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Introduction
1. Introduction
1.1 Conducting polymers
The insulating properties of most polymers represent a significant advantage for
many practical applications of plastics. During the last 20 years, however, organic
polymers characterized by good electrical conductivity have been found. Due to their low
specific weight, good processibility and resistance to corrosion and the exciting prospects
for plastics fabricated into electrical wires, films or electronic devices, these materials
have attracted the interest of both industrial and academic researchers in domains ranging
from Chemistry to Solid State Physics and Electrochemistry. The close interaction
between scientists from diverse background has been a significant factor in the rapid
development of the field of conducting polymers.
105
Scm-1. Discovery and development of conducting polymers has opened up new frontiers
in Materials Chemistry and Physics. This new generation of polymers combines the
mechanical properties and processibility of traditional polymers with electrical and
optical properties which are unknown earlier. The enormous technological potential that
this rare combination offers is beginning to be trapped. The Noble prize awarded in
Chemistry to Alan Heeger, Alan MacDiarmid and Hideki Shirakawa for the discovery
and development of conducting polymers in the year 2000 is a grand recognition of the
dawn of the new plastic age [1].
The search for conducting polymers, incidentally goes back to the days of Natta
(of Zeigler Natta catalyst fame), who polymerized acetylene gas using his newly
developed catalyst, that revolutionized the plastic industry by providing a route of
synthesis of polypropylene (Zeigler and Natta jointly won the Noble Prize in Chemistry
in 1963 for their discovery). What they obtained from acetylene polymerization was a
black powder which looks much like charcoal. With the anticipation that such conjugated
structure would exhibit electrical conductivity, the conductivities (of pressed pellets)
measured in their samples were found to be semi-conducting (10-7 Scm-1).
Conductivity
(Scm-1)
107
106
10
Copper metal
Polyacetylene doped
with AsF5
Polyacetylene doped
with I2
104
Liquid mercury
103
Poly(p-phenylene)
doped with AsF5
102
Polypyrrole doped
with I2
10
Polyaniline
(emeraldine)
is due to four conditions in their molecular organization: namely, the existence of charge
carriers, an overlap of molecular orbitals to aid carrier mobility,
charge hopping between polymer chains [2].
bond
mobility.
Most ICPs are unprocessible. Therefore, physical properties of the polymer are
determined at the synthesis stage. For example, the electrical, dielectric, microwave and
morphological properties of the polymer can be tailored by adjusting synthesis
parameters such as dopant and monomer concentration, dopant type, synthesis time,
synthesis temperature and electrolyte pH. Ideally, the electrical properties of a metal
Since then it has been found that about a dozen of different polymers and polymer
derivatives undergo transition to conducting state when doped with a weak oxidation or
reducing agent. They are all various conjugated polymers. The early conjugated polymers
were unstable in air and were not capable of being processed. The recent research in this
area has been focused towards the development of highly conducting polymers with good
stability and acceptable processing attributes.
electricity. However, it turns out that the polymer can more efficiently lower its energy
by band alteration (alternating short and long bonds), which introduces a band width of
1.5 eV making it a high energy gap semi-conductor. The polymer is transformed into a
conductor by doping it with either an electron donor or electron acceptor. This is
reminiscent of doping of silicon based semi-conductors where silicon is doped with either
arsenic or boron. However, while the doping of silicon produces a donor energy level
close to the conduction band or an acceptor level close to the valance band, this is not the
case with conducting polymers. The evidence for this is that the resulting polymers do
not have a high enough concentration of free spins, as determined by electron spin
spectroscopy.
Polymer
Maximum
conductivity
after doping
in Scm-1
Structure
Stability
Processibility
1.5x105
2000
100
Stable
Insoluble and
infusible
10
Stable
Soluble in
neutral form
Polyphenylene
1000
Stable
Insoluble and
infusible
Polyphenylene
vinylene
1000
Stable in
undoped
form
Soluble
precursor route
available
Polyacetylene
Polypyrrole
Polythiophene
Polyaniline
H
N
H
N
The polymer may store charge in two ways. In an oxidation process, it could
either lose an electron from one of the bands or it could localize the charge over a small
section of the chain. Localizing the charge causes a local distribution due to change in
geometry, which costs the polymer some energy. However, the generation of this local
geometry decreases the ionization energy of the polymer chain and increases its electron
affinity making it more able to accommodate the newly formed charges. This is
consistent with an increase in disorder detected after doping by Raman Spectroscopy. A
similar scenario occurs for a reductive process.
