Lecture 6 Nano Materials CNT, Fullerenes

Established as per the Section 2(f)
of the UGC Act, 1956

Approved by AICTE, COA and BCI,
New Delhi
CHEMISTRY OF ENGINEERING MATERIALS
School of Applied sciences, Department of

chemistry
CARBON NANOMATERIALS
Synthesis, Properties and Applications
Fullerenes
 CNT
Graphene
FULLERENES (EXAMPLE FOR 0D)
 A Fullerene is any molecule composed entirely of carbon, in the form of a
hollow sphere, ellipsoid, or tube.
 Spherical fullerenes are also called buckyballs, and cylindrical ones are
called carbon nanotubes or buckytubes.
 The most famous fullerene is C60 and C20 being the smallest one.
DISCOVERY AND STRUCTURE
 Discovered by H W Kroto and R Smalley at Rice University ,USA (1985).
 Popularly known as Buckminsterfullerene in honor of the American architect
Buckminster Fuller.
 The shape of C60 resembles the dome structure based on hexagons and pentagons
designed by Fuller.
 Fullerenes are closed hollow cage structure consisting of carbon atoms
interconnected in pentagonal and hexagonal rings.
STRUCTURE & PROPERTIES OF
C60
 It contains 12 pentagons are surrounded by 20 hexagons.

 60 vertices for the carbon atoms and 90 covalent bonds between them, 60
single bonds and 30 double bonds.
 Each carbon is part of one pentagon and two hexagons, each has two
single bonds and one double bond for the traditional carbon valence of
four.
 The fullerene hybridization is not fixed but has variable characteristics
depending on the number of carbon atoms in the molecule.
 The pentagonal rings contain only single bonds; double bonds have a
Theshorter bond pentagon
isolated length and lead
ruleto instability
states the in the pentagonalwith
fullerenes ring. isolated
pentagons are kinetically much more stable than their fused
pentagon counter parts.
THE ISOLATED PENTAGON RULE
 C60 is the first stable fullerene because it is the smallest one possible
to obey this rule. Both C60 and its relative C70 obey this so-called
IPR.
This rule can be verified as follows:
 From the thermodynamics standpoint since the fusion of two
pentagons is not favorable energetically due to increased ring strain,
and carbon structures with adjacent pentagons are unstable.
 A π bond shared by two pentagons has a large negative bond
resonance energy, thus contributing significantly to the increase in
kinetic instability or chemical reactivity of the molecule.
Synthesis of fullerenes by arc discharge method
 Fullerenes are prepared by
vaporizing a graphite rod in a
helium atmosphere .
 The graphite electrodes are
brought into close contact with
each other and an arc is struck
between them.
 The soot generated is collected
on water cooled surfaces.
 After sustaining the arc for
several minutes, the vacuum is
broken and soot is collected
soxhlet extracted in toluene or
benzene, resulting in a dark
reddish-brown solution.
 Mixtures of fullerenes like C60,
C70 are formed which are
separated by solvent extraction.
 pure C60 is isolated from this
APPLICATION OF FULLERENES
 It was revealed that potassium-
doped C60 becomes
superconducting at 18 K. This
was the highest transition
temperature for a molecular
superconductor. Since then,
superconductivity has been
reported in fullerene doped with
various other alkali metals forms
a superconductor with alkali
metals.
 As organic photovoltaic (OPV)
 Hydrogen Gas Storage: Due to its unique molecular structure, fullerene
is the only form of carbon, which potentially can be chemically
hydrogenated and de-hydrogenated reversibly. When fullerenes are
hydrogenated, the C=C double bonds become C- C bonds and C-H bonds.
 Takes part in catalytic processes.
As Sensors
OTHER APPLICATIONS
1. Used in Scanning tunneling microscopy.
2. Instead of CRT and LCD displays, Bucky paper can be used
in Television screens because its higher efficiency.
3. As filter membranes.
4. Has the potential to carry a drug in the interior of the molecule
and release the drug once the Buckyball reaches a certain cell
or tissue within the body.
CARBON NANOTUBES
What are CNTs?
 Carbon nanotubes (CNTs) are allotrope of
Carbon with a cylindrical nanostructure.
 Nanotubes are members of the fullerene structural family.
 Their name is derived from their long, hollow structure with the walls
formed by one atom thick sheets of carbon, called graphene.
 Carbon Nanotubes are formed from
essentially the graphite sheet and
the graphite layer appears some
what like a rolled-up continuous
unbroken hexagonal mesh and carbon
molecules at the apexes of the hexagons.
TYPES OF CNT
There are many different types of carbon nanotubes, but they are
normally categorized as either
1. Single-walled (SWNT): consist of sheets of graphene, rolled up to

