UNIT III

Engineering Materials
The materials have been used for the development of
revolutionary technologies
polymers,
semiconductors, superconductors,
biomaterials etc.
Polymers 7 Nobel Prizes (Chemistry-6
and Physics-1)
Fullerenes
Carbon Allotropes
Introduction to Carbon Materials
 History
C60 - Buckminsterfullerene (Buckyball)
was named after Richard Buckminster
Fuller.
1996 Nobel Prize to Kroto, Curl &
Smalley
 Fullerenes
Kroto and co-workers discovered an entirely new form of carbon
known as C60 or the fullerene molecule (only diamond and graphite
were known before this).
The original discovery of C60 was in the soot produced from the
laser ablation of graphite.
Only in the early 1990s fullerenes could be synthesized in large
enough quantities for significant research in this field to be
undertaken.
Fullerene cages are about 7-15 angstroms in diameter ( 1A = 10-
10m).
In atomic terms, their sizes are enormous.
But fullerenes are still small compared to many organic molecules.
Chemically, they are quite stable; breaking the balls requires
temperatures of over 10000 C.
At much lower temperatures (a few hundred degrees C) fullerenes
will "sublime.
 Types of Fullerenes
buckyball clusters: smallest member is C20 ; the most common is
C60; C540 one of the largest fullerenes.
nanotubes: hollow tubes of very small dimensions, having single or
multiple walls; potential applications in electronics industry;
megatubes: larger in diameter than nanotubes and prepared with
walls of different thickness; potentially used for the transport of a
variety of molecules of different sizes
polymers: chain, two-dimensional and three-dimensional polymers
are formed under high pressure high temperature conditions
nano"onions": spherical particles based on multiple carbon layers
surrounding a buckyball core; proposed for lubricants
linked "ball-and-chain" dimers: two buckyballs linked by a carbon
chain
fullerene rings
 Fullerene- C60
Buckminsterfullerene (C60) has 60
carbon atoms arranged in a
spherical structure (resemblance of
this shape to the geodesic domes
designed and built by the architect
R Buckminster Fuller)

Pure C60 consists of 60 carbon atoms arranged

as 12 pentagons and 20 hexagons.
Visually C60 it is quite different from both
graphite and diamond.
It is a dark black powder, which turns pink
when dissolved in certain solvents such as
toluene.
When exposed to strong ultraviolet light, the
Pentagon (C5) buckyballs polymerize,forming bonds between
adjacent balls.
Hexagon (C6) In crystalline form C60 is cubic (at each lattice
point of a cube, there is a buckyball).
It is Electrically insulating.
It shows electro-negativity and forms
compounds easily with alkali atoms.
 Fullerene C70

The rugby-ball shaped C70has 12 pentagons and 25 hexagons

Gives red colour with dichlorobenzene
Fullerenes - C72, C76, C84 and even up to C100 are known.
Preparation of fullerene by Arc Method
It is basically a DC arc chamber
reactor chamber with
- ensembles of electrodes (anode &
cathode),
- cooling system reactor chamber,
- cooling system for electrode
assembly
- vacuum system,
- electrical system and
- electronic system.

The operating conditions are:

- diameter of the electrodes: 6 mm;
- discharge voltage: 25 V
- current on the electrodes: 60 A
- cooling water flow of the discharge
chamber: 300L/h(approx.);
- cooling oil flow of the electrodes:
60L/h;
- control gas pressure (helium):
100 to 200 mmHg.
 The soot from Arc method
The soot collected in the arc method contains
a) Carbon clusters mixture = 25-30%
b) C60 and C70 fullerenes = 1.2-2.5%

To extract the fullerenes from the soot

Soxhlet extraction with toluene followed by
extraction in a sonic bath is carried out

The C60+C70 mixture obtained is separated by

column chromatography
 Purification of Fullerenes by Chromatography
Soot is extracted with Toluene
(C60+C70+impurities) Deep Red colour

o The column is first filled with carbon granules.

Crude soot solution
o Toluene is filled into the column until the level of (in organic solvent)
toluene equals to the height of carbon granules.
o Then the solution containing C60& C70 is added into
the column through a dropper flask.
Silica (SiO2)
o ~20 mL fullerene solutionshaken vigorously
filtered chromatography Carbon granules
o The initial solution coming out of the column is
collected separately in a conical flask and thrown
into waste.
C60 Band

o Colour starts to change to magenta after 20 to 25 C70 Band

minutes the fraction is collected as C60. impure band-1
o After 20 to 30 minutes the solution with magenta impure band-2
colour stops coming out.
o At this stage, dichlorobenzene is added to the
column.
o A red colour separation will be seen for C70 fraction
will appear. 1. pure C60 (magenta) in Toluene
o This fraction C70 is collected separately in a flask.
2. pure C70 in Dichlorobenzene (Red)
o From both the flasks, the solvent is evaporated to
obtain pure C60 and C70 fractions separately.
Characterization of fullerenes

The fullerene C60 and C70 separated

and purified are characterized by:
o X-ray diffraction
o 13CNuclear Magnetic Resonance
spectroscopy (NMR)
o Mass spectroscopy

o Infra-red spectroscopy(IR)
 Applications of fullerene C60
A. Super conductivity in
A3C60 (A = Alkali metal)
Resistance of a substance tends to
zero at a transition temperature (Tc)

Resistance
Eg.: K3C60

C60 - Non conducting

K3C60 - Conducting at RT
K3C60 - Super conducting
at Tc ~18 K
0 Temp. (K)
o K3C60Partial filling of Conduction
band

o It retains the basic FCC structure of

C60 and lattice constants to
accommodate the alkali ions

o Holczer et al. demonstrated that

potassium-doped C60 has only a single
stable superconducting phase, K3C60,
with a transition temperature of 19.3 K.

o Rb2CsC60 shows Tc of 31K

 Superconductivity of Doped C60
o When K3C60 is cooled, its resistivity begins to drop sharply at about
18K, indicating the onset of superconductivity (Hebard, 1991).

o As larger alkali-metal cations are incorporated into the lattice and

the fcc lattice parameter (a) increases, the superconducting
transition temperature, T, also increases (see Figure ).

o The T for Rb3 C60 rises to 28K. This rise in T may be related to an
increase in the density of states at the Fermi level with increasing
lattice constant.
 HIV Protease Inhibition by C60

o Derivatives of C60 are currently

being investigated as potential
inhibitors of the protease Hydrophobic sites
enzyme, which is specific to the
HIV (virus) generation.
l
e rica
o Active site of the enzyme C60 (as inhibitor) lind
Cy
roughly described as an open-
ended cylinder structure, which
is with large hydrophobic amino HIV protease site
acids.

o The C60 has the same radius as

cylinder & C60 and derivatives
are primarily hydrophobiccan Cartoon for the C60 HIV protease
able to block the active side inhibition.
reduce the HIV (virus)
generation

Other applications: Cancer treatments, antimicrobial agents, Hydrogen

storage (H2@C60), Trapping Reactive species, Geochemistry &
Astro-chemistry etc.