D. Y.

Patil College of Engineering & Technology, Kolhapur Applied Chemistry

Unit 6- Chemistry Nanomaterials and applications

Nanomaterials
 Introduction:-
1) Nanomaterials are the materials of which a single unit is sized (in at least one
dimension) between 1 and 1000 nanometers (10−9 meter) but is usually 1 to 100 nm
(the usual definition of nanoscale).
2) Materials with structure at the nanoscale often have unique optical, electronic, or
mechanical properties.
3) Naturally occurring nanomaterials may be organic & inorganic.
Organic- wax crystals covering a lotus leaf, spider and spider-mite silk, natural
colloids (milk, blood), horny materials (skin, hair), our bone matrix etc.
Inorganic- Natural inorganic nanomaterials occur through crystal growth in the
chemical conditions of the earth crust like fires represent particularly complex
reactions and can produce pigments, cement, fumed silica etc
4) Nanomaterials are also prepared artificial or synthesized in laboratories. The organic
nanomaterials are carbon-based fullerenes while inorganic nanomaterials such as
silicon.

 Synthesis:-
1) Synthesis of nanomaterials (material having size 1 to 100 nm) can be done by various
ways these methods are divided as Bottom up & Top down.
2) Bottom Up Methods:-
a) In bottom methods arrangement of atoms or molecules is in nanostructured arrays.
Bottom methods use raw materials that may be solid, liquid or gas. These methods
are of two types Chaotic And controlled.
b) Chaotic processes involve the elevating the constituent atoms or molecules to a
chaotic state and then suddenly changing the conditions so as to make that state
unstable. Control of nanoparticle formation is controlled through manipulation of
the end state of the products.
e.g. of chaotic processes are Laser ablation, Exploding wire, Arc, Flame pyrolysis,
precipitation synthesis etc.
c) Controlled Processes involve the controlled delivery of the constituent atoms or
molecules to the site(s) of nanoparticle formation such that the nanoparticle can
grow to a prescribed size in a controlled manner.
e.g. of controlled processes are Self-limiting growth solution, Self-limiting
chemical vapor precipitation and Shaped pulse fem to second laser techniques,

3) Top Down Methods:-

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 D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

Knowledge of processes for bottom-up assembly of structures remains in their

infancy in comparison to traditional manufacturing techniques. As a result, the most
mature products of nanotechnology (such as modern CPUs) rely heavily on top-down
processes to define structures. The traditional example of a top-down technique for
fabrication is lithography in which instruments (such as a modern stepper) are used to
scale a macroscopic plan to the nanoscale.

 Applications:-
1) Most applications are limited to the bulk use of passive nanomaterials.
Examples include titanium dioxide and zinc oxide nanoparticles in sunscreen,
cosmetics and some food products.
2) Silver nanoparticles in food packaging, clothing, disinfectants and household
appliances such as Silver Nano; carbon nanotubes for stain-resistant textiles; and
cerium oxide as a fuel catalyst.
3) Medicinal use of nanomaterials-To help treat disease and prevent health issues.
Nanotechnology has provided the possibility of delivering drugs to specific cells
using nanoparticles. The overall drug consumption and side-effects may be lowered
significantly by depositing the active agent in the morbid region only and in no higher
dose than needed.
4) Industrial applications of nanotechnology- also applied to or developed for application
to a variety of industrial and purification processes.
5) Green Nanotechnology- Purification and environmental cleanup applications include
the desalination of water, water filtration, wastewater treatment, ground water
treatment etc.
6) Applications of nanomaterials can be extended for construction materials, military
goods, and nano-machining of nano-wires, nano-rods, few layers of grapheme.
7) Energy- Nanomaterials can be used as insulators which help saving energy. Reduction
of energy consumption or increasing the efficiency of energy production is achieved.
E.g. solar cells, panels, or surfaces sprayed with nanoparticles turning to a solar
energy collector etc.
8) Information and communication is improved with the use of nanoparticles e.g. in
CPUs or DRAM devices.
 Types of Nanomaterials
The unique properties of these various types of intentionally produced nanomaterials
give them novel electrical, catalytic, magnetic, mechanical, thermal, or imaging features
that are highly desirable for applications in commercial, medical, military, and
environmental sectors. These materials may also find their way into more complex
nanostructures and systems. As new uses for materials with these special properties are
identified, the number of products containing such nanomaterials and their possible
applications continues to grow.

