Basic Concepts of Nanomaterials

Chapter 2 Concept of Nanotechnology
Chapter 2
Concept of Nanotechnology
2.0. Basic concept of Nanotechnology
The nanomaterials are cornerstones of nanoscience and nanotechnology. The
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.
Fig. 2.1: Evolution of science and technology and the future
It is already having a significant commercial impact, which will assuredly increase
`in the future (Fig.2.1). Imagine being able to observe the motion of red blood cell as
it moves through our vain, or being able to watch as a type of white blood cell
41 Synthesis and Characterization of Nonlinear Optical Nanoparticles and their
application …. B.R.Chavan
(Called A “T-cell”) destroys an invading microbe by engulfing it. What would it be
like to observe the vibration of molecules as the temperature rises in a pan of water?
To observe sodium and chlorine atoms as they get close enough to actually transfer
electrons and form a salt crystal? New scientific look developed and improved over
the last few decades, make such observations increasingly feasible. These are
example of the effort to view measure and even manipulate materials at the
molecular or atomic scale- the major focus of nanotechnology [1].
Thenanotechnology is defined as study and use of structure between 1 nanometer
and 100 naometers in size. Thenanotechnology is concerned with materials and
systems whose structure component exhibit novel and significantly improved
physical, chemical, and biological properties, phenomena and process because of
their nanoscale size. The structuralfeatures in the range of ~ 10-9 to 10-7 m i.e. 1 to
100 nanometer determine important changes as compared to the behavior of isolated
molecules (1nanometer) or of bulk materials. More generally nanotechnology can be
defined as any technique able to work at a submicron scale [2]. It is an
interdisciplinary science involving physics, chemistry, biology, engineering
materials science, computer science etc.
The past few years, a little word with big potential has been rapidly putting itself
into the world’s consciousness. That word is “Nano”. It has conjured up speculation
about a seismic shift in almost every aspect of science and engineering with
implications for ethics, economics, international relations, day to day life, and even
humanity’s conception of its place in the universe. Alarmists see it as the next step
in biological and chemical warfare or in extreme cases, as the opportunity for people
to create the species that will ultimately replace humanity.Nano is big business. The
National science foundation predicts that nano-related goods and services could be a

$ trillion market by 2015, marking it not only one of the fastest-growing industries
in history but also larger than the combined telecommunications and information
technology industries at the beginning of the technology companies like HP,NEC
and IBM all of whom have developed massive research capabilities for studying and
developing nano devices. Despite this impressive lineup, well-recognized
abbreviations are not the only organizations that can play. A host of start-ups and
smaller concerns are jumping into the nano game as well. Specialty venture capital
funds, trade shows, and periodicals are emerging to support them.There is even a
stock index of public companies working on nano.
2.1. Nanomaterials
The nanoscale materials are defined as a set of substances where at least one
dimension is less than approximately 100 nanometers. The nanomaterials are of
interest because at this scale they posses unique optical, magnetic, electrical, and
other properties emerge. These emergent properties have the potential for great
impacts in electronics, medicine, and other fields.
Some nanomaterials occur naturally but for particular interest those are Engineered
Nanomaterials(EN), which are designed for and being used in many commercial
products and processes. They can be found in things as sunscreens, cosmetics,
sporting goods, stain-resistant clothing, tires, electronics, as well as many other
everyday items and are used in medicine for purposes of diagnosis, imaging, and
drug delivery. Engineered nanomaterials are resources designed at the molecular
(nanometre) level to take advantage of their small size and novel properties which
are generally not seen in their conventional, bulk counterparts. The two main
reasons why materials at the nano scale can have different properties are increased
relative surface area and new quantum effects. The nanomaterials have a much

greater surface area to volume ratio than their conventional forms, which can lead to
greater chemical reactivity and affect their strength. Also at the nano scale, quantum
effects can become much more important in determining the materials properties and
characteristics, leading to novel optical, electrical, and magnetic behaviors.
The nanomaterials are already in commercial use, with some having been available
for several years or decades. The range of commercial products available today is
very broad, including stain-resistant and wrinkle-free textiles, cosmetics, sunscreens,
electronics, paints, and varnishes. The nanocoatings and nanocomposites are usedin
diverse consumer products, such as windows, sports equipment, bicycles, and
automobiles. There are novel UV-blocking coatings on glass bottles which protect
beverages from damage by sunlight, and longer-lasting tennis balls using butyl
rubber/ nano-clay composites. Nanoscale titanium dioxideis used in cosmetics, sun-
block creams, and self-cleaning windows and nanoscale silica is being used as filler
in a range of products, including cosmetics and dental fillings.
2.2.Nanotechnology in Nature
There are lots of nano materials in nature. Nature processes such as sea spray and
erosion can also create nanoparticles. Nature is expert in fabricating organic
structures at the nano scale. Best and most known example of a self cleaning surface
is the socalled lotus effect. Lotus leaves in particular have the unique ability
tohydrophobic particles. When water contacts these particles it does not wet the
leaves. Instead it simply rolls off, taking with it any dirt in its path. The human body
uses natural nanoscale materials such as proteins and other molecules to control the
body’s many systems and processes. For hemoglobin which carries oxygen through
the bloodstream is 5nm in diameter (4).

2.3.Significant impact: Nanoscience and Nanotechnology
The nanotechnology literally means any technology performed on a nanoscale
that has applications in the real world. The nanotechnology encompasses the
production and application of physical, chemical, and biological systems at scales
ranging from individual atoms or molecules to submicron dimensions as well as the
integration of the resulting nanostructures into larger systems. The nanotechnology
is likely to have a profound impact on our economy and society in the early twenty-
first century, comparable to that of semiconductor technology, information
technology or cellular and molecular biology. Science and technology research in
nanotechnology promises breakthroughs in such areas as materials and
manufacturing,medicine and healthcare, energy, biotechnology, information
technology and national security. It is widely felt that nanotechnology will be the
next industrial revolution.
Nanometer-scale features are mainly built up from their elemental constituents.
Chemical synthesis – the spontaneous self-assembly of molecular clusters
(molecular self-assembly) from simple reagents in solution or biological molecules
(e.g., DNA) are used as building blocks for the production of three-dimensional
nanostructures, including quantum dots (nanocrystals) of arbitrary diameter (about
10 to 105 atoms). A variety of vacuum deposition and nonequilibrium plasma
chemistry techniques are used to produce layered nanocomposites and nanotubes.
Atomically controlled structures are produced using molecular beam epitaxy and
organo-metallic vapor phase epitaxy. Micro and nanosystem components are
fabricated using top-down lithographic and nonlithographic fabrication techniques
and range in size from micro to nanometers. Continued improvements in lithography
for use in the production of nanocomponents have resulted in line widths as small as

