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Chapter –1
Introduction to
Nanoscience and
Nanotechnology
In the past few decades, a tiny word paying enormous attention, interest and
aspect of the way that we think in science and technology and will absolutely
bring more and more surprises into our daily life as well as into the world in the
future.[1-8] Nano science research has been rapidly increasing across the world
important position in the field of energy. The present natural energy resources
will exhaust one day. The future generation will have to look for the alternative
energy sources like solar energy and hydrogen based fueles. There is
sun light in presence of nanomaterials. Materials like carbon nano tubes used
for hydrogen storage. Current cost of carbon nano tubes is very high but
scientists are trying to find out very economical way of preparing them in
high surface area, ultra light weight materials like aerogels are found to be
molecular structures with at least one dimension measuring between 1 and 100
studies on the behavior of ultrafine particles with dimensions at this scale (e.g.,
from diesel engine emissions) that are accidentally released into the air can be
introduced in the late 1970. While many definitions for nanotechnology exist,
most groups use the National Nanotechnology Initiative (NNI) definition. The
range. Creating and using structures, devices, and systems that have novel
Feynman quoted that there’s plenty of room at the bottom [10]. “in his
introduction to the topic of his lecture he said, I would like to describe a field
in which little has been done but in which an enormous amount can be done in
principle.This field will not tell us much of fundamental physics but it might
tell us much of great interest about strange phenomena that occur in complex
controlling things on a small scale. Nano science research has been rapidly
structures. Nano scale science and technology has emerged as a fast growing
systems lie at the threshold between classical and quantum behavior and exhibit
Quantum dots (QD) are nanometer scale “boxes” for selectively holding or
releasing electrons. Quantum dots are tiny devices that contain free electrons.
few nanometers. The size and shape of these structures and thus the number of
potential energy barriers that form the QD’s boundaries, QD’s of desired
properties can be created by tailoring the size, shape and composition. The
electrons.
quantum confinement effects are investigated in detail. They are also referred to
crystal, the energy level form bands. At 0˚ K the valence band is completely
filled and the conduction band is completely empty and these bands are
excitations, an electron hole pair is created. The electron in the conduction band
and the hole in the valence band can be bound when they approach each other at
a finite distance. This bound pair is called “exciton” which is deloc alized
Where
ε = dielectric constant
optical properties, together with both the absorption and emission of light.
These particles are called quantum dots as their electrons are confined to a
point in space. They have no freedom in any dimension and electrons are said to
properties.
A perfect quantum dot is probable only when the electronic states within
the quantum dot face a discontinuity at the edge of the material. Therefore the
electron within the dot feels an interactable barrier at the edge. When a material
order to decrease the surface energy, the surface reconstructs, which leads to
energy levels in the prohibited gap of the semiconductor. The electrical and
larger band gap. In an ideal semiconductor quantum dot, when there are no
defect sites for charges to get trapped, the quantum yield of luminescence will
be very high and emission will also be sharp. Better light emission occurs as
the electrons and holes are confined spatially. This is achieved by chemically
protecting the surface with protecting molecules called “capping agents”. Since
1.3 Nanomaterial
1857 that Michael Faraday carried out path breaking work on what he called
ruby green, violet or blue etc; consists of that substance in a metallic divided
state. One type of gold particles prepared by Faraday are still preserved in the
Royal Institution in London .In the nano world we cannot see objects with our
necked eyes, we can not touch or manipulate them by our hands or any of the
tools that we generally use. The objects that we deal with the nanow orld are
very tiny and are close to the size of the atoms and molecules. The effects of
gravity and inertia are less dominating in the nanoworld, but surface tension
and other molecules forces do play a role. Comparing an object with diameter
of nanometer to that of meter is like comparing the size of the marble to the
size of the earth. A single strand of human hair around 20000 nanometers
diameter. Bulk materials properties are independent of its size, where as when
In nano materials
3) Spatial confinement
bulk materials.
The melting point ( m.p) drastically falls when the particle size is much
nanotubes and nano particles, which all melt at lower temperature than bulk
from the same materials.The change is m.p is because , nano scale materials
All nano materials posses high mechanical strength than bulk.The cutting
tools should be harder than the materials which is to be cut are made of
nanomaterials .These cutting tools are higher erosion- resistant and durable than
nano scale.
