Accepted Manuscript

Conducting polymer nanocomposite based temperature sensors: A

review

R. Megha, Farida A. Ali, Y.T. Ravikiran, C.H.V.V. Ramana,

A.B.V. Kiran Kumar, D.K. Mishra, S.C. Vijayakumari, D. Kim

PII: S1387-7003(18)30642-7
DOI: doi:10.1016/j.inoche.2018.09.040
Reference: INOCHE 7131
To appear in: Inorganic Chemistry Communications
Received date: 28 June 2018
Revised date: 21 September 2018
Accepted date: 24 September 2018

Please cite this article as: R. Megha, Farida A. Ali, Y.T. Ravikiran, C.H.V.V. Ramana,
A.B.V. Kiran Kumar, D.K. Mishra, S.C. Vijayakumari, D. Kim , Conducting polymer
nanocomposite based temperature sensors: A review. Inoche (2018), doi:10.1016/
j.inoche.2018.09.040

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 ACCEPTED MANUSCRIPT
CONDUCTING POLYMER NANOCOMPOSITE BASED TEMPERATURE SENSORS: A REVIEW
R. MEGHA1, FARIDA A ALI 2, Y. T. RAVIKIRAN 1*, CH. V. V. RAMANA 3,4*, A. B. V. KIRAN
KUMAR5*, D. K. MISHRA 2*, S. C. VIJAYAKUMARI 6 AND D. KIM3*
1
Department of PG Studies and Research in Physics, Government Science College, Chitradurga 577 501,
Karnataka, India
2
Faculty of Engineering and Technology (ITER), Siskha ‘O’ Anusandhan (Deemed to be University),
Bhubaneswar 751 030, Odisha, India
3
Department of Electronic Engineering, Institute for Wearable Convergence Electronics, Kyung Hee University,
1732 Deogyeong-daero, Giheung-gu, Yongin 17104, Republic of Korea
4
Department of Electrical and Electronics Engineering Science, University of Johannesburg, Auckland Park
Campus, PO Box 524, Johannesburg 2006, South Africa
5
Amity Institute of Nanotechnology, J-2 Block, Amity University, Sector-125, Noida-201303, NCR, India

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6
Department of Physics, SJM College of Arts, Science and Commerce, Chitradurga 577 501, Karnataka, India

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ABSTRACT
The absolute necessary for measuring temperature with large accuracy and with a wide range in various industrial

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sectors increases the need for researcher to choose a suitable material, which is useful especially in bio-medical
applications, food packaging and air conditioning system. A slight deviation of temperature creates a lot of
problems which cannot be controlled rapidly. Hence, the temperature sensor needs to have the properties of high
sensitivity, fast response, low cost, high volume production, and high reliability. Considering the essentialities of

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the temperature measurement almost in all types of industrial sectors, the sensing materials used for fabricating
the sensors should have flexibility for both temperature and pressure sensing ability. In this aspect, conducting
polymers have an efficient candidate for temperature sensor. As the conducting polymers are fabricated by the
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incorporation of conducting filler in polymers, the resistivity of such materials is very sensitive to temperature for
which response to the signal very fastly. The high accuracy measurement as well as wide measurement scale can
only be achieved by conducting polymer based sensors which are more stable at high temperature. However, the
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sensitivity and selectivity of nanostructure conducting polymer-based sensors still needs a lot of enhancement. In
the present review, fabrication of conducting polymers and their importance as temperature sensors have been
discussed.
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Keywords: Conducting polymers; Temperature sensors; Resistivity; Fabrication;

Corresponding authors: E-mail: ytrcta@gmail.com; ramana6@gmail.com; bharanichem@gmail.com;
dilipuac@gmail.com; daewon@khu.ac.kr;
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Content
1 Introduction to sensor technology
1.1 Sensors characteristic and mechanisms of operation
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1.1.1. Static characteristics

1.1.2. Dynamic characteristics
1.2 Basics of a sensor operation
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1.3 Temperature sensor

1.4 Conducting polymer nanocomposites as sensors
1.5 Conducting polymers based temperature Sensors
2 Synthesis and characterization of conducting polymers
2.1 Introduction
2.2 Synthesis of conducting polymers
2.3 Characterization of conducting polymers
2.3.1. Raman Spectroscopy (RS)
2.3.2. XRD
3 Properties of conducting polymer
3.1 Properties
3.2 Optical and infra red studies
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3.3 Electronic properties
4 Fabrication of conducting polymers based temperature sensors
5 Summary
References

1. INTRODUCTION TO SENSOR TECHNOLOGY

Sensor technology is an extremely broad field, and its future development will involve the interaction of nearly

every scientific and technical discipline. The advancement of science and technology through new discoveries is

seldom possible without a parallel progress in the field of sensor technology. These advances are the result of an

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unending chain of new sophisticated measurement techniques and at the heart of every measuring instrument is its

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sensor.

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In a broad sense, ‘a sensor is defined as a device that receives and responds to a stimulus.’ This definition is so

broad that it covers almost every stimulus-sensing object, whether natural or man made. Based on that initial

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classification, sensors can be categorized as natural sensors and man-made sensors. Natural sensors can be found in
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living beings, where the stimulus signal is processed and transmitted as an electro chemical signal generated due to

ion exchange. In the case of man-made sensors the stimulus signal is transmitted and processed in the form of an
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electrical signal due to charge exchange (specifically due to electron transport mechanism). Thus, the word Sensor
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can be redefined as ‘a device that converts a physical phenomenon into an electrical signal’, so that the physical

world and electrical devices can be interfaced [1]. Generally, sensors are characterized in the same way as
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electronic devices are as the output of the sensor is an electrical signal. Depending on the performance, cost, and
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range of applicability, electronic devices are often designed to go along with the physical sensor element, which is

thus very important to the overall electronic circuit. If a sensor can be designed properly, then optimal extraction
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of information is possible even from a noisy signal.

For such an optimal extraction, the electrical signal is required to be channeled, amplified, and modified by various

other electronic devices. Therefore, sensor is always a part of a bigger system incorporating many other detectors,

conditioners, processors, memory units, data recorders, actuators etc. The output signal of a sensor may be in the

form of voltage, current, charge or described in terms of amplitude, polarity, frequency, phase, or in the form of

digital signal. Thus, various physical properties such as temperature, force, pressure, flow, position, light intensity,

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etc. are measured using sensors and their associated circuits. The corresponding physical properties act as stimulus

to the sensor and the sensor output is conditioned and processed to provide the measured value of the physical

property.

Sensors can be classified in different ways. Depending upon the placement of sensor in a device they may be either

intrinsic or extrinsic [2]. An intrinsic sensor is a part of the input of a system to perceive the outside effects and

sends a signal about the variations outside the system. Whereas, extrinsic sensor; can be an internal part of a device

to monitor the devices’ own state for its appropriate performance, because the sensing device have very small size.

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When the size of three dimensions is reduced to the nano order, the technology of novel conducting polymer

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formation has a great effect on its morphology and physical properties which mean nanomaterials exhibit

promising properties that are quite different from their related bulk materials. However; one dimensional

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nanostructures play an important role in understanding of their material properties for many years, research

scientists have aided communities in their tremendous efforts towards environmental remediation [3-12].
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From the point of view of signal conditioning, sensors are classified as either active or passive depending on the
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need of external active circuitry to produce the electrical output signal from the sensor [2]. A sensor that requires

an external power source for its operation is called an active sensor, for example, resistor-based sensors such as
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thermistors, Resistance Temperature Detectors (RTDs), and strain gauges. On the other hand, passive (or self-
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generating) sensors detect and respond to the physical environment and generate their own electrical output signal.

These include thermocouples and photo diodes which generate thermoelectric voltages and photo currents,
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respectively.
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Another kind of sensor classification is dependent on the selected reference, based on which sensors can be

classified into either absolute or relative. An absolute sensor detects a stimulus in reference to an absolute physical

scale independent of the measurement conditions, like an absolute pressure sensor that produces signal in reference

to vacuum considered as zero pressure. On the other hand, a relative sensor produces a signal with respect to a

selected baseline that is not zero pressure, for example, to the atmospheric pressure.

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A fourth way of classifying sensors is based on various physical phenomenon measured, like temperature, pressure,

distance, angular motion, magneto electric, photoelectric, electro plastic, thermoplastic, chemical transformation,

physical transformation, electro chemical process, biochemical process etc. Besides these, other ways of

classifying sensors depend on the type of operation (analogue or digital), whether the quantity is measured directly

or indirectly, sensor applications, materials used, means of detection used, field of application and stimulus applied

[2].

1.1 SENSORS CHARACTERISTIC AND MECHANISMS OF OPERATION

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The stimulus once sensed by a sensor need to be processed accurately. This depends on a few things like, (a)

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operation of the sensor (b) nature of the acquired signal, and (c) information about static and dynamic

characteristics of the sensing systems. The operation of a sensor must be well understood to choose the right tools

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and circuits for acquiring information from the sensor. Also, it is necessary to know, in advance’ the nature of the

received signal to interpret the data correctly finally, understanding the static and dynamic characteristics is
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imperative to correctly map the output with respect to the input of the sensor.
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The knowledge of the performance characteristic of a sensor is very essential for its selection for a suitable

application and also may be due to the design purpose of a sensor. As sensors are either designed to indicate the
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value of the measurand under static conditions or record and produce the variation of the measurand with respect to
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time. Therefore, the performance characteristics of a sensor can be classified into two groups:

(a) Static Characteristic

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(b) Dynamic Characteristics

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Sensors showing satisfactory static characteristics need to satisfy a few criteria to be used under dynamic

conditions, but few sensors are only designed for dynamic conditions that are considered unsuitable for static

characteristics [13-15].

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1.1.1 STATIC CHARACTERISTICS
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In general, static characteristics of a sensor are considered for measuring unvarying process conditions obtained by

the process of static calibration. Calibration of a sensor is important since in this process the sensor responds to the

quantity under study along with the influence of quantities other than the desired signal. In this process all, other

quantities except the desired signal are held constant within an approved level, and this static calibration process is

repeated for each undesirable condition varying over a known range. The process of static calibration requires the

presence of a known standard so as to find subsequent errors and accuracy. Therefore, calibration process involves

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a comparison of the sensor output with either (i) an absolute standard, or (ii) a secondary standard, or (iii) a

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working standard or a sensor with known accuracy. Thus, the process of static calibration allows one to determine,

for better understanding of the sensor, (i) accuracy (ii) precision (iii) resolution (iv) sensitivity (iv) reproducibility

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(v) repeatability (vi) linearity (vii) drift (viii) dead zone and (ix) hysteresis. Besides these quantities, many other

static characteristics may be determined.

