Nanomaterials :

They have emerged as an exciting class of materials

Application of nanomaterials:
Silver nanoparticles are used as antibiotics in textiles, wound dressings, and medical devices.

Gold nanoparticles selectively accumulate on tumour cells. It helps precise imaging and targeted laser
destruction of the tumour

Nano sized clays are added to products ranging from auto parts to packaging materials to enhance
mechanical, thermal and flame retardant properties.

Nanomaterials exhibit extraordinary catalytic activity, selectivity better than their respective bulk
materials

TiO2 can be used to remove hazardous heavy metal ions, inorganic anions, and organics in water, and
sterilise water.

Nanomaterials are used for the commercial fabrication of electrochemical sensors.

The electrochemical sensing of glucose is important for important for the determination of blood sugar
level.

Nanomaterials are used in the fabrication of wind turbine blades to make them light and strong in order
to increase energy conversion efficiency.
In the ancient days, the nanomaterials were used as dyes in ceramics.

Ultrahigh definition displays and televisions use quantum dots to produce vibrant
colours.

Nanomaterial/Polymer composites are used in baseball bats, tennis rackets, bicycles,

helmets, and automobile parts to make them light weight.

Good cholesterol[HDL-high density lipoprotein] helps to shrink plaque in arteries.

Researchers have developed nanoparticles that mimics the property of good
cholesterol.

Using nanoparticles many new batteries have been developed which are fast charging,
efficient, light weight, having high power density, andholding electrical charge longer.
Metal nano particles as drug carriers:
Important for targeted drug release. The cancer drug ,
fluouracil, is adsorbed on the surface of gold
nanoparticles. The mixture is then injected into
the party. The gold nanopartcles are strongly
adsorbed on the surface of the tumour.
Fluorouracil is then released to kill the cancerous cells.
Gold nanoparticles are injected into the body. They are
strongly adsorbed on the tumour surface. The gold
particles are then excited with light. The excited particles
excite the triplet oxygen to singlet oxygen. Singlet oxygen
is a powerful oxidant, so, it kills the cancerous cells.
Semiconductor photocatalysis:
Water is decontaminated by
dispersing nano TiO2 in it and exposing
to sunlight. Sunlight excites TiO2 by
promoting valence band electrons to
conduction band. Holes generated in the
valence band oxidise water and form
hydroxide radicals. These radicals are
highly unstable, powerful oxidant. They
decompose water borne organics and
mineralise them. Harmful inorganics are
oxidised to harmless products.
Conduction band electrons are
transferred to dissolved oxygen to form
peroxide anions which are also strong
oxidants.
Dye sensitised solar cells:
FTO(Fluoride doped tinoxide)
is coated with nanoTiO2 an dit acts as
the anode. An organic dye is
adsorbed on the TiO2 surface. I2/KI
dissolved in water is used as the
electrolyte. The anode is Pt cathode
externally. When exposed to
sunlight, the dye is excited. The
electrons of the excited dye
molecules are transported to FTO
through TiO2 and finally to the
cathode Pt. So, current is produced.
FTO vs Anatase TiO2 FTO vs Rutile TiO2
H2/O2 Fuel cells:
Nano Pt particles coated metal plate acts
as the anode over which H2 dissolves and
produces electrons. The released electrons reach
the Pt cathode through the external circuit. At
the cathode the electrons are transferred to O2
to form hydroxide ions . Hydroxide ions and H+
ions combine to form water
1.Classifocation of nanomaterials.
Nanomaterials are classified according to their dimensions.
0-D nanomaterials
1-D nanomaterials
2-D nanomaterials
3-D nanomaterials
0-D nanomaterials materials : No dimension is larger than 100nm
1-D nanomaterials : One dimension is larger than 100nm
2-D nanomaterials : : Two dimensions are larger than 100nm
3-D nanomaterials : All the three dimensions are larger than 100nm(nanocomposites)
They may be amorphous or crystalline.
They are single crystalline or polycrystalline
They may be metallic, ceramic or polymeric

2. They have high surface to volume ratio

For a sphere, the surface area = 4πr2.Surface volume = 4/3πr3
The ratio = = 3/r
For a cylindrical particle, the ratio = 2/r
For a cube, the ratio = 6/a, where a is the side of the cube.
Nanomaterials:
3.The have higher surface area than the bulk materials.

