UNIT 4
Engineering Materials
Nanomaterials: Introduction, Synthesis of nanomaterials (bottom-up and topdown approach), and
nano materials (fullerene, graphene, and carbon nanotubes), their applications.
Fullerene Graphene Carbon nanotubes
Nanomaterials
Nanomaterials can be defined as materials possessing, at minimum, one external dimension
measuring 1-100nm.
A nanometer is one millionth of a millimeter - approximately 1,00,000 times smaller than the
diameter of a human hair. 1 nm = 10−9 metre.
The idea of nanotechnology appeared for the first time in the famous talk “There is plenty of
room at the bottom” given by the physicist Richard Feynman at the American Physical
Society meeting at Caltech on December 29, 1959. Feynman described a process by which
the ability to manipulate individual atoms and molecules might be developed, using one set of
precise tools to build and operate another proportionally smaller set and so on down to the
needed scale. In the course of this, he noted, scaling issues would arise from the changing
magnitude of various physical phenomena: gravity would become less important whereas
surface effects would become increasingly more significant. Richard Feynman works on
quantum electrodynamics.
The term nanotechnology was originally defined by Norio Taniguchi (Tokyo Science
University) in 1974 as follows: “Nano-technology mainly consists of the processing of
separation, consolidation and deformation of materials by one atom or by one molecule.”
Carbon (C)
Nonmetallic chemical element in Group 14 (IVa) of the periodic table. Although widely
distributed in nature, carbon is not particularly plentiful—it makes up only about 0.025% of
Earth’s crust—yet it forms more compounds than all the other elements combined. In 1961
the isotope carbon-12 was selected to replace oxygen as the standard relative to which the
atomic weights of all the other elements are measured.
The Most Abundant Elements In The Earth's Crust
Allotropy is the property of some chemical elements to exist in two or more different forms,
or allotropes, when found in nature. There are several allotropes of carbon.
Allotropes of carbon: a) Diamond, b) Graphite, c) Lonsdaleite, d) C60 (Buckminsterfullerene
or buckyball), e) C540, f) C70, g) Amorphous carbon, and h) single-walled carbon nanotube,
or buckytube.
Fullerene
• The 1996 Nobel Prize for Chemistry has been won by Harold W. Kroto, Robert F. Curl
and Richard E. Smalley for their discovery in 1985 of a new allotrope of carbon, in
which the atoms are arranged in closed shells.
• The new form was found to have the structure of a truncated icosahedron, and was
named Buckminsterfullerene, after the architect Buckminster Fuller who designed
geodesic domes in the 1960's.
Richard Buckminster Fuller, (born July 12, 1895, Milton, Massachusetts, U.S.—died July 1,
1983, Los Angeles, California), American engineer and architect, who developed the geodesic
dome—the only large dome that can be set directly on the ground as a complete structure and
the only practical kind of building that has no limiting dimensions.
Geodesic dome, spherical form in which lightweight triangular or polygonal facets consisting
of either skeletal struts or flat planes, largely in tension, replace the arch principle and
distribute stresses within the structure itself.
The 1996 Nobel Prize for Chemistry has been won by Harold W. Kroto, Robert F. Curl and
Richard E. Smalley for their discovery in 1985 of a new allotrope of carbon, in which the
atoms are arranged in closed shells. The new form was found to have the structure of a
truncated icosahedron, and was named Buckminsterfullerene, after the architect Buckminster
Fuller who designed geodesic domes in the 1960's.
About Fullerene
• Buckminsterfullerene is the third allotrope of carbon
along with graphite and diamond.
• Buckyball soot: Very finely divided black powder
(Black solid).
• Odourless, Density: 1.65 g/cm3
• Buckyballs are defined as - Compounds composed
solely of an even number of carbon atoms, which
form a cage-like fused-ring polycyclic system with
twelve five-membered rings and the rest six-
membered rings.
• C60 behaves like an electron deficient alkene, and
reacts readily with electron rich species.
• The structure consists of 32 faces of which 20 are hexagons and 12 are pentagons.
• The term has been broadened to include any closed cage structure consisting entirely of
three-coordinate carbon atoms. Each carbon atom is bonded to three others and is sp2
hybridised.
• C60 tends to avoid double bonds in the pentagonal rings, resulting in poor electron
delocalisation.
• The basic C60 structure consists of 60 carbon atoms that link together to form a hollow
cage-like structure.
• Other similar structures have since been discovered that have more then 60 carbon
atoms.
• Some of the more popular ones include C 70 and C76, although many contain as few as 28
and as many as 600 carbon atoms.
