NANOMATERIALS

DEFINITIONS

In nanoscience and technology, a particle is defined as a small object that behaves as a

whole unit in terms of its transport and properties. It is further classified according to size: In
terms of diameter, fine particles cover a range between 100 and 2500 nanometers, while ultrafine
particles, on the other hand, are sized between 1 and 100 nanometers. Similar to ultrafine
particles, nanoparticles are sized between 1 and 100 nanometers, though the size limitation can
be restricted to one or two dimensions. In general, nano structures are defined as those having at
least one of the dimensions between 1 and 100nm.

Nanotechnology is a broad term that encompasses many application specific technologies

& research into objects that are a nanometer or smaller (Nanometer being one billionth of a
meter). Nanotechnology is expected to revolutionize our world much the same way that
Airplanes, Televisions & Telecom revolutionized the 20th century. Imagine a thousand machines
being able to fit in an area the size of a pinhead, or a spaceship that can repair itself mid-flight.

The foundation of nanotechnology is understanding how to manipulate specific atoms to

create a desired result. Since it is known that positive & negative atoms attract much like
magnets, the next step is to begin to use these atoms one at a time to produce a machine using the
least amount of atoms possible. There are three primary stems to creating nanotechnology-based
good.

1. Manipulation of Single Atoms – The basis for all nanotechnology, the manipulation &
control of individual atoms is essential to begin the development & programming of assemblers.

2. Development of nanoscopic machine called assemblers – The assemblers will have the
ability to be programmed to manipulate molecules & atoms to create materials one atom at a
time. Since it would take many years for a single assembler to create a desired material, billions
or even trillions of assemblers will work together to develop products in an acceptable
timeframe.
3. Application of Replicators – Replicators will be manufactured & employed to mass produce
assemblers. Since the creation of assemblers manually is extremely resource consuming it makes
sense to develop a nanofactory where nano machines will build themselves. The Replicators &
assemblers will work in tangent to create products automatically. Eventually this will allow
products to be reproduced more efficiently & at a reduced cost.

Nanoparticles exhibit a wide range of physical, chemical and electronic properties which
depend sensitively on shape and structure. At the small end of the size range, nanoparticles are
often referred to as clusters. Nanospheres, nanorods, nanofibers, and nanocups are just a few of
the shapes that have been grown. Nanoclusters have at least one dimension between 1 and 100
nanometers and a narrow size distribution. Nanopowders are agglomerates of ultrafine particles,
nanoparticles, or nanoclusters. Nanometer sized single crystals, or single-domain ultrafine
particles, are often referred to as nanocrystals.

Nanoparticle research is currently an area of intense scientific research, due to a wide

variety of potential applications in biomedical, optical, and electronic fields. The National
Nanotechnology Initiative has led to generous public funding for nanoparticle research in the
United States.

PROPERTIES OF NANOPARTICLES

Nanoparticles are of great scientific interest as they are effectively a bridge between bulk
materials and atomic or molecular structures. A bulk material should have constant physical
properties regardless of its size, but at the nano-scale this is often not the case. Size-dependent
properties are observed such as quantum confinement in semiconductor particles, surface
plasmon resonance in some metal particles and superparamagnetism in magnetic materials.

The properties of materials change as their size approaches the nanoscale and as the
percentage of atoms at the surface of a material becomes significant. For bulk materials larger
than one micrometre the percentage of atoms at the surface is minuscule relative to the total
number of atoms of the material. The interesting and sometimes unexpected properties of
nanoparticles are partly due to the aspects of the surface of the material dominating the
properties in lieu of the bulk properties.
 Nanoparticles exhibit a number of special properties relative to bulk material. For
example, the bending of bulk copper (wire, ribbon, etc.) occurs with movement of copper
atoms/clusters at about the 50 nm scale. Copper nanoparticles smaller than 50 nm are considered
super hard materials that do not exhibit the same malleability and ductility as bulk copper. The
change in properties is not always desirable. Ferroelectric materials smaller than 10 nm can
switch their magnetization direction using room temperature thermal energy, thus making them
useless for memory storage. Suspensions of nanoparticles are possible because the interaction of
the particle surface with the solvent is strong enough to overcome differences in density, which
usually result in a material either sinking or floating in a liquid. Nanoparticles often have
unexpected visible properties because they are small enough to confine their electrons and
produce quantum effects. For example gold nanoparticles appear deep red to black in solution.

