1

CHAPTER 1

1.1 INTRODUCTION TO 89C51 MICROCONTROLLER [1, 2]

A digital computer on a single chip is called a microcontroller. A single chip

microcontroller has a CPU, RAM, ROM or EPROM, Input/Output (I/O) lines,
programmable timer/counter, interrupt controller etc., integrated on the same IC. Intel
introduced the 8051 (MCS – 51) series of microcontrollers which are more powerful
than Intel 8048 series. The 8051 are second generation microcontrollers. Some
chosen versions of microcontrollers have capacities like DMA channels, analog to
t•

digital (ADC) converter, pulse width modulator (PWM) and so forth. Table 1.1
demonstrates the particulars of MCS-51 arrangement.

The Atmel Corp. has a wide choice of 8051 chips. For example, the AT89C51
is a well known and economical chip utilized in many small projects. It has 4K bytes tes

of flash ROM. In AT89C51-12PC, the letter "C" before the 51 stands for CMOS,
• t• t• t•

which has low power utilization, "12" shows 12 MHz, "P" stands for plastic DIP
t• t•

package and another "C" is for business.

 2

Atmel 89C51 is a CMOS 8 bit microcontroller. This gadget is perfect with

8051 microcontrollers. A flash programmable and erasable read only memory
(PEROM) is present in Atmel 89C51.

Flash memory is generally a non-volatile memory, which can be electrically

erased for lines and blocks. The system for deleting the memory is trouble-free and
faster than that needed for EEPROM. There is no delay time for deleting the program
memory. Typically, 1000 write /delete cycles are conceivable, which are more than
adequate for any application improvement. 89C2051 microcontroller has 128 byte
on- chip RAM sorted out as shown in Fig 1.1. The initial 32 memory areas (00H-
1FH) are characterized as register banks (RB0- RB3). Every register bank contains
eight registers (R0-R7). Using the Program Status Word (PSW), a register bank can be
t• t• t•

selected by setting bank select flags RS0 and RS1. The figure drawn beneath
demonstrates the eight bits of PSW register.

RS 1 RS0
Auxiliary User
Carry flag flag Register Register
Carry Bank Bank Overflow Reserved Parity
(CY)
(AC) FO Select Select
Bit 1 Bit 0
PSW.7 PSW.6 PSW.5 PSW.4 PSW.3 PSW.2 PSW.1 PSW.0

The CPU registers and other different registers together are called
special function registers (SFRs). It possesses the address range of 80H to FFH. The
memory guide of SFR is given in Fig 1.2. The Stack Pointer (SP) is a 8-bit register.
Upon Reset, the SP begins in Bank 1. The beginning of stack can be changed by the
Register Bank select Bits. The stack must be built inside the internal RAM, if not,
initialized with the register bank.

Development apparatus like simulators and assemblers implied for 8051 may
likewise be utilized for 89C51. The instruction set of 89C51 is the same as that of
Intel's MCS-51 family microcontrollers. Another component of 89C51, which is also
there in 8051 microcontrollers, is that they support completely static operation. The
working frequency of 89C51 could be from 0 Hz to 24 MHz. By this device two
software power saving modes are supported.
 3

Fig. 1.1 (a) Structure of Internal Data Memory Map

Fig. 1.1(b) Structure of the Lower 128 bytes of Internal RAM

 4

Fig. 1.2 Structure of SFR Memory Map

1.1.1 Architectural Overview of 89C51

The outline of Atmel 89C51 is as shown in Fig 1.3. The design has almost all
the blocks, which are available in MCS-51. There is a 4 kilobytes on-chip flash
program memory in 89C51. Registers and memory organisation are same as that of
the MCS-51 items. It comprises of two 16 bit clock/counters (T0 and T1), one full
t• t •

duplex serial port (UART), and 32 programmable I/O lines, 128 bytes of on chip
t•
 5

RAM; clock hardware and on-chip oscillator. Six interrupt sources authenticate it. In
89C51 "Idle Mode" and "Shut down mode" are the two power saving modes that are
possible. 89C51 is an intense microcontroller which gives extremely–flexible and
economical, compact and adaptable solutions for some embedded control
applications.

Fig. 1.3 Block Diagram of 89C51 microcontroller

1.1.2 Pin Description

The controller Atmel 89C51 is a 40 pin device. Fig 1.4 illustrates the pin
configuration of 89C51. In 89C51controller, there is no external address/data bus
while it consists of two 16-bit timers and 32 programmable I/O lines. Hence, there
are no external memory connections. The connections for external crystal and reset
circuit for 89C51controller is similar to that of MCS-51. The block diagram with the
external crystal connection and RESET button is shown in the conversation of
interrupt feature (RESET).
 6

Fig. 1.4 Pin configuration of 89C51 Microcontroller

1.1.3 Interrupt Features

The key role in the application of the microcontroller is the interrupt. There
are six interrupts in 89C51 microcontroller. Among these six interrupts, five are
accessible to the user. These are

*RESET */INT0 */INT1 *TF0 *TF1 *RI+TI

In the order of priority, the sequence is as follows:

/INT0>TF0>/INT1>TF1>RI (or) TI

The interrupt polling is done by the internal hardware. When the

microcontroller finds two interrupts with different priorities, higher priority is
serviced first and then the lower one. Interrupt events set interrupt flags of the
microcontroller. These set flags are sampled during the S5 state of the machine cycle.
A brief description on these interrupts is as follows:
 7

 RESET
Pin 9 of 89C51 is RESET. When this pin is activated, the control jumps to the
memory location 0000H. This is generally known as “Power-On-Resеt”. For
effective operation of the RESET input, it should be high for a minimum duration of
t• t•

2 machine cycles prior to the signal goes to low. The customary RESET signal is
t•

obtained as shown in Fig. 1.5

Fig. 1.5 Reset Connection

 TIMER 0 INTERRUPT (TF0)

The vector memory location for Timer 0 is 000BH. The bit ET0 (IE.1) of
Interrupt Enable register must be set to enable the Timer 0 interrupt. This is
accomplished by the software instruction: SETB IE.1. When the timer rolls over, the
timerflag (TF0) is elevated and the switch is shifted to 000BH. This interrupt is
useful in the generation of square wave, frequency measurement etc.

 TIMER 1 INTERRUPT (TF0)

The vector memory location for Timer 1 is 001BH. The bit ET1 (IE.3) of
Interrupt Enable register must be set to enable the Timer 1 interrupt. This is
accomplished by the software instruction: SETB IE.3. When the timer rolls over, the
 8

timer flag (TF1) is elevated and the switch is shifted to 001BH. This interrupt is
useful in the generation of square wave, frequency measurement etc.