10 nanometers in experimental prototypes. The nanotechnology field, in addition to
the fabrication of nanosystems provides the impetus to development of experimental
and computational tools. The micro and nanosystems include micro/nano
electromechanical systems (MEMS/NEMS) (e.g., sensors, actuators, and
miniaturized systems comprising sensing, processing and/or actuating functions),
micromechatronics, optoelectronics, microfluidics and systems integration. These
systems can sense, control and activate on the micro/nanoscale and function
individually or in arrays to generate effects on the macroscale. Due to the enabling
nature of these systems and because of the significant impact they can have on the
commercial and defense applications, venture capitalists, industry, as well as the
federal government have taken a special interest in nurturing growth in this field.
Micro and nanosystems are likely to be the next logical step in the “silicon
revolution.” [10-19]
Science and technology continue to move forward in making the fabrication of
micro/nanodevices and systems possible for a variety of industrial, consumer, and
biomedical applications. A range of MEMS devices have been produced, some of
which are commercially used [12-20]. A variety of sensors are used in industrial,
consumer, and biomedical applications. Various microstructures or micro
components are used in micro instruments and other industrial applications such as
micro mirror arrays. The largest “killer” industrial applications are accelerometers
(about 85 million units in 2002) and digital micro mirror devices (about $ 400
million in sales in 2001). Integrated capacitive type, silicon accelerometers have
been used in airbag deployment in automobiles since 1991 [21- 25]. Other major
industrial applications include pressure sensors, inkjet printer heads, and optical
switches. Silicon-based piezoresistive pressure sensors for manifold absolute

pressure sensing for engines were launched in 1991 by Nova-Sensor and their
annual sales were about 25 million units in 2002. Annual sales of inkjet printer
heads with microscale functional components were about 400 million units in 2002.
Capacitive pressure sensors for tire pressure measurements were launched by
Motorola. Other applications of MEMS devices include chemical sensors, gas
sensors, infrareddetectors, and focal plane arrays for earth observations, space
science and missile defense applications, pico-satellites for space applications, and
many hydraulic, pneumatic, and other consumer products. MEMS devices are also
being pursued in magnetic storage systems [25], wherethey are being developed for
super-compact and ultrahigh recording-density magnetic disk drives. Several
integrated head/suspension micro devices have been fabricated for contact recording
applications [28-19]. High-bandwidth, servo-controlled micro actuators have been
fabricated for ultrahigh track-density applications which serve as the fine-position
control element of a two-stage, coarse/fine servo system coupled with a
conventional actuator [30–31]. Millimeter-sized wobble motors and actuators for tip
based recording schemes have also been fabricated [32].
BIOMEMS are increasingly used in commercial and defense applications.[33–37].
Other BIOMEMS applications include minimal invasive surgery such as endoscopic
surgery, laser angioplasty and microscopic surgery. Implantable artificial organs can
also be produced Micro-instruments and micro-manipulators are used to move,
position, probe, pattern and characterize nanoscale objects and nanoscale features.
Miniaturized analytical equipment includes gas chromatography and mass
spectrometry. Other instruments include micro-STM, where STM stands for
scanning tunneling microscope. Examples of NEMS include nanocomponents,
nanodevices, nanosystems and nanomaterials, such as micro cantilever with

integrated sharp nanotips for STM and atomic force microscopy (AFM), AFM array
data storage, AFM tips for nanolithography, dip-pen nanolithography for printing
molecules, biological (DNA) motors, molecular gears, molecularly thick films (e.g.,
in giant magneto-resistive or GMR heads and magnetic media), nanoparticles, (e.g.,
nanomagnetic particles in magnetic media), nanowires, carbon nanotubes, quantum
wires (QWRs), quantum boxes (QBs) and quantum transistors [38-42]. BIONEMS
include nanobiosensors a microarray of silicon nanowires, roughly a few nm in size,
to selectively bind and detect even a single biological molecule, such as DNA or
protein, by using nanoelectronics to detect the slight electrical charge caused by such
binding or a microarray of carbon nanotubes to electrically detect glucose,
implantable drug-delivery devices e.g., micro/nanoparticles with drug molecules
encapsulated in functionized shells for a site-specific targeting application and a
silicon capsule with a nanoporous membrane filled with drugs for long term
delivery, nanodevices for sequencing single molecules of DNA in the human
genome project, cellular growth using carbon nanotubes for spinal cord repair,
nanotubes for nanostructured materials for various applications, such as spinal
fusion devices, organ growth and growth of artificial tissues using nanofibers. The
nanoelectronics can be used to build computer memory, using individual molecules
or nanotubes to store bits of information, as well as molecular switches, molecular or
nanotube transistors, nanotube flat-panel displays, nanotube integrated circuits, fast
logic gates, switches, nanoscopic lasers and nanotubes as electrodes in fuel cells.
2.4. Classification of Nanomaterials
The nanomaterials have extremely small size which having at least one
dimension 100 nm or less. The nanomaterials can be nanoscale in one dimension
(eg. surface films), twodimensions (eg. strands or fibers), 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(Fig2.2). Nanomaterials have
applications in the field of nano technology and displays different physical chemical
characteristics from normal chemicals (i.e., silver nano, carbon nanotube, fullerene,
photo catalyst, carbon nano, silica). According to Siegel nanostructured materials are
classified as zero dimensional,one dimensional, two dimensional, three dimensional
nanostructures.
Fig.2.2: Classification of Nanomaterials (a) 0D spheres and clusters, (b) 1D
nanofibers,wires, and rods, (c) 2D films, plates, and networks, (d) 3D
nanomaterials.
The nanomaterials are materials which are characterized by an ultra fine grain size
(< 50 nm) or by a dimensionality limited to 50 nm. The anomaterials can be created
with various modulation dimensionalities as defined by Richard W. Siegel: zero
(atomic clusters, filaments and cluster assemblies), one (multilayers), two (ultrafine-
grained over layers or buried layers), and three (nanophase materials consisting of
equaled nanometer sized grains) as shown in the above figure 2.2
There are a large number of techniques available to synthesize different types of
films etc. Some of the already existing conventional techniques to synthesize

different types of materials are optimized to get novel nanomaterials and some new
techniques are developed. Nanotechnology is an interdisciplinary subject. There are
therefore various physical, chemical, biological and hybrid techniques available to
synthesisnanomaterials. It can be seen in Fig. 2.3.Synthesis Techniques of
Nanomaterial.
Fig. 2.3: Synthesis Techniques of Nanomaterials
2.5. ImportanceofNanomaterials
These materials have created a high interest in recent years by virtue of their unusual
below:
1) Nanophase ceramics are of particular interest because they are more ductile
at elevated temperatures as compared to the coarse-grained ceramics.

2) Nanostructured semiconductors are known to show various non-linear
optical properties. Semiconductor Q-particles also show quantum
confinement effects which may lead to special properties, like the
luminescence in silicon powders and silicon germanium quantum dots as
infrared optoelectronic devices. Nanostructured semiconductors are used as
window layers in solar cells.
3) Nanosized metallic powders have been used for the production of gas tight
materials, dense parts, and porous coatings. Cold welding properties
combined with the ductility make them suitable for metal-metal bonding
especially in the electronic industry.
4) Single nanosized magnetic particles are mono-domains and one expects that
also in magnetic nanophase materials the grains correspond with domains,
while boundaries on the contrary to disordered walls. Very small particles
have special atomic structures with discrete electronic states which give rise
to special properties in addition to the superparamagnetism behavior.
Magnetic nanocomposites have been used for mechanical force transfer
(ferrofluids), for high density information storage and magnetic refrigeration.
5) Nanostructured metal clusters and colloids of mono or plurimetallic
composition have a special impact in catalytic applications. They may serve
as precursors for new type of heterogeneous catalysts (Cortex-catalysts) and
have been shown to offersubstantial advantages concerning activity,
selectivity, and lifetime in chemicaltransformations and electro catalysis
(fuel cells).
6) Nanostructured metal-oxide thin films are receiving a growing attention for
the realization of gas sensors (NOx, CO, CO2, CH4, and aromatic

