EEE514
CARBON NANOTUBES,
INORGANIC NANOWIRES
AND FUNCTIONALIZATION
Dr. Anita S. Ethiraj
Associate Professor
ALLOTROPY
IT IS THE PROPERTY OR BEHAVIOUR EXHIBITED BY SOME CHEMICAL
ELEMENTS TO EXIT IN TWO OR MORE FORMS. THE DIFFERENT FORMS ARE
KNOWN AS ALLOTROPES.
EXAMPLES - C, Fe, P etc.
DIFFERENT ARRANGEMENT OF ATOMS DUE TO CHEMICAL BONDING
AT DIFFERENT ENERGY STATES
ALLOTROPES OF CARBON
Eight Allotropes of Carbon
(a)
(a)Diamond
(b)Graphite
(c)Lonsdaleite
(d) (d)C60 – Buckminsterfullerene
or Buckyball
(e)C540
(f)C70
(g) (g)Amorphous Carbon
(h)Single-walled Carbon nanotube
or buckytube
Diamond
Diamond is one of the best known allotropes of carbon
Each carbon atom in a diamond is covalently bonded to four other carbons in a tetrahedron. These
tetrahedrons together form a 3-dimensional network of puckered six-membered rings of atoms.
The crystal structure of diamond is a face-centered cubic (FCC) lattice, with a basis of two identical carbon
atoms associated with each lattice point: one at (0, 0, 0) and the other at (1/4, 1/4, 1/4), where the
coordinates are given as fractions along the cube sides. This is the same as two interpenetrating FCC
lattices, each with atoms at only the lattice points, offset from one another along a body diagonal by one-
quarter of its length.
Sp3 Hybridization 3.567 Angstrom
Side Length, a0
(0.3567 nm)
C - C Bond Length 1.54 Angstrom
Atomic Density 1.76 x
10 atoms/m3
29
Packing Fraction 0.34
Why Diamond is strong?
Stable network of covalent bonds and the 3-D
arrangement of bonds
Applications
Industrial Applications
Cutting Drilling Grinding Polishing
In Lab used as containment or high pressure
experiments
Jewelry
Graphite
Most common allotropes of carbon
Each carbon atom is bonded to 3 other carbon atoms to give
layers of hexagonal rings. The carbon atoms are sp2 hybridized.
The remaining p orbital electron is delocalized to form weak
bonds between the layers. The covalent layer lattice has all sigma
bonds.
In thermochemistry it is used as a state
for defining the heat of formation of
carbon compounds because under
standard conditions it is the most stable
form of carbon.
At a temperature of 2500°C, it can be
transformed into diamond and about &
700°C it burns in pure oxygen forming
carbon dioxide.
It is also good conductor of electricity because of the delocalized
electrons such as lead pencils, carbon rods, can be used as the
material in the electrodes of an electrical arc lamp etc.
Its specific gravity is 2.3
which make it lighter than
diamond. Chemically it is
slightly more reactive than
diamond.
Applications:
Graphite powder is used as a dry lubricant.
In its pure synthetic forms, pyrolytic graphite and carbon fiber graphite
is an extremely strong, heat resistant (~3000 °C) materials used in solid
rocket engines, missile nosecones, electric motor brushes, brake shoes
and high temperature reactors.
Property Graphite Diamond
Each carbon atom is bonded
Each carbon atom is bonded to
3 other carbon atoms in layers to 4 other carbon atoms in a
Structure with delocalized electrons 3-dimensional covalent
between the layers. network. All valence electrons
are used in bonding.
Color Black Colorless
Melting Point (K)
sublimes at ~3500 sublimes at ~4000
good poor (an insulator)
Electrical Conductivity delocalized electrons between no delocalized electrons to
the layers allow an electric allow for the flow of electrical
current to pass through current
1-2 (soft) 10
Hardness (Mohs Scale)
delocalized electrons allow the (hardest known natural
sheets to move over each other mineral)
Lonsdaleite
This is a hexagonal allotrope of the carbon allotrope
diamond, hence known as hexagonal diamond. It is
thought to be formed when meteoric graphite falls to
earth.
The transformation of graphite into diamond occurs
due to heat and stress of impact. But it retains the
Graphite’s hexagonal structure.
Buckminsterfullerene or Buckyball
These were discovered by team of Scientists from Rice and Sussex University
in 1985 ( Richard Smalley, Robert Curl , Harry kroto). They vaporized a
sample of graphite with an intense pulse of laser light and used a stream of
helium gas to carry the vaporized carbon into a mass spectrometer. The
mass spectrum showed peaks corresponding to clusters of carbon atoms,
with a particularly strong peak corresponding to molecules composed of 60
carbon atoms, C60.
Vancouver Geodesic
Resemblance of their allotropic structure
to the geodesic structures devised by the
Scientist and the architect Richard
Buckminster Bucky Fuller.
Is one member of a family of spherical
carbon molecules sometimes called
“buckyballs” with formula C60.
The C atoms are arranged in hexagons and pentagons to give a geodesic
spherical structure similar to a football/Soccer ball with 32faces. Of the
32 faces, 12 were pentagons and 20 were hexagons.
Fullerenes are molecules of varying sizes composed entirely of carbon,
which takes the form of a hollow sphere, ellipsoid or tube
Like in graphite, each carbon atom is bonded to 3 other and each carbon
atom is sp2 hybridized.
There are also delocalized electrons, hence C60 can conduct electricity
slightly.
AMORPHOUS CARBON
Carbon that does not have any crystalline structure . Natural
amorphous carbon such as soot actually contains microscopic
crystals of graphite, sometimes even diamond.
Amorphous carbon has no definite structure when we talk on the
macroscopic scale as it consists of small irregular crystals,
Coal and soot both are informally called amorphous carbon
although both are products of pyrolysis which does not produce
true amorphous carbon under normal conditions. Depending on
the amount of carbon and impurity present the Coal industry
classifies different grades of coal
Anthracite Coal - 90% carbon and 10% other elements
Bituminous Coal- 75-90% carbon
Lignite Coal- 55% carbon