Nanoparticles have a very high surface area to volume ratio. This provides a tremendous
driving force for diffusion, especially at elevated temperatures. Sintering can take place at lower
temperatures, over shorter time scales than for larger particles. This theoretically does not affect
the density of the final product, though flow difficulties and the tendency of nanoparticles to
agglomerate complicates matters. The large surface area to volume ratio also reduces the
incipient melting temperature of nanoparticles.

Metal, dielectric, and semiconductor nanoparticles have been formed, as well as hybrid
structures (like core-shell nanoparticles). Nanoparticles made of semiconducting material may
also be labeled quantum dots if they are small enough (typically sub 10nm) that quantization of
electronic energy levels occurs. Such nanoscale particles are used in biomedical applications as
drug carriers or imaging agents.

CHARACTERIZATION

Nanoparticle characterization is necessary to establish understanding and control of

nanoparticle synthesis and applications. Characterization is done by using a variety of different
techniques, mainly drawn from materials science. Common techniques are electron microscopy
(TEM, SEM), Atomic Force Microscopy (AFM), Dynamic Light Scattering (DLS), X-ray
Photoelectron Spectroscopy (XPS), powder X-ray Diffractometry (XRD), Fourier Transform
Infrared spectroscopy (FTIR), Matrix-Assisted Laser- Desorption Time-of-flight mass
spectrometry (MALDI-TOF), and Ultraviolet-Visible spectroscopy.
 Whilst the theory has been known for over a century, the technology for Nanoparticle
Tracking Analysis (NTA) allows direct tracking of the Brownian motion and this method
therefore allows the sizing of individual nanoparticles in solution.