Let a spherical particle of radius 10,000 nm be converted into some number of particles each
with radius 10nm.
The volume the bulk particle = 4/3x22/7x 10,0003 = 12.57x 1012nm3

The volume of single nanoparticle = 4/3x22/7x103 = 1257nm3 = 12.57x103nm3

Therefore the number of nanoparticles =12.57x1012/12.57x103 = 109 particles

The surface area of 1 particle = 4x 22/7x102=1257nm2

Therefore, the surface area of 109particles = 1257x109 = 12.57x1011 nm2

The surface area of the bulk particle = 4x22/7x 100002 = 12.57x108 nm2

So, the increase in surface area is 1000 times.

4.The nanoparticles exhibit high tendency to sintering even at room temperature because of
tangling bonds at the surface

STEM image of two nanoparticles

5.The lattice parameter of nanoparticles decreased with the decrease in particle
size. It is due to strong inward attraction of surface atoms. It is high for
nanomaterials than the bulk materials
Lattice parameter of aluminium
6.With the decrease in the particle size of the semiconductors the bandgap increases{Quantum
size effect].
[Quantum dots are semiconductors with size less than 10nm.]
7. The total volume of the bulk materials remains the same when they are
subdivided. When a bulk material is subdivided, the surface area
increases.
8. Magnetic properties:
i). Non-magnetic bulk metals become magnetic at nano size.
Au and Pt are non-magnetic in bulk but becomes magnetic at nano size.

a) Paramagnetic
b) Antiferromagnetic
c) Ferromagnetic
d) Ferrimagnetic

CoFe2O4 : Both Co and Fe

are magnetic, but differ
in strength
Magnetic properties of nanomaterials:
There is a critical size below which the material will be
single domain.
Dcri =

A is the exchange constant also called exchange stiffness

µ0 is the permittivity of free space
Ms is the saturation magnetization.
The critical diameter of Co is 70 nm, and Fe 15 nm.

If the size is well below critical size, there will be loss of

magnetization due to thermal fluctuations. These materials are
called super paramagnetic.
9.Melting vs crystal size of metals:
The melting temperature of bulk materials is independent of size,
but the melting temperature of nanomaterials decreases with the decrease in
size. It is due to weakly bound(bonded) surface atoms and these atoms have high
surface energy.
10. Thermal properties:
Thermal conductivity of nanomaterials is lower than the bulk materials. Electrons are confined in
nanomaterials, but delocalised in bulk materials. Free electrons are the major carriers of heat.
Thermal conductivity of bulk Pt and platinum films are compared.
Thinner the film smaller the thermal conductivity, due to fewer number of free electrons.
11.Optical properties of nanomaterials:
In bulk metals the surface plasma resonance occurs over a wide range of wavelengths.
In nanometals the plasma resonance is localised.
For example., by decreasing the size of nanomaterials, emission of light shifts from near infrared to ultraviolet
region.
Nanomaterial loose their plasma resonance and become photoluminescent.
So, the wavelength of visible light emission can be tuned by varying the size nanomaterials.
So, matter can change colour at nanoscale.

