Advanced Material

Engineering Chemistry
INTRODUCTION-:
Nanomaterial is the branch of nanoscience and nanotechnology. Now a
days in research & development the major sectors are energy,
environment, water technology, pharmaceuticals etc. The use of
nanomaterials in energy storage devices such as fuel cells, detection of
threats in defense, navy, drug delivery and water purification processes.
Today’s high speed personal computers and mobile communications
needs the use of nano science and nano technology.

Nanomaterials-:
➢ Nanoscale materials are defined as a set of substances whose
size is less than approximately 100 nm.
➢ A nanometer is one millionth of a millimeter - approximately
100,000 times smaller than the diameter of a human hair.
➢ Nanomaterials shows unique optical, magnetic, electrical, and
other properties.
➢ These emergent properties have the potential for great impacts
in electronics, medicine, and other fields.

Properties of nanomaterial-

[Link] exhibit different colour depending upon their size.

2. Nanomaterial when irradiated with UV light , emit visible light.

3. Melting point nanomaterial is lower than the melting point of bulk.

4. Reactivity of nanomaterial is more than that of bulk material.

5. Inert material acts as catalyst.

6. Insulator becomes act as conductors.

7. These materials are exceptionally strong, hard, ductile at high

temperature.

8. Materials are wear resistant, corrosion resistant, chemically very active.

Classification of Nanomaterials

The classification of nanomaterials is based on the size of the material

and they are classified as

Zero Dimension

These materials don’t have any dimensions. Point materials including

oxides, semiconductors, quantum dots, hollow spheres, etc…

Zero Dimension
Nanomaterials

One Dimension-:

The one billionth of any given unit that is a film of thin type is known as
one dimension nanoparticles. It is used in engineering, electronics,
chemistry, and so on for many decades. These are used in the
construction of nanorods, nanowires, nanotubes, etc.

One Dimension
Two Dimension

This structure consists of two dimensions that are outside the range of
nanometric size. It has characteristics dependent upon the shapes.
Monolayer, Multilayer, Self- assembled, etc… comes under this
category.

Two Dimension Nanomaterials

Three Dimension

In this, the structure consists of three dimensions. These are most widely
used in magnetic materials, catalysts, and so on. These 3-D structures
are further categorized as Fullerenes, Dendrimers, and Quantum Dots.

Three Dimension

From the classification, it is evident that the behaviour of these particles is

purely based on shapes, sizes, morphologies, and dimensions.
 Synthesis of Nano-materials:

1. Solution combustion method:

➢ Solution combustion synthesis can be accomplished in an aqueous
solution of the oxidizer and fuel, which is sufficiently exothermic
chemical reaction.
➢ e.g. ZnO, CuO, Fe2O3 etc nanoparticles can be synthesized.

Procedure: Choose the chemical such that from which we can get the
resultant component

1. Oxidizer
- For CuO – Cu(NO3)2 copper nitrate
- For ZnO – Zn(NO3)2 Zinc nitrate
2. Fuel: Choose the fuel containing carbon and hydrogen as
main components
e.g. C6H8O6 – Ascorbic acid
➢ By using the electrical balance take the chemicals like fuel and
oxidizer.
➢ Dissolve the oxidizer into distilled water and mix up by using
magnetic stirrer and add fuel and stirred it again.
➢ Put the container on electrical heater.
➢ The following steps will takes place
➢ Boiling, frothing, smoldering, flaming, fumes.
➢ After cooling the container, collect the material and send for the
calcination.
3. Chemical equation:
 4. Calcination:

➢ Thermal decomposition, phase transition or removal of volatile

fraction.
➢ The calcination process normally takes place at temperatures
below the melting point of the product materials.
Advantages of Solution combustion:
• 20-50 nm size nanoparticle can be synthesized
• Less time is required
• No need of vacuum
• Less cost
Synthesis of Nano-materials by Sol-gel method:

Fig.: Schematic of So-gel

method

Sol-gel method is performed in the liquid phase. This is useful

process for fabricating nanoparticles and three-dimensional material
such as Aerogels.

A sol is type of colloid in which a dispersed solid phase is mixed in a

homogenous liquid medium. Sol gel process involves the formation of
colloidal suspension (Sol) and gelation of sol to form a network in a
continuous liquid phase (gel).
The first stage in a sol-gel process is synthesis of colloid. The
precursor used are ions of a metal.

A sol gel process consists of four steps-

• First is the hydrolysis reaction, in which bond -OR group is substituted
with - OH group. Hydrolysis reaction can occur by using the catalysts.

• The second and third stage can be condensation and polymerization.

• The fourth step is agglomeration of particles.
• All the four steps given above are affected by some conditions like PH,
Temp., and nature of catalyst used. Sol-gel method is used to prepare
silica gel.
Carbon Nanotube
• A carbon nanotube (CNT) is one of the most important
nanomaterials. In short, it is represented as CNTs. Carbon
nanotubes are also called buckytubes.
• 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.

