Module-4

Introduction.

The Scientists studied a multidisciplinary convergence of new technology materials of so small

where we can't see it even with a light microscope, that new field is named as nanotechnology, the
realm of atoms and nanostructures. Nanotechnology is so new no one is really sure what will come of
it. Even so, predictions range from the ability to reproduce things like diamonds and food to the
world being devoured by self-replicating nano robots.

Nanornaterials are cornerstones of nanoscience and nanotechnology. Nanostructure science and

technology is a broad and interdisciplinary area of research and development activity that has
been growing explosively worldwide in the past few years. It has the potential for
revolutionizing the ways in which materials and products are created and the range and nature of
functionalities that can be accessed. It is already having a significant commercial impact, which
will assuredly increase in the future.

Nanomaterials

Nanoscale materials are defined as a set of substances where at least one dimension is less
than approximately 100 nanometers. A nanometer is one millionth of a millimeter -
approximately 100,000 times smaller than the diameter 'of a human hair. Nanomaterials are of
interest because at this scale unique optical, magnetic, electrical, and other properties emerge.
These emergent properties have the potential for great impacts in electronics, medicine, and
other fields.
 The word 'nano 'is to a Greek prefix meaning dwarf or something very small and depicts one
billionth (10-9) of a unit. Nanomaterials, therefore, refer to the class of material-with at least
one of the dimensions in the nanometric range. Nanomaterials can be metals, ceramics,
polymers or composites. Nanotechnology is an umbrella term for many areas of research
dealing with objects that have one of their dimensions in the realm of a few hundreds of
nanometres.

The term `nanotechnology' was first coined by Norio Taniguchi in 1974 to describe
semiconductor processes such as thin film deposition and ion beam milling, where the features
can be controlled at the nano metric level.

The most widely accepted definition of nanotechnology to date appears on the NASA
website: .the creation of functional materials, devices and systems through control of matter on
the nanometer length scale (1-100 nm), and exploitation of novel phenomena and properties
(physical, chemical, biological) at that length scale.

Nanomaterials are not new and have been produced and used by humans for hundreds of years.
However, the understanding of certain materials as nanostructured materials is relatively recent,
made possible by the advent of advanced tools that are capable of resolving information at
nanoscale.

 Beautiful ruby red colour of some ancient glass paintings is due to gold and silver
nanoparticles trapped in the glass matrix
 The decorative glaze or metallic film known as 'luster', found on some medieval
pottery, contains metallic spherical nanoparticles dispersed in a complex way in
the glaze, which gives rise to special optical properties. The techniques used to
produce these materials were a closely guarded secret, and are not completely
understood even now

 Carbon black is a nanostructured material that is used in car tyres to increase the life of the
tyre and impart black colour. This material was discovered in the 1900s. Fumed silica, a
component of silicon rubber, coatings, sealants and adhesives, is also a nanostructured
material. It became commercially available in the 1940s.
 Steel (an alloy of iron and carbon) is believed to have been first prepared in India about 1500
years ago and is popularly known as wootz. This steel was used to make swords, which were so
strong and sharp that they could easily cut a helmet into two pieces. Very recently high-
resolution electron microscopy of such a steel (picked up from a museum) showed the presence
of carbon nanotubes in them, which has surprised scientists. People now believe that the- high
 strength of these steels may be due to the presence of these -carbon nanotubes, which are -known
for their exceptionally large Young's modulus.

Benefit and Application of Nano technology

Nanotechnology is helping to considerably improve, even revolutionize, many
technology and industry sectors: information technology, homeland security, medicine,
transportation, energy, food safety, and environmental science, and among many others.
Described below is a sampling of the rapidly growing list of benefits and applications of
nanotechnology

a) Every day materials

Many benefits of nanotechnology depend on the fact that it is possible to tailor the structures
of materials at extremely small scales to achieve specific properties, thus greatly extending the
materials science toolkit. Using nanotechnology, materials can effectively be made stronger,
lighter, more durable, more reactive, more sieve-like, or better electrical conductors, among many
other traits. Many everyday commercial products are currently on the market and in daily use that
rely on nanoscale materials and processes:

 Nanoscale additives used for surface treatments of fabrics can provide _lightweight
ballistic energy deflection in personal body armor, or can help them resist wrinkling, staining,
and bacterial growth

 Clear nanoscale films on eyeglasses, computer and camera displays windows and
other surfaces can make them water-<,; and residue-repellent, antireflective,
cleaning, resistant to ultraviolet or infrared light, antifog, antimicrobial, scratch
resistant, or electrically conductive.

 Nanoscale materials are beginning to enable washable, durable "smart fabrics" equipped
with flexible nanoscale sensors and electronics with capabilities for health monitoring,
solar energy capture, and energy harvesting through movement.
 Light weighting of cars, trucks, airplanes, boats, and space craft could lead to significant
fuel savings. Nanoscale additives in polymer composite materials are being used in
baseball bats, tennis rackets, bicycles, motorcycle helmets, automobile parts, luggage, and
power tool housings, making them lightweight,, stiff, durable, and resilient. Carbon
nanotubes sheets are now being produced for use in next-generation air vehicles. For
 example, the combination of light weight and conductivity makes them ideal for
applications such as electromagnetic shielding and thermal management.
 Nano-engineered materials in automotive products include high-power
rechargeable battery systems; thermoelectric materials for temperature control; tires with
lower rolling resistance; high-efficiency/low-cost sensors and electronics; thin-film smart
solar panels; and fuel additives for cleaner exhaust and extended range.
 Nanostructured ceramic coatings exhibit much greater toughness than
conventional wear-resistant coatings for machine parts. Nanotechnology-enabled
lubricants and engine oils also significantly reduce wear and tear, which can significantly
extend the lifetimes of moving parts in everything from power tools to industrial
machinery.

b) Electronic application

Nanotechnology has greatly contributed to major advances in computing and electronics;

leading to faster, smaller, and more portable systems that can manage and store larger and larger
amounts of information. These continuously evolving applications include:

 Transistors, the basic switches that enable all modern computing; have gotten smaller
and smaller through nanotechnology. At the turn of the century, a typical transistor was
130 to 250 nanometers in size. In 2014, Intel created 14 nanometer transistors, then
IBM created the first seven nanometer transistors in 2015, and then Lawrence Berkeley
National Lab demonstrated a one nanorneter transistor in 2016 Smaller, faster, and
better transistors may mean that soon your computer's entire memory may be stored on
a single tiny chip.
 Using magnetic random access memory (MRAM), computers will be able to "boot"
almost instantly. MRAM is enabled by nanometer-scale magnetic tunnel junctions and
can quickly and. effectively save data during a system shutdown or enable resume-play
features.

