Nano Pre

Engg.
Chemistry I
Preclass notes- Nanochemistry
INTRODUCTION
James C Maxwell The mind of man has perplexed itself with many hard questions.
Is space infinite, and in what sense? Is the material world infinite in extent? Do
atoms exist or is matter infinitely divisible?
NANOTECHNOLOGY
The term nano originated from the Greek nanos which means dwarf. It is one
billionth of a meter (10-9 of a meter). So, whenever we think about nanotechnology,
very small objects come to the mind. Indeed, this technology deals with materials
having at least one spatial dimension in the size range of 1 to 100 nm.
HOW SMALL IS NANO TECNOLOGY??
Here are a few illustrative examples:
There are 25,400,000 nanometers in an inch
A sheet of newspaper is about 100,000 nanometers thick
A human hair is approximately 80,000- 100,000 nanometers wide
A single gold atom is about a third of a nanometer in diameter
One nanometer is about as long as your fingernail grows in one second
Material prepared by: Chemistry faculty
Engg. Chemistry I
Nanotechnology definition (NASA)

The creation of functional materials, devices and systems through control of matter
on the nanometer length scale (1100 nm) and exploitation of novel phenomena and
properties (physical, chemical, biological) at that length scale.
A very succinct definition for nanotechnology is simply engineering with atomic
precision.
HISTORY
Carl Sagan - "Somewhere, something incredible is waiting to be known."
Physics Nobel Laureate Richard Feynman gave the first lecture regarding the
applications for nanoscale materials. His talk, entitled Theres Plenty of Room at
the Bottom, was delivered on 29 December 1959 at the annual American Physical
Society meeting on the campus of Caltech.
Feynman pointed out that designing materials atom-by-atom is a real possibility, as it
would not violate any physical laws. He also predicted such sci-fi accomplishments
as writing 24 volumes of the Encyclopedia Brittanica on the head of a pin.
Richard P. Feynman- They walk around; they wiggle; and they do all kinds of
marvelous things all on a very small scale.
NANOTECHNOLOGY AN INTERDISCIPLINARY SCIENCE
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NANOTECHNOLOGY TIMELINE
4th Century
The Lycurgus Cup (Rome) is an example of dichroic glass; colloidal gold
and silver in the glass allow it to look opaque green when lit from outside but
translucent red when light shines through the inside.
1857
Michael Faraday discovered colloidal ruby gold, demonstrating that
nanostructured gold under certain lighting conditions produces differentcolored solutions.
1947
John Bardeen, William Shockley, and Walter Brattain at Bell Labs
discovered the semiconductor transistor which laid the foundation for
electronic devices and the Information Age.
1958
Jack Kilby of Texas Instruments originated the concept of, designed, and
built the first integrated circuit (Nobel Prize in 2000).
1959
Richard Feynman of the California Institute of Technology gave what is
considered to be the first lecture on technology and engineering at the
atomic scale, "There's Plenty of Room at the Bottom" at an American
Physical Society meeting at Caltech.
1974
Prof.Norio
Taniguchi
coined the
term
nanotechnology to
materials to within atomic-scale dimensional tolerances.
describe
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1981
Gerd Binnig and Heinrich Rohrer at IBMs Zurich lab invented
the scanning tunneling microscope, allowing scientists to
"see" (create direct spatial images of) individual atoms for the
first time. Binnig and Rohrer won the Nobel Prize for this
discovery in 1986.
1985
Rice University researchers Harold Kroto, Sean OBrien,
Robert
Curl,
and
Richard
Smalley
discovered
the Buckminsterfullerene (C60), commonly known as the

buckyball, which is a molecule resembling a soccerball in
shape and composed entirely of carbon. (1996 Nobel Prize)
1991
Sumio Iijima of NEC is credited with discovering the carbon
nanotube (CNT), although there were early observations of
tubular carbon structures by others as well.
1999 till date
Consumer products making use of nanotechnology began

appearing in the marketplace.
Lightweight golf balls, stiffer tennis rackets and baseball bats,
nano-silver antibacterial socks, wrinkle resistant clothing,
scratch-resistant
glass
coatings,
improved
televisions, cell phones, and digital cameras.
displays
for
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NANOTECHNOLOGY: GENERATIONS
Learning Objectives
At the end of the lecture the students are able to
1. Define nanochemistry.
2. Distinguish between molecules, nanoparticles and bulk materials.
3. Understand the importance of nanotechnology
4. Appreciate uniqueness of nano scale.
5. Calssify the types of nanomaterials: Nano rods, Nano wires, Nano belts,
Nano tubes,fullerene, quantum dots etc.
6. Understand and appreciate size dependent properties of nano particles.
7. Learn various physical and chemical methods used for the synthesis of
nanomaterials.
8. Know the applications of nanotechnology in diverse fields.
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Classification of Nanomaterials
Nanomaterials can be nanoscale in zero dimension (atomic clusters, filaments and
cluster assemblies), one dimension (eg. surface films), two dimensions (eg.
strands or fibres), or three dimensions (eg. particles). They can exist in single,
fused, aggregated or agglomerated forms with spherical, tubular, and irregular
shapes. Common types of nanomaterials include nanotubes, dendrimers, quantum
dots and fullerenes.
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Examples of Nanomaterials
Nanomaterials (gold, carbon, metals, meta oxides and alloys) with variety of
morphologies (shapes) are depicted in the figure below.
Comparison of 0D Nanoarchitectures with Traditional Colloids