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1.1.2 DYNAMIC CHARACTERISTICS
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A sensing system when exposed to a time-invariable measurand behaves differently than when it is exposed to

dynamically-changing measurand. To describe the responses of the sensing systems responding to the changing
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measurand, another set of characteristic features, called as dynamic characteristics, must have to be considered [16]
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and the behavior of the sensing system under such conditions are called dynamic responses. Dynamic inputs are of

two types — (a) transient input (signal magnitude is not constant with time variation) and (b) steady state periodic
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input (signal magnitude has a definite repeating time cycle). The dynamic characteristics, specified in such a way
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as to distinguish one sensor system from other for its dynamic performance, are (a) dynamic error (b) fidelity (c)

bandwidth, and (d) speed of response.

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1.2
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BASICS OF SENSOR OPERATION

The physical quantity or the measured makes its first contact with a primary sensing element i.e. the sensor of a

system. Thus, the input signal carries the information either in the form of a physical phenomenon or in the form

of an electrical signal. Thus, the first and foremost classification of sensors was based on the energy forms involve

as shown in the below table:

Energy Forms Signal Measured

Mechanical Energy Length, area, volume, linear velocity, angular velocity, linear acceleration, angular
acceleration, mass, flow, torque, pressure

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Thermal Energy Temperature, specific heat, heat, flow, matter

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Magnetic Energy Flux, flux density, magnetic moment, field intensity, permeability
Electrical Energy Voltage, current, charge, resistance, inductance, capacitance, dielectric constant,

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polarization, electric field, frequency, dipole moment
Chemical Energy Concentration, oxidation potential, reduction potential, reaction rate, pH, composition
Radiant Energy Phase, Wavelength, Reflectance, Intensity, transmittance, polarization, refractive index

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In 1969, Lion classified sensors depending on the form of signal energy received or generated to or from a sensor

[14]. Later in 1989, Gopel et al again classified the sensors as per the common transduction principles where they
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convert the input quantity into resistance, inductance or capacitance [15]. They are classified into various
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categories like thermoelectric, piezoelectric, electro kinetic, optical etc. excluding biological principles [16-20] as
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shown in the below table:

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 Electrical
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Principal of Operation Applications
Parameter
Potentiometer By varying the position of the slider of a potentiometer resistance Linear/ angular
has been varied by an external force. displacement,
pressure.
Strain gauge Due to the application of external stress, a conductor or a Displacement,
semiconductor either elongates or compresses thereby its force, torque
resistance changes.
Pirani Gauge Resistance of a heating element is varied by convection cooling of Gas flow, gas
a stream of gas pressure
Photo With the variation of intensity of incident light resistance of the Photosensitive
conductive cell cell as a circuit element varies. relay
Dielectric Changes in the dielectric or dielectric constant alter the Liquid level,

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Gauge capacitance. thickness

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Reluctance By changing the position of the iron core of the coil reluctance of Pressure,
pick up the magnetic circuits is varied. displacement,

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vibrations,
position
Differential By varying the position of the magnetic core through an externally Pressure,

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transformer applied force the differential voltage of two secondary windings of position, force,
a transformer is varied. displacement
Hall effect When magnetic flux interacts with an external field a potential Current, power,
Pickup difference is generated across a semiconductor plate. magnetic flux
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Ionization Electron flow induced by ionization of gas due to radio- active Radiation,
chamber radiation. particle counting
Photo multiplier Due to incident radiation on photosensitive cathode, absorption of Light and
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tube a photon takes place causing a secondary electron emission radiation,

photosensitive
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relays
Moving coil Motion of a coil in a magnetic field generates a voltage Velocity,
generator vibration
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Photo voltaic A voltage is generated in a semiconductor junction device when Light meter,
radiant energy falls on the junction region to stimulate the charges. solar cell
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Later, in 1982, Middlehoek and Noorlag undertook a rigorous attempt to classify sensors based on the form of their

input and output energy [18]. Similarly, other possible classification methods for sensors incorporate:
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 Physical or chemical principle

 Primary input variable
 Application
 Cost and accuracy
 Output signal type
 Material of the sensor element

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1.3 TEMPERATURE SENSOR
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Temperature is one of the frequently used process parameters in almost all chemical process and reactions,

metallurgical industries, industries associated with steam raising and electricity generation, plastic manufacture and

moulding, milk and dairy product and many other food industries. Then, of course, temperature sensors are present

in an application most of us are most aware of, which is in heating and air-conditioning for people’s personal

comfort. Thus, sensors are available in a wide range of configurations to sense temperature depending on different

temperature effects [19]. In laboratories and under special industrial conditions, a variety of sensors are available in

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a wide range as summarized in the below table:

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Range (K) Technique Application Resolution (K)
0.01-1.5 Magnetic susceptance of para magnetic salt Laboratory 0.001
0.2-2 Vapour Pressure Laboratory 0.01
1.5-100 Carbon resistance thermometer Laboratory 0.001

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210-430 Silicon P-N junction Laboratory 0.1
4-500 Thermistor Laboratory 0.001
Industrial 0.1
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15-1000 Platinum resistance thermometer Standard 0.00001
Industrial 0.1
130-950 Liquid-in-glass General 0.1
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purpose
130-700 Bimetal Industrial 1-2
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270-5000 Spectrally selective radiation thermometer Industrial 2

Therefore, temperature sensors are designed according to the property that changes in response to temperature and
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are classified into two broad groups: (a) contact type sensors and (b) non-contact type sensors.
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Contact type temperature sensors

Contact type temperature sensors measure the temperature of the substance to which they remain in contact and it
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is assumed that there is a thermal equilibrium existing between them with no heat flow between them. Few

examples of contact type temperature sensor are: Thermocouple, ballistic thermometer, Resistance temperature

detectors (RTD) etc.

Non-Contact type temperature sensors

Most commercial and scientific temperature sensors are of non-contact type which measure the thermal radiant

power of the infrared or optical radiation received from either of its surface or volume within it. The pyrometer, the

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laser, the infra-red sensor, the ultrasonic and the fibre optics-based techniques have been used as noncontact

temperature sensors.

1.4 CONDUCTING POLYMER NANOCOMPOSITES AS SENSORS

Before coming to a general conclusion concerning the research needs in the area of temperature sensors, it is

necessary to identify sensor material issues related to the application. Making new types of sensors is possible with

the introduction of new materials produced using advanced processing technology. Because of the diversity of

sensor technology, it is possible that to satisfy a given need, more than one of sensor may be available. Thus, the

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diverse nature of sensor technology development requires not only an interdisciplinary culture but also applications

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based on sensor technologies and materials. This has led to the manufacturing of sensor devices from different

materials like metals, semiconductors, insulators, electrolytes, catalytic materials etc. One such novel material used

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in the area of sensor technology is the polymers [20-31]. Basically, polymers are insulators in their neutral state.

Therefore, their insulating property is mostly used in the electronic industry. Conductive polymers are made either
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by oxidizing or reducing the neutral polymers. From the day of the discovery of conducting polymers, a
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tremendous amount of research has been going on, as they show unique electrical, electronic, magnetic and optical

properties that are applicable in the field of science and technology. Better selectivity and rapid measurement has
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allowed for the development of polymer-based sensors in the field of gas sensors, biosensors, pH sensors, ion
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sensors, chemical sensors, humidity sensors etc. as discussed in the below table:

Polymer Used Field of application Sensor type

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Polysiloxane Blood Glucose Determination Bio sensor

Polypyrrole Can sense H2O2 Bio sensor
Poly Vinyl Chloride Estimates Pethidine Hydro chloride in tablets Chemical Sensor
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and injections and detection of Phosphate ions

Epoxy Resin Detects Lithium ions Chemical Sensor
Polystyrene beads Volatile organic compounds can be detected Odour sensor
Polyaniline (PANI) Can differentiate between various grades of Odour sensor
virgin olive oil
Polymethylmethacrylate Can identify gases from a mixture of gases Gas sensor
Nafion Can detect concentration of ethanol gas Gas Sensor
Poly Vinyl Chloride Optical humidity sensing Humidity sensor
Polyethylene oxide Can sense humidity Humidity sensor
Polyaniline Can sense Uric acid Chemical sensor
Nano-BaTiO3-quaternary Can sense Humidity Humidity sensor
acrylic resin composite
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1.5 CONDUCTING POLYMER NANOCOMPOSITE-BASED TEMPERATURE SENSORS

Temperature assessment plays an important role especially in food storage, air conditioning control and wide range

of medical applications. Hence, the temperature measurement in above mentioned applications should be of high

accuracy. However, thermocouples, thermistors, and resistance temperature detectors have errors in measuring the

temperatures due to the involvement of electromagnetic disturbances which limit their application in medical, food

storage and air conditioning control etc. In order to avoid such limitations polymer-based conductors are the most

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applicability candidate, measuring the temperature with a high sensitivity of 1.04 10-3C-1. Mostly polymer-based

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temperature sensors are widely used for measurement of low temperature preferably up to 110 C. The temperature

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dependent elasticity modulus is considered as the parameter to measure the temperature with accuracy. Polymer

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optical fibre [32] is used for temperature measurement. In this case, a constant force is applied on the fiber for

which the stress on the fibre varies with the temperature variation. As the stress varies, the variation in its refractive
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index occurs due to the stress-optical effect and which creates a variation of POF output power with the
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temperature variation. So, the mechanical stress induces the variation of optical property gives rise to the

possibility of measurement of temperature.

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Again, conducting polymer is synthesized by dispersing conducting fillers (metal nanoparticles) in polymer and
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variations of resistivity have been observed by the variation of temperature. The sensitivity unit is determined as

negative temperature coefficient unit (NTCU) or positive temperature coefficient unit (PTCU). Where the
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resistivity of the conducting polymer decreases with the increase of temperature, it is treated as a negative
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temperature coefficient unit, whereas where resistivity increases with the increase of temperature, it is treated as a

positive temperature coefficient unit [33]. The sensitivity of the materials are determined by measuring the voltage

in the conducting polymer with the variation of temperature. In this case, the high accuracy temperature can be

measured up to 75 C with high sensitivity 50 mV/C. Even in some cases, the conducting polymer can be used to

measure the temperature up to 200 C depend on the nature of polymer (Epoxies) and conducting fillers. Mostly in

a conducting polymer, the composites consist of insulating phase and conducting phase. This characteristic feature

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is always considered as a variation of resistivity with the variation temperature. At low temperature, the resistivity

is very high as the conducting fillers are separated by the insulated phase of polymer for which no current flows

through the composites. As temperature increases, polymer comes to a semi-molten state and the conducting fillers

comes close to each other for which the free electron tunnels form one conducting filler to another and resistivity

starts to decrease. Here, the variation of current is taken as the standard parameter for the measurement of

temperature. The limiting value of the temperature measurement completely depends on the transition temperature

of polymer composites from insulating phase to conducting phase. Such phase transition temperature varies

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according to the nature of the polymer and the conducting fillers. However, for high temperature measurement, the

conducting polymer is replaced by polymer-ceramics with which temperature up to 850 C can be measured [34,

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35].

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Still this needs a suitable technique and choice of material for the design of temperature sensor with which it can be

used at any kind of harsh environment. Again, for this, a sensor is required which can be used for both low-
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temperature as well as high-temperature measurements accurately. Till to date, no sensor is able to measure the
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thermal gradient accurately which is very essential for medical science, food storage and temperature controlling
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environment. It is expected that the choice of appropriate polymers and conducting or ceramic fillers will solve this

problem in the future.

