1.

Introduction to Polyaniline:
Polyaniline (PANI) is a conducting polymer of the semi-flexible rod polymer family. Although the compound itself was discovered over 150 years ago, only since the early 1980s has polyaniline captured the intense attention of the scientific community. This interest is due to the rediscovery of high electrical conductivity. Amongst the family of conducting polymers and organic semiconductors, polyaniline has many attractive processing properties. Because of its rich chemistry, polyaniline is one of the most studied conducting polymers of the past 50 years. Polyaniline (PANI) exists in a variety of forms that differ in chemical and physical properties [14]. The most common green protonated emeraldine has conductivity on a semiconductor level of the order of 100 S cm-1 , many orders of magnitude higher than that of common polymers (<10-9 S cm-1) but lower than that of typical metals (>104 S cm-1) Protonated PANI, (e.g., PANI hydrochloride) converts to a nonconducting blue emeraldine base when treated with ammonium hydroxide.

1 Polyaniline (emeraldine) salt is deprotonated in the alkaline medium to polyaniline (emeraldine) base. A-1 is an arbitrary anion, e.g., chloride.

1.1 Synthesis and Properties:

Polymerized from the inexpensive aniline monomer, polyaniline can be found in one of three idealized oxidation states:

leucoemeraldine white/clear & colourless (C6H4NH)n emeraldine green for the emeraldine salt, blue for the emeraldine base ({[C6H4NH]2[C6H4N]2}n) (per)nigraniline blue/violet (C6H4N)n

In above figure, x equals half the degree of polymerization (DP). Leucoemeraldine with n = 1, m = 0 is the fully reduced state. Pernigraniline is the fully oxidized state (n = 0, m = 1) with imine links instead of amine links. Studies have shown that most

forms of polyaniline are one of the three states or physical mixtures of these components. The emeraldine (n = m = 0.5) form of polyaniline, often referred to as emeraldine base (EB), is neutral, if doped (protonated) it is called emeraldine salt (ES), with the imine nitrogens protonated by an acid. Protonation helps to delocalize the otherwise trapped diiminoquinone-diaminobenzene state. Emeraldine base is regarded as the most useful form of polyaniline due to its high stability at room temperature and the fact that, upon doping with acid, the resulting emeraldine salt form of polyaniline is highly electrically conducting. Leucoemeraldine and pernigraniline are poor conductors, even when doped with an acid. The efficient polymerization of aniline is achieved only in an acidic medium, where aniline exists as an anilinium cation. A variety of inorganic and organic acids of different concentration have been used in the syntheses of PANI; the resulting PANI, protonated with various acids, differs in solubility, conductivity, and stability. The colour change associated with polyaniline in different oxidation states can be used in sensors and electrochromic devices. Although colour is useful, the best method for making a polyaniline sensor is arguably to take advantage of the dramatic changes in electrical conductivity between the different oxidation states or doping levels. Treatment of emeraldine with acids increases the electrical conductivity by ten orders of magnitude. The same material can be prepared by oxidation of leucoemeraldine. The handling of solid aniline salt is preferred to liquid aniline from the point of view of toxic hazards. To minimize the presence of residual aniline and to obtain the best yield of PANI, the stoichiometric peroxydisulfate/aniline ratio 1.25 is recommended Polyaniline is nobler than copper and slightly less noble than silver which is the basis for its broad use in printed circuit board manufacturing (as a final finish) and in corrosion protection.

1.1.1 Synthesis
Although the synthetic methods to produce polyaniline are quite simple, the mechanism of polymerization is probably complex. The formation of leucoemeraldine can be described as follows, where [O] is a generic oxidant: n C6H5NH2 + [O] [C6H4NH]n + H2O The most common oxidant is ammonium peroxodisulfate. The components are each dissolved in 1 M hydrochloric acid (other acids can be used), and the two solutions slowly combined. The reaction is very exothermic. The polymer precipitates as an unstable dispersion with micrometer-scale particulates. is prepared by oxidation of the emeraldine base, one typical oxidant being mcpba: {[C6H4NH]2[C6H4N]2}n + RCO3H [C6H4N]n + H2O + RCO2H

1.1.2 Meta-Chloroperoxybenzoic acid (mCPBA):

Meta-Chloroperoxybenzoic acid (mCPBA) is a peroxycarboxylic acid used widely as an oxidant inorganic synthesis. mCPBA is often preferred to other peroxy acids because of its relative ease of handling. The main areas of use are the conversion of ketones to esters (Baeyer-Villiger oxidation), epoxidation of alkenes (Prilezhaev reaction), conversion of silyl enol ethers to silyl -hydroxy ketones (Rubottom oxidation), oxidation of sulfides to sulfoxides and sulfones, and oxidation of amines to produce amine oxides. mCPBA is a strong oxidizing agent that may cause fire upon contact with flammable material.

