EKB4293

GREEN AND SUSTAINABLE CHEMICAL

PROCESS

Chemical Engineering

Manipal International University

2018
Introduction to nanoscience and
nanotechnologies
Nanoscience in nature
History of nanotechnologies
Fundamental ‘nano-effects
Overview of nanomaterials
Characterisation methods
Fabrication methods
APPLICATIONS AND
IMPLICATIONS
 What is nano?

 How do properties change at the nanoscale?

 Are nano products safe?

 What are some careers related to nanotechnology?

 nanoscience
Definition of and
nanotechnologies
‘Nanoscience is the study of phenomena and
manipulation of materials at atomic, molecular and
macromolecular scales, where properties differ
significantly from those at a larger scale’

‘Nanotechnologies are the design, characterisation,

production and application of structures, devices
and systems by controlling shape and size at the
nanometre scale.’
Figure 1: Three and a half gold atoms placed in a row
equal 1 nm (assuming a covalent radius of 0.144 nm
each)
Image: L. Filipponi, iNANO, Aarhus University, Creative C
What is Nano?
 How Big is a Nanometer?

http://www.nisenet.org/catalog
 How Big is a Nanometer?

http://www.nisenet.org/catalog
How Big is a Nanometer?

http://www.nisenet.org/catalog
What is a nanomaterial?
A nanomaterial is an object that has at least one dimension in
the nanometre scale (approximately 1 to 100 nm).
Nanomaterials are categorised according to their dimensions
as shown in Table 1.
Table 1: Nanomaterials are categorised according to their
dimensions
Nanomaterial dimension Example
All three dimensions < 100 nm Nanoparticles, quantum
dots, nanoshells, nanorings, microcapsules
Two dimensions < 100 nm Nanotubes, fibres, nanowires
One dimension < 100 nm Thin films, layers and coatings
Nanomaterials are larger than single atoms but smaller
than bacteria and cells. It is useful to use a scale such as
the one shown in Figure 2 where students can visualise
the relationship between bulk materials, for example a
tennis ball, and nanomaterials.
Figure 3: Nanoscience is a horizontal-integrating
interdisciplinary science that cuts across all vertical
sciences and engineering disciplines
Some good examples to bring to the classroom:
our fingernails grow at the rate of 1 nm per second;
the head of a pin is about 1 000 000 nm in diameter;
a human hair is about 80 000 nm in diameter;
a DNA molecule is 1–2 nm wide;
the transistor of a latest-generation Pentium Core Duo
processor is 45 nm.
Figure 4: Nanotechnologies are horizontal-enabling
convergent technologies which cross all ver tical
industrial sectors. The different heights of the
industrial sectors in the graph are only indicative
and are intended to emphasise the fact that the
level of impact of nanotechnologies will be different
in each industrial sector.
Figure 1: The colour of gold depends on its size
Unique material properties at the
nanoscale

Surface properties
physical and chemical properties depend on many of
its surface properties. Surfaces perform numerous
functions: they keep things in or out; they allow the flow of
a material or energy across an interface; they can initiate
or terminate a chemical reaction, as in the case of
catalysts. : the material and the surrounding environment
(liquid, solid or gas).
If a bulk material is subdivided into an ensemble of
individual nanomaterials, the total volume remains the
same, but the collective surface area is greatly
increased.
How Surface Area Scales (Changes)

For a fixed total

volume, decreasing
the radius by a factor
of two doubles the
surface

Crushing a 1cm
particle into nano
particles increases the
surface area
thousands of times!