hydrocarbons) with enhanced sensitivity and selectivity. Nanostructured
metal-oxide (MnO2) finds application for rechargeable batteries for cars or
consumer goods. Nanocrystalline silicon films for highly transparent contacts
in thin film solar cell and nano-structured titanium oxide porous films for its
high transmission and significant surface area enhancement leading to strong
absorption in dye sensitized solar cells.
7) Polymer based composites with a high content of inorganic particles leading
to a high dielectric constant are interesting materials for photonic band gap
structure.
2.6. Synthesis Methods
The synthesis of nanomaterials can perform by physical methods and
Chemical methods.
2.6.1. Physical methods
1. High Energy Ball Milling
2. Melt Mixing
2.6.2.Physical methods based on evaporation
1. Physical vapor deposition with consolidation
2. Ionized cluster beam deposition
3. Laser vaporization
4. Laser pyrolysis
2.6.3.Sputter Deposition
1. DC sputtering
2. RF sputtering
3. Magnetron sputtering
4. ECR plasma deposition

2.6.4.Chemical Vapor deposition
1. Electric arc deposition
2. Ion beam techniques
3. Molecular beam epitaxy
2.7.Chemical methods
Advantages of Chemical Synthesis
1. Simple techniques
2. Inexpensive, less instrumentation compared to any physical methods
3. Low temperature (<350 degree C) synthesis
4. Doping of foreign atoms possible during synthesis
5. Large quantities of the materials can be contained
6. Variety of sizes and shapes are possible
7. Materials are obtained in the form of liquid but can be converted into
dry powder of thin films quite easily
8. Self assembly or patterning is possible.
In some cases nanomaterials are obtained as colloidal particles in solutions
which can filtered and dried to obtained powder. In some methods we can obtain
thin films or nanoporous materials by electrode position, etching etc., as in many
cases nanoparticles synthesized by chemical method form colloids.
2.7.1.Colloids and Colloids in solution
The colloids are known since very long time. A class of materials in which
two or more phases (Solid, liquid or gas) of same or different materials co-exist with
at least one dimension less than a micrometer is known as colloids. Colloids may be
particles plates or fibers. Different types of colloids, spherical, lamellar, fibers etc.

Nanomaterials are a subclass of colloids in which one of the dimensions of colloids
is in about 1 to 100 nanometer range. There are several examples

mples around us having
different
ifferent combinations of phases in the form of colloids like liquid in gas (fog),
liquid in liquid (fat droplets in milk), solid in liquid (tooth paste), Solid in solid
(tinted glass), gas in liquid (foam) etc. There can be multiple exiting colloids like
water and oil bubbles in porous mineral rocks. Organic and inorganic materials can
be dispersed in into each other to form colloids. Several

Se examples exist even of bio-
bio
colloids. Blood and bones are good examples of bio-colloids.

bio colloids. Blood has corpuscles
dispersed in serum and bone has colloids of calcium phosphate embedded in
collagen. Colloids may even form networks. For examples aero gel is network of
colloids particles, pores of which are filled with air.
2.7.2. Interactions of Colloids and Medium
The colloids
olloids are particles with large surface to volume ratio. Correspondingly
there are a large number of atoms/molecules on the surface of a colloidal particle,
which do not have as many neighbors as those for an atom/ molecule inside the
interior.
Fig.2.4: Brownian motion of colloidal particles

Therefore atoms on the surface are in a highly reactive state which easily interacts to
form bigger particles are tend to coagulate. It is thus necessary to understand the
stability of collides i.e. howcollides dispersed in a medium can remain as separated
particles.
In general there are number of interactions involved. For the sake of
understanding these interactions we consider the inorganic spherical colloids of
equal size, dispersed in a liquid medium. When fine particles are dispersed in a
liquid medium it is known that they undergo what is known as Brownian motion. If
we are able to tag a particle in the liquid as depicted Fig 2.4
It would appear as if it is making a random motion. All other particles
also execute random motion, hitting each other and changing their direction of
motion in the liquid. Distance travelled between successive collisions is random too.
An average distance travelled by a colloidal particle can be found as

∆ = ∆ -------------------------------- (2.1)
Where ∆ -distance travelled by a particle from its original position in time ∆ , k
– Boltzamn constant, T- Temperature of liquid, r- particle radius and n –Viscosity
of the liqud .
Interactions of such constantly and randomly moving particles with each other and
with liquid in general would be quite complex. Consider for example the Vander
Waal’s interaction between two atoms or molecules. There are two parts in the
interaction viz. attractive and repulsive parts given by equation 2.2 irrespective of
whether there exist permanent dipoles or not. The interaction is given as

= − ---------------------------------(2.2)
Where interaction energy, A, B constants and R distance between two
particles. Here the first term is repulsive interaction i.e. born repulsive
interaction effective only at short and second term represents long range
attractive interaction i.e. Van der Waals attraction. is the interaction energy,
A and B are constants and R is distance between electron clouds in each atom
and attractive part is due to interaction between fluctuating or permanent dipoles
of atoms molecules.
Fig. 2.5: Van der Walls interaction
2.7.3. Colloids in Vacuum
Lennard –Jones equation 2.2 is sufficient to describe an interaction between two
atoms or molecules. When we consider colloids with large number of atoms in them,
we need to take into
Account all the atoms and their interactions with each other. This is quite a
complex situation as shown in Fig. 2.6

Fig.2.6: Interaction even between two spherical particles of same material and
same size is complex due to presence of large number of atoms in each particle.
To describe the interaction between colloidal particles, Deraguin, Landau, Verwey
and Over beck proposed a theory known as DLVO theory. In other to reduce the
complexity of the problem, they assumed two interacting spherical particles of equal
size. Let thee radius of each particle be r and let two particles be separated by a
distance R.
2.7.4. Colloids in a Medium
So far we considered the colloids just in vacuum.. Consider now a situation in which
inorganic spherical colloids are immersed in a liquid. The attractive interactions
between
etween the colloids get modified through the change of Hamaker constant as AH ,
which can be written now as

= …………………………..
………………………… (2.3)
where A1Vis the Hamaker constant for particle of inorganic solid under
consideration in vacuum and A2V is Hamaker constant of colloid of medium in
vacuum. It can seen from above equation of colloid particle.

particle Hence the attractive
force between colloid particles will in general reduce.
2.7.5. Stearic Repulsion
The stability
tability of colloids can be increased by creating what is known as stearic
steari
hindrance or repulsion.
repulsion. By adsorbing some layer of a different material on colloidal

particles e.g. polymer or organic molecules on inorganic colloidal particles, it is
possible to reduce the attractive forces between them. With addition of adsorbed
layers, the effective size of the particles changes, this helps them to stay at a longer
distance by reducing the attractive interaction. However in case where the coating
material is similar in properties to that of the solvent the effect of coating would be
negligible. By anchoring long chain molecules on the particles, it is possible to keep
them apart with negligible interaction. This idea is the basis of capped nanoparticles.
Thus the colloids interact with each other dynamically and are affected by Van der
Waals forces, colloids-colloid interaction medicated through dispersing medium,
electric double layer and stearic interactions. All the interactions may not be set in
for every case. In general contributions of these various attractive and repulsive
interactions, also dictated by temperature, concentration of colloids and dispersing
medium are additive and can written as follows.
∆ = ∆ + ∆ + ∆ + ∆ + ∆! --------------------(2.4)
Where ∆ is attractive and repulsive, ∆ is colloid-colloid attractive, and ∆
is electrostatic repulsion, ∆ is stearic repulsion and any other.
2.7.6. Synthesis of Colloids
The colloids are thus phase separated submicrometre particles in the form of
spherical particles or particles of various shapes and sizes like rods, tubes, plates etc.
They are the particles suspended in some host matrix. Metal, alloy, semiconductor,
and insulator particles of different shape and sized can be synthesized in aqueous or
no aqueous media. Colloidal particles in liquids are stabilized as discussed above as
by Coulomb repulsion, which arises due to similar charges they may have acquired
on their surfaces. In some cases surface passive molecules may be used which
provide sufficient stearic hindrance inhibiting coalescence or aggregation.