 EXTERNAL INTERRUPT INT0

Pin 6 (P3.2) of 89C51 works as the input or the external interrupt INT0. The
bit IE.0 facilitates to enable (SETB IE.0) or disable (CLR IE.0) this interrupt. This is
designated as EX0 in the Interrupt Enable (IE) register. This interrupt can be
activated either by level triggerring or edge triggering The default mode of activating
this interrupt is level triggered, in which this pin will be normally ‘HI’ and activated
be a ‘LO’ level signal. To make the interrupt respond to edge of the trigger input, the
TCON register must be programmed such that TCON.0 must be ‘HI’. This can be
done in the software by using the instruction: SET TCON.0. A ‘HI to LO’ transition
will trigger the input. When this interrupt is enabled, the control is transferred to
address location: 0003H.
 EXTERNAL INTERRUPT INT1
Pin 7 (P3.3) of 89C51 works as the input or the external interrupt INT1. The
bit IE.2 facilitates to enable (SETB IE.2) or disable (CLR IE.2) this interrupt. This is
designated as EX1 in the Interrupt Enable (IE) register. This interrupt can be
activated either by level triggered or edge triggered. The default mode of activating
this interrupt is level triggered, in which this pin will be normally ‘HI’, and activated
be a ‘LO’ level signal. To make the interrupt to respond to edge of the trigger input,
the TCON register must be programmed such that TCON.2 must be ‘HI’. This can be
done in the software by using the instruction: SET TCON.2. A ‘HI to LO’ transition
will trigger the input. When this interrupt is enabled, the control is transferred to
address location: 0013H.
 SERIAL COMMUNICATION INTERRUPT (RI OR TI)
In 89C51 microcontroller, for serial communication, there is only one interrupt
set to one side. This is generally used to both send and receive data. When the bit IE.4
t• t• t• t•

in the IE register is set, this interrupt is active. This can be completed by the
t•

instruction: SETB IE.4. Popularly, this interrupt is frequently used during receiving
the data from a peripheral. The internal arrangement is as shown below.
 9

At the activation of RI or TI, the control jumps to the memory location:

0023H. It is crucial to note that the RI or TI has to be cleared before leaving the
interrupt routine by the RETI instruction. This can be accomplished in the software
by using either CLR TI or CLR RI instruction. The interrupt vector table for 89C51
is shown in table 1.2.
Table 1.2
Interrupt Vector Table for the 89C51
t• t• t•
 10

1.2 SERIAL COMMUICATION FACILITIES

1.2.1 Serial Communication Presented by 89C51

Serial data transmission is very frequently used for digital data

communication. Its main benefit is that the number of wires needed for
transmission/reception is reduced as compared to that of parallel communication.
89C51 supports a full duplex communication serial port. In communication, if
transmission and receiving of data is done simultaneously it is called as full duplex.
89C51 has TXD and RXD pins for transmission and reception of serial data
respectively. The 89C51 serial communication lines can be made RS232 compatible
by interfacing with MAX232. The term “RS” stands for Recommended Standard. In
serial transmission, one of the significant factors is baud rate. It is defined as the
reciprocal of the time to send 1 bit. Baud rate may or may not be equal to number of
bits per second. This is because, each byte is prefixed by a start bit and subsequently
t• t•

by one stop bit. To coordinate the serial receivers the start and stop bits are used.
t•

With least significant bit as first, the data byte is always transmitted. For error
checking purpose, it is possible to include a parity bit as well, just prior to the stop bit.

For error free serial transmissions, it is crucial that the quantity of stop bits, the
baud rate, the quantity of data bits and the existence or nonexistence of a parity bit
together with its status is similar at the receiver and transmitter ends.

The serial data stream format is revealed as shown below:

In serial transmission, the basic mechanism is that a data byte in parallel form
is transformed into serial data stream. As shown above, a few more bits like start,
stop and parity bits are also transmitted along with eight data bits. This structures a
data frame that is sent on the transmission line. In order to establish serial
communication link between 89C51 and any other gadget the internal special function
 11

register called SCON (Serial Control) is used. Brief explanation of this register is
given below.

SCON REGISTER: It is an 8-bit register having address: 98H and it is addressed

bitwise. Various bits of the SCON register are as shown below:

SCON REGISTER

In the above register, bits D7 and D6 determine the mode of operation, D5 is

used to select uni/multi-processor environment (0/1). When D4 (Receive ENable,
SCON.4) bit is set (SETB SCON.4), the controller receives data on RXD pin.
Further, when this bit is HI, the controller receives and transmits the data. On the
other hand, if D4 bit (SCON.4) is LO (CLR SCON.4) the receiver is disabled. The
D3 bit of SCON register is TB8 (Transfer Bit8). This bit is used in modes 2 and 3 of
t• t•

serial mode transmission. This bit is set to zero in the present application. In SCON
t•

register the D2 bit is RB8 (Receive Bit 8). In mode 1, this bit gets a copy of the stop
bit when the data is collected. Transmit Interrupt (TI) is the bit D1 which is a
remarkable flag. This flag becomes HI (i.e., at the initiation of the stop bit) when the
t• t•

controller conveys an 8-bit data, demonstrating that another byte is available to send.
RI (Receive Interrupt) is the least remarkable bit (D0) of SCON register. This bit when
t• t• t•

goes to HI, indicates that a byte is framed and placed in SBUF register. The start and
stop bits are removed by the controller from the received data stream. The RI bit rises
halfway through te received stop bit. Using 89C51, the various modes of serial
communication are briefly explained in the following Table 1.3.

1.2.2 Baud rate selection in the 89C51

At distinct baud rates the 89C51 transfers and receives data serially. In 89C51
the baud rate is programmable. With the support of timer 1 (T1) this is done. The
baud rate generally relies on the crystal frequency of the microcontroller.
Additionally, the serial data transmission is accomplished using the on-chip UART.
 12

The clock frequency specified to the UART is equal to the crystal frequency divided
by 12.

As mentioned in the architecture of 89C51, there are basically two on-chip 16-
bit timers T0 and T1. Out of these existing timers, T1 is utilized for baud rate
selection in serial programming. Timer 1 register is shown below:

Selection of the working mode of timers is accomplished using the SFR TMOD
(Timer MODE) register. A short explanation of the TMOD is given below:

In the above TMOD register D0 to D3 are similar to D4 to D7 in functionality,

excepting that they belong to two different timers (T0, T1 respectively). The lower
ordered two bits of the each nibble are employed to select the timer mode. The
various timer modes are given in table 1.4. To set baud rates compatible with the PC,
we must load TH1 with the values as shown in Table 1.5.
 13

The bit D7 (D3) selects gating control for timer 1 (timer 0). These bits are
practically useful to enable/disable the timers by hardware means.

(i) If the GATE bit (D7/D3) is LO (low) the timers are permitted under
software control by TR0/TR1.
(ii) If the GATE bit (D7/D3) is HI (high), then the timers are enabled/disabled
by means of hardware using INT0/INT1 pin.
Table 1.3
Mode selections in SCON register

Table 1.4
Mode Selection for Timer/ Counter in TMOD Register
 14

Table 1.5
Baud Rates Compatible to PC

SBUF register:

SBUF is one of the special function 8-bit register (SFR) used solely for serial
communiation. Basically to shift a byte of data through the TXD line (pin 3), it should
t t• t•

be placed in the SBUF register. Similarly, SBUF keeps the byte of data when it is
t• t•

received by the 8051’s RXD line (pin 2). Like any other register, SBUF can be
t• t•

accessed by means of instruction.

Once a byte of data is positioned into SBUF, it is formulated with the start and
stop bits and subsequently transferred serially through the TXD pin. In the same way,
when the bits of data are received serially on RXD line, the 89C51 frames it into a
t• t• t•

byte by eliminating the start and stop bits and then places it in the SBUF rеgister.

In the present work, the SCON rеgister is usеd in Mode 1, which is generally a
popular mode. A brief description on the serial programming in Mode 1 is as follows.

Mode 1:

In mode 1, ten bits are transmitted through TXD pin or received via RXD pin.
There is a start bit (0) followed by 8 bits (LSB first) and a stop bit (1).The figure
illustrated below indicates the serial transmission of ten bits in Mode 1.
 15

On receiving a byte data, the stop bit goеs in RB8 of SCON register.
t• t• The
baud rate is basically resolved by the timer 1 overflow rate and is a variable one.
t• t• t• t•

Therefore, before using this mode one has to initialize timer 1.

The baud rate is calculated using the formula

Baud rate = 2SMOD / 32X (Timer 1 overflow rate)

In the above equation, SMOD is the D7th bit of the power control
register: PCON. This is an SFR (87H). In SMOD, this register is not bit addressable
and it is normaly used to double the baud rate of the microcontroller when the
t• t• t •

frequency of the crystal is permanent.

t•

On reset, the SMOD bit of register receives a LO logic (2SMOD = 20=1). By

setting this bit through software, one can easily double the baud rate (2SMOD=21=2,
according the above formula).