22
How Surface Area Scales (Changes)

1 nm particles  1010 m2
1 micron particles  107 m2
1 cm particles  103 m2

nano 24
Smallness Leads to New Properties

Reactivity
Melting point Bulk Gold
Bulk Aluminum
Strength
Conductivity
Color
Nano Aluminum
Nano Gold

http://www.carterrecycling.com/myimages/aluminum_cans.jpg http://healthewoman.org/2008/11/11/how-healthy-is-your-workplace/
http://mrsec.wisc.edu/Edetc/nanolab/gold/images/goldp6.jpg http://texasenterprise.org/article/warren-buffet-and-new-calculus-gold
Stained Glass: Size and Shape
Matter

Controlling the Quantum World: The Science of Atoms, Molecules, and Photons, 2007
Stained Glass: Size and Shape
Matter
Particle shape also affects the color!

http://commons.wikimedia.org/wiki/File:Native_gold_nuggets.jpg
http://www.cat.gov.in/technology/laser/lpas/pps.html
Surface energy
Atoms and molecules that exist at the surface or at an
interface are different from the same atoms or
molecules that exist in the interior of a material. This
is true for any material. Atoms and molecules at the
interface have enhanced reactivity and a greater
tendency to agglomerate: surface atoms and
molecules are unstable, they have high surface
energy.
Schematic illustration of the valence and conduction
bands in materials based on their electrical properties:
insulator, semiconductor and conductor
 Optical properties
Some nanomaterials display very different optical properties,
such as colour and transparency, compared to bulk
materials. In this section, the reason for this behaviour is
discussed and some examples provided. Before going into
detail, some fundamentals are reviewed.
 SIZE
A meter is about the distance from the tip of your
nose to the end of your hand (1 meter = 3.28 feet).

Millimeter- One thousandth of meter.(10-3m)

Micron: a micron is a millionth of a meter (or) one

thousandth of millimeter (10-6m)

Nanometer:

A nanometer is one thousandth of a micron (10–9m)

(or) a billionth of a meter. ie.,one billion nanometers
in a meter.
• Composites made from particles of nano-size ceramics or metals
smaller than 100 nanometers can suddenly become much stronger
than predicted by existing materials-science models.

• For example, metals with a so-called grain size of around 10

nanometers are as much as seven times harder and tougher than
their ordinary counterparts with grain sizes in the micro meter
range.

• The Nano particles affects many properties such as

Melting point
Boiling point
Band gap
Optical properties
Electrical properties
Magnetic properties
• .Even the structure of materials changes with respect to Size
Effects of Nano size
• Properties depends on size, composition and
structure
• Nano size increases the surface area
• Change in surface energy (higher)
• Change in the electronic properties
• Change in optical band gap
• Change in electrical conductivity
• Higher and specific catalytic activity
• Change thermal and mechanical stabilities
• Different melting and phase transition
temperatures
• Change in catalytic and chemical reactivities
The properties of materials can be different at the Nanoscale for two
main reasons:
First, Nanomaterials have a relatively larger surface area when
compared to the same mass of material produced in a larger form.

Nano particles can make materials more chemically reactive and affect
their strength or electrical properties.
Second, quantum effects can begin to dominate the behaviour of matter
at the Nanoscale
Nanoscale materials are divided into three category,
1. Zero dimension – length , breadth and heights are confined at single
point. (for example, Nano dots)
2. One dimension – It has only one parameter either length (or) breadth
(or) height ( example:very thin surface coatings)
3. Two dimensions- it has only length and breadth (for example,
nanowires and nanotubes)
4. Three dimensions -it has all parameter of length, breadth and height.
(for example, Nano Particles).
Nano Particles are the particles of size between 1 nm to 100 nm
• 1 nm is only three to five atoms wide.
• ~40,000 times smaller than the width of an average human hair

Nanometer - One billionth (10-9) of a meter

• The size of Hydrogen atom 0.04 nm

• The size of Proteins ~ 1-20 nm
• Feature size of computer chips 180 nm
• Diameter of human hair ~ 10 µm
At the nanoscale, the physical, chemical, and biological properties
of materials differ in fundamental and valuable ways from the
properties of individual atoms and molecules or bulk matter
 Why Nano Particles ?
Noparticles are of interest because of the new properties (such as
chemical reactivity and optical behaviour) that they exhibit compared
with larger particles of the same materials.

For example, titanium dioxide and zinc oxide become transparent at

the nanoscale and have found application in sunscreens.

Nanoparticles have a range of potential applications:

In the short-term application such as in cosmetics, textiles and

paints.
In the longer term applications such as drug delivery where they
could be to used deliver drugs to a specific site in the body.