1.1.3 Processing
The synthesis of polyaniline nanostructures is facile. Using special polymerisation procedures and surfactant dopants, the polyaniline powder can be recovered after polymerisation can be made dispersible and hence useful for practical applications. Bulk synthesis of polyaniline nanofibers has led to a highly scalable and commercially applicable form of polyaniline that has been researched extensively since their discovery in 2002. A two stage model for the formation of emeraldine base is proposed. In the first stage of the reaction the pernigraniline PS salt oxidation state is formed. In the second stage pernigraniline is reduced to the emeraldine salt as aniline monomer gets oxidized to the radical cation. In the third stage this radical cation couples with ES salt. This process can be followed by light scattering analysis which allows the determination of the absolute molar mass. Polyaniline is typically produced in the form of long-chain polymer aggregates, surfactant (or dopant) stabilized nanoparticle dispersions, or stabilizer-free nanofiber dispersions depending on the supplier and synthetic route. Surfactant or dopant stabilized polyaniline dispersions have been available for commercial sale since the late 1990s.

1.2 Characteristics of Polyaniline:

Polyaniline of higher molar mass is produced at lower reaction temperatures [1921], but the electrical properties of the polymer are not greatly influenced by molar mass. We have selected ambient temperature for the present study while being aware of the ambiguous definition of such conditions. As temperature increases during the reaction, this increase being dependent on the surface-to-volume ratio of the experimental set-up, the precise control of temperature was not attempted. The effect of reaction temperature on the conductivity of PANI was assessed and is discussed. Polymerization in the presence of excess 1 M HCl, i.e., at higher acidity,

proceeds faster than in its absence and yields a product of enhanced conductivity. A still higher concentration of HCl above 2 M concentration leads to the reduction of conductivity. The rate of aniline oxidation depends on the presence of various impurities and additives that may promote the progress of oxidation . Distilled water was used; the potential presence of iron(III) ions in tap water may accelerate the aniline oxidation. Washing the PANI precipitate with 0.2 M HCl removes residual monomer, oxidant, and its decomposition products. The treatment with hydrochloric acid solution provides a more uniform protonation of PANI with chloride counterions, although some of the sulfate or hydrogensulfate anions from the decomposition of peroxydisulfate also participate as counterions. A final washing with acetone removes low-molecular-weight organic intermediates and oligomers. It also prevents the aggregation of PANI precipitate during drying, and the product is obtained as a fine powder. The greenish PANI (emeraldine) hydrochloride was stored in polyethylene containers.

1.3 Properties of Polyaniline: 1.3.1 Polymerization yield:

Based on the stoichiometry of the oxidation reaction, the polymerization of 1.0 g aniline hydrochloride yields theoretically 0.840 g of PANI hydrochloride. The apparent yield of PANI hydrochloride under the standard polymerization conditions approaches 100 % within the experimental error. The elemental analysis indicates that more bulky counterions, like sulphate or hydrogensulfate anions, may participate in the protonation of PANI along with the chloride anions. This would lead to an apparent increase in the yield. The yield is higher when the polymerizations are carried out at reduced temperature. Increased acidity of the reaction medium leads, on the other hand, to its reduction. Elemental composition of PANI

0.2 M aniline hydrochloride oxidized with 0.25 M ammonium peroxydisulfate at room temperature and in the presence of excess HCl as specified.

1.3.2 Elemental composition:

The differences in elemental composition of PANI prepared under standard conditions and in an excess of 1 M HCl are small . The results of elemental analysis clearly indicate the presence of oxygen in PANI (12.5 % in hydrochloride and 5.1 % in the base). This may be due to bound water molecules or, more likely, to partial oxidation of the PANI chains. The structure depicted in figure is thus idealized. The presence of sulfur in hydrochlorides is partly due to the residual sulfate counterions produced by the reduction of peroxydisulfate during polymerization. Hydrochloric acid is removed from the aniline hydrochloride after deprotonation with ammonium hydroxide . The relative participation of carbon and nitrogen in PANI base is thus increased, at the expense of the lower content of chlorine. We can see that some chlorine remains in PANI base even after deprotonation, indicating a partial benzene-ring substitution with chlorine. The content of covalently bound chlorine is higher when the oxidation of aniline hydrochloride takes place in excess HCl . Partial sulfonation of benzene rings is responsible for the presence of sulfur in the PANI base.