1.3 INTRODUCTION TO EMBEDDED SYSTEMS [3,4,5]

1.3.1 Concept of Embеdded System

An Embеdded system is the fastest computing device that does a particular

job. Both the software and hardware in an embеdded system are optimized for that
definite job. A microcontroller is basically utilized by an embedded product to
perform only one function. This is basically due to the fact that microcontroller
contains a microprocessor in conjunction with on-chip facilities such as memory
(RAM and ROM), serial, parallel input/output (I/O) ports, programmable timers,
interrupt features etc. Micro controllers are extensively used in smart instruments,
household appliances, Communication equipments, robotics etc.

‘Embedded’ means ‘hidden’ or ‘buried’. The embеdded information is truly

concealed inside the device/product that is in use. This is possible by programming
security bit/code in a microcontroller program. In the commonly used home
appliances like washing machine, the embedded software examines the water level
based on the load and adjusts the water cycle basing on the dirtiness of the water.

The utilization of microprocessor in the embedded intelligence has gradually

decreased and the use of microcontroller in such anvironment has not only increased
 16

but also brought in a revolutionary change. This is indeed due to the incorporation of
t• t•

microprocessor and certain peripherals (including memory) on a single chip called

t• t• t• t• t•

“microcontroller”. Thus the microcontroller can be contemplated as µp++.

t• t•

Embedded control system enables manufactures to differentiate their

products, replace less efficient elelctro-mechanical control devices, add product
functionality and significantly reduce product costs. In addition, the embedded
system facilitates the emergence of completely new classes of products. These
products typically incorporate a microcontroller to perform the principle activity.

A microcontroller can be thought of as a computer on a chip. This is because

it includes a CPU, non-volatile program memory, RAM for data storage and various
I/O capabilities. In addition to the microcontroller, a complete embedded control
system incorporates application specific software (ASS) and may include specialized
peripheral controllers and external non-volatile memory components, such as
EEPROM to store additional program software. Worldwide, embedded control
solutions have been incorporated into thousands of products and sub-assemblies in a
wide variety of markets.

The increasing demand for embedded control has made the market for
microcontroller as the largest segments of the semiconductor market. Currently
available microcontroller architectures range from 8-bit to 32-bit.

1.3.2 Applications of Microcontrollеrs in Embеdded Systems

There are two diverse areas of embеdded control applications:

 Event control (real time control) and

 Data control
Microcontrollers that are utilized for real time application are usually
dеdicated to single function applications, which include the control of a motor, an
engine, an indicator etc. Data control applications include data processing, data
formatting, I/O control etc. For such purpose, the embеdded controller is often found
in a sub-system, which performs multiple functions repeatedly and supports programs
that move vast quantities of data. Such appliances include and require a combination
of processing power, DMA and I/O bus bandwidth. The controllers that are used in
 17

data control applications must perform many different functions while handling large
programs using huge amount of data. Examples of high-end data controlling
applications are:

 Control of laser printer

 Image processing
 Networking
 Sophisticated industrial control
 Digital switching networks
 Medical instrumentations
 LAN controllers etc
The embеdded applications include

 Industrial environment
 Avionics
 Image processing
 Designing intelligent machines
 Security controls
 Graphics etc
Certain other examples of embеdded system are: printers, modem, sound card,
disk controller, CD-ROM driver, mouse, toaster, small ASCII data terminal etc.
Description of analog circuits for divergent applications as well as review of the
necessary hardware and software is discussed by Morrison.[8] and issues regarding
Embedded System design are described by Koopman [9].

1.3.3 Features of Embеdded System

Embеdded systems are characterized by the subsequent exceptional features:

1) Embedded systems have very limited resources, particularly memory. For the
most part, they don't have auxiliary storage devices like (CDROM) or floppy
disk.

2) In real time systems, embеdded systems need to conflict with some deadlines and
these deadlines are stringent. Missing this dead line may become catastrophic.
 18

3) Embedded systems do a very specific task. They cannot be programmed to do

different things.

4) Power is the basic constraint in embedded system. As large numbers of

embedded systems are to be operated through battery, the consumption of power
should be minimum.

5) Some embеdded systems need to work in extraordinary natural conditions, for

example, high temperatures and humidity.

6) Embedded system should be profoundly reliable.

1.3.4 Specialties of Embedded Systems

For designing an embedded system the following remarkable contemplations are

comprised:

 Performance
 Reliability
 Cost
 Size
 Power Consumption
 Software upgradation ability
 Restricted user interface
Processor power, programming languages, memory, operating systems,
communication interfaces and networking ability, development tools and
programmable hardware are the contemporary growths in the embedded systems. t•

1.3.5 Application Areas of Embedded Systems

t• t• t•

The embedded system is one of the highest growing areas as these systems are
used in every market segment like modern computerization, bio-therapeutic
engineering, consumer hardware, office robotization, information communication,
broadcast communications, image representation, transportation, remote
communication, military, picture handling, and so forth. The overall applications in
various divisions of an embedded system are depicted briefly in the Fig. 1.6.
 19

Fig. 1.6 Application Areas of Embedded System

1.3.6 Categories of Embеdded Systеms [6,7,8]

Based on the necessities like performance and functionality, the embedded

systems can be sorted out into:

 Real-time systems
 Stand-alone embedded systems
 Network information appliances
 Mobile devices
 20

The stand alone systems work in stand alone mode. They take inputs, process
them and produce the desired output.

Embedded systems utilized in process control, automobiles, customer

electronic things etc., fall into this category. Some of the embedded systems utilized
at home are Digital Camera, Microwave oven, CD player, Air conditioner and
Television and so on.

In real time systems, the embedded systems have to perform a particular work
t• t• t• t•

in a specific time. This real time embedded system is categorized as hard real-time
system and soft real-time system. In hard real-time system, if a deadline is missed it
leads to catastrophe. While in soft real-time system missing the dead line may not
lead to catastrophe.

Embedded systems that include network interfaces and accessed by networks

such as local area network or the Internet are called networked information
appliances. Cell phones, Personal digital assistant, smart mobile phones and so forth
are a unique classification of embedded system. The PDAs are presently equipped for
supporting universally useful application programming, for example, word
processors, amusements and so forth.

1.3.7 Simplified Hardware Architecture of an Embedded System

In Fig. 1.7 the hardware framework of an embedded system is illustrated

The building blocks of an embedded system’s hardware the are:

 Input devices
 Output devices
 CPU
 Memory
 Application-specific circuitry
 Communication interfaces
 21

Fig. 1.7 Simplified Architecture of an Embedded System

The CPU can be of the following: Microcontroller or Digital Signal Processor

(DSP), Microprocessor. The microcontroller is an inexpensive processor. Since the
quantity of external necessary constituents will be very cheap for smaller executions
the microcontroller can be considered as the finest alternative. Microprocessors on the
contrary are more superior but we need to use many external components with them.
DSP is used primarily for executions wherein the signal processing like the video and
audio processing are taken into consideration.

The ROM and RAM are the constituents into which the memory is sorted. The
data existing in the RAM will be erased if the power is switched off to the chip,
whereas if the power is switched off, the ROM will retain the data. So, the firmware is
stored in the ROM. When the power is switched on, the processor reads the ROM,
the program is transferred to RAM and the program is executed.

Unlike desktops, the input devices to an embedded system have very limited
capability. Many embedded systems used in process control do not have any input
device for user interaction: they take inputs from sensors or transducers and produce
electrical signals that are inturn fed to other systems.
 22

. The output devices of embedded systems also have very limited capability.
Some embedded systems will have a few LEDs to indicate the health status of the
system modules or for visual indication of alarms. To exhibit particular domineering
variables a Liquid Crystal Display (LED) may probably be used.