Optical properties of nano materials are much different from their bulk
increased band gap for semiconductor nano particles absorption edge shift
Chemical properties of the materials are changed when they are in nano
From the detailed study of nano materials it has been realized that
materials in nano dimensions exhibit properties that are different from their
industries and daily lives[12-13].This is becoming more and more evident in the
catalysis [14,15], biosensors [16 -19], diagnostic [20], cell labeling [21-23],
solar cells [24,25], fuel cells[26]. Photonic band gap materials [27], single
[41-46].
properties.The factors that can strongly modulate their properties include their
in properties of nano materials are due to their dimensions. One of the readily
metal nano particle originates due to surface plasmons [69]. Surface Plasmon is
the nano materials leading to discrete energy levels in the conduction band and
model[70,71]. The quantum size effect has been well studied in case of semi -
conducting nano particles and the energy level spacing for a spherical particle
decrease in size the effective band gap increases and the relevant absorption
bulkmaterial into smaller units using some form of grinding mechanism. This is
beneficial and simple to execute and avoids the use of volatile and poisonous
with the material produced by modern bottom up methods. The main drawbacks
include defect problems from grinding equipment, low particle surface areas,
asymmetrical shape and size distributions and high energy needed to produce
distinguished that the nano-material produced from grinding still finds use, due
This has the advantage of being potentially much more convenient than the top
the growing nanoparticle, then the size, shape and composition of the
bottom up, chemically based and designed, reactions are normally seen as being
of higher quality and having greater potential applications. This has led to the
and growth. One of the key differences that can be used to sub divide these
decomposed . It is beyond the scope of this thesis to describe all the current and
Top Down
Bulk
Powder
Nanoparticles
Clusters
Atom
s
Bottom Up
There are different types of nano materials. They range from zero
least one dimension in the nanometer range. Any multilayered material with
grains are 2D modulated. This includes coatings hidden layers and thin films.
materials. To achieve this goal, researchers are trying to follow the “top-down”
be considered as the one with which the human race first learned to fabricate
materials and in due course of time, perfected this art by being able to engineer
physics and materials science [74-78]. The metal elements are able to form a
large diversity of oxide compounds [79]. These can adopt a vast number of
devices, fuel cells, coatings for the passivation of surfaces against corrosion ,
and chemical properties due to their limited size and a high density of corner or
edge surface sites. Particle size is expected to influence three important groups
of basic properties in any material. The first one comprises the structural
characteristics, namely the lattice symmetry and cell parameters. Bulk oxides
structures. However, the growing importance of surface free energy and stress
requirement, phases that have a low stability in bulk materials can become very
zinc oxide (ZnO)[92], tin oxides and industrially employed metal oxides since
last fifty years. These oxides have become important both scientifically and
industrially because of their applications for sound and picture recording, data
chemistry but under special circumstances some compounds of trivalent are also
found, it is known that this trivalent copper survives not more than few seconds
in that particular state. Copper (I) compound are dimagitic nature with few
application. CuO is a promising material for fabricating solar cells due to the
Among the Copper oxides only cupric oxide (CuO) phase is rep orted as
narrow band gap of 1.2eV, with low electrical resistance values. The electrical
with band gap of about 1.4eV. The band gap is identitical as being of charge-
associated with Cu-O bond, the copper oxide atom is co-ordinated by 4 oxygen
pressure seem to indicate a phase transition. The magnetism of the Cu (II) ion
Copper oxide is used as a pigment in ceramic to produce blue, red & green
colour. It is also used in welding with copper alloys. It is also used to dispose
Tin forms two series of compounds stannous or tin (II) compounds and
stanic or tin (IV) compounds. Both are stable oxidation state . Stannous oxide is
above this temperature it gets convertrd into stannic oxide, a white coloured
compound. In Chemical industries, SnO is used in making tin salts for regents
catalyst.
