Conducting polymers basic properties

The text covers all relevant aspects of PEDOT beginning with a historical view on conducting polymers and polythiophenes, in particular. The story continues by describing the invenhon of PEDOT based on the development of the suitable monomer EDOT and subsequent important polymerization routes to the conducting polymer. The properties of PEDOT depend on counterions, which led to the development of PEDOTPSS, or poly(3,4-ethyl-enedioxythiophene) poly(styrenesulfonate), dispersions, which is the basic form of the commercial product. In the second part of the book, important applications in electronics and organic electronics concomitant with technical and commercial aspects are extensively described. 

Since one of the main chemical and technological problems of conducting polymers is their low stability for long-term applications, and since storage capacity is a quantification of the basic property of these... 

However, despite this lack of a basic understanding of the electrochemistry of these materials, much progress has been made in characterizing polymerization mechanisms, degradation processes, transport properties, and the mediation of the electrochemistry of species in solution. These advances have facilitated the development of numerous applications of conducting polymers, and so it can be anticipated that interest in their electrochemistry will remain high. 

Besides synthesis, current basic research on conducting polymers is concentrated on structural analysis. Structural parameters — e.g. regularity and homogeneity of chain structures, but also chain length — play an important role in our understanding of the properties of such materials. Research on electropolymerized polymers has concentrated on polypyrrole and polythiophene in particular and, more recently, on polyaniline as well, while of the chemically produced materials polyacetylene stih attracts greatest interest. Spectroscopic methods have proved particularly suitable for characterizing structural properties These comprise surface techniques such as XPS, AES or ATR, on the one hand, and the usual methods of structural analysis, such as NMR, ESR and X-ray diffraction techniques, on the other hand. 

Some of the most important applications for conducting polymers which might show at least some commercial viability in the near future are listed in Table 3. The list is by no means complete, and is growing all the time. However, one should not expect fundamental progress in practical applications until basic research on conducting polymers moves beyond the stage of trial and error, and develops concepts to obtain quantitative information about molecular structures and properties, on the one hand, and the resultant material properties on the other hand. 

A basic property of all conducting polymers is the conjugation of the chain-linked electroactive monomeric units, that is, the monomers interact via a jt-electron system. In this respect, they are fundamentally different from redox polymers. Although redox polymers also contain electroactive groups, the polymer backbone is not conjugated and the interaction between the isolated redox counters is weak. Consequently, redox polymers are nonconductors [17]. They will not be discussed in this context. 

The blending of two or more polymers is frequently used to try to combine the separate desirable properties of each system rather than trying to develop one system with all the properties. In the case of PEMs, this has led to the blending of proton-conducting polymers with non-ionic polymers, low lEC polymers, or polymer-containing basic moieties, particularly for DMFC applications in order to decrease MeOH crossover. These different types of blends will be briefly discussed next. 

In this chapter we will attempt to provide a brief but illustrative description of the various aspects of the research and technology of conducting polymers. To appreciate fully the diverse range of operations that these materials may fulfil, it is crucial to understand their basic properties. Therefore, particular attention will be devoted here to the description of the mechanism of charge transport and to the characteristics of the electrodic processes in electrochemical cells. 

In addition to new ion conducting strategies, basic polymer characterization measurements must be identified and used to more advantage in the development of new PEMs. Issues of molecular weight, mechanical properties, and chemical/physical degra-dative mechanisms need to be addressed with much more rigor than they have been in the past. 

In Chapter 1 we explain the motivation and basic concepts of electrodeposition from ionic liquids. In Chapter 2 an introduction to the principles of ionic liquids synthesis is provided as background for those who may be using these materials for the first time. While most of the ionic liquids discussed in this book are available from commercial sources it is important that the reader is aware of the synthetic methods so that impurity issues are clearly understood. Nonetheless, since a comprehensive summary is beyond the scope of this book the reader is referred for more details to the second edition of Ionic Liquids in Synthesis, edited by Peter Wasserscheid and Tom Welton. Chapter 3 summarizes the physical properties of ionic liquids, and in Chapter 4 selected electrodeposition results are presented. Chapter 4 also highlights some of the troublesome aspects of ionic liquid use. One might expect that with a decomposition potential down to -3 V vs. NHE all available elements could be deposited unfortunately, the situation is not as simple as that and the deposition of tantalum is discussed as an example of the issues. In Chapters 5 to 7 the electrodeposition of alloys is reviewed, together with the deposition of semiconductors and conducting polymers. The deposition of conducting polymers... 

The optical properties of conducting polymers are important to the development of an understanding of the basic electronic structure of the material. These and other problems were described in various books and review papers [90-93]. Raman spectroscopy is also an ideal tool for predicting many important electronic properties of molecular materials, organic conductors, and superconductors as well as for understanding their different physical properties, since it is a nondestructive tool, which can be used in situ and with spatial resolution as good as 1 xm. 

After establishing the basic principles of polymer chemistry, the book pinpoints the dynamic properties of the more useful conducting polymers, such as polypyrroles, polythiophenes, and polyanilines. It then demonstrates how the control of these properties enables cutting-edge applications in nano, biomedicine, and MEMS as well as sensors and artificial muscles. Subsequent chapters discuss the effect of nanodimensionai control on the resultant properties. 

Studies of an isolated chain in solution may appear as very fundamental work. Generally, the physics of the solid state is basically the theoretical framework used to describe the properties of conducting polymers. The material is considered as a semiconductor or a conductor of low dimensionality with non-linear electronic excitations and states in the gap which are interpreted with a more or less refined one-dimensional or two-dimensional hamiltonian [1-4]. 

The development of conductive polymers, since 1977, has been mainly devoted to fundamental physics and basic chemistry for a better understanding of these materials. For that purpose, microwave properties have been mainly studied for information about their transport properties, particularly with frequency or temperature variations. 

Nowadays a promising way to control the bulk polymer properties, such as conductivity, processability, thermal, and mechanical stabihties, is through the organization of the polymeric chains on the nanometer scale [7-9]. The first approach used to achieve this goal was the synthesis of conducting polymers in cavities of porous hosts. Commonly named nanocomposites, these materials have two or more different components on the nanoscale, and can show catalytic, electronic, magnetic, and optical properties better than those of the individual phases. The basic reason for this synergism is still not fully understood, but it is considered that confinement and electrostatic interactions between the components play an important role. 

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