of hexagons are parallel to the axis of the
nanotube.
(b) Zig-zag structures: The lines of carbon bonds are down the centre.
(c) Chiral nanotubes: It exhibits twist or spiral around the nanotubes.
It has been confirmed that arm-chair carbon nanotubes are metallic while
zig-zag and chiral nanotubes are semiconducting.

Single-walled carbon nanotube (SWCNT).

 Multi-walled CNT
• MWCNT consist of several graphene sheets rolled up together to form
concentric cylinders with large annular space at centre.
 • PROPERTIES OF CARBON NANOTUBES
MECHANICAL PROPERTIES : Strength and elasticity
• 1. Carbon nanotube is one of the strongest materials in nature.
• The strength of the carbon–carbon bond is among the highest and
as a result, any structure based on aligned carbon–carbon bonds
will have the ultimate strength.
– Single wall carbon nanotubes are stiffer than steel and are
very resistant to damage from physical forces
• 3. It is highly conducting and behaves like metallic or semiconducting
materials.
• 4. It has very high thermal conductivity and kinetic properties.
Uses of CNTs
1. It is used in battery technology and in industries as catalyst.
2. It is also used as light weight shielding materials for protecting
electronic equipments.
3. CNTs are used effectively inside the body for drug delivery.
4. It is used in composites, ICs.
 PREPARATION OF NANOMATERIALS
1.1. Top-down approach
1.2. Bottom-up approach : In bottom-up approach, the atoms or
molecules are used as the building blocks to produce nanoparticles,
nanotubes, nanorods, thin films or layered structures.

PREPARATION OF NANOMATERIALS
• There are physical as well as chemical methods to prepare nanomaterials.
However, the most powerful methods are the chemical methods.
• 1. Physical methods: Ball milling, Inert gas condensation, Arc discharge, Ion
sputtering, Laser ablation, Spray pyrolysis, Flame pyrolysis, Thermal
evaporation, Pulsed laser deposition, Molecular beam epitaxy.
• 2. Chemical methods: Metal nanocrystals by reduction, Solvothermal
synthesis, Photochemical synthesis, Electrochemical synthesis, Micelles
and Microemulsions, Chemical vapour deposition (CVD), Sol-gel process.
1. PHYSICAL METHODS
(i) BALL MILLING
TOP DOWN APPROACH

• A ball mill (a type of grinder) is a cylindrical device used for grinding (or
mixing) materials to as small as few nanometers.
• A ball mill consists of a cylindrical capped container that sits on two
drive shafts (pulleys and belts are used for rotary motion) or directly
connected to motor for rotation.
• Size of container, of course, depends upon the quantity of interest.
• Different materials are used as grinding media, including tungsten
carbide balls, ceramic balls, flint pebbles and stainless steel balls
• Larger balls used for milling, produce smaller grain size and larger
defects in the particles.
 (ii) ARC DISCHARGE
TOP DOWN APPROACH
• This is one of the simplest and useful method which leads to mass scale
production of fullerens and carbon nanotubes.
• Basically, it requires water cooled vacuum chamber and electrodes to
strike an arc between them.
• The positive electrode itself acts as the source of material (usually
graphite).
• Electrodes made of coal can be used in these syntheses too; only the
yields drop to 4 – 6% of the employed carbon.

Schematic lay out of a typical arc discharge system.

• MWCNT are prepared by this process if both electrodes are pure
graphite
• On the other hand, if graphite anode containing metallic particles (Fe, Co,
Ni, Cu) is used with a graphite cathode SWCNT are generated.
• Inert gas or reactive gas introduction is necessary.
• Usually electrodes with a diameter of less than 6 mm are used for the arc
method because the output of fullerene decreases on larger dimensions.
• When high voltage is applied to two graphite electrodes immersed in an
inert gas, an arc flashes between them and an arc develops.
• The temperature (3000 C - 4000C) is sufficient to vaporize the graphite
• During cooling down CNT is formed.
• CNT is attached mainly to anode.
 Laser ablation
• TOP DOWN APPROACH
• Arc discharge method produces SWCNT in low yield
• This method is superior and yields high-purity SWCNT than arc discharge
method
• Synthesis of CNT by laser ablation method is carried out as follows:
• Graphite is heated to 1200C
• Then the graphite is vaporized using a pulsed laser under flowing argon at
500 Torr
• Then vaporized carbon is crystallized again, SWCNT and fullerene are
produced with carbon soot
• If pure graphite is used, fullerene is produced
• In order to obtain SWCNT a small amount (1 atomic %) of metallic catalyst
(Ni/Co) is usually added to graphite material. This method yields nearly 60%
of SWCNT
• However, it is more expensive than either arc discharge or chemical vapor
deposition.
2. CHEMICAL METHODS
 Chemical vapour deposition
BOTTOM UP APPROACH
• By this method both SWCNT and MWCNT can be prepared by varying the
carbon source and the metal catalyst.
• Furnace – The furnace is ~ 70 cm length.
• Furnace tube – This is a quartz tube of about 65 cm length and 3 cm
internal diameter. Both ends are open for sample access and ends can be
fitted with stainless steel caps.
• Metallic fine particles (Fe, Co, Mo or their alloys) are used as catalyst .
• In most cases a substrate that is made of alumina (Al2O3), silica (SiO2),
magnesia (MgO), zeolite is used. Upon this substrate a layer is deposited
with the metal catalysts. This substrate can withstand high temperature.
• By using the substrate it is possible to gain the fine metal nanopartcles
• A mixture of gases is used – hydrocarbon gas (CH4, C2H4, C2H2, CO etc)
acts as carbon source plus carrier gas (inert gas like Ar / He etc)
• This mixture of gases is flowed into the reactor where catalyst is there
• Temperature of the reactor is typically 800C -1000C.
• CO was the first gas used (along with Mo catalyst) for the synthesis of
SWCNT. Nowadays, Co-Mo binary catalyst is used to get high yield (large
amount of SWCNT).
• Synthesis of SWCNT is based on the disproportionation reaction of CO in
presence of metallic catalyst.
2CO C + CO2
Sol-gel Processing