 Ultra-high definition displays and televisions are now being sold that use quantum
dots to produce more vibrant colors while being more energy efficient.
c) Medical and health care

Nanotechnology is already broadening the medical tools, knowledge, and therapies,,

currently available to clinicians. Nanomedicine, the application of nanotechnology in
medicine, draws on the natural scale of biological phenomena to produce precise solutions for
disease prevention, diagnosis, and treatment. Below are some examples of recent advances in
this area:
  Commercial applications have adapted gold nanoparticles as probes for the detection
of targeted sequences of nucleic acids, and gold nanoparticles are also being clinically
investigated as potential treatments for cancer and other diseases.
 Better imaging and diagnostic tools enabled by nanotechnology are paving the way for
earlier diagnosis, more individualized treatment options, and better therapeutic success
rates.
 Nanotechnology is being studied for both the diagnosis and treatment of
atherosclerosis, or the buildup of plaque in arteries. In one technique, researchers
created nanoparticles that mimic the body's "good" cholesterol, known as HDL (high-
density lipoprotein), which helps to shrink plaque.
 Nanotechnology researchers are working on a number of different therapeutics where
a nanoparticles can encapsulate or otherwise help to deliver medication directly to
cancer cells and minimize the risk of damage to healthy tissue. This has the potential
to change the way doctors treat cancer and dramatically reduce the toxic effects of
chemotherapy.
Energy Sector

Nanotechnology is finding application in traditional energy sources and is greatly

enhancing alternative energy approaches to help meet the world's increasing energy demands.
Many scientists are looking into ways to develop clean, affordable, and renewable energy
sources, along with means to reduce energy consumption and lessen toxicity burdens on the
environment:

 Nanotechnology is improving the efficiency of fuel production from raw petroleum

materials through better catalysis. It is also enabling reduced fuel consumption in
vehicles and power plants through higher-efficiency combustion and decreased friction.

 Nanotechnology is also being applied to oil and gas extraction through, for example, the
use of nanotechnology-enabled gas lifts valves in offshore operations.
 Nanotechnology can be incorporated into solar panels to convert sunlight to electricity
more efficiently, promising inexpensive solar power in the future. Nanostructured solar
cells could be cheaper to manufacture and easier to install, since they can use print-like
manufacturing processes and can be made in flexible rolls rather than discrete panels.
Newer research, suggests that future solar converters might even be "paintable."
Environment Remediation

In addition to the ways that nanotechnology can help improve energy efficiency are also many
ways that it can help detect and clean up environmental contaminants:

 Nanotechnology could help meet the need for affordable, clean drinking water through
rapid, low-cost detection and treatment of impurities in water.
 Engineers have developed a thin film membrane with nanopores for energy-efficient
desalination. This molybdenum di-sulphide (MoS2) membrane filtered two to five
times more water than current conventional filters.
 Nanoparticles are being developed to clean industrial water pollutants in ground water
 through chemical reactions that render the pollutants harmless. This process would cost
less than methods that require pumping the water out of the ground for treatment.
 Researchers have developed a nanofabric "paper towel" woven from tiny wires of
potassium manganese oxide that can absorb 20 times its weight in oil for cleanup
applications. Researchers have also placed magnetic water-repellent nanoparticles in
oil spills and used magnets to mechanically remove the oil from the water.

Challenges and Future Prospects

It can be foreseen that nanotechnology leads to tiny robotic devices, utilizing nano
electronics, sensors and MEMS for in-vivo monitoring and diagnosis of electro optic deficiencies
and malfunctions of human systems. Yet, the current applications of nanotechnology are much
more lacking interest: stain-resistant trousers, better sun creams, and tennis rackets reinforced
with carbon nanotubes! There is a huge gap between what nanotechnology is believed to have
promised and what it has actually delivered so far.

In the book, Engines of Creation: The Coming Era of Nanotechnology, published in 1986,
Drexler imagined sophisticated nanoscale machines that could operate with atomic precision.
He envisaged a particular way of achieving nanotechnology, which involved using hard
materials like diamond to fabricate complex nanoscale structures by moving reactive molecular
fragments into position. His approach was essentially mechanical, whereby tiny gears and
bearings are integrated to make tiny robot factories, probes and vehicles.

Drexler postulated that since nanoscale machines are expected to be extensively employed
in biological systems and .Would be synthesized in significantly large quantities under ambient
conditions, it should be possible to discover the growth conditions to synthesize them for a
variety of other applications as well.

The beauty of nanotechnology is that it is truly multidisciplinary, re-unifying-the common

threads between science, engineering and technology. It is so vivid, with possibilities left only to
the constraint of perhaps human imagination. With a little exaggeration, it seems possible that
materials with any desired physical, chemical or electronic properties can be tailor-made by playing
with the nano-dimensions.

The next generation is going to be directly or indirectly exposed to a variety of wiry)

products ranging from cosmetics to sports, from medical to industrial, and also space
applications. With the advent of any new revolutionary technology with enormous potential for
applications, it is perhaps even more pertinent to assess the risks and challenges accompanying
them.