The embedded systems may need to convey the information into a desktop or
have to integrate with numerous embedded systems. To facilitae this, the embedded
systems are provided with one or a few communication interfaces such as RS455,
RS232, RS422, USB and IEEE 1394, Ethernet etc

Embedded system may require sensors, transducers, exceptional processing

and control hardware which depend upon its application. This hardware
communicates with the processor to complete the fundamental work.

1.4 INTRODUCTION TO CONDUCTING POLYMERS

Polymer is a large molecule (macromolecule) composed of repeating

structural units connected by covalent chemical bonds. The word is derived from the
Greek words πολυ (poly), meaning "many"; and μέρος (meros), meaning "part".

The conducting polymers are the basic class of materials with a broad variety
t• t•

of applications that have been accustomed for themselves like the non-linear optical
t• t•

materials, oscillators, electroluminescence devices, intensifiers, EMI securing, radar

absorption, frequency converters, sensors etc.

In the electrical and microwave frequencies interesting properties are

established by the conducting polymers in which they are enhanced remarkably more
than the ideal dielectric materials. In this study, the dielectrical and microwave
properties and components of leading polymers like polythiophene, polyaniline, poly
t •t t t t t t• t•

para phenylene diazomethine and Poly (3, 4-ethylenedioxythiophene) (PEDOT) are of

t• t• t t •t t• t t

significance.

The poor processability is highlighted among the most crucial drawbacks of

t •

conducting polymers and in this study a solution to control this is necessitated. By the
polymerization scheme the conducting polymer/thermoplastic composites are
familiarized to expand the homogeneity of the composites to a semi IPN degree.
t• t • t•
 23

The major outcome of this study is the enhancement of a processable leading

t tt t t •t

composite with great mechanical, electrical and microwave properties which can be
t t• t t •t t t

simply dissolved into cast or coated on distinct surfaces.

t t t t

1.4.1 Intrinsically conducting polymers

Due to their best optical, electrical and synthetic properties the intrinsically
(purely) conducting polymers (ICP) have appeared as another class of material. By
using suitable doping the conductivity of these materials can be altered from semi-
t t• t t t• t t• t t

conducting phase to metallic range. Conducting polymers of this kind is extensively

t •t t t •t

used in variety of applications like semiconductors, electroluminescence gadgets,

battery anodes or cathodes, diodes, sensors, energy storage and transformation
gadgets, intensifiers, frequency converters, radar absorbers oscillators, EMI
protecting and non-linear optical materials [9].

Enhancing of bio-sensing gadgets are the most motivating zones of

considerations in microelectronics. With the objective of restricting biologically
active particles in contradictory zone on the cathodes the accumulation of enzymes in
leading polymer films exhibit a controlled procedure [10]. The light weight
rechargeable batteries are the diverse fields which are probable to be exposed to the
current executions. Currently a few of the model cells which are better and analogous
to nickel-cadmium cells are obtainable [11]. Executions in a quantity of zones is
established by the microwave dielectric properties of conducting polymers, for
instance, EMI materials, frequency specific surfaces, covering in reflector antenna,
microchip radio wires, radar absorbing materials, covering in electronic equipment,
links in satellite communications, and so on [12].

1.4.2 Conjugated Polymers

Comprehensively conjugated molecules are conducting polymers. In their

perfect neutral conditions the conjugated polymers are either wide-gap
semiconductors or insulators with less conductivity. When introduced to the
procedure of doping whatever may be the condition, various polymers transform into
metallic type conductors. In 1975, polythiazyl (SN), the fastest conjugated polymer is
 24

discovered which is a superconductor at a crucial temperature of 0.29 K and it

acquired metallic conductivity [13].

In 1977, with the inventions of Shirakawa et a1, the conducting polymers, due
to their electrical conducting properties, are evolved. [15]. The iodine doped trans- t•t t

polyacetylene, (CH)n with conductivity of 103 S/cm is identified by him. Subsequently

t•t t• t t
t

a dynamic enthusiasm for combining other natural polymers comprising of this

property has been initiated. For investigating them in various executions, numerous
conducting polymers, therefore, comprising of pi-electron conjugated frameworks, such
t t• t t• t t

as polypyrrole (PPY), polythiophene (PTH), polyaniline (PANI), polyfuran (PFU),

t•t t•t t• t•

polycarbazole and poly (para phenylene vinylene) [15] have been integrated. The
t• t• t•

structural formulae of important conjugated polymers have been confirmed in Fig1.8.

A spatially delocalized band-like electronic configuration is obtained by the

conjugated polymers and are been reported [16]. The quasi infinite π structure
expanding in abundance of countless monomer units is the fundamental structural
feature for each single conjugated polymer. Materials strongest through the axis of the
chain and with directional conductivity are produced by this element [17].

Under climatic situations "n" is somewhat small because basically the band
gap of conjugated polymers is fairly comprehensive.

Fig 1.8 Structural formulae of various conjugated polymers

 25

In any case, if an electron travels a long distance, it must tunnel through a

much longer effective barrier. The probability of tunneling a distance 'R' decreases
exponentially with 'R' as exp(-2a.R).
It is,tgenerally, accepted thatt the technique oft conductivity inttheset
polymers depends ont the movement oftcharged deformities insidetthet conjugatedt
structuret[18]. Oxidationt of thetpolymer at first creates a radicalt cationt witht both
spin and charge.t This speciest is alluded to as a polaront• and involves botht thet•
holet site andt• the basic mutilation that• goes with it. The cation and radical form
a bound species, since any increase in the distance between them would necessitate
the creation of additional higher energy quinoid units. Hypothetical treatmentst[19]
have exhibited thatttwo close-by polaronstjoin to frame the lowertenergy
bipolarontappeared in Fig.1.9.

Fig. 1.9 polaron and bipolaron schematic representations.

t• t•

The conductivity, σ of a conducting polymer is identified with the quantity of

t• t t t•t t

charge carriers "n" and their mobility, µ is given by

t t•t t t t•

σαnµ

Since the band gap of conjugated polymers is normally genuinely extensive, "n" is
t t •t t t•t t t•

somewhat small under ambient conditions. t• t•

1.5 CONDUCTION IN MICROWAVE FIELD

t•t t t• t t

At the microscopic level, a material may have a few dielectric components or

t•t t t •t t t t t t t• t

polarization impacts that add to its general permittivity (Fig1.10) [21].

t• t t t•
 26

Fig. 1.10 Frequency responses of dielectric mechanisms

t• t•

At microscopic level some polarization influences on dielectric elements

which add on to its extensive permittivity are probably comprised by the material are
illustrated in (Fig1.10) [21].

The dipole moment generated to the polarizability elevates at the phase when
an electric field is given to a material. Some types of polarization that prevail [22] are
t• t• t•

• A dipolar polarization is produced by the rotation or dipolar or orientation of

permanent dipoles.

• The electronic cloud displacing around the atom will generate the electronic
t t• t t• t t t

polarization. t

• The electric area can alter the electron repartition in nuclear polarization and
t t• t •t t •

thus the equilibrium position of the atoms in the molecule.

t• t • t•
 27

1.5.1 Orientation (dipolar) polarization

Fig. 1.11 Dipole rotations in the presence of electric field

In an asymmetrical manner wherein the result is no polarization during the

disappearance of electric field, the permanent dipole moments are aligned. Torque "T"
on the electric dipole is executed by the electric field "E" and to adapt to the electric
field the dipole will rotate making dipolar or orientation polarization to occur (Fig
1.11).