Among the various semiconducting metal oxides, SnO 2 has been the
most popular gas sensing material. SnO 2 Crystalizes in the tetragonal crystal
system and is isostrucutral with rutile phase. Each unit cell consists of two tin
atoms and four oxygen atoms. The octahedral are sharing edges and form linear
chains along the c-axis.The n-type SnO 2 has been explored and widely used for
the most extensively studied for gas sensing applications, by using bulk, thick
and thin films to fabricate gas sensors. Most of the commercially available gas
sensors are made mainly of SnO 2 in the form of thick films, thin films, or
porous pellets. The well-known advantage of this material includes its low-cost,
nanostructures, whose configurations are far richer than any other known
pressures above 8 GPa it undergoes a phase change to rock salt structure. It has
substrates[95]. Electrical properties Zinc oxide (ZnO) has a wide direct band
gap (3.37 eV) and a relatively large excitation binding energy (60 meV). Owing
to its unique properties wide band gap and large excitation binding energy, ZnO
devices etc. ZnO nanowires are also reported to have behaved like n-
100]. The major road block of ZnO for wide spread applications in electronics
and photonics is its problems with p-type doping. Quite a few p-type doping
efforts have been reported like Ga and N co- doping method which resulted in
the formation of low resistivity (0.5 Ohms/cm) p-type ZnO thin films.
Successful p-type doping for ZnO nanostructures will give a boost to their
type and n-type ZnO nanowires can serve as p-n junction diodes and LEDs.
Field effect transistors (FETs) fabricated from them can be used to make
1.7 Surfactants
interfacial activity. It is important to note that all amphiphiles do not show such
does not take place if the amphiphilic molecules is too hydrophilic or too
surface tension between two liquids or between a liquid and a solid, when used
and a water soluble component. Surfactants will diffuse in water and adsorb at
interfaces between air and water or interface between oil and water.The
insoluble hydrophobic group may extend out of the bulk water phase, into the
air or into the oil phase, while the water soluble head group remains in the
hydrophobic tails form the core of the aggregate and the hydrophilic heads are
According to polar head group surfactants are classified into five types.
Those surfactants which have no charged groups in its head are called as
ether, ester, or amide. A large portion of these non ionic surfactants are made
condensation of ethylene oxide. In the past decade, glycoside head groups have
Ex: Polyethylene glycol, alkyl ethers, glycoside alkyl ethers, Triton x-100 etc.
positive charge, are called cationic surfactants. These surfacts are dissociated
ammonium and natural fatty acids. These surfactants are more expensive than
sulphate, etc.
both cationic and anionic centers attached to the same molecule.The cationic
part may be primary, secondary, or tertiary amines and the anionic part can be
1.7.1.5 Biosurfactants
are used to remove petroleum from contaminated sites has been studied and
found to be safe and effective in the removel of petroleum products from soil.
smell of rotten eggs which is denser than air may pool in low areas in still
conditions.
initially but over time turns cloudy.This is because of slow reaction of H 2 S with
alcohols.
It occurs naturally such as sulphur springs, swamps and salt marshes and
water and surface water bodies, due to bacteria which convert sulphur materials
into hydrogen sulphide.This may be the case where acid sulphate soils have
been disturbed. It also exists in hydrocarbon reservers like natural gas and oil.
production of heavy water plants by dual temperature exchange reac tion and in
no longer discerns its smell before the dangerous threshold values of 50 -100
ppm is reached. Hence there is a need to detect H 2 S gas when present at a few
ppm levels and preferably at sub ppm levels in the air. H 2 S also occurs
in volcanic gases, natural gas, and in some sources of well water. The human
hydrogen sulfide to boil at a lower temperature than water. The human body,
volcanic gases, unrefined petroleum and natural gas all contain hydrogen
sulfide. This gas is heavier than air so it often accumulates in low-lying areas.
Food processing plants, paper mills and other industries can also create H 2 S as
organic compounds.
The main use for hydrogen sulphide is in the production of sulfuric acid
sulphur compounds.
agricultural disinfectant and you will find it in some cutting oils, which are
coolants and lubricants designed specifically for metal working and machining
class as cyanide and carbon monoxide, and is extremely toxic. Therefore, it's
important to minimize exposure to this gas; 50 to 200 parts per million can
1.9 Nanocomposites
1.9.1 Ex situ
accomplished by mixing with a solution of the polymer, which can then be spin
Even with this step it is tricky to produce well dispersed composites, and a
polymer-particle-solvent systems.