The effect of nanoparticles on biological and ecological systems in large is a subject to be

studied with the highest priority. A new field, nano-toxicology, has evolved in order to probe
this field. It is important to qualify the application of Nanomaterials for industrial and large-
scale societal applications, not only based on their properties but also based on their possible
long-term side effects.

Bottom up and Top-down approaches

Nanomaterials fabrication methods can be classified according to whether their assembly

followed either

(i) Bottom-up approach: In Bottom up approach, smaller components of atomic or molecular

dimensions self-assemble together, according to a natural physical principle or an externally
applied driving force, to give rise to larger and more organized systems.

Various Nano manufacture technique followed are

 Physical vapor deposition (PVD)

 Chemical vapor deposition
 Spray conversion processing
 Sol—gel process
 Wet chemical synthesis
 Self-assembly
(ii) Top-down approach: Top-down approach process starts, from a large piece and
subsequently uses finer and finer tools for creating correspondingly smaller structures.

These two approaches are schematically presented in Fig. There are advantages and
disadvantages in both approaches, which are estimated according to their speed, reproducibility,
and cost.

Various Nano manufacture technique followed are

 Mechanical alloying
 Equal channel angular pressing (ECAP)
 High-pressure torsion (ITEPT)
 Accumulative roll bonding (ARB)
 Nanolithography

Methods for creating nano-structures: There are many different ways of creating nanostructures:
macromolecules or nanoparticles or Bucky balls or nanotubes and so on can be synthesized artificially
for certain specific materials. They are arranged by methods based on equilibrium thermodynamics
such as methods of self-organization and self-assembly (sometimes also called bio-mimetic processes).
Using these methods, synthesized materials can be arranged into useful shapes so that finally the
material can be applied to a certain application.

Mechanical grinding.
Mechanical attrition is a typical example of 'top down' method of synthesis of nanomaterials, where
the material is prepared not by cluster assembly but by the structural decomposition of coarser-
grained structures as the result of severe plastic deformation.
 It is widely used and popular method to make nano crystalline materials because of its
simplicity, inexpensive experimental set up and the applicability to essentially the synthesis of all
classes of materials.
 Advantage here is the possibility of easily scaling up to tonnage quantities of material for
various applications.
 Some problems usually occur are
 Contamination from milling media and/or atmosphere,
 To consolidate the powder product without coarsening the nano microstructure.

Principle of working:

 Mechanical milling is typically achieved using high energy shaker s 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. Milling in cryogenic
liquids can greatly increase the brittleness of the powders influencing the fracture
process. As with any process that produces fine particles, an adequate step to prevent
oxidation is necessary,
 Hence this process is very restrictive for the production of non-oxide materials since
then it requires that the milling take place in an inert atmosphere and that the powder
particles be handled in an appropriate vacuum system. or glove box. .

 This method of synthesis is suitable for producing amorphous or nanocrystalline alloy

particles, elemental or compound powders. If the mechanical milling imparts
sufficient energy to the constituent powders a homogeneous alloy can be formed.
 Based on the energy of the milling process and thermodynamic properties: of the
constituents the alloy can be rendered amorphous by this processing

Wet Chemical Synthesis of Nanomaterials

 This is a Bottom up approach Solution-based processing routes used for the synthesis of
nanoparticles include precipitation of solids from a supersaturated solution, homogeneous
liquid phase chemical reduction and ultrasonic decomposition of chemical precursors.
 These processes are attractive due to their simplicity, versatility and availability of low
cost precursors.
 Inorganic salt compounds used in the wet chemical synthesis routes are more versatile
and economical than alkoxides employed in the sol—gel process.
 A typical example is the formation of nanocrystalline titania powders via hydrolysis of
TiC14 at lower temperatures:

 Once the solution becomes saturated, crystallization of titania takes place either through
homogeneous or heterogeneous nucleation. In the latter case, crystal seeds are added to
the solutions to promote the crystallization of titania nanoparticles. Salt reduction is
one of the most commonly adopted methods to generate the metal colloid particles.
 The process involves the dissolution of metal salts in aqueous or non-aqueous
environments followed by the reduction of metal cations to the zero-valent state. The
nature of the metal salts determines the kind of reducing agent to be applied.
  Metal nanoparticles can also be generated via ultrasonic and thermal decomposition of
metal salts or chemical precursors. Power ultrasonic waves can stimulate certain novel
chemical processes due to the formation of localized hot spots in the liquid of extremely
high temperatures ( 3000 K) and high pressures (1000 atm).
 The main event in the process is the nucleation, growth and collapse of cavitation
bubbles formed in the liquid. The cooling achieved during the cavitation collapse is
estimated to be greater than 2 x 109 K. This process is commonly referred to as the
sonochemical method.
 Transition metal nanoparticles can be produced via sonication of their respective
chemical. Precursors. For example, Ni(CO)4 has been sonicated under argon
atmosphere to obtain amorphous nickel.
 One disadvantage of the sonication process is the difficulty in controlling the resulting
particle size and distribution due to the agglomeration of particles, into a porous coral-
like microstructure.
A number of traditional and herbal methods of materials processing could also possibly
lead to nanostructure formation.

Sol-gel process

The sol-gel process, involves the evolution of inorganic networks through the suspension (sol)
and gelation of the sol to form a network in a continuous liquid phase (gel). The precursors
for synthesizing these colloids consist usually of a metal or metalloid element surrounded by
various reactive ligands.

 The starting material is processed to form a dispersible oxide and forms a sol in contact
with water or dilute acid.
 Removal of the liquid from the sol yields the gel, and the sol/gel transition controls the
particle size and shape.
 Calcination of the gel produces the oxide.
 Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based
precursors such as Si(OEt)4 (tetraethyl orthosilicate, or TEOS). The reactions involved in
the sol-gel chemistry based on the hydrolysis and condensation of metal alkoxides.
M(OR)z can be described as follows:
 MOR + H2O •--+ MOH + ROH (hydrolysis)
 MOH + ROM M-O-M + ROH (condensation)
  Sol-gel method of synthesizing nanomaterials is very popular amongst chemists and is
widely employed to prepare oxide materials. The sol-gel process can be characterized by
a series of distinct steps.