1.4 Standard preparation of Polyaniline:

Oxidize 0.2 M aniline hydrochloride with 0.25 M ammonium peroxydisulfate in aqueous medium. Aniline hydrochloride (purum; 2.59 g, 20 mmol) was dissolved in distilled water in a volumetric flask to 50 mL of solution. Ammonium peroxydisulfate (purum; 5.71 g, 25 mmol) was dissolved in water also to 50 mL of solution. Both solutions were kept for 1 h at room temperature (~1824 C), then mixed in a beaker, briefly stirred, and left at rest to polymerize. Next day, the PANI precipitate was collected on a filter, washed with three 100-mL portions of 0.2 M HCl, and similarly with acetone. Polyaniline (emeraldine) hydrochloride powder was dried in air and then in vacuo at 60 C. Polyanilines prepared under these reaction and processing conditions are further referred to as standard samples. Additional polymerizations were carried out in an ice bath at 02 C. The acidity of the reaction mixture was increased by replacing 10 mL of water with 10 mL of 10 M HCl in several experiments.

1.5 Applications:
Polyaniline and the other conducting polymers such as polythiophene, polypyrrole, and PEDOT/PSS have potential for applications due to their light weight, conductivity, mechanical flexibility and low cost. Polyaniline is especially attractive because it is relatively inexpensive, has three distinct oxidation states with different colors and has an acid/base doping response. This latter property makes polyaniline an attractive for acid/base chemical vapor sensors. The different colours, charges and conformations of the multiple oxidation states also make the material promising for applications such as actuators, super capacitors and electrochromics. They are suitable for manufacture of electrically conducting yarns, antistatic coatings, electromagnetic shielding, and flexible electrodes.

Attractive fields for current and potential utilization of polyaniline is in antistatic, charge dissipation or electrostatic dispersive (ESD) coatings and blends, electromagnetic (EMI), anti-corrosive coatings, hole injection layers, transparent conductors, actuators, chemical vapour and solution based sensors, electrochromic coatings (for colour change windows, mirrors etc.), PEDOT-PSS replacements, toxic metal recovery, catalysis, fuel cells and active electronic components such as for non-volatile memory. Currently, the major applications are printed circuit board manufacturing (final finishes, used in millions of m every year), antistatic and ESD coatings, and corrosion protection. Polyaniline is commercially available from Ormecon which with Enthone (CooksonElectronics), Eeonyx, Crosslink. recently merged

1.5.1 Melt and Solution Processable Material:

Polyaniline based compositions can be processed using conventional techniques such as blow and injection moulding, extrusion, calendering, film casting, and fibre spinning. These compositions withstand temperatures as high as 230-240C for short periods of time (5-10 minutes) without significant change in electrical properties, and can be melt blended with many commodity polymers. Selected industrial solvents can be used for solution processing neat polyaniline compositions.

1.5.2 Conductive Blends with Many Commodity Polymers

Electrically conductive polyaniline based blends with commodity polymers can be produced by using common solution and melt processing techniques. Examples of commodity polymers are polyethylene, polypropylene, polystyrene, PVC, phenolformaldehyde resins, and different types of thermoplastic elastomers. Unlike conventional filled materials, the mechanical properties of these blends are close to those of the insulating matrix polymer.

1.5.3 Function as Processing Aids in Addition to Providing Conductivity

Plasticised polyaniline compositions improve melt processing performance by lowering the melt-viscosity, lowering the processing temperature and shortening the processing time. The improved melt flow properties make, for example injection moulding of complex shapes easier.

1.5.4 Coloured and Transparent Electrically Conductive Products

Electrically conductive, coloured and transparent thin films and coatings, which would otherwise be difficult to achieve with conventional filled materials, can be made using polyaniline based compositions.

1.5.5 Applications using Polyaniline Based Conductive Polymers, Neat Materials, Blends, Compounds and Solutions
Polyaniline based conductive polymers can be used neat, or as blends and compounds with commodity polymers. Several prototype objects and articles have been made of these compounds with polyethylene, polypropylene, polystyrene, soft PVC, poly-(methylmetacrylate), phenol-formaldehyde resins, melamineformaldehyde resins, epoxies, and thermoplastic elastomers. The solution processing properties of polyaniline based conductive polymers make totally new product ideas possible. These include electroactive inks, paints, coatings, and adhesives, electrochromic smart windows, electrically conductive transparent films, and conductive high performance fibres. Solution processing can be carried out using the neat material or a blend.

1.5.6 Electrostatic Discharge (ESD) Protection Materials

One target application of these materials is the protection from ElectroStatic Discharge (ESD). ESD causes problems when handling sensitive electronic components, explosive chemicals or dry powders. The use of, e.g. antistatic materials in specific environments reduce ESD related problems, such as the amount of damaged valuable end products in an assembly line. The controllable conductivity in ESD protection materials is one of the basic benefits of conductive polymer technology.