Electron-hole recombination emits light

 Photoluminescence of CdSe nanoparticles

Nanoparticle size increases from blue to red, and so the bandgap decreases from left to right,
so, the luminescence maximum shift towards longer wavelengths.
Wavelengths of colour absorbed and complementary colour
12. Electrical properties of nanomaterials:
Ceramic is an insulator, but becomes a semiconductor at nanoscale.
Metal is a conductor, but becomes a semiconductor at a nano scale.
In a bulk metal, electrons can freely move in all directions, but in nanomaterials,
electron delocalization can occur along the axis of nanotubes, nanorods and nanowires.
Carbon nanotube can also be a semiconductor, when the size is reduced.
13.Mechanical properties:
Until 20th century, it was believed that mechanical properties of materials are scale (size) independent.
Now it is proved that the nanoscale materials have high strength and hardness. Hence the mechanical properties
of materials are size dependent.
High surface to volume ratio of nanomaterials alters hardness, elastic modulus, fracture toughness,
scratch resistance, and fatigue strength.
An increase in mechanical strength is due to low probability of defects and an
increase in surface imperfection
Hardness of copper decreases with the increase in grain size. So, nanomaterials
are harder than the bulk materials
Strength of nanolaminates:
With the increase in the bilayer thickness of the laminates, the tensile
strength decreases
 To remember
Quantum dots are nanomaterials that have quantum confinement and size dependent
photoluminescence emission. The size varies from 2 -10nm.
The terms clusters and nanoclusters are exchangeable. Nanodot is similar to clusters.
Ag nanocluster are stable and fluoresce only in the presence of protective groups.
Quantum well is a kind of hetero structures in which a thin layer(well) is sandwiched by two
barrier layers. Both the electrons and holes have lower energy in the well.
Quantum confinement is a process that occurs in nanomaterials. It is the spatial confinement
of electron-hole pairs( called excitons) in one or more dimensions within a material. The
electronic energy levels are discrete. Quantum confinement increases the bandgap of quantum
dots and creates discrete energy bands.
Catalytic properties:
In homogeneous catalysis, ions or molecules act as catalysts.
They are highly active and selective.
Their recovery from the product and recycling is difficult.
In heterogeneous catalysis, the catalyst particles are large.
They have low activity and selectivity compared to homogeneous
catalysts, but they can be easily recovered and recycled.
In contrast, when nanomaterials are used as catalysts, a definite
transition can be seen. Nanomaterials are more active than the
bulk materials, but less active than the molecules or ions.
After the reaction, the mixture will be centrifuged, and the
catalyst recovered and recycled.
MO theory of bonding
Optical properties of nanomaterials:
Dependence of refractive index(n) on frequency is due to
Electronic polarization
Orientation polarization
Ionic polarization
Space charge polarization
Preparation of nanomaterials
Disassemble solids

Assemble atoms
 1.Preparation of Ag nanoparticles using
NaBH4 and sodium citrate(Reducing agents) It is a chemical route.

Bottom-up method: Here ions are converted into nanomaterials .

1.Sol-Gel method: Bottom-up approach: Preparation of silica nanoparticles
The process involves acid catalysed hydrolysis of TEOS[Tetraethyl orthosilicate]
and condensation. Initially a sol of silica in water is formed by the condensation silicic acid.
Silica particles in turn combine to form porous silica net work. It is aided by the residual OH
groups on the surface. The condensed matrix forms a hydrogel by adsorbing water. It is aged
for some time and transferred to autoclave, heated in the oven at a definite temperature,
cooled, filtered, and the residue washed with excess water and then dried at 200°C to form
nano silica.
Metal alkoxides are the common precursors, as they are commonly available.

The process is run at low temperature(below 100°C)

Initially a colloid[sol] is formed.

The colloidal particles joining together to form a gel.

When the gel is dried under supercritical condition, the solvent is removed and an extremely
low dense, porous aerogel will be obtained.

Freeze drying of gel gives cryogel.

Simple evaporation of solvent gives xylogel.

Conversion of sol and gel
2.Hydrothermal synthesis : Bottom-up approach:
Synthesis of inorganic nanomaterials in water above ambient temperature and pressure.
The aqueous mixture of inorganic materials is heated in an autoclave above the boiling point of water
There is a dramatic increase in pressure inside the autoclave. Both the high temperature and pressure provide a one step
process to produce a highly crystalline nanomaterial.
There is no need for post annealing treatment for the product.

Preparation of ZnO nanoparticles

by hydrothermal method:
Solution of zinc nitrate in water is treated with sodium hydroxide
to form zinc hydroxide ppt. It is transfered to a teflon lined
autoclave. The autoclave is tightly closed and heated in the oven
at 120°C for 10h. A suspension formed is filtered and the residue
dried at 120°C to get ZnO nanorod.
3.Laser ablation method for nanoparticles.:
Semiconductor quantum dots, carbon nanotube, nanowires, core shell nanoparticles
can be produced by this method.
In this method Laser is used as an energy source to ablate solid target material,

An extremely high energy is concentrated at a specific point on a solid surface to evaporate

light absorbing material.