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2 SYNTHESIS AND CHARACTERIZATION OF CONDUCTING POLYMERS

2.1 Introduction
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For the past decades, plastics or polymers are used as insulators in day-to-day life. One of their most familiar uses
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is as coatings on wires or cables in electrical applications. However, in 1977, Hideki Shirakawa, Alan G.

MacDiarmid and Alan J Heeger discovered that halogen-doped polyacetylene is 109 times more conductive than

the undoped polymer [26]. Based on that discovery, the Nobel Prize in Chemistry won in the year 2000 [27],

heralded a new era of the application of conducting polymers.

Conducting Polymers (CPs) have a wide variety of characteristics such as tunable chemical and electrochemical

properties, low weight, and the ability to be processed in solution, flexibility, and comparatively low cost. These

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unique properties made them suitable as replacement of metals and semiconductors. A considerable amount of

research has been done on the use of these promising materials in many applications [28-29], for example, in thin

film transistors(TFT), organic light emitting diodes(OLED), organic solar cells as energy storage [30-32] and as

flexible and transparent electrodes for display applications [33]. Recently, CPs has received much attention from

many researchers on exploring their ability to be used in biomedical and sensing applications as electrode materials

[28].

Among all the CPs, Polyaniline (PANI), polypyrrole (PPY), polythiophene (PTh) and its derivatives, for example,

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Poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PDOT: PSS) are the most common CPs for sensing

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applications due to their stability and for their redox-reaction-based conducting and optical properties. This

chapter mainly focuses on the review of published literature on different methods of synthesizing and

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characterizing PANI and PPY. Several methods have been reported for the preparation of CPs including chemical,

electrochemical, enzyme-catalyzed and photo-chemistry-initiated polymerizations.

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2.2 Synthesis of Conducting Polymers
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Many research groups have reported different methods for synthesizing CPs including oxidative polymerization,

photo-polymerization, emulsion polymerization, interface polymerization, enzyme catalyzed polymerization etc.

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Among all these methods, a few important synthetic methods will be discussed in this review. Unlike conventional
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free-radical polymerization, oxidative polymerization has been used for the synthesis of CPs such as PANI, PPY

and PTh. Based on the process for oxidizing the monomer, polymerization methods can be broadly classified as
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chemical, electrochemical and photo-oxidation synthesis. Based on these methods, CPs has been prepared as
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powder, film or micro and nano-structures.

Chemical Oxidation Polymerization

The final product properties (molecular weight, electrical and optical properties) play a key role on physical

conditions and polymerization method. Chemical synthesis is a simple and scalable procedure particularly for CP

powders. The chemical synthesis has to be performed in low acidic conditions by using a strong oxidizing agent to

produce aniline radical ions. Typically, in this method, the oxidation of the monomers is the initial step for the CPs

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preparation. Many researchers have reported different kinds of oxidizing agents. But a few important oxidizing

agents are listed in Table 1.

Ammonium persulfate (APS) is a very common oxidizing agent, particularly for synthesizing PANI. However,

according to few studies; the effect was not significant in the presence of Hydrochloric Acid. However, CPs

synthesized using KIO3 showed a higher conductivity of 103 S cm-1 than those made with other oxidizing agents

such as APS, FeCl3 and H2O2 [36]. Further, some reports concluded that in presence of H2O2, a high yield could be

achieved. Though FeCl3has the lowest oxidation potential, its use in synthesizing Polyaniline has resulted in

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reports of a CP with the highest molecular weight of 200000 Daltons [35].

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Chemical Oxidation Process

Chemical oxidation polymerization can be classified into the following steps:

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Step1: Radical Cation Formation

The first step is involved in the formation of monomer radical cations by oxidation of monomer by chemical or
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electrochemical oxidation using a suitable oxidizing agent. This process is reversible and stable radical ion is
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formed at resonance. In the case of aniline (figure 2a), the para radical cation is the stable form, which leads to end-

to-end coupling in the next step. At the same time, the oxidized pyrrole gives three resonance forms as shown
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figure 2b. The latter is the more stable resonance form [37].
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Step 2: Dimerization

This step is also called ‘coupling of radicals’. In this stage aniline radical cations couple each other in a head-to-tail
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manner to yield p-aminodiphenylamine (PADPA), or (N-N’-diphenylhydrazine and benzidine) dimer. This

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oxidation step is the slowest step in oxidation polymerization and hence, the rate determining step, because the

aniline oxidation potential is higher than that of its dimers, oligomers and polymer [38, 39]. The oxidized pyrrole

radical cations couple at the alpha position to form a doubly-charged sigma dimer [28]. The doubly charged dimer

undergoes re-aromatization by losing two protons, leading to the formation of an aromatic neutral dimer.

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Step-3: Chain Growth or Propagation

Dimmers formed in the step 2 have extended conjugation length and so get readily oxidized again undergoing

coupling with monomeric radical cation via an electrophilic aromatic substitution, followed by deprotonation to

form a trimer, which propagates forming a continuous cascade of steps as shown in scheme. Finally, the

termination step involves the formation of unproductive dimers followed by reaction between radical cations [40].

2.3 Preparation of Conducting Polymer Nanostructures

CP nanostructures have attracted attention due to their superior properties over bulk CPs [41,42]. In general, nano

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CPs exhibit larger surface area, have better electrical properties due to shorter ion transport distances and better

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electrochemical properties [43]. Because of these improved properties, nano CPs are promising materials for

energy- and sensing-applications [44,45].

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Nano CPs can be prepared by two main approaches — namely the template free method and the template-based

method [45]. These two methods are discussed in brief in this section.
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Template-Free Method
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This method is one of the easiest methods to make nano CPs. Also, it is a low-cost method because there is no need

for the removal of template after making the nano CP [46]. For example, PANI nano tubes can be prepared using
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this method. These nano tubes can be achieved in the presence of β-naphthalene sulfonic acid (β-NSA) as dopant.
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However; controlling the morphology of the nano CP in this method is poor when compared with template-based

synthesis. Mainly, in this method, nano CPs morphology is influenced by the natures of monomer, dopant and
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oxidant as well as polymerization conditions.

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Template-Based Synthesis

In this method nano CPs are prepared using a template to control their shape and size. This is an efficient method

for producing high quality nano CPs with a controlled morphology. Again, this method can be classified into two

methods — namely, hard-template synthesis [47] where molds are used for molding the nano CPs into certain

shapes, and soft-template synthesis nano CPs, where the morphology is controlled by self-assembly of the polymer.

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2.4 Characterization of Conducting Polymers

2.4.1 X-Ray Powder Diffraction

In general, depending on the method of preparation, conducting polymers are semi crystalline or amorphous in

nature. For example, the figure shows X-Ray Diffraction (XRD) patterns of different morphologies of PANI such

as nanotubes, nanofibers and nanoparticles, respectively [47]. All three polymers showed a semi-crystalline nature.

This crystallinity arises from the arrangement of the benzenoid or quinonoid forms in the polymer chain. Typically,

nanotubes and nano-fibers show two characteristic peaks at 2θ = 20° and 25°, which indicates they are semi

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crystalline in nature. In addition, a peak at 2θ= 6.49° is observed because of dopant interactions with polymeric

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chains. Similar peaks are also observed for nanoparticles.

2.4.2 Raman Spectroscopy

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Raman spectroscopy is a useful technique to study of vibrational, rotational, and low frequency modes of

molecules. In general, Raman spectroscopy analysis is used in Chemistry for structural analysis and identification
AN
of new compounds. It gives important information regarding structural differentiation's of various oxidation states,
M

and protonated and deprotonated forms of PANI. Many researchers have contributed in the characterization of

PANI prepared and oxidized in different conditions using Raman spectroscopy [48]. In this section, some of the
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published results are summarized.

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Miroslava Trchová et. al. [48] studied PANI films grown on a silica substrate in different experimental conditions

using Raman spectroscopy. Figure 6 shows Raman spectrum's of protonated and deprotonated PANI prepared in
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the presence of different redox reagents.

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Some important bond vibrations of PANI can be observed from the Figure 6. In a typical PANI prepared in the

presence of 0.1 M H2SO4, vibrational peaks can be observed as follows— a sharp band at 1623 cm-1 represents C-

C stretching vibrations of the benzenoid ring in the quinonoid ring vibrations, a strong band at 1585 Cm -1 indicates

the C=C stretching; another band at 1490 cm-1occurs due to C=N stretching vibrations. In addition, a C-N

deformation band is observed with a shoulder at 1512 cm-1.Further, Raman analysis gives evidence of the presence

of polarons in protonated PANI. For example, C-N+• exhibits the polaronic vibrational band at 1350 cm-1 with a

15
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shoulder at 1326 cm-1.Also, a benzene ring deformation vibration band can observed at 1260 cm-1 [49-51].A cation-

radical segment of the semi-quinonoid ring exhibits a band at 1170 cm-1 with a 1190 cm-1 shoulder band for C-H

the in-plane bending vibrations of the benzenoid ring. In addition, a band at 874 cm-1 indicates C-N-C wagging

vibration of benzene-ring deformation in the emeraldine salt polaronic or bipolaronic form. The Raman Vibrational

bands for PANI oxidation under various acidic conditions and deprotonated PANI are summarized in Tables 2 and

3.

3 PROPERTIES OF CONDUCTING POLYMER NANOCOMPOSITES

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3.1 General Properties

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3.1.1 Oxidation States of PANI

Usually CPs exhibits different types of oxidation states. Typically, PANI contains benzenoid and quinonoid forms

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as repeating units; the ratio of these units decides the final oxidation state of PANI. The oxidation state can be

donated by 1-y here y represents the number of benzenoid units present in the polymer (Figure 7). The benzenoid
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unit is the reduced form and the quinonoid unit is the oxidized form of the polymer. PANI can exhibit three
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oxidation states as fully reduced PANI called leucoemeralidine (LE) where all units are in the benzenoid form,

where 1-y= 0, Fully oxidized pernigraniline (PE) consists only quinonoid units, where 1-y=1.In the half-oxidized
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half-reduced emeraldine base (EB) both benzenoid and quinonoid forms are in equal ratio, where 1-y = 0.5.Among
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all oxidation states, EB is the most conductive material.

3.2 Optical Properties

CE

3.2.1 UV-Visible Spectroscopy

AC

UV-Visible spectroscopy is a useful technique to characterize the PANI EB base and salt forms. The UV spectrum

of non-protonated PANI, called emeralidine base (PANI EB), and protaned PANI, called as PANI emeralidine salt

(PANI ES) is shown in Figure 8. PANI EB showed two characteristic absorption peaks at 340 and 602 nm, an

absorption peak at 340nm due to benzenoid-ring π-π* transitions, and an excite on absorption peak at 602 nm that

represents the absorption of the quinonoid rings. However, protonated PANI ES shows three absorption peaks at

360 nm, 430 nm and 796 nm respectively. The π-π* transition absorption peak is red shifted to 360nm.The new

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peak at 430 is due to formation a radical cation, also known as polaron-bipolaron transitions. In PANI ES exhibits

a broad peak at 796 nm due to polaron to π* transitions.