Typical oxidizing dopants used include iodine, arsenic pentachloride, iron (III)
chloride and NOPF6. A typical reductive dopant is sodium naphthalide. The main criteria
is its ability to oxidize or reduce the polymer without lowering its stability or whether or
not they are capable of initiating side reaction that inhibit the polymers ability to conduct
electricity. An example of the latter is the doping of a conjugated polymer with bromine.
Bromine is too powerful oxidant and adds across the double bonds to from sp3 carbons.
The same problem may also occur with NOPF6 if left too long.
the frequency of the current used. These tests show that a variety of conduction
mechanisms are used. The main mechanism used is by movement of charge carriers
between localized sites or between solitons, polaron or bipolaron states. Alternatively,
where inhomogeneous doping produces metallic island dispersed in an insulating matrix,
conduction is by movement of charge carriers between highly conducting domains.
Charge transfer between these conducting domains also occurs by thermally activated
hopping or tunneling. This is consistent with conductivity being proportional to
temperature.
1.1.5. Stability
There are two distinct types of stability. Extrinsic stability is related to
vulnerability to external environmental agent such as oxygen, water and peroxides. This
is determined by the polymers susceptibility of charged sites to attack by nucleophiles,
electrophiles and free radical. If a conducting polymer is extrinsically unstable then it
must be protected by a stable coating.
Many conducting polymers, however, degrade over time even in dry, oxygen free
environment. This intrinsic instability is thermodynamic in origin. It is likely to be cause
by irreversible chemical reaction between charged sites of polymer and either the dopant
counter ion or the -system of an adjacent neutral chain, which produces an sp3 carbon,
breaking the conjugation. Intrinsic instability can also come from a thermally driven
mechanism which causes the polymer to lose its dopant. This happens when the charge
sites become unstable due to conformational changes in the polymer backbone. This has
been observed in alkyl substituted Polythiophenes.
Neutral Soliton
H
N
A
H
N
N
H
Polaron
H
N
H
+
A- N
BiPolaron
H
N
H
+
A- N
H
A-
Valance Band
Conduction Band
Neutral Polymer
Polaron
Bipolaron
Bipolaron Bands
1.1.6. Processibility
Conjugated polymers may be made by a variety of techniques, including cationic,
anionic, radical chain growth, co-ordination polymerization, step growth polymerization
or electrochemical polymerization. Electrochemical polymerization occurs by suitable
monomers which are electrochemically oxidized to create an active monomeric and
dimeric species which react to form a conjugated polymer backbone. The main problem
with electrically conductive plastics stems from the very property that gives its
conductivity, namely the conjugated backbone. This causes many such polymers to be
intractable, insoluble films or powders that cannot melt. There are two main strategies to
overcome these problems. These are, either to modify the polymer so that it may be more
easily processed, or to manufacture the polymer in its desired shape and form. There are
four main methods used to achieve these aims.
The third method is to grow the polymer into its desired shape and form. An
insulating polymer impregnated with a catalyst is fabricated into its desired form. This is
then exposed to the monomer, usually a gas or a vapour. The monomer then polymerizes
on the surface of the insulating plastic producing a thin film or a fiber. This
doped in the usual manner. A variation of this technique is
is
then
The final method is the use of Longmuir Blodgett technique to manipulate the
surface active molecules into highly ordered thin films whose structure and thickness are
controllable at the molecular layer. Amphiphilic molecules with hydrophilic and
hydrophobic groups produces monolayer at the air-water surface interface of Longmuir
Blodgett films. This is then transferred to a substrate creating a multiple structure
comprised of molecular stacks which are normally about 2.5 mm thick. The main
advantage of this technique is its unique ability to allow control over the molecular
architecture of the conducting films produced. It can be used to create complex multiple
structures of functionally different molecular layers. By producing alternating layers of
conductor and insulator, it is possible to produce highly anisotropic film which is
conducting within the plane of the film, but insulating across it. The stability and
processing attributes of some conducting polymers are given in the following table.