Ablation refers to removal of surface atoms

There is a single photon process to break the bonds of atoms in the target but also
multiphoton excitation(Thermal evaporation).

It is difficult to control size distribution, agglomeration, and crystal structure, as nanoparticles

are produced by random motion of atoms/molecules.
4.Electrospinning: Top-down method:
It is used to form one dimensional nanowire or quantum wire. Electro spun materials find applications in materia
science, biomedicine, tissue engineering, energy storage, environmental science, and sensing. This technique is
cheap, operationally simple, and highly efficient.
Polymer nanofibers can also be produced by this technique.
This technique was patented in 1990, but continuously attracting
researchers around the world who have interest
to produce nanofibers.
The deposited fibers will not inter mix,
as they repel and get solidified as the solvent
gets evaporated.
The electrospinning apparatus is built with a syringe, syringe pump, spinneret, collector, high voltage power
supply.
A solution of a solute, which is to be spun, is taken in the syringe, and pumped through a nozzle by a syringe
pump.
For pumping two solutions, the core solution is pumped through the needle and the sheath solution through the
space between the nozzle and needle
A potential of 10 – 50 kV
The spinneret and the collector plate are conducting and separated at an optimum distance.
When high voltage is applied, the solution becomes highly charged, and so, the solution droplet at the tip of the
needle, will experience two types of electrostatic charges: the repulsion between the surface charges and
attractive forces with the external electric field.
When a critical voltage is reached, these electrostatic charges cause the pendant droplet of the fluid to deform
into a conical structure called Taylor cone.
When the applied voltage is higher than the critical value, the repulsive electrostatic forces overcome the surface
tension of the pendant droplet, and so, a fiber jet is ejected from the apex of the Tayler cone and accelerated
towards the grounded collector.
The fiber set continuously elongates due to electrostatic repulsion. So, the quality of the nano fiber is affected by
applied potential, solution concentration, viscosity, surface tension, conductivity, and flow rate.
 CuO nanoparticles by electrospinning

a) TEM image of nanofibers after calcination, b) and c) magnified images of a), d), nanofibers changing to nanoclusters after
sonication in water.
5. Chemical vapour deposition(CVD):Bottom-up
method:
Different types of nanofibers and their applications
1. Inert gas condensation:
An inorganic material is vaporized inside a vacuum chamber
Helium or Argon is periodically admitted into the chamber
The vapouring inorganic atom collides on the inert gas and gets cooled.
The cooled vapours combine nanoparticles of size 1-100 nm.
These nanoparticles collect on the finger cooled by nitrogen.
Alloy particles are made using dual sources.
Process parameters are to be adjusted to avoid bulk particles.
2.Inert gas expansion:
The evaporated atoms are carried by high pressure He gas.
They then expand through a nozzle into a low pressure chamber.
It leads to cooling and the cooled atoms combine to form nanoclusters.
The clusters are collected in a tray.
3.Sonochemical processing:
In this technique ultrasound is used to nucleate atoms to form nanoclusters.
Ultrasonic waves have wavelengths from 1- 10000µ.
They are generated in a liquid filled reaction vessel.
The wavelengths are not of molecular dimensions, so thee is
no direct coupling between them.
The reaction occurs because of cavitation.
The tensile part of the first wave can push the liquid apart and form a cavity.
The compressive part of the wave compresses it.
Even before compression some reactants vapourise and get
into the cavity.
The tensile part of the second wave re-expands the bubble,
and more and more reactants get into the bubble.
When the bubble reaches critical size , it collapses.
The collapse occurs adiabatically. So, a hot spot is produced.
A hot spot is produced with the temperature around 5000C(sun surface)
and pressure 2000atm (pressure of deep sea).
It triggers a reaction and creates nanoparticles.
The size of the spot decides the size of the nanoparticles.
4.Electrodeposition:Bottom-up method:

By applying a potential equal to that of the decomposition

potential of any easily reducible metal ions , metal
nanoparticles can be obtained.