Nanomaterials are a special class of colloids particles which are few hundreds of
nanometer or smaller in size. Synthesis of colloids is very old method. Marking
nanoparticles using colloids route goes back to 19th century when Faradays
synthesized gold nanoparticles by wet chemistry route. The particles are so stable
that even today the colloidal solution made by him can be seen in British Museum in
London. Here we shall discuss some commonly used synthesis methods of metal
semiconductor and insulator nanopaticles with some examples. Chemical reactions
in which colloidal particles are obtained are carried out in some glass reactor of
suitable size. Glass reactor usually has a provision to introduce some precursors,
gases, as well as measure temperature, PH etc during the reaction. It is usually
possible to remove the products at suitable time intervals reaction is usually carried
out under inert atmosphere like argon or nitrogen gas so as to avoid any uncontrolled
oxidation of the products. There is also a provision made to stir the reactants during
the reaction by using Teflon coated magnetic needle. Fig.2.7:Atypical chemical
reactor to synthesize nanoparticles.
Fig.2.7: A typical chemical reactor to synthesize nanoparticles.

2.8. Growth of Nanoparticles
A multi-step process are involving the nucleation and formation of metal seeds,
growth of seeds to form nanoparticles and control of the growth using a capping
agent and/or quenching. Monitoring batch synthesis requires ultrafast spectroscopic
and imaging techniques. Although chemical synthesis of nanopaticles may appear as
a complex process, by understanding how nucleation and growth of particles takes
place, it is possible to control the various steps and try to achieve monodispered
nanopaticles. This can be done with help of LaMer diagram shown in Fig 2.8
As we keep on increasing the concentration of the reactants in the solution, at certain
concentration, say C0 the formation of nuclei begins.
CN
CO
CS
Fig. 2.8: La Mer Diagram Regions I, II and III are for saturation, nucleation, and
growth respectively.
There is no precipitate at this concentration. Further increase in concentration
increases nuclei formation up to concentration CN and CS . Concentration CN denotes
the maximum rate of nuclei formation. When nuclei formation reduces, again CO the
minimum contraction for nucleation is reached. No new nuclei can be formed and
crystal growth reduces the concentration. At this concentration CS, equilibrium is
obtained. If new
w nuclei are formed during the growth of particles, particles with
large size distribution are obtained. Therefore it is very important that concentration
of solute and its

ts diffusion to dissolve speciman be adjusted properly in order that no
fresh nuclei are

re formed once the concentration has reached CN. Particles can grow at
the expense of smaller particles. Larger particles are more stable and grow at the
expense of smaller particles. This growth mode is known as Ostwald ripening
(Fig2.9).. The driving force

force for larger particle is the reduction in surface free energy.
Experimentally it is found that there is sometimes aggregation of particles.
Aggregation also reduces the energy of the system. Thus Ostwald ripening and
aggregation are competing processes and

and wither of them is responsible to reduce the
surface free energy.
Fig.2.9: Growth and aggregation of colloids.

2.9. Synthesis of Semiconductor nanoparticles by colloidal route
The compound semiconductor nanoparticles can be synthesized by wet chemical
route using appropriate salts. Here we shall discuss some methods to obtain
semiconductor nanopaticles. Sulfide semiconductors like CdS and Zones can be
synthesized easily by co-precipitation. For example to obtain Zones nanoparticles
any zinc salt like zinc sulphate (ZnSO4) , zinc chloride (ZnCl2 ) , Zinc
nitrate(ZnNO3) or zinc acetate (Zn(CH3COO)2) can be dissolved in aqueous liquid
and Na2S is added to the solution.
Following simple reaction
ZnCl2 + Na2S ZnS + 2NaCl
Results to give particles of ZnS.
To obtain zinc oxide particles one can use following reactions.
ZnCl2 + 2NaOH Zn(OH)2 + 2NaCl
Zn(OH)2 ZnO + H2O
However all these nanoparticles need to be surface passivated as colloids formed in
liquids have a tendency to coagulate or ripen due to attractive forces existing
between them. The electrostatic and other repulsive forces may not be sufficient to
keep them apart. However as it was also discussed earlier, stearic hindrance can be
created by appropriately coating the particles to keep them a part. This is often
known as chemical capping and has become a widely used method in the synthesis
of nanopaticles. Advantage with this chemical route is that, one can get stable
particle of variety of materials not only in the solution, but even after drying off the
liquid. One can even make thin films of the capped particles by spin coating or dip
coating techniques. The coating however has to stable and non-interactive with the
particle itself except at the surface. Coatings may be a part of post treatment or a part

of the synthesis reaction to obtain nanoparticles. If it is a part of the synthesis
reaction the concentration of capping molecules can be used in two ways to control
the size as well as to protect the particles form coagulation.
Chemical capping can be carried out as high or low temperature depending on the
reactants. In high temperature reactions, cold organometallic reactants are injected in
some solvent like Trioctyphosphineoxide (TYOPO) held at temperature >300 OC.
For example when Dimehtyl Cadmium and Se powder were injected in TOPO,
CdSe nanopaticles capped with PO4groups were obtained. There are however other
chemical also which can be used as precursors to obtain high quality particles. It is
possible to remove the particles of different sizes. The particles with high quality
and as narrow size distribution as < 5% have been achieved by this method.
Although this is a very good route of synthesizing the nanoparticles, most of the
organo-metallic compounds are prohibitively expensive, besides they are also toxic
and difficult to handle. Such synthesis should therefore be carried out only under the
expert guidance.
2.10. Chemical capping of Nanoparticles
A variety of molecules can be used to cape the nanopartilces.For example capping of
metal sulphide nanoparticles by Thiophenol and Mercaptoethanol. In another
variation of chemical capping method, reactions of inexpensive and nontoxic
chemicals like metal chlorides, nitrates, acetates, inorganic salts are performed at
moderate temperatures like 80 to 120. In some cases, it is even possible to
synthesize nanoparticles at room temperature. However the initial size distribution
can be quite broad. The size distribution can be narrowed down by a method known
as size selective precipitation. For this one needs to use a proper pair are Pyridine-
Hexane, Chloroform-Methanol, Dimethyl Sulphoxide – Diethyl Ether etc. The