1. Formation of different stable solutions of the alkoxide or solvated metal precursor.

2. Gelation resulting from the formation of an oxide- or alcohol- bridged network (the gel) by
a polycondensation reaction results in a dramatic increase in the viscocity of the solution

3. Aging of the gel during the polycondensation reactions continue until the gel transforms into a
solid mass, accompanied by contraction of the gel network and expulsion of Solvent from gel
pores. The aging process of gels can exceed 7 days and is critical to the prevention of cracks in
gels that have been cast.

4. Drying of the gel is carried out when water and other volatile liquids are removed from the
gel network. This process is complicated due to fundamental changes in the structure of the
gel. The drying process has itself been broken into four distinct steps:

 Constant rate period,

 Critical point,
 Falling rate period,
 Second falling rate period.
 5. Dehydration occurs during which surface- bound M-OH groups are removed, there by
stabilizing the gel against rehydration. This is normally achieved by calcining the monolith
at temperatures up to 8000C.

6. Densification and decomposition of the gels at high temperatures (T>8000C). The

pores of the gel network are collapsed, and remaining organic species are volatilized.

4.9 Gas Phase synthesis of Nanomaterials

The gas-phase synthesis Methods are of increasing interest because they allow elegant way to
control process parameters in order to be able to produce size, shape and chemical
composition controlled nanostructure.

In conventional chemical vapor deposition (CVD) synthesis, gaseous products either are allowed to
react homogeneously or heterogeneously depending on a particular application.

1. In homogeneous CVD, particles form in the gas phase and diffuse towards a cold
surface due to thermophoretic (thermo diffusion) forces, and can either be scrapped of
from the cold surface to give nano-powders, or deposited onto a substrate to yield what
is called 'particulate films'.
2. In heterogeneous CVD, the solid is formed on the substrate surface, which
catalysis the reaction and a dense film is formed.
In order to form nanomaterials several modified CVD methods have been developed and Gas
phase processes have inherent advantages, some of which are;

 An excellent control of size, shape, crystallinity and chemical composition

 Highly pure materials can be obtained
 Multicomponent systems are relatively easy to form
 Easy control of the reaction mechanisms
Most of the synthesis routes are based on the production of small clusters that Than
aggregate to form nano particles (condensation). Condensation occurs only when the vapor is
supersaturated and in these processes homogeneous nucleation in the gas phase is utilized to
form particles. This can be achieved both by physical and chemical methods.

4:10 Furnace

The nanoparticles are produced by heating the desired material in a heat resistant crucible
containing the desired material. This method is appropriate only for materials that have a high
vapour pressure at the heated temperatures that can be as high as 2000°C. Energy is normally
introduced into the precursor by arc heating, electron beam heating or Joule heating. The atoms
are evaporated into an atmosphere, which is either inert (e.g. He) or reactive (so as to Corm a
compound). To early out reactive synthesis, materials with very low vapour pressure have to be
fed into the furnace in the form of a suitable precursor such as organometallics, which
decompose in the furnace to produce a condensable material. The hot atoms or the evaporated
matter lose energy by collision with the atoms of the cold gas and undergo condensation into
small clusters via homogeneous nucleation. In case a compound is being synthesized, these
precursors react in the gas phase and form a compound with the material that is separately
injected in the reaction chamber. The clusters would continue to grow if they remain in the
supersaturated region. To control their size, they need to be rapidly removed from the
supersaturated environment by a carrier gas. The cluster size and its distribution are controlled
by only three parameters:

1) The rate of evaporation (energy input),

2) The rate of condensation (energy removal), and
3) The rate of gas flow (cluster removal).

Because of its inherent simplicity, it is possible to scale up this process from laboratory
(mg/day) to industrial scales (tons/day).

4.11 Flame Assisted Ultrasonic Spray Pyrolysis

In this process, precusrsors are nebulized and then unwanted components are burnt in a flame
to get the required material, eg. ZrO2 has been obtained by this method from a precursor of Zr
(CH3 CH2 CH2O)4. Flame hydrolysis that is a variant of this process is used for the manufacture of
fused silica. In the process, silicon tetrachloride is heated in an oxyhydrogen flame to give highly
dispersed silica. The resulting white amorphous powder consists of spherical particles with sizes
in the range 7-40 nm. The combustion flame; synthesis, in which the burning of a gas mixture,
e.g. acetylene and oxygen or hydrogen and oxygen, supplies the energy to initiate the pyrolysis
of precursor compounds, is widely used for the industrial production of powders in large
quantities, such as carbon black, fumed silica and titanium dioxide. However, since the gas
pressure during the reaction is high, highly agglomerated powders are produced which is
disadvantageous for subsequent processing.

The basic idea of low pressure combustion flame synthesis is to extend the pressure range to the
pressures used in gas phase synthesis and thus to reduce or avoid the agglomeration. Low
pressure flames have been extensively used by aerosol scientists to study particle formation in
the flame.

A key for the formation of nanoparticles with narrow size distributions is the exact control of the
flame in order to obtain a flat flame front. Under these conditions the thermal history, i.e. time
and temperature, of each particle formed is identical and narrow distributions result. However,
due to the oxidative atmosphere in the flame, this synthesis process is limited to, the formation of
oxides in the reactor zone.