The layer thickness depends on current density and the

time for which the current flows.

Sometimes the particle may grow like pillars. It can be

avoided using pulsed voltage and adding little growth
inhibitors.

The layer then can be detached.

5.Physical vapour deposition:
A thin layer of metal is deposited on a plate.
The vapour is created in a vacuum chamber by direct
heating
Methods for making 3-D nanomaterials
 Nanoparticle characterization:
SEM(Scanning electron microscope) and TEM(Transmission electron microscope)

Electron sources, and interaction between matter and electron beam:

Thermionic emitters:
Tungsten and LaF6 filaments are the common thermionic emitters
LaF6 gives much brightness, but is sensitive to thermal shock and expensive.
Field emission emitters:
A very sharp tungsten tip is subjected to a very high electric field to
reduce the surface potential barrier for electron release. So, it gives a narrow
probe, and increased brightness which facilitates enhanced contrast
and resolution.
The electron beam is accelerated toward the specimen.
Sem uses both the secondary and backscattered electrons to get the image.
TEM uses transmitted and elastically and inelastically scattered electrons to get the image.
SEM images the surface of the specimen. If the specimen is not conductive, it is coated with Au or carbon to avoid electron
charging and image degradation. Non-conducting specimen accumulates charges(electrons) leading to image distortion.
If the detector is given positive potential, it will capture both the secondary and backscattered electrons. If it is given a
negative potential, it can capture only secondary electrons.

S lay out
Scanning electron microscope:
It produces detailed, magnified image of an object by scanning
the surface using a focused beam of electrons. The main components
are Electron gun
Accelerating anode
Condenser lens
Scanning coil
Objective lens,
Detectors
Magnification can go up to 300,000 X
EDS provides qualitative and quantitative results
The spot size produced from the gun is too large, so, there are
condensing lens to focus them
In sem, a spot size of 10nm interacts with the specimen and penetrates
to a depth of 1µm and generates the signal to produce the image. The
image of the specimen is formed point by point with the help of
scanning coil
Both the secondary and back scattered electrons are used to form the
image.
With accelerating voltage of 5kV specimen surface can be analysed.
With the accelerating voltage of 15 – 30kV, the interior of the
sample(different phases) can be analysed.
There is an electron gun at the top of the instrument. It is a tungsten filament or LaF6. It is electrically heated to
2700C to emit electrons. The filament is kept inside a Wehnelt(it is a cylinder) which controls the number of
electrons leaving the gun. The electrons are accelerated with an anode at a potential of 200V to 30kV . By
increasing the accelerating voltage short wavelength electrons can be produced. For biological specimens,
125000V accelerating voltage can be used. Then there are two condenser lenses to produce thin, coherent,
electron beam. They collect the electrons and focus them onto the specimen to illuminate only the area being
examined. These lenses focus the beam 1000 times lower than the original size. So, they are responsible for the
intensity of the electron beam.
The objective lense is used to magnify the image.
An objective aperture is used to enhance specimen contrast.
An aperture is used to reduce spherical operation
Intermediate lenses are used to magnify the images from the objective lense.
Finally the projector lenses further magnify the image coming from the intermediate lenses and projects
it onto the phosphorescent screen.
The phosphorescent screen gives off photons when irradiated by the electron beam.
A film camera is located beneath the phosphorescent screen
The photographic film may be replaced by digital capture with the computer digitizing and
archiving(CCD) camera