Polymer
Conductivity (
-1
cm-1)
Stability
(Doped state)
Processing
Possibilities
Polyacetylene
103 105
Poor
Limited
Polyphenylene
1000
Poor
Limited
PPS
100
Poor
Excellent
PPV
1000
Poor
Limited
Polyaniline
10
Good
Good
Polythiophenes
100
Good
Excellent
Polypyrroles
100
Good
Good
1.1.7. Applications
The extended
chemical or electrochemical oxidation or reduction. These can alter the electrical and
optical properties of the polymer, and by controlling this oxidation and reduction, it is
possible to precisely control these properties. Since these reactions are often reversible, it
is possible to systematically control the electrical and optical properties with a great deal
of precision. It is even possible to switch from a conducting state to an insulating state.
There are two main groups of applications for these polymers. The first group
utilizes their conductivity as its main property. The second group utilizes electro activity.
They are shown below.
Group 1
Group 2
Electrostatic materials
Molecular electronics
Conducting adhesives
Electrical displays
Electromagnetic shielding
Artificial nerves
Antistatic clothing
Optical computers
Thermal sensors
Piezoceramics
Electromechanical actuators
Smart structures
Aircraft structures
Much research will be needed before many of the above application will become
a reality. The stability and processibility both need to be substantially improved if they
are to be used in the market place. The cost of such polymers must also be substantially
lowered. However, one must consider that, although conventional polymers were
synthesized and studied in laboratories around the world, they did not become
widespread until years of research and development had been done. In a way, conducting
polymers are at the same stage of development as their insulating brothers were some 50
years ago. Regardless of the practical applications that are eventually developed for them,
they will certainly challenge researchers in the years to come with new and unexpected
phenomenon. Only time will tell, whether the impact of these novel plastics would be as
large as their insulating relatives.
1.2. Polyaniline
1.2.1 A Brief History
Polyaniline, probably the oldest known synthetic organic polymer, consisted of an
ill-defined class of materials obtained by the chemical or electrochemical oxidative
polymerization of aniline. Polyaniline (PANI) has attracted considerable attention not
only from fundamental scientific interest but also from practical applications due to its
novel properties (special doping mechanism, good environmental stability, low cost and
high conductivity, etc.) and potential applications in batteries, molecular devices, sensors
etc. PANI is a typical conducting polymer resulting from oxidative polymerization of
aniline, whose resistivity can be affected by doping concentration, dopant, morphology
and degree of crystallization. In 1991, the conductivity of PANI was enhanced to 300
400 Scm-1 with the development of the counter-ion induced processibility of PANI.
Typically, conducting PANI is synthesized by electrochemical or chemical oxidation of
aniline in acidic conditions and an aqueous medium is preferred [12, 13]. Alternative
methods have been designed to improve the solubility and processibility of the
synthesized PANI. Gong et al. have reported solid-state synthesis of PANI doped with
H4SiW12O40 under 20
solvent-free mechanochemical route for the synthesis of PANI in which the reaction
between aniline salt and the oxidant, ammonium peroxydisulfate was carried out by ball
milling the reactants for one hour, in the absence of solvent at ambient temperature [15].
Presently chemical synthesis, described in sec 2.2, provides the only satisfactory route in
the synthesis of polyaniline.
1. There are four quinoid stages derived from the parent compound
leucoemeraldine.
2. The minimum molecular weights of these primary oxidations of aniline are in
accordance with an eight-nuclei structure.
3. The conversion emeraldine into nigraniline consumes one atom of oxygen.
4. The conversion of emeraldine into perinigraniline consumes two atom of oxygen
5. The conversion of nigraniline into peinigraniline consumes one atom of oxygen.
6. The reduction of nigranline to leucoemarldine consumes four atoms of hydrogen.
7. The reduction of nigraniline to leucoemarldine consumes six atoms of hydrogen
8. The reduction of perinigraniline to leucoemraldine consumes eight atoms of
hydrogen.