PREPARATION OF NANOPARTICLES
There exist a wide variety of techniques to produce nano particles. These essentially fall
into three categories: condensation from a vapor, solid state processes such as milling, and
chemical synthesis. Particles can then be coated, with hydrophilic or hydrophobic substances, for
example depending on the desired applications.
Vapor Condensation: This approach is used to make metallic or metal oxide ceramic
nanoparticles. It involves evaporation of solid metal followed by rapid condensation to form
nanosized clusters that settle in the form of a powder. Various approaches to vaporize the metal
can be used and variation of the medium into which the vapor is released affects the nature and
size of the particles. Inert gases are used to prevent oxidation when creating metal nanoparticles,
whereas a reactive oxygen atmosphere is used to produce metal oxide ceramic nanoparticles. The
main advantage of this approach is low contamination levels. Final particle size is controlled by
variation of parameters such as temperature, gas environment and evaporation rate.
Another variation on the vapor condensation technique is the vacuum evaporation on
running liquids (VERL) method. This uses a thin film of a relatively viscous material, an oil, or a
polymer, for instance, on a rotating drum. A vacuum is maintained in the apparatus and the
desired metal is evaporated or sputtered into the vacuum. Particles form in suspension in the
liquid and can be grown to a variety of sizes.
Chemical-Vapor Deposition: Among other growth methods, chemical-vapor deposition (CVD)
technology is particularly interesting not only because it gives rise to high-quality films but also
because it is applicable to large-scale production. This technique is widely used in the fabrication
of epitaxial films toward various GaN-based optoelectronic devices, and similar trend might be
expected for future applications of ZnO. There are several modifications of this method
depending on precursors used. When metal-organic precursors are used, the technique is called
MOCVD, metal-organic vapor-phase epitaxy (MOVPE), or organometallic vapor-phase epitaxy
(OMVPE). In the case of hydride or halide precursors, the technique is named hydride or halide
CVD or VPE.
Pulsed Laser Deposition: In the pulsed-laser deposition (PLD) method, high power laser pulses
are used to evaporate material from a target surface such that the stoichiometry of the material is
preserved in the interaction. As a result, a supersonic jet of particles (plume) is directed normal
to the target surface. The plume expands away from the target with a strong forward directed
velocity distribution of different particles. The ablated species condense on the substrate placed
opposite to the target.
The main advantages of PLD are its ability to create high-energy source particles,
permitting high quality film growth at low substrate temperatures, typically ranging from 200 to
800°C, its simple experimental setup, and operation in high ambient gas pressures in the 10−5–
10−1 Torr range.
Solid State Processes: Grinding or milling can be used to create nanoparticles. The milling
material, milling time and atmospheric medium affect resultant nanoparticle properties. The
approach can be used to produce nanoparticles from materials that don’t readily lend themselves
to the two previous techniques. Contamination from the milling material can be an issue.
Wet Chemical Synthesis: The most widely used chemical synthesis technique consists
essentially of growing nanoparticles in a liquid medium composed of various reactants.
Chemical techniques are generally better than vapor condensation techniques for controlling the
final shape of the particles. The ultimate shape of the nanoparticles might be dictated, as with
vapor condensation approaches by stopping the process when the desired size is reached, or by
choosing chemicals that form particles that are stable, and stop growing at a certain size. The
approaches are generally low-cost and high-volume but contamination from the precursor
chemicals can be a problem. This can interfere with one of the common uses of nanoparticles,
sintering, to create surface coatings.
Hydrothermal Synthesis: Hydrothermal/solvothermal method is one of the highly used
techniques in this wet chemical synthesis. The term ‘hydrothermal’ came from the earth
sciences, where it implied a regime of high temperatures and water pressures. For a typical
hydrothermal synthesis, one needs a high temperature, high-pressure apparatus called
‘autoclaves’ or ‘bombs’. Hydrothermal synthesis involves H2O both as a catalyst and
occasionally as a component of solid phases in the synthesis at elevated temperature (> 100°C)
and pressure (> a few atmosphere). At present, one can get many kinds of autoclaves to cover
different pressure, temperature and volume ranges. For hydrothermal experiments the
requirements for starting materials are, (i) accurately known composition, (ii) as homogeneous as
possible, (iii) as pure as possible and (iv) as fine as possible, etc.
Sol gel method: The sol-gel process is a wet-chemical technique used primarily for the
fabrication of materials starting from a chemical solution which acts as the precursor for an
integrated network (or gel) of either discrete particles or network polymers. Typical precursors
are metal alkoxides and metal chlorides, which undergo various forms of hydrolysis and
polycondensation reactions. The formation of a metal oxide involves connecting the metal
centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore generating metal-oxo or
metal-hydroxo polymers in solution. Thus, the sol evolves towards the formation of a gel-like
diphasic system containing both a liquid phase and solid phase whose morphologies range from
discrete particles to continuous polymer networks.
Removal of the remaining liquid (solvent) phase requires a drying process, which is
typically accompanied by a significant amount of shrinkage and densification. The rate at which
the solvent can be removed is ultimately determined by the distribution of porosity in the gel.
The ultimate microstructure of the final component will clearly be strongly influenced by
changes imposed upon the structural template during this phase of processing. Afterwards, a
thermal treatment, or firing process, is often necessary in order to favor further polycondensation
and enhance mechanical properties and structural stability via final sintering, densification and
grain growth. One of the distinct advantages of using this methodology as opposed to the more
traditional processing techniques is that densification is often achieved at a much lower
temperature.
The precursor sol can be either (i) deposited on a substrate to form a film (e.g., by dip
coating or spin coating), (ii) cast into a suitable container with the desired shape or (iii) used to
synthesize powders (e.g., microspheres, nanospheres). The sol-gel approach is a cheap and low-
temperature technique that allows for the fine control of the product’s chemical composition.
Even small quantities of dopants, such as organic dyes and rare earth elements, can be introduced
in the sol and end up uniformly dispersed in the final product. It can be used as a means of
producing very thin films of metal oxides for various purposes.

Applications:

Some of the important applications and technologies based on the nanomaterials are the
following:

1. Production of nanopowders of ceramics and other materials.

2. Nanocomposites

3. Development of nanoelectrochemical systems(NEMS)

4. Applications of nanotubes for hydrogen storage and other purposes.

5. DNA chips and chips for chemical/biochemical assays

6. Gene targeting/drug targeting

7. Nanoelectronics and nanodevices

The last one, which is probably the most challenging area, includes new lasers,
nanosensors, nanocomputers (based on nanotubes and other materials), defect- free electronics
for the future molecular computers, resonant tunneling devices, spintronics and the linking of the
biological motors with inorganic nanodevices.

