SYNTHESIS AND CHARACTERIZATION OF CONDUCTING POLYMER AND NANO COPPER DOPED COMPOSITE

Dissertation submitted in partial fulfilment for the award of degree of MASTER OF PHILOSOPHY IN PHYSICS

Submitted by
Mr. S. SURYARAJKUMAR, M.Sc. Reg. No. 10MPPH114

Under the guidance of Dr. G. VELRAJ, M.Sc., Ph.D.,

DEPARTMENT OF PHYSICS PERIYAR UNIVERSITY SALEM- 636 011 AUGUST-2011

Dr. G.VELRAJ M.Sc., Ph.D. Assistant Professor Department of Physics Periyar University Salem - 636 011

CERTIFICATE
This is to certify that the dissertation entitled SYNTHESIS AND CHARACTERIZATION OF CONDUCTING POLYMER AND NANO COPPER DOPED COMPOSITE by Ms. S. Suryarajkumar

(Reg.No.10MPPH114) to Periyar University, Salem in partial fulfilment for the award of Degree of Master of Philosophy in Physics, is bonafide Project work done by the candidate under my supervision during 2010-2011 in the Department of Physics, Periyar University, Salem. The dissertation has not formed the basis for the award of any other degree/diploma/associateship/ fellowship or other similar titles and it represents the independent work of the candidate.

Place: Salem Date:

(G.VELRAJ) Project Guide

Head of the Department

DECLARATION
I, S. Suryarajkumar, hereby declare that the dissertation entitled SYNTHESIS AND CHARACTERIZATION OF CONDUCTING POLYMER AND NANO COPPER DOPED COMPOSITE submitted to Periyar University, Salem in partial fulfilment of the requirements for the award of the degree of MASTER OF PHILOSOPHY IN PHYSICS is a bonafide research work carried out by me under the guidance and supervision of Dr. G. Velraj, M.Sc., Ph.D Assistant Professor in Physics, Periyar University, Salem and no part of the dissertation has been submitted for the award of any other degree, diploma, associateship, fellowship or other similar titles.

Place: Salem Date:

Signature of the candidate (S.SURYARAJKUMAR)

PREFACE The present project was carried out by the author during the year 2010 2011 in the Department of Physics, Periyar University, Salem 636011. An attempt has been made to compare characteristics of conducting polymer and Nano copper doped conducting polymer composite. The conducting polymer polypyrrole was synthesised in the libratory with 99.9% AR grade chemicals and the resultant material obtained from the chemical oxidation polymerization method. The Nano copper material was doped with the sample of polymer and synthesis has been done the same method. The Nano copper of 100 mg doped conducting polymer and without doping Polypyrrole have been characteristics using FT-IR spectroscopy, X-Ray diffraction method and the conductivity measurements using two method probe method. The part of the work has been presented in the National conference on Nano science and Nano Technology (NCNN 2011), Organized by National Centre for Nano science and Nanotechnology, University of Madras Maraimalai Campus, Chennai 600 025

ACKNOWLEDGEMENTS
The author ever indebted to my guide Dr. G. VELRAJ., M.Sc, Ph.D., Assistant Professor, Department of Physics, Periyar University, Salem-11 for his excellent constructive guidance, continued keen interest, almost motivation throughout the period of the study. It has been pleasing experience to work under his guidance. forever grateful to him. I wish to place my hearty and sincere thanks to my respectful Professor Dr. V. Krishnakumar., M.Sc., M.Phil., Ph.D, Professor and Head of the Department of Physics, Periyar University, for his constant encouragements, wealthy advice and administrative support given in all aspects during the period of study. I would like to thank the faculty members of the Department of Physics, Periyar University, Salem, for their valuable advice and encouragement during the entire period of study. I express my special thanks to Mr.Ramachandran University Research Fellow (URF), Department of Physics, Periyar University, Salem for his timely help in XRD and FT-IR analysis of my samples. I take this opportunity to thank all my friends and family members for giving encouragement either directly or indirectly in finishing this course. I remain

(S.SURYARAJKUMAR)

CONTENTS
PAGE NO 1 28 78 91

S.NO
1 2 3 4 CHAPTER-I INTRODUCTION CHAPTER- II

TITLE

EXPERIMENTAL TECNIQUES CHAPTER-III RESULTS AND DISCUSSIONS REFERENCES

LIST OF TABLES
S.No 2.1. 3.1. TABLES Most suitable prism material in the infrared region FT-IR absorption frequencies [cm-1] and relative intensities of PPy and CPPy 79 P. No 44

LIST OF FIGURES
S.No 1.1 1.2 1.3 1.4 1.5 1.6

FIGURES
Several typical conducting polymers. Chemical structure of the pyrrole monomer Chemical oxidative polymerization and doping process of pyrrole Oxidation states of pyrrole Chemical structure of polypyrrole (PPy) Electronic energy diagrams for (a) neutral, (b) polaron, (c) bipolaron and (d) fully doped polyprrole (C.B.: conduction band, V.B.: valence band) Temperature effect on conductivity of polypyrrole Application of Conducting Polymers Insertion of a spacer to decouple the functionalized chain ends Device design for polymer a photovoltaic device Device design for a polymer light emitting diode Flow chart for synthesis of Polypyrrole Schematic of a two plane mirror Michelson interferometer Block diagram of the major components of a dispersive infrared spectrophotometer Fourier Transform infrared spectrometer-optical arrangement Generic X-ray Tube Debye-Scherrer camera without a cover showing cylindrical sample, collimator, incident beam trap, and the location of the

P. No 4 4 7 7 9 9 14 14 25 25 26 32 37 40 41 61 61

1.7 1.8 1.9 1.10 1.11 2.1 2.2 2.3 2.4 2.5 2.6

2.7

x-ray film. The schematic of a powder diffractometer with the vertical goniometer axis, cylindrical sample in the transmission mode 66 72 72 80 81 84 85 87 88 and a curved position sensitive detector (PSD). Two probe setup psm1735 frequency response analyzers FT-IR spectrum of the PPy FT-IR spectrum of the CPPy The XRD pattern of the PPy The XRD pattern of the CPPy Frequency dependence of conductivity of PPy Frequency dependence of conductivity of CPPy

2.8 2.9 3.1 3.2 3.3 3.4 3.5 3.6

CHAPTER-I INTRODUCTION

ABSTRACT

In this chapter, a brief introduction of conducting Polymers and properties of Polypyrrole are discussed. It also contains information about the application of Polypyrrole.

1.1 INTRODUCTION Polymers are long chain giant organic molecules are assembled from many smaller molecules called monomers. Polymers consist of many repeating monomer units in long chains. A polymer is analogous to a necklace made from many small beads (monomers).

Another common name for many synthetic polymers is plastic which comes from the Greek word "plastikos", suitable for molding or shaping. Many objects in daily use from packing, wrapping, and building materials include half of all polymers synthesized. Other uses include textiles, TV's, CD's, automobiles, and many other all are made from polymers.

1.1.1 CONDUCTING POLYMERS The Development of Conducting Polymers The discovery of the electrically conducting properties of doped polyacetylenes by Shirakawa, MacDiarmid and Heeger [1, 2] in the 1970s heralded a new era in materials science. The use of a large excess of the polymerization catalyst produced, a shiny brittle metallike material that conducted electricity instead of the previously prepared amorphous polyacetylene. Subsequent doping of the metallike material with iodine produced a material with a conductivity approaching the of copper (up to 105 S cm-1)[3]. This discovery led to the new field of conducting organic polymers, recognized by the award of the 2000 Nobel Prize in Chemistry to the co-discovers [4,5]. Conducting polymers are material capable of being doped or dedoped resulting in change to their electrical properties. In recent years

conducting polymers with conjugated double bonds have attracted much attention as advanced materials. A large variety of CEPs have now been made, some of the most common one are polypyrrole (PPy), Polythiophene (PTh), and Polyaniline (PAn) (Figure 1.1) [5]. Another type of conducting polymer, frequently used in photovoltaic devices, is poly (P-phenylenevinylene) (PPV). Numerous conducting polymers have been prepared and studied due to their potential use in a wide ranger of applications. Conducting polymers have been applied in areas such as sensors [6-7], ion-selective membranes [8-9], polymeric batteries, corrosion inhibitors, microactuators, electronic wires, electrochromic devices, electromagnetic shielding and electronic textiles [10]. Most of these applications make use of the electro activity and conductivity of conducting polymers, as well as their physical and chemical properties.

Figure 1.1 The several typical conducting polymers.