Nanoparticles/nanoclusters
Colloids
Size: 1100 nm (nanoclusters: 110 nm)
Typically>10 nm
Homogeneous molecular composition
Heterogeneous molecular composition
Reproducible synthesis (control over
Nonreproducible, uncontrollable
size, shape, and composition)
morphology/composition
Soluble in polar/nonpolar organic
Typically only soluble in polar solvents
solvents (depending on stabilizing agent)
WHY AND HOW IS NANOPARTICLES DIFFERENT FROM OTHER

PARTICLES?
Nanoparticles are larger than individual atoms and molecules but are smaller than
bulk solid. Hence they obey neither absolute quantum chemistry nor laws of
classical physics and have properties that differ markedly from those expected.
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The
reasons
for
their
difference in behaviour are (i)

large fraction of surface atoms;
(ii) high surface energy; (iii)
spatial
confinement;
(iv)
reduced imperfections, which

do
not
exist
in
the
corresponding bulk materials.

Some features exclusive to nano size
Electromagnetic forces: Due to the smallness of nanomaterials, their mass
is extremely small and gravitational forces become negligible. Instead
electromagnetic forces are dominant in determining the behaviour of atoms
and molecules.
Wave-corpuscle duality of matter: For objects of very small mass such as
nanoparticles the wave nature has a more pronounced effect.
Quantum tunneling: Tunnelling is the penetration of an electron into an
energy region that is classically forbidden.
Quantum confinement: In a nanomaterial electrons are confined in space
rather than free to move in the bulk of the material.
Quantisation of energy: Electrons can only exist at discrete energy levels.
Quantum dots are nanomaterials that display the effect of quantisation of
energy.
Random molecular motion: Molecules move randomly due to their kinetic
energy. At the macroscale this motion is very small compared to the sizes of
the objects and thus it is not influential on how the object moves. At
nanoscale, however, these motions can be of the same scale as the size of
the particles and thus have an important influence on how they behave. One
example of a random kinetic motion is the Brownian motion.
Increased surface-to-volume ratio: One of the distinguishing properties of
nanomaterials is that they have an increased surface area.
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Size-dependent properties
At the nanometer scale, properties become size-dependent.
Some of the major size dependent properties are
(1) Thermal properties melting temperature
(2)
Optical properties absorption and
scattering of light
(3) Chemical properties reactivity, catalysis
(4)
Mechanical
properties
adhesion,
capillary forces
(5) Electrical properties tunneling current
(6) Magnetic properties superparamagnetic effect
1. THERMAL PROPERTY (REDUCED MELTING POINT)

A solid melts when thermal energy (kT) is comparable with its lattice energy so that
the particles vibrate at higher amplitude from its mean position and eventually it
melts at higher temperature.
Bulk: At macroscopic dimensions, melting point is size independent. For example,
an ice cube and a glacier both melt at same temperature.
Nanoscale: Nanomaterials may have a significantly lower melting point or phase
transition temperature and appreciably reduced lattice constants (spacing
between atoms is reduced), due to a huge fraction of surface atoms in the total
amount of atoms. The difference in melting point can be as large as 1000C(!!!!!).
Surface atoms require less energy to move because they are in contact with
fewer atoms of the substance. (Surface energy to volume energy ratio changes
dramatically)
Nanocystal size decreases
Surface energy increases
Melting
point decreases
Example: 3 nm CdSe nanocrystal melts at 700 K compared to bulk CdSe at 1678 K
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Melting point as a function of size
2. OPTICAL PROPERTY (ABSORPTION & SCATTERING OF LIGHT)

The optical properties of nanomaterials depend on parameters such as feature size,
shape, surface characteristics, and other variables including doping and interaction
with the surrounding environment or other nanostructures.
Nanoscale gold illustrates the unique properties. Nanoscale gold particles are not
the yellow color with which we are familiar; nanoscale gold can appear red or purple.
Reason
At the nanoscale, the motion of the golds electrons is confined. The particles are so
small that electrons are not free to move about as in bulk gold. Because this
movement is restricted, the particles react differently with light when compared to
larger-scale gold particles.
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Colour generation from nanoparticles and nanostructures

Reason for color
Example for nanoparticle

Butterfly wings (photonic crystals within).
The cuticle on the scales of butterfly wings are
Interference: The color is based on the composed of nano-sized, transparent, chitinconstructive interference of light wavelengths and-air layered structures that can absorb and
as they interact with the nano material.
reflect certain light wavelengths.