3.2.2 Infrared Spectroscopy

The three possible types of oxidation states of PANI can be characterized using Infrared spectroscopy [60]. To

understand the Infrared vibrations of different forms of PANI, a few research groups compared the experimental

band positions with theoretical calculations [61]. Absorption bands appear with similar intensities with migration.

For example, C-N stretching of LE- PANI causes an absorption band at 1423cm-1; in E and PN PANI, C-N

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stretching vibration scan be observed at 1377 cm-1.Some important vibrations such as stretching and deformation

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vibration positions summarized in Table 4 and Figure 9 [60, 62-65].

3.3 Electrical Properties

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3.3.1 Conduction Mechanism

The bases of CPs can undergo redox reactions to form CP salts. In other words, imine groups in the CP bases can
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be wholly or partially protonated to form CP salts. However, optical and conducting properties of the CPs are
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controlled by these redox reactions [58]. The protonation of EB results the formation of poly semi quinone radical

cation, which causes an increase in conductivity by about ten of orders of magnitude. Protonated CPs or CP salts
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can be deprotonated with aqueous basic solutions such as ammonium hydroxide to give emeraldine base. The
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degree of protonation and deprotonation of CPs depends on the CPs oxidation state and the pH of the solution.

Thus partial oxidation or protonation and reduction or deprotonation leads to formation of anions (electron
CE

acceptors) and cations (electron donors) called p-doping and n-doping respectively. The doping process results in
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the introduction of charge carriers such as polarons, bi polarons and solitons into the CPs structure. The charge

carrier formation mechanism is shown in Figures 10a and b respectively.

For example, the mechanism of formation of charge carriers by adding electrons to a polymeric chain is shown in

Figures 10a and b respectively. According to the Molecular Orbital theory (MOT), the difference of highest

occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels is the band gap. The

addition of one electron to the trans-polyacetylene chain leads the formation of carbanion and carbon radical. The

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combination of a charged site and a radical is called a polaron. Typically, the addition of an electron injects an

electronic state below the conduction band. Further addition of another electron to the polymeric chain leads the

formation of spineless di-ion pair, called a bi polaron. Upon high doping; these polaron and bipolaron forms into

polaron bands, which cause an alteration of the band gap of the conducting polymer. However, unlike in CPs such

as PANI, polythiophene, PEDOT and PPy, a special type charge defects called solitons can be formed in linear

conjugated polymers like Polyacetylene, with degenerate ground states in polyacetylene due the degeneracy of 

electrons, charged ions, that are independent of one another, can freely move along the polymeric chain. The

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combination of separated charged ions, as shown in Figure 10a is called a soliton. The soliton formation results in

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the creation of new energy levels with opposite orientation of charge domains and identical energy. Finally, when

CPs has been highly doped, interaction of solitons with each other leads to the formation of soliton bands, which

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can later merge either with the HOMO or LUMO.

3.3.2 Effective Medium Theory

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The Effective Medium Theory (EMT) is a classical approximation employed to explain the dielectric dispersion of
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conductor-insulator composites [68]. The mathematical method developed by Bruggeman [69] assumes that the
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two phases of the mixture are of spherical nature. According to this theory the conductivity and dielectric constant

of a binary phase composite are governed by the Equation:

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1   m  2   m
   1     (1)
1  2 m  2  2 m
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Where 1 ,  2 and  m are the complex dielectric constants of the two components and the composite respectively,
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 is the volume fraction of the conducting material. Inherent to this formulation is the fact that a three-dimensional

system undergoes an insulator-conductor transition at  =1/3. At this point, a maximum of  m for   (real part of

dielectric constant of the composite) is reached. The magnitude of this maximum depends on both components.

The higher the difference between the conductivities the higher the value of  m . Conductivity and dielectric

constant exhibit strong frequency dependence when a characteristic frequency is achieved.

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There are two special cases for which effective medium theory applies, called the symmetric and the asymmetric

cases. The symmetric case assumes that all space is filled by a random mixture of spherical (or ellipsoidal)

particles of two or more components. When one component is a perfect insulator, the symmetric media theory has

a conductor-insulator transition. In the asymmetric case, the surface of the particles of one component is always

completely covered by the other component. This case does not have a transition.

3.3.3 Percolation Theory

Percolation theory gives a phenomenological description of the conductivity of a system near a conductor-insulator

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transition. Conductivity of insulator-conductor composites can be analyzed by the percolation theory, which has

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been actively studied in the past few years [70, 71]. According to this approach, the bulk conductivity of a

composite system suffers an insulator-conductor transition at a critical volume fraction c of the conducting phase.

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At this point, charge carriers percolate through a continuous infinite network of conducting elements which are in

physical contact. After c is achieved the conductivity scales as:

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      c  (2)
n
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with a parameter n between 1.65 and 2 for a three-dimensional system [69]. c is called the percolation threshold.
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Percolation theory is often limited to the cases in which either the insulating medium has zero conductance or the

conducting filler has zero resistance.

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CPs can be used as additives to build up advanced composites with interesting electrical properties. Polyacetylene
CE

or polypyrrole can be incorporated into a thermoplastic matrix by an in-situ polymerization process either

chemically [66, 67] or electro-chemically [72]. Conductivities as high as 10 S/cm have been achieved.
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3.3.4 Charge Carrier Transport in Composites

The process of charge-carrier transport in CP composites can be divided into two steps — the injection of charge

carriers into the material, and the motion of charge carriers through the material via hopping, tunneling, ballistic

transport, diffusion, or metallic conduction. In diphasic composites, four different conduction aspects have to be

taken into account — the conduction in the polymer matrix, in the filler material, between adjacent filler particles,

and from the filler into the matrix and vice versa. Five different regimes of charge-carrier transport mechanisms are
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possible, which are governed by the chemical and physical properties of the material [73]. Those are charge

carrier transport mechanism (thermionic emission limited conduction (TELC) model, Fowler-Nordheim

(FN) tunneling theory, space-charge-limited-current (SCLC) conduction model, Poole-Frenkel emission

model and Ohmic model) expressed in terms of equations (1) to (5) [74-81].

(1) Thermionic emission limited conduction (TELC) model:

J α A*T2 exp  - (q0)/kT + q q3V/41/2-------------- (1)
(2) Fowler-Nordheim (FN) tunneling theory:

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I α V2 exp -kd/V -------------------------------- (2)

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(3) Space-charge-limited-current (SCLC) conduction model:

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I  V ----------------------- (3)
(4) Poole-Frenkel emission model:
   
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J  V exp  q   qV / 4 / kT ---------------------- (4)
(5) Ohmic model:
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J α V exp - Eae)/kT -------------------------- (5)
where A*, T, , 0, q, d, V, Eae represent Richardson’s constant, absolute temperature, dielectric permittivity,
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barrier height, electronic charge, thickness, electric field and activation energy of electrons respectively.

For composites with very low filler loading, well below the percolation threshold, it is expected that the mean
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distance between conducting filler-particles is large and no conducting paths throughout the whole composite are
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established. The mean separation distance between neighboring filler particles is larger than 10 nm, which means

that even tunneling from particle to particle cannot take place. In this case, the composite conductivity is the result
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of transport processes within the polymer host matrix. Therefore, the loading at low fields has little effect on the

electrical conductivity of the entire composite.

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In the second case, the filler-particles are still well separated, but their mean distance is below a certain threshold

mean particle-particle distance of 10 nm. In this case, electrical-field-assisted tunneling can occur between

neighboring filler particles, as suggested by Beek [82].The expression for the electrical field dependence of the

tunneling current is given by the equation:

jTunn  AE n exp    (3)

W

 E 

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W 
The factor exp   characterizes the transition probability of charge carrier from the filler into the polymer and
 E 

vice versa, W is a measure of the energy barrier between the polymer and the filler material, E is the electric field

strength, and A and n (with typical value between 1 and 3) are constants. Alternatively, a model introduced by

Frenkel [83] suggests an electrical-field-assisted hopping mechanism (i.e., electron-hole separation) for the charge

carrier transport according to the equation:

 KE 2  
1

T
jHopp  ART exp  
2  (4)
 k T 

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 
B

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where AR  1.2  106 A / K 2 m2 is the Schottky-Richardson constant, k is a numerical constant, k B the

Boltzmann’s constant,  is the work function of the filler material, and T the temperature. Equation 4 has been

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successfully applied to describe the charge carrier transport in mono-component toner material, for example,
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carbon-black-filled polymer [84]. In this context, both the polymer matrix and the carbon black particles determine

the charge carrier transport through the composite. The surface properties of the filler particles, the inter facial
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region, and the work function of both materials are important. For composite systems close to the percolation limit,
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the conductivity is determined by the properties of the polymer, the filler material, the interface and, of course, by

the dispersion of the filler material in the polymer.

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Finally, at sufficiently high loading the conducting filler particles are in close contact, touching each other. The
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conduction of charge carriers occurs through the continuous structure of the chain of filler particles in the polymer

matrix. The conductivity is mainly determined by the filler material and its microscopic contacts to adjacent filler
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particles.

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4. FABRICATION OF CONDUCTING POLYMER NANOCOMPOSITES BASED TEMPERATURE

SENSORS

Looking into the essentialities of the temperature measurement almost in all type of industrial sectors, the sensing

materials used as a sensor should have flexibility for both temperature and pressure sensing ability. In

consideration to this present demand, conducting polymer composites is found to be potential candidate for both

flexible temperature and pressure sensing device. Again the electrical resistance of this material is very sensitive to

the temperature as well as pressure; much more extensive research work has been carried out. The current research

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problem which demands the temperature measurement in a particular zone should be have high accuracy and also

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extended to a large measurement range. The high accuracy measurement as well as wide measurement scale can

only be achieved by conducting polymer based sensors which are more stable at high temperature. Here, a

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comparative study related to the fabrication of polymers as well as conducting polymers based temperature sensors

has been provided in a tabular column.

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S Au Paper Princi Method and Device Result Conclusion Ref.
. th ple/M Structure
M

N or echan
o ism
1 Lu Differ A Temperature L Wang et [23]
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he ential proper sensor is al, reported

ng Struct ty- designed using that the
W ure for induce carbon-black- average
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an Temp d filled silicone sensitivity

g eratur differe rubber for the
e ntial composite/carbo differential
CE

Sensin structu n-nanotube- sensor with

g re. filled the full-
Based polyurethane bridge
AC

on foam composite structure is

Condu as the sensitive >50 mV/°C,
ctive material in and the
Polym PTCU/NTCU. maximum
er of the
Comp measureme
osites nt range is
75 °C.