H
N
H
N
H
these two states of nitrogen and further, whether they are in their quantized state or not,
various forms of polyaniline can result. The structure of these forms can be best
represented by choosing a minimum of four repeat units, as shown in figure 1.5.
The only form that is conducting among four is the green protonated emeraldine
form, which has both the oxidized minimum and reduced amine nitrogens, in equal
amounts (i.e., it is half oxidized). Thus, the blue insulating emeraldine form can be
transformed to conducting by converting the pH of the medium and vice-versa. Another
interesting feature of polyaniline is that, by use of an organic counter ion (x-), it can be
transformed to the conducting state.
During this period, it did not occur to any one to investigate its electrical and
magnetic properties of polyaniline for the obvious reasons that organic compounds are
insulators, though in 1911 Mecoy and Moore suggested electrical conduction in organic
solids [25]. Almost 50 years later, Surville et al [26] in 1968 reported proton exchange
and redox properties with the influence of water on the conductivity of polyaniline.
However, interest in polyaniline was generated only after the fundamental discovery in
1977 that iodine doped polyacetylene has metallic conductivity [27] which triggered
research interest in new organic materials in the hope that these would provide new or
improved electrical, magnetic and optical materials or devices. The hope was based on
electronic structure and the combination of metal like or semi conducting conductivity
with processibility and flexibility of classical polymers and above all the ease with which
modifications can be carried out via synthetic organic chemistry methodologies.
Leucoemeraldine base
Emeraldine base
Pernigraniline base
Figure 1.5. Chemical Structure of various forms of polyaniline with four repeat units
adopted from ref. 28 and 29.
of two carbon and two hydrogens, which provides fundamental structure to understand
basic transport in conducting polymer systems. The two kekule structures derived from
this structure are equal in energy, thus the structure is doubly degenerate energetically.
Of the four valance electrons per carbon, three form relatively deeply bound molecular
orbital in (CH)x and remaining single (-orbital) electron per carbon atom determines the
location of double bound. Two energetically equal structures at a point where they couple
to give a surface effect is known as kink or soliton. The term soliton means solitary
wave. This means that soliton has a movement. In conjugated systems solitons may be
neutral, positively or negatively charged according to the number of electrons in the
orbital. The motionless charged states are known as carbonium (+ve) and carbonion (-ve)
radicals. Such a situation is also encountered in polymers which do not have two
degenerate ground states. That is, their ground state is non degenerate due to non
availability of two energetically equal kekule structures. Therefore there cannot be a link
to connect them. The conventional distortion is self consistently stabilized.
Thus the charge coupled to surrounding lattice distortion to lower the total
electronic energy is known as polaron (i.e., an ordinary radical ion) with a unit charge
and spin = . A bipolaron consists of two coupled polarons with charge 2e and spin zero.
The energy increase due to columbic repulsion (in the formation of bipolaron) is more
than compensated for the energy gained when the two charges share the same lattice
distortion. Quantum chemical calculations indicate that the formation of bipolaron
requires a 0.4 eV less energy than the formation of two polarons [30, 31]. However,
bipolarons are not created directly but must form by the coupling of pre- existing
polarons or possibly the addition of charge to pre-existing polaron.
All dopants cannot induce charge transport in polymer. It depends upon the redox
energy of the host and guest molecules and electrons will transfer from high to low redox
energy. The initial charge transfer on doping will be between dopant molecule and the
proximal polymer site, but subsequently some diffusion of polymer charge, away from
the immediate dopant to the site can be expected and polymer pair states will be
generated. In equilibrium, the number of polymer pair states will be equal to the number
of ionized dopants.
by involving models such as variable range hopping (VRH) [37, 39], the quasi
1D VRH model [40] or the metallic rods model [41].
2. Thermo power (s) is the function of temperature and degree of protonation. At a
38% doping it is independent of temperature [42]. These thermo power
measurements indicate p-type of metal.