Liquid crystals (e.g., soap).
liquid crystals change color as a result of
nanoscale shifts in the arrangement of their
molecules
Scattering: The colours arises from the fact

that different particle sizes scatter different
Colloids (milk)
wavelengths.
Surface plasmons (SP):
A SP is a natural oscillation of the electron gas
inside a metal nanosphere. SP frequency
Metal colloids (nano-gold)
depends on the dielectric function of the metal,

and the shape of the nanoparticle.
Quantumfluorescence:
The
quantum
confinement in nano-sized semiconductors

leads to discrete energy levels from which Semiconductor quantum dots (QDs)
energy can be emitted (fluorescence) after it
has been absorbed by the semiconductor.
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Applications
Gold particles size and optical properties can be put to practical use. Nanoscale gold
particles selectively accumulate in tumors, where they can enable both precise
imaging and targeted laser destruction of the tumor by means that avoid harming
healthy cells.
Nano-Gold particles of vary in color based on particle size and concentration. Ruby
red or purple is the most potent as medicine.
3. CHEMICAL PROPERTY (CATALYSIS)

A catalyst is a substance that increases a chemical reaction rate without being
consumed or chemically altered. Greater the surface area of the heterogeneous
catalyst, the more efficient will be the catalyst. Active site is the site where the
reaction takes place. The active site increases when the size of the catalysts is
decreased: the smaller the catalyst
particles, the greater the ratio of
surface-to-volume.
The
spatial
organisation of the active sites in a

catalyst is also important.
Both properties (nanoparticle size
and molecular structure/distribution)
can
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be
controlled
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nanotechnology. Hence, nanotechnology has great potential to expand catalyst

design with benefits for various industries. The use of nanoparticles that have
catalytic properties will allow a drastic reduction of the amount of material used, with
resulting economic and environmental benefits.
A good example of how nanoscience can impact the development of catalytic
materials is that of gold. Bulk gold is a noble metal: it is stable, non-toxic, and
resistant to oxidation and chemical attack. On the other hand nanoscale gold
particles can catalyse chemical reactions. Finely dispersed gold nanoparticles on
oxide supports are catalytically very active. In many cases the catalytic activity and
selectivity of dispersed gold nanoparticles exceed those of the commonly used
transition metal catalysts such as Pt, Rh, and Pd. This is an exciting result because
metals like Pt and Pd (commonly used in catalysis such as automobile catalytic
converters) are toxic and are also very rare metals, hence more expensive than
gold.
4. MECHANICAL PROPERTIES
Mechanical properties of nanomaterials may reach the theoretical strength, which
are one or two orders of magnitude higher than that of single crystals in the bulk
form. The enhancement in mechanical strength is simply due to the reduced
probability of defects.
Filling polymers with nanoparticles or nanorods and nanotubes, respectively, leads
to significant improvements in their mechanical properties. Such improvements
depend heavily on the type of the filler and the way in which the filling is conducted.
Some nanomaterials have inherent exceptional mechanical properties which are
connected to their structure. One such material is carbon nanotubes (CNT): these
are extremely small tubes having the same honey-comb structure of graphite, but
with different properties compared to graphite. They can be single-walled or multiwalled. Carbon nanotubes are 100 times stronger than steel but six times lighter!!
The different structures, properties and potential applications of carbon nanotubes
are discussed bit later.
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5. ELECTRICAL PROPERTIES
Substances
can
be
classified into insulators,

semiconductors
and
conductors based on the

energy
between
separation
valence
band
and conduction band. The

electrons present in the
conduction band leads to
conduction.
For nanomaterials, Quantum confinement causes the energy of the bandgap to
increase as illustrated in figure below. Also, at very small dimensions when the
energy levels are quantified, the band overlap present in metals disappears and is
actually transformed into a bandgap. This explains why some metals become
semiconductors as their size is decreased.
The
increase
energy
due
of
bandgap
to
quantum
confinement means that more

energy will be needed in order
to
be
bandgap
absorbed
of
the
by
the
material.
Higher energy means shorter

wavelength (blue shift). The
same
applies
for
the
wavelength of the fluorescent light emitted from the nano-sized material, which will
be higher, so the same blue shift will occur. This gives a method of tuning the optical
absorption and emission properties of a nano-sized semiconductor over a range of
wavelengths by controlling its crystallite size.
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Some nanomaterials
exhibit
electrical
properties
that
truly
are
exceptional.
Their
electrical
properties are related

to
their
unique
structure.
Two
of
these are fullerenes

and
carbon
nanotubes.
For
instance, carbon nanotubes can be conductors or semi-conductors depending on