22
2 Su Flexib
ACCEPTED MANUSCRIPT
Polym Cellulose–PPy S K [85]
res le erizati nanocomposite Mahadeva
ha humid on- et al,
K. ity and induce reported
M tempe d that the
ah rature adsorp capacitance
ad sensor tion of flexible
ev based sensor
a on increased
cellulo Reprinted from [85], linearly (R2
se– with the permission of Reprinted = 0.9933)
from
polyp Elsevier Publishing with
[85], with the
yrrole increasing

T
permission of
nanoc the
Elsevier

IP
ompos temperature.
Publishing
ite Temperatur

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e sensing
characteristi
cs of CP
nanocompo

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site (CP-16)
at 70% RH
3 Ko Low Hopin Polyaniline with K Majid et [86]
AN
ws tempe g of Mn3O4 al, reported
ar rature electro that the
M sensin ns composite
M

aji g possesses
d capabi Wanin the
lity of g resistance in
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polyan interac the range of

iline tion kilo-ohms
and at ambient
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Mn3O Reprinted from temperature,

4 [86], with the which starts
compo decreasing
CE

permission of
site as Elsevier with the
NTC Publishing increase in
materi temperature
AC

al and
becomes
minimum at
170 ◦C and
remains
constant up
to 200 ◦C.
After 200
◦C the
resistance
values of
composite
23
 ACCEPTED MANUSCRIPT again starts
increasing
slowly,
indicates
that
interaction
betweenMn
3O4 and
PANI starts
weakening.
Above 300
◦C the
resistance

T
values

IP
further
increases

CR
indicates
decompositi
on of
polyaniline.

US
4 Ju Enhan Anti- Solution-melt J W Zha et [87]
n- ced oxidat mixing al, reported
W positiv ion method that the
AN
ei e action PTC
Zh tempe of The intensity of
a rature coupli functionalized the HDPE
M

coeffi ng carbon black composites

cient agent (CB) and multi- increased
behavi walled carbon by 15.4%
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or of nanotubes and 18.3%,

the (MWNT) were respectively
high- introduced into .
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densit the high-density

y polyethylene
polyet (HDPE) matrix
CE

hylene to achieve the

compo improved PTC
sites behaviors. The
AC

with CB/MWNT/HD
multi- PE and Reprinted from
dimen CB/HDPE [87], with the
sional composites. permission of
carbon RSC Publishing
fillers
and
their
use for Reprinted
tempe from [87],
rature- with the
sensin permission
24
 g
ACCEPTED MANUSCRIPT of RSC
resisto Publishing
rs

5 Li Electri Volu Solution mixing L He et al, [88]

nxi cal me followed by reported
an behavi expan coagulation and that the 0.04
g or and sion thermal hot vol %
He positiv pressing. TRG/1 vol
e The re- %
tempe aggregation of AgNW/PV
rature conductive DF hybrid

T
coeffi fillers in molten exhibited

IP
cient polymer, pronounced
effect generating a PTC

CR
of conductive path behavior,
graphe in the composite rendering
ne/pol this
yvinyl composite

US
idene an attractive
fluorid Reprinted from material for
e [88], with the making
AN
compo permission of current
sites Springer limiting
contai Publishing devices and
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ning temperature
silver sensors. The
nanow resistivity
ED

ires of hybrid
composites
increased
PT

with
increasing
temperature,
CE

particularly
at the
melting
AC

temperature
of PVDF,
generating a
pronounced
PTC effect.
This effect
was caused
by the
volume
expansion
of PVDF
matrix with

25
 ACCEPTED MANUSCRIPT increasing
temperature,
which
disrupted
the
synergistic
effect and
reduced
electrical
contacts
among the
conductive
fillers.

T
6 Yo Positi Conventional Z You et al, [89]

IP
u ve melt-mixing reported
Ze tempe methods that the

CR
ng rature Hot-pressing, CNT-based
coeffi and packaging thermistors
cient methods show much
thermi larger hold

US
stors current and
based higher hold
on voltage,
AN
carbon Reprin increasing
nanotu ted by 129% in
be/ from comparison
M

polym [89], with the

er with commercial
compo the carbon
ED

sites permis black (CB)

sion Reprinted from
filled HDPE
of [89], with the
thermistors.
PT

Spring permission of
Such high
er Springer
current-
Publis Publishing
bearing and
CE

hing voltage-
bearing
Reprinted from [89], capacity for
AC

with the permission of the

Springer Publishing CNT/HDPE
thermistors
is mainly
attributed to
high
thermal
conductivity
and heat
dissipation
of entangled
CNT
26
 ACCEPTED MANUSCRIPT networks.
7 W Flexib Volu An automatic W P Shih et [90]
en- le me dispensing al, reported
Pi Temp fractio method that the
n eratur n polymer
Sh e mixed with
ih Sensor conductive
Array fillers
Based exhibits
on a resistance
Reprinted from [90], Reprinted from
Graph [90], with the variation
with the permission of
ite- permission of when it is
MDPI Publishing
Polydi subjected to

T
MDPIPublishing
methy ambient

IP
lsiloxa temperature
ne change.

CR
Comp Graphite
osite powders
mixed with
PDMS is

US
found to
have the
highest
AN
Reprinted from [90], temperature
with the permission of Reprinted from sensitivity
MDPI Publishing [90], with the and higher
M

permission of stability
MDPI Publishing compared
with the
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composites
using other
carbon
PT

fillers. As
the volume
fraction of
CE

graphite
powders
reaches the
AC

percolation
threshold,
the
resistivity
of the
composites
drops
substantiall
y.
8 M Polyis variab M Knite et [91]
ari oprene le al, reported
s /Nano range that the
27
Kn structu hoppi
ACCEPTED MANUSCRIPT variable
ite red ng range
Carbo Neare hopping
n st (VRH)
Comp Neigh conduction
osites bour is
for Hoppi dominated
Applic ng or by hopping
ations consta of carriers
in nt among
Temp range localized
eratur hoppi states in a
e ng low-

T
Sensor temperature

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s range. At
higher

CR
temperature
s the nearest
neighbour
hopping

US
(NNH)
conductivity
or constant
AN
range
hopping
charge
M

transport
takes place.
The
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reversibility
as well as
small
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hysteresis
of
resistance
CE

change
versus
temperature
AC

indicates
prospective
temperature
sensor
application
for PCBC.

28
5. SUMMARY
ACCEPTED MANUSCRIPT
Conducting polymers are good materials for both nanotechnology and temperature sensors (PTC & NTC). The

strength of conducting polymers is increasing rapidly in the fabrication of temperature sensors. For example,

temperature sensors fabricated based on conducting polymers shows several attractive characteristics depend on

the composite materials as well as on the CPs’ configuration method. Again, the electrical resistivity of the

conducting polymer is so sensitive to temperature and pressure that conducting polymers are chosen to be futuristic

potential smart materials for the development of high accuracy, measurement and wide temperature range sensors.

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The flexibility property of conducting polymer also widens its area of application in industrial sector.

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Acknowledgment

The authors (R Megha, Y T Ravikiran, S C Vijayakumari) say thanks to UGC [41-917/2012 (SR)] for grant

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support, F A Ali and D K Mishra say thanks to Siskha ‘O’ Anusandhan (Deemed to be University) for grant

support, CH V V Ramana and D Kim say thanks to Kyung Hee University (KHU-20170719) for grant support and
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A B V Kiran Kumar say thanks to UGC-DAE Consortium for Scientific research project with reference number
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CSR-IC-BL-48/CRS-165/2016-17/829 & 2017-18/786 for grant support.

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AC

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References
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[1] E. B. Jones, Instrument technology: instrumentation systems V.4, Elsevier science and technology, Oxford,
UK, 1987.

[2] R. W. White, A sensor classification scheme in: Microsensors, IEEE Press, New York, 1991.

[3] K Kanimozhi, S K Basha, V S Kumari, K Kaviyarasu, M Maaza, “In vitro cytocompatibility of

chitosan/PVA/methylcellulose-nanocellulose nanocomposite scaffolds using L929 fibroblast cells”,
Applied Surface Science, Vol. 449, pp.574-583 (2018)

[4] C. Jayakumar, C. Maria Magdalane, K. Kaviyarasu, M. Anbu Kulandainathan, Boniface Jeyaraj, and M.
Maaza, “Direct Electrodeposition of Gold Nanoparticles on Glassy Carbon Electrode for Selective

T
Determination
Catechol in the Presence of Hydroquinone”, J. Nanosci. Nanotechnol, Vol. 18(7), pp. 4544–4550 (2018)

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[5] Kaviyarasu K, Geetha N, Kanimozhi K, Maria Magdalane C, Sivaranjani S, Ayeshamariam A, Kennedy

CR
J, Maaza M, “In vitro cytotoxicity effect and antibacterial performance of human lung epithelial cells A549
activity of Zinc oxide doped TiO2 nanocrystals: Investigation of bio-medical application by chemical
method”, Mater Sci Eng C Mater Biol Appl, Vol.74 (1), pp. 325-333 (2017)

US
[6] K. Kaviyarasua, L. Kotsedia, Aline Simoa, Xolile Fuku, Genene T. Mola, J. Kennedy, M. Maazaa,
“Photocatalytic activity of ZrO2 doped lead dioxide nanocomposites: Investigation of structural and optical
microscopy of RhB organic dye”, Applied Surface Science, Vol. 421, pp. 234–239 (2017)
AN
[7] S Valentine, M Malose, et.al, “Optical and Structural Properties of Multi-wall-carbon-nanotube-modified
ZnO Synthesized at Varying Substrate Temperatures for Highly Efficient Light Sensing Devices”, Sensors
M

& Transducers Journal, Vol. 195(12), pp.9-17 (2015)

[8] F Fang, J Futter, A Markwitz and J Kennedy, “UV and humidity sensing properties of ZnO nanorods
ED

prepared by the arc discharge method”, Nanotechnology, Vol. 20(24), 245502 (2009)

[9] B.Sathyaseelan, E.Manikandan, K.Sivakumar, J.Kennedy, M.Maaza, “Enhanced visible photoluminescent

PT

and structural properties of ZnO/KIT-6 nanoporous materials for white light emitting diode (w-LED)
application”, Journal of Alloys and Compounds, Vol. 651, pp. 479-482 (2015)
[10] Kaviyarasu, K and Manikandan, E and Kennedy, J and Maaza, M, “Synthesis and analytical applications of
CE

photoluminescent carbon nanosheet by exfoliation of graphite oxide without purification”, Journal of

Materials Science: Materials in Electronics, Vol. 27(12), pp. 13080 – 13085 (2016)
AC

[11] J.Kennedy, F.Fang, J.Futter, J.Leveneur, P.P.Murmu, G.N.Panin, T.W.Kang, E.Manikandan, “Synthesis
and enhanced field emission of zinc oxide incorporated carbon nanotubes”, Diamond and Related
Materials, Vol.71, pp. 79-84 (2017)
[12] F Fang, J Kennedy, J Futter, T Hopf, A Markwitz, E Manikandan and G Henshaw, “Size-controlled
synthesis and gas sensing application of tungsten oxide nanostructures produced by arc discharge”,
Nanotechnology, Vol. 22(33), 335702 (2011)
[13] D.V.S. Murthy, Transducers and Instrumentation, PHI learning PVT Ltd., 2010.