4.12 Gas Condensation Processing (GPC)

In this technique, a metallic or inorganic material, e.g. a sub oxide, is vaporized using
thermal evaporation sources such as crucibles, electron beam evaporation devices or sputtering
sources in an atmosphere of 1-50 m bar He (or another inert gas like Ar, Ne, Kr). Cluster form in
the vicinity of the source by homogenous nucleation in the gas phase and grow by coalescence
and incorporation of atoms from the gas phase.
 The cluster or particle size depends critically on the residence time of the particles in the growth
system and can be influenced by the gas pressure, the kind of inert gas, i.e. He, Ar or Kr, and on the
evaporation vapor pressure of the evaporating material. With increasing gas pressure, vapor pressure
and mass of the inert gas used the average particle size of the nanoparticles increases. Lognormal
size distributions have been found experimentally and have been explained theoretically by the
growth mechanisms of the particles. Even in more complex processes such as the low pressure
combustion flame synthesis where a number of chemical reactions are involved the size
distributions. are determined to be lognormal.

Originally, a rotating cylindrical device- cooled with liquid nitrogen was employed for the
particle collection: the nanoparticles in the size range from 2-50 nm are extracted from the gas flow
by thermophoretic forces and deposited loosely on the surface of the collection device as a powder of
low density and no ,agglomeration. Subsequently, the nanoparticles are removed from the surface of
the cylinder by means of a scraper in the form of a metallic plate. In addition to this cold finger
device several techniques known from aerosol science have now been implemented for the use in gas
condensation systems such as corona discharge, etc. These methods allow for the continuous
operation of the collection device and are better suited for larger scale synthesis of nanopowders.

4.13 Chemical Vapour Condensation (CVC)

As shown schematically in Figure, the evaporative source used in GPC is replaced by a hot wall
reactor in the Chemical Vapour Condensation or the CVC process. Depending on the processing
parameters nucleation of nanoparticles is observed during chemical vapour deposition (CVC) of
thin films and poses a major problem in obtaining good film qualities. The original idea of the novel
CVC process which is schematically shown below where it was intended to adjust the parameter
field during the synthesis in order to suppress Cam formation and enhance homogeneous
nucleation of particles in the gas flow, it found that the residence time of the precursor in the
reactor determines if films or particles are formed. In a certain range of residence time both
particle and film formation can be obtained.

Adjusting the residence time of the precursor molecules by changing the gas flow rate, the
pressure .difference between the precursor delivery system and the main chamber occurs. Then
the temperature of the hot wall reactor results in the fertile production of nanosized particles of
metals and ceramics instead of thin films as in CVD processing, In the simplest form a metal
organic precursor is introduced into the hot zone of the reactor using mass flow controller.
Besides the increased quantities in this continuous process demonstrated that a wider range of
ceramics including nitrides and carbides can be synthesized. Additionally, more complex oxides
such as BaTiO3 or composite structures can be formed as well. Appropriate precursor
compounds can be readily found in the CVD literature. The extension to production of
nanoparticles requires the determination of a modified parameter field in order to promote
particle formation instead of film formation. In addition to. the formation of single phase
nanoparticles by CVC of a single precursor the reactor allows the synthesis of

I. Mixtures of nanoparticles of two phases or doped nanoparticles by supplying two

precursors at the front end of the reactor, and s.

2. Coated nanoparticles, i.e., n-Zr02 coated with n-A1203 or vice versa, by supplying a
second precursor at a second stage of the reactor. In this case nanoparticles which have
been formed by homogeneous nucleation are coated by heterogeneous nucleation in a
second stage of the reactor.

Because CVC processing is continuous, the production capabilities are much larger. Quantities in
excess of 20 g/hr have been readily produced with a small scale laboratory reactor. A further
expansion can be envisaged by simply enlarging the diameter of the hot wall reactor and the
mass flow through the reactor
4.14 Optical Microscopy
It is a type of microscope which uses visible light and a system of lenses to magnify
images of small samples.
Image from an optical microscope can be captured by normal light sensitive cameras to
generate a micrograph.
The function is to create a magnified image of a specimen consists of three basic
functions of obtaining a clear sharp image changing a magnification and bringing to focus.

It create a magnified image by combing an objective lends and making an inverted real
image, and magnifies the image further more with an eyepiece to allow the user to observe it
by naked eye.

Applications

 Microelectronics
 Nanophysics
 Biotechnology
 Medical diagnosis
Advantages
 Medium cost, simple devices
 Fast and adaptable to all kinds of sample systems
 Easy to be integrated with digital camera systems for data storage and analysis
 Disadvantage

 High level of magnification cannot be achieved

 Low resolution
4.15 Scanning Electron Microscope (SEM)
A Scanning Electron Microscope (SEM) is a powerful magnification tool that utilizes
focused beams of electrons to obtain information. The high-resolution, three-dimensional
images produced by SEMs provide topographical, morphological and compositional
information makes them invaluable in a variety of science and industry applications.

SEM Working principle and Imaging

 A Scanning Electron Microscope provides details surface information by tracing a

sample in a raster pattern with an electron beam.
 The process begin's with an electron, gun generating a beam of energetic electrons
down the column and onto a series of electromagnetic lenses. These lenses are
tubes, wrapped in coil and referred to as solenoids.
 The coils are adjusted to focus the incident electron beam onto the. sample; these
adjustments cause fluctuations in the voltage, increasing/decreasing the speed_ in
which the electrons come in contact with the specimen surface.
 Controlled via computer, the SEM operator can adjust the - beam to control
Magnification as well as determine the surface area to be scanned.
  The beam is focused onto the stage, where a solid sample is placed. Most samples
require some preparation before being placed in the vacuum chamber. Of the variety
of different preparation processes, the two most commonly used prior to SEM
analysis are sputter coating for non-conductive samples and dehydration of most
biological specimens.
 In addition, all samples need to be able to handle the low pressure inside the vacuum
chamber.
 The interaction between the incident electrons and the surface of the sample is _
determined by the acceleration rate of incident electrons, which carry significant
amounts of kinetic energy before focused onto the sample.