their nanostructure. These materials are discussed later.
6. MAGNETIC PROPERTIES
Magnetic properties of nanostructured materials are distinctly different from that of
bulk materials. Ferromagnetism disappears and transfers to superparamagnetism
in the nanometer scale due to the huge surface energy. Superparamagnetism is
a form of magnetism, which appears in small ferromagnetic or ferrimagnetic
nanoparticles.
In
sufficiently
small
nanoparticles,
magnetization
can
randomly
flip
direction
under
influence
the
of
temperature.
The typical time
between two flips is called the Nel relaxation time. In the absence of external
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magnetic field, when the time used to measure the magnetization of the
nanoparticles is much longer than the Nel relaxation time, their magnetization
appears to be in average zero: they are said to be in the superparamagnetic state.
In this state, an external magnetic field is able to magnetize the nanoparticles,
similarly to a paramagnet. However, their magnetic susceptibility is much larger than
the one of paramagnets.
Bulk gold and Pt are non-magnetic, but at the nano size they are magnetic. Surface
atoms are not only different to bulk atoms, but they can also be modified by
interaction with other chemical species, that is, by capping the nanoparticles. This
phenomenon opens the possibility to modify the physical properties of the
nanoparticles by capping them with appropriate molecules.
Nanoclusters
Nanoclusters constitute an intermediate state of matter between molecules and
solids. Nanocluster sizes range from sub-nanometer to about 10 nm in diameter and
are of technological interest in numerous areas of applied science (e.g. materials
science, catalysis, electronics). Often one differentiates between: (i) nanoclusters
consisting of up to a couple of hundred atoms, and (ii) larger aggregates containing
103 or more atoms which are more often called nanoparticles. The properties of
nanoparticles gradually approach those of bulk materials or extended surfaces, i.e.
are scalable with size. Nanoclusters, however, have properties and structures which
are very sensitive to their composition and size (i.e. every atom counts) which can
lead to new and interesting properties not realised in the corresponding bulk
material.
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Applications
Nanoclusters have potential applications in microelectronics, magnetic storage,
optical data storage, spintronics devices, telecommunications, sensors, transducers,
biological markers, switches, electroluminescent displays, chemical reactors,
catalysts, etc.
Nanorods
Nanorods
are
nanostructures,
shaped like long sticks or dowels with

a diameter in the nanoscale but
having
Standard
length
aspect
that
is
ratios
longer.
(length
divided by width) are 1-20. Each of

their dimensions range from 1100
nm. If length to width ratio exceeds
20, they are called nanowires.
The optical properties of metallic nanorod depend on shape This is due to the
absorption of visible light both along the length of the nanorod and along the width of
the nanorod.
Applications
Gold nanorods are useful materials for sensing, photo thermal therapy, and imaging.
It is also used for the treatment of cancer.
Carbon Nanotubes
What are carbon nanotubes?
CNT can be described as a sheet of graphite (grapheme) rolled into a cylinder
Constructed from hexagonal rings of carbon
Can have one layer or multiple layers
Can have caps at the ends making them look like pills
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History
Carbon nanotubes were discovered in 1991 by the Japanese electron microscopist
Sumio Iijima who was studying the material deposited on the cathode during the
arc-evaporation synthesis of fullerenes. He found that the central core of the
cathodic deposit contained a variety of closed graphitic structures including
nanoparticles and nanotubes, of a type which had never previously been observed.
Types of CNT
Single Wall CNT (SWCNT)
SWNT is formed by wrapping a one-atom-thick
layer
of graphene into a seamless cylinder.
Most single-walled nanotubes (SWNT) have a

diameter of close to 1 nanometer, with a tube
length can be many thousands of times longer.
Multiple Wall CNT (MWCNT)
Multi-walled carbon nanotubes can be seen as
several concentric cylinders and the interlayer space is about 0.34 nm. The diameter
of MWNTs is generally within 10 to 20 nm.
There are three unique geometries of carbon nanotubes. The three types are
armchair, zig-zag and chiral. These types can be classified by how the carbon
sheet is wrapped into a tube (see pictures below).
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PROPERTIES OF CNT
The physical properties carbon nanotubes based on the length and diameter
of the nano tube as well as the twist (also known as the chirality).
Due to their hollow cylindrical structure, carbon nano tubes are significantly
lighter than conventional engineering materials.
Tensile strength 10-50 times higher than steel and Young's modulus of the
some nanotubes can be five times higher than steel.
Because of tremendously high surface area (~1000 m 2/g) CNT have good
electrical conductivity. It can be conducting or semi conducting according to
its structure.
Due to the tubular structures of carbon nano tubes, they have extreme high
thermal conductivity in axial directions, leaving high anisotropy in the heat
transport in the materials.
APPLICATIONS OF CNT
Structural Support
Hydrogen storage devices
Supercapacitors
Display devices
Water and oil purifiers
Catalysts
Medicine
Biosensors
Fuel cells
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Nanowire and nanobelts

Nanowires
exhibit
aspect
ratios
(length-to-width ratio) of 1000 or more.