NANOCARBON:

Nanocarbons are Carbon-based materials that can be bonded at the molecular level in
differing ways to achieve unique properties. This family of materials includes Nanotubes,
buckytubes, fullerenes & more.
 The development into nanocarbon manipulation & control is vital for the production &
creation of nanomachines & nanobots. Through the successful creation of Molecular level
machines we will be able to program these machines to do the molecular manipulation for us, the
beginning of the molecular age.

Fullerenes:

Fullerene is a family of carbon allotropes, molecules composed entirely of carbon, in the

form of a hollow sphere, ellipsoid, or tube. Spherical fullerenes are also called buckyballs, and
cylindrical ones are called carbon nanotubes or buckytubes. Fullerenes are similar in structure to
graphite, which is composed of stacked sheets of linked hexagonal rings, but may also contain
pentagonal (or sometimes heptagonal) rings that would prevent a sheet from being planar.
Fullerenes are unique carbon structures that have great potential for uses in future
nanotechnological applications.

The structure of C60 is a truncated (T=3) icosahedran, which resembles a soccer ball of
the type made of twenty hexagons and twelve pentagons, with a carbon atom at the vertices of
each polygon and a bond along each polygon edge. The van der Waals diameter of a C60
molecule is about 1 nanometer (nm). The nucleus to nucleus diameter of a C60 molecule is about
0.7 nm. The C60 molecule has two bond lengths. The 6:6 ring bonds (between two hexagons) can
be considered "double bonds" and are shorter than the 6:5 bonds (between a hexagon and a
pentagon). Its average bond length is 1.4 angstroms.

Carbon nanotube science and technology:

Carbon nanotubes are molecular-scale tubes of graphitic carbon with outstanding

properties. They are among the stiffest and strongest fibres known, and have remarkable
electronic properties and many other unique characteristics. For these reasons they have attracted
huge academic and industrial interest, with thousands of papers on nanotubes being published
every year. Commercial applications have been rather slow to develop, however, primarily
because of the high production costs of the best quality nanotubes.

Structure:

The bonding in carbon nanotubes is sp², with each atom joined to three neighbors, as in
graphite. The tubes can therefore be considered as rolled-up graphene sheets (graphene is an
individual graphite layer).

Synthesis:

The arc-evaporation method, which produces the best quality nanotubes, involves passing
a current of about 50 amps between two graphite electrodes in an atmosphere of helium. This
causes the graphite to vaporise, some of it condensing on the walls of the reaction vessel and
some of it on the cathode. It is the deposit on the cathode which contains the carbon nanotubes.

Single-walled nanotubes are produced when Co and Ni or some other metal is added to
the anode. It has been known since the 1950s, if not earlier, that carbon nanotubes can also be
made by passing a carbon-containing gas, such as a hydrocarbon, over a catalyst. The catalyst
consists of nano-sized particles of metal, usually Fe, Co or Ni. These particles catalyze the
breakdown of the gaseous molecules into carbon, and a tube then begins to grow with a metal
particle at the tip.

It was shown in 1996 that single-walled nanotubes can also be produced catalytically.
The perfection of carbon nanotubes produced in this way has generally been poorer than those
made by arc-evaporation, but great improvements in the technique have been made in recent
years. The big advantage of catalytic synthesis over arc-evaporation is that it can be scaled up for
volume production. The third important method for making carbon nanotubes involves using a
powerful laser to vaporize a metal-graphite target. This can be used to produce single-walled
tubes with high yield.

Properties:

The strength of the sp² carbon-carbon bonds gives carbon nanotubes amazing mechanical
properties. The stiffness of a material is measured in terms of its Young's modulus, the rate of
change of stress with applied strain. The Young's modulus of the best nanotubes can be as high
as 1000 GPa which is approximately 5x higher than steel. The tensile strength, or breaking strain
of nanotubes can be up to 63 GPa, around 50x higher than steel. These properties, coupled with
the lightness of carbon nanotubes, gives them great potential in applications such as aerospace. It
has even been suggested that nanotubes could be used in the “space elevator”, an Earth-to-space
cable first proposed by Arthur C. Clarke.