Types of Carbon Nanotubes:

There are mainly two types of Carbon Nanotubes.

1. Single-walled Carbon nanotubes

2. Multi-walled Carbon nanotubes

Single-Walled Nanotubes

Single-walled Carbon Nanotubes is represented as SWCNT. They

exist in a one-dimensional structure. Some of the examples for a
Single-walled CNT are zig-zag and armchair Single-walled Carbon
nanotubes

The properties of Single-walled Carbon Nanotubes are:

A Single-walled Carbon nanotube’s diameter is around 2 nm.

They are also known as a nanowire as they exist in just one
dimension.
A single-walled Carbon nanotube can be used to miniaturize
Electronics.
They have conductive properties like that of a semiconductor.
Therefore, they show both semiconductive and metallic behaviour.
 • Fig. Single-walled Carbon Nanotubes

Multi-walled Carbon Nanotubes

They are represented as MWCNT. They are made up of various nested

carbon nanotubes. This kind of nanotubes has two different diameters,
one is called the outer diameter while the other is called the inner
diameter. Chiral Multi-walled Carbon nanotubes is example of Multi-
walled Carbon nanotubes.

The Properties of Multi-walled Carbon Nanotubes are as follows:

Electrical- MWNTs are highly conductive material.

Physical- MWNTs have an excellent tensile strength.
Thermal- WNTs have a thermal stability above 600 °C

Fig. Multi-walled Carbon

Nanotube
Synthesis of carbon nanotubes:

Chemical vapor deposition (CVD): CVD is a technique in which the

vaporized reactants react chemically and forms a nanomaterial product
that is deposited on the substrate as shown in Figure 1.

Fig. CVD method

Sources for carbon: The precursor for carbon nanotubes are
hydrocarbon gases such as acetylene, ethylene, methane, etc.

Substrate used: Substrates are materials on which the CNTS are

grown. Thecommonly used substrates in CVD method are zeolite,
silica, silicon plate coated with iron particles, etc.

Catalyst used: To produce single-walled carbon nanotubes metal

catalyst nanoparticles such as iron, cobalt, nickel, etc. are used.

Heating Source for CVD: Based on the heating source, the CVD
can be classified as:
 Thermal activated CVD which is heated by IR radiation, RF heater,
etc.
Photo assisted CVD which is heated by Arc lamps, Argon ion laser,
etc.
Plasma assisted CVD which is heated by microwave radiation, etc.

Conditions: The following conditions are maintained inside the furnace.

Temperature: 500–900 °C.

Inert gas atmosphere: Argon gas.

Procedure for synthesis of CNTs by thermal CVD method:

• CNTs are synthesized by thermal CVD method by using hydrocarbon

gas as carbon source.
• In this method, a quartz tube is placed inside a furnace maintained at
high temperature (500–900°C) heated by RF heater.
• A crucible containing the substrate coated with catalyst nanoparticles is
placed inside quartz tube filled with inert gas such as argon gas.
• The hydrocarbon gas (carbon source) is pumped into the quartz tube
which undergoes pyrolysis reaction and forms vapor carbon atoms.
These carbon atoms bind to the substrate and join to each other by
Van der waal force of attraction and grow as multi-walled carbon
nanotubes (MWCNTs) on the substrate.
• To synthesize single-walled carbon nanotubes catalyst like Fe, Co, Ni
nanoparticles are used.
• The obtained CNTs are further purified to get the pure form of CNTs.
Applications of Carbon Nanotubes
1. Breast cancer tumor destruction:
Nanotubes are used to destroy breast cancer tumors. They play
with an antibody. The antibody along with nanotubes is attracted to
the proteins by cancer cells in the body and nanotubes absorb the
laser beam and kill the tumor cells.
2. Windmill blades:
Hello tubes are also used in the windmill blades because of their
low weight, it increases the efficiency of the windmill and helps to
produce more electricity at a faster rate.
3. Filtration:
Carbon nanotubes can be used to separate particles of size
greater than the diameter of carbon nanotubes during the filtration.
They can also be used to trap smaller sized ions from a solution.
4. Carbon nanotubes as Nano cylinders:
Gas like H2, for energy, battery for vehicles can be safely stored
inside the carbon nanotubes and the problem of H2 storage hazards
can be solved.
5. Aircraft stress reduction:
Nanotubes are also used in space and aircraft to reduce the
weight and stress of the various components.

Other uses of carbon nanotubes – they are used as catalysts in some

reactions & also used in drug delivery systems.
Borazine:

Borazine is a chemical compound highly similar to benzene. Borazine

is isoelectronic and isostructural with benzene. For this reason
borazine is known as “inorganic benzene”.
Structure of Borazine/ /inorganic Benzene:
(1) Borazine is an inorganic compound with the chemical
formula (B3N3H6). It is a heterocyclic compound,
containing the alternate 3-(BH) units and 3-(NH) units.
(2) Borazine formed by reaction of B2H6 and NH3 in the ratio of
1:2 at high temperature.