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 D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

Most current nanomaterials could be organized into four types:

I. Carbon Based Materials
II. Metal Based Materials
III. Dendrimers
IV. Composites
I. Carbon Based Materials
These nanomaterials are composed mostly of carbon, most commonly taking the
form of a hollow spheres, ellipsoids, or tubes. Spherical and ellipsoidal carbon
nanomaterials are referred to as fullerenes, while cylindrical ones are called nanotubes.
These particles have many potential applications, including improved films and coatings,
stronger and lighter materials, and applications in electronics.
II. Metal Based Materials
These nanomaterials include quantum dots, nanogold, nanosilver and metal oxides,
such as titanium dioxide. A quantum dot is a closely packed semiconductor crystal
comprised of hundreds or thousands of atoms, and whose size is on the order of a few
nanometers to a few hundred nanometers. Changing the size of quantum dots changes
their optical properties.
III. Dendrimers
These nanomaterials are nanosized polymers built from branched units. The surface of a
dendrimer has numerous chain ends, which can be tailored to perform specific chemical
functions. This property could also be useful for catalysis. Also, because three-
dimensional dendrimers contain interior cavities into which other molecules could be
placed, they may be useful for drug delivery.
IV. Composites
Composites combine nanoparticles with other nanoparticles or with larger, bulk-type
materials. Nanoparticles, such as nanosized clays, are already being added to products
ranging from auto parts to packaging materials, to enhance mechanical, thermal, barrier,
and flame-retardant properties.

 Characteristics and Applications

A. Fullerenes
i) Fullerene is one of the allotropic forms of the carbon. The other name of fullerene is
buckminsterfullerene. In this allotropic form of carbon, the carbon molecules are arranged
in a series and form a cage like structure. This structure of fullerene is hollow in nature.In

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 D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

this allotropic form when the carbon molecules are arranged in a cylindrical form, they
form a tube like structure. These tube-like structures are known as carbon nanotubes.
ii) In nature, fullerenes, especially the C60 sphere, are highly symmetrical. Fullerenes have a
similar structure to graphite, which is made up of a sheet of connected hexagonal rings,
but they have pentagonal (or sometimes heptagonal) rings that prevent the sheet from
being planar. Buckyballs and buckytubes are terms used to describe them depending on
their shape. Cylindrical fullerenes are referred to as nanotubes. C 60 is the most common
fullerene, with no two pentagons sharing an edge. A C 60 molecule's average carbon-
carbon bond length is 1.44 angstrom.
iii) Types of fullerene- Buckminsterfullerene, Endohedral Fullerene, Herbal fullerenes,
Buckyball Clusters, Nanotubes, Megatubes, Linked bucky ball and chain Dimers, Herbal
fullerenes

iv) Properties of Fullerene

Physical Properties of Fullerene
 Fullerene shows variation in behaviour and structure on changing the temperature. At
a higher temperature the fullerene is converted into the C70 form.
 Fullerene shows change in structure under different pressures.
 The ionization enthalpy of fullerene is 7.61 electron volts.
 The electron affinity of fullerene is 2.6 to 2.8 electrons volts.
Chemical Properties of Fullerene
 Fullerene (C60) resembles an electrophile in the chemical reactions.
 Fullerene can act as an electron acceptor group. It can easily accept three electrons or
more. Therefore, it can behave as an oxidizing agent.
 Fullerenes are doped with the alkali or alkaline earth metals, so that it can exhibit
superconductivity properties.
 Ferromagnetism is a property of fullerene.
 Carbon molecules abound in fullerene. As a result, it's very soluble in organic
solvents.
v) The use of buckminsterfullerene is based on its chemical properties and its physical
properties.
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 D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

• Fullerene is used as conductors.