nanoparticles are dispersed in a solvent so as to get an optically clear solution.
Nonsolvent solution is then added so that flocculation occurs. Supernatant and
flocculate are separated by centrifugation. Precipitate has larger particles and can be
separated; bigger particles therefore pair of solvent-nonsolvent liquids. Some of the
solvent nonsolvent pairs are Pyridine – Hexane, Chloroform - Methanol, Dimethyl
Sulphoxide - Diethyl Ether etc. The nanoparticles are dispersed in a solvent so as to
get an optically clear solution. Nonsolvent solution is then added so that flocculation
occurs. Supernatant and flocculate are separated by centrifugation. Precipitate has
larger particles and can be separated. Bigger particles there are first separated from
smaller particles and redispersed in the solvent solution. The process is continued
until no change in the size distribution is observed by repeating the procedure.
Advantage of chemical capping method is mainly that nanoparticles are chemically
stable over a long time. The thermal stability depends upon the capping molecules
used. In most cases, where organic molecules are used particles are stable up to
about 200-250 and may find considerable range of applications. Another advantage
with both the methods is that while synthesizing the nanopartilces they can be doped
with some metal ions so as to get fluorescent particles at relatively low temperature.
A wide range of semiconductor nanoparticles can be synthesized by this way and are
found to be useful in any applications.
A wide range of metal oxides and other insulators with the wide band gap can be
synthesized by chemical precipitation method along with suitable surface passivant,
if necessary. Some of the oxides and insulators may be stable and may not
agglomerate or coalesce easily.

.2.11. Methods for creating nanostructures
There are many different ways of creating nanostructures of course macromolecules
or nanoparticles or buckyballs or nanotubes and so on can be synthesized artificially
for certain specific materials. They can also be arranged by methods based on
equilibrium or near-equilibriumthermodynamics 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.
2.11.1. Mechanical grinding
The 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. This has become a popular method to make
nanocrystalline materials because of its simplicity, the relatively inexpensive
equipment needed, and the applicability to essentially the synthesis of all classes of
materials. The major advantage often quoted is the possibility for easily scaling up
to tonnage quantities of material for various applications. Similarly, the serious
problems that are usually cited are;
1. Contamination from milling media and/or atmosphere and
2 To consolidate the powder product without coarsening the nanocrystalline
microstructure. In fact, the contamination problem is often given as a reason to
dismiss the method, at least for some materials. Here we will review the mechanisms
presently believed responsible for formation of nanocrystalline structures by
mechanical attrition of single phase powders, mechanical alloying of dissimilar
powders, and mechanical crystallisation of amorphous materials. The two important

problems of contamination and powder consolidation will be briefly considered.
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.
Then 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
Fig.2.10: Schematic representation of the principle of mechanical milling
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.
2.11.2. Wet Chemical Synthesis of Nanomaterials
The wet chemical synthesis of nanomaterials can be classified into two broadgroups:
1. The top down method: where single crystals are etched in an aqueous
solution for producing nanomaterials, For example, the synthesis of porous
silicon by electrochemical etching.
2. The bottom up method: consisting of sol-gel method, precipitation etc. where
materials containing the desired precursors are mixed in a controlled fashion
to form a colloidal solution.
2.11.2.1. Sol-gel process
The sol-gel process, involves the evolution of inorganic networks through the
formation of a colloidal 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
legends. 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. Calcinations of the
gel produce the oxide. Sol-gel processing refers to the hydrolysis and condensation
of alkoxide-based precursors such as Si (OEt)4’ Tetraethyl Orthosilicate (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
iswidely 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 that results in a dramatic increase in the
viscosity of the solution.
3.Aging of the gel (Synthesis) during which the poly condensation reactions
continue until the gel transforms into a solid mass, accompanied by contraction of
Fig. 2.10: Schematic representation of sol-gel process of synthesis of

nanomaterials.

the gel network and expulsion of solvent from gel pores. Ostwald ripening (also
referred to as coarsening, is the phenomenon by which smaller particles are
consumed by larger particles during the growth process) and phase transformations
may occur concurrently with synthesis. The aging process of gels can exceed 7 days
and is critical to the prevention of cracks in gels that have been cast.Drying of the
gel, 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:
i. the constant rate period,
ii. the critical point,
iii. the falling rate period,
iv. the second falling rate period.
If isolated by thermal evaporation, the resulting monolith is termed a xerogel. If
the solvent (such as water) is extracted under supercritical or near super critical
conditions, the product is an aerogel.
4. Dehydration, 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 80000C.
5. Densification and decomposition of the gels at high temperatures (T>80000C).
The pores of the gel network are collapsed, and remaining organic species are
volatilized. The typical steps that are involved in sol-gel processing are shown in the
Fig.2.12. The interest in this synthesis method arises due to the possibility of
synthesizing nonmetallic inorganic materials like glasses, glass ceramics or ceramic
materials at very low temperatures compared to the high temperature process
required by melting glass or firing ceramics. The major difficulties to overcome in

developing a successful bottom-up approach is controlling the growth of the
particles and then stopping the newly formed particles from agglomerating. Other
technical issues are ensuring the reactions are complete so that no unwanted reactant
is left on the product and completely removing any growth aids that may have been
used in the process. Also production rates of nano powders are very low by this
process. The main advantage is one can get monosized nano particles by any bottom
up approach.
2.12. Gas phase synthesis of nanomaterials
The gas-phase synthesis methods are increasing interest because they allow
elegant way to control process parameters in order to be able to produce size, shape
and chemical composition controlled nanostructures. Before we discuss a few
selected pathways for gas-phase formation of nanomaterials, some general aspects of
gas-phase synthesis needs to be discussed. 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 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
catalyses the reaction and a dense film is formed. In order to form
nanomaterials several modified CVD methods have been developed. Gas
phase processes have inherent advantages, some of which are noted here:
An excellent control of size, shape, crystallinity and chemical
composition

Highly pure materials can be obtained
Multicomonent 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 can
aggregate to form nanoparticles (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.
2.12.1. Furnace
The simplest fashion to produce nanoparticles is by heating the desired material in a
heatresistant crucible containing the desired material. This method is appropriate
only for materials that have a high vapor 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 form a compound).
To carry out reactive synthesis, materials with very low vapor pressure have to be
fed into the furnace in the form of a suitable precursor such as organo metallic,
which decompose in the furnace to produce a condensable material. The hot atoms
of 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).
Fig.2.13: Schematic representation of gas phase process of synthesis of single
phase
2.12.2. Gas Condensation Processing (GPC)
This technique includes, a metallic or inorganic material, e.g. a suboxide, is
vaporized using thermal evaporation sources such as crucibles, electron beam
evaporation devices or sputtering sources in an atmosphere of 1-50 mbar 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 rate/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.
Fig.2.14: Schematic representation of typical set-up for gas condensation

synthesis ofnanomaterials followed by consolidation in a mechanical press or
collection in an appropriate solvent media
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. However, these methods can
only be used in a system designed for gas flow, i.e. a dynamic vacuum is generated
by means of both continuous pumping and gas inlet via mass flow controller. A
major advantage over convectional gas flow is the improved control of the particle
sizes. It has been found that the particle size distributions in gas flow systems, which
are also lognormal, are shifted towards smaller average values with an appreciable
reduction of the standard deviation of the distribution. Depending on the flow rate of
the He-gas, particle sizes are reduced by 80% and standard deviations by 18%. The
synthesis of nanocrystalline pure metals is relatively straightforward as long as
evaporation can be done from refractory metal crucibles (W, Ta or Mo). If metals
with high melting points or metals which react with the crucibles, are to be prepared,
sputtering, i.e. for W and Zr, or laser or electron beam evaporation has to be used.
Synthesis of alloys or intermetallic compounds by thermal evaporation can only be
done in the exceptional cases that the vapor pressures of the elements are similar. As
an alternative, sputtering from an alloy or mixed target can be employed. Composite
materials such as Cu/Bi or W/Ga have been synthesized by simultaneous
evaporation from two separate crucibles onto a rotating collection device. It has been
found that excellent intermixing on the scale of the particle size can be obtained.
However, control of the composition of the elements has been difficult and
reproducibility is poor. Nanocrystalline oxide powders are formed by controlled post