1.5.2 Electronic and atomic polarization

t•

Electronic polarization happens in the neutral atoms when an electric area shifts
t• t• t•

the nucleus associated to the electrons which surround it. The atomic polarization occurs
t• t t t• t t t t

during the t execution of electric area when adjacent positive and negative ions
"extend". Excluding the resonant frequencies the amplitude generated will be lesser
for any frequency.

1.5.3 Intеrfacial or spacеcharge polarization

When the activity of relocating charges is obstructed the space charge or

interfacial polarization happens. Inside the interfaces of a material evidently the
charges can get captured. When the charges cannot be openly exchanged or
discharged at the terminals the activity may similarly be obstructed. The extensive
capacitance of a material is enlarged by the area alteration which is generated by the
accumulation of these charges that elevates as an expansion in 'ε'.
 28

1.6 MICROWAVE PROPERTIES

t•

1.6.1 Relaxation time

t• t•

For an eliminated system adapted in an electric area relaxation time " τ " is the time
needed to come back to '1/e' of its random equilibrium value (or in an electric area the t• t• t•

time needed for dipoles to evidently become organized). Internal friction occurs due to
t•

the constant collision of molecules which, in turn, exponentially and constantly reach
with relaxation time constant 'τ' the last situation of orientation polarization. The
configuration is shifted at the level when the area is turned off and random circulation
is reestablished with an analogous time constant.

= =

1.6.2 Dielectric constant and dielectric loss

t• t• t•

The quantity of energy reserved in a material from an outer electric area is

calculated by the term " ε' " which is the actual section of the permittivity. The loss t• t•

factor is the imaginary section of permittivity ε", which is the rate of how lossy or
destructive a material is to an outer electric area. The A.C electric area is adequately
moderate at frequencies below the relaxation and the dipoles can keep speed with the
area discrepancy. The dielectric loss ε'' is precisely associated to the frequency
because the polarization wi developed to the complete material. εr', keeps on growing
as the frequency elevates and the storage ε'' additionally begins to decrease due of the t t• t t t• t t t

stage lag between the executed electric area and the dipole configuration. Both ε' and
t t• t t t

ε" decline over the relaxation frequency since the electric area is too rapid to influence t t t

the dipole rotation and disappears the orientation polarization.

t• t t• t t t

1.6.3 Cole-Cole diagram

t•

The composite permittivity on a Cole-Cole arrangement may be illustrated by

t• t• t• t• t

plotting the imaginary part ‘ ε'' 'on the vertical axis and the real part ‘ ε' 'on the horizontal
t t t• t t• t t t• t t t t •t t •

axis (x-axis) with the free variable been frequency (Fig. 1.12)
t t• t
 29

Fig. 1.12 Showing of Cole-Cole diagram of water at 30°C [20]. t t t

By the amalgamation of materials with electrically conducting fields which are

not associated to each other (concealed by insulated areas) at low frequencies is
demonstrated by the Maxwell-Wagner effect.

The tangent loss exhibits the proportion of the displacement current to the t t t t• t

conduction current in a material. Conduction current may be described as the current

t t• t t t• t

which is due to withdrawal in the material. The displacement current is identified in an t t•t t t•t

intrinsic dielectric by the current that is available in the material [24].

t•

It can be inferred from above that if both the real and imaginary elements of t• t•

the permittivity and permeability are analogous, then the reflectivity coefficient will be
t• t• t t t•

zero. At lower speed or through free space (at the speed of light, c == 3 x 108 m/s) this t t t t

electromagnetic wave can disperse through materials. Let us contemplate that a flat tfffr rff •

slab of material (MUT-Material under Test) in space with a TEM (Transverse Electro-
t t •t t t t•t t t t t t•t t•t

Magnetic) wave present on its surface.

t t t t

There will be transmitted, incident and reflected waves here. Since, in the
t t t t

material the impedance of the wave "Z" is typical (lower) from the free space impedance
tt tt t tt t t t t t t t t

'η (or Zo) there will be impedance mismatch that will cause the wave to reflect. Some
t t t t t t t t t t

amount of energy will enter the material. Generall, in the flat slab the wave speed 'v'
is slower than the velocity of light 'c'. Hence, the wavelength “ λd ” is shorter than the
wavelength " λo " in free space as illustrated by the below conditions. Since the
 30

material certainly will have some loss, there will be an attenuation loss or insertion
loss (Fig. 1.13).

Fig 1.13 Showing the Reflected and transmitted signals from a material under
test (MUT).

In Fig. 1.14 the relation between the Material under Test (MUT) and the
t• t•

dielectric constant of the reflection coefficient |Γ| for an infinitely long specimen (zero
t• t•

reflection from the back of the specimen is considered) is illustrated. In the reflection
t• t•

coefficient for a less modification of the dielectric constant there is a rapid growth for
t•

small examinations of the dielectric constant (nearly below 20).

t• t•

Fig. 1.14 Showing the Reflection coefficients vs. dielectric constant [21].
t• t• t• t•
 31

Microwave Absorbing Materials are utilized in

• Airplanes & Ships

t•

• Camouflage Nets & Radar Camouflage t• t•

• Electromagnetic t•t Interference Suppression- t •t false t echoes from ships t •t own

superstructure

• Antenna Performance Enhancement - Side and black lobes.

t t• t t• t t•

The different types of microwave absorbing materials are given in Fig. l.15.
t• t• t t•

Fig. 1.15 Types of Radar Absorbing Materials (RAMs). t• t•

1.7 MEASUREMENT OF MICROWAVE PROPERTIES

t• t•

The microwave properties of materials can be examined with a free space, t• t•

parallel plate, coaxial probe, resonant cavity and transmission line techniques [21]. t•

1.7.1 Coaxial probe t•

The open-end coaxial probe is a cut-off segment of the transmission line. The
t t t• tt t t•

properties of the material are evaluated by immersing the probe into a fluid or by
t t• t• t t t t•

touching the probe to the flat surface of a strong (or powder) material. When the probe
t•t t• t t t t• t t

end approaches in contact to the material they vary and the fields "fringe" into the
t•

material.
 32

1.7.2 Transmission line

t•t t• t

Transmission line strategies include setting the material inside the segment of
t t t• t•t t •

an encased transmission line. The line is normally a segment of a rectangular waveguide

t t •t t t t• t• t

or coaxial line (Figure 1.16). εr* and µr* are obtained from the estimation of the
t t• t t t• t t t

reflected wave (S11) and transmitted signal (S2l).

t•t t t• t•t t

The distinctive sorts of microwave retaining materials are given in Figure l.16.
t• t•

Fig. 1.16 Transmission line, wave guide and coaxial line methods.
t• t• t•

1.7.3 Free space

t• t•

Free-space methods use antennas to focus microwave energy at or through a

slab of material without the need for a test fixture. This method is non-contacting and
can be applied to materials to be tested under high temperatures and hostile
environments (33).

1.7.4 Parallel plate

t•

The parallel plate capacitor method involves sandwiching a thin sheet of

material between two electrodes to form a capacitor. A typical measurement system
using the parallel plate method consists of an LCR meter or impedance analyzer and a

fixture.
 33

1.7.5 Rеsonant cavities

t•t

Rеsonant cavitiеs arе elеvated "Q" structures

t•f t that rеsound at spеcific
t•

frequencies. A bit of specimеn influеnces the middle frequеncy "f" and quality variablе t• t t

"Q" of the cavity. From these parameters, the complex permittivity "εr" or permeability
t t•t t t

"µr" of the material can be obtained at a fixed single frequency. There are a wide range
t t t• t t t t•

of cavities and techniques.