Resolution is defined as the distance at which two points or objects can be distinguished.
Secondary electron SEM image of Secondary SEM image of
lactic acid glycolic acid co carbon nanotube
polymer
Transmission electron miccroscope
Transmission electron microscope:
TEM can tell us crystallization, morphology and size of nanomaterials
The specimen is placed on copper or molybdenum gold platinum grid of
about 3mm diameter mesh
The electron lenses are composed of iron, iron-cobalt or nickel-coballt
alloy. They are magnetic.
The darker areas of image represent those areas of the sample that fewer
electrons are transmitted, while the bright areas of the image represent those
areas of the sample that much electrons are transmitted.
The accelerating voltages of 120,200 and 300kV are commonly
used.
The specimen thickness is 50 to 100nm, as the image is formed by
the electrons that penetrate the sample.
The electron beam is demagnified by the first condenser lens.
The second condenser lens converses the beam at the specimen
and controls the spot size.
The condenser aperture controls the intensity of the electron
beam.
The overall magnification is controlled by al the parts below the
specimen.
Transmission electron microscope

It is useful to study morphology, crystal

structure, bonding, chemical
composition
 Nanotubes, nanowires, nanorods and nanoclusters

They find applications in energy, electronics optics and other fields.

They are made of metals, semiconductors, insulators and other organic
compounds.
They have high surface to volume ratio.
So, they are important in the fabrication of sensors
Carbon nanotubes:
They are essentially sheets of graphene rolled up into a cylinder.
So, they are one atom thick sheets pure carbon.
The research paper was published in 1991 by a physicist Sumio
Ijima.
They are one dimensional, the other two dimensions are in the
nanometer scale. Single walled carbon nanotube
They can grow to a length of few hundreds of micrometre. [SWCNT]
They have high surface to volume ratio.
So, they are important in the fabrication of sensors.
They are exceptionally strong, and so they are used as
reinforcing fibers in advanced composite materials
Their diameter may vary from 1-4nm.
Hey are biocompatible, non-biodegradable and
nonimmunogenic nature Multiwalled carbon nanotubes
[MWCNTs]
The are highly elastic and have minimum cytotoxicity.
They have ultra-lightweight and do not breakdown during processing.
Their tubular and needle nature facilitates easy entry of cells.
They can be easily functionalized with drugs, proteins nucleic acids.
The inner diameter of SWCNTs may vary from 0.4 to 2nm. The surface area may be
1300m2/g
The SWCNT and anticancer drug complex has high blood circulation time, and so it leads
to prolonged and sustainable uptake of drug by tumour cells. Once drug is released it is
easily excreted from the body.
The MWCNTs consists of several coaxial cylinders each made of single graphene sheets,
surrounding the hollow core.
The outer diameter varies from 2 -100nm and their length 1 – several µm.
The carbon is sp2 hybridised and the structure has delocalized electron cloud.
Preparation of carbon nanotubes:
By CVD method:
Hydrocarbon gas is used as the carbon source.
A substrate coated with a catalyst is placed inside a quartz tube filled with
argon gas. The tube is placed inside the furnace heated between 500 and
900°C. The hydrocarbon is decomposed by the catalyst to carbon which then combines to
form single or multi-walled carbon nanotubes.
Nanowires
Any solid material in the form of wire less than 100nm.
There is no room for defects.
The electrons move through the wire unimpeded.
Their length can extend to hundreds of micrometer.
Silicon nanowires have been used in field effect transistors, inverters and light
emitting diodes.
Nanowires of Ni, Pd, Au and YBCO super conductor were reported.
Metal nanowires are prepared by electrodeposition. It results in dense nanowires
in high yield.
A thin film of a metal is deposited on a substrate. It is then placed in the
electrolyte solution containing the metal ions. When electric current is passed
the metal ions are reduced to metal atoms, which grow on the substrate as metal
nanowires.
Nanorods: Synthesis

Synthesis of GaN nanorods

ZnO nanorods
Nanoclusters:
They have ultra small size.
They are strongly fluorescing
They are stable
They are highly reactive.
Their size is greater than separate
nanoparticles.
They have high wear resistance.
A number of metal centers are
Iron oxide nanoclusters.
grouped together by metallic bonding
Photoluminescence of Au
or a bridging ligand. doped Ag nanoclusters(Ag29)
Quantum dots were also called
semiconductor nanoclusters.
Metal clusters can be obtained by
reduction of metal ions
AFM image of copper nanoclusters Gold nanoclusters
Deposited on silicon substrate.