They are often referred to as 1Dimensional materials. Nanobelts are
a class of nanostructure often viewed
as a type of nanowire. Nanobelts form
ribbon-like structures with widths of 30300 nm, thicknesses of 10-30 nm, and
lengths in the millimeter range.
Figure (a) Nanowire (b) Nanobelt
Fullerene
The most symmetrical large molecule
Discovered in 1985
Nobel prize Chemistry 1996, Curl, Kroto, and Smalley
C60, also 70, 76 and 84.
32 facets (12 pentagons and 20 hexagons)
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SYNTHESES OF NANOPARTICLES
Nanotechnologists have offered two approaches for synthesis
and fabricating materials or manipulating devices using
nanotechnology: top down and bottom up.
Top down approach involves the breaking down of the bulk

material into nano sized structures or particles. These
techniques are an extension of those that have been used for
producing micron- sized particles. By nature, this methos is not
cheap and quick to manufacture. Slow and not suitable for
large scale production.
An example of such a technique is high-energy wet ball milling.
Basic top-down approaches in nanofabrication
Pattern transfer (lithography)
Deposition (or film growth)
Etching ( or removal of material)
Bottom up approach refers to the build up of a material from the bottom: atom-byatom, molecule-by-molecule, or cluster-by-cluster.
This has the potential of
creating less waste and hence the more economical, is the bottom- up.
Basic bottom-up approaches in nanofabrication
Chemical vapor growth: vapor-solid-liquid growth
Self assembly: colloidal chemistry
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Characteristics of Nano particles that should posses by any fabrication

technique:
Getting merely a small size is not the only requirement. It should have
i.
Identical size of all particles (also called mono sized or with uniform size
distribution.
ii.
Identical shape or morphology.
iii.
Identical chemical composition and crystal structure that are desired among
different particles and within individual particles, such as core and
composition must be the same.
iv.
Individually dispersed or mono dispersed i.e., no agglomeration.
SYNTHESIS OF NANOSTRUCTURED MATERIALS (NSM)

1. MECHANICAL GRINDING (PHYSICAL METHOD)
Mechanical grinding is a typical example of top down method of synthesis of
nanomaterials. Mechanical milling is typically achieved using high energy shaker,
planetary ball, or tumbler mills. The energy transferred to the powder from refractory
or steel balls depends on the rotational (vibrational) speed, size and number of the
balls, ratio of the ball to powder mass, the time of milling and the milling atmosphere.
Nanoparticles are produced by the
shear action during grinding.
Advantages:
a) Simple
b) Inexpensive
equipment
requirements
c) Can easily be scaled up.
Disadvantages:
a) contamination
from
milling
media and/or atmosphere
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2. LASER ABLATION (PHYSICAL METHOD)

Synthesis of nanomaterials like CNT
could be carried out in a horizontal
flow tube under a flow of inert gas at
controlled pressure. In this set-up the
flow tube is heated to ~1200C by a
tube furnace. Laser pulses enter the
tube and strike a target consisting of a
mixture of graphite and a metal
catalyst such as Co or Ni. SWNTs
condense from the laser vaporization
plume and are deposited on a collector outside the furnace zone.
3. RF PLASMA METHOD (PHYSICAL METHOD)

Nanoparticles can be synthesized by plasma
generated by RF heating coils. The starting metal
in taken in a pestle in a evacuated chamber. The
metal is heated above its evaporation point using
high voltage RF coils wrapped around the
evacuated system in the vicinity of the pestle.
Helium gas is then allowed to enter into the
system, forming a high temperature plasma in the
region of the coils. The metal vapour nucleates on
the helium gas atoms and diffuses upto the colder
collector rod where the nanoparticles are formed.
The particles are generally passivated by the introduction of some gas such as
oxygen.
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4. THERMOLYSIS (CHEMICAL METHOD)

Nanoparticles can be made by decomposing solids at high temperature having metal
cations, molecular anions or metal organic compounds. The process is called
thermolysis. For example, small lithium
particles can be made by decomposing
lithium azide, LiN3. The material is placed
in evacuated quartz tube, and heated
upto 400C as shown in the figure. At
370C decomposes releasing nitrogen
gas, which is observed by the increase in
pressure in the vacuum gauge. In few
minutes the pressure drops back to the original low value, indicating that all nitrogen
has been removed. The remaining lithium atoms coalesce to form small colloidal
metal particles. Particles of less than 5 nm can be obtained using this method.
Similarly, metal complexes can be decomposed to obtain nano particles.
5.
HYDROTHERMAL SYNTHESES (CHEMICAL METHOD)
Hydrothermal synthesis is a method to produce different chemical compounds

and materials using closed-system physical and chemical processes flowing in
aqueous solutions at temperatures above 100C and pressures above 1 atm.
The method is based on the ability of water to dissolve substances which are
practically insoluble under normal conditions under high temperature (500C) and
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pressure (10-80 MPa) (eg:

some
oxides,
silicates,
sulphides). The synthesis is

carried out in autoclaves
which
are
sealed
steel
cylinders that can withstand

high
temperatures
and
pressure for a long time.

