Nanotechnology

SUWARNA DATAR| AP 608

Definition of surface energy
It is called as the energy required to create a unit area of a new
surface
On a newly created surface, each atom on
the surface will move towards interior

Extra force is required to pull back the atoms
to their original position

For each atom on the surface, the energy
required to get it back to the original
position:
1. proportional to the number of broken
bonds N
b

2. Bond strength

= N
b

A

A
: no. Of atoms/unit area on the new surface
Surface energy
Concepts of thermodynamics are used to calculate the surface
energy of a material.
G = H- TS
Surface energy of FCC structure
1. Atoms labelled D are the nearest neighbours of atom A

2. These bonds would be broken when the new surface is
formed
3. Therefore for each newly formed surface 4 bonds are
broken
4. Thus, for each atom on the new (100) surface, four
bonds must be broken
Two dimensional unit cell of the (100) surface:

There is one atom in the centre of each cell and four atoms
that are each shared between four cells.

This means that the number of atoms per unit cell on the
(100) surface of an FCC crystal is:
Surface Energy
Each 2D unit cell has an area of a
2
where a is the lattice parameter
Thus, the number of bonds broken per unit area is
Surface Energy Atom A is on the (110) surface that will form the new surface
created by removing the atoms to the right in the figure.

The five atoms marked D, are all equidistant from atom A.

Thus, for each atom A on the new (110) surface, five nearest
neighbors will be removed and five bonds will be broken.

The four corner atoms are shared between four 2D unit cells,
while the two atoms on the center of two sides are shared
between two unit cells. This means the number of atoms per
unit cell on the (110) surface is
Surface Energy
Three nearest neighbors are removed for each
atom in the new surface or three bonds are
broken per atom on the final (111) surface

Surface Enrgy
Thermodynamics tells us that any material or system is stable only
when it is in a state with the lowest Gibbs free energy.
Therefore, there is a strong tendency for a solid or a liquid to
minimize the total surface energy.
Ways to minimize the surface energy:
surface relaxation
surface restructuring through combining surface dangling bonds into
strained new chemical bonds
surface adsorption through chemical or physical adsorption of terminal
chemical species onto the surface by forming chemical bonds or weak
attraction forces such as electrostatic or van der Waals forces
= N
b

A



Reduction of Surface Energy
At overall system level there are two basic ways:
Combination of individual nanostrcutures to form larger structure
Sintering
Ostwald Ripening
Agglomeration of individual particles

Result: Macroscopically? Reduction of surface energy
Chemical Potential
It is a potential a substance has to produce in order to alter the system.



Similar to ball rolling down the hill, when molecules move they react,
dissolve, melt etc, they always tend to go from higher chemical
potential to lower chemical potential
Molecules have higher chemical potential in high concentrated area, low in
low concentrated area
Eg : ICE


Gibbs Energy is the chemical potential that is minimized when the system reaches equilibrium
Relationship between chemical
potential and surface curvature






Where = Atomic volume, = surface energy, R =
radius of particle
This is known as Young Laplace equation which
describes the chemical potential of an atom in a
spherical surface with respect to the a flat surface
Generalized form:




(1)
Relationship between chemical
potential and surface curvature
Chemical potential of an atom on convex surface is higher than
that of the flat surface
When a mass is transferred from flat surface to convex surface
chemical potential increases whereas when the mass is transferred
from flat to concave chemical potential decreases
Thermodynamically, an atom on a convex surface possesses the
highest chemical potential, whereas an atom on a concave
surface has the lowest chemical potential.
Ostwald Ripening
Such a relationship is also reflected by the difference in vapor
pressure and solubility of a solid.
Assuming the vapor of solid phase obeys the ideal gas law, for the
flat surface:

Where is the chemical potential of vapour atom and is the vapour
pressure of flat solid surface
for the curved surface
(2)
Ostwald Ripening
Combining equation (1) and (2)



For spherical particle



This is known as the Kelvin equation
Ostwald Ripening
Similarly, solubility dependence of on the surface curvature can be written as



This is known as Gibbs Thompson relation
When two particles with different radii, assuming R1 >> R2, are put into a solvent, each particle
will develop an equilibrium with the surrounding solvent
solubility of the smaller particle will be larger than that of the larger particle.
Therefore, there would be a net diffusion of solute from proximity of the small particle to
proximity of the large particle.
To maintain the equilibrium, solute will deposit onto the surface of the large particle, whereas
the small particle has to continue dissolving so as to compensate for the amount of solute
diffused away
Ostwald Ripening
Therefore larger particles become larger and smaller become
smaller to compensate for the amount of solute diffused
Agglomeration
Due to van der Waals:
Prevention:
Electrostatic stabilization
Steric stabilization

Nernst Equation
Where E
0
= standard electrode potential when the concentration of ions
is unity
R
g
= gas constant, T = temp, f = Faradays constant, a
i
= activity of ions
n
i
= valance state of ions


Agglomeration
Surface potential of solid varies with the concentration of ions in the
surrounding solution (positive/negative)
Ions adsorbed on the surface determine the surface charge,
therefore called charge determining ions
Concentration of charge determining ions can be described by pH
pH = - log[H
+
]
Concentration of charge determining ions, corresponding to the zero
charged surface is called point of zero charge (PZC)
At pH > PZC negatively charged (covered by OH
-
)
At pH < PZC positively charged (covered by H
+
)
Therefore,
Agglomeration
In solution: (1) charge determining ions
(2) counter ions
Although charge neutrality is maintained overall the distribution
of charges is controlled by various forces
(1) coulombic/electrostatic force
(2) Entropic force
(3) Brownian motion

The combined result is that the concentration of counter ions is the highest near the solid surface and
decreases as the distance from the surface increases, whereas the concentration of determining ions
changes in the opposite manner.
Such inhomogeneous distributions of ions in the proximity of the solid surface lead to the formation of so-
called double layer structure
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