The electronic properties of carbon nanotubes are also extraordinary. Especially notable
is the fact that nanotubes can be metallic or semiconducting depending on their structure. Thus,
some nanotubes have conductivities higher than that of copper, while others behave more like
silicon. There is great interest in the possibility of constructing nanoscale electronic devices from
nanotubes, and some progress is being made in this area. However, in order to construct a useful
device we would need to arrange many thousands of nanotubes in a defined pattern, and we do
not yet have the degree of control necessary to achieve this. There are several areas of
technology where carbon nanotubes are already being used. These include flat-panel displays,
scanning probe microscopes and sensing devices. The unique properties of carbon nanotubes will
undoubtedly lead to many more applications.

Applications:
 Carbon Nanotubes are largely used in the research & development of nanomachines, new
nanofibres & nanostructures. Some of its applications are:

1. Structural Composites Applications: The exceptional strength of nano carbon tubes benefits
several sporting goods applications based on carbon fibre composites. TechNano’s chemically
modified nano carbon tubes are far easier for integration and better bonding with the binder (e.g.
epoxy or polyurethane). Typical improvement measured on the fibre-reinforced composite is
between 10 to 50% in strength and impact. This level of enhancement is immensely meaningful
for this type of composite, generally limited by the resin properties.

2. Coating Applications: A network of very thin conductive structures such as nanocarbon tubes
gives also new possibilities in thin film technology such as antistatic transparent and conductive
coatings with permanent conductivity, better mechanical properties and chemical resistance.
CNTs based highly conductive transparent films are under development and could compete in
the near future with metal oxide-based technologies for producing flexible displays.

3. Reinforced Elastomers: Carbon blacks are widely used for reinforcing rubbers in tyres and
other industrial rubbers. Currently, reinforced rubber contains high loading of fillers (more than
50% wt.) for increasing stiffness and strength. At the same time, they lack elasticity for some
applications. CNTs developed by Nano have overcome this problem. By addition of 5-10% of
multi-wall nano carbon tubes will give you similar level of stiffness and strength in high
performance elastomers along with improved elasticity, offering a new balance of mechanical
properties that cannot be matched with conventional fillers.

4. Conductive Plastics: The use of nano carbon tubes for antistatic and conductive applications in
polymers is already a commercial reality and is growing in sectors such as electronics and the
automotive industry. The loading for achieving electrical percolation with multi-wall nano
carbon tubes can be 5-10 times lower than with conductive carbon black grades. Similar
comparisons are made in thermoset resins like epoxies but at much lower loading. The geometric
aspect ratio of carbon nanotubes is typically superior to 100 compared to short carbon fibre (<
30) and carbon black (> 1) in the final product (e.g. injection moulded part). This explains the
lower content needed for a given resistivity.

ZINC OXIDE NANOSTRUCTURES:

One-dimensional (1D) nanostructures have attracted considerable attention due to their

potential as building blocks for fabricating nanoscale electronic, optoelectronic, electrochemical
and sensor devices. Three-dimensional (3D) nanostructures are highly desirable for advanced
materials. Among these, zinc oxide, with a wide band gap (3.4 eV) and a large exciton binding
energy (60 meV), is recognized as one of the most promising semiconductor materials for
electronic and photonic applications. Up to now, various physical and chemical methods have
been widely reported for the preparation of 1D (nanowires, nanorods, nanobelts, etc.) and
complex (tetrapod-like, rotorlike, hierarchical, nanosprings, etc.) ZnO nanostructures.

Synthesis:

One-dimensional nanostructures of ZnO can be synthesized by either physical vapor

deposition methods at high temperature (500-600°C) or chemical approaches at low temperature
(~70°C) on a wide range of substrates without using sophisticated or expensive equipment. Its
diverse and versatile morphologies are probably greater than any material known today.

Recently, hierarchical and complex ZnO micro/nanoarchitectures have stimulated much

attention since such architectures combine the features of micrometer- and nanometer-scaled
building blocks and show unique properties different from those of the mono-morphological
structures. Many micro/ nanocomposite ZnO architectures, such as bridge and nails, propellers,
and microcrystals, nanocavities, nanowalls, and nanorods, have been synthesized by gas-phase
reactions. Alternatively, two main solution-based routes have also been developed to fabricate
various hierarchical micro/nanostructured ZnO. Such routes are attractive because of their mild
synthetic conditions, low-cost, and mass production. Both solution-based routes involve a multi-
step process. One is a precursor-induced synthesis, in which the low solubility of the pre-
synthesized precursor in the reaction solvent induces a controlled release of Zn2+ ions favorable
for ZnO hierarchical growth. For example, ZnO hierarchical structures with ring like nanosheets
that stand on spindle-like rods were synthesized from a flake-like precursor Zn5(OH)8Cl2.2H2O.