Figure 1.2 The Chemical structure of the pyrrole monomer

1.1.2 Polypyrrole Overview Polypyrrole was first synthesised in 1916 using acidified hydrogen peroxide oxidant to polymerise pyrrole yielding a product which became known as pyrrole lack. Polypyrrole is believed to be a cross-linked polymer because it is insoluble in every solvent tested to date. As a consequence, its exact chemical structure is still a matter of debate. The cross-linking also means that the polymer does not melt and therefore has very poor processability. In spite of these unfavorable properties the polymer has attracted world-wide attention, much of which has been directed towards overcoming the processability problem. The Polypyrrole is an important conducting polymer with high electrical conductivity and appreciable

environmental stability. The interested reader is directed to reviews on the subject of polypyrrole [11]. Polypyrrole is one of the most widely studied members of intrinsic conducting polymer family in different areas of science and industry. The first solid information about the conductivity level of iodine doped, chemically oxidized polypyrrole is dating back to 1963[12]. With this information in hand, polypyrrole can be considered as the first derivative of polyacetylene that exhibits a high level of conductivity. Throughout the time polypyrrole research

has been extended to the very different parts of chemistry and polymer science to gain a deeper knowledge and to improve different properties of this polymer for further applications. The most common methods applied to synthesize polypyrrole are the chemical oxidative polymerization with doping, electrochemical polymerization, plasma polymerization and the organic synthesis. Chemical oxidative polymerization of pyrrole monomer is very similar to that of thiophene with one distinct difference that should be kept in mind during the reaction which related to the reactive nitrogen-hydrogen bond. Due to this reactive bond in its structure, protection of amine is required to prevent undesired side reactions to take place such as cross linking. General mechanism of the oxidative polymerization of pyrrole can be briefly explained in the following way (Figure 1.3). Formation of cationic free radicals after the loss of an electron from the monomer structure is followed by the coupling of active resonance structures in different positions during the reaction (oxidation of monomer, radicalradical coupling). These already coupled structures finally form the polypyrrole chain at the end of the polymerization reaction (deprotonation, re-aromatization and chain propagation).

Figure 1.3 Chemical oxidative polymerization and doping process of pyrrole

Figure 1.4 Oxidation states of pyrrole

The traditional conjugated -bond backbone structure of polypyrrole usually is not enough to possess significant conductivity on its own. The conductivity level of this polymer can remarkably be changed from an insulating level to a metallic one through the doping process [13]. That is why the partial charge extraction (doping) process is enquired and can be explained for this polymer in the following way. Again, first of all, an electron is removed from the polymer backbone by yielding a radical and a spin less positive charge. Next, the newly formed cation and the radical are coupled to each other by local resonance. During coupling, quinoid-like sequential rings are also formed and utilized to provide higher energy of distortion than the remaining part of the chain. The created lattice distortion is usually extended over four pyrrole rings (charged site) and when they coupled with a radical, this structure is called polaron. As a result, further oxidation of the polaron yields a new spin less defect called bipolaron having a lower energy than two distinct polarons. At higher doping levels, polarons are eventually replaced by bipolarons. For a heavily doped polypyrrole it is suggested that the upper and lower bipolarons merge to the valence and conduction bands respectively to produce partially filled bands and provide metallic-like conductivity for the final polymer [14].

Figure 1.5 Chemical structure of polypyrrole (PPy)

Figure 1.6 Electronic energy diagrams for (a) neutral, (b) polaron, (c) bipolaron and (d) fully doped polyprrole (C.B.: conduction band, V.B.: valence band)

1.2 Polypyrrole Properties The properties of polypyrrole are largely dependent on the synthesizing conditions such as temperature, substrate, concentration and dopant. Different concentration of pyrrole monomers or and dopant will induce a different anion flux. Also, the geometry of the cathode and anode, and the distance between them contribute to the overall effect of the performance. Many researchers have recently investigated on the mechanical properties of polypyrrole in order to gain a better understanding of its physical behavior. One journal article stated an unexpected large strain actuation (~14% at 2.5MPa) in

electrodeposited polypyrrole. Another one recorded 26% strain. The large strain was because of interaction of the large doping anions (i.e. TFSI). As the study continued, they further verified that the freestanding polypyrrole actuators with the same doping anions (TFSI) obtained a response rate of 10.8% /S [15]. Thus, these findings give rise and promises to many areas in which lightweight and large displacement actuators are needed. A summary of some of the physical properties of the product is given below [16].

 = 1.48 g cm-3 Molecular Weight - due to cross-linking Crystallinity - low Tg - unknown Mpt - none, decomposes without melting Conductivity = 1-100 S cm-1

Appearance - Black solid film (electrochemical) or powder (chemical synthesis) 1.2.1. Electrical Properties Polypyrrole conducts electricity via electrons hopping along the polymer chains and its conjugated backbones. The conductivity also depends on the doping level (n-doping vs. p-doping) and type of counterions [17]. Dating back to 1970s, there was a major discovery of dopants ability to increase the conductivity of certain polymers such as pyacetylene and polysulfur nitride. Dopant is an additive which allows charge transfer through its complex with the polymer involved revealed that without the aid of moisture in the polymer, the doping of lithium still aided the ion transport effectively. Thus, the highly doped organic semiconductors or polymers are also known as organic metals. Since doping ions enhance the conductivity of the polymers, the amount of conductivity increase would certainly depend on the type of dopant and its concentration. Revealed explained that certain dopant

concentration gives greater and continuous conjugate lengths, thus improving the electron mobility. For ClO 4 -, 0.1 M gives optimal value [18]. Nonetheless, PPy-based nano-composites and blends are proven to have outstanding electrical conductivity. They can be as high as 103S/cm depending on the electrodeposition conditions as well as the doping ion involved. One example is PPy/TiO2 composites. A conductivity of 135 S/cm for such composite where electrochemically synthesized pure polypyrrole only had a conductivity of 14.5S/cm . A different paper explored the PMMA/PPy composites and discovered optimal conductivity range at 10-3S/cm which was a much lower order of magnitude. However, knowing that PMMA is a non-conductive polymer, conductivity of PMMA/PPy composite was still quite high. Furthermore, the electrical conductivity is related to the amount of pores that the polymer has as explained [20]. Their studies described that the presence of gaseous oxygen induced large amount of pores. This resulted in decreased pathways for electron movement within the pyrrole chains. For solid metals, it is known that the conductivity decreases with increasing temperature according to the following Thomas-Fermi equation [18]:

1.1.1

The equation essentially describes the screening of Columb potential and the electron distribution in an atom [19]. P is the population of given i orbital, and Ef is Fermi Energy. This is similar to the behavior of Boltzmanns equation where there is an exponential decay with increasing temperature. In other words, the resistivity rises in parallel with the temperature increase. At a very cold temperature, there is no resistance to the electrical flow. In other cases such as organic semiconductors, the conductivity increases with temperature due to small energy gap. A wide range of polymers can be classified as organic semiconductors with long chains such as polypyrrole and polyanaline. The conduction in the polymers amorphous structure is largely dependant on polaron-assisted tunneling whereas crystallized

structures provide aligned chains as electron passageways. Thus, it is expected that an increase in temperature, past the crystallization peak, would increase the electron mobility or conductivity. The thermal energy should also excite the electrons to leap across the band gap. The higher the activation energy the more and the faster electrons travel. In

rising the temperature and the conductivity increases in experiment [19].

Figure 1.7 Temperature effect on conductivity of polypyrrole

Figure 1.8 Application of Conducting Polymers

1.3 Application of conducting polymers There are two main groups of applications for conducting polymers. The first group utilizes their conductivity as its main property whereas the second group utilizes their electroactivity. The extended -systems of conjugated polymer are highly susceptible to chemical or electrochemical oxidation or reduction. These alter the electrical and optical properties of the polymer, and by controlling this oxidation and reduction, it is possible to precisely control these properties. Since these reactions are often reversible, it is possible to systematically control the electrical and optical properties with a great deal of precision. It is even possible to switch from a conducting state to an insulating state. The two groups of applications are shown in Figure 1.8. 1.3.1 Applications that utilizes conductivity These applications make use of the polymer's conductivity only. The polymers are used due to either their light weight, biological compatibility for ease of manufacturing or cost. By coating an insulator with a very thin layer of conducting polymer, it is possible to prevent the buildup of static electricity. This is particularly important where such a discharge is undesirable. Such a discharge can be dangerous in an environment with flammable gasses and liquids and also in the explosives industry. In the computer industry the sudden

discharge of static electricity can damage microcircuits. This has become particularly acute in recent years with the development of modern integrated circuits. To increase speed and reduce power consumption, junctions and connecting lines are finer and closer. The resulting integrated circuits are more sensitive and can be easily damaged by static discharge at a very low voltage. By modifying the thermoplastic used by adding a conducting plastic into the resin results in a product that can be used for the protection against electrostatic discharge [21]. By placing monomer between two conducting surfaces and allowing it to polymerize it is possible to stick them together. This is a conductive adhesive and is used to stick conducting objects together and allow an electric current to pass through them. Many electrical devices, particularly computers, generate electromagnetic radiation, often radio and microwave frequencies. This can cause malfunctions in nearby electrical devices. The plastic cases used in many of these devices are transparent to such radiation. By coating the inside of the plastic case with a conductive surface, this radiation can be absorbed. This can best be achieved by using conducting plastics. They are cheap, easy to apply and can be used with a wide range of resins. The final finish generally has good adhesion, gives a good coating,

thermally expands approximately the same as the polymer it is coating, needs just one step and gives a good thickness [22]. Many electrical appliances use printed circuit boards. These are copper coated epoxyresins. The copper is selectively etched to produce conducting lines used to connect various devices. These devices are placed in holes cut into the resin. In order to get a good connection the holes need to be lined with a conductor. Copper has been used, however the coating method, electroless copper plating, has several problems. It is an expensive multistage process, the copper plating is not very selective and the adhesion is generally poor. This process is being replaced by the polymerization of a conducting plastic. If the board is etched with potassium permanganate solution, a thin layer of manganese dioxide is produced only on the surface of the resin. This will then initiate polymerization of a suitable monomer to produce a layer of conducting polymer. This is much cheaper, easy and quick to do, is very selective and has good adhesion. Due to the biocompatability of some conducting polymers they may be used to transport small electrical signals through the body, i.e. act as artificial nerves. Perhaps modifications to the brain might eventually be contemplated. Weight is a premium importance for aircraft and spacecraft. The use of polymers with a density of about 1 g cm-3 rather than 10 g cm-3 for metals is

attractive. Moreover, the power ratio of the internal combustion engine is about 676.6 watts per kilogram. This compares to 33.8 watts per kilogramme for a battery-electric motor combination. A drop in magnitude of weight could give similar ratios to the internal combustion engine. Modern planes are often made with light weight composites. This makes them vulnerable to damage from lightning bolts. By coating aircraft with a conducting polymer the electricity can be directed away from the vulnerable internals of the aircraft [23].