[14] K. S. Lion, Transducers – problems and prospects. IEEE Transactions on Industrial Electronics 16, 1

(1969), 2-5.
30
[15]
ACCEPTED MANUSCRIPT
W. Gopel, J. Hesse and J. N. Zemel, Sensors: A comprehensive survey, Vol. 1, New York: VCH, 1989.

[16] E. O. Doeblin, Measurement Systems: application and design, 4th edition, McGraw-Hill, New York, 1990.

[17] B. E. Noltingk, Jones’ Instrumentation technology: Instrumentation systems V.1, fourth edition,

Butterworth-Heinemann International Edition, 2001.

[18] S. Middlehoek and D.J.W Noorlag, Three-dimensional representation of input and output transducers.

Sensors and actuators, 2, 1 (1982), 29-41.

[19] B. E. Noltingk, Jones’ Instrumentation technology: Measurement of Temperature and chemical

T
IP
composition V.2, fourth edition, Butterworth-Heinemann International Edition, 2001.

CR
[20] Rajesh, Tarushee Ahuja, Devendra Kumar, Recent progress in the development of nano-structured

conducting polymers/nanocomposites for sensor applications, Sensors and Actuators B 136 (2009) 275–286

US
[21] Ulrich Lange, Nataliya V. Roznyatovskaya1, Vladimir M. Mirsky, Conducting polymers in chemical

sensors and arrays, Analytica Chimica Acta 614 (2008) 1–26.

AN
[22] Arnaldo Leal-Junior, Anselmo Frizera-Neto, Carlos Marques and Maria José Pontes, A Polymer Optical
M

Fiber Temperature Sensor Based on Material Features, Sensors 18 (2018) 301.

[23] Luheng Wang, Differential Structure for Temperature Sensing Based on Conductive Polymer Composites,
ED

IEEE Transactions on Electron Devices 62 (2015) 3025.

PT

[24] Ran Zhaoa, Gang Shaob, Yejie Cao, Linan An, Chengying Xu, Temperature sensor made of polymer-

derived ceramics for high-temperature applications, Sensors and Actuators A 219 (2014) 58.
CE

[25] Ralf Strumpler, Polymer composite thermistors for temperature and current sensors, Journal of Applied
AC

Physics 80 (1996) 6091.

[26] Shirakawa, H.; Louis, J.; Macdiarmid, A. G. Synthesis of Electrically Conducting Organic Polymers :

Halogene Derivatives of Polyacetylene, (CH)x. J. C. S. Chem. Comm1977, 578–580.

[27] Heeger, A. J. Semiconducting and Metallic Polymers:  The Fourth Generation of Polymeric

Materials&#x2020. J. Phys. Chem. B2001, 105, 8475–8491.

[28] J Heinze, Frontana-uribe, B. A., S Ludwigs, "Electrochemistry of Conducting Polymers- Persistent Models

31
 ACCEPTED MANUSCRIPT
and New Concepts", Chemical Reviews, Vol. 110(8), pp. 4724–4771 (2010).

[29] Naveen, M. H.; Gurudatt, N. G.; Shim, Y. B. Applications of Conducting Polymer Composites to

Electrochemical Sensors: A Review. Appl. Mater. Today2017, 9, 419–433.

[30] Kumar, N. A.; Choi, H.; Shin, Y. R.; Chang, D. W.; Dai, L. Polyaniline-Grafted Reduced Graphene Oxide

for Efficient Electrochemical supercapacitors. ACS Nano.2012, 1715–1723.

[31] A. B. V. Kiran Kumar, Bae Chang wan, Seo Dong Min, Longhai Piao and Sang-Ho Kim “Silver Nanowire /
Polymer Composite Transparent Electrode: Improved Surface Properties",Materials Research Bulletin,
Vol.57,pp.52 - 57 (2014)

T
IP
[32] Meng, C.; Liu, C.; Chen, L.; Hu, C.; Fan, S. Highly Flexible and All-Solid-State Paperlike Polymer

CR
Supercapacitors. Nano Lett.2010, 10, 4025–4031.

[33] Kumar, A. B. V. K.; Jiang, J.; Bae, C. W.; Seo, D. M.; Piao, L.; Kim, S. H. Silver Nanowire/polyaniline

US
Composite Transparent Electrode with Improved Surface Properties. Mater. Res. Bull.2014, 57, 52–57.

[34] Nguyen, D. N.; Yoon, H. Recent Advances in Nanostructured Conducting Polymers: From Synthesis to
AN
Practical Applications. Polymers (Basel).2016, 8, 118.
M

[35] Molapo, K. M.; Ndangili, P. M.; Ajayi, R. F.; Mbambisa, G.; Mailu, S. M.; Njomo, N.; Masikini, M.; Baker,

P.; Iwuoha, E. I. Electronics of Conjugated Polymers (I): Polyaniline. Int. J. Electrochem. Sci.2012, 7,
ED

11859–11875.
PT

[36] Cnrs, E.R. the effect of the oxidation conditions on the chemical Polymerization of Aniline, Synthetic Metals

1988, 24, 193–201.

CE

[37] Bocchini, S.; Chiolerio, A.; Porro, S.; Accardo, D.; Garino, N.; Bejtka, K.; Perrone, D.; Pirri, C. F. Synthesis
AC

of Polyaniline-Based Inks, Doping Thereof and Test Device Printing towards Electronic Applications. J.

Mater. Chem. C2013, 1, 5101.

[38] Tat'yana V Vernitskaya and Oleg N Efimov, "Polypyrrole: a conducting polymer; its synthesis, properties
and applications", Russ.Chem.Rev, Vol. 66(5), pp. 443 (1997)

[39] Gospodinova, N.; Terlemezyan, L. Conducting Polymers Prepared by Oxidative Polymerization:

Polyaniline. Prog. Polym. Sci.1998, 23, 1443–1484.

[40] Beregoi, M.; Busuioc, C.; Evanghelidis, A.; Matei, E.; Iordache, F.; Radu, M.; Dinischiotu, A.; Enculescu, I.

32
 ACCEPTED MANUSCRIPT
Electrochromic Properties of Polyaniline-Coated Fiber Webs for Tissue Engineering Applications. Int. J.

Pharm.2016, 510, 465–473.

[41] Virji, S.; Huang, J.; Kaner, R. B.; Weiller, B. H. Polyaniline Nanofiber Gas Sensors:  Examination of

Response Mechanisms. Nano Lett.2004, 4, 491–496.

[42] Arsat, R.; Yu, X. F.; Li, Y. X.; Wlodarski, W.; Kalantar-zadeh, K. Hydrogen Gas Sensor Based on Highly

Ordered Polyaniline Nanofibers. Sensors Actuators B Chem.2009, 137, 529–532.

[43] Wu, C.-G.; Bein, T. Conducting Polyaniline Filaments in a Mesoporous Channel Host. Science .1994, 264,

T
IP
1757–1759.

CR
[44] Otero, T. F.; Sanchez, J. J.; Martinez, J. G. Biomimetic Dual Sensing-Actuators Based on Conducting

Polymers. Galvanostatic Theoretical Model for Actuators Sensing Temperature. J. Phys. Chem. B2012, 116,

US
5279–5290.

[45] Pan, L.; Qiu, H.; Dou, C.; Li, Y.; Pu, L.; Xu, J.; Shi, Y. Conducting Polymer Nanostructures: Template
AN
Synthesis and Applications in Energy Storage. Int. J. Mol. Sci.2010, 11, 2636–2657.
M

[46] Wan, M. A Template-Free Method Towards Conducting Polymer Nanostructures. Adv. Mater.2008, 20,

2926–2932.
ED

[47] Mohd Khalid, J J S Acuna, A T Milton, J A Fischer, V C Zoldan and A A pasa, "Sulfonated porphyrin
PT

doped polyaniline nanotubes nd nanofibers: synthesis and characterization", Journal of materials Chemistry,

Vol. 22, pp. 11340 (2012).

CE

[48] Trchová, M.; Morávková, Z.; Bláha, M.; Stejskal, J. Raman Spectroscopy of Polyaniline and Oligoaniline
AC

Thin Films. Electrochim. Acta2014, 122, 28–38.

[49] Rozlívková, Z.; Trchová, M.; Šeděnková, I.; Špírková, M.; Stejskal, J. Structure and Stability of Thin

Polyaniline Films Deposited in Situ on Silicon and Gold during Precipitation and Dispersion Polymerization

of Aniline Hydrochloride. Thin Solid Films2011, 519, 5933–5941.

[50] Ćirić-Marjanović, G.; Trchová, M.; Stejskal, J. The Chemical Oxidative Polymerization of Aniline in Water:

Raman Spectroscopy. J. Raman Spectrosc.2008, 39, 1375–1387.

33
 ACCEPTED MANUSCRIPT
[51] Šeděnková, I.; Trchová, M.; Stejskal, J. Thermal Degradation of Polyaniline Films Prepared in Solutions of

Strong and Weak Acids and in Water – FTIR and Raman Spectroscopic Studies. Polym. Degrad. Stab.2008,

93, 2147–2157.

[52] Silva, C. H. B.; Ferreira, D. C.; Ando, R. A.; Temperini, M. L. A. Aniline-1,4-Benzoquinone as a Model

System for the Characterization of Products from Aniline Oligomerization in Low Acidic Media. Chem.

Phys. Lett.2012, 551, 130–133.

[53] do Nascimento, G. M.; Temperini, M. L. A. Studies on the Resonance Raman Spectra of Polyaniline

T
IP
Obtained with near-IR Excitation. J. Raman Spectrosc.2008, 39, 772–778.

[54] Morávková, Z.; Trchová, M.; Tomšík, E.; Zhigunov, A.; Stejskal, J. Transformation of Oligoaniline

CR
Microspheres to Platelike Nitrogen-Containing Carbon. J. Phys. Chem. C2013, 117, 2289–2299.

US
[55] Barbero, C.; Silber, J. J.; Sereno, L. Formation of a Novel Electroactive Film by Electropolymerization of

Ortho-Aminophenol: Study of Its Chemical Structure and Formation Mechanism. Electropolymerization of

AN
Analogous Compounds. J. Electroanal. Chem. Interfacial Electrochem.1989, 263, 333–352.
M

[56] Salavagione, H. J.; Arias, J.; Garcés, P.; Morallón, E.; Barbero, C.; Vázquez, J. L. Spectroelectrochemical

Study of the Oxidation of Aminophenols on Platinum Electrode in Acid Medium. J. Electroanal.

ED

Chem.2004, 565, 375–383.

PT

[57] Tucceri, R.; Arnal, P. M.; Scian, A. N. Spectroscopic Characterization of Poly(ortho-Aminophenol) Film

Electrodes: A Review Article. J. Spectrosc.2013, 2013, 1–26.

CE

[58] Niziol, J.; Sniechowski, M.; Podraza-Guba, A.; Pielichowski, J. Alternative Oxidizers in Polyaniline
AC

Synthesis. Polym. Bull.2011, 66, 761–770.