1.9.2 In situ
The in situ methods that have been used for the manufacture of metal
situ methods, though often less simple and straight-forward as ex situ, are
The composite in which one of the phase shows at least in Nano meter
colloids, gels and co-polymers. Most of materials and nano materials are
which materials long predates the understanding of the physical and chemical
nature of these materials. Nano composites are found in nature for example in
the structure of the abalone shell and bone. The use of nano particles rich
materials long predates the undnerstading of the physical and chemical nature
of these materials. Jose yacaman et al. investigated the origin of the depth of
colour and resistance to acids and bio-corrosion of Maya blue paint, attributing
volume ratio of the reinforcing phase. The reinforcing materials can be made up
of particles, sheets, or fibres. The area of interface between the matrix and
the vicinity of the reinforcement. Ajayan et al. note that with polymer
chain ordering or crystalline can all vary significantly and continuously from
the interface with reinforce into the bulk of the matrix. This large amount of
reinforcement can have an observable effect on the macroscale pro perties of the
general, the nano reinforcement is dispersed into the matrix during processing.
The percentage by weight of the nano particles int roduced can remain very low
due to the low percolation threshold, particularly for the most commonly used
material retains its separate chemical, physical, and mechanical properties. The
two constituents are reinforcement and a matrix. The main advantages of nano
composite materials are their high strength and stiffness, combined with low
density, when compared with bulk materials, allowing for a weight reduction in
the finished part. The reinforcing phase provides the strength and stiffness.
[111]
classification is usually made with respect to the matrix constituent. The major
fibres are improved strength and stiffness, improved creep and fatigue
resistance, and increased hardness, wear and abrasion resistance, combined with
the possibility of higher operating temperatures than for the unreinforced metal
rubbers, which are very good insulators. Even many conducting polymers were
well known in their non conducting forms before their electrical properties were
reported by Letheby as early as 1862 [115]. However, it was not until a hundred
years later, in the 1970s, that Hideshi Shirakawa, Alan G. Mac Diarmid, Alan J.
related materials, have been synthesized. These polymers are often called
charge carriers introduced into the π-conjugated system that is formed by the
varied by adding a dopant to change the charge carrier density on the polymer
level.[117]
and conductors. A band model explains why some materials conduct electrical
charge, while some do not, as shown in Figure 1.8. According to the band
produce electronic bands. The valence electrons overlap to form a valence band,
while electrons in the conduction band have higher energies, which are
sufficient to allow electrons to move freely within the materi als. The energy
difference between these two bands is called band gap, usually denoted as E g .
In metal conductors, the valence band and the conduction band overlap; thus,
electrons can move freely in a background of positive charge formed by the ion
cores. The band gap of insulators is generally very high, resulting in a low
conductivity at room temperature. If the band gap is small (e.g., 2 eV), the
valence electrons can be excited into the conduction band by thermal or pho ton
excitation. The electrons then become mobile, and the material is termed a
conjugation. The overlapping of the π-bands is the valence band, and the π*-
band is the conduction band in the conducting polymers. If the band gap is
as conductive as a metal.[121]
implies
doping),
(2) The associated insertion of a counter ion for the overall neutrality, and
on the type of dopant and on its distribution in the polymer. [124-126] .P-type
removal of electrons from the valence band, leadin g to the presence of positive
band, causing an n-type doping. P-type doping is normally more common than
n-type because most n-type doped conducting polymers are not as stable in the
of charge carriers, such as polaron, bipolaron, and soliton. Assuming that the
electron hopping was dependent on the initial and final energy states between
semiconductors, such as α-Ge. This VRH model predicts that the conductivity
Hz), e is the electron charge, N(E f ) is the density of states at the Fermi level,
and T is the temperature. This model has been widely used to study
D hopping model,[130] while for PANI, a quasi 1-D hopping model was found
[132-136]
σ= σ o exp(-βδ)
1.13.1 Chemical
into a radical cation, which has several resonance forms of cations. The
coupling of two radical cations results in a dimer. The dimer can then be
reaction conditions. The mixture is then filtered, washed, and dried to yield
1.13.2 Electrochemical
and purified
The conducting polymers are mainly classified into two types depending upon
alternate single and double bonds that leads to one unpaired electron per carbon
atom [141].