1.3.2 Applications that utilizes electroactivity Molecular electronics are electronic structures assembled atom by atom. One proposal for this method involves conducting polymers. A possible example is a modified polyacetylene with an electron accepting group at one end and a withdrawing group at the other. A short section of the chain is saturated in order to decouple the functional groups. This section is known as a spacer or a modulable barrier. This can be used to create a logic device (Figure 1.9). There are two inputs, one light pulse which excites one end and another which excites the modulable barrier. There is one output, a light pulse to see if the other end has become excited. To use this there must be a great deal of redundancy to compensate for switching errors [24].

Depending on the conducting polymer chosen, the doped and undoped states can be either colorless or intensely colored. However, the color of the doped state is greatly redshifted from that of the undoped state. Because conducting polymers are intensely colored, only a very thin layer is required for devices with a high contrast and large viewing angle. Unlike liquid crystal displays, the image formed by redox of a conducting polymer can have a high stability even in the absence of an applied field. The switching time achieved with such systems has been as low as 100 s but a time of about 2 ms is more common. The cycle lifetime is generally about 106cycles. Experiments are being done to try to increase cycle lifetime to above 10 7 cycles [25]. The chemical properties of conducting polymers make them very useful for use in sensors. This utilizes the ability of such materials to change their electrical properties during reaction with various redox agents (dopants) or via their instability to moisture and heat. An example of this is the development of gas sensors. It has been shown that polypyrrole behaves as a quasi 'p' type material. Its resistance increases in the presence of a reducing gas such as ammonia, and decreases in the presence of an oxidizing gas such as nitrogen dioxide.

The gases cause a change in the near surface charge carrier (here electron holes) density. Another type of sensor developed is a biosensor. This utilizes the ability of trioxide to oxidize polyacetylene as a means to measure glucose concentration. Glucose is oxidized with oxygen with the help of glucose oxidase. This produces hydrogen peroxide which oxidizes iodide ions to form trioxide ions. Hence, conductivity is proportional to the peroxide concentration which is proportional to the glucose concentration [26]. Probably the most publicized and promising current applications are light weight rechargeable batteries. Some prototype cells are comparable to, or better than nickel-cadmium cells now on the market. The polymer battery, such as a polypyrrole-lithium cell operates by the oxidation and reduction of the polymer backbone. During charging the polymer oxidizes anions in the electrolyte enter the porous polymer to balance the charge created simultaneously, lithium ions in electrolyte are electrodeposited at the lithium surface. During discharging electrons are removed from the lithium, causing lithium ions to reenter the electrolyte and to pass through the load and into the oxidized polymer. The positive sites on the polymer are reduced, releasing the charge-balancing anions back to the electrolyte. This process can be repeated about as often as a typical secondary battery cell [27].

Conducting polymers can be used to convert electrical energy into mechanical energy. This utilizes large changes in size undergone during the doping and dedoping of many conducting polymers. This can be as large as 10%. Electrochemical actuators can function by using changes in a dimension of a conducting polymer, changes in the relative dimensions of a conducting polymer and a counter electrode and changes in total volume of a conducting polymer electrode, electrolyte and counter electrode. The method of doping and dedoping is very similar as that used in rechargeable batteries discussed above. The applications of this include microtweezers, microvalves, micropositioners for microscopic optical elements, and actuators for micromechanical sorting (such as the sorting of biological cells) [28]. One of the most futuristic applications for conducting polymers are intelligent structures. An intelligent material is capable of recognizing appropriate environmental stimuli, processing the

information arising from the stimuli and responding to it in an appropriate manner and time frame. A further desirable feature is that the material should ideally be self-powered, having energy conversion and storage functions. Conducting electroactive polymers have emerged as one of the champions in intelligent materials research. CEPs have all the desirable properties:

 They are readily engineered at the molecular level to recognize

specific stimuli.

Because they are conductive, they facilitate transport of

electrical information.

They are capable of localized processing as well as actuation of

response mechanisms. Recent research has suggested that conducting polymers are set to emerge in devices used to store energy in the form of super capacitors. The intense interest in these applications is driven by developments in electricpowered vehicles and alternative energy in general. Supercapacitors are those devices able to store a charge of 50 F/g (or 30 F/cm3) of the device, or higher. This high storage capacity and ability to deliver high power density can be utilized in electronic equipment and electric vehicles. The fast discharge rate obtainable from capacitors means that high power can be delivered for short periods. Conducting polymers are being researched for redox supercapacitors. In these devices, the redox chemistry of the polymer is used in the same way as described above for batteries. However, the design of the device is such that the conducting polymer is applied as a thin coating on a high-surface-area

substrate. This design allows for very rapid charging and discharging of the polymer so that capacitor-like performance is obtained. All solid-state redox supercapacitors using PTh and PPy with a solid polymer electrolyte have been reported as having storage capacities of 18 F/g. Polymer photovoltaics using conducting polymers are also being developed. In a typical arrangement, the photosensitive polymer (such as polyphenylene vinylene (PPV) and its derivatives) is sandwiched between two electrodes (Figure 1.10). One is a transparent material, typically indium tin oxide (ITO)-coated glass, and the other electrode is a low-work-function metal such as aluminum or calcium. It is necessary the put hole transport layer (HTL) and electron transport layer (ETL) in this sandwich confugration. Light is 21 absorbed by the polymer, creating excitons (electron-hole pairs) that dissociate at an appropriate interface to give charge separation and, hence, current flow. Efficiencies of polymer-based photovoltaics are very low compared with silicon semiconductor materials. However, polymer photovoltaics have the potential to be manufactured very cheaply and can be applied to very large areas, such as roof tops and exterior walls of buildings. The large surface areas can compensate for the lower efficiencies to provide an adequate supply of electricity. Of course,

efficiencies are being improved by chemical modification of the polymer and better design of the photovoltaic device. One approach to polymer modification is to attach light harvesting groups to the polymer chains so as to increase the amount of light absorbed. Once again, the fabrication of the device is critical in determining device performance. It has been shown that formation of interpenetrating networks of donor- and acceptor-type polymers results in marked improvements in photovoltaic efficiency, as reviewed recently [29]. The process used for the photovoltaic device can be reversed to produce a light emitting diode (LED). When an electric field is applied to the two electrodes shown in Figure 1.11, electrons are injected into the conduction band of the polymer layer from the cathode (usually a low-work-function metal such as aluminum or calcium). At the ITO anode, electrons are removed from the valence band of the polymer to produce vacancies, or holes. The free electrons and holes move in opposite directions under the influence of the electric field and, when they combine, a photon of light is emitted. The color of the light emitted depends on the band gap between the valence and conduction bands in the polymer. Appropriate derivation of PPV polymers has produced PLEDs that emit the three colors red, blue and green.

Figure

1.9

Insertion of a spacer to decouple the functionalized chain ends

Figure 1.10 Device design for polymer a photovoltaic device

Figure 1.11 Device design for a polymer light emitting diode

1.4. Scope of the work

The objective of present study is to synthesis of Polypyrrole and copper composite of Polypyrrole using chemical oxidation method and its characterization.

CHAPTER II EXPERIMENTAL TECHNIQUE ABSTRACT

In this part provides the information about the synthesis of pure Polypyrrole and Nano copper doped Polypyrrole by chemical oxidation method. The experimental techniques for FI-IR spectroscopy, Powder X-ray diffraction pattern and electrical conductivity measurement are briefly discussed. The detailed sampling techniques of each method and their applications are also given in this chapter.

2.1 INTRODUCTION Polypyrrole and many of its derivatives can be synthesized via simple chemical or electrochemical methods. Photochemically initiated and enzyme-catalyzed polymerization routes have also been described but less developed. Different synthesis routes produce Polypyrrole with different forms; chemical oxidations generally produce powders, while electrochemical synthesis leads to films deposited on the working electrode and enzymatic polymerization gives aqueous dispersions. In present work Chemical oxidation method was carrying out to prepare Polypyrrole [30]. The chemically polymerized

Polypyrrole and nano copper doped Polypyrrole were obtained by oxidation polymerization using K2Cr2O7 as oxidant in aqueous medium Spectroscopy techniques are widely used to study the type of functional group present in the sample. In characterization of polymers sample many scientific techniques were used. The most widely used one.