 When the incident electrons come in contact with the sample, energetic electrons
released from the surface of the sample. The scatter patterns made by the interaction
yields information on-- size shape, texture and composition of the sample.
 A variety of detectors are used to attract different types of scattered electrons, including
secondary and backscattered electrons as well as x-rays.
 Backscatter electrons are incidental electrons reflected backwards; images provide
composition data related to element and compound detection.
 Diffracted backscatter electrons determine crystalline structures as well as the
orientation of minerals and micro-fabrics. X-rays, emitted from beneath the sample
surface, can provide element and mineral information.
 SEM produces black and white, three-dimensional images. Image magnification can be up
to 10 nanometers and, although it is not as powerful as its TEM counterpart, the intense
interactions that take place on the surface of the specimen provide a greater depth view,
higher-resolution and, ultimately, a more detailed surface picture.
Applications

 SEMs have a variety of applications in a number of scientific and industry-related

fields, especially where characterizations of solid materials is beneficial.
 In addition to topographical, morphological and compositional information, a
Scanning. Electron Microscope can detect and Analyze surface fractures, provide
information in microstructures examine surface contaminations, reveal spatial
variations in chemical compositions, provide qualitative chemical analyses and identify
crystalline structures.
 SEMs can be as essential research-: tool in fields such as life science, biology, gemology,
medical and forensic science metallurgy.
  In addition, SEMs have practical industrial and technological applications such as
semiconductor inspection, production line of miniscule products and assembly of
microchips for computers.
 SEMs equipped with diffracted backscattered electron detectors can be used to
examine micro fabric and crystallographic orientation in many materials
Advantages
 Advantages of a Scanning Electron Microscope include its wide-array of applications,
the detailed three-dimensional and topographical imaging and the versatile
information garnered from different detectors.
 SEMs are also easy to operate with the proper training and advances in computer
technology and associated software make operation user-friendly.
 It is important to note that these applications are a very small subset of the scientific
and industrial applications that exist for this instrumentation. Most SEM's are
comparatively easy to operate, with user-friendly "intuitive" interfaces. Many
applications require minimal sample preparation.
Limitations

 The disadvantages of a Scanning Electron Microscope start with the size and cost.
 SEMs are expensive, large and must be housed in an area free of any possible electric, magnetic
or vibration interference.
 'Maintenance involves keeping a steady voltage, currents to electromagnetic and
circulation of cool water.
 Special training is required to operate an SEM as well as
 . ■

prepare samples.
 The preparation of samples can result in artifacts. The negative impact can h e minimized with
knowledgeable experience researchers being able to identify artifacts from actual data as well
as preparation skill. There is no absolute way to eliminate or identify all potential artifacts.
 In addition, SEMs are limited to solid, inorganic samples small enough to fit inside the
vacuum chamber that can handle moderate vacuum pressure.
 Finally, SEMs carry a small risk of radiation exposure associated with the electrons that
scatter from beneath the sample surface.
4.16 Transmission Electron Microscopy
A Transmission Electron Microscope (TEM) utilizes energetic electrons to provide
morphologic, compositional and crystallographic information on samples.
At a maximum potential magnification of 1 nanometer, TEMs are the most powerful
microscopes. TEMs produce high-resolution, two-dimensional images, allowing for a wide
range of educational, science and industry applications.

A Transmission Electron Microscope produces a high-resolution, black and which

images from the interaction that takes place between prepared samples and energetic
electrons in the vacuum chamber.

 Air needs to be pumped out of the vacuum chamber, creating a space where electrons
are able to move.
 The electrons then pass through multiple electromagnetic lenses. These solenoids are
tubes with coil wrapped around them:
  The beam passes through the solenoids, down the column, makes contact with the
screen where the electrons are converted to light and form an image.
 The image can be manipulated by adjusting the voltage of the gun to accelerate or
decrease the speed of electrons as well as changing the electromagnetic wavelength
via the solenoids.
 The coils focus images onto a screen or photographic plate.
 During transmission, the speed of electrons directly correlates to electron
wavelength; the faster electrons move, the shofter wavelength and the greater the
quality and detail of the image.
 The lighter areas of the image represent the places where a greater number of electrons
were able to pass through the sample and the darker areas reflect the dense areas of the
object.
 These differences provide information on -the structure, texture, shape and size of the
sample.
 To obtain a TEM analysis, samples need to have- certain properties. They need to be
sliced thin enough for electrons to pass through, a property known as electron
transparency.
 Samples need to be able to withstand the vacuum chamber and often require special
preparation before viewing.

 Types of preparation include dehydration, sputter coating of non-conductive

materials, cir fixation, sectioning and staining.

TEM Applications
 A Transmission Electron Microscope is ideal for a number of different fields such as
life sciences, nanotechnology, medical, biological and material research, forensic
analysis, gemology and metallurgy as well as industry and education.
 TEMs provide topographical, morphological, compositional and crystalline
information.
 The images allow, researchers to view samples on a molecular level, making it
possible to analyze structure and texture.
 This information is useful in the study of crystals and metals, but also has industrial
applications.
  Technology companies use TEMs to identify flaws, fractures and damages to
micro sized objects; this data can help fix problems and/or help to make a more durable
efficient product.
Advantages
A Transmission Electron Microscope is an impressive instrument with a number of
advantages such as:

 TEMs offer the most powerful magnification, potentially over one million
times or more
 TEMs have a wide-range of applications and can be utilized in a variety of
different scientific, educational and industrial fields
 TEMs provide information on element and compound structure a Images are high-
quality and detailed
 TEMs are able to yield information of surface features, shape, size and structure
 They are easy to operate with proper training
Disadvantages
 TEMs are large and very expensive
 Laborious sample preparation

 Potential artifacts from sample preparation

 Operation and analysis requites special training--
 Samples are limited to those that are electron transparent, able to tolerate the
vacuum chamber and small enough to fit in the chamber