3. An in-situ ESR study indicates first an increase and then a decrease in spin
concentrations. However, on increasing anodic potential to 0.7 V again there is an
increase in spin concentration, indicating probably a bipolaron or a new type of
polaronic species [43].
4. Bredas et al [44, 45] have pointed out that polyaniline has only defect (polaron or
bipolaron) in the band gap, unlike other conducting polymers, where two defects
bands are always observed. Heeger [46, 47] has shown that intrinsic self
localization in quasi-one-dimensional systems is especially sensitive to
localization induced by disorder. Disorder induced localization is known to
convert doped conducting polymers from true metals with large mean free paths
and coherent transport into poor conductors in which the transport is limited by
phonon assisted hopping. However, Philips and Wu [48] pointed out that if a
bipolaron band is localized it should carry no current when disorder is present.
They have suggested a simple model in which defects by virtue of the pairing
constraints have an internal structure. This structure leads to resonance effect and
narrow band of conducting states when the defects are randomly placed.
Heeger [63] has estimated the world wide market of conducting polymers of
about US $ 1 billion in the year 2000. Some of the known applications of polyaniline are
shown in the figure 1.6.
Plastic
Batteries
LEDs
Photocopiers
Micromotors
Transducers
Conductivity
Photoconducting
Piezoelectric
Optical Storage
Lithography
Photochemical Reactions
Conducting
Composites
Supercapacitors
Solid State
Sensors
Conductive
Surface
EMI/ESD
Membranes
(Gases)
Nonlinear Optics
Harmonic Generators
Electrochromic
Display Devices
Ferromagnetism
Magnetic Recording
Figure 1.6 Chart showing the various known and envisaged application of Polyaniline
Conventional type of capacitors store electrostatic energy when an electric field is applied
across a dielectric. In an ideal capacitor the amount of charge storage is proportional to
the potential difference. Thus Genies et al, [73] reported a charge density of 450 C g-1 for
polyaniline in a polypropylene/LiClO4 system whereas Gottesfield et. al, [74] claim a
capacity of 800 C cm-1 under aqueous acidic conditions.
Organic electroluminescent devices have been the subject of intense research for
almost one and half decade. The major breakthrough came in 1990 when Buroughes et.
al, [75] showed that polymer can be used as an emitter in a electroluminescent device.
Brauan and Heeger [76] and Gustafsson et.al, [77] fabricated light emitting diodes where
a thin layer of polyaniline was described as a hole injecting material. These devices
have cell voltage requirements of approximately 2 4 V compared to earlier organic
luminescent devices where the cell voltage requirement was 20 100 V. Cao et.al, [78]
achieved flexible light emitting diodes by using high conductivity coating of
polyaniline with camphor sulphonic acid (CSA) as a dopant. Li et.al, [79] have reported
polyaniline films which were spun cast onto porous silicon and it has been observed that
transmittance and surface resistance of polyaniline can be controlled by controlling spin
rate. Thus 0.3 mm polyaniline film has 80% transmittance in visible region. In the above
studies, electroluminescence began to be visible under forward bias at 12 V, 1mA emits
red light and has a better intensity than that of p-n porous silicon.
anywhere
from
ferromagnetism
(e.g.
CrO2,
La0.5Sr0.5MnO3)
to
antiferromagnetism (e.g. NiO, LaCrO3. -Fe2O3) are known. Many oxides posses
switchable orientation states as in ferroelectric (e.g. BaTiO3, KNbO3) and ferroelastic
[e.g. Gd2 (MoO4)3] materials. Then, there is a variety of oxides bronzes showing a gamut
of property [86]. Superconductivity in transition metal oxides has been known for some
time and the highest Tc reached in the HTSC compound (e.g. YBa2Cu3O7-y) was around
90 K; we now have oxides with Tc in the region of 160 K. The discovery of high Tc
superconductors [87] has focused worldwide scientific attention on the chemistry of
metal oxides and, at the same time, revealed the inadequacy of our understanding of these
Among the transition metals oxides, zinc oxide (ZnO), aluminium oxide (Al2O3),
titanium oxide (TiO2), tin oxide (SnO2), tungsten oxide (WO3), Vanadium oxide (V2O5),
cerium oxide (CeO2), iron oxide (Fe2O3), cobalt oxide (Co3O4), etc are mostly widely
known oxides and industrially employed transition metal oxides since the last fifty years.