Fourier Transform Infrared Spectroscopy X-ray diffraction method Raman Spectroscopy

 Scanning Electron Microscopic (SEM) technique with

(EDS)

Electron Spin Resonance Spectroscopy

Of these, Fourier transform Infrared, XRD and measurement techniques were found to be more informative and simple. The FT-IR have been used to study the functional groups of the sample and X-ray diffraction have been used to identify crystalline materials. It can provide quantitative information about the chemical composition of a sample, containing different crystalline phase. Electrical conductivity measurement of the sample was carrying out two probe method using graphite for ohmic contact. It can provide the absolute electrical conductivity of the Polypyrrole and nano copper doped polypyrrole. 2.1.1 Synthesis: The Polypyrrole was prepared by using chemical method. Briefly solution of 1 M C5H6N (6.7 ml of C5H6N in 100 ml distilled water), 1 M H2SO4 (9.8 ml of H2SO4 distilled water). The Pyrrole monomer solution was stirred at ice temperature and the H2SO4 solution was added drop wise into this Pyrrole monomer solution one by one. The reaction mixture was stirred one hour at constant rpm value. After the solution 0.5M K2Cr2O7 (2.8g of K2Cr2O7 in 20 ml

distilled water), was added drop wise into the Pyrrole and H 2SO4 mixture one by one. The reaction mixture kept in

under the ice temperature and stirred constant RPM value at 24 hours continuously. The black precipitate was separated out by filtering. The final suspension was dried in Laboratory oven at 100C for 90 minutes. Finally the product was ground into fine powder using mortar and pestle. 2.1.2 SYNTHESIS OF NANO COPPER DOPED POLYPYRROLE: The 100mg Polypyrrole powder was mixed into 100ml distilled water and the mixture was added 100mg nano copper practical and stirred constant RPM value of 12 hours continuously. Then the precipitate was separated out by filtering. The final suspension was dried in laboratory oven at 100C for 60 minutes.

1M Pyrrole Mixing under vigorous stirring ice temperature at 1 hour 0.5M K2Cr2 O7

9.8 ml H2SO4

Oxidation

Reaction mixer stirring under Ice temperature at 24 hours Filtering

Black Precipitate

Dried (100C,90m)

Crushed

Powder

Figure. 2.1 Flow chart for synthesis of Polypyrrole

2.2 FTIR SPECTROSCOPY Fourier transformation technique is now of great importance in infrared spectroscopy. The absorption spectrum in a Fourier transform infrared spectrometer is obtained through interference technique. Interferometer is therefore known as Fourier transform spectroscopy. The structural information from the observed diffraction patterns are obtained through a mathematical manipulation known as Fourier transformation. In a Fourier transform spectrometer, a time domain plot is converted into a frequency domain spectrum. In mathematics, the Fourier transform of the function f (t) is defined by
G ( ) = 1/ 2 f ( t ) eit dt

..

(2.1)

Then the inverse relation is

f ( X ) = 1/ 2 G ( ) e it dt

..

(2.2)

These two equations are said to form a Fourier transform pair.

Fourier transform infrared spectroscopy (FT-IR) is rapidly becoming a common feature in modern spectroscopy laboratories. A wide range of commercial FT-IR spectrometers with very different specifications are now available. This has become possible with the availability of sophisticated computers. The absorption spectrum in a Fourier transform infrared spectrometer is obtained through interface technique. Interferometer is therefore known as Fourier transform spectroscopy. Many laboratory spectrometers are the dispersive design, meaning that a prism is used to separate the spectral components in the IR radiation of the source. Most industrial process analyzers use nondispersive infrared (NDIR) designs. With recent improvements in instrumentation, the infrared region of the electromagnetic spectrum is now considered to cover the range from approximately 125000 to 10 cm1 (0.81000m). It is generally subdivided into three sections: near infrared (125004000cm1), mid infrared region (4000-400cm1) and the far infrared (400 10 cm 1). The mid infrared region is the most commonly used for standard laboratory investigations as it covers almost all the vibrational and rotational transitions. The FT-IR spectrums of the sample were recorded in mid and far IR region and are used for the present investigation. Fig 2.2 shows the block

diagram of the major components of a dispersive infrared spectrophotometer. A source provides radiation over the whole range of the infrared spectrum and is passed alternatively through the sample and the reference placed before the monochromator. This minimizes the effect of stray radiation emanating from the sample and cell before it reaches the detector. The transducer measures the energy and transforms it into an electric signal. This signal is further amplified and registered by a recorder. Temperature and relative humidity in the room housing the instrument must be controlled. Fourier transform infrared spectroscopy is preferred over dispersive or filter methods of infrared spectral analysis for several reasons: It is a non-destructive technique It provides a precise measurement method which requires no external calibration It can increase speed, collecting a scan every second It can increase sensitivity one second scans can be co-added together to ratio out random noise It has greater optical throughput

 It is mechanically simple with only one moving part An instrument for chemical analysis converts information stored in the physical or chemical characteristics of the analyze to information that may be manipulated and interpreted by a human. Thus an analytical instrument can be viewed as a communication device between the system under study and the investigator. Modern spectrometers generally attached with sophisticated computers and high energy sources like lasers, which permit spectrum storage and retrieval, scale expansion, repetitive scanning, spectral comparison, spectral simulation, atomic control of slit, etc. Often these are under the control of a microprocessor and microcomputers. Accessories such as beam condensers, reflectance units, polarizers

and microcells can usually be added to extend versatility or accuracy. In Fourier transform instruments, the microprocessor also performs the mathematical operation required to generate the spectrum from the detector output. 2.2.1 Principle The Michelson interferometer is essentially an optical assembly composed of a beam splitter, a moving mirror (M2) and a stationary or fixed mirror (M1). The interferometer is used to split a beam of radiation into two beams and then recombining the beam after a path

difference is introduced. The division of the beam is achieved with the beam splitter, which transmit, about fifty percentages and reflects about fifty percentage of the radiation. If radiation from an infinitely narrow line source lights the beam of splitter, one parts of the beam (A), goes to the fixed mirror and the other beam (B), to the moving mirror.

Figure 2.2 Schematic of a two plane mirror Michelson interferometer

2.2.2 INSTRUMENTATION A FT-IR spectrometer consist of two parts: (a) an optical system which uses an interferometer and (b) a dedicated computer which stores data, perform computations on data and plots the spectra. Fig. 2.3 shows optical arrangement of a Fourier transform infrared spectrometer. It consists of a movable mirror, a stationary mirror and a beam splitter. Radiation from an infrared source is passed on to the mirror through the beam splitter and beam splitter partly transmits and partly reflects the incident light. The transmitted and the reflected beams fall on the stationary and movable mirrors, respectively. These beams which are sent in two directions at right angles to each other are brought together after reflections two, to interfere with each other. 2.2.3 SOURCE The source of radiation in infrared spectrophotometer is ideally a black body radiator. The energy emitted by a black body radiator varies with wavelength and temperature. In particular, increasing the temperature of the source raises the energy of emission enormously in

the short wavelength region, but has relatively small effect at long wavelengths. The optimum infrared source is an inert heated electrically to temperature between 1500-2200K. The maximum radiant intensity at these temperatures occurs at 5000 to 6000 cm1 (1.7 to 2m). At longer wavelengths, the intensity reduces continuously, until it is about 1% of the maximum at 667 cm1 (15m). On the shorter wavelength side also, the decreased is much more rapid and a similar reduction is noticed at about 10,000cm1 (1m). The common practical infrared sources are described here. A. NERNST GLOWER It is a hollow rod of about 1 inch long and 0.1 inch in diameter composed of rare earth oxides. It is operated at temperature of 1000 to 1800C. The intensity of the radiation from a Nernst glower is steady for long periods of time. However, the main disadvantage of the Nernst glower is that, it is nonconducting at ambient temperature and when heated by external means it becomes conducting. B. NICHROME COIL A close-wound Nichrome coil can be raised to incandescence by resistive heating. A black oxide film forms on the coil which gives acceptable emissivity. Temperature upto 1100C can be reached. The

maintenance and

ampling area Detector

Monochromator

Figure 2.3 Block diagram of the major components of a dispersive infrared spectrophotometer

Nichrome coil requires no water-cooling and little or no

Recorder

Amplifier

Figure2.4 Fourier Transform infrared spectrometer-optical arrangement

Radiation source condensing optics and beam chopper

gives long service. This source is recommended where reliability is essential, such as in nondispersive process analyzers and inexpensive spectrophotometers or filter photometer. C. THE GLOBAR SOURCE The Globar, a rod of silicon carbide 6-8 mm in diameter and 50 mm length, possesses characteristics intermediate between heated wire coil (Nichrome) and Nernst glower. It is self starting and has an operating temperature near 1300C. Unlike the Nernst glower, it is conducting at room temperature. Globar is satisfactory over a longer frequency region (4000-100cm1). However it is less intense than a Nernst glower. D. THE MERCURY ARC LAMP In the far-infrared, beyond about 200cm1 (50m), blackbodytype sources lose effectiveness since their radiation decreases with the fourth power of wavelength. High pressure mercury arcs, with an extra quartz jacket to reduce thermal loss, gives intense radiation in this region. Output is similar to that from block body sources, but additional radiation is emitted from plasma which enhances the longwavelength output. E. THE TUNGSTEN FILAMENT LAMP

