Electronic electroactive polymers

Electronic electroactive polymers (EAPs), 22 718. See also Electroactive polymers (EAPs)... 

Figure 18-5 shows the displacement output of the actuator as a function of voltage (Vp p) and relative humidity (%) at 4Hz. At 5 V, it exhibited the maximum displacement of 4.3 mm. This value corresponds to the electric field strength of 0.25 V/pm, which is very low comparing with other electronic electroactive polymers (150 V/pm) (Su et al. 1999). This low actuation voltage is an advantage of the EAPap actuautor. The tip displacement result shows that the displacement increases with the humidity. Normally, there is a decrease in the elastic modulus of paper when the... 

Since model compounds reveal well-defined cyclic voltammograms for the Cr(CNR)g and Ni(CNR)g complexes (21) the origin of the electroinactivity of the polymers is not obvious. A possible explanation (12) is that the ohmic resistance across the interface between the electrode and polymer, due to the absence of ions within the polymer, renders the potentially electroactive groups electrochemically inert, assuming the absence of an electronic conduction path. It is also important to consider that the nature of the electrode surface may influence the type of polymer film obtained. A recent observation which bears on these points is that when one starts with the chromium polymer in the [Cr(CN-[P])6] + state, an electroactive polymer film may be obtained on a glassy carbon electrode. This will constitute the subject of a future paper. 

Modification of electrodes by electroactive polymers has several practical applications. The mediated electron transfer to solution species can be used in electrocatalysis (e.g. oxygen reduction) or electrochemical synthesis. For electroanalysis, preconcentration of analysed species in an ion-exchange film may remarkably increase the sensitivity (cf. Section 2.6.4). Various... 

The above mechanistic aspect of electron transport in electroactive polymer films has been an active and chemically rich research topic (13-18) in polymer coated electrodes. We have called (19) the process "redox conduction", since it is a non-ohmic form of electrical conductivity that is intrinsically different from that in metals or semiconductors. Some of the special characteristics of redox conductivity are non-linear current-voltage relations and a narrow band of conductivity centered around electrode potentials that yield the necessary mixture of oxidized and reduced states of the redox sites in the polymer (mixed valent form). Electron hopping in redox conductivity is obviously also peculiar to polymers whose sites comprise spatially localized electronic states. 

The covalent chemistry of fullerenes has developed very rapidly in the past decade in an effort to modify fuUerene properties for a number of applications such as photovoltaic cells, infrared detectors, optical limiting devices, chemical gas sensors, three-dimensional electroactive polymers, and molecular wires [8, 25, 26, 80-82]. Systematic studies of the redox properties of Cgo derivatives have played a crucial role in the characterization of their unique electronic properties, which lie at the center of these potential applications. Furthermore, electrochemical techniques have been used to synthesize and separate new fullerene derivatives and their isomers as well as to prepare fullerene containing thin films and polymers. In this section, to facilitate discussion of their redox properties, Cgo derivatives have been classified in three groups on the basis of the type of attachment of the addend to the fullerene. In group one, the addends are attached via single bonds to the Cgo surface as shown in Fig. 6(a) and are referred to as singly bonded functionalized derivatives. The group includes... 

An enormous number of polymers have been used to prepare chemically modified electrodes. Some examples are given in Table 13.2 Albery and Hillman provide a more extensive list [8]. As indicated in Table 13.2, these polymers can be divided into three general categories—redox polymers, ion-exchange and coordination polymers, and electronically conductive polymers. Redox polymers are polymers that contain electroactive functionalities either within the main polymer chain or in side groups pendant to this chain. The quintessential example is poly(vinylferrocene) (Table 13.2). The ferrocene groups attached to the polymer chain are the electroactive functionality. If fer-... 

The third class of polymers used to prepare chemically modified electrodes is the electronically conductive polymers [25]. The polymer chains in this family of materials are themselves electroactive. For example, the polymer redox reaction for polypyrrole (Table 13.2) can be written as follows ... 

Polymer films can also be electropolymerized directly onto the electrode surface. For example, Abruna et al. have shown that vinylpyridine and vinyl-bipyridine complexes of various metal ions can be electropolymerized to yield polymer films on the electrode surface that contain the electroactive metal complex (see Table 13.2) [27]. The electronically conductive polymers (Table 13.2) can also be electrosynthesized from the corresponding monomer. Again, a polymer film that coats the electrode surface is obtained [25]. Electropolymerized films have also been obtained from styrenic, phenolic, and vinyl monomers. 

The modification of electrode surfaces with electroactive polymer films provides a means to control interfacial characteristics. With such a capability, one can envisage numerous possible applications, in areas as diverse as electronic devices, sensors, electrocatalysis, energy conversion and storage, electronic displays, and reference electrode systems [1, 2]. With these applications in view, a wide variety of electroactive polymeric materials have been investigated. These include both redox polymers (by which we imply polymers with discrete redox entities distributed along the polymer spine) and conducting polymers (by which we imply polymers with delocalised charge centres on the polymer spine). 

First we review processes that ordinarily accompany the redox switching of an electroactive polymer. The key step is coupled electron/ion transfer, which converts one or more reduced forms of the polymer to one or more oxidized forms of the polymer. Solvent and neutral species transfers and polymer structural changes (reconfigurations or coordination state changes) accompany the switching process under permselective conditions. Under nonpermselective conditions, salt transfer also occurs [12]. 

A key issue in the redox switching of electroactive polymers relates to the value of the potential at which coupled electron/ion transfer occurs. The importance of this issue is illustrated in Fig. 13.3. The six cubes in... 

It has been shown that electroactive polymer films on electrodes can mediate electron transfer for metal deposition (9-11). Haushalter and Krause (5) have described the treatment of PMDA-ODA films with highly reactive Zintl complexes (e.g., Sn9 4, SnTe4 4) to yield an intercalated material able to reduce ions of platinum, palladium and silver at the film surface. Mazur et al., (12) reported the deposition of conductive Ag, Cu, and Au metal interlayers within a PMDA-ODA film by electrochemical reduction. 

This paper describes a new seeding process for electroless metallization of polyimides and other electroactive polymers. Polyimide films can be reduced electrochemically at an electrode surface or by contact with an appropriate reducing agent in an electrolyte solution. In the latter case, only the outer surface of the film undergoes reduction. Once the polyimide surface is reduced it then can mediate electron transfer to metal ions or metal complexes in solution causing metal to be deposited at the surface with concurrent reoxidation of the polyimide. 

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