Nano materials

Introduction
• Nanomaterials have one of its dimensions in the range of 1- 100 nm are
known to use for centuries.
For example
Chinese used gold nanoparticles as an inorganic dye into their ceramic porcelains
more than thousand year ago.
* Nanomaterials are promising because at nanoscale, its physical and chemical
properties differ significantly from its bulk structured materials.
For instance, bulk silver is non-toxic whereas silver nanoparticles can kill viruses
upon contact.
• Properties like electrical conductivity, colour and strength change when the
nanoscale is reached.
• It is already having a significant commercial impact, which will assuredly
increase in the future.
Applications of Nanomaterials in Real life
1.The range of commercial products available today is very broad, including
stain-resistant and wrinkle free textiles, cosmetics, sunscreens, electronics, paints
and varnishes etc.
2.Nanocoatings and nanocomposites are finding uses in consumer products, such
as windows, sports equipment, bicycles and automobiles.
3.There are UV- blocking coatings on glass bottles which protect beverages from
damage by sunlight, and longer lasting tennis balls using butyl rubber/nano-clay
composites.
4.Nanoscale titanium dioxide for instance is finding application in cosmetics,
sunblock cleans, and self-cleaning windows, and nanoscale silica is being used
as filler in a range of products, including cosmetics and dental fillings
 Scheme 2: Applications of Nano
General properties and applications of nanomaterials
• Nanophase ceramics are of interest because they are ductile at elevated
temperature as compared to the coarse-grained ceramics.
• Nano structed semiconductor are known to show various non-linear optical
properties.
• Nanosized metallic powders have been used to produce gas tight materials
dense parts and porous coatings.
Magnetic nanocomposites have been used for mechanical Materials in the
nanometer scale exhibit physical properties distinctively
• force transfer, for high density information storage and magnetic
refrigeration.
• Nanostructured metal clusters and colloids have a special impact in
catalytic applications.
• Nanostructured metal-oxide (MnO2) finds application for rechargeable
batteries for cars or consumer goods.
Size dependent properties of nanomaterials
Materials in the nanometer scale exhibit physical properties distinctively different
from that of the bulk material
1. Surface area
2. Electrical properties
3. Optical properties
4. Catalytic properties
5. Thermal properties
Surface Area
1.When a bulk material is subdivided into individual nanomaterials, the total
volume remains the same, but the collective surface area is enormously increased.
2.Nanomaterials have a large proportion of atoms existing at the surface.
3.Properties like catalytic activity gas adsorption and chemical reactivity depend
on the surface area.
4.Therefore nanomaterials can show specific surface related properties that are
not observed in bulk materials.
Example:
Bulk gold is catalytically inactive, but gold nanoparticles are catalytically very
active for selective redox reaction.
Electrical properties
1.Some metals which are good conductor in bulk become semiconductor or
insulator as their size is decreased to nano level.
2.The reason is that the electronic bands in bulk material are continuous due to
overlapping of orbitals of billions of atoms.
3.Nanomaterials very few atoms or molecules are present and so the electronic
bonds become separate and separation between different electronic states varies
with the size of nanomaterial
Optical properties
1.The nanomaterials of different size can scatter radiation of different
wavelengths.
Example:
Colour of few colloidal solutions are due to this scattering effect.
2.Nano particles of metals exhibit unique optical property called as surface
‘Plasmon resonance’.
3.when lights hit the surface of metals particle, electron present on the surface
(Surface plasmon) starts oscillating back and forth in a synchronized way in a
small space and the effect is known as surface plasmon resonance.
4.Depending on the frequency of oscillation resonating electrons capture
radiation of different wavelength.
Catalytic properties
1.The catalytic property of materials depends on particle size.
2.If the size of the particles reduces from bulk to nanoscale, surface to volume
increases drastically, that leads to very high catalytic activity of same material.
Example:
Catalytic properties of gold nanoparticles. Although bulk gold samples are
practically inert, nanometer sized gold particles have been proven to be highly
active for several reactions, including
• Low- temperature oxidation of CO
• Partial oxidation of hydrocarbons.
• The water-gas shift reaction.
• Reduction of nitrogen oxides when dispersed over certain oxides and
carbides.

