What are Nanomaterials?

 Size (classical definition: 1 -100 nm)

 Properties of materials change at the nano-
scale
 Size and shape dependent Why ??

Exponential increase in Silver and Gold particles have

surface area with decrease different colors depending on size
in size and shape
Surface energy
Origin :

Surface atoms are situated in a different environment compared with their

bulk counterparts.

Atoms on the surface have fewer neighboring atoms due to their unique
terminating locations.

Any atom in bulk materials with FCC or HCP structure will have 12 nearest
neighbours and thus 12 inter atomic bonding. But surface atoms will have
some unsaturated or dangling bonds , which is in-turn will add extra energy to
the surface atoms compared with those in bulk materials.
This extra energy is the origin of the surface energy.
 Surface Energy and Surface tension
 Every finite object has surface area and therefore carries
surface energy.
 However the portion of this ‘extra energy’ in overall system
energy is not the same.
In the bulk of the liquid, each molecule is pulled
equally in every direction by neighbouring liquid
molecules, resulting in a net force of zero. At
the surface of the liquid, the molecules are
pulled inwards by other molecules deeper inside
the liquid and are not attracted as intensely by
the molecules in the neighbouring medium (be
it vacuum, air or another liquid). Therefore, all
of the molecules at the surface are subject to an
inward force of molecular attraction which is
balanced only by the liquid's resistance to
compression, meaning there is no net inward
force. However, there is a driving force to
diminish the surface area.
Surface Tension
For the liquid to minimize its energy state, it
must minimize its number of boundary
molecules and must therefore minimize its
surface area.

Surface tension is caused by the attraction

between the liquid's molecules by various
intermolecular forces

Diagram of the forces on Surface tension, represented by the symbol γ

two types of molecules of is defined as the force along a line of unit
liquid. length, where the force is parallel to the
surface but perpendicular to the line.

Surface tension is therefore measured in forces per

unit length. Its SI unit is newton per metre but the
cgs unit of dyne per cm is also used.[5] One dyn/cm
corresponds to 0.001 N/m.
 Water Striders
Water striders are
small insects that are
adapted for life on
top of still water,
using surface tension
to their advantage so
they can “walk on
water.”

Water acts different at the surface. Water molecules are attracted to

each other and like to stay together, especially on the surface where
there is only air above. The attraction between water molecules creates
tension and a very delicate membrane. Water striders walk on this
membrane.

Water striders are about a half-inch long with a thin body and three sets
of legs. The water strider's secret is its legs. The legs have tiny hairs
that repel water and capture air. By repelling water, the tiny water
striders stand on the water’s surface and the captured airs allows them
to float and move easily.
If the surface is hydrophobic then the contact angle of a drop of
water will be larger. Hydrophilicity is indicated by smaller contact
angles and higher surface energy.
Water has rather high surface energy by nature; it is polar and
forms hydrogen bonds).
Young's equation

where γSL, γLV, and γSV are the interfacial tensions between the solid
and the liquid, the liquid and the vapor, and the solid and the vapor,
respectively.

The equilibrium contact angle that the drop makes with the surface is
denoted by θc. To derive the Young equation, normally the interfacial
tensions are described as forces per unit length and from the one-
dimensional force balance along the x axis Young equation is obtained.
 Surface area in Nano Materials

 Assume we have made some perfect spherical particles with a

uniform radius R.
Volume = 4/3 Π R3
surface area = 4 Π R2

Two particles of different size,

1 µm Which should consider surface energy

1 nm more significantly?
 Total volume ‘V’ is same .
 Total surface area is
V 3V
* 4R 
2

4 / 3R 3
R

 R- radius of particle.
 For a fixed total volume of a spherical particle, total surface area
and the total surface energy are proportional to 1/R .
 Total Surface Energy - R is 1 µm~1/10-6m or 1nm~1/10-9m.
 So the total surface area of 1nm particle is 1000(103) times higher
than that of 1µm particles and 1 million times (106 ) than that of
1mm particle
 Surface area and energy associated with surface is extremely
significant when the materials size being studied is on the
nanometer scale.
 Percentage of surface vs. bulk atoms in a nano meter sized
particle.
 Assume a cubic structure having inter atomic spacing is 2.5 Å.
 Surface region is four layers
 10 Å or 1 nm thick surface layer
 10 nm cubic shaped nano particle.
◦ Total number of atoms is ,
◦ 40X40X40 or 64,000 atoms in the particle
◦ Four layers of surface atoms on each side
◦ Atoms in bulk region are 32X32X32 or 32,768.
◦ Atoms on surface are 64,000 – 32,768

◦ Bulk atoms ~ 51 %
◦ Surface atoms ~ 49 %

10 nm
 The percentage of surface atoms increases dramatically as the
particle size decreases .

 When particle size is in micrometer region the surface atom account

for less than 1% of overall atoms.
Properties dominated by bulk atoms

 Particle size reduces to nanometer region , the percentage of surface

atoms increases dramatically.

 2 nm ~ all the atoms properties completely dominated by surface.

 10 nm ~ 50% of all atoms on surface
 10 nm is transition point

 Nano technology also known as

 ‘surface technology’
 100 ▲

80
▲
Surface Atom %

60
Nano ▲
Technology
40

20 ▲

▲
▲
▲
0
10 100 1000
Nanoparticle Size (nm)
1 Kg of particles of size 1 mm3 is same as 1 mg of particles
of size 1nm3
 Surface energy in nano particles is much higher

 Surface energy ( ǿ) surface energy per unit area .

 Total surface area (S)
 Total surface energy E = ǿ S.
 ‘Surface energy’ is ‘extra’ energy.

 Nature will always want to decreases this term & their overall
energy.
 Surface Energy of Nanoparticles

Silver is one of the most widely studied materials, and there is a

wide range of values reported for the surface energy.

The value obtained from SDLP ( Size Dependent Lattice Parameter )

nearly free Ag nanoparticles is 6.4 J/m2 ,

embedded Ag nanoparticles is in the range 1.3–5.9 J/m2

bulk is in the range 1.065–1.54 J/m2.

The different values of surface energy clearly indicate its dependency

on the surrounding matrix as well as on the particle-substrate
interaction.
 Stability of TiO2 polymorphs

Rutile is more thermodynamically stable but

photocatalytic activity is higher for anatase
 Crystal form of TiO2

Anatase 94% crystal surface

Rutile 56% crystal surface

a) anatase b) rutile and c) brookite TiO2

surface sites
 Minimization through one of the two ways or combination

1. Minimization of the surface energy per unit surface area (ǿ )

through either exposing predominant surface planes that have a
lower surface ‘surface relaxation or reconstruction’ on altering
the local surface atomic geometry to reduce surface energy
(surface reconfiguration).

2. Reducing the amount of surface area exposed (S)

 “Nano particles have tendency to coalesce and form aggregates”.

 ‘Preferred planes’.

 Surface related to physics, chemistry, thermo dynamics and

material science

 ‘Nanometer region’
 “Surface layer is not only the top most layer of atoms
but at least 3 to 5 atomic layer beneath the top layer.”
 Decrease in surface energy by interacting
with atoms in the immediate environment

 Adsorption
 Physical
 Chemical

 Wetting