this system are provided by the electron transfer between the electron donors
(D) and acceptor (A) molecules. In case of ionically conducting polymers, the
Conducting Polymers
powders etc. are used as conductive fillers. These fillers are loaded in the
common insulating polymers, which have been used as major matrix, like PC,
PET, PP, PVC, HDPE, Nylon etc. to get conducting polymer composites or
the polymer is decided by the volume fraction of the filler. A transition from
more than 20% is required. This higher addition of these rigid fillers will cause
problems. Moreover, these fillers also affect the properties of finished products
like aesthetics, brittleness, poor finish, etc. Hence, there is a need to develop
conducting polymers.
orbital of metal may overlap with p-orbital of the organic structure and thereby
increases the electron delocalization. The d - orbital may also bridge adjacent
bridge of transition metal complexes forms one of the stable systems exhibit
molecules are added to the insulating polymers. There are many charge transfer
bromine, chlorine etc [144]. The reason for high conductivity in polymeric
charge transfer complexes and radical ion salts are still somewhat obscure. It is
electron delocalization.
four decades ago when Shirakawa and his group found drastic increase in the
[146]. In 1975, the first papers on the novel metallic polymer, poly (sulfur-
nitride), (SN) x appeared in the literature. That event heralded the dawn of a
polymers. The unique electronic properties of these polymers are due to the
presence of π-electrons and the wave functions of which are delocalized over
long portions of polymer chain when the molecular structure of the backbone is
planar [147]. Therefore, it is necessary that there are no torsion angles at the
bonds, which would decrease the delocalization of the π-electron system [148].
–bonds are as fallows: Band gap E g (electronic band gap) is small (~ 1 to 3.5
eV) with corresponding to low excitations and semiconducting behavio ur. The
reactions with atomic or molecular dopant species. The charge carrier mobility
in the conducting state is large enough and because of this, high electrical
move relatively freely through the material [149, 150].The electrical and optical
proportional to both the density and drift mobility of the charged carriers. The
carrier drift mobility is defined as the ratio of the drift velocity to the electric
field and reflects the ease with which carriers are propagated. To enhance the
wide range from insulating to metallic by proper doping, addition of fillers and
Y 2 O 3 [157], TiO 2 [158], TaS 2 [159], CdPS 3 [160], V 2 O 5 [161], MoO 3 [162] and
FeOCl [163].
extended (π) orbital system and conjugated carbon system [ 164]. The
insulators. As such, the energy gap can be > 2 eV, which is too great for
conductivity similar to metals. Even at a very low level of doping (<1 %),
polymers. Highest values reported up to now are for the conductivity of stretch
double bonds which are 0.145 nm and the longer bond length is 0.135 nm,
increases. [167-172].
and molecular electronic devices [173, 174]. Amongst the family of conducting
conducting polymers.
1.15.1 Conjugation
Table 1.1 lists the repeat units and conductivities for few common
conjugated polymers [175] as can be seen in Table 1.1, the conjugated structure
with alternating single and double bonds or conjugated segments coupled with
just as metals have high conductivity due to the free movement of electrons
they must possess not only charge carriers but also an orbital system that allows
the charge carriers to move. The conjugated structure can meet the second
back bone. Due to its simple conjugated molecular structure and fascinating
electronic properties, polyacetylene has been widely studied as a proto type for
dye and has been studied over 100 years. It was not until the middle 1980’s that
the polymer chain flanked by phenyl ring on either side. Polyaniline represents
insulator to a conductor by the redox process. The conducting state of PANI can
be obtained in its 50% oxidized emeraldine state in aqueous acids like HCl and
fully oxidized pernigraniline. However, the fully oxidized and reduced state of
PANI is not conducting. Only when the moderately oxidized states (especially
the emeraldine form) are doped, does PANI become conductive. The structure
compound. Reverse switching between emeraldine salt and emeraldine base can
Figure 1.12. The conductivity of PANI varies with the doping level, which is
takes place in presence of aqueous acid e.g., 1M HCl solution. The polymer
formed is called emeraldine salt. The different oxidizing agents are used in
peroxide, ferric chloride [183] and ceric nitrate and sulfate [184,185]. ]. It has
also been reported that, the high molecular weight PANI can be synthesized
Oxide (ITO) glass electrode. In this method the polymerization of aniline can
repeatedly cycling the applied voltage between two pre -selected potentials
[191].