• It can be used as an absorbent for gases.
• Fullerene is used as lubricants.
• Some forms of the fullerenes are used in making cosmetics related materials.
• Carbon nanotubes are made up of graphene sheets.
• Some forms of fullerenes are used in biomedical applications.
• Fullerenes are used in making carbon nanotubes based fabrics and fibres.

B. Carbon Nanotubes
A carbon nanotube (CNT) is one of the most important nanomaterials. Before 1991, only
two main allotropes of carbon were known. In 1991, a Japanese physicist, SumioLizima
invented CNT (another allotrope of carbon).
Nanotubes are formed by folding or rolling two-dimensional graphite into a
cylindrical shape structure. Nanotubes are hollow from inside. The diameter of the
nanotube is around 1-3 nanometers. The length of the carbon nanotube is much higher
than its diameter. Nano tube length generally goes to a few micrometers. In short, carbon
nano (CNT) is a folded form of the two-dimensional graphene sheet. CNT (carbon
nanotubes) exhibit extraordinary mechanical properties.

 Properties of Carbon Nanotube

i) Carbon nanotubes are stiff. They are as stiff as a diamond (the hardest natural material
in nature).
ii) The gravitational weight of the nanotube is very low.&density of the carbon
nanotubes is one-fourth of that of steel.
iii) Carbon nanotubes are stronger than steel. They exhibit extraordinary mechanical
properties. Carbon nanotubes are ten times stronger than steel.
iv) Carbon nanotubes have a high thermal capacity. Therefore, it does not expand on
heating like that of steel. Therefore carbon nanotubes uses in making bridges and
aircrafts material
v) In carbon nanotubes, each carbon atom is surrounded by three other carbon atoms
through covalent bonds. These carbon-carbon covalent bonds forms lattice in the
shape of hexagons.The crystalline structure of carbon nanotubes exists in the form of
regular hexagons.
vi) Carbon nanotubes are elastic, good conductors of heat&electricticity.
vii) Carbon nanotubes are chemically neutral. So, they are chemically stable. Therefore,
carbon nanotubes resist corrosion.

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D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

 Types of Carbon Nanotubes

a. Single-walled Carbon nanotubes
Single-walled Carbon Nanotubes- it is represented as SWCNT. The Single-walled
Carbon nanotubes exist in a 1-d structure. Some examples of Single-walled CNT are
armchair and zig-zag Single-walled Carbon nanotubes
Properties of Single-walled Carbon Nanotubes are:
 The diameter of Single-walled Carbon nanotubes is 2nm.
 The length of Single-walled Carbon nanotubes is around 2 micrometres.
 They exist in a one-dimensional structure. Therefore, it is also known as a
nanowire.
 Electronics can be miniaturized by using a Single-walled Carbon nanotube.
 Their band gap varies from 0-2 electron volts (eV).
 They show conductivity like a semiconductor. Therefore, they exhibit both
metallic and semiconductivitybehaviour.

b. Multi-walled Carbon nanotubes

Multi-walled Carbon Nanotubes- It is represented as MWCNT. It is composed of
several nested carbon nanotubes. This type of nanotubes has two diameters, one is
known as outer diameter and another one is known as inner diameter. An example of
Multi-walled Carbon nanotubes is chiral Multi-walled Carbon nanotubes.
Properties of Multi-walled Carbon Nanotubes are given below:
 The outer diameter of Multi-walled Carbon nanotubes is around 2-20
nanometres.
 The inner diameter of Multi-walled Carbon nanotubes is 1-3 nm.
 The length of Multi-walled Carbon nanotubes is around 5-6 micrometres.

 Uses
 Composite materials containing carbon nanotubes are being used in sporting goods.

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 D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

 Carbon nanotubes are used to make bullets proof jackets.

 Carbon nanotubes can be used to make aircraft and space craft’s body.
 Carbon nanotubes can be used to build high-performance nanoscaled thin-film
transistors to replace silicon-based transistors because of the semiconducting properties
of carbon nanotubes.
 Carbon nanotubes can be used to make biosensors and electrochemical sensors.
 Carbon nanotubes are used in making electrodes to study electrochemical reactions
because of their excellent electrical properties.