oxidation of primary nanoparticles of a pure metal (e.g. Ti to TiO2) or a sub oxide
(e.g. ZrO to ZrO2). Although the gas condensation method including the variations
have been widely employed to prepared a variety of metallic and ceramic materials,
quantities have so far been limited to a laboratory scale. The quantities of metals are
below 1 g/day, while quantities of oxides can be as high as 20 g/day for simple
oxides such as CeO2 or ZrO2. These quantities are sufficient for materials testing
but not for industrial production. However, it should be mentioned that the scale-up
of the gas condensation method for industrial production of nanocrystalline oxides
by a company called nanophase technologies has been successful.
2.12.3. Chemical Vapor Condensation (CVC)
The evaporative source used in GPC is replaced by a hot wall reactor in the
Chemical Vapor Condensation or the CVC processas shown schematically in Figure
2.15. Depending on the processing parameters nucleation of nanoparticles is
observed during chemical vapor deposition (CVD) 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 film formation and enhance
homogeneous nucleation of particles in the gas flow. It is readily 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 compared to GPC has been 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 mixtures of nanoparticles of two
phases or doped nanoparticles by supplying two precursors at the front end of the
reactor, and Coated nanoparticles, i.e., n-ZrO2 coated with n-Al2O3 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 than in GPC processing.
Fig.2.15: A schematic of a typical CVC reactor

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.
2.13. Properties of Nanomaterials
The nanomaterials have the structural features in between of those of atoms and the
bulk materials. While most microstructured materials have similar properties to the
corresponding bulk materials, the properties of materials with nanometer dimensions
are significantly different from those of atoms and bulks materials. This is mainly
due to the nanometer size of the materials which render them: (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. Due to their
small dimensions, nanomaterials have extremely large surface area to volume ratio,
which makes a large to be the surface or interfacial atoms, resulting in more
“surface” dependent material properties. Especially when the sizes of nanomaterials
are comparable to length, the entire material will be affected by the surface
properties of nanomaterials. This in turn may enhance or modify the properties of
the bulk materials. For example, metallic nanoparticles can be used as very active
catalysts. Chemical sensors from nanoparticles and nanowires enhanced the
sensitivity and sensor selectivity. The nanometer feature sizes of nanomaterials also
have spatial confinement effect on the materials, which bring the quantum effects.
The energy band structure and charge carrier density in the materials can be
modified quite differently from their bulk and in turn will modify the electronic and
optical properties of the materials. For example, lasers and light emitting diodes
(LED) from both of the quantum dots and quantum wires are very promising in the
future optoelectronics. High density information storage using quantum dot devices

is also a fast developing area. Reduced imperfections are also important factor in
determination of the properties of the nanomaterials. Nanosturctures and
Nanomaterials favors of a self purification process in that the impurities and intrinsic
material defects will move to near the surface upon thermal annealing. This
increased materials perfection affects the properties of nanomaterials. For example,
the chemical stability for certain nanomaterials may be enhanced, the mechanical
properties of nanomaterials will be better than the bulk materials. The superior
mechanical properties of carbon nanotubes are well known. Due to their nanometer
size, nanomaterials are already known to have many novel properties. Many novel
applications of the nanomaterials rose from these novel properties. Applications
based on optical properties of nanomaterials include optical detector, laser, sensor,
imaging, phosphor, display, solar cell, photo catalysis, photo electrochemistry, and
biomedicine. 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. Likewise,
Fig.2.16: Fluorescence emission of (CdSe) ZnS quantum dots of various sizes and
absoption spectra of various sizes and shapes of gold nanoparticles.

shape can have dramatic influence on optical properties of metal
nanostructures.With the CdSe semiconductor nanoparticles, a simple change in size
alters the optical properties of the nanoparticles. When metal nanoparticles are
enlarged, their optical properties change only slightly as observed for the different
samples of gold nanospheres in fig.2.16.However, when anisotropy is added to the
nanoparticle, such as growth of nanorods, the optical properties of the nanoparticles
change dramatically.
2.13.1. Electrical properties
The electrical Properties of Nanoparticles discuss about fundamentals of
electricalconductivity in nanotubes and nanorods, carbon nanotubes,
photoconductivity of nanorods, electrical conductivity of nanocomposites. One
interesting method which can be used to demonstrate the steps in conductance is the
mechanical thinning of a nanowire and measurement of the electrical current at a
constant applied voltage. The important point here is that, with decreasing diameter
of the wire, the number of electron wave modes contributing to the electrical
conductivity is becoming increasingly smaller by well-defined quantized steps. In
electrically conducting carbon nanotubes, only one electron wave mode is observed
which transport the electrical current. As the lengths and orientations of thecarbon
nanotubes are different, they touch the surface of the mercury at different times,
which provides two sets of information: (i) the influence of carbon nanotube length
on the resistance and (ii) the resistances of the different nanotubes. As the nanotubes
have different lengths, then with increasing protrusion of the fiber bundle an
increasing number of carbon nanotubes will touch the surface of the mercury droplet
and contribute to the electrical current transport.

Fig.2.17: Electrical behavior of naotubes
2.13.2.Mechanical properties
“Mechanical Properties of Nanoparticles” deals with bulk metallic and ceramic
materials, influence of porosity, influence of grain size, super plasticity, filled
polymer composites, particle-filled polymers, and polymer-based nanocomposites
filled with platelets, carbon nanotube-based composites. The discussion of
mechanical properties of nanomaterials is in to some extent only of quite basic
interest the reason being that it is problematic to produce macroscopic bodies with a
high density and a grain size in the range of less than 100 nm. However, two
materials, neither of which is produced by pressing and sintering, have attracted
much greater interest as they will undoubtedly achieve industrial importance. These
materials are polymers which contain nanoparticles or nanotubes to improve their
mechanical behaviors and severely plastic-deformed metals, which exhibit
astonishing properties. However, because of their larger grain size, the latter are
generally not accepted as nanomaterials. Experimental studies on the mechanical
properties of bulk nanomaterials are generally impaired by major experimental
problems in producing specimens with exactly defined grain sizes and porosities.
Therefore, model calculations and molecular dynamic studies are of major
importance for an understanding of the mechanical properties of these materials.
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. The
latter point is of special importance, as any specific advantages of a nanoparticulate
filler may be lost if the filler forms aggregates, thereby mimicking the large
particles. Particulatefilled polymer-based nanocomposites exhibit a broad range of
failure strengths and strains. This depends on the shape of the filler, particles, or
platelets and on the degree of agglomeration. In this class of material, polymers
filled with silicate platelets exhibit the best mechanical properties and are of the
greatest economic relevance. The larger the particles of the filler or agglomerates,
the poorer are the properties obtained. Although, potentially, the best composites are
those filled with nanofibers or nanotubes, experience teaches that sometimes such
composites have the least ductility. On the other hand by using carbon nanotubes it
is possible to produce composite fibers with extremely high strength and strain at
rupture. Among the most exciting nanocomposites are the polymerceramic
nanocomposites, where the ceramic phase is platelet-shaped. This type of composite
is preferred in nature and is found in the structure of bones, where it consists of
crystallized mineral platelets of a few nanometers thickness that are bound together
with collagen as the matrix. Composites consisting of a polymer matrix and
defoliated phyllosilicates exhibit excellent mechanical and thermal properties.
2.13.3. Magnetic properties
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, i.e. by capping the nanoparticles. This
phenomenon opens the possibility to modify the physical properties of the
nanoparticles by capping them with appropriate molecules. Actually, it should be