1.7.6 Cavity perturbation technique

t• t t

The measurements of permeability and permittivity of the dielectric materials

t t t• t •t

are accomplished by embedding a small and precisely devised specimen into a cavity t t

and from the resultant modification in the stacked quality factor of the cavity and
t• t t

resonant frequency establishing the properties of the specimen. The fundamental

t•

concept of cavity perturbation involves the modification in the typical geometric

t t•

design of the electromagnetic fields with the inclusion of a small specimen [26].
t t t t t•

When a small sample is inserted in a cavity which has an electric field 'Eo' and
magnetic field 'Ho' in the unperturbed state and the fields in the interior of the sample
is 'E' and 'H " then for loss less sample, the variation of resonance frequency is given
by equation (1.1) as
∗ ∗)
∫(∆ ∆
= ∗ ∗) ------------------ (1.1)
∫(
'ε' and 'µ' which in the unperturbed cavity are the permittivity and permeability of the t t t t

medium. Here 'dτ' is the fundamental volume and 'Δε' and 'Δµ' are the modifications in
t t t

the permittivity and permeability [27]. The composite frequency fluctuates because of
t t t

the lossy sample in the cavity without influencing the generality of Maxwell’s
t t t t t t

equations, and is illustrated as

∗ ( ) ∫ ∗ ( ) ∫ ∗
∗
= ∗ ∗) ------------------ (1.2)
∫(

Since the permittivity of empirical materials is a composite quantity wherein 'df*’ is

t t t

the composite frequency t shift, the resonance frequency is also composite. In the
unperturbed cavity the areas are 'Ho', 'Do', 'Bo'and 'Eo' and in the intrinsic of the sample t t t

'E' and 'H' are the areas [26, 30].

t t
 34

Only the first term in the numerator is remarkable when a dielectric sample is t t t t

incorporated into the cavity resonator wherein the maximum perturbation happens at
t t t t

the location of maximum electric field, due to a small alteration in 'εr' at zero point
t t t

electric area or a small alteration in 'µr' at zero point magnetic area that will not alter
the resonance frequency. Thus equation (24) can be illustrated as

∗ ( )∫ ∗
∗ = ------------------ (1.3)
∫| |
'εr' is a specimen of composite permittivity which is located under the maximal
electric area position of the cavity. The specimen which is taken will utilize the
complete narrow dimension of the cavity, since the cylinder with consistent length
and cross sectional field 's' is greater than the narrow dimension 'b'. The futile
resonant frequency and Q-factor will modify after the initiation of the sample,
because of the overall modification in the conductance and capacitance of the cavity.
Thus, the quality factor 'Q' is illustrated as,
Q = f/Δf ------------------ (1.4)
Where 'f' is the resonant frequency and 'Δf' is the corresponding 3 dB bandwidth which is
t t t t t t t t t t

known as bandwidth.
Let 'f0 ' and 'Qo'are the resonance frequency and quality factor of the cavity
without sample and 'fs' and 'Qs' are the corresponding parameters of the cavity loaded
with the sample then the complex resonant frequency shift is related to measurable
quantities. On comparing the real and imaginary parts of equations 1.5 and 1.6 we have
t t t t t t

For real part:

( ′ ) ∫( ∗ )
− = -------------------- (1.5)
∫| |
We may assume that E = Eoand the value of 'Eo' in the TE10 mode is [22,23]
Eo= Eo max sin (pπz/l) p = 1, 2,3, etc. -------------------- (1.6)
Where 'a' is the broader dimension of the wave guide and 'l' is the length of the cavity.
Integrating and rearranging the equation (27), we obtain

′ ( )
= -------------------- (1.7)
 35

where, Vc = a x b x l (volume of the cavity), 'Vs' is the volume of the sample and ‘r' is
t t t t t t t t

the radius and 'h ' is the length of the sample.

t t t t t

For Imaginary part:

t

ε′′ ∫( ∗ )

− = ----------------- (1.8)
∫| |
Integrating and rearranging the equation (30), we obtain
t t t t

′′
− = ----------------- (1.9)

∇ x H = (σ + jwε)E = (σ + wε")E + jωε'E ----------------- (1.10)

The loss tangent

′′
tan = ------------------ (1.11)
′

When σ is very small, the effective conductivity is reduced to [23].

′′ ′′
= =2 ----------------- (1.12)

A rectangular wave guide is used in Cavity Perturbation Method with iris-

coupled end plates, operating in TE10nmode (Fig 1.17). To measure the dielectric the

specimen should be positioned in a maximum electric field while for a magnetic

measurementit will be placed in a maximum magnetic field. If the specimen is

introduced through a hole in the core of the waveguide length, then an odd number of

half wavelengths (n = 2k + 1) will bring the maximum electric field to the specimen

location, so that the dielectric properties of the specimen can be measured. If there are
 36

even number of half wavelengths (say n = 2k) then the maximum magnetic field to

the specimen location and the magnetic properties of the specimen can be measured.

Fig 1.17 Resonant cavity measurements, cavity perturbation method.

A tiny spеcimеn for thе cavity pеrturbation mеthod is rеquirеd so that thе t•

fiеlds in thе singlе cavity arе somеwhat altеrеd to movе thе calculatеd rеsonancе
t• t•

frеquеncy and cavitiеs ‘Q’. This hypothеsis simplifiеs thе thеory of using the required
equations above and approximating thе diеlеctric propеrtiеs of thе material. Fig. 1.18
shows mеasurеmеnts of thrее diffеrеnt samplеs with this cavity. Thе thrеe measures
arе presented in thе same chart for comparison.

Thе rеsonant frеquency of thе empty cavity is fc = 9.9375 GHz (for TE10n
t• t•

mode) and switch to a lower frеquency whеn thе samplе is inserted into thе cavity.
t• t•

Whеn thе rеsonator is loaded with a sample, the resonance curve widens and translates
t• t•

into a lower Q-factor. In the Fig. 1.17, Y- axis gives the magnitudе of the linеar
t•

transmission coеfficient |S21|. t• To the lеft of thе figurе is a calculation for the
samplе 2 having a cross sеction of 0.29 by 0.157 cm [21].
t• t• t•
 37

Fig 1.18 Resonant cavity measurements, cavity perturbation method.

t• t• t•

1.7.7 Comparison of Methods

t• t•

Many factors such as precision, comfort and shape of the material arе
t• t•

important for sеlеcting thе most appropriatе mеasurеmеnt tеchniquе. Somе of the
t• t•

important factors to be considered are summarized in Fig. 1.19.

t• t•

Fig 1.19 Summary of measurement techniques.

t• t• t•

1.8 POLY AZOMETHINES

Polymeric aldimines or poly (schiff base)s are classes of materials known as

polyazomethines. The thermal stability of these materials is comprised by the
 38

amalgamation of nitrogen particles into the conjugated atomic chains which supports
this.

1.8.1 Synthesis of Polyazomethines

t• t•

1.8.1.1 Solution polycondensation

t•

Many researches havе studied the synthеsis of polyazomеthinеs by the

t• t•

arrangement of polycondеnsation [29]. A polyazomеthinе еther is combined by

t• t•

polycondеnsation response of a singlе monomеr containing nitro and in addition

t• t• t•

hydroxyl group in the nearness of large K2C03 in DMAC and toluenе solvеnt systеm . t• t• t•

1.8.1.2 Chemical Vapour Deposition (CVD)

t• t•

This procedure includes co-sublimation of at least two receptive monomers

which encroach onto a substrate surface, where they respond to form a polymer film,
has been shown to be an effective and proficient method for creating polyazomethines
with high conjugation lengths [30]. Electric-field-assisted CVD (EFCVD) has also
been used to change the macroscopic structure of these materials. This method is
particularly appropriate to create polymer films for optic and electronic application.