Cauliflower-like ZnO nanostructures which have surface one dimensional (1D)

nanoarrays with 10 nm diameter can be successfully fabricated through a simple sonochemical
route. Zinc acetate is added to solvent containing water and triethanolamine under vigorous
stirring. After the dissolution is complete sodium hydroxide pellets are added to the mixture. The
resulting solution is then irradiated in an ultrasonic bath (Power Sonic 410, 500 W) for 2 h under
the ambient atmosphere. The resulting white powder obtained after irradiation is centrifuged and
washed several times with deionized water and dried in an oven.

Flower and rod like ZnO nanostructures can be synthesized in a hydrothermal phase by
simply tuning the ratios of zinc acetate to sodium hydroxide. The aqueous solutions of the two
are added to a Teflon lined autoclave and heated at a particular temperature. Later the product is
separated by centrifugation and washed with distilled water several times. The supersaturation of
the precursors results in various nucleation habits, which induce the ZnO nanostructures with
different morphologies. The choice of appropriate concentration of starting materials is very
important in the shape control of ZnO nanocrystals. As no catalyst or template is introduced, this
method is simple, controllable and extendible.
 Flower-like cupped-end ZnO micro-rod bundles can be hydrothermally synthesized from
a sheet-shaped precursor ZnCl2(N2H4)2 heated at 140°C for 12 h. Hierarchical nanostructured
ZnO with a bladed bundle-like architecture can be fabricated from a flower-like precursor ZnO·
0.33ZnBr2·1.74H2O. The other route is a sequential nucleation and growth route, by which the
oriented primary ZnO rods, the secondary needle-like nanobranches (or nanoplates), and the
tertiary nanoplates (or nanobranches) are synthesized stepwise on specific sites of previous
structures.

Both the size and morphology have a significant influence on the properties of the
semiconductor oxides. New properties and promising applications in many fields may be
induced from the unique structures. However, fabrication of more complex ZnO
micro/nanoarchitectures in one step is still a significant challenge.

Applications:

Research in ZnO nanostructures was first inspired by the discovery of oxide nanobelts in
2001. As for one-dimensional (1-D) nanostructures, ZnO has equal importance to silicon-based
1-D nanostructures, according to published articles in the literature and it is playing an
increasingly key role in developing nanoscience and nanotechnology. It is fair to state that
carbon nanotubes, silicon nanowires, and ZnO nanowires/nanobelts are probably the most
important 1-D nanomaterials in today’s research.

The piezoelectric and pyroelectric properties of ZnO make it a great candidate for
sensors, transducers, energy generators, and photocatalysts for hydrogen production. ZnO is also
a “green” material that is biocompatible, biodegradable, and nontoxic for medical applications
and environmental science. ZnO 1-D nanoforms are found to be highly suitable for nanoscale
applications such as room temperature laser, field effect transistor nanoresonator, etc. One
dimensional nanostructures, specially aligned ZnO nanoforms, are especially important for their
enhanced optical properties.

Electronics: ZnO has wide direct band gap (3.37eV or 375nm at room temperature). Therefore,
its most common potential applications are in laser diodes and light emitting diodes (LEDs).
Some optoelectronic applications of ZnO overlap with that of GaN, which has a similar bandgap
(~3.4eV at room temperature). Compared to GaN, ZnO has a larger exciton binding energy
(~60meV, 2.4 times of the room-temperature thermal energy), which results in bright room-
temperature emission from ZnO. Other properties favorable for electronic applications of ZnO
include its stability to high-energy radiation and to wet chemical etching. Radiation resistance
makes ZnO a suitable candidate for space applications.