A tungsten filament lamp has also been found satisfactory for near infrared region of 12500 to 4000cm1 (0.8 to 2.5m). F. THE CARBON-DIOXIDE LASER SOURCE For monitoring the concentrations of certain atmospheric pollutants and for determining absorbing species in aqueous solutions, a tunable carbon-dioxide laser is used as an infrared source. A carbondioxide laser produces a band radiation in the 1100 to 900 cm 1 (9 to 1m) range, which consists of about 100 closely spaced discrete lines. Any one of these lines can be chosen by tuning the laser. An important property of the laser source is the radiant power available in each line, which is several orders of magnitude greater than that of blackbody sources. Thus, this source is useful for quantitative determination of important species. In the recent years, tunable dye lasers are emerging as very precise source with resolution of 106 cm1 often attainable. The wavenumber range of tunable laser is severely restricted and hence their applicability is presently limited. 2.2.4 MONOCHROMATOR A monochromator is a means of separating the wavelength of the source radiation. The monochromator is used to separate

polychromatic radiation into a suitable monochromator form. This is achieved by means of prisms or diffraction grating. Materials for prism construction, which are found most suitable in the infrared region are listed in the following Table 2.2.1 Most suitable prism material in the infrared region Material Glass (SiO2) Quartz Lithium fluoride Calcium fluoride Sodium chloride (NaCl) Potassium bromide (KBr) Cesium iodide (Csl) Optimum range as prisms 300 m to 2 (5000cm1) 800 m to 3 12500 to 3300cm1 600m to 6 (1670cm1) 200m to 9 (1100cm1) 200 m to 14.5 (625cm1) 10 to 25 (400 cm1) 10 to 38 (260 cm1)

An ideal prism instrument would contain large number of prisms made from different optical materials, so that could be used in sequence in its effective region. High resolution prism instruments contain combination of SiO2, NaCl and KBr Prisms. Low-cost

instruments use an NaCl prism over the full range. They give highest resolution in the vital finger-print region.

A monochromator thus carries out three functions: (i) it disperses the radiation according to its wave number components (ii) it restricts the radiation falling on the detector into a narrow wave

number range, and (iii) it maintains the energy incident on the detector to an approximately constant level when no sample is present throughout the wave number range of the instrument. Some instruments use a double monochromator. That is, the exit slit of the first monochromator serves as the entrance slit of the second monochromator. A double monochromator produces more dispersion than a single monochromator. As a result, the spectra obtained with spectrophotometers having double monochromator have higher resolution. 2.2.5 Detector Detectors used in infrared spectrophotometers usually convert the thermal radiant energy into electrical energy, which can subsequently be plotted on a chart recorder. Two types of the detectors are commonly used. a. b. Thermal detector Photon detector

Thermal detectors, in which the infrared radiation produces heating effect that alters some physical property of the detector.

Thermal detectors: Material properties affected in thermal detectors include an expansion of a solid or fluid (Golay cell), electrical resistance (thermisto , r), Voltage induced at a junction of two dissimilar materials (thermocouple and thermopile) and electric polarization (pyroelectric). Thermocouples have been used most frequently. In this, the radiant energy heats one of the two bimetallic junctions and the emf reduced between the two junctions is proportional to the degree of heating. The thermocouple most commonly used is constructed from pure bismuth wire soldered to another wire which is an alloy of bismuth - 95% and tin - 5%. Thermistor - Bolometer functions by

changing resistance when illuminated by infrared radiation. To minimize noise and draft, an infrared thermistor detector contains two closely spaced thermistor flakes, the thermally sensitive resistors are sintered oxides of manganese, cobalt and nickel which have high active detector while the other acts as a compensating detector. The active flake is coated with black material to increase the infrared radiation, whereas the compensating flake is optically shielded to prevent exposure to the incident radiation. (Flakes are separately mounted on an insulating substrate that is configuration and (optically coupled

configuration. I either configuration, the shielded wafer, when connected in a bridge circuit, compensates for ambient temperature changes). In general, however, the response time and responsibility must be traded. Greater thermal contact assures faster response time. The Golay pneumatic detector, utilizes the expansion of a gas as a measuring device. The golay cel consists of a small metal cylinder closed by a rigid blackened metal plate at one end and by a flexible silvered diaphragm at the other end. The chamber is filled with Xenon. Radiation passes through a small infrared-transmitting window and is absorbed by the blackened plate. Heat conducted to gas, causes it to expand and deform the flexible diaphragm (mirror). To amplify distortions of the mirror surface, light from a lamp inside the detector housing is focussed upon the mirror, which reflects the light beam onto a phototube. This leads to distortion of a mirror membrance with which other end of gas chamber is sealed. An alternating radiation signal will therefore produce a an alternating voltage. Response time is approximately 20 m sec. The golay is superior as a detector for the far infrared. Since the angular aperture is 60, the detector must be used with a system of condensing mirrors to concentrate the incident radiation. Pyrolectric detector contains a

non centro-symmetrical crystal which, below its Curie temperature,

exhibits an internal electric field (or polarization) along the polar axis. The electric field resulting from radiation absorption produces thermal alternation of the crystal lattice normal to the polarization axis and then develop a polarization change. Unlike other thermal detectors, the pyroelectric effect depends on the rate of change of the detector temperature rather than on the value of the temperature itself. This allows the pyroelectric detector to operate with a much faster response time. It also means that this type detector will respond only to changing radiation that is chopped, pulsed or otherwise modulated, but will ignore steady background radiation. The detector is a thin plate of pyroelectric material with two electrodes, forming a capacitor. Pyroelectric materialsl include triglycine sulfate (TGS),

deuterated triglycine sulfate (DTGS), LiTaO3, LiNbO3, and some polymer materials. Generally TGS and DTGS show superior features, but are limited in use because of their hygroscopicity and low Curie points (approximately 49C). For higher Curie points and ease in handling, LiTaO3 or LiNbO3 is frequently used. The detector in a Michelson interferometer must have noise that is independent of the signal-level or at least is dependent on it to less than the first power. If this is not the case, Fellgett's multiplex

advantage lost as the part of Jacquinot's throughput advantage. Table 2.1 shows some properties of the frequently used FT-IR detectors. The cooled detectors often do not yield the full benefit over the usual cheaper room-temperature DTGS detector, that is suggested by the comparison of their D* (Peak) values that gives a measure of their relative signal-to-noise ratios. This is because they often do not give a linear response (output a radiant-input) when exposed to maximum radiation, from the source. To obtain a linear response the source aperture must be reduced, thus reducing the incident radiation intensity i.e., the signal. 2.2.6 AMPLIFIERS AND RECORDERS The radiant energy received by the detector is converted into measurable electrical signal and is amplified by the amplifiers. The amplified signal is registered by a recorder or a plotter. The recorder is driven with a speed which is synchronized with that of a monochromator, so that, the pen moving across the chart, records the transmittance of the sample as a function of the wave number.

2.2.7 BEAM-SPLITTERS Beam splitters are constructed by transparent materials with refractive indices such that approximately 50% of the radiation is

reflected and 50% is transmitted. A widely used material for the farinfrared region is a thin layer of mylar sandwiched between two plates of a low-refractive-index solid. Thin Films of germanium or silicon deposited on cesium iodide or bromide, sodium chloride, or potassium bromide are satisfactory for the mid-infrared region. 2.2.8 SAMPLE HANDLING Sample handling is considered as an important technique in the infrared spectroscopy. One of the advantages of infrared spectroscopy is that it can be applied to nearly all types of substances. There are various methods of sample preparation to enable almost any type of sample to be examined. Sample preparation is now the most timeconsuming, most error-prone and most labour-intensive step of an analysis. No Matter how simple or complex the procedures appear, the same five general principles apply to all sample preparations. 2.2.9 SAMPLE PREPARATION The sample preparation should be done without losing any one of the analyte(s). The sample preparation should include bringing the analyte(s) into the best chemical form to be used. The sample preparation should, if necessary, include removing interferents in the matrix.