 TEMs require special housing and maintenance

 Images are black and white
4.17 X-ray powder diffraction (XRD)
X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of a crystalline material and can provide information on unit cell dimensions. The
analyzed material is finely ground, homogenized, and average bulk composition is determined
Max von Laue, in 1912, discovered that crystalline substances act as three-dimensional diffraction
gratings for X-ray wavelengths similar, to the spacing of planes in a crystal lattice. X-ray diffraction
is now a common technique for the study of crystal structures and atomic spacing.
Essential Parts of the Diffractometer

 X-ray Tube: the source of X Rays

 Incident-beam optics: condition the X-ray beam before it hits the sample
 The goniometer: the platform that holds and moves the sample, optics, detector, and/ or tube
 The sample & sample holder
 Receiving-side optics: condition the X-ray beam after it has encountered the sample
 Detector: count the number of X Rays scattered by the sample
Principle of Working

 X-ray diffraction is based on constructive interference of monochromatic X-rays and a

crystalline sample. These X-rays are generated by a cathode ray tube, filtered to produce
monochromatic radiation, collimated to concentrate, and directed toward the sample. The
interaction of the incident rays with the sample produces constructive interference, when
conditions satisfy Bragg's Law (n=2dsin). This law relates the wavelength of
electromagnetic radiation to the diffraction angle and the lattice spacing in a crystalline
sample.
 These diffracted X-rays are then detected, processed and counted by scanning the sample
through a range of 2angles, all possible diffraction directions of the lattice should be
attained due to the random orientation of the powdered material.
 Conversion of the diffraction peaks to d-spacing (the distance between planes of atoms
that give rise to diffraction peaks.) allows identification of the mineral because each
 mineral has a set of unique d-spacing. Typically, this is achieved by comparison of d-
spacing with standard reference patterns.
 All diffraction methods are based on generation of X-rays in an X-ray tube. These X-
rays are directed at the sample, and the diffracted rays are collected. A key component
of all diffraction is the angle between the incident and diffracted rays. Powder and
single crystal diffraction vary in instrumentation beyond this
Applications

X-ray powder diffraction is most widely used for the identification of unknown crystalline
materials. (e.g. minerals, inorganic compounds). Determination of unknown solids is critical to
studies in geology, environmental science, material science, engineering and biology

Other applications include:

 Characterization of crystalline materials

 Identification of fine-grained minerals such as clays and mixed layer clays that are
difficult to determine optically
 Determination of unit cell dimensions
 Measurement of sample purity
With specialized techniques, XRD can be used to:

 Determine crystal structures using Rietveld refinement

 Determine of modal amounts of minerals (quantitative analysis)
 Characterize thin films samples by
 Determining lattice mismatch between film and substrate and to inferring
stress and strain
 Determining dislocation density and quality of the film by rocking curve
measurements
 Measuring superlattices in multilayered epitaxial structures
 Determining the thickness, roughness and density of the film- using
glancing incidence X-ray reflectivity measurements
 Make textural measurements, such as the orientation of grains, in a polycrystalline
sample

Advantages
 Powerful and rapid (< 20 min) technique for identification of an unknown mineral
 In most cases, it provides an unambiguous mineral determination
  Minimal sample preparation is required
 XRD units are widely available
 Data interpretation is relatively straight forward

Limitations
 Homogeneous and single phase material is best for identification of an unknown
 Must have access to a standard reference file of inorganic compounds (d-spacing, hkls)
 Requires tenths of a gram of material which must be ground into a powder
 For mixed materials, detection limit is 2% of sample
 For unit cell determinations, indexing of patterns for non-isometric crystal systems
is complicated
 Peak overlay may occur and worsens for high angle 'reflections'

4.18 Scanning Probe Microscope (SPM)

The scanning probe microscope gives researchers imaging tools for the future as these
specialized microscopes provide high image magnification for observation of three dimensional-
shaped specimens. This renders not only enhanced images but specimen properties, response and
reaction or non-action when specimens are stimulated or touched.
Rohrer and Binning were awarded the Nobel Prize in Physics in 1986 for their work
bringing scanning probe microscope technology from the drawing board to the laboratory,
Scanning probe technology at the microscopic level is found in both academic and industrial
laboratories today including physics biology, and chemistry and is now standard analysis tools
for research and development.

SPM Technology

The ability to observe a. specimen in three dimensions, in real time plus manipulating,
specimens through the application of an electrical current with a physical interaction using
the tip of the probe. Viewing a specimen in a variety of environments is why scanning probe
microscopes, SPMs, are so widely used.

Specimens can now be viewed at the nanometer level and instead of light waves or
electrons, SPMs use a delicate probe to scan a specimen's surface eliminating many of the
restrictions that light waves -or electron imaging has.
Working Principle

 SPMs are a very powerful family of microscopes, sometimes with. a resolution of

less than a nanometer. (A nanometer is a billionth of a meter.)
 An SPMs has a probe tip mounted on the end of a cantilever. The tip can be as sharp
as a single atom. It can be moved precisely and accurately back and forth across the
surface, even atom by atom.
 When the tip is near the sample surface, the cantilever is deflected by a force. SPMs
can measure deflections caused by many kinds of forces, including mechanical
contact, electrostatic forces, magnetic forces, chemical bonding van der Waals
forces, and capillary forces.
 The distance of the deflection is measured by a laser that is reflected off the top of the
cantilever and into an array of photodiodes (similar to the devices used in digital
cameras).
 SPMs can detect differences in height that are a fraction of a nanometers diameter
of a single atom. The tip is moved across the sample many times. this is why these are called
"scanning" microscopes
 A computer combines the data to create an image. The images are inherently colorless
because they are measuring properties other than the reflection of light. However, the
images are often colorized, with different colors representing different properties (for
example, height) along the surface.
 Scientists use SPMs in a number of different ways, depending on the information
they're trying to gather from a sample. The two primary modes are contact mode and
tapping mode.
  In contact mode, the force between the tip and the surface is kept constant. This allows
a scientist to quickly image a surface.
 In tapping mode, the cantilever oscillates, intermittently touching the surface. Tapping
mode is especially useful when a scientist is imaging a soft surface.
There are several types of SPMs. Atomic force microscopes (AFMs) measure the
electrostatic forces between the cantilever tip and the sample. Magnetic force microscopes
(MFMs) measure magnetic forces. And scanning tunneling microscopes (STMs) measure the
electrical current flowing between the cantilever-tip and the sample.