The pointed tips of ZnO nanorods result in a strong enhancement of an electric field.
Therefore, they can be used as field emitters.
Zinc oxide nanorod sensor: Zinc oxide nanorod sensors are devices detecting changes in
electrical current passing through zinc oxide nanowires due to adsorption of gas (example:
hydrogen) molecules. Selectivity to hydrogen gas was achieved by sputtering Pd clusters on the
nanorod surface. The addition of Pd appears to be effective in the catalytic dissociation of
hydrogen molecules into atomic hydrogen, increasing the sensitivity of the sensor device. The
sensor detects hydrogen concentrations down to 10 parts per million at room temperature,
whereas there is no response to oxygen.

TITANIUM DIOXIDE NANOSTRUCTURES:

Titanium dioxide (TiO2), occasionally called titanium white or titanium pigment, is truly
the white of 20th century. The past decade has witnessed an exponential growth of activities in
TiO2 nanomaterials research, driven by both the excitement of the scientific discoveries at the
nanometer scale and the potential of the economic impact resulted from photovoltaic and
photocatalytic applications.

Synthesis:

Nanocrystalline TiO2 can be synthesized by the hydrolysis of titanium tetrabutyl in the

presence of water and ethanol under high- intensity ultrasonic irradiation. The structure and
particle sizes of the product were dependent upon the reaction temperature, the acidity of the
medium and the reaction time.

The sonochemical formation mechanism of nanocrystalline TiO2 is as follows: The

hydrolytic species of titanium tetrabutyl in water, condensed to form a large number of tiny
nuclei, which aggregated to form large clusters. Ultrasound irradiation generated many local
hotspots within the gel, and the crystal structure unit was formed near the hotspots with decrease
in the gel nuclei, which led to the formation of nanocrystal particles.

Nonhydrolytic sol-gel processes have been developed to obtain high quality TiO2
nanoparticles in nonhydrous solutions. These processes usually apply to the reaction of titanium
chloride with a variety of oxygen donor molecules. The formation of Ti-O-Ti bridges results
from the condensation between Ti-Cl and Ti-OR. The alkoxide functions can be provided by
titanium alkoxides or can be formed in situ by reaction of the titanium chloride with alcohols or
ethers. For example TiCl4 is slowly added to anhydrous benzyl alcohol under vigorous stirring at
room temperature and the reaction vessel is kept at 40-150° C for 1-21 days. After centrifuge, the
precipitate is thoroughly washed with ethanol and THF, and calcinated at 450° C for 5 hour.

Microwave- hydrothermal synthesis of titanium dioxide under various reaction conditions

have been reported till now. Crystallization of rutile from TiOCl2 solutions was found to be
extremely rapid. TiO2, particle size, morphology and polymorph can be controlled by changing
various parameters, such as: concentration, pH, pressure or temperature, time, and anionic
species. The main advantages of microwave- hydrothermal processing of TiO2 are: Rapid heating
to required temperature and extremely rapid kinetics of crystallization.

TiO2 can also be synthesized from the alkoxide by the polyol method using various
polyols (1,4- butanediol, 1,5- pentanediol, or 1,6- hexanediol) under MW radiation. The
crystallite size, which is always less than 10nm, could be controlled by the quantity of water
added and by the nature of the polyol.

Applications:

TiO2 nanomaterial normally has electronic band gap larger than 3.0 eV and high
absorption in the UV region. Its optical properties allow it to be a good candidate for UV
protection applications. Besides that, TiO2 nanomaterial is very stable, non toxic and cheap. It
has shown very high photocatalytic activity against various pollutant and has been regarded as
the most promising and widely used nanomaterials as environmental- benign photocatalyst for
the decomposition of various aqueous and gas pollutants.

The strong oxidizing power of illuminated TiO2 can be used to kill tumor cells in cancer
treatment. Fogging of the surface of the mirror and glass occurs when humid air condenses, with
the formation of many small water droplets, which scatter light. Various glass products, i.e.
mirrors and eyeglasses, can now be imparted with antifogging functions with TiO2 nanomaterials
having super hydrophilic or super hydrophobic surface. TiO2 nanomaterials have been widely
used as photocatalytic electrodes for solar energy applications.

TiO2 nanomaterials have been widely studied for water splitting and hydrogen production
due to its suitable electronic band structure with the redox potential of water. Another application
of TiO2 nanomaterials when sensitized with dyes or metal nanoparticles is to build photochromic
devices. TiO2 nanomaterials have also been used as sensor for various gases and humidity.