C. Graphite
1) Graphite is one of the very common allotropes of carbon. It is also the most stable
allotrope of carbon and thus used in electrochemistry as the standard state for defining the
heat of formation of carbon compounds.
2) Graphite is not an element or a compound, it's an allotrope of carbon. It doesn’t have any
chemical formula of its own. Graphite is a good conductor of heat and electricity with a
density of 2.09–2.23 g/cm3. Graphite was accidentally synthesized by Edward G.
Acheson for the first time when he was working on a high-temperature experiment on
carborundum. He found that at around 4150 0C, the silicon in the carborundum gets
vaporized, whereas leaving behind the carbon in the graphitic form.
3) Graphite is a big covalent structure with each carbon atom joined with three other carbon
atoms with covalent bonds. Each carbon atom is sp 2 hybridized. These carbon atoms form
a layer like structure with a hexagonal arrangement of carbon atoms. These layers have
weak forces between them. Due to these weak forces, the layers can slip over each very
easily. Each carbon atom has one non bonded electron, which becomes delocalized.

4) Properties of Graphite
Physical Properties of Graphite

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 D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

 Graphite is a good conductor of electricity due to its free delocalized electron which is
free to move throughout the sheets.
 Graphite is insoluble in organic solvents and water, this is because the attraction
between solvent molecules and carbon atoms is not strong enough to overcome the
covalent bonds between the carbon atoms in the graphite.
 Graphite has a high melting point of 3650 0C near the melting point of Diamond.
 Due to its layer-like structure, it is soft and slippery in nature.
 Graphite has the ability to absorb high-speed neutrons.
Important Chemical Reactions
 Reaction with air - Carbon in the form of Graphite, burns in the air to form Carbon
Monoxide and carbon Dioxide depending upon the availability of air or oxygen.
C(s)+O2→CO2(g)C(s)+O2 → CO2(g)
2C(s)+O2(g) → 2CO(g)
2C(s)+O2(g) → 2CO(g)
 Reaction with Water - Carbon in the form of Graphite doesn’t react with water in
normal conditions. Under certain circumstances, the given reaction becomes possible
and forms water gas which is a mixture of carbon monoxide and hydrogen gas.
C+H2O → CO+H2
5) Types of Graphite
a. Natural Graphite- Natural Graphite, an excellent conductor of heat and electricity, is a
mineral composed of graphitic carbon. It is stable over a range of temperatures, with
the melting point of around 3650°C. There are three types of natural graphite.
High crystalline – Amorphous - Flake
b. Synthetic Graphite- Synthetic graphite is produced from coke and pith. It is less
crystalline in nature than the natural one. There are basically two types of synthetic
graphites. The first one is electro graphite, pure carbon produced from coal tar pitch,
and calcined petroleum coke in an electric furnace. The second one is synthetic
graphite produced by heating calcined petroleum pitch to 28000C.

6) Uses of Graphite
i) Graphite is used in making pencil lead.
ii) Graphite is used in the nuclear reactor to control the nuclear fission reaction because
of the ability of graphite to absorb fast-moving neutrons.
iii) Due to the slippery nature of Graphite, it is used as a lubricant in the machine parts.
iv) Graphite is used as a conductor of heat and electricity in several processes due to its
free electrons.
v) Graphite is used in high-temperature applications like in the production of phosphorus
and calcium carbide.
vi) Graphite is used as an anode in aqueous electrolytic processes such as in the
production of halogens.
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 D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

vii) Graphite is used as an electrical material in the electric motor as a carbon brush.
viii) Due to its resistant nature towards chemicals and high melting temperatures, it is used
to make crucibles.
ix) Graphite materials are used as the anode material for lithium-ion batteries.
x) Chemical Industry - In the chemical field, graphite is used in many hot climates,
such as in the production of phosphorus and calcium carbide in arc furnaces. Graphite
is used as an anode in certain electrolytic processes in liquids such as halogen
production (chlorine and fluorine).
xi) Nuclear Industry - Large quantities of high-purity electro graphite are used to
produce presidential sticks and display components in nuclear reactors. The lowest
absorption of neutrons leads to the building of suitability of electro graphite and high
thermal conductivity, with high strength and high temperatures.
xii) Electricity applications - The manufacture of carbon brushes in electric motors have
incorporated a huge amount of graphite which is used as an electric material. Here,
the service life of a component and performance depends largely on the distance and
structure.
xiii) Mechanical Applications - Graphite is widely used as an engineering material in all
applications such as piston rings, thrust bearings, journal bearings, and vanes. Carbon-
based seals are used in petrol pumps and on the engine walls of several aircraft
engines.

