Nanomaterials

WHAT ARE THE NANOMATERIALS?

• Nanomaterials could be defined as those materials which have
structured components with a size less than 100nm at least in
one dimension.

• Nanoscience is the study and understanding of the properties

of nanoparticles.

• Nanotechnology can be defined as the design, production

characterization, and application of structures, devices and
systems by controlling shape and size at the nanometer scale.
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1.NANO MEANS 10 -9. I.E. NANOMETRE IS ONE THOUSAND
MILLIONTH OF A METRE.
2. ATOMS ARE VERY SMALL MEANS DIAMETER OF A SINGLE
ATOM CAN VARY FROM 0.1 TO 0.5 NM IN DIAMETER. EX:
CARBON ATOMIC SIZE IS 0.15 NM IN DIAMETER.
3. SIMPLE WAY TO UNDERSTAND NANO TERM IS BLOOD CELL
IS IN ORDER OF 7000 NM SIZE…… MEANS SUCH A VERY
SMALL SIZE STRUCTURE.
4. SOME MATERIALS ATOMIC SIZE IN ORDER OF MICRO SIZE,
THEY CAN BE TREATED AS CONVENTIONAL MATERIALS, IF
MATERIAL IS BULK ITS AREA OR SIZE EXPRESSED IN 3-
DIMESION.
5. IF IT IS PLANAR MATERIAL(2-D),LINEAR MATERIAL (1-D)
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Nanorods: Nanostructures that are shaped like long sticks with a
diameter in the nanoscale and a length very much longer.
Nanowires: Another term for nanorods, especially nanorods that
can conduct electricity.
Nanotubes: Almost always carbon nanotubes, referring to the
wires of pure carbon that look like rolled sheets of graphite or like
carbon soda straws.
 RED BLOOD CELLS ≈ 7,000 nm
WHITE BLOOD CELLS ≈
Examples 10,000nm
 A VIRUS IS ≈ 100nm
A Hydrogen Atom is ≈ 1nm

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 MATERIALS USED IN NANO TECHNOLOGY

1. FULLERENCE

2.INORGANIC NANOPARTICLES

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 FULLERENCES
• Fullerene is a family of carbon allotropes, molecules
composed entirely of carbon in the form of a hollow
sphere, ellipsoid, tube, or plane.

• Some elements exist in different chemical

modifications; the different forms are called allotropes.

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 BUCKY BALL
• IT BELONGS TO THE FAMILY OF FULLERENCE.
• C60 IS CALLED AS BUCKY BALL
• 60 CURBON ATOMS ARE ARRENGED IN A SERIES OF INTERLOCKING
HEXAGONALS AND PENTAGONS,FORMING A STRUCTURE THAT
LOOKS LIKE SOCCER BALL.
• IT WAS DISCOVERED BY Prof.HARRY KROTO,RICHARD .E SMALLEY* &
ROBERT F.CURL*
• * THEY GOT NOBLE PRIZE FOR THEIR DISCOVERY IN 1996.

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BUCKY BALL

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 BUCKY BALL

• RED BOND REPRESENT A SINGLE BOND

• YELLOW BONDS REPRESENT DOUBLE BONDS.

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 WHAT IS QUANTUM DOT?
•A quantum dot is a particle of matter
so small that the addition or removal of
an electron changes its properties in
some useful way.

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 Why the properties of nanoparticles
are different?
1. Increase in surface area to volume ratio:
for a sphere:-
Its surface area = 4Πr2
Its volume = 4/3 Πr3
surface area to its volume ratio =(3/r)
2. Quantum confinement effect:-
When the dimensions of the potential well are of the order of
de Broglie wavelength of electrons or mean free path of
electrons., energy levels of electrons change .this effect is
called quantum confinement.

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 0.5 cm

1 cm

12 cm2
6 cm2
0.01 cm
.………………………
………………………
……………….
600 cm2
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 Electrical properties

•The electronic structure of Nanomaterials is different from its bulk material.

•The density of the energy states in the conduction band changes.
•When the energy spacing between two energy levels is more than KBT, energy gap is created.
•Nano clusters of different sizes will have different electronic structures and different energy leve
separations.
•The Ionization potential at Nano sizes is higher than that for the bulk materials.
•Nanoparticles made of semiconducting materials Germanium, Silicon and cadmium are no
semiconductors.