 The sample preparation should be done without adding any new interferents. The sample preparation should include, if necessary, diluting of concentrating the analyte(s) to bring their concentrations into the best range. Some significant problems arise when trying to construct sample containers for vibrational spectrometry, since every material has some vibrational absorption. SOLIDS Solids are sampled in a wide variety of ways. If the sample is soluble, it may be dissolved and handled as for a liquid. Solid samples for which no solvent is suitable can be prepared for analysis by incorporating them into a pressed pellet of alkali halide, usually potassium bromide sample is mixed with a weighted amount of powered potassium bromide and the mixture is admitted to a pressure of several tones in a die, to produce a highly transparent plate or disc which can be inserted into the spectrophotometer. The most popular method of preparation of specimens for infrared measurements is the alkali halide (KBr) pelleting technique. The powdered sample is mixed with KBr pellet technique is the most appropriate method for recording infrared spectra for solid samples. For getting a good spectrum the

samples were ground to a particle size below 2m. Larger fractions need to be reduced in size to minimize the loss of intensity of transmission line. The use of KBr eliminates the problems of additional bands due to the mulling agent. KBr does not absorb infrared light in the region 2.5-15m and a complete spectrum of the sample is obtained. Solid

samples have also been examined in the form of a thin layer deposited by sublimation or solvent evaporation on the surface of a salt plate. Another method, called mulling has also been developed, in which the powered sample is mixed to form a paste with little heavy paraffin oil. The mull is sandwiched between salt plates for measurement. Mulls are formed by grinding 2 to 5 mg of finely powered sample in the presence of one or two drops of a heavy hydrocarbon oil called Nujol. Grinding was done manually with a conventional agate morter and pestle. In this, sample was mixed with spectra grade KBr in powder form and finely grounded and mixed at the ratio 1:20 by weight. The samples of 2mg mixed with 40mg of spectra grade KBr. The pellets were prepared at a pressure of 8 atmosphere. The FTIR spectra of as-synthesized samples were recorded on Perkin Elmer spectrophotometer in the wavenumber range of 4000 400 cm1 with 1 cm1 resolution by using KBr pellet technique.

2.2.10 APPLICATION Some of the major advantages of FT-IR over the dispersive technique include: Speed: Because all of the frequencies are measured simultaneously, most measurements by FT-IR are made in a matter of seconds rather than several minutes. This is sometimes referred to as the Felgett Advantage. Sensitivity: Sensitivity is dramatically improved with FT-IR for many reasons. The detectors employed are much more sensitive, the optical throughput is much higher referred to as the Jacquinot Advantage which results in much lower noise levels, and the fast scans enable the co-addition of several scans in order to reduce the random measurement noise to any desired level (referred to as signal averaging). Mechanical Simplicity: The moving mirror in the interferometer is the only continuously moving part in the instrument. Thus, there is very little possibility of mechanical breakdown. Internally Calibrated: These instruments employ a He-Ne laser as an internal wavelength calibration standard (referred to as the Connes Advantage). These instruments are self-calibrating and never need to be calibrated by the user.

These advantages, along with several others, make the measurements made by FT-IR extremely accurate and reproducible. Thus, it a very reliable technique for positive identification of any sample. The sensitivity benefits enable identification of even the smallest of contaminants. This makes FT-IR an invaluable tool for quality control or quality assurance applications whether it is batchto-batch comparisons to quality standards or analysis of an unknown contaminant. In addition, the sensitivity and accuracy of FT-IR detectors, along with a wide variety of software algorithms, have dramatically increased the practical use of infrared for quantitative analysis. Quantitative methods can be easily developed and calibrated and can be incorporated into simple procedures for routine analysis. Thus, the Fourier Transform Infrared (FT-IR) technique has brought significant practical advantages to infrared spectroscopy. It has made possible the development of many new sampling techniques which were designed to tackle challenging problems which were impossible by older technology.

2.3 Introduction to X-Ray Diffraction 2.3.1Basic principles X-ray diffraction analysis uses the property of crystal lattices to diffract monochromatic X-ray light. This involves the occurrence of interferences of the waves scattered at the successive planes, which are described by Bragg's equation: n=2d sin (n=1,2,3,...)------------------------------ (2.3) where is the wavelength, d is the lattice plane distance and is half the diffraction angle. This relation is used for the structure analysis of crystals. In diffractograms of powders not free from phase shift,

several diffraction patterns of different crystalline fractions can be superimposed. The detector is a position-sensitive proportional counter for high-speed recording or a scintillation counter for better angular resolution. Instruments that work on this principle are called diffractometers.

X-ray Sources

In general, light is created by accelerating electrical charges, or equivalently (but less obviously) by quantum transitions of charged particles from one energy state to another. Examples: radio (electrons oscillate in antenna), mercury lamp (transitions between atomic states). When an electron hits an anode: Figure 2.5 shows the generic X-Ray tube. When an electron hits an anode: 1. It bumps into atoms and slows down, creating radiation of a continuous distribution of wavelengths (``bremstrahlung'') 2. It causes sharp atomic transitions, resulting in x-rays with definite wavelengths. 2.3.2 SAMPLING TECHNIQUES The powder diffraction experiment is the cornerstone of a truly basic materials characterization technique - diffraction analysis - and

it has been used for many decades with exceptional success to provide accurate information about the structure of materials. Although powder data usually lack the three-dimensionality of a diffraction image, the fundamental nature of the method is easily appreciated from the fact that each powder diffraction pattern represents a one-dimensional

snapshot of the three-dimensional reciprocal lattice of a crystal quality of the powder diffraction patterns usually limited by the nature and

the energy of the available radiation, by the resolution of the instrument, and by the physical and chemical conditions of the specimen. Since many materials can only be prepared in a polycrystalline form, the powder diffraction experiment becomes the only realistic option for a reliable determination of the crystal structure of such materials. Powder diffraction data are customarily recorded in virtually the simplest possible fashion, where the scattered intensity is measured as a function of a single independent variable - the Bragg angle. What makes the powder diffraction experiment so powerful is that different structural features of a material have different effects on various parameters of its powder diffraction pattern. Diffraction experiment When atomic parameters, e.g. coordinates of atoms in the unit cell or populations of different sites in the lattice of the crystalline phase are altered, this change affects relative intensities and/or positions of the Bragg peaks that correspond to this phase. When the changes are microscopic, e.g. when the grain size is reduced below a certain limit or when the material has been strained or deformed, then

the shapes of Bragg peaks become affected in addition to their intensities and positions. Hence, much of the structural information about the material is embedded into its powder diffraction pattern, and when experimental data are properly collected and processed, a great deal of details about a material's structure at different length scales, its phase and chemical. Brief history of the powder diffraction method The x-ray powder diffraction method dates back to Debye and Scherer' who were the first to observe diffraction from LiF powder and succeeded in solving its crystal structure. Later, Hull2 suggested and Hanawalt, Rinn and Freve13 formalized the approach enabling one to identify crystalline substances based on their powder diffraction patterns. Since that time the powder diffraction method has enjoyed enormous respect in both academia and industry as a technique that allows one to readily identify the substance both in a pure form and in a mixture in addition to its ability to provide information about the crystal structure (or the absence of crystallinity) of an unknown powder.

In the early days of the method, powder diffraction data were recorded on x-ray film in a variety of cameras. Using film, the resulting diffraction pattern is usually observed as a series of elliptically distorted narrow concentric ring segments, where each ring corresponds to one or more Bragg peaks. Multiple Bragg peaks may be convoluted into a poorly resolved or completely unresolved single ring due to the limitations imposed by the one-dimensionality of the technique and by the resolution of both the film and the instrument, e.g. the Debye-Scherrer camera (Figure 2.6). From the locations of Debye rings on the film plus their varying intensity (degree of darkening), it is possible to identify the material and to establish its crystal structure. Given the analogue nature of the film, it is nearly as easy to grasp the overall "structure" of the diffraction pattern, as it is difficult to convert it into a digital format, and considerable effort is usually required to measure both the Bragg angles and diffracted intensities with high precision. Cameras for x-ray powder diffraction are relatively simple but precise optical instruments, and require dark room for loading and developing x-ray film. Debye-Schemer cameras (Figure 2.6) were in the most common use in crystallographic laboratories in the past, and many are still on display today. Debye-Schemer cameras are

exceptionally reliable and nearly aintenancefree devices. When the camera has been loaded with both the ample and the film, the entire diffraction pattern was recorded all at once, in a single exposure (Figure 2.6). The typical time to register one powder diffraction pattern on film is from 1 to 3 hours depending on the radius of the camera, the crystallinity of the specimen and the sensitivity of the film.' Powder diffraction data today are almost exclusively collected using much more sophisticated analytical instruments - powder diffractometers. A powder diffractometer furnishes fully digitized experimental data in the form of diffracted intensity as a numerical function of Bragg angle (see Figure). By their nature, powder diffractometer data are exceptionally well suited for computerized processing. They usually provide accurate information about the structure of materials, especially when coupled with Rietveld analysis: in which subtle anomalies of Bragg peak shapes are used in addition to the integrated ntensities of Bragg reflections.

Figure 2.5 Generic X-ray Tube

Figure 2.6 Debye-Scherrer camera without a cover showing cylindrical sample, collimator, incident beam trap, and the location of the x-ray film.