possible that non-ferromagnetic bulk materials exhibit ferromagnetic-like behavior
when prepared in nano range. One can obtain magnetic nanoparticles of Pd, Pt and
the surprising case of Au (that is diamagnetic in bulk) from non-magnetic bulk
materials. In the case of Pt and Pd, the ferromagnetism arises from the structural
changes associated with size effects.
However, gold nanoparticles become ferromagnetic when they are capped with
appropriate molecules: the charge localized at the particle surface gives rise to
ferromagnetic-like behavior. Surface and the core of Au nanoparticles with 2 nm in
diameter show ferromagnetic and paramagnetic character, respectively. The large
spin-orbit coupling of these noble metals can yield to a large anisotropy and
therefore exhibit high ordering temperatures. More surprisingly, permanent
magnetism was observed up to room temperature for thiol-capped Au nanoparticles.
For nanoparticles with sizes below 2 nm the localized carriers are in the 5d band.
Bulk Au has an extremely low density of states and becomes diamagnetic, as is also
the case for bare Au nanoparticles. This observation suggested that modification of
the d band structure by chemical bonding can induce ferromagnetic like character in
metallic clusters.
2.14. Selected applications of nanomaterials
The nanomaterials having wide range of applications in the field of electronics, fuel
cells, batteries, agriculture, food industry, and medicines, etc... It is evident that
nanomaterials split their conventional counterparts because of their superior
chemical, physical, and mechanical properties and of their exceptional formability.
2.14.1. Fuel cells
A fuel cell is an electrochemical energy conversion device that converts the
chemical energy from fuel (on the anode side) and oxidant (on the cathode side)

directly into electricity. The heart of fuel cell is the electrodes. The performance of a
fuel cell electrode can be optimized in two ways; by improving the physical
structure and by using more active electro catalyst. A good structure of electrode
must provide sample surface area, provide maximum contact of catalyst, reactant
gas, and electrolyte, facilitate gas transport, and provide good electronic
conductance. In this fashion the structure should be able to minimize losses.
2.14.2. Carbon nanotubes - Microbial fuel cell
Microbial fuel cell is a device in which bacteria consume water-soluble waste such
assugar, starch, and alcohols and produces electricity plus clean water. This
technology will make it possible to generate electricity while treating domestic or
industrial wastewater. Microbial fuel cell can turn different carbohydrates and
complex substrates present in wastewaters into a source of electricity. The efficient
electron transfer between the microorganism and the anode of the microbial fuel cell
plays a major role in the performance of the fuel cell. The organic molecules present
in the wastewater posses a certain amount of chemical energy, which is released
when converting them to simpler molecules like CO2. The microbial fuel cell is thus
a device that converts the chemical energy present in water-soluble waste into
electrical energy by the catalytic reaction of microorganisms. Carbon nanotubes
(CNTs) have chemical stability, good mechanical properties, and high surface area,
making them ideal for the design of sensors and provide very high surface area due
to its structural network. Since carbon nanotubes are also suitable supports for cell
growth, electrodes of microbial fuel cells can be built using of CNT. Due to three-
dimensional architectures and enlarged electrode surface area for the entry of growth
medium, bacteria can grow and proliferate and get immobilized. Multi walled CNT
scaffolds could offer self-supported structure with large surface area through which

hydrogen producing bacteria (e.g., E. coli) can eventually grow and proliferate. Also
CNTs and MWCNTs have been reported to be biocompatible for different
eukaryotic cells. The efficient proliferation of hydrogen producing bacteria
throughout an electron conducting scaffold of CNT can form the basis for the
potential application as electrodes in MFCs leading to efficient performance.
2.14.3.Catalysis
Higher surface area available with the nanomaterial counterparts, nano-catalysts
tend to have exceptional surface activity. For example, reaction rate at nano-
aluminum can go so high, that it is utilized as a solid-fuel in rocket propulsion,
whereas the bulk aluminum is widely used in utensils. Nano-aluminum becomes
highly reactive and supplies the required thrust to send off pay loads in space.
Similarly, catalysts assisting or retarding the reaction rates are dependent on the
surface activity, and can very well be utilized in manipulating the rate-controlling
step.
2.14.4. Phosphors for High-Definition TV
The resolution of a television, or a monitor, depends greatly on the size of the pixel.
These pixels are essentially made of materials called "phosphors," which glow when
struck by a stream of electrons inside the cathode ray tube (CRT). The resolution
improves with a reduction in the size of the pixel, or the phosphors. Nanocrystalline
zinc selenide, zinc sulfide, cadmium sulfide, and lead telluride synthesized by the
sol-gel techniques are candidates for improving the resolution of monitors. The use
of nanophosphors is envisioned to reduce the cost of these displays so as to render
high definition televisions (HDTVs) and personal computers affordable to be
purchase.

2.14.5. Next-Generation Computer Chips
The microelectronics industry has been emphasizing miniaturization, whereby the
circuits, such as transistors, resistors, and capacitors, are reduced in size. By
achieving a significant reduction in their size, the microprocessors, which contain
these components, can run much faster, thereby enabling computations at far greater
speeds. However, there are several technological impediments to these
advancements, including lack of the ultrafine precursors to manufacture these
components; poor dissipation of tremendous amount of heat generated by these
microprocessors due to faster speeds; short mean time to failures (poor reliability),
etc. Nanomaterials help the industry break these barriers down by providing the
manufacturers with nanocrystalline starting materials, ultra-high purity materials,
materials with better thermal conductivity, and longer-lasting, durable
interconnections (connections between various components in the microprocessors).
Example: Nanowires for junction less transistors
Transistors are made so tiny to reduce the size of sub assemblies of electronic
systems and make smaller and smaller devices, but it is difficult to create high-
quality junctions. In particular, it is very difficult to change the doping concentration
of a material over distances shorter than about 10 nm. Researchers have succeeded
in making the junction less transistor having nearly ideal electrical properties. It
could potentially operate faster and use less power than any conventional transistor
on the market today. The device consists of a silicon nanowire in which current flow
is perfectly controlled by a silicon gate that is separated from the nanowire by a thin
insulating layer. The entire silicon nanowire is heavily n-doped, making it an
excellent conductor. However, the gate is p-doped and its presence has the effect of
depleting the number of electrons in the region of the nanowire under the gate. The