The main factors that influence hydrothermal synthesis are the initial pH of the
medium, the duration and temperature of synthesis, and the pressure in the system.
Nanopowders are normally produced by means of either high temperature hydrolysis
reactions
of
various
compounds
directly
in
the
autoclave.
Advantages: Ability to synthesize crystals of substances which are unstable near

the melting point, and the ability to synthesise large crystals of high quality.
Disadvantages: High cost of equipment and the inability to monitor crystals in the
process of their growth.
6. SOLVOTHERMAL SYNTHESES (CHEMICAL METHOD)

Solvothermal process is very similar
to hydrothermal process. Here a nonaqueous solvent, which is sealed in
an autoclave and maintained in its
superheated state is the reaction
medium where the reactants and
products are effectively prevented
from
oxidation
and
volatilization.
Reaction and crystallization can be

done
simultaneously.
Organic
solvents may be favourable for the dispersion of non oxide nano crystallites and may
stabilize some metastable phases.
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Solvothermal synthesis allows for the precise control over the size, shape
distribution, and crystallinity of metaloxide nanoparticles or nanostructures. These
characteristics can be altered by changing certain experimental parameters,
including reaction temperature, reaction time, solvent type, surfactant type, and
precursor type.
Solvothermal synthesis has been used in laboratory to make nanostructured titanium
dioxide, graphene, carbon and other materials.
7. ELECTRODEPOSITION (CHEMICAL METHOD)

Electrodeposition is a method
to deposit metal layers on a
conducting substrate. Ions in
solution are deposited onto the
negatively charged cathode,
carrying charge at a rate that
is measured as a current in the
measured as a current in the
external circuit. The process is
relatively cheap and fast and
allows complex shapes.
The layer thickness simply
depends on the current density and the time for which the current flows. The deposit
can be detached if the substrate is chosen to be soluble by dissolving it away.
Electrodeposition is relatively cheap and can be performed at low temperatures. The
film thickness can be controlled by monitoring the amount of charge delivered.
Electrodeposition is now
used to make complex 3D electrical interconnects in
computer chips.
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8. CHEMICAL VAPOUR DEPOSITION (CHEMICAL METHOD)

In this method the material to be deposited is first heated to its gas form and then
allowed to deposit as a solid on a surface. This method is usually performed
under vacuum. The deposition can be direct or through chemical reaction so that
the material deposited is different from the one volatilized. This method is usually
used to prepare the nanopowders of oxides and carbides of metals if carbon and
oxygen are present in the metal. This method can be used for the preparation of
nanopowders of pure metals, though not easily.
Chemical vapour deposition is usually used to deposit a material on a flat
surface. When a surface is exposed to a chemical vapour, the first layer of atoms
or molecules that deposited on the surface can act as a template on which
material can grow. The structures of these materials are often aligned.Aligned
structure starts to grow vertically. This is an example of self assembly.
9.
SOL-GEL PROCESS (CHEMICAL METHOD)
This method is performed in liquid phase. It is an useful self assembly process for
fabricating nanoparticles as well as nano structured surfaces.
A sol is a type of colloid in dispersed solid phase is mixed in a homogenous liquid
medium. As the name suggests, sol-gel process involves the evolution of networks
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through the formation of colloidal suspension (sol) and the gelation of sol to form a
network in a continuous liquid phase(gel).
1. Synthesis of colloids (Metal alkoxide precursor commonly used). Hydrolysis of
the precursor (-OR replaced by OH) in presence of a catalyst.
2. Condensation
and
polymerization
of
sol.
Particles
grow
and
then
agglomerate.
3. Formation of network throughout the liquid medium, results in thickening,
which forms the gel.
This method is most commonly used to make silica gel.
10. PRECIPITATION PROCESS (CHEMICAL METHOD)

Precipitation of a solid from a solution is a common technique for the synthesis of
fine nanoparticles. The general procedure involves reactions in aqueous or
nonaqueous solutions containing the soluble or suspended salts. Once the solution
becomes supersaturated with the product, the precipitate is formed by either
homogeneous or heterogeneous nucleation. The formation of a stable material with
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Engg. Chemistry I
or without the presence of a foreign species is referred to as heterogeneous or

homogeneous nucleation. The growth of the nuclei after formation usually
proceeds by diffusion, in which case concentration gradients and reaction
temperatures are very important in determining the growth rate of the particles.
Concentration of reactants, reaction temperature, pH, and the order of addition of
reactants to the solution are important in this method.
IS NANO ALL GOOD????

Health impacts of nano particles are yet to be understood properly. It is quite
possible that nanoparticles can have adverse health effects.
Since these particles are very small, problems can actually arise from the
inhalation of these minute particles, much like the problems a person gets
from inhaling minute asbestos particles.
Atomic weapons can now be more accessible and made to be more powerful
and more destructive. These can also become more accessible with
nanotechnology.
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Engg. Chemistry I
HOW TO PREPARE GOLD NANO PARTICLES IN THE LAB????
1. Heat a solution of chloroauric acid (HAuCl4) up to reflux (boiling). HAuCl4 is a