1.8.1.3 Oxidative polymerization

t•

Simionescu and his associates have evaluated a novel technique for the
t• t• t•

fabrication of entirely aromatic polyazomеthinеs by oxidativе polymеrization of t• t•

monomеrs containing a azomеthinе linkage. t• Thiophenes t• or furan-containing t •

polyazomеthinеs are incorporated with ferric (III) chloride by substance oxidative

t• t•

polymerization [32]. t•

1.9 POLYTHIOPHENES

1.9.1 Synthesis of Polythiophenes

t• t•

1.9.1.1 Chemical combination of unsubstituted polythiophenes

t• t•

The dissolvability and fusibility to the polymer is provided by the side chains
which additionally associate the repeating units [33].

On the polymerization of 2, 5-dihalothiophene, Yamamoto's group [33] and t•

also others [75] have performed efficient investigations. Berlin and associates have t• t •
 39

described the amalgamation of thiophene with butyl lithium to generate 2, 5-dilithio

t• t•

thiophene which can be polymerized with CuCl3 to produce polythiophenes. (Schem

t• t• t•

1.1)

Scheme 1.1 Synthesis of poly thiophene by polycondensation dehalogenation

reaction.
Sugimoto illustrated a very simple and effective synthesis of polythiophenc by
treating thiophene with FeCl3 (Scheme 1.3).

Scheme 1.2 Synthesis of polythiopbene by oxidative polymerization reaction.

1.9.1.2 Chemical synthesis of polyalkylthiophenes (PATs)

It was illustrated by Elsenbaumer and associates in 1985 about the initial

chemical fabrication of environmentally soluble and stable poly (3- alkylthiophenes)
(PATs) [36]. Subsequent to this investigation other groups too [37] have illustrated
both the electrochemical and chemical fabrication of PATs.

1.9.1.3 Metal-catalyzed cross-coupling polymerizations

The polyalkyl thiophenes are generated by the Kumada cross coupling

reaction [36] wherein, 5-diiodo-3-alkylthiophene is utilized with one equivalent of
Mg in THF to generate a mixture of Grignard species [34]. After addition of a
catalytic amount of Ni(dppp)Cl2 by a halo-Grignard coupling reaction the polymer is
generated (Scheme 1.3).
 40

The FeCl3 initiates an oxidation of the alkylthiophene to generate a

comprehensive significance at the 2-and 5-places of thiophene immensely which
t. t. t• t. t• t. t• t.

scatters to configure the polymer (Scheme 1.3).

t. t.

Scheme 1.3 Poly (alkyl thiophenes) from cross coupling Polymerization t. t.

The electrochemical polymerization is basically conducted by the

electrochemical oxidation of thiophene on a Pt-covered substrate to generate a thin
uniform film.

Through the alternative electrochemical depositions of PTH and metal into the
pores of a micro (small) porous alumina membrane the metallic gold (Au) and silver
(Ag) nanowire bundles coated with polythiophene (PTH) films were manufactured
[38].

1.9.2 Regioregular poly alkyl thiophenes (PAT)

t. t. t.

When 3- alternative (disproportionate) thiophene monomers are utilized in a

mixture of four chemically distinct groups of three regioisomers, due to
Polymerisation it will be precipitated [39].

The Regioregular eventually creates head-to-tail (H-T) poly (3-alternative) t• t. t.

thiophene definite technique low energy planar affirmation which supports the much
t•

conjugated polymers. McCullough and Lowe revealed in the early 1992, that a head- t•

to-tail coupled poly (3-alkylthiophenes) (PATs) can be fabricated by the considerable

t• t. t. t •t. t•

mixture of regioregular [40].

 41

1.9.3 Applications

Nonlinear optical gadgets, antistatic coatings, polymer LEDs, electro chromic

t. t•t. t. t•t.

or smart windows, photoresists, electrical channels, sensors, batteries, solar cells,

t. t. t•t. t•t. t.

anodes, nanoswitches, optical modulators and valves, nanoelectronic and optical

gadgets, transistors, microwave absorbing materials, imaging materials and polymer
electronic interconnects, electromagnetic protecting materials, simulated noses and
muscles and new kinds of memory gadgets are utilized which are the competent
elements of polythiophenes [33,41].

1.10 POLY (3, 4-ETHYLENEDIOXYTHIOPHENE) - PEDOT

In the labs of Germany, during the second half of the 1980s, researchers at t• t•

Bayer AG investigated to fabricate poly (3, 4-ethylenedioxythiophene) which is

t• t• t•

another polythiophene t• substitute [42] which consists of the following spine

configuration.

Although PEDOT has high conductivity ( 300 S/cm), it is observed to be thin

t•

and transparent oxidized film and in the oxidized form it demonstrated a high strength
t• t• t•

[42,43] as shown in the scheme 1.4.

Scheme 1.4 Spine structure of PEDOT

1.10.1 Synthesis of Poly Poly (3, 4-Ethylenedioxythiophene)

t• t•

The PEDOT descendants (3, 4-Ethylenedioxythiophene) union can t• be

segregated into three distinct types of polymerization reactions:
t• t• t•

a. Electrochemical polymerization of the EDOT-based monomers.

t•
 42

b. Transition metal arbitrate coupling of dihalo alternatives of EDOT.

c. Oxidative chemical polymerization of the EDOT-based monomers.

t• t•

The chemical polymerization of EDOT alternatives can be conducted by the

t•

Oxidative mixture polymerization of the EDOT-based monomers by utilizing a few

oxidants and strategies [41,44]. By using Fe3(OTs)3 at maximum temperature in
t.t. t• t•t.

association with imidazole as a base, De Leeuw et al [44] have contemplated another

t. t• t.

polymerization strategy for EDOT (Scheme 1.5). PEDOT fabrication by chemical t•

oxidative technique displayed conductivities of up to 550 S/cm. t• t•

Scheme 1.5 Chemical oxidative polymerization of EDOT (154].

In this method the polymerization of EDOT in an aqueous polyelectrolyte (most

t. t. t. t. t. t.

generally PSS) solution utilizing Na2S20g as the oxidizing agent is used.

t. t. t. t.

An interesting characteristic is included in BAYTRON P and numerous

applications are observed wherein the existing PEDOT/PSS film is highly conducting,
transparent, mechanically durable and insoluble in any of the typical solvents after
drying.

The result of electrochemical polymerization is producing a highly polarized

blue film, doped with PEDOT in the anode [45].

Different thiophene –based polymers have been designed over years with
transition metal catalyzed by coupling of metallic organic alternatives. From a spray
storage (~ 2 years) or light heating (50-80°C) of highly conducting 2,5,5-dibromo-3,
4-ethylenedioxythiophene, a bridged doped crystalline PEDOT is produced. Using
 43

this technique, thin films have been manufactured with such high conductivity
20 S / cm flexible plastic insulating surfaces [104]

1.10.2 Applications of PEDOT

t. t.

PEDOT-based polymers are employed in various applications like transparent

t. t.

electrodes for inorganic electroluminescent devices, antistatic coatings for cathode ray t. t•t. t.

tubes to intercept dust attraction, through-hole plating of printed circuit boards, hole-
t• t. t. t•

injecting layers on ITO derivatives for organic electroluminescent devices, primers for
t•t. t. t. t. t•

electrostatic spray coating of plastics, sensors, rechargeable batteries, corrosion

t•

protection, photodiodes, electro-chromic windows, cathode radiation tubes and

t• t•

photovoltaic devices. PEDOT is among the few organic conducting polymers of

t•

supreme importance as demonstrated by these examples and it has victoriously found t•

its way into multiple technical applications from an unusual laboratory [47].