Sol-Gel Method

The sol-gel method is a versatile and widely used technique for the preparation of
nanoparticles and other materials. It involves the transition of a solution (sol) into a gel-like
network (gel) and is particularly useful for creating materials with high purity, uniformity,
and control over composition and structure. Here’s a detailed look at the sol-gel method for
nanoparticle preparation:

1. Sol Preparation:

 Sol: A sol is a stable colloidal suspension of fine particles in a liquid. In the sol-gel
process, the sol is typically a liquid containing metal alkoxides or metal chlorides that
serve as precursors.
 Precursor Selection: Common precursors include metal alkoxides (e.g., titanium
tetraisopropoxide, tetraethyl orthosilicate (TEOS)) and metal chlorides. These
precursors hydrolyze and polymerize to form metal-oxide networks.

2. Gelation:

 Hydrolysis and Condensation: During gelation, the precursors undergo hydrolysis

(reaction with water) and condensation (formation of a network structure). This
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D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

process forms a three-dimensional network of metal-oxide particles suspended in the

liquid.
 Chemical Reactions:

 3. Gel Aging and Maturation:

 Aging: The gel is aged to allow for further polymerization and network formation,
which strengthens the gel structure and improves particle uniformity.
 Maturation: This step helps to enhance the mechanical properties and stability of the
gel.

4. Drying and Heat Treatment:

 Drying: The gel is dried to remove the solvent, resulting in a porous network of metal
oxides or metal-containing compounds.
 Heat Treatment (Calcination): The dried gel is subjected to high temperatures to
remove any remaining organic components and to crystallize the metal oxides. This
step is crucial for achieving the desired nanoparticle size and phase.

Ball Milling Process

1. Preparation:
o Material Selection: Choose appropriate materials for the milling process,
including the milling media and container.

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D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

o Loading: Place the material and milling media into the container. The ratio of
material to media and the volume of the container are optimized for effective
milling.
2. Milling:
o Rotation: The container is rotated at a specific speed, which influences the
impact energy and milling efficiency.
o Duration: Milling time affects the particle size and properties. Longer milling
times can lead to finer particles but may also cause unwanted changes in
material properties.
3. Discharge:
o Collection: After milling, the processed material is collected from the
container, often requiring separation from the milling media.
4. Post-Processing:
o Sieving: The material may be sieved to obtain particles of desired size.
o Heat Treatment: In some cases, additional heat treatment is applied to
improve material properties or remove residual stresses.

Advantages of Ball Milling

1. Scalability: Suitable for both laboratory and industrial-scale production.

2. Versatility: Can be used for various types of materials, including metals, ceramics,
and polymers.
3. Control: Allows for control over particle size, distribution, and morphology.
4. Cost-Effective: Generally low cost compared to other high-energy milling methods.

Limitations of Ball Milling

1. Particle Size Distribution: The method may produce a broad particle size
distribution, which may not be suitable for all applications.
2. Contamination: There is a potential for contamination from the milling media and
container materials, especially in sensitive applications.
3. Energy Consumption: High energy consumption and wear on milling equipment can
be significant factors.
4. Long Processing Time: For very fine powders, extended milling times may be
required.

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 D. Y. Patil College of Engineering & Technology, Kolhapur Applied Chemistry

Optical Properties
Because of the quantum confinement in nanomaterials, the emission of visible light
can be tuned by varying the nanoscale dimensions. It is observed that the size reduction in
nanomaterials shifts the emission of peak towards the shorter wavelength (blue shift).

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