form hollow tubes with walls one atom thick (diameter < 3 nm).
2. Multi-walled nanotubes (MWNT): multiple single-walled carbon

nanotubes are nested inside one another. Diameter of MWCNTs
varies up to 50nm.
PROPERTIES OF CNTS
1. Strength :- Carbon nanotubes are the strongest, flexible and stiffest
materials yet discovered in terms of tensile strength and elastic modulus
respectively.
2. Hardness :- The hardness (152 Gpa) and bulk modulus (462–546 Gpa) of
carbon nanotubes are greater than diamond, which is considered the
hardest material.
3. Electrical Properties:- Because of the symmetry and unique electronic
structure of graphene, nanotube has a very high current carrying capacity.
4. Thermal Conductivity:- All nanotubes are expected to be very good
thermal conductors along the tube.
5. EM Wave absorption:- There has been some research on filling MWNTs
with metals, such as Fe, Ni, Co, etc., to increase the absorption
effectiveness of MWNTs in the microwave region.
6. Thermal properties:- All nanotubes are expected to be very good thermal
conductors along the tube.
SYNTHESIS OF CNT
Chemical vapour deposition method
 Techniques have been developed to produce nanotubes are arc
discharge, laser ablation of graphite, and chemical vapor deposition
(CVD).
 In the first two processes, graphite is combusted electrically or by

means of a laser, and the CNTs developing in the gaseous phase are
separated. All three methods require the use of metals (e.g. iron, cobalt,
nickel) as catalysts.
 The advantages of the CVD process were low power input, lower
temperature range, relatively high purity and, most importantly,
possibility to scale up the process. This method can produce both
MWNTs and SWNTs depending on the temperature, in which
production of SWNTs will occur at a higher temperature than MWNTs.
SYNTHESIS OF CNT
 A mixture of hydrocarbon, metal catalyst along with inert gas is
introduced into the reaction chamber.
 During the reaction, nanotubes form on the substrate by the
decomposition of hydrocarbon at temperatures 700–900 ℃ and
atmospheric pressure.
 The diameters of nanotubes that are to be grown are related to the size of
the metal particles
 This technique offers more control over the length and structure of the
produced nanotubes compared to arc and laser methods.
APPLICATIONS OF CNT
1. Carbon nanotubes can store lithium due to which they can be used in
batteries. CNT’s can also store hydrogen and hence find potential
applications in fuel cells.
2. They are used in the tips for atomic force microscope probes.
3. They are being used to develop flat panel displays for television and
computer monitors.
4. They are being used to develop light weight shield for electromagnetic
radiation.
5. Field effect transistors are being developed using semi conducting CNT’s
which can be used to build faster processors for computers. It is estimated
that these processors will ne 104 times faster than the present processors.
6. CNT’s are being used to produce light weight materials with higher
strength than steel. These can be used in Auto mobile, Aircraft and rocket
parts.
APPLICATIONS OF CNTS
• Electrodes
Carbon nanotubes have been widely used as electrodes for chemical
and biological sensing applications and many other electrochemical
studies.
• Displays
Given their high electrical conductivity, and the incredible sharpness
of their tip. Carbon nanotubes are considered the most promising
material for field emitters and a practical example are CNTs as
electron emitters for field emission displays (FED).
APPLICATIONS OF CNT
• Electrical
 Field emission in vacuum electronics
 Building block for next generation of VLSI
 Nano lithography
• Energy storage
 Lithium batteries
 Hydrogen storage
• Biological
 Bio-sensors
 Functional AFM tips
 DNA sequencing
DISCUSSION
THANK YOU

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Established as per the Section 2(f)

of the UGC Act, 1956

CHEMISTRY OF ENGINEERING MATERIALS

School of Applied sciences, Department of

 It contains 12 pentagons are surrounded by 20 hexagons.

1. Single-walled (SWNT): consist of sheets of graphene, rolled up to

2. Multi-walled nanotubes (MWNT): multiple single-walled carbon

 In the first two processes, graphite is combusted electrically or by

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