NH NH N N
y 1-y x
The Figure 1.13. represents the general structure of PANI [192], which was
first predicted by Green and Woodhead [193]. According to them PANI has a
Step I: The formation of the radical cation by an electron transfer from the 2 s
energy level of the aniline nitrogen atom, as shown in Figure 1.14. The aniline
radical cation has four resonant forms[(a),(b),(c) and (d)], in which (c) is the
more reactive one due to its important substituent inductive effect and absence
of steric hindrance.
Fig.1.14: The formation of the aniline radical cation and its different resonant structures
Step II: The step corresponds to the dimer formation due to “head-to-tail”
reaction between the radical cation and its resonant form in acidic medium.
Then the dimer is oxidized to form a new radical cation dimer, as shown in
Figure 1.15.
Step III: The formed radical can react either with the radical cation
respectively. If this continues, similar to the above steps, the polymer is finally
Gas sensors have been widely used in many areas like environmental
and traffic safety. They are also used for the detection of toxic environmental
pollutants [199] and prevention of hazardous gas from industrial exhaust [200].
Development of gas sensors are getting more and more attention in civil and
taking advantage of high surface area and or quantum mechanical effects for
suibably engineered material on nano scale. Thus metal oxide gas sensors have
Now a days the research on the gas sensors is focused at obtaining new
materials to get high sensitivity and selectivity with long term operating
devices.. Metal oxides have emerged as the suitable materials for the gas
sensors applications. The present work is one such effort to develop metal oxide
Different kinds of gas sensors to detect hazardous gases have been developed
during the past decades. These sensors work on different principles. A few of
chemically adsorbed on electrode surface [202]. These sensors react with the
1.17.1.2Catalytic Sensors
Catalytic sensors work on the principle of redox reaction [203]. The principle
combustible gas comes in contact with the catalyst surface it is oxidized and
exothermic reaction takeplace. The heat released causes the change in the
chemical bond due to the resonance phenomena [204] Infrared radiation is less
scattered by particles of gas than visible radiation due to its longer wavelength.
The gas is present in the optical path will interfere with the power of the
light transmission between transmitter and receiver. This brings in the change
in the state of light, which helps to quantify the amount of gas present in a
Gas sensors based on the sound are known as acoustic wave based gas
sensor [206]. This type of sensor is used in piezoelectric material either in the
form of thin films or pallet form which uses one or more transducers.
between the electrodes varies with the concentration of the probing gas. The
There are different classes of material used for gas detection, Conducting
polymer and Metal Oxides are widely used for gas sensor applications.
their derivatives have been used as gas sensing layers. They exhibit high
Metal oxides are extensively used for making gas sensing devices as they
offer many advantages. They are simple to operate, low cost, suitable for large
number of gases, etc. The idea of using semiconductors for gas sensing wa s
first reported in 1952 by Brattain and Bardeen using Ge. [ 210] Shavar PJ and
Seiyama et al., found the gas sensing behavior of metal oxides [ 211, 212] It was
Tugachi who finally brought out commercial semiconductor gas sensor based
on metal oxide and was named as Tugachi-type sensor [213]. Thus metal oxides
emerged as a class of material useful for gas sensing in addition to many other
environment.
Here the change in the physical properties of the film upon gas exposure
is measured . This sensing behaviour is the most important and well -known
wide band gap semiconductors and are more stable and hence operate in harsh
oxides are divided into two categories. Transition metal oxides (Fe 2 O 3 , NiO,
transition metal oxides (Al 2 O 3 , MgO, etc., ) and post-transition (SnO 2 , ZnO,
etc., )
Pre-transition metal oxides are rarely used as gas sensor material because
they have very large band gap and are found to be quite an inert. Whereas the
post transition metal oxides are more sensitive to the environment as compared
configurations are found to be more suitable for the gas sensing applications.
Among various metal oxides studied for gas sensing applications, SnO 2
is the widely studied. Sensing behavior of SnO 2 has been extensively reported
[216]. The advantages of using this material being low cost, higher response to
the n type or the p-type. When a n-type material interacts with a reducing gas
gases.