1.11 POLYANILINE

Currently the most important conducting polymer evidently is Polyaniline

because of its simple processing and fabrication, environmental stability, cost
economics and comparatively high conductivity [48]. Depending on the extent of
doping polyaniline four discrete oxidation forms [49] namely Emeraldine salt (ES),
Leucomeraldine base (LEB), Pemigraniline (PNB) and Emeraldine (EB) are obtained.

Distinctly polyaniline can be generated under the acidic conditions by

chemical or electrochemical oxidation of aniline. Ammonium per sulphate or t• t•

potassium dichromate can be used to initiate the reaction [52]. The conventional molar
t• t•

ratio of the monomer to acid to oxidizing agent is established to be 1: 1: 1 [53]. The t•

aniline salt of protonic acid after continuous stirring for 4 hrs in the protonic acid
t• t• t•

medium is amalgamated with aqueous solution t• of ammonium per sulphate.

Subsequently the obtained precipitate is washed and filtered with distilled water to
extract emeraldine salt.

To obtain a better-configured and clean polymer as a thin film during the

anodic oxidative polymerization this method is selected.

At the platinum electrode 0.1 mole of protonic acid is dissolved in distilled

water to conduct the electrochemical reaction. The first step in the oxidation of aniline
 44

is the fabrication of an extensive cation which is independent of pH. Mohilner et.al

reported the grouping of the oxidation of aniline as an ECE reaction (a sequence of
rapid electrochemical-chemical--electrochemical reactions). Blue (0.0 V), green (0.65
V) and yellow (--0.2 V) are the observed color modifications with polyaniline that are
associated with discrete oxidation types (doping levels).

PANI's conductivity can be reversibly governed either electrochemically (by

t• t•

oxidation-reduction) or chemically (by protonation/deprotonation) and by doping from

t• t• t•

the undoped insulating base form to entirely doped conducting acid form with elevated
t• t• t• t•

conductivity as its outcome.

t•

The other applications for conducting PANI include anticorrosion coating,

electrostatic charge diversion, electromagnetic interference, light emitting diodes and
batteries. Currently for the production of electrically conducting polymers with
increased processability the protonation of PANI with macromolecules and organic
sulphonic acids has been illustrated [50,51] for its beneficial production in various
applications. Shacklette et al reported a surface-core doping technique [51] in which
PANI is predominantly doped with one acid at the core of a particle and
conventionally at the surface of a particle by a second dopant so that it acquires an
elevated uniformity between the second polymer matrix and PANI particles e.g.
Polystyrene (PS), Nylon , low density polyethylene (LDPE).

1.12 DESIGN OF EXPERIMENTS (DOE)

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1.12.1 Taguchi method

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Dr. Genichi Taguchi from Japan redesigned the conventional DOE technique
t• t• t•

using 'orthogonal arrays' to elevate the quality ofa product/procedure.

t•

• Selecting the maximum combination of control factors and generation of factor

effect plots

1.12.2 Orthogonal array

Orthogonal arrays require only a small quantity of investigations to establish

major elements and are remarkable investigational designs.
 45

They include a quantity of organized matrix in rows and columns. In the

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columns orthogonal arrays are mutually orthogonal.

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L4(23) : 4 experiments, 2 levels and 3 columns

L8(27) : 8 experiments, 2 levels and 7 columns

Table 1.6

Standard L4 orthogonal array

Experiment Columns

1 2 3

1 1 1 1

2 1 2 2

3 2 1 2

4 2 2 1

At the frequency range of 6 GHz to 13 GHz of conducting polymers the

evaluation of dielectric properties is not extensive at microwave frequencies (X-
band). So in this study initially an embedded system is designed using
microcontrollers and interfacing the microwave bench to the personal computer. For
future evaluations, the microwave properties of four remarkable conducting polymers
relating to polyaniline polythiophene and polyazomethine families have been
suggested. The electrical properties of the polymer collaborate depending on the
aspect ratio of the additive. It is thus suggested to add short fibres to the conducting
polymers to elevate the electrical properties of rubber.

Depending on PPy in the present research to elevate the various properties of

conducing elastomer composites addition of Nylon -5 fibre as filler is investigated.

PEDOT, PTH, Poyaniline (PANI) and PPDA microwave properties like

dielectric constant, heating coefficient, dielectric loss, loss tangent conductivity, skin
depth and absorption coefficient are compared and evaluated.
 46

1.13 SCOPE AND OBJECTIVES OF THE WORK

t. t. t. t. t.

The evaluation of dielectric properties at microwave frequencies (X- band) in

t.

the frequency range of 6 GHz to 13 GHz of conducting polymers has not been t. t. t.

exhaustive. Some studies have been done on various polymers like in polyaniline,
t. t. t. t.

polypyrrole and to a lesser extent on polythiophenes. So, in this study initially an

t. t. t. t. t. t. t. t. t.

embedded system is designed using microcontrollers and interfacing the microwave

bench to the personal computer. A software using LAB VIEW has been written and
using two point method, the various dielectric properties like dielectric constant,
dielectric loss, loss factor, A.C conductivity, skin depth, heating coefficient of the
sample are estimated precisely at X-band frequencies and the variations in various
properties are to be studied graphically.

Secondly, the proposed microwave properties explores four major conducting

polymers belonging to the families of polyaniline, polyotype and polyazomethine.
Poliazomethins are particularly interesting because they exhibit good mechanical t. t. t. t.

strength, thermal stability, nonlinear optical properties and photoconductivity.

t. t. t. t. t. t. t •t. t •

Polyaniline and polythiophenes have been widely studied for a wide range of t.

applications and are used in many commercial fields. The experiment design technique
t•t. t. t. t.

has been used to reduce the number of tests required to produce an optimal product at
t. t. t• t. t. t. t. t•t.

the lowest cost. One of the major drawbacks of conducting polymers is their poor t. t. t. t•t. t.

workability and suggests that the issue is addressed in this research. It has been found t• t•

that the preparation of conducting polymer compounds improves machinability. A t•

review of the literature reveals that studies of incorporated PPy elastomeric compounds t• t•

are totally inadequate or rarely reported. The electrical And mechanical properties of t. t • t. t•

polymeric mixtures depend on the aspect ratio of the additive. Conducting polymers t•t. t. t. t. t.

are generally of spherical shape with a small aspect ratio. But in general, fibers are
t• t. t. t• t. t. t• t.

characterized by large proportions. Thus, with the addition of short-fibers, conducting

t. t•

polymers can improve the electrical and mechanical properties of rubber. Generally,
t• t•

short mixes are popular in industrial applications due to its low cost, processing t•

advantages. In this document, Nylon -5 fiber as a filler is studied to improve some

properties of PPy-based elastomeric compounds. Generally, Nylon fiber is a dielectric
 47

material that influences conductivity. So PPy is coated on the fiber. This can improve
t•

the conductivity and dielectric properties.

The objectives of the study are summarized as follows

t•

I. To design an embedded system to measure dielectric properties of

conducting polymers using microprocessor based technology
II. To write a software using LAB View and to study the various dielectric
properties using two point technique. Comparison is to be made
graphically.
III. To evaluate and compare the microwave properties like dielectric constant,
dielelctric loss,loss tangent conductivity, absorption coefficient, heating
coefficient and skin depth of PPDA, PTH, PEDOT and Poyaniline (PANI).
IV. To synthesize and characterize Polypyrrole and Polypyrrole coated with
short Nylon-5 fibres.
V. Fabrication of Conducting elastomer polymers of Polypyrrole and Nylon-5
fibres coated with Polypyrrole based on natural rubber and acrylonitrile
butadiene (NBR) by dry rubber compounding.
VI. Conducting elastomer polymers based on Natural Rubber (NR) by in situ
polymerization of Pyrrole of the prepared composites is to be fabricated.
VII. To study dielectric and microwave characteristics of the composites in the
X-band using the embedded system designed.