The cause of these oxides have become important both scientifically and industrially
because of their applications for sound and picture recording, data storage, humidity and
gas sensors, conducting composite super capacitors, electrochromic display devices, etc.
1.4 Sensors
There is an escalating need and desire for us to monitor all aspects of our
environment in real time and this has been brought about by our increasing concerns with
pollution, our health and safety. There is also a desire to determine contaminants and
analytes at lower levels and one could say that the aim of all modern science is to lower
the detection limits and to improve the accuracy and precision at those limits.
Instrumentation has become so sophisticated that we are now able to detect chemicals in
amounts smaller than we ever imagined of a few years ago. In fact, this has shown that
manufactured chemicals and byproducts have been introduced into almost every aspect of
our environment and lives.
In monitoring the environment one can imagine similar devices which could be
used to test for, say, heavy metal pollutants in natural waters or the presence of bacteria
in drinking water, swimming pools or at beaches. Bathers might carry such device with
them to test the water before swimming. The possibilities are limitless and are controlled
only by ones imaginations. Well, that is not strictly true, the possibilities are really
controlled by the Physics, Chemistry and electronics of such devices and the art of that
particular point in time. We should never lose sight of the fact that all these sensing
systems depend on principles of basic science [93].
It was already known in the 1950s that metal oxides such as ZnO and NiO
change semiconducting properties with change in partial pressure of oxygen, N2O or
other gases in the surrounding atmosphere. Relevant theories were proposed by many
researchers understanding the nature of the gas-solid interactions as well as for
controlling surface chemical processes such as catalysis. However, an approach in the
opposite direction i.e. utilizing the phenomenon for the detection of gases was not
conceived until 1962. In that year, Seiyama et al. from Japan reported that inflammable
gases in air could be detected from a change in the electric resistance of a thin film on
ZnO, while Taguchi claimed that a porous sintered block of SnO could also work in the
same way. These findings clearly demonstrated the possibility of a sensing device based
on an oxide semiconductor.
(a)
(b)
Industrial hygiene has become very important because of the published health
hazards and related atmospheric pollution. The general public has become
more sensitive to these various gases. As a result much effort is being focused
on producing relatively inexpensive sensors of medium sensitivity and
selectivity to meet these needs.
(c)
(d)
(f)
(b)
(c)
(d)
(e)
FET devices: These can be closely related to several of the other methods but
made possible by silicon technology and typified by such devices as ion
selective field effective transistors (ISFETS) chemical FETS (CHEMFETS)
and enzyme FETS (ENFETS).
(f)
(g)
(h)
(i)
tissue, etc. as recognition agent, whereas a chemical sensor does not contain these agents.
Sensor devices have been made from classical semiconductors, solid electrolytes,
insulators, metals and catalytic materials. Since the chemical and physical properties of
polymers may be tailored by the chemist for particular needs, they gained importance in
the construction of sensor devices. Although a majority of polymers are unable to
conduct electricity, their insulating properties are utilized in the electronic industry. A
survey of the literature reveals that polymers also acquired a major position as materials
in various sensor devices among other materials. Either an intrinsically conducting
polymer is being used as a coating or encapsulating material on an electrode surface, or
non-conducting polymer is being used for immobilization of specific receptor agents on
the sensor device. Because their chemical and physical properties may be tailored over a
wide range of characteristics, the use of polymers is finding a permanent place in
sophisticated electronic measuring devices such as sensors. During the last 5 years,
polymers have gained tremendous recognition in the field of artificial sensor in the goal
of mimicking natural sense organs. Better selectivity and rapid measurements have been
achieved by replacing classical sensor materials with polymers involving nanotechnology
and exploiting either the intrinsic or extrinsic functions of polymers. Semiconductors,
semiconducting metal oxides, solid electrolytes, ionic membranes, and organic
semiconductors have been the classical materials for sensor devices. The developing role
of polymers as gas sensors, pH sensors, ion-selective sensors, humidity sensors,
biosensor devices, etc., are continuously reviewed. Both intrinsically conducting
polymers and non-conducting polymers are used in sensor devices. Polymers used in
resulted in the formation of a mixed iron oxide phase for lower polypyrrole
concentration, stabilizing to a single cubic iron oxide phase at higher polypyrrole
concentration.