Synthesis of nanomaterials:
There are two approaches to the synthesis of nanomaterials
1.Bottom-up synthesis
2.Top-down synthesis
In the bottom-up approach, molecular components arrange themselves into more
complex assemblies’ atom-by-atom, molecule-by-molecule, cluster-by-cluster
from the bottom
Example:
Growth of a crystal
In the top-down approach, nanoscale devices are created by using larger
externally controlled devices to direct their assembly. The top-down approach
often uses the traditional workshop or micro-fabrication methods in which
externally controlled tools are used to cut, mill, shape and order. Attrition and
milling for making nanoparticles are typical top-down processes.
Bottom-up approaches, in contrast arrange molecular components themselves
into some useful conformation using concept of molecular self -assembly. The
bottom -up approach has been well known to the chemists for a long time. This
approach plays a very important role in preparing nanomaterials having very
small size where the top-down process cannot deal with the very tiny objects.
The bottom-up approach generally produces nanostructure with fewer defects as
compared to the nanostructures produced by the top-down approach.
The main driving force behind the bottom-up approach is the reduction in Gibbs
free energy. Therefore, the materials produced are close to their equilibrium state.
In top-down techniques, significant crystallographic defects can be introduced to
the processed patterns.
Example Nanowires made by lithography are not smooth and can contain a lot of
impurities and structural defects on its surface.
In spite of the defects, the top down approach plays an important role in the
synthesis and fabrication of nanomaterials. The present state of nanoscience can
be viewed as an amalgamation of bottom up chemistry and top-down engineering
techniques.

Synthesis by Sol-Gel method

Sol-gel method of synthesizing nanomaterials is very popular amongst chemists
and is widely employed to prepare oxide nanomaterials.
The sol-gel process can be characterized by a series of distinct steps.
1. Preparation of sol
A stable colloidal solution called sol is prepared. (The sol is a liquid suspension
of solid particles ranging in size from 1nm to 1 micron). It is prepared by
hydrolysis and partial condensation of precursors such as metal alkoxide.
M-O-R + H2O → M-OH + ROH (hydrolysis)
Metal alkoxide
M-O-R + M-OH → MOM + ROH (condensation)
Metal alkoxide
2. Conversion of Sol to Gel
Further condensation of sol into a three-dimensional network produce a gel
material
(The gel is a diphasic material in which the solids encapsulate the solvent)
3. Aging of the Gel
Polycondensation reaction continue until the gel transforms into a solid mass
accompanied by contraction of the gel networks and expulsion of solvent from
gel pores. The aging process of gels can exceed 7 days.
4. Drying of Gel
Water and other volatile liquid are removed from the gel network.
If isolated by thermal evaporation, the resulting monolith is termed a Xerogel. If
the solvent (such as water) is extracted under-critical or near super critical
conditions, the product is an aerogel.
5. Dehydration
To stabilize the gel against any rehydration the surface-bound M-OH groups are
removed by calcining(heating) the monolith at temperature up to 800oC.
The typical steps that are involved in sol-gel processing are shown in the
schematic diagram below.
 Diagram 6: Sol-Gel process
Advantages Sol-gel method
• Low temperature route (below 2000C)
• Uniform particle size distribution
• Can easily shape materials into complex geometries in gel state
• Simple, effective method to produce high quality coatings

Precipitation method
1.Preparation of nanoparticles can be achieved by careful precipitation of the
substance from its solution.
2.In this process, acid or base is added to the precursor solution to adjust the pH
to the desired level.
3.Then a precipitating agent is added to it to initiate nucleus formation. The
nucleus formed grows into particles and gets precipitated. The precipitate is
filtered, washed, air dried and calcined to obtain nanoparticles.
For example:
Precipitation of Zinc sulphide nanoparticles is carried out from Zinc acetate
precursor solution by adding precipitating agent. Thioacetate (TAA) which
provide sulphide ions.
 Zn2+ + S2- → ZnS

Advantages of precipitation method

• This simple and rapid method of preparation of nanoparticles.
• Particle size and crystallinity can be controlled by optimizing conditions
• Homogenous mixing of reactants reduces the reaction temperature.
• Simple, direct process for the synthesis of fine metal oxide powders, which
are highly reactive in low temperature sintering.
• The process is relatively economical.
• A wide range of single and multi-components of oxide nano powders can
be synthesized.
Disadvantages:
1) This process is not suitable for the preparation of high purity, accurate
stoichiometric phase.
2) This method does not work well, if the reactants have very different solubility
as well as the different precipitation rate.
3) Universal experimental condition for the synthesis of various types of metal
oxides is not applicable.
4) Inability to control the size of the particles and chances of aggregation of nano
particles.

Nanoscale materials:
Fullerenes
1. Fullerenes is a “0” dimensional carbon allotrope named after Buckminster
fuller.
2. Fullerene molecules composed entirely carbon, in forms of a hallow
sphere. There are called Buckyball.
3. The C60 fullerene is often compared to a soccer football
4. Fullerenes have 20 hexagonal and 12 pentagonal rings.
 5. Fullerenes is icosahedral symmetry.
6. Fullerenes is sp2 hybridized.