[59] Flavel, B. S.; Yu, J.; Shapter, J. G.; Quinton, J. S. Patterned Polyaniline & Carbon Nanotube–polyaniline

Composites on Silicon. Soft Matter2009, 5, 164.

[60] Planes, G. A.; Rodríguez, J. L.; Miras, M. C.; García, G.; Pastor, E.; Barbero, C. A. Spectroscopic Evidence

for Intermediate Species Formed during Aniline Polymerization and Polyaniline Degradation. Phys. Chem.

Chem. Phys.2010, 12, 10584.

34
 ACCEPTED MANUSCRIPT
[61] Ibrahim, M.; Koglin, E. Spectroscopic Study of Polyaniline Emeraldine Base: Modelling Approach. Acta

Chim. Slov.2005, 52, 159–163.

[62] Brožová, L.; Holler, P.; Kovářová, J.; Stejskal, J.; Trchová, M. The Stability of Polyaniline in Strongly

Alkaline or Acidic Aqueous Media. Polym. Degrad. Stab.2008, 93, 592–600.

[63] Kazim, S.; Ali, V.; Zulfequar, M.; Haq, M. M.; Husain, M. Electrical, Thermal and Spectroscopic Studies of

Te Doped Polyaniline. Curr. Appl. Phys.2007, 7, 68–75.

[64] Singh, R.; Arora, V.; Tandon, R. P.; Chandra, S.; Kumar, N.; Mansingh, A. Transport and Structural

T
IP
Properties of Polyaniline Doped with Monovalent and Multivalent Ions. Polymer (Guildf).1997, 38, 4897–

CR
4902.

[65] Yang, C.; Chen, C.; Zeng, Y. Fourier Transform Infrared Spectra of Transition Metal Ion-Containing

US
Polyanilines Synthesized in Different Reaction Conditions. Spectrochim. Acta Part A Mol. Biomol.

Spectrosc.2007, 66, 37–41.

AN
[66] J.A. Manson and L.H. Sperling, Polymer Blends and Composites, Plenum Press, New Yark 1976.
M

[67] D. Stauffer, Introduction to Percolation Theory, Taylor & Francis, London 1985.

[68] R. Landauer, J. Appl. Phys. 23 (1952) 779.

ED

[69] D.A.G. Bruggeman, Ann. Phys. (Leipzig) 24 (1935) 636.

PT

[70] D. Stauffer, Introduction to Percolation Theory, Taylor & Francis, London 1985.

[71] A. B. V. Kiran Kumar, Chang wan Bae, L. H. Piao, and Song-Ho Kim, “conducting polymer Silver
CE

nanowire transparent composite electrodes”, Materials Research Bulletin, Vol.48 (8), pp. 2944 - 2949
(2013).
AC

[72] S.E. Lindsey, G.B. Street, Synth. Met. 10 (1984) 67.

[73] A.I. Medalia, Rubber Chemistry and Technology 59 (1986) 432.

[74] CH.V.V.Ramana, V.Kannan and V.V.Srinivasu, “Negative differential resistance device from
organic/inorganic hybrid nanostructures”, Journal of Nanoscience and Nanotechnology, Vol. 17, pp. 671-
675(2017)

[75] CH.V.V.Ramana, M.K.Moodley, A.B.V.Kiran Kumar and V.Kannan, “Charge carrier transport mechanism
based on stable low voltage organic bistable memory device”, Journal of Nanoscience and Nanotechnology,
Vol. 15 (5), pp. 3934-3938(May 2015)

35
[76]
ACCEPTED MANUSCRIPT
CH.V.V.Ramana, M.K.Moodley and V.Kannan, “Electrical characteristics of ITO/MEH-PPV/ZnO/Al
structure”, Nanoscience and Nanotechnology Letters, Vol. 6, No.3, pp. 238-241 (2014)

[77] CH.V.V.Ramana, M.K.Moodley, V.Kannan and A.Maity, “Solution based-spin cast processed organic
bistable memory device”, Solid State Electronics, Vol.81, pp.45-50 (2013).

[78] CH.V.V.Ramana, M.K. Moodley, A.B.V.Kiran Kumar, A.Maity and V.V.Srinivasu, “Hysteresis type
Current-Voltage characteristics of Indium Tin Oxide/ poly-[2-methoxy-5-(2-ethyl-hexyloxy)-1,4-
phenylenevinylene] (MEHPPV)+Zinc Oxide (ZnO)/Al STRUCTURE: TOWARDS MEMORY DEVICE”,
Nanoscience and Nanotechnology Letters, Vol. 4, No. 12 (2012).

[79] CH.V.V.Ramana, M.K.Moodley, V.Kannan, A.Maity, J.Jayaramudu and W.Clarke, “Fabrication of stable

T
low voltage organic bistable memory device”, Sensors & Actuators B:Chemical, Vol 161, Issue 1, pp. 684-

IP
688 (2012).

[80] V. Kannan, Y S Chae, CH.V.V.Ramana and J K Rhee, “All inorganic spin-cast quantum dot based bipolar

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non-volatile resistive memory”, Journal of Applied Physics, Vol. 109, No.9, doi: 10.1063/1.3573601
(2011).

US
[81] V. Kannan, M R Kim, Y S Chae, CH.V.V.Ramana and J K Rhee, “Observation of room temperature
negative differential resistance in multi-layer heterostructures of quantum dots and conducting polymers”,
Nanotechnology, Vol. 22, No.2, doi: 10.1088/0957-4484/22/2/025705 (2011).
AN
[82] L.K.H. van Beek, J. Appl. Polymer Sci. 6 (1962) 651.
M

[83] J. Frenkel, Physical Review, 36 (1930) 1604.

[84] W. Imaino, K. Loeffler, R. Balanson, in Colloids and Surface in Reprographic Technology ACS
ED

Symposium Series 200, p. 249 (American Chemical Society, Washington, 1982).

PT

[85] S K Mahadeva, S Yun, J Kim, “Flexible humidity and temperature sensor based on cellulose-polypyrrole

nanocomposite”, Sensors and Actuators A: Physical, vol.165, pp. 194-199 (2011)

CE

[86] K Majid, S Awasthi, M L Singla, “Low temperature sensing capability of polyaniline and Mn3O4
AC

composite as NTC material”, Sensors and Actuators A: Physical, Vol. 135, pp. 113-118 (2007)

[87] J W Zha, D H Wu, Y Yu, Y H Wu, K Robert, Y Li, Z M Dang, “Enhanced positive temperature coefficient

behavior of the high-density polyethylene composites with multi-dimensional carbon fillers and their use

for temperature-sensing resistors”, RSC Adv, Vol.7, pp.11338-11344 (2017)

[88] L He, Sie-Chin Tjong, “Electrical and positive temperature coefficient effect of graphene/polyvinylidene

fluoride composites containing silver nanowires”, Nanoscale Research Letters, Vol. 9, pp. 375 (2014)

36
[89]
ACCEPTED MANUSCRIPT
Z You, G Lu, H Wang, J Du, Z Ying, C Liu, “Positive temperature coefficient thermistors based on carbon

nanotubes/polymer composites”, Scientific Reports, Vol.4, pp. 6684, DOI: 10.1038/srep06684 (2014)

[90] Wen-Pin Shih, Li-Chi Tsao, Chian-Wen Lee, ming-Yuan Cheng, C Chang, Yao-Joe Yang, Kuang-Chao

Fan, “Flexible temperature sensor array based on a graphite-polydilethylsiloxane composite”, Sensors,

Vol.10, pp.3597-3610 (2010)

[91] M. Knite, S. Zike, Z. Juris, L. Artis, “Polyisoprene/nanostructured carbon composites for applications in

temperature sensors”, Material Science and Applied Chemistry, pp. 28-33, doi: 10.7250/msac.2013.005

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R Megha
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R. Megha received her M.Sc. degree in Physics in 2015 from the Davangere University, India. She is pursuing her

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PhD in Physics under the guidance of Dr.Y.T. Ravikiran. She has published 12 articles in international peer

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revived journals. Her research interest includes synthesis, device fabrication on humidity and gas sensors,
electrical, optical studies in nanostructured materials and conducting polymer based nanocomposites.

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Dr. (Mrs.) Farida Ashraf Ali
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Farida Ashraf Ali is an Assistant Professor of Electronics and Instrumentation Engineering at Siksha ‘O’
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Anusandhan (Deemed to be University), where her research and teaching focus on solid state physics,
characterization and simulation of classical and novel semiconductor devices including oxide semiconductors, thin
films, DVLSI, Embedded systems and sensors. She received her B. Tech in Electronics and Instrumentation
Engineering from Gulbarga University, Karnataka (1998), M. Tech in VLSI and Embedded Systems (2010) and
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later Ph.D. thesis in electronics engineering from the S’O’A (deemed to be) University (2018). She is author or
co-author of over 15 journal and conference papers in various semiconductor research areas. She has two patents
on indigenously developed heterosructures. She has also acted as a reviewer for the book chapter and for few
reputed international journals. She is a life member of Indian Society of Technical Education and IEEE EDS
Kolkata chapter for last nine years. Her professional experience as a teacher provided her a broad view that is
useful in assisting students with projects and assignments and motivate them to develop their own learning interests
and critical thinking—to establish a learner-centered environment in the classroom.

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Dr.Y T Ravikiran
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Dr. Y.T. Ravikiran received his M.Sc. degree in Physics in 2002 and M.Phil. degree in 2003, and Ph.D degree in
Physics in 2008 from Gulbarga University, India. He is currently Assistant Professor of Physics in Government

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Science College, Chitradurga, India. He has published 32 articles in international pre revived journals. His research
interests are, studies on humidity and gas sensing properties of conducting polymers and their composites, solid

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state battery and super capacitor technology using polymer electrolytes.

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Dr.CH.V.V.Ramana

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Dr. CH.V.V. Ramana is working in the Department of Electronic Engineering, Institute of Wearable Convergence
Electronics, Kyung Hee University, Global campus, Republic of korea. He also working as a Senior Research
Associate (Honoree) of Department of Electrical and Electronics Engineering Science, University of Johannesburg,
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Auckland Park Campus, Johannesburg, South Africa. He published 45 scientific articles in referred journals, 07
books and 01 book chapter. His research work encompasses scientific instrumentation (design and development of
instruments), PC/microcontroller based instrumentation, embedded based systems, dielectric studies (solids, natural
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fibers, fluids, composites and liquids), digital design, device fabrication (OLEDs, PLEDs, NDR and memory) and
Sensors, Photo catalytic, Super Capacitors. He received his BSc in Instrumentation from the Andhra University,
A.P., India in 2000, MSc, MPhil and PhD in Instrumentation from the Sri Krishnadevaraya University, A.P., India
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in 2002, 2005 and 2008 respectively.