The gas sensing mechanism is based the variation of resistance when the
metal oxide particles are exposed to the gas under test.This is due to the
nanomaterial [217].
bond at the surface by a chemical reaction. The metal oxide causes the gas to
electrons from to gas molecules or vice versa. The resistance of the material
decreases when exposed to reducing gas where as it increases for oxidizing gas
Probing Gas
Contact
Pallet
Ohm Meter
modulation in the height of the energy barriers for free electrons to flow, which
air, oxygen is adsorbed at the surface. Adsorbed oxygen attracts free electrons
(a) (b)
Fig.1.18 : Shows the adsorbed oxygen species and the depletion regions at the grain
boundaries when the sensor is exposed to (a) air (b) reduced gas.
from inside metal oxide forming a potential barrier at the grain boundaries. This
potential barrier prevents the flow of electrons causing high sensor resistance in
hydrogen sulphide, the oxidation take place and the adsorbed oxygen density
decreases, which reduces the height of the potential barrier The flow of
electrons begin through the reduced potential barrier. Therefore the resistance
(PANI) and nanofibers reinforced with copper oxide nano particles were
prepared on glass substrate using spin coating technique. Polyaniline has been
Susheel Kumar singh and et al [219] have reported that PANI-Coper oxide
studied only optical and electrical properties. They characterised XRD, FT-IR,
UV-Visible only.
their better ability to store electrical potential energy under the influence of
PANI/Ag composite
prepared by spin coating techniques. The structural analysis revealed that the
Their study shows that different weight composites CuO constitutes different
nanoparticales of different nature and size can be combined with the conducting
route in the presence of the surfactant hydrazine at 100 o C for 12 hours. The size
of the particles was calculated and found to be 22.4 nm./ They used anamic
surfactant hydrazine which plays a key role in the formation of SnO 2 nano
particles.
decrease in band gap value from 3. 55 electron volt down to 3.27 as shown by
UV-Visible spectra. It is shown that the crystallite size is less than 10nm.
chemical digenstion method from the starting material as sncl 2 . The SnO 2 was
. The response and recovery time of sensor was calculated as 129 s ec and 206
sec. respectively. The reported better efficiency compared with the bulk SnO2
material.
conductive nano size composite of PANI with SnO 2 sythesise of SnO 2 and poly
control the size of SnO 2 nano particles in the range of from 10 to300nm to
syntheses.
S. B. Kondawar et al [229] have reported that tin oxide nano particles have
built up using four porbe resistivity unit and the response of the prepared
tested.
organic nano composite, in which SnO 2 nano particles were embedded within
D.S. Dhawale, et al [231] has carried out the liquefied petroleum gas (LPG)
chemical bath deposited ZnO film. The formation of diffusion free interface of
sensor has quick and high response towards LPG as compared to N 2 and
LPG
composite was investigate the optical behavior after doping the ZnO
nanoparticle into the polymer matrix. The inclusion of ZnO nanoparticle giv es
rise to the red shift of p-p transition of Pani. The nanocomposite was found to
-
be thermally stable upto 130°C and showed conductivity value of 3.0 x10
2
S/cm [138]
than pure PANI. Ammonia gas sensing behaviour of the ZnO/PANI nano-
conductivtiy retention was also studied using two slightly differ ent techniques.
The nanocompostes were also charecterized using FTIR, SEM TEM amd XRD.
conducing polymer display novel properties resulting from the molecular level
PANI films. They showed that the ZnO/ PANI composite coating on steel and
charecterized XRD, FTIR SEM and TEM and their result revealed that the
of synthesize composite was mainly due to the capping agent. The enhance
XRD, FT-IR, SEM etc. A simple room temperature LPG sensing device based
on the composte thin films of ZnO/PANI showed 38% sensitivity upon exposure
The materials with excellent properties are the fast expanding study area of
synthetic methods are used to prepare polymer nano composites and are
reliable. These methods can provide the base for research and applications.To
stability, processibility, sensitivity etc are the main objective of the present
work.
Polymer –metal oxide nano composites are a part of many important world wide
researchers due to size dependent properties and their many uses like
polymers are best host materials for nanoparticles of metal oxdes. There are
number of methods available for synthesis of nano compostes like sol - gel
precipitation method.
copper oxide, tin oxide, Zinc oxide are used to construct nanocomposites with
Polyaniline. The author has tried to reduce the size of nanoparticles by using
with UV-Vis, XRD and SEM techniques to bring out the changes occurred due
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