Powder diffractometers As mentioned in the previous section, beginning approximately in the 1970's, powder cameras and x-ray film were steadily replaced by automated analytical instruments - powder diffractometers. Despite a large variety of both commercial and one-of-a-kind apparatus found in analytical laboratories around the world, nearly all of them have many common characteristics dictated by the properties of x-rays.' Since standard x-ray tubes produce divergent beams, most of the high resolution powder diffractometers use self-focusing geometries, which improve both the diffracted intensity and the resolution of the instrument. This is usually achieved by highly precise x-ray optics, which is incorporated into the critical part of powder diffractometer

hardware - the goniometer (or goniostat), and by a thorough alignment of the latter. The most common features of focusing optics in powder diffractometry. Focusing powder diffractometers usually operate in the 8 - 28 scanning regime (or scanning mode), where the incident and diffracted beams both form the same angle 8 with the surface of a flat sample, while the diffracted beam forms a 28 angle with the incident beam . The directions of beams are shown by arrows in Figure and in other schematics found in this chapter. The incident beam passes through at least two slits before reaching the sample. The so-called Soller slit limits the divergence of the incident beam in the direction perpendicular to the plane in which the diffracted intensity is measured, also known as out of plane or axial divergence.' Axial divergence of the incident beam is not shown in Figure 2.7. The divergence slit establishes the in-plane aperture of the incident beam and the in-plane divergence.' Since the sample is irradiated by the divergent incident beam, the diffracted beam converges (self-focuses) at the receiving slit, which is located at the same distance from the center of the sample as the focal point of the source. These two distances remain constant at any Bragg angle, and both the focal point of the x-ray source and the receiving slit of the

detector are located on the circumference of an imaginary circle (cylinder), which is known as the goniometer circle. The radius of the goniometer cylinder is identical to the goniometer radius. The diffracted beam passes through the second Soller slit before reaching the detector when no monochromator is employed, or it is reflected in a crystal-monochromator on its path to the detector. An additional catter slit, located before the receiving slit, can be employed to reduce the background. The Soller slit on the diffracted beam side can be placed between the scatter and receiving slits. The diffracted beam is monochromatized using a P-filter or a crystal monochromator. Quite rarely themonochromatization

geometries shown in Figure are reversed, i.e. the incident beam rather than the diffracted beam is monochromatized using either a P-filter or a crystal monochromator. The monochromatization of the diffracted beam is advantageous in that fluorescent x-rays (which may be quite intense in some combinations of samples and photon energies) can be suppressed, thus reducing the background. The common optical features described above may be realized in different ways in the actual hardware design of a powder diffractometer goniostats and thus, goniometers differ from one another by:

1. The orientation of both the goniometer axis and specimen

surface (or specimen axis) with respect to the horizon, i.e. they may be located in a vertical or horizontal plane. 2. Diffraction geometry - reflection or transmission - when scattered intensity is registered after the reflection from or after the transmission through the sample, respectively. 3. Motions of the goniometer arms, i.e. according to which arms of the goniometer are movable and which are stationary.

Goniostats with area detectors The schematic of a powder diffractometer goniostat utilizing transmission geometry with a cylindrical specimen and a curved position sensitive detector (PSD) is shown in Figure 2.7. When using a curved position sensitive detector covering a long (from -0 to -90-140') 28 range, generally there is no need to rotate the detector arm and only sample spinning is required to improve particle orientations averaging and minimize preferred orientation. The greatest advantage of this geometry is in the speed of data collection: the entire diffraction pattern can be recorded in as little as few seconds because the diffracted intensity in the whole range of Bragg angles covered by the

circumference of the simultaneously. The

curved position sensitive detector is registered downside is that it is impossible to

monochromatize the diffracted beam effectively, which results in the increased background, particularly when the sample is strongly fluorescent. Another difficulty may occur in the interpretation of powder diffraction data collected using the

geometry shown in Figure 2.7, because of the lower resolution of curved position sensitive detectors and increased widths of

Figure 2.7 The schematic of a powder diffractometer with the vertical goniometer axis, cylindrical sample in the transmission mode and a curved position sensitive detector (PSD).

Bragg peaks when compared with point detectors. ' When the goniometer radius increases, the size of a flat specimen, needed to maintain high intensity in the Bragg-Brentano geometry, becomes unreasonably large. The schematic diagram of a powder diffract meter with the vertical goniometer axis, cylindrical sample in the transmission mode and a curved position sensitive detector (PSD). Solid arrows indicate the incident beam and broken arrows indicate the diffracted beams pathways. F - focal point of the x-ray source, M - monochromator, DS - divergence slit, T - incident beam trap. In principle, curved position sensitive detector can be replaced by a linear position sensitive detector covering segments 5 to 10' (28) wide. This approach considerably increases resolution and decreases Bragg peak widths, but the problem of the enhanced background remains. Recently, image plate detectors are becoming popular in powder diffractometry. The monochromatized and collimated beam

passes through a cylindrical or flat sample and the diffracted beams are registered by the image plate detector in all directions simultaneously. Because of the size of the detector, which can be made as large as necessary. The entire circumference of the Debye ring is normally registered instead of just a small sector as it is done in any other powder diffraction geometry considered above. The use of image plate detectors restores the pseudo twodimensionality of the x-ray powder diffraction pattern, which was standard in film-based registration. Experimental diffraction data can be collected at high speeds, nearly identical to those achievable with curved position sensitive detectors. Furthermore, the incident beam can be collimated into a small area and it is fundamentally possible to examine powder diffraction from just a few crystalline grains or even from a single grain, provided all possible grain orientations with respect to the incident beam have been arranged by properly varying the orientation of the specimen. The problems encountered in today's image plate detectorequipped powder diffractometers are similar to those noted above for curved position sensitive detectors: high background and relatively low resolution.

XRD pattern of synthesized sample was carried out using a Rigaku D/MAX ULTIMA diffractometer, with voltage and current setting of 40 kV and 30 mA, respectively and uses of Cu-K radiation (1.5406 ). Crystallographic identification of the phases of synthesized sample was accomplished by comparing the experimental XRD patterns to standards compiled by the International Center for Diffraction Data (ICDD). The the lowest value of 2 in between the data have been arranged from range 10o -80o.

2.3.3 Identification of materials The presence of materials have been identified by the mineral data matching with the JCPDS file. The PDF has been a successful means of compiling data in powder diffraction pattern and it is recognized as the standard reference source for x-ray pattern diffraction analysis.

The procedure adopted to identify the materials present is carried out following the steps given hereunder. 1. Search manual has been scanned to locate the group, which includes the d spacing value of the strongest line.

2. Starting at the first phase of the group, read down the second column to find a close match (or matches) for the d value of second strongest line. 3. Look in the third column to find the best match (or matches) for the third strongest line. If there were several matches some of them may be rejected by comparing the relative intensities. 4. If a match is found for the three strongest reflections, then compared the d values of the next fine most intense line. If the match was in agreement, the PDF number was noted.
5. Compared the entire d and I/I0 data with those of the unknown.

If the data were in close or exact agreement it is taken for the discussion in the present study.

The materials analysis have been done following the procedure meticulously as stated above and those peaks of the materials, which do not are considered for identification purposes. X- ray powder diffraction method is undoubtedly the most widely used technique for identification and characterization of polymers. XRD is the most direct standard and non-destructive technique for the identification of the crystalline materials. The distances between planes of atoms that constitute the sample can be

measured and provide a characteristic set of data corresponding to the chemical composition of the material. Comparison against standard reference patterns and measurements allows for identification and analysis of the material. Other advantageous information such as degree of crystallinity and any deviation from ideal composition or the presence of impurities can be obtained [31]. 2.4 A. C. CONDUTIVITY 2.4.1 TWO PROBE METHOD FOR RESISTIVITY

MEASUREMENT DESCRIPTION The Two Probe Method is one of the standards and most commonly used method for the measurement of resistivity of very high resistivity samples like sheets/films of polymers. The resistivity measurement of such samples is beyond the range of Four Probe Method. 2.4.2 DESCRIPTION OF THE EXPERIMENTAL SET-UP TWO PROBES ARRANGEMENT It has two spring load contact probes. These probes move in a pipe and are insulated by Teflon washers. This probes arrangement is mounted in suitable stand, which also hold the sample plate and RTD sensor. The stand also serves as the lid of PID controlled Oven. Teflon

coated leads are provide for connecting with High Voltage Power Supply EHT-11 and Digital Picoammeter DPM-111. With the set-up assuming max. Voltage = 1500V; current 100x10-12 A (max) and

thickness of sample 1mm. The resistivity of the sample could be measured up to 1014 ohm.cm.

Figure 2.8 Two probe setup

Figure 2.9 psm1735 frequency response analyzers

2.4.3 FREQUENCY RESPONSE ANALYSER NumetriQ measures the gain and phase of channel 2 relative to channel 1 using a discrete Fourier transform (DFT) algorithm at the fundamental frequency. The DFT technique can measure phase as well as magnitude and is inherently good at rejecting noise it is much more reliable than measuring the rms at one point relative to another point. The circuit can be characterised by computing the gain and phase at a number of points over a frequency range. This gives results that show the transfer function of the circuit as a graph on the display. The DFT analysis yields two components in phase and quadrature, or a and b values from which the magnitude and phase can be derived. Considering the components at the fundamental frequency: The fundamental in-phase and quadrature values of a periodic waveform, v(), are given by:
2

a1 = 1/2 v().cos() d . (2.4)

0

b1 = 1/2 v().sin() d .. (2.5)

0

For a sampled signal, the formulae become:

i = n-1

a1 = 1/n v[i].cos(2ci/n) ..................................................... (2.6)

i=0 i = n-1

b1 = 1/n v[i].sin(2ci/n) ..................................................... (2.7)

i=0

where n is the number of samples for an integral number of complete cycles of the input waveform, and c is the number of cycles. Having computed the real and quadrature components, the magnitude and phase of each channel can be derived: mag = (a1 2 + b1 = tan-1(b1/a1) The relative gain and phase of the circuitry under test at that particular frequency is derived from the real and quadrature components by vector division: vector gain = (a + jb) {ch2} / (a + jb) {ch1} gain = magnitude (vector gain) phase = tan-1(b/a (vector gain)) The gain is usually quoted in dB: dB = 20 log10(gain) To look at differences in gain from a nominal value, an offset gain can be applied either manually or by pressing ZERO. Offset gain = measured dB offset dB