Nanoparticles can also be arranged into layers on surfaces, providing

a large surface area and hence enhanced activity, relevant to a
range of potential applications such as catalysts.
• Examples
- Carbon Nanotubes
- Proteins, DNA
- Single electron transistors

AFM Image of DNA

Carbon Nanotubes
Nanotechnology deals with the creation of USEFUL
materials, devices and systems using the particles of
nanometer length scale and exploitation of NOVEL
properties (physical, chemical, biological) at that length
scale
Based on the size and shape, the Nano materials are classified as
follows

• Nanoparticles • Nanotubes
• Nanocapsules • Nanosprings
• Nanofibers • Nanobelts
• Nanowires • Quantum dots
• Fullerenes (carbon 60) • Nanofluidies
Quantum well
• It is a two dimensional system
• The electron can move in two directions and restricted in one
direction.

Quantum Wire
• It is a one-dimensional system
• The electron can move in one direction and restricted in two
directions.

Quantum dot
• It is a zero dimensional system
• The electron movement was restricted in entire three
dimensions
 Quantum wire
Quantum wires are ultra fine wires or linear arrays of Nano
dots, formed by self-assembly
They can be made from a wide range of materials such as
Semiconductor Nanowires made of silicon, gallium nitride and
indium phosphide.
Nanowires have potential applications in

1. In high-density data storage, either as magnetic read heads or as

patterned storage media

2. In electronic and opto-electronic Nanodevices, for metallic

interconnects of quantum devices and Nanodevices.

Nanowires can be prepared by growth techniques such as

1. Chemical Vapour deposition (CVD)
2. Electroplating
 Quantum wire cont…

In quantum wire, Two dimensions are reduced and one

dimension remains large

Therefore, the electrical resistivity of quantum wire can be

calculated using conventional formula as follows,

We need two dimension to calculate area of conducting material,

but not present in quantum wire
General properties of Nanowire
 Diameter – 10s of nanometers
 Single crystal formation -- common crystallographic
orientation along the nanowire axis
 Minimal defects within wire
 Minimal irregularities within nanowire arrays

Some example of Nanowire

Magnetic nanowires
 Example: Cobalt, gold, copper and cobalt-copper
nanowire arrays
 Important for storage device applications
 Electrochemical deposition is the fabrication
technique
 <20 nm diameter nanowire arrays can be fabricated
by electrochemical deposition

Cobalt nanowires on Si substrate

(UMass Amherst, 2000)
In quantum dot all the three dimensions are reduced to zero

Quantum dot
Dimension Variation 
Properties of Nano Materials
Applications of Nano Materials
1. Nanotechnology Applications in Medicine

• Because of their small size, nanoscale devices can readily

interact with biomolecules on both the surface of cells and
inside of cells.
• By gaining access to so many areas of the body, they have the
potential to detect disease and the deliver treatment.

• Nanoparticles can can deliver drugs directly to

diseased cells in your body.
• Nanomedicine is the medical use of molecular-
sized particles to deliver drugs, heat, light or
other substances to specific cells in the human
body.
• Quantum dot- that identify the location of cancer
cells in the body.
• Nano Particles - that deliver chemotherapy drugs
directly to cancer cells to minimize damage to healthy
cells.
• Nanoshells - that concentrate the heat from infrared
light to destroy cancer cells with minimal damage to
surrounding healthy cells.
• Nanotubes- used in broken bones to provide a
structure for new bone material to grow.
Nano shells as Cancer Therapy
Nano shells are injected into cancer area and they recognize
cancer cells. Then by applying near-infrared light, the heat
generated by the light-absorbing Nano shells has successfully
killed tumor cells while leaving neighboring cells intact.
 Nanowires – used as medical sensor

• In this diagram (next page), Nano sized sensing wires are laid
down across a micro fluidic channel. As particles flow through the
micro fluidic channel, the Nanowire sensors pick up the molecular
identifications of these particles and can immediately relay this
information through a connection of electrodes to the outside
world.
• These Nanodevices are man-made constructs made with carbon,
silicon Nanowire.
• They can detect the presence of altered genes associated with
cancer and may help researchers pinpoint the exact location of
those changes
 2. Nano Computing Technology