(3) Like benzene, borazine has delocalized electrons and

aromatic character and it is a colourless liquid.

Even though Borazine and Benzene have same structure,

but theirchemical properties are different.

Applications:

➢ Borazines are used as starting material for ceramics.

➢ They are used as starting materials for inorganic polymers.
➢ They are used during manufacturing of fibres, Foams, fuel pipes.
 ➢ It is widely used as main component during manufacturing of
various batteries.
➢ Borazines may be useful in H2 storage application.

Graphene:

Graphene is a two-dimensional nanomaterial formed by the sp2

hybridization of carbon atoms. These sheets of carbon atoms are
packed in the form of a honeycomb lattice (Geim 2009). This lattice
consists of two equivalent sub- lattices with sigma bonds. The term
‘Graphene’ was first introduced in the late 80s to describe single sheets
of graphite.

Fig. Structure of graphene

oxide
Preparation of graphene oxide by a modified hummer’s method:

• Graphene oxide (GO) was produced using modified hummers method

from pure graphite powder.
• In this method sulfuric acid (H2SO4) and phosphoric acid (H3PO4)
were mixed and stirred for several minutes.
• Then graphite powder was added into mixing solution under stirring
condition.
• Potassium permanganate was then added slowly into the solution.

• This mixture was stirred for 6 hours until the solution became dark
green. To eliminate excess of KMnO4, hydrogen peroxide (H2O2) was
dropped slowly and stirred for 10 minutes.

• The exothermic reaction occurred and let it to cool down.

• Hydrochloric acid (HCl) and deionized water (DIW) was added and
centrifuged for 7 minutes.

• Then, the supernatant was decanted away and the residuals was then
rewashed again with HCl and DIW for 3 times.

• The washed GO solution was dried using oven at 90 °C for 24 hours

to produce the powder of GO.

Applications of Graphene and Graphene oxide:

1) Energy storage:

Nanocomposites of rGO have been used for high-capacity energy

storage in lithium ion batteries.

2) Biomedical Application:
One use of GO in the biomedical field is as a component in drug delivery
systems. Functionalized nanographene oxide has been used in several
studies on targeted delivery of anti-cancer drugs.
3) Biosensors:
• GO have been used as components in several systems designed to
detect biologically relevant molecules. functionalized GO was used as
a component in a system used to detect human cervical cancer and
human breast cancer cells
piezoelectric material-:

The piezoelectric effect is extensively encountered in nature and many

synthetic materials. Piezoelectric materials are capable of transforming
mechanical strain and vibration energy into electrical energy.

Piezoelectric materials are materials that have the ability to generate

internal electrical charge from applied mechanical stress.
The Greek word for piezo is to "push."

Applications of Piezoelectric Materials:

Piezoelectric materials are used in multiple industries, including:

Manufacturing
Medical devices
Telecommunications
Automotive
Information technology (IT)

High-voltage power sources:

Electric cigarette lighters. When you depress the button on a

lighter, the button causes a small spring-loaded hammer to hit a
piezoelectric crystal, producing a high-voltage current that flows
across a gap to heat and ignite the gas.
Gas grills or stoves and gas burners. These work similarly to the
lighter, but on a larger scale.

Piezoelectric Sensors

Ultrasound transducers are used in routine medical imaging. A

transducer is a piezoelectric device that acts as both a sensor and an
actuator. Ultrasound transducers contain a piezoelectric element that
converts an electrical signal into mechanical vibration and mechanical
vibration into electric.
Other types of Piezoelectric sensors include:

Piezoelectric microphones.
Sonar waves: The sound waves are both generated and sensed
by the piezoelectric element.
Electronic drum pads: The elements detect the impact of the
drummers’ sticks on the pads.
World War I: The first technological application of a piezoelectric
material was the ultrasonic submarine detector created during
World War
I. The detector plate was made from a transducer (a device that
transforms from one type of energy into another) and a type of
detector called a hydrophone. The transducer was made of thin
quartz crystals glued between two steel plates.
The resounding success of the ultrasonic submarine detector
during the war stimulated intense technological development of
piezoelectric devices.
World War II: Applications of piezoelectric materials advanced
significantly during World War II due to independent research by
Japan and the United States.
The developments in research shifted the approach toward
piezoelectric technology entirely. For the first time, engineers were
able to manipulate piezoelectric materials for a specific device
application.
This development created many war-related applications of
piezoelectric materials such as super-sensitive microphones,
powerful sonar devices, and radio-transmitting capabilities for
monitoring movement of ocean vessels) and piezo ignition
systems for single cylinder ignitions.