Conducting polymers oxidation

The flow of a current through an electrochemical system demonstrates the main difference between material based on conducting polymers and all the other industrial nonconducting polymers conducting polymers oxidize and reduce electrochemically in a reverse way, as do metals or redox couples ... 

Intercalation of electroactive polymers such as polyaniline and polypyrrole in mica-type layered silicates leads to metal-insulator nanocomposites. The conductivity of these nanocomposites in the form of films is highly anisotropic, with the in-plane conductivity 10 to 10 times higher than the conductivity in the direction perpendicular to the film. Conductive polymer/oxide bronze nanocomposites have been prepared by intercalating polythiophene in V2O5 layered phase, which is analogous to clays. °° Studies of these composites are expected not only to provide a fundamental understanding of the conduction mechanism in the polymers, but also to lead to diverse electrical and optical properties. 

M. G. Kanatzidis, C-G. Wu, H. O. Marcy, D. C. DeGroot, and C. R. Kannewurf, Conductive polymer/oxide bronze nanocomposites. Intercalated polythiophene in V2O5 xerogels, Chem. Mater., 2, 222-224 (1990). 

It was first thought that the conducting polymer oxidized the metal and initiated the passivation process. Later it was assumed that oxygen reoxidized the reduced ICR... 

In this section blends or composites obtained by the combination of two conductive polymers are discussed. Frequently, one conductive polymer is used as working electrode and is electrochemically coated with another conductive polymer. Some examples of conductive copolymers are also given here. Also, the anodic photocurrent generated by the irradiation of an n-type semiconductor can be used to coat with a conductive polymer layer or to form the tracks of a conductive polymer. Oxidation sites in intercalation compounds or in porous solids can be also used to obtain composites with conductive polymers. 

Kanatzidis, Wu C.G., Marcy H.O., DeGroot D.C. and Kannewurf C.R. (1990) "Conductive polymer/oxide bronze nanocomposites.lntercalated polythiophene in V2O5 xerogels" Chem. Mater. 2, 222-24. 

Reversible oxidation and reduction of polymers is commonly used to increase conductivity in these systems. Ions from the electrolyte are usually incorporated into the polymer as part of this process (see Electrically conducting polymers). 

Polypyrroles. Highly stable, flexible films of polypyrrole ate obtained by electrolytic oxidation of the appropriate pyrrole monomers (46). The films are not affected by air and can be heated to 250°C with Htde effect. It is beheved that the pyrrole units remain intact and that linking is by the a-carbons. Copolymerization of pyrrole with /V-methy1pyrro1e yields compositions of varying electrical conductivity, depending on the monomer ratio. Conductivities as high as 10 /(n-m) have been reported (47) (see Electrically conductive polymers). 

Because of the aqueous solubiUty of polyelectrolyte precursor polymers, another method of polymer blend formation is possible. The precursor polymer is co-dissolved with a water-soluble matrix polymer, and films of the blend are cast. With heating, the fully conjugated conducting polymer is generated to form the composite film. This technique has been used for poly(arylene vinylenes) with a variety of water-soluble matrix polymers, including polyacrjiamide, poly(ethylene oxide), polyvinylpyrroHdinone, methylceUulose, and hydroxypropylceUulose (139—141). These blends generally exhibit phase-separated morphologies. 

Electrochemical polymeriza tion of heterocycles is useful in the preparation of conducting composite materials. One technique employed involves the electro-polymerization of pyrrole into a swollen polymer previously deposited on the electrode surface (148—153). This method allows variation of the physical properties of the material by control of the amount of conducting polymer incorporated into the matrix film. If the matrix polymer is an ionomer such as Nation (154—158) it contributes the dopant ion for the oxidized conducting polymer and acts as an effective medium for ion transport during electrochemical switching of the material. 

Electrogenerated conducting polymer films incorporate ions from the electrolyte medium for charge compensation (182). Electrochemical cycling in an electrolyte solution results in sequential doping and undoping of the polymer film. In the case of a -doped polymer, oxidation of the film results in the... 

The changes in the optical absorption spectra of conducting polymers can be monitored using optoelectrochemical techniques. The optical spectmm of a thin polymer film, mounted on a transparent electrode, such as indium tin oxide (ITO) coated glass, is recorded. The cell is fitted with a counter and reference electrode so that the potential at the polymer-coated electrode can be controlled electrochemically. The absorption spectmm is recorded as a function of electrode potential, and the evolution of the polymer s band stmcture can be observed as it changes from insulating to conducting (11). 

An example of an ionically conductive polymer is polyethylene oxide containing LiC104, which is used as a solid phase electrolyte in batteries. 

Figure 13. Schematic presentation of a small segment of polyheteromicrophase SEI (a) and its equivalent circuit (b) A, native oxide film B, LiF or LiCl C, non conducting polymer D, Li2CO, or LiCO, R GB, grain boundary. RA,/ B,RD, ionic resistance of microphase A, B, D. Rc >Rqb charge-transfer resistances at the grain boundary of A to B or A to D, respectively. CA, CB, CD SEI capacitance for each of the particles A to D.

Conducting Polymers Electronically conducting polymers (such as polypyrrole, polythiophene, and polyaniline) have attracted considerable attention due to their ability to switch reversibly between the positively charged conductive state and a neutral, essentially insulating, form and to incorporate and expel anionic species (from and to the surrounding solution), upon oxidation or reduction ... 

Most of the usual conducting polymers have a cross-linked stmcture (Fig. 3), but again they can be electrochemically oxidized and reduced. The electrochemical responses must follow electrochemical models and... 

Later we will describe both oxidation and reduction processes that are in agreement with the electrochemically stimulated conformational relaxation (ESCR) model presented at the end of the chapter. In a neutral state, most of the conducting polymers are an amorphous cross-linked network (Fig. 3). The linear chains between cross-linking points have strong van der Waals intrachain and interchain interactions, giving a compact solid [Fig. 14(a)]. By oxidation of the neutral chains, electrons are extracted from the chains. At the polymer/solution interface, positive radical cations (polarons) accumulate along the polymeric chains. The same density of counter-ions accumulates on the solution side. 

Figure 16. Evolution of the population of the polaronic and bipolaronic bands during polymer oxidation. CB, conducting band, P.B., polaronic band, V.B., valence band, B.P.B., bipolaronic band.

The flow of an anodic current oxidizes the conducting polymer and the film swells. At the polypyrrole/tape interface, electrochemically stimulated conformational changes in the polymer promote an expansion that... 

Figure 20. Artificial muscle under work. In reduction (A) electrons are injected into the polymer chains. Positive charges are annihilated. Counter-ions and water molecules are expelled. The polymer shrinks and compaction stress gradients appear at each point of the interface of the two polymers. The free end of the bilayer describes an angular movement toward the left side. (B) Opposite processes and movements occur under oxidation. (Reprinted from T. F. Otero and J. Rodriguez, in Intrinsically Conducting Polymers An Emerging Technology, M. Aldissi, ed., pp. 179-190, Figs. 1,2. Copyright 1993. Reprinted with kind permission of Kluwer Academic Publishers.)...

Oxidized conducting polymers, or conducting polymer composites can be envisaged as stores of anions or cations, respectively. As stated earlier, these ions can be liberated, under a well-defined control, in a solution. This idea is being developed in order to store ions of pharma-... 

Most of the models developed to describe the electrochemical behavior of the conducting polymers attempt an approach through porous structure, percolation thresholds between oxidized and reduced regions, and changes of phases, including nucleation processes, etc. (see Refs. 93, 94, 176, 177, and references therein). Most of them have been successful in describing some specific behavior of the system, but they fail when the... 

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