Nanotechnology

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Melting point depression is a very important issue for applications
involving nanoparticles. Nanoparticles are currently used or proposed for
prominent roles in catalyst, sensor, medicinal, optical, magnetic, thermal,
electronic, and alternative energy applications. Nanoparticles must be in
the solid state to function at elevated temperatures in several of these
applications.
Two techniques allow measurement of the melting point of nanoparticle.
The first one is by electron beam of the transmission electron microscope
(TEM) which can be used to melt nanoparticles. The melting temperature is
estimated from the beam intensity, while changes in the diffraction
conditions to indicate phase transition from solid to liquid. This method
allows direct viewing of nanoparticles as they melt, making it possible to
test and characterize samples with a wider distribution of particle sizes.
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The second one is by developed nanocalorimeters that directly
measure the enthalpy and melting temperature of
nanoparticles. Nanocalorimeters provide the same data as bulk
calorimeters, however additional calculations must account for
the presence of the substrate supporting the particles.
Nanoparticles have a much greater surface to volume ratio
than bulk materials. The increased surface to volume ratio
means surface atoms have a much greater effect on chemical
and physical properties of a nanoparticle. Surface atoms bind
in the solid phase with less cohesive energy because they have
fewer neighboring atoms in close proximity compared to
atoms in the bulk of the solid.

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Each chemical bond an atom shares with a neighboring atom provides
cohesive energy, so atoms with fewer bonds and neighboring atoms have
lower cohesive energy. The average cohesive energy per atom of a
nanoparticle has been theoretically calculated as a function of particle size
according to Equation (1).

.......................................................................... (1)

Where: D=nanoparticle size

d=atomic size
Eb=cohesive energy of bulk
As Equation (1) shows, the effective cohesive energy of a nanoparticle
approaches that of the bulk material as the material extends beyond atomic
size range (D>>d).

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 Atoms located at or near the surface of the nanoparticle have
reduced cohesive energy due to a reduced number of
cohesive bonds.

The cohesive energy of an atom is directly related to the

thermal energy required to free the atom from the solid.
According to Lindemann’s criterion, the melting
temperature of a material is proportional to its cohesive
energy, av (TM=Cav). Since atoms near the surface have fewer
bonds and reduced cohesive energy, they require less energy
to free from the solid phase. Melting point depression of high
surface to volume ratio materials results from this effect. For
the same reason, surfaces of bulk materials can melt at lower
temperatures than the bulk material.

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The theoretical size-dependent melting point of a material can be
calculated through classical thermodynamic analysis. The result
is the Gibbs–Thomson equation shown in Equation (2).

............................................................. (2)

Where: TMB=Bulk Melting temperature

σsl=solid–liquid interface energy
Hf=Bulk heat of fusion
ρs=density of solid
d=particle diameter

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On the other hand, there is another important factor; it is the shape of
nanoparticles. Nanoparticle shape impacts the melting point of a
nanoparticle. Facets, edges and deviations from a perfect sphere all change
the magnitude of melting point depression. These shape changes affect the
surface to volume ratio, which affects the cohesive energy and thermal
properties of a nanostructure. Equation (3) gives a general shape corrected
formula for the theoretical melting point of a nanoparticle based on its size
and shape.

)3( . .

Where: c=materials constant

z=shape parameter of particle

The shape parameter is (1) for sphere and (3/2) for a very long wire,
indicating that melting-point depression is suppressed in nanowires
compared to nanoparticles.
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 Electrical Properties:-
The properties like conductivity or resistivity are come under category of
electrical properties. These properties are observed to change at nanoscale
level like optical properties. The examples of the change in electrical
properties in nanomaterials are:
Conductivity of a bulk or large material does not depend upon dimensions
like diameter or area of cross section and twist in the conducting wire etc.
However it is found that in case of carbon nanotubes conductivity changes
with change in area of cross section.
It is also observed that conductivity also changes when some shear force
(in simple terms twist) is given to nanotube.
3) Conductivity of a multiwalled carbon nanotube is different than
that of single nanotube of same dimensions.
4) The carbon nanotubes can act as conductor or semiconductor in
behaviour but we all know that large carbon (graphite) is good conductor
of electricity.

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 In electrically conducting carbon nanotubes, only one
electron wave mode is observed which transport the electrical
current. As the lengths and orientations of the carbon
nanotubes are different, they touch the surface of the
mercury at different times, which provides two sets of
information:
(i) The influence of carbon nanotube length on the resistance;
and
(ii) The resistances of the different nanotubes.
As the nanotubes have different lengths, then with increasing
protrusion of the fiber bundle an increasing number of
carbon nanotubes will touch the surface of the mercury
droplet and contribute to the electrical current transport.

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 Figure (2) Electrical behavior of naotubes

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 There are three categories of materials based on their
electrical properties: (a) conductors; (b) semiconductors; and
(c) insulators. The energy separation between the valence
band and the conduction band is called Eg (band gap). The
ability to fill the conduction band with electrons and the
energy of the band gap determine whether a material is a
conductor, a semiconductor or an insulator.

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 In conducting materials like metals, the valence band and the
conducting band overlap, so the value of (Eg) is small: thermal energy
is enough to stimulate electrons to move to the conduction band. In
semiconductors, the band gap is a few electron volts. If an applied
voltage exceeds the band gap energy, electrons jump from the valence
band to the conduction band, thereby forming electron-hole pairs called
excitons. Insulators have large bandgaps that require an enormous
amount of voltage to overcome the threshold. This is why these
materials do not conduct electricity (Figure 3).

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 Figure 3: Schematic illustration of the valence and conduction
bands in materials based on their electrical properties:
insulator, semiconductor and conductor

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Quantum confinement and its effect on material electrical
properties:-
Quantum confinement causes the energy of the band gap to
increase as illustrated in Figure 4. Furthermore, at very small
dimensions when the energy levels are quantified, the band
overlap present in metals disappears and is actually
transformed into a band gap. This explains why some metals
become semiconductors as their size is decreased

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 Figure 4: The image compares the energy of the band gap (arrow) in a
bulk semiconductor, a quantum dot and an atom. As more energy
states are lost due to the shrinking size, the energy band gap increases.

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