The filtering is applied to the real and quadrature components individually, rather than the derived magnitude and phase values. This gives superior results as any noise contribution to the components would have random phase and therefore would be reduced by filtering. NumetriQ can operate either in real time mode at a single frequency where the gain and phase are filtered and updated on the display; or it can sweep a range of frequencies and present the results as a table or graphs of gain and phase. The frequency points to be measured are specified with three parameters:

number of steps start frequency end frequency NumetriQ computes a multiplying factor that it applies to the

start frequency for the specified number of steps. Note that due to compound multiplication it is unlikely that the end frequency will be exactly that programmed. The frequency sweep is initiated by the START key, and when completed the data can be viewed as a table or graphs. Following a sweep on a control loop, the gain and phase margins can be computed and displayed on the graph. The window over which the measurements are computed is adjusted to give an

integral number of cycles of the input waveform. In real time mode the results from each window are passed through a digital filter equivalent to a first order RC low pass filter; in sweep mode each result comprises a single window without any filtering unless repeat sweep is selected. The top of the vertical axis for the graph is normally set to be the highest measured value during the sweep. The bottom of the vertical axis is normally either set to the lowest measured value or the result of the highest value less 20dB/decade of frequency. The vertical axis can be fixed to a manual scale using the menus. The ZOOM function can be used to select up to four parameters from the display when in real time mode. It has no function following a sweep. Following a sweep the GRAPH key selects between:

graph of gain v frequency graph of phase v frequency

graph of gain and phase v frequency. Pressing HOME or TRIG restarts the real time measurement at the selected frequency. Although it is most usual to use the NumetriQ generator when performing gain/phase analysis, there may be circumstances where this is impractical, for example measuring across a transformer under load. In this case, turn off the NumetriQ generator (OUT menu)

and the frequency reference for the analysis is measured from channel 1. Provided that the signal is clean enough for an accurate frequency measurement (and for DFT analysis the frequency does need to be accurately known), then the gain and phase can be measured reliably. When using an external frequency reference there can be no sweep function. The electrical conductivity of as synthesized Polypyrrole and copper Polypyrrole were measured on two probe method with PSM1735 Frequency Response Analyzers.

CHAPTER-III RESULDS AND DISSCUSSION

ABSTRACT Polypyrrole (PPy) and Nano copper doped polypyrrole composite (CPPy) was synthesized from chemical oxidation method. The Fourier Transform Infrared (FT-IR) spectra were recorded in the mid range 4000 - 400 cm -1 and powder X-ray diffraction pattern in the region 2=10-80. The electrical conductivity measurements were investigated by two probe method using graphite for ohmic contact. The results obtained by various methods are discussed in detail.

3.1 INTRODUCTION Polypyrrole (PPy) and Nano copper doped polypyrrole composite (CPPy) is one of the most promising conducting polymers because of its high conducting nature, stability and ease of synthesis. In earlier part has been discussed synthesis of conducting PPy and CPPy. The synthesized samples were subjected to FT-IR analysis and XRD studies. The main characteristic peaks of the PPy are assigned available literature. X-ray diffraction (XRD) is a highly developed and documented technique that is widely used to identify crystalline materials. It can provide quantitative information about the chemical composition of a sample, containing different crystalline phase. Crystallographic

identification of the phases of synthesized sample was accomplished by comparing the experimental XRD patterns to standards compiled by JCPDS. The conductivity of both the samples was investigated by two probe method using graphite for ohmic contact. The conductivity of CPPy increased.

3.1.1 FT-IR analysis Table-3.1 FT-IR absorption frequencies [cm-1] and relative intensities of PPy and CPPy Samples (Freq. cm-1) PPy 3420(VS) -1570(S) 1204(VS) 1050(VS) CPPy 3430 (VS) 2924(VS) 1575(VS) 1199(VS) 1044(VS) Tentative vibration assignment (Description) N-H stretching for the nitrogen in the pyrrole rings vibration. Peak is assigned for aromatic C-H stretching vibration PPy ring vibration C-N stretching vibration C-H out of plane bending vibration, C=C-C out of plane deformation vibration, C=C-N out of plane deformation vibration C-H out of plane bending vibration, C=C-C in plane deformation vibration, C=C-N in plane deformation vibration C-H wagging vibration C-H out of plane bending C-H outer bending vibrations

880(S)

--

----

927(M) 791(M) 668(M)

Figure. 3.1 FT-IR spectrum of the pure Polypyrrole

The FT-IR spectra of as synthesized PPy and CPPy are shown in the Figures 3.1 and 3.2. The absorption peaks observed in the spectra with their relative intensity and the corresponding tentative vibrational assignments are given in the Table 3.1. The broad peak occurring at 3420 cm-1 in PPy is attributed to the N-H stretch and shift to the 3430 cm-1 in CPPy. The vibration peak at

Figure 3.2 FT-IR spectrum of the CPPy

2924 cm-1 is assigned for aromatic C-H stretching in CPPy [32]. The appearance of strong band around 1570 cm-1 is due to Polypyrrole ring vibration in PPy and shifts into the 1575 cm -1 at CPPy. The very strong band around in the range of 1204 cm-1, at PPy, is due to C-N stretching vibration, and shifts to the 1199 cm-1, in CPPy [34]. A very strong band of 1050 cm-1 in PPy and shifts to the 1044 cm -1 CPPy are found which is due to the presence of C-H out of plane bending and C=C-C out of plane deformation. A medium band around 927 cm-1 is due to C-H wagging vibration, within CPPy. The presence of 880 cm -1 frequency at PPy is due to C-H out of plane bending vibration, C=C-C in plane deformation vibration, and C=C-N in plane deformation vibration [32]. The frequency of 791 cm-1 is due to C-H out of plane bending and it is medium band. The appearance of absorption medium band at 668 cm -1 in CPPy of the study indicates the presence to C-H outer bending vibrations [34]. The very strong bonds in the range 3420 cm -1 Shift higher to 3430 cm-1. This is due to increase in chain length of the polymer. The very strong bands below the range 1204 cm-1 shifted lower to 1199 cm-1 and 1050 cm-1 shifted lower to 1044 cm-1 due to input of doping. The frequency of 927 cm -1 in CPPy is due to doping reaction of the metal [33].

3.2 XRD analysis

Figure 3.3 The XRD pattern of the PPy Figure 3.4 The XRD pattern of the CPPy

In Figure 3.3 present X-ray diffraction pattern of PPy .The X-rd spectra showed that the PPy is amorphous in nature. The most intense peak exists at about 23.94. Figure 3.4 present X-ray diffraction pattern of CPPy. The sharp peaks are at about 43.27 and 50.43 , which attributed copper present in PPy matrix. The broad peak at around 23.96 indicates amorphous PPy. The XRD pattern of CPPy indicated as the formation of cubic crystalline phase along with amorphous PPy which is in agreement with the standard JCPDS data. The average crystallite sizes for composite material was estimated using Scherrers formulae given below [34]
D = K / cos

The size was found to be 31 nm.

3.3 Electrical conductivity The frequency dependent electrical conductivities of PPy has given in Figure 3.5. The absolute conductivity for the sample increases as a function of frequency. The a.c. conductivity of PPy has bring into being with the magnitude of 1.11542X10-8 Scm-1 and end with 2.53204X10-5 Scm-1, at corresponding frequency of 100 Hz and 5.1617X106 Hz.

Figure. 3.5 Frequency dependence of conductivity of PPy

Figure. 3.6 Frequency dependence of conductivity of CPPy

The effect of copper content on the electrical conductivity of CPPy is plotted in Figure 3.6. In these plots the lower a.c. conductivity of CPPy has found at 2.29849 X10-6 Scm-1 for corresponding frequency range of 100 Hz. The absolute electrical conductivity of the CPPy increases as a function of frequency. The higher a.c electrical conductivity range of CPPy was obtained at the range of 9.19915

X10-5 Scm-1 for corresponding frequency range of 5.1617X106 Hz. This shift is due to the copper particles are fixed into PPy matrix, and also increasing the inter chain distance, which makes for CPPy has high conductivity. The CPPy had better electrical conductivity than the PPy conducting polymer indicated the role of copper in the sample.

Polypyrrole (PPy) and nano copper doped Polypyrrole composite (CPPy) were synthesized by adopting a facile chemical oxidation method. The as synthesized PPy and CPPy were characterized using powder spectroscopy. The electrical X-ray diffraction and FT-IR conductivity measurements were

investigated by two probe method using graphite for ohmic contact. The powder XRD pattern showed that the PPy and the CPPy are amorphous and the latter case crystalline in nature. The frequency dependent electrical conductivity at room temperature of both of the CPPy were discussed in detail. The achieved results showed that the CPPy had better electrical conductivity than PPy indicated the incorporation of copper in the sample. From the X-ray diffraction study, the doped cooper nano particle is equivalent in the size of 31 nm, in the copper doped polymer composite.

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