water soluble gold salt.
2. Add trisodium citrate, which is a reducing agent.
3. Continue stirring and heating for about 10 minutes.
During this time, the sodium citrate reduces the gold salt (Au 3+) to metallic
gold (Au0) . The neutral gold atoms aggregate into seed crystals. The seed
crystals continue to grow and eventually form gold nanoparticles.
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Engg. Chemistry I
MECHANISM OF NANOPARTICLE FORMATION
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Engg. Chemistry I
GLOSSARY
Atomic force microscope (AFM): A scientific instrument for analyzing the surface of
a rigid material all the way down to the level of the atom. AFM uses a mechanical
probe to magnify surface many fold, and it produces 3-D images of the surface.
Bottom Up: Building larger objects from smaller building blocks. This use atoms and
molecules as those building blocks to prepare nano sized material.
Buckyball: A familiar, nontechnical synonym for fullerene.
Carbon nanotube (CNT): An allotrope of carbon, cylindrical carbon molecules with
hexagonal rings and have novel properties that make them useful in a wide variety of
applications in nanotechnology, electronics, optics and materials science.
Chemical Vapour Deposition (CVD): A technique used to deposit coatings, where
chemicals are first vaporized, and then applied using an inert carrier gas such as
nitrogen.
Fullerene: A category of roughly spherical carbon nanoscale structures named after
Buckminster Fullers geodesic spheres.
Nanocomposite: A material composed of two or more substances, of which at least
one has a nanoscale dimension, such as nanoparticles dispersed throughout another
solid material.
Nanocrystals: also known as nanoscale semiconductor crystals. "Nanocrystals are
aggregates of anywhere from a few hundred to tens of thousands of atoms that
combine into a crystalline form of matter known as a "cluster."
Nanofabrication: General terms for methods to create, assemble, or otherwise form
nanoscale structures.
Nanometer: A distance unit representing one-billionth of a meter, or one-millionth of a
millimetre.
Nanoporous: Substances that have holes or pores on the nanoscale, used, for
example, to separate particles or molecules by size.
Nanosensor: A device for sensing radiation, forces, chemicals, or biological agents,
in which some portion of a device operates at the nanoscale, for example, by having
receptors into which the particular molecules to be sensed fit.
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Engg. Chemistry I
Quantum dot: A nanoscale crystal with a diameter that is typically between 2-20 nm,
having unique electrical and optical properties that are dependent on its size. They find
commercial applications in new light sources, enhanced medical imaging, and being
explored as compenents in quantum computers etc.
Quantum Tunneling: When electrons pass through a barrier, without overcoming it or
breaking it down.
Scanning tunneling microscope: This can make images of nanoscale details on an
electrically conductive surface by moving a sharp metal probe very close to that
surface, passing a low-voltage electric current across it, and measuring tiny
fluctuations in the current as the probe is scanned across the surface.
Self-assembly: A process in which a given nanostructure spontaneously constructs
itself, generally limited to very specific structures in chemical environments precisely
defined in order to promote self-assembly.
Vapor deposition: A chemical process commonly used in the semiconductor industry
to apply thin films of one substance onto a surface composed of another substance.
Books for your reference

1. Nanostructured Materials
and Nanotechnology: Edited by
Hari Singh
Nalwa, Academic Press, 2002.

2. Introduction to Nanotechnology: Charles P. Poole Jr. and Frank J. Owens,
John Wiley & Sons, 2003.
3. Introduction to nanoscience and nanotechnology: Banerjee A. N,
Chattopadhyay K. K, Phi Learning, 2009.
4. Nanotechnology: RK Rathi, S. Chand Publisher, 2009.
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Engg. Chemistry I
Websites for your reference

1. http://crnano.org/whatis.htm
2. www.nano.gov
3. http://www.azonano.com/
Must watch youtube videos

1. http://www.youtube.com/watch?v=xlYIex2TF5g
2. http://www.youtube.com/watch?v=FhiFamF-M0c
3. http://www.youtube.com/watch?v=WOqEk440JZ8
4. http://www.youtube.com/watch?v=icHRs3qMj9g
In brief
Nano is one billionth of a meter (10-9 of a meter). Nanotechnology deals with
materials having at least one spatial dimension in the size range of 1 to 100
nm.
Nanomaterials can be nanoscale in zero dimension (atomic clusters,
filaments and cluster assemblies), one dimension (eg. surface films), two
dimensions (eg. strands or fibres), or three dimensions (eg. particles).
Nanomaterials differ from bulk due to (i) large fraction of surface atoms; (ii)
high surface energy; (iii) spatial confinement; (iv) reduced imperfections,
which do not exist in the corresponding bulk materials.
At the nanometer scale, properties become size-dependent. Thermal,
optical, mechanical, magnetic, chemical properties of nano scale are all size
dependent.
Nanomaterials can be nanocluster, nanorod, nanowire, nanobelt etc.
Top down and bottom up approaches are used to prepare nanomaterials.
Top down method involves the breaking down of the bulk material into nano
sized structures or particles. Bottom up approach refers to the build up of a
material from the bottom: atom-by-atom, molecule-by-molecule, or cluster-bycluster.
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Engg. Chemistry I
Many physical and chemical methods are used for the synthesis of
nanomaterials. These include hydrothermal, solvothermal, chemical vapour
deposition, sol-gel method etc.
CONCLUSION
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Engg. Chemistry I
CHECK YOUR UNDERSTANDING

Question 1: The prefix "nano" comes from a ...
French word meaning billion
Greek word meaning dwarf
Spanish word meaning particle
Latin word meaning invisible
Question 2: Who first used the term nanotechnology and when?