Past
Shared computing thousands of
people sharing a mainframe computer

Present
Personal computing

Future
Ubiquitous computing thousands of computers sharing each
and everyone of us; computers embedded in walls, chairs, clothing,
light switches, cars….; characterized by the connection of things in
the world with computation.
3. Sunscreens and Cosmetics
• Nanosized titanium dioxide and zinc oxide are currently used in
some sunscreens, as they absorb and reflect ultraviolet (UV) rays.
• Nanosized iron oxide is present in some lipsticks as a pigment.
4. Fuel Cells
The potential use of nano-engineered membranes to intensify
catalytic processes could enable higher-efficiency, small-scale fuel
cells.
5. Displays
• Nanocrystalline zinc selenide, zinc sulphide, cadmium sulphide and
lead telluride are candidates for the next generation of light-emitting
phosphors.
• CNTs are being investigated for low voltage field-emission displays;
their strength, sharpness, conductivity and inertness make them
potentially very efficient and long-lasting emitters.
 6. Batteries

• With the growth in portable electronic equipment (mobile phones,

navigation devices, laptop computers, remote sensors), there is great
demand for lightweight, high-energy density batteries.

• Nanocrystalline materials are candidates for separator plates in

batteries because of their foam-like (aerogel) structure, which can
hold considerably more energy than conventional ones.

• Nickel–metal hydride batteries made of nanocrystalline nickel and

metal hydrides are envisioned to require less frequent recharging and
to last longer because of their large grain boundary (surface) area.
7. Catalysts
In general, nanoparticles have a high surface area, and hence provide
higher catalytic activity.
8. Magnetic Nano Materials applications
• It has been shown that magnets made of nanocrystalline yttrium–
samarium–cobalt grains possess unusual magnetic properties due
to their extremely large grain interface area (high coercivity can be
obtained because magnetization flips cannot easily propagate past
the grain boundaries).

• This could lead to applications in motors, analytical instruments

like magnetic resonance imaging (MRI), used widely in hospitals,
and microsensors.

• Nanoscale-fabricated magnetic materials also have applications in

data storage.

• Devices such as computer hard disks storage capacity is increased

with Magnetic Nano materials
 9. Medical Implantation
• Unfortunately, in some cases, the biomedical metal alloys may wear
out within the lifetime of the patient. But Nano materials increases
the life time of the implant materials.
.
• Nanocrystalline zirconium oxide (zirconia) is hard, wear resistant,
bio-corrosion resistant and bio-compatible.

• It therefore presents an attractive alternative material for implants.

• Nanocrystalline silicon carbide is a candidate material for artificial

heart valves primarily because of its low weight, high strength and
inertness.
10. Water purification
•Nano-engineered membranes could potentially lead to more energy-
efficient water purification processes, notably in desalination process.
11. Military Battle Suits

• Enhanced nanomaterials form the basis of a state-of- the-art

‘battle suit’ that is being developed.

• A short-term development is likely to be energy-absorbing

materials that will withstand blast waves;

• longer-term are those that incorporate sensors to detect or

respond to chemical and biological weapons (for example,
responsive nanopores that ‘close’ upon detection of a
biological agent).
SUMMARY
Nanomaterials have been extensively investigated during the
last decade due to their Wide variety of applications. It is
observed that field of nanomaterial synthesis is very
dynamic. Many process such as gas condensation, chemical
vapor synthesis, mechanical attrition, chemical precipitation,
Sol-Gel technique, electrodeposition, some other methods
widely used are molecular beam epitaxy, ionised cluster
beam, liquid metal ion source, consolidation, sputtering and
gas aggregation of monomers chemical precipitation in
presence of capping agents, reaction in microemulsions and
autocombustion are commonly used techniques for synthesis
of nanophosphors. Nanomaterials prepared using the
processes include a wide variety.