Properties
• The C60 molecule is extremely stable, being able to withstand high temperatures and
pressures. The exposed surface of the structure is able react with other species while
maintaining the spherical geometry.
• The hollow structure is also able to entrap other smaller species such as helium. In fact the
interior of most buckyballs is so spacious, they can encase any element from the periodic
table.
• Buckyballs do not bond to one another. They do however, stick together via Van der Waals
forces.
• By doping fullerenes, they can be electrically insulating, conducting, semiconducting or
even superconducting.
Production Methods
The Kratschmer–Huffman Arc-Discharge Apparatus
• In 1990 when W. Kratschmer and R. D. Huffman invented a method for producing
fullerenes in large amounts.
• This method consisted in evaporating graphite electrodes via resistive
heating in an atmosphere of approx. 100 torr of helium. Although the soot contained
only a few per cent by weight of C60, it could be conveniently extracted using
benzene as solvent.
• An electric arc is established between two graphite electrodes. Hence, most of the power is
dissipated in the arc and not in resistive heating of the rod.
• The entire electrode assembly is enclosed in a reaction chamber under a reduced pressure
(approx.100 torr) of helium: black soot is produced and extraction with organic solvents
yields fullerenes.
Electric arc
Electrical arcing is when electrical current jumps a gap in a circuit or between two electrodes
(conductors of electricity).
An electric arc is a visible plasma discharge between two electrodes that is caused by
electrical current ionizing gasses in the air. Electric arcs occur in nature in the form of
lightning.
With proper control, electric arcs can be harnessed and used industrially for welding, plasma
cutting and even certain types of lighting such as fluorescent lighting where a high voltage
ionizes the inert gas within a glass tube
The Combustion Process
• In 1991, J. B. Howard and collaborators reported
their observations that both C60 and C70 fullerenes were produced in varying
amounts from premixed laminar benzene/oxygen/argon flames operated under
ranges of conditions including pressures of 12–100 Torr and C/O ratios from
0.717 to 1.072, the critical value for soot formation being 0.760.
• Based upon incomplete combustion of hydrocarbons in sooting flames.
• The proper selection of flame conditions gave fullerenes in yields up to 0.26% of the fuel
carbon burned and allowed control of the C70/C60 molar ratio over the range
0.26–5.7.
• The yield of C60 and C70 and the C70/C60 ratio were found to depend
on temperature, pressure, carbon/oxygen ratio, and residence time in the
flame.
• Significant yields of fullerenes from laminar sooting flame of premixed mixture of
benzene and oxygen at low pressure.
• Pressure is an influential factor and formation of fullerene could be done at low pressure
and at temperatures lower than 1700 K (1427 ℃).
• Furthermore, combustions methods including laser pyrolysis of vapor hydrocarbons and
laser irradiation of polycyclic aromatic hydrocarbons have been used to produce fullerene.
• In 2002, Frontier Carbon Corporation (Japan) started mass production of fullerenes with a
capacity of 400 kg per year by the use of such a combustion method, and the price of
fullerenes was decreased drastically.
• The production capacity was increased 100-fold to 40 tons per year in 2003.
• This improved flame-based technology is most suited for mass production of fullerenes,
since it is a continuous process and uses inexpensive hydrocarbons as its starting materials,
which is similar to that employed in the commercial carbon-black production
process.
• Fullerene yield in the resulting soot is now around 20%, which demonstrates that the
combustion method is a practical technology for fullerene-soot production.
Chemical Synthesis
Pyrolytic Dehydrogenation or Dehydrohalogenation
As C60 consists of six dehydronaphthalene moieties located at the octahedral sites, Taylor or
Scott showed that the pyrolysis of naphthalene produces C60, as does corannulene, 7,10-
bis(2,20-dibromovinyl)fluoranthene, and 11,12-benzofluoranthene.
11,12-Benzofluoranthene
Corannulene
7,10-Bis(2,20-dibromovinyl)fluoranthene,
Some other potential applications for fullerenes include:
• Lubricants
• Drug delivery systems, pharmaceuticals and targeted cancer therapies.
• Hydrogen storage as almost every carbon atom in C60 can absorb a hydrogen atom
without disrupting the buckyball structure, making it more effective than metal hydrides.
This could lead to applications in fuel cells.
• Chemical sensors
• Photovoltaics
• Polymer electronics such as Organic Field Effect Transistors (OFETS)
• Polymer additives
• Cosmetics, where they “mop up” free radicals (safely interact with free radicals and
neutralize them).