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Dr.A.B.V. Kiran Kumar
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Dr.A.B.V. Kiran Kumar is working as an Assistant Professor of Nanotechnology at Amity University, Noida,
India. He has ten years post PhD experience. After completion of PhD in Synthetic Organic Chemistry, he worked

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for four years as a post-doc researcher in South Korea. During this period, he worked on the development of
nanomaterials for various applications such as phosphors, antimicrobial membranes incorporating nanoparticles,

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MRI contrast agents. Development of flexible transparent conducting electrodes using AgNWs to replace ITO for
OLED and OPV applications. His present research area is development of nanomaterials and nanocomposites for

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photocatalysis and supercapacitor applications.

Dr. Dilip Kumar Mishra

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D. K. Mishra is an Associate Professor of Department of Physics, Institute of Technical Education and Research,
Siksha ‘O’ Anusandhan (Deemed to be University), Bhubaneswar, India. He had received his M.Sc. and M. Phil degree
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in Physics from Berhampur University in the year 2000 and 2002 respectively. He joined Institute of Materials
Science, Bhubaneswar in year 2003 as CSIR-NET qualified research fellow and received his Ph.D. degree from
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Utkal University, India in the year 2008. From year 2008-2009, he served as Research Associate at inter-University
Accelerator centre, New Delhi and from 2009-2012, he continued his research work in Advanced Materials
Technology Department, Institute of Minerals and Materials Technology (CSIR), Bhubaneswar as Scientist
Fellow. He had also visited UNISA-South Africa for one year (2014-2015) as Visiting Researcher. He has been
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conferred with the Young Physicist Award from Orissa Physical Society and Young Scientist Award from Orissa
Bigyan Academy, Odisha, India. The research area of interest of Dr. Mishra includes dilute magnetic
semiconductor, defect and interface properties including magnetism, thin film fabrication, nanostructures, novel
methods of materials processing, and studies of nano materials. He has published more than 90 research articles in
peer-reviewed journal of international repute. He has also acted as guest editor for special issue in Advanced
Science Letters and International Journal of Nano and Bio Materials.

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Prof. S C Vijayakumari
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Prof. S.C. Vijayakumari obtained her M.Sc. degree in Physics in the year 1982 from The university of Mysore,

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India. She has obtained her M.Phil. degree in Physics in 2009. She is currently Associate professor in the
Department of Physics, SJM College of Arts, Science and Commerce, Chitradurga, India. She has published 30

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articles in international peer-revived journals. Her research areas include humidity and gas sensing
properties of conducting polymers, polymer blends and composites.

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Dr. D Kim

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Dr. Daewon Kim is an Assistant Professor in the Department of Electronic Engineering at Kyung Hee University,
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Korea. He received his B.S. and Ph.D. degrees from the Korea Advanced Institute of Science and Technology
(KAIST) in Daejeon, Korea, in 2009 and 2016, respectively. He worked as a postdoctoral researcher at the
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University of Pennsylvania, Philadelphia, USA. His current research interests include energy
harvesting/conversion/storage devices and advanced micro/nano electronic devices.
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Figure 1: Selected building units of conducting polymers: 1,polyacetylene (PA); 2, polypyrrole (PPy),

polythiophene (PTh); 3,poly-p-phenylene (PPP); 4, polyaniline (PANI); 5, polycarbazole;6, polyazulene;

7,poly(isothionaphthalene);8,poly(dithienothiophene);9,poly(dithienylbenzene);

10,poly(ethylenedioxythiophene)(PEDOT);11,poly(3-alkylthiophene);

12,poly(phenylenevinylene)(PPV);13,poly(thienylenevinylene);14,poly(bipyrrole),poly(bithiophene). Reprinted

from [28], with the permission of ACS publishing.

Figure 2a: Radical Cation Formation and Stabilization of Aniline

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Figure 2b: Radical Cation Formation and Stabilization of Pyrrole

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Figure 3a: Dimerization and Re-aromatization of Radical Cation of Aniline

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Figure 3b: Dimerization and Re-aromatization of Radical Cation of Pyrrole

Figure 4a: Chain Propagation Step of Aniline Dimer

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Figure 4b: Chain Propagation Step of Pyrrole Dimer
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Figure 5: XRD Patterns of Different Structures of PANI.Reprinted from [47], with the permission of Elsevier

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Figure 6: Raman spectra of the final films produced on silicon supports during oxidation of aniline in 0.1 M
sulfuric (S) , 0.4 M succinic (Su), 0.4 M acetic acids (Ac) , in water (W) , and in 0.2 M ammonium hydroxide (Am
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0.2) (a), and of the corresponding products after deprotonation in 1 M ammonium hydroxide (marked with label
B) (b). Reprinted from [48], with the permission of Elsevier Publishing.
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Figure 7: Structure of Different Oxidation States of Polyaniline

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Figure 8: UV-Vis spectra of polyaniline films deposited for 50 minutes inthe a) non-conducting and b) conducting
forms. Reprinted from [59], with the permission of RSC Publishing.
Figure 9: Vibrational band assignments for polymeric species. Reprinted from [50], with the permission of RSC
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Figure 10a: Schematic Representation of Formation of a Polaron, Bipolaron and Soliton in Trans-polyacetylene

Figure 10b: Schematic Band Structure of Formation of a Polaron, Bipolaron and Soliton

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Table 1: Oxidizing Agents and their Oxidation Potential [34,35]

Oxidizing agent name Formula Oxidation potential

Ammonium Persulfate (NH4)2S2O8 1.94 V
Potassium iodate KIO3 0.84 V
Ferric chloride (FeCl3) 0.77 V
Hydrogen peroxide H2O2 1.78 V
Cerium (IV) sulfate Ce(SO4)2 1.72 V
Potassium dichromate K2Cr2O7 1.23V

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Table 2: Raman Vibrational Frequencies of Functional Groups of PANI in different Acidic and Basic Conditions

Wavenumbers (cm−1)
Type of bond
Acidic Alkaline
Phz, ν (C=O) of benzoquinone [52] 1630 (sh) 1630
ν(C∼C)B[49-51] 1623 (sh) --
ν(C–C)Q in pernigraniline-like and 1566 (sh) 1570 (ms)
pseudomauveine base-like units [49-51]
N–H bending (SQ) [49-53] 1512 (s/sh) 1512 (m)
ν(C=N)Q [49-51] 1490 (s) 1475 (ms)
Phz [53] 1412 (w) 1419 (w)

T
C∼N+ ring-stretching vibrations of substituted -- 1376 (s)
N-phenylphenazines [54]

IP
ν(C∼N+• ) of delocalized polaronic structures 1350 (s) 1350 (sh)
[49-51]

CR
ν (C∼N+• ) 1326 (s) 1338 (s)
ν (C–N)B[49-51] 1260 (m) 1250 (w)
ν (C–N)Q [49-51] 1221 (w) --

US
ν (C–H) in SQ [49-51] 1170 (s) 1165 (w)
C–N–C wagging (o.p.); B ring deformation 874 (w) --
(i.p.) in polarons and bipolarons [49-51] ;
AN
substituted Bring deformation
B ring deformation [49-51]; substituted B ring 810 (w) --
deformation
M

Amine deformation in bipolaronic form of 718 (w) --

emeraldine salt [49-51]
Sulfate anion [49-51] 656 (w) --
ED

Phenoxazine-type units [53, 55-57] 575 (w) --

Ring deformation (o.p.) + silicon vibrations 520 (w) 520 (s)
[49-51]
PT

Ring deformation (o.p.) [49-51] 417 (w) 417 (w)

Abbreviations: s-strong; m–medium; w-weak; sh-shoulder; ν-stretching; δ-
in- plane bending; γ-out-of-plane deformation; B-benzenoid ring; Q-
CE

quinonoid ring; SQ-semi-quinonoid ring; Phz-phenazine-like segment; ∼-a

bond intermediate between a single and a double bond; o.p.-out-of-plane;
i.p.-in plane.
AC

44
 ACCEPTED MANUSCRIPT
Table 3: Raman Vibrational Frequencies of Functional Groups of Protonated and Deprotonated PANI.

Wavenumbers (cm−1)
Assignment
Acidic Alkaline
Phz32 ; ν (C=O) of p-benzoquinone [52] 1640 (sh) 1631 (sh)
ν (C=C)Q [49-51] 1606 (s)
ν (C=C)Q [49-51] 1592 (s) 1592 (s)
N–H bending 1560 (m) 1527 (s)
ν (C=N)Q [49-51] 1468 (s) 1479 (sh)
Phz [50] 1412 (w) 1412 (w)
C∼N+ ring-stretching vibrations of

T
substituted 1378 (w) 1378 (w)
N-phenylphenazines [50, 54]

IP
ν (C∼N+• )[50] 1336 (m) --
ν (C–N)B[49-51] 1262 (w) --

CR
ν (C–N)Q[49-51] 1220 (m) --
ν (C–H)Q[49-51] 1162 (s) 1162 (m)
C–H wag (o.p.) 840 (w) --

US
Q ring deformation 778 (w) --
Q ring bending (o.p.); C–C ring
748 (w) --
deformation (o.p.); Phz [50]
AN
ν (C–S), ν (SO2); B ring deformation
608 (w) 608 (w)
(i.p.) [50]
phenoxazine-type units [39, 43] 578 (w) 578 (w)
M

Phz, C–N bending (i.p.)[50] ; ring

417 (w) 417 (w)
deformation (o.p.) [49-51]
Abbreviations: s-strong; m–medium; w-weak; sh-shoulder; ν-stretching; δ-
ED

in- plane bending; γ-out-of-plane deformation; B-benzenoid ring; Q-

quinonoid ring; SQ-semi-quinonoid ring; Phz-phenazine-like segment; ∼-a
bond intermediate between a single and a double bond; o.p.-out-of-plane;
PT

i.p.-in plane.
CE
AC

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 ACCEPTED MANUSCRIPT

Table 4: IR Vibrational Frequencies for Functional Groups of PANI

Wave Number (Cm-1) Vibration Oxide form of PANI

1581 N=Q=N* str. EM
1512 C=C aromat. str., N-B-N LE
1475 C=C aromat. str.,N-B-N PN
1450 C=C aromat. str.,N-B-N PN
1423 C-N str. LE
1377 C-N str.c EM and PN

T
1342 C-C str.,N-H o.o.p. bend, EM
1288 C–N str. sec. LE

IP
aromaticamine
1238 C-N stretch, C-C-C ring EM

CR
i.p. def.
1218 -NH2+ bend. LE

US
1157 N=Q=NC-H in plane EM
bending
Q = quinonoid unit, B= benzenoid unit,
AN
LE = leucoemeraldine unit, EM = emeraldine unit, PN = pernigraniline unit
M
ED
PT
CE
AC

46
 ACCEPTED MANUSCRIPT
Highlights

 Conducting polymers have an efficient candidate for temperature sensor.

 The strength of conducting polymers is increasing rapidly in the fabrication of temperature sensors.

 Temperature sensors fabricated based on conducting polymers shows several attractive characteristics depend
on the composite materials as well as on the CPs’ configuration method.

T
IP
 The flexibility property of conducting polymer also widens its area of application in industrial sector.

CR
US
AN
M
ED
PT
CE
AC

47
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