Diagram 8: Structure of Fullerene

Properties of Fullerenes
1.Fullerence is a black powdery material.
2.Fullerenes are the only known carbon allotropes that can be dissolved in
common solvents at room temperature.
3.Fullerenes is a very tough and thermally stable material.
4.Fullerene can be compressed to 30% of its volume without destroying its cage
structure.
Application of fullerene
1.Fullerene is used as hydrogen storage material for fuel cells and some secondary
batteries.
2.Fullerene are used in the preparation of superconductor.
3.Fullerenes are used as lubricants due to its spherical structure.
4.Fullerenes are used in tennis racket frames where lightness and strength needed.
5.Fullerenes is used to carry drugs into cells, the cage like fullerenes molecules
could contain drug.
 Carbon Nanotubes
1. Carbon Nanotubes is a 1-dimensional carbon allotrope having a cylindrical
structure and a central hollow core formed by rolling up of graphene sheets.
2. Diameter of CNT is 1 – 50 nm and the length is in few micrometers.
3. Carbon Nano-tube Aspect ratio (length/Width) is generally greater than
1000.

Types of CNT’s
1.Single walled carbon nanotubes (SWCNT’s)
They are formed by rolling a graphene layer. Diameter 1 to 2 nm.

Diagram 9: Structure of SWCNT

2.Multiwalled carbon nanotubes (MWCNT’s)

 Diagram 10: Structure of MWCNT

(a) They are made by rolling multiple layers of graphene sheets arranged in
concentric cylinder form.
(b)MWCNT’s diameter 2 to 25 nm.
(c) The open ends of CNT’s are closed with fullerene caps.

Properties CNT’S (carbon nanotubes)

1. CNT’s having outstanding high electrical property. (six times of copper)
2. CNT’S have the highest tensile strength of an any material known.
3. CNT’s has high chemical (Such a lithium storage capacity) storage
capacity.
4. CNT’s can be easily functionalized.
5. CNT’s are excellent field emitter; high aspect ratio and small tip radius of
curvature are ideal for field emission.

Application of CNT’s (carbon nanotubes)

1.CNT’s having electrical and thermal conductivity hence used as electrode
materials for lithium ion batteries.
2.CNT’s having low density and high mechanical strength hence it is used as
composite materials.
3.SWCNT’s (Single walled carbon nanotubes) have well defined diameter 1.4
nm. They are used for synthesis of nanorods.
4.SWCNT’s (Single walled carbon nanotubes) efficiently absorbs radiation in the
near infrared range and converts it to heat. Hence it used in cancer chemotherapy
to kill cancer cells without affecting nearby healthy tissues.

Graphene’s

Diagram 11: Structure of Graphene

1.Graphene is two-dimensional crystalline allotrope of carbon consisting of

single layer of carbon consisting of a single layer of carbon atoms arranged in
hexagonal lattice.
2.Graphene has high electrical conductivity and act like a semimetal with a small
overlap between the valence and the conduction bands.
3.Graphene carbon atoms are densely packed in a regular hexagonal pattern.
4.Graphene atom are about 1-42 Ao a part. Graphene carbon atom is bonded to
three carbon atoms and is sp2 hybridized.
Properties of Graphene’s
1.Graphene has excellent electronic conductivity, because its conduction and
valence bands meet at the Dirac points (Zero-gap semiconductor).
2.Graphene has unique optical properties produce an unexpectedly high opacity
for an atomic monolayer in vacuum.
3.Thermal transport in graphene is an active area of research which has attracted
attention because of the potential for thermal management applications.
4.Graphene melts at nearly ≈ 4125 K graphene melts into an agglomeration of
loosely coupled doubled bonded chains before becoming a gas.
5.Graphene is the strongest material ever tested, with an intrinsic tensile strength
of 130.5GPa

Graphene’s application
1.Graphene is a flexible conductor that holds promise for various device
applications including solar cells, light -emitting diodes (LED) touch panels and
smart windows or phones.
2.Graphene has also been used in other fundamental electronic devices, such as
capacitors and field effect transistors (FET’s) in which it can acts as an atomically
thin channel.
3.Graphene supercapacitors serve as energy storage alternative to traditional
batteries. Among advantage are fast charging, long life span and environmentally
friendly production.
4.Functonalized Graphene’s has important application as biological and chemical
sensors.