Sensitivity
to
humidity
increased
with
increasing
polypyrrole
concentration [97].
Jain et.al. [98] have synthesized weak acid doped polyaniline and its composites
for humidity sensing. They reported maximum sensitivity in case of PANI-CSA.
Synthesis and characterization of Poly (2, 3 dimethylaniline) is studied by
Kulkarni et.al [99]. The test samples were reported as a competent material for humidity
sensor. Somani et. al [100] have synthesized conducting polyaniline / V2O5 composites
by a technique of in-situ polymerization of aniline over fine graded V2O5. The composite
is studied by using physio-chemical characterization. In addition a study of charge
transport and hysteresis (I-V) characteristics were also undertaken.
Suresh Raj et al., [101] synthesized Zinc(II) oxide zinc(II) molybdate
composites for humidity sensing. Composites having different mol ratios of Cr2O3
WO3 were synthesized and studied for humidity sensing applications by Pokhrel et.al
[102].
Jing Wang et.al [103] have carried out systematic study of Lanthanum
ferrite/polymer quaternary acrylic resin for humidity sensing by citrate method. They
investigated the electrical property of this humidity sensor, including the resistance
versus RH, humidity hysteresis, response recover time and long term stability.
Su Pi et al [104] fabricated a resistive-type humidity sensor by thick film
deposition using poly(2-acrylamido-2-methylpropane sulfonate) (poly-AMPS) modified
with tetraethyl orthosilicate (TEOS) as the sensing material, without a protective film or
complicated chemical procedures.
Shi-Jian Su et al [105] carried out in situ polymerization of anatase TiO2 to
synthesize polyaniline / TiO2 composite (PANI/TiO2) by dispersing fine powder of
anatase TiO2 in polyaniline matrix to obtain nanocomposite. The characterization of these
composites was also carried out. The measured conductivities of these composites shows
a increase upto 30 wt % of TiO2 in polyaniline and decreases there after.
Polyaniline blended with either polyvinyl alcohol or a butyl acrylate/vinyl acetate
copolymer was studied by McGovern et.al. [106] and used as a sensing medium in the
construction of a resistance-based humidity sensor. The sensors had an overall final
thickness of less than 150 m and showed high sensitivity, low resistance, and good
reversibility without hysteresis.
Despite good progress in the study of charge transfer in conducting polymers,
factors affecting electrical conductivity in terms of device applications are not entirely
understood. Mzenda et.al [107] investigated charge transfer in polyaniline using DC
measurements over the temperature range 300 < T(K) < 450, thermal analysis and
Fourier transform infrared spectroscopy (FTIR). FTIR results show molecular structure
changes as a result of the annealing process and thermal analysis indicate the loss of
moisture at around 373 K.
Some insight into recent trends in sensor research is obtained from the number of
papers being published per year in various analytical journals, which are useful indicators
of systems that are directly applied to solving real problems. Fig. 1.7 shows the number
of hits for various subgroups of sensors, including ISEs, optical sensors, amperometric,
biosensor, acoustic, and solid-state sensors, as a percentage of the total number of sensor
papers published each year [108]. A survey of the sensor market [109] identified medical
applications as a major driving force for the development of the emerging sensor
technologies: fiber-optic sensors, smart sensors, silicon micromachined sensors, and thin
film devices.
Fig. 1.7. Trends in the absolute numbers of papers for each sensor type abstracted from
Analytical Abstracts over the period 1980 to 1994.
Therefore, this present work is oriented towards the better understanding of basic
electrical and humidity sensing properties in polyaniline composites. These parameters
which have been studied here may provide better route for technological applications in
the near future.
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