Advantages of SPM Technology

 It provides larger variety of specimen observation environments using the same
microscope and specimen reducing the time required to prepare and study specimens.
 Specialized probes, improvements and modifications-to scanning probe instruments
continues to provide faster, more efficient and revealing specimen mages with minor
effort and modification.
Disadvantages of SPM Technology

 Here images are produced in black and white or grayscale which can in some
circumstances exaggerate a specimen's actual shape or size.

 Computers are used to compensate for these exaggerations and produce real time
color images that provide researchers with real time information including
interactions within cellular structures, harmonic responses and magnetic energy.
4.19 Atomic Force Microscope (AFM)

Binnig, Quate, and Gerber invented the AFM in 1985. Their original AFM consisted of a
diamond shard attached to a strip of gold foil. The diamond tip contacted the surface directly,
with the interatomic van der Waals forces providing the interaction mechanism. Detection of
the cantilever's vertical movement was done with a second tip — an STM placed above the
cantilever.

Working Principle

 Sharp tip is raster-scanned over a surface using a feedback loop to adjust parameters
needed to image a surface. Atomic Force Microscope does not need a conducting
sample, Instead of using the quantum mechanical effect of tunneling atomic forces
are used to map the tip-sample interaction.
 Often referred to as scanning probe microscopy (SPM), there are Atomic- Force
Microscopy techniques for almost any measurable force interaction — Van der Waals,
 electrical, magnetic, thermal. For some of the more specialized techniques, modified tips
and software adjustments are needed.

In addition to Angstrom-level positioning and feedback loop control, there are 2 components
typically included in Atomic Force Microscopy: Deflection and Force Measurement.

AFM Probe Deflection

Traditionally most Atomic Force Microscopes use a laser beam deflection system where a laser
is reflected from the back of the reflective AFM lever and onto a position-sensitive detector.
AFM tips and cantilevers are typically micro-fabricated from Si or Si3N4

Measuring Forces
Atomic Force Microscope relies on the forces between the tip and sample, these forces impact
AFM imaging. The force is not measured directly, but calculated by measuring the deflection of the
lever, knowing the stiffness of the cantilever.
Hooke's law gives:
F= -kz
Where F is the force, k is the stiffness of the lever, and z is the distance the lever is bent.
Feedback Loop for Atomic Force Microscopy

Atomic Force Microscopy has a feedback loop using the laser deflection to control the force
and tip position. As shown, a laser is reflected from the back of a cantilever that includes the AFM
tip. As the tip interacts with the surface, the laser position on the photo detector is used in the
feedback loop to track the surface for imaging and measuring.

Limitations
 AFM can only image a maximum height on the order of 10-20 micrometers and a
maximum scanning area of about 150 x150 micrometers.
 The scanning speed of an AFM is also a limitation.
 Highly Dependent on AFM probes.
Applications
 It can image for biological processes, such as imaging of proteins.
 Any sample like ceramic material, human cells or individual molecules of DNA,
Dispersion of metallic Nanoparticles can be imaged

4.20 Electron Probe Micro Analyzer

An electron probe micro-analyzer is a micro beam instrument used primarily for the in situ non-
destructive chemical analysis of minute solid samples. It is also informally called an electron
microprobe, or just probe. It is fundamentally the same as an SEM, with the added capability of
chemical analysis. The primary importance of an Electron probe micro-analyzer is the ability to acquire
precise, quantitative elemental analyses at very small "spot" sizes (as little as 1.2 microns), primarily by
wavelength-dispersive spectroscopy (WDS).

Electron probe micro-analyzer works by bombarding a micro-volume of a sample with a

focused electron beam (typical energy = 5-30 keV) and collecting the X-ray photons, thereby
emitted by the various elemental species. As the Wavelengths of these X-rays are characteristic
of the emitting species, the sample composition can be easily identified by recording Wavelength
Dispersive Spectroscope. Wavelength Dispersive spectrometers operate based on Bragg's law
and use various moveable, shaped mono crystals as mono chromators.

 Electron probe .micro-analyzer is a fully qualitative and quantitative method of non-

destructive elemental analysis of micron-sized volumes at the surface of materials, with
sensitivity at the level of ppm.
 It is fully compatible with routine analysis sessions, with easy and direct interpretation
of the results.
 Determination of thickness and elemental composition from urn to mm thick layers in
stratified materials is possible.

Applications

 Quantitative Electron probe micro-analyzer analysis is the most commonly used method
for chemical analysis of geological materials at small scales.
  It chooses where individual phases need to be analyzed, or where the material is of
small size
 It is also widely used for analysis of synthetic materials such as, optical wafers, thin
films, microcircuits, semi-conductors,- and. superconducting ceramics.
Advantages
 Equipped with a wide range of crystal spectrometers that enable quantitative
chemical analysis.
 An electron probe is the primary tool for chemical analysis of solid materials at
small spatial scales hence the user can analyze even minute single phases in a material.
 Electron probes- commonly have an array of imaging detectors that allow the
investigator to generate images of the surface and internal compositional structures that
help with analyses.
Limitations

 Unable to detect the lightest elements such as Hydrogen, Helium, Lithium etc.,
 Some elements generate x-rays with overlapping peak positions..
 Probe analysis cannot distinguish between the different valence states of Fe, so the
ferric/ferrous ratio cannot be determined