Richard Feynman, 1959
Norio Taniguchi, 1974
Eric Drexler, 1986
Sumio Iijima, 1991
Question 3: What is a buckyball?

A carbon molecule (C60)
Nickname for Mercedes-Benz's futuristic concept car (C111)
Plastic explosives nanoparticle (C4)
Concrete nanoparticle with a compressive strength of 20
nanonewtons (C20)
Question 4: Which of these historical works of art contain nanotechnology?

Lycurgus cup
Medieval stained glass windows in churches
Damascus steel swords
All of the above
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Engg. Chemistry I
Question 5: Richard Feynman is often credited with predicting the potential of

nanotechnology. What was the title of his famous speech given on December 29,
1959?
There is a tiny room at the bottom
Things get nanoscopic at the bottom
Bottom? What bottom?
There is plenty of room at the bottom
Question 6: How many oxygen atoms lined up in a row would fit in a one nanometer
space?
None; an oxygen atom is bigger than 1 nm
One
Seven
Seventy
Question 7: Which one of these statements is NOT true?

Gold at the nanoscale is red
Copper at the nanoscale is transparent
Silicon at the nanoscale is an insulator
Aluminum at the nanoscale is highly combustible
Question 8: Which of these consumer products is already being made using

nanotechnology methods?
Fishing lure
Golf ball
Sunscreen lotion
All of the above
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Engg. Chemistry I
Question 9: What is graphene?

A new material made from carbon nanotubes
A one-atom thick sheet of carbon
Thin film made from fullerenes
A software tool to measure and graphically represent
nanoparticles
Question 10: Nanorobots (nanobots)...

Do not exist yet
Exist in experimental form in laboratories
Are already used in nanomedicine to remove plaque from
the walls of arteries
Will be used by NASA in the next unmanned mission to
Mars
Question 11: And what exactly is a quantum dot?

A semiconductor nanostructure that confines the motion of
conduction band electrons, valence band holes, or excitons
in all three spatial directions.
The sharpest possible tip of an Atomic Force Microscope
A fictional term used in science fiction for the endpoints of
wormholes
Unexplained spots that appear in electron microscopy
images of nanostructures smaller than 1 nanometer
Answers given in the next page
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Engg. Chemistry I
ANSWERS
1. Greek word meaning dwarf
2. Norio Taniguchi, 1974
3. A carbon molecule (C60)
4. All the above
5. There is plenty of room at the bottom
6. Seven (The diameter of one oxygen atom is approximately 0.14 nanometers)
7. Silicon at the nanoscale is an insulator.
8. All of the above
9. A one-atom thick sheet of carbon
10. Do not exist yet
11. A semiconductor nanostructure that confines the motion of conduction band
electrons, valence band holes, or excitons in all three spatial directions.
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Preclass notes- Nanochemistry

There are 25,400,000 nanometers in an inch

A sheet of newspaper is about 100,000 nanometers thick

A human hair is approximately 80,000- 100,000 nanometers wide

A single gold atom is about a third of a nanometer in diameter

One nanometer is about as long as your fingernail grows in one second

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

Nanotechnology definition (NASA)

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

materials to within atomic-scale dimensional tolerances.

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

the Buckminsterfullerene (C60), commonly known as the

1999 till date

Consumer products making use of nanotechnology began

televisions, cell phones, and digital cameras.

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

Comparison of 0D Nanoarchitectures with Traditional Colloids

Size: 1100 nm (nanoclusters: 110 nm)

Homogeneous molecular composition

Heterogeneous molecular composition

Reproducible synthesis (control over

size, shape, and composition)

Soluble in polar/nonpolar organic

Typically only soluble in polar solvents

solvents (depending on stabilizing agent)

WHY AND HOW IS NANOPARTICLES DIFFERENT FROM OTHER

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

difference in behaviour are (i)

reduced imperfections, which

corresponding bulk materials.

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

Optical properties absorption and

1. THERMAL PROPERTY (REDUCED MELTING POINT)

Surface energy increases

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

Melting point as a function of size

2. OPTICAL PROPERTY (ABSORPTION & SCATTERING OF LIGHT)

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

Colour generation from nanoparticles and nanostructures

Example for nanoparticle

reflect certain light wavelengths.

Scattering: The colours arises from the fact

Metal colloids (nano-gold)

depends on the dielectric function of the metal,

confinement in nano-sized semiconductors

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry

3. CHEMICAL PROPERTY (CATALYSIS)

organisation of the active sites in a

Material prepared by: Chemistry faculty

Preclass notes- Nanochemistry