device also has near-ideal electrical properties and behaves like the most perfect of
transistors without suffering from current leakage like conventional devices and
operates faster and using less energy.
Fig. 2.18: Silicon nanowires in junction less transistors
2.14.6. Elimination of Pollutants
The nanomaterials possess extremely large grain boundaries relative to their grain as
catalysts to react with such noxious and toxic gases as carbon monoxide and
nitrogen oxide in automobile catalytic converters and power generation equipment
to prevent environmental pollution arising from burning gasoline and coal.
2.14.7. Sun-screen lotion
Prolonged UV exposure causes skin-burns and cancer. Sun-screen lotions containing
nanoTiO2 provide enhanced sun protection factor (SPF) while eliminating stickiness.
The added advantage of nano skin blocks (ZnO and TiO2) arises as they protect the
skin by sitting onto it rather than penetrating into the skin. Thus they block UV

radiation effectively for prolonged duration. Additionally, they are transparent, thus
retain natural skin color while working better than conventional skin-lotions.
2.14.8. Sensors
The sensors rely on the highly active surface to initiate a response with minute
change in the concentration of the species to be detected. Engineered monolayers
(few Angstroms thick) on the sensor surface are exposed to the environment and the
peculiar functionality (such as change in potential as the CO/anthrax level is
detected) is utilized in sensing.
2.15. Disadvantages of Nanomaterials
1) Instability of the particles - Retaining the active metal nanoparticles is highly
challenging, as the kinetics associated with nanomaterials is rapid. In order to
retain nanosize of particles they are encapsulated in some other matrix.
Nanomaterials are thermodynamically metastable and lie in the region of high-
energy local minima. Hence they are prone to attack and undergo transformation.
These include poor corrosion resistance, high solubility, and phase change of
nanomaterials. This leads to deterioration in properties and retaining the
structure becomes challenging.
2) Fine metal particles act as strong explosives owing to their high surface area
coming in direct contact with oxygen. Their exothermic combustion can easily
cause explosion.
3) Impurity - Because nanoparticles are highly reactive they inherently interact with
impurities as well. In addition, encapsulation of nanoparticles becomes necessary
when they are synthesized in a solution (chemical route). The stabilization of
nanoparticles occurs because of a non-reactive species engulfing the reactive
nano-entities. Thereby these secondary impurities become a part of the

synthesized nanoparticles and synthesis of pure nanoparticles becomes highly
difficult. Formation of oxides, nitrides etc. can also get aggravated from the
impure environment/ surrounding while synthesizing nanoparticles. Hence
retaining high purity in nanoparticles can become a challenge hard to overcome.
4) Biologically harmful - Nanomaterials are usually considered harmful as they
become transparent to the cell-dermis. Toxicity of nanomaterials also appears
predominant owing to their high surface area and enhanced surface activity.
Nanomaterials have shown to cause irritation and have indicated to be
carcinogenic. If inhaled their low mass entraps them inside lungs and in no way
they can be expelled out of body. Their interaction with liver/blood could also
prove to be harmful (though this aspect is still being debated on).
5) Difficulty in synthesis, isolation, and application: It is extremely hard to retain
the size of nanoparticles once they are synthesized in a solution. Hence, the
nanomaterials have to be encapsulated in a bigger and stable molecule/material.
Hence free nanoparticles are hard to be utilized in isolation, and they have to be
interacted for intended use via secondary means of exposure. Grain growth is
inherently present in nanomateirals during their processing. The finer grains tend
to merge and become bigger and stable grains at high temperatures and times of
processing.
6) Recycling and disposal - There are no hard-and-fast safe disposal policies
evolved for nanomaterials. Issues of their toxicity are still under question, and
results of exposure experiments are not available. Hence the uncertainty
associated with affects of nanomaterials is yet to be assessed in order to develop
their disposal policies.

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Chapter 2 Concept of Nanotechnology

2.0. Basic concept of Nanotechnology

The nanomaterials are cornerstones of nanoscience and nanotechnology. The

nanostructure science and technology is a broad and interdisciplinary area of

Fig. 2.1: Evolution of science and technology and the future

It is already having a significant commercial impact, which will assuredly increase

(Called A “T-cell”) destroys an invading microbe by engulfing it. What would it be

molecular or atomic scale- the major focus of nanotechnology [1].

Thenanotechnology is defined as study and use of structure between 1 nanometer

and 100 naometers in size. Thenanotechnology is concerned with materials and

systems whose structure component exhibit novel and significantly improved

physical, chemical, and biological properties, phenomena and process because of

100 nanometer determine important changes as compared to the behavior of isolated

molecules (1nanometer) or of bulk materials. More generally nanotechnology can be

defined as any technique able to work at a submicron scale [2]. It is an

interdisciplinary science involving physics, chemistry, biology, engineering

materials science, computer science etc.

42 Synthesis and Characterization of Nonlinear Optical Nanoparticles and their

technology industries at the beginning of the technology companies like HP,NEC

developing nano devices. Despite this impressive lineup, well-recognized

stock index of public companies working on nano.

dimension is less than approximately 100 nanometers. The nanomaterials are of

impacts in electronics, medicine, and other fields.

products and processes. They can be found in things as sunscreens, cosmetics,

sporting goods, stain-resistant clothing, tires, electronics, as well as many other

drug delivery. Engineered nanomaterials are resources designed at the molecular

43 Synthesis and Characterization of Nonlinear Optical Nanoparticles and their

characteristics, leading to novel optical, electrical, and magnetic behaviors.

very broad, including stain-resistant and wrinkle-free textiles, cosmetics, sunscreens,

diverse consumer products, such as windows, sports equipment, bicycles, and

rubber/ nano-clay composites. Nanoscale titanium dioxideis used in cosmetics, sun-

in a range of products, including cosmetics and dental fillings.

erosion can also create nanoparticles. Nature is expert in fabricating organic

the bloodstream is 5nm in diameter (4).

44 Synthesis and Characterization of Nonlinear Optical Nanoparticles and their

2.3.Significant impact: Nanoscience and Nanotechnology

The nanotechnology literally means any technology performed on a nanoscale

production and application of physical, chemical, and biological systems at scales

ranging from individual atoms or molecules to submicron dimensions as well as the

integration of the resulting nanostructures into larger systems. The nanotechnology

first century, comparable to that of semiconductor technology, information

technology or cellular and molecular biology. Science and technology research in

nanotechnology promises breakthroughs in such areas as materials and

manufacturing,medicine and healthcare, energy, biotechnology, information

next industrial revolution.

Nanometer-scale features are mainly built up from their elemental constituents.

Chemical synthesis – the spontaneous self-assembly of molecular clusters

(molecular self-assembly) from simple reagents in solution or biological molecules

nanostructures, including quantum dots (nanocrystals) of arbitrary diameter (about

10 to 105 atoms). A variety of vacuum deposition and nonequilibrium plasma

chemistry techniques are used to produce layered nanocomposites and nanotubes.

organo-metallic vapor phase epitaxy. Micro and nanosystem components are

fabricated using top-down lithographic and nonlithographic fabrication techniques

and range in size from micro to nanometers. Continued improvements in lithography

45 Synthesis and Characterization of Nonlinear Optical Nanoparticles and their

10 nanometers in experimental prototypes. The nanotechnology field, in addition to

the fabrication of nanosystems provides the impetus to development of experimental

and computational tools. The micro and nanosystems include micro/nano

electromechanical systems (MEMS/NEMS) (e.g., sensors, actuators, and

miniaturized systems comprising sensing, processing and/or actuating functions),