BOTTOM UP APPROACH
 Metal alkoxides are typical precursors.
 They undergo hydrolysis and polycondensation reactions in
presence of water and acid catalyst to form a colloid that
ultimately forms an inorganic continuous network containing a liquid
phase (gel). Gel consists of oxo (M-O-M) or hydroxo (M-OH-M)
bridges, therefore generating metal-oxo or metal-hydroxo
polymers in solution.
After a drying process, the liquid phase is removed from the gel.
Then, a thermal treatment (calcination) may be performed in order
to favor further polycondensation and enhance mechanical
properties.
 Purification
• The main impurities : graphite (wrapped up) sheets,
amorphous carbon,
metal catalyst and
the smaller fullerenes…
• Rules :
-separate the SWNTs from the impurities
- give a more homogeneous diameter or size distribution.

• The techniques are : oxidation, acid treatment, annealing,

ultrasonication, micro filtration, ferromagnetic separation, cutting,
functionalisation and chromatography techniques.

•
V. NANOTECHNOLOGY APPLICAION
 FUTURE SCOPE IN NANOTECHNOLOGY
• Nanotechnology for flexible Electronics
• Nanotechnology for wireless devices
• Nanotechnology for molecular devices
• One can use 'self cleaning' glass so that it is not necessary to wash the
windows with water.
• Self cleaning glass can be made by dissolving small amount of titania
(TiO2) nanoparticles in it while manufacturing it by melting together its
other ingredients like silica (SiO2), CaO, Ba2O3 etc.
• Titania is able to dissociate organic dust in presence of UV light available
in sunlight.
• Once dissociated it may fall down or simply evaporate.
• Even drops of waters on glass give hazy look. But TiO2 containing glass
can spread water evenly giving clear sight.
 DOMASTIC APPLICATIONS
Use of silver nanoparticles is made in refrigerators, air purifiers or air
conditioners and water purifiers. It is well known for long time that silver has
antibacterial property. That is why it has been used as utensils material since
long.
Therefore some manufacturers have special Ag-nanoparticles lining in
refrigerators, air conditioners or even in washing machines.
Food in refrigerators can remain fresh and prevent fungal growth for longer time
than ordinary refrigerators.
The clothes washed in silver nanoparticles lined washing machines are claimed
to stay sterile for about a month. This should be quite useful in hospitals.
Air conditioners or water filters with silver nanoparticles also are claimed to
have advantages and are being marketed with very little additional price.
One can maintain the inside temperature of the houses reducing heating!
cooling effects due to outside weather using appropriate window materials like
 Nanotech Fabrics
• Nanotechnology was first used in fabric in
1998 by a chemist named David Soane, who
founded Nano-Tex while the first widespread
commercial use began in 2001.
• Fabrics are engineered on a molecular level so
that clothing becomes wrinkle resistant, stain
repellent and even able to brush away body
moisture and body odour.
 SPORTS AND TOYS
Nanotechnology has already been introduced into the sports equipment
and toys.
Good quality tennis racquets are made of carbon. Lightweight and
toughness or strength is necessary for such racquets.
It is possible that carbon nanotube composites would serve as a high
strength, lightweight material for racquets.

Toy industry also has been well geared to embrace nanotechnology. Eye
movements of dolls, robot movements etc. are enjoyed by children.
 FUEL CELLS
A fuel cell is an electrochemical energy conversion device that converts the
chemical energy from fuel (on the anode side) and oxidant (on the cathode
side) directly into electricity. The heart of fuel cell is the electrodes.

Carbon nanotubes have applications in battery technology.

Storing hydrogen in nanotubes is another possible application.

HYDROGEN STORAGE
• It has been predicted that carbon nanotubes can store a liquid or a gas in
the inner cores through a capillary effect, because of their cylindrical and
hollow geometry, and nanometre-scale diameters.
 Applications of Medical Nanotechnology
Applications of medical nanotechnology span across a variety of
areas such as
• In Drugs, Medicines, Therapeutics, etc
• In Diagnostics of diseases, abnormal conditions etc.
• In Surgery
• In Medical Robotics
• In the general sake of increasing knowledge of the human body

• Medical applications of colloidal gold present another example.

Colloidal gold was, and is still, used for treatment of arthritis.
• A number of diseases were diagnosed by the interaction of
colloidal gold with spinal fluids obtained from the patient.
VAMS