Magnetic properties
• The magnetic moment of nanoparticles is found to be very less when
compared to its bulk size.
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 Nanomaterials: Basic Processes

(A) Top-Down (Fabrication of components from larger materials)

• electric arc, flame pyrolysis, ball milling, laser ablation, Nanolitheoghraphy

(B) Bottom-up (Building things by combining smaller components)

• Physical Vapor Deposition (PVD)

• Chemical Vapor Deposition (CVD)

• Sol-Gel-Chemistry

• Spray Drying

• Hydrothermal Synthesis

• Plasma

• Microemulsion

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 Sol-Gel Method
The Sol-Gel process is a wet chemical process, i.e chemical solution deposition
technique used for the production of high purity and homogeneous
nanomaterials particularly metal oxide nanoparticles.

Sol : The starting material from a chemical solution leads to the formation of
colloidal suspension known as sol. The colloids in which molecules of size
ranging from 20 nm to 100 nm.
Gel : The sol evolves to wards the formation of inorganic network containing a
liquid phase is called as gel. The removal of liquid phase from sol leads gel.
Method:
(1)The desired colloidal particles once dispersed in a liquid to form a sol.

(2) The deposition of sol solution produces the coatings on the substrates by
spraying, dipping or spinning.

(3) The particles in sol are polymerized through the removal of the stabilizing
components and produce a gel in a state of a continuous network.
Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based
precursors such as Si(OEt) 4 (tetraethyl orthosilicate, or TEOS).
The reactions involved in the sol-gel chemistry based on the hydrolysis and
condensation of metal alkoxides M(OR)z can be described as follows:

Sol-gel method of synthesizing nanomaterials is very popular amongst chemists

and is widely employed to prepare oxide materials. The sol-gel process can be
characterized by a series of distinct steps.
The final heat treatments pyrolyze the remaining organic or inorganic
components and form an amorphous or crystalline coating.
The sol-gel approach is easy and cheap low-temperature technique that
allows for the fine control on the product’s chemical composition like
organic dyes and rare earth metals, can be introduced in the sol and end up
in the final product finely dispersed.
Advantage: The possibility of synthesizing nonmetallic, inorganic materials like
glasses, glass ceramics or ceramic materials at very low temperatures.
Disadvantage: controlling the growth of the particle is difficulty.
Applications: The sol-gel derived nanoparticles have wide spread application in
various fields like optics, electronic, space, bio sensors, and drug delivery.
BALL MILLING :
1. IT IS MECHANICAL CRUSHING.
2. SMALL BALLS ARE ALLOWED TO ROTATE AROUND
THE INSIDE OF A DRUM AND THEN FALL ON A
SOLID.
3. TO CRUSH THE SOLID INTO NANOCRYSTALLITES.
4. THIS IS USED TO PREPARE WIDE RANGE OF
ELEMENTAL OXIDE POWDERS.
5. EX: IRON WITH 10 – 30 NM CAN BE FORMED, AL
AND NI MIXED POWDER… METAL OXIDE
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POWDERS.
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Advantages of ball milling process over conventional synthesis method are :
1. Low installation cost and low cost of grinding medium.
2. Materials of any hardness can be grounded.
3. Nanopowder with size distribution of 2 to 20 nm bulk quantity can be produced.
4. It is an inexpensive and easy process.
Disadvantages of ball milling process:
1. As the process is not so sophisticated, therefore the shape of the nanomaterial is irregular.
2. There may be contaminants inserted from ball and milling additives.
3. This method produces more crystal defects.
4. Non metal oxides required an inert medium or glove box to handle powder particles.
Applications :
1. It is extensively employed to grind materials like coal, pigments, and feldspar for pottery.
2. Both wet and dry grindings are possible, however wet grinding is usually done at low
speeds.
3. Ball-milling increases the solid-state chemical reactivity in multiple components systems.
4. Furthermore, it can also be used to produce amorphous materials.
 Chemical Vapor Deposition
In this method, nanoparticles are deposited from the gas phase.
Materials are heated to form a gas and then allowed to deposit on solid surface usually
under vacuum condition.
The deposition may be either physical or chemical. I
n deposition by chemical reaction new product is formed.
Nano powder of oxides and carbides of metals can be formed, if vapors of carbon or oxygen
are present with the metal.
Working Concept : A material, often a metal is evaporated from a heated metallic source
into a chamber which has been previously evacuated to about 10–7 torr and backfilled with
inert gas to a low-pressure.
The metal vapor cools through collisions with the inert gas atoms, becomes supersaturated
and then nucleates homogeneously; the particle size is usually in the range 1–100 nm and can
be controlled by varying the inert gas pressure.
Ultimately, the particles are collected and may be compacted to produce a dense nano
material.
Fig. Schematic diagram of the chemical vapor deposition apparatus.
During the process of chemical vapor deposition, the reactant gases not only react
with the substrate material at the wafer surface (or very close to it), but also in gas
phase in the reactor's atmosphere.
Reactions that take place at the substrate surface are known as heterogeneous
reactions, and are selectively occurring on the heated surface of the wafer where
they create good-quality films
. Reactions that take place in the gas phase are known as homogeneous reactions.
In short, heterogeneous reactions are much more desirable than homogeneous
reactions during chemical vapor deposition.
Advantages
The increased yield of nanoparticles.
A wider range of ceramics including nitrides and carbides can be synthesized.
More complex oxides such as BaTiO3 or composites structures can be formed.
 CHARACTERIZATION OF
• XRD
NANOPARTICLES
• ELECTRON MICROSCOPE
• SCANNING ELECTRON MICROSCOPE (SEM)
• TRANSMISSION ELECTRON MICROSCOPE (TEM)

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X-RAY DIFFRACTION(XRD)

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Transmission of Electron Microscopy (TEM)

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• It consists of an electron gun to produce electrons.
Magnetic condensing lens is used to condense the electrons
and is also used to adjust the size of the electron that falls
on to the specimen. The specimen is placed in between the
condensing lens and the objective lens, as shown in Fig.
• The magnetic objective lens is used to block the high-angle
diffracted beam and the aperture is sued to eliminate the
diffracted beam (if any) and, in turn, increases the contrast
of the image.
• The magnetic projector lens is placed above the fluorescent
screen in order to achieve higher magnification. The image
can be recorded by using a fluorescent (Phosphor) screen or
(CCD – Charged Coupled device) also.
 Working principle
• A stream of electrons is produced by the electron gun and is made to fall over the
specimen using the magnetic condensing lens.
• Based on the angle of incidence, the beam is partially transmitted and partially
diffracted. Both these beams are recombined to form the image.
• In order to increase the intensity and the contrast of the image, an amplitude
contrast has to be obtained. This can be achieved only by using the transmitting
beam, and thus the diffracted beam can be eliminated.
• Now in order to eliminate the diffracted beam, the resultant beam is passed through
the magnetic objective lens and the aperture. The aperture is adjusted in such a way
that the diffracted image is eliminated. Thus, the final image obtained due to the
transmitted beam alone is passed through the projector lens for further
magnification.
• The magnified image is recorded on a fluorescent screen or CCD. This high-
contrast image is called Bright Field Image.
• Also, it has to be noted that the bright field image obtained is purely due to the
elastic scattering (no energy change), i.e., due to the transmitted beam alone.
 Applications of TEM
• 1. Morphology of the specimen can be determined
• 2. crystallography information can be investigated
• 3. Compositional information can be studied

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 1.Material Technology

• MRI SCAN
• Water purification process
• Sunscreens(ZnO2 & TiO2)
• Nanosized iron oxide is present in some lipsticks
• Carbon nanoparticles act as fillers to reinforce car tyres.
• TiO2 is used as self-cleaning windows and walls.(TiO2 is highly
hydrophobic and antibacterial.)
• Nano paints lead to cool a room( change colour in response to change in
temperature) (optical properties)
• Nanoparticles react with pollutants in soil and groundwater and
transform them into harmless compounds.

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2.INFORMATION TECHNOLOGY
• Nano scale fabricated magnetic materials have
applications in data storage devices.
• Flat-Panel displays (ZnS,CdS)
• Nano particles are used in information storage
3.Medical
• Drug delivery system
• Active agents
• Agent in cancer therapy

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4.Energy
• Fuel cells
• Solar cells
• Batteries
• capacitors

5. Cosmetics
Sun protection
Lipsticks
Skin creams
Toothpaste
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