Polymeric electrodeposits with

Preparation and Characterization of Polymeric Electrodeposits Modified with Dispersed Metallic... 

The reproducibility of the electrodeposition of conducting polymer films has been a very difficult issue. It has long been realized that each laboratory produces a different material and that results from different laboratories are not directly comparable.82 We have experienced reproducibility problems with almost all of the electrochemically polymerized materials used in our work. 

The results presented here seem to indicate that 1) the local order about ruthenium centers in the polymers is essentially unchanged from that in the monomer complex and 2) that the interaction with the electrode surface occurs without appreciable electronic and structural change. This spectroscopic information corroborates previous electrochemical results which showed that redox properties (e.g. as measured by formal potentials) of dissolved species could be transferred from solution to the electrode surface by electrodepositions as polymer films on the electrode. Furthermore, it is apparent that the initiation of polymerization at these surfaces (i.e. growth of up to one monolayer of polymer) involves no gross structural change. 

Similar approach has also been taken by Ferain and Legras [133,137,138] and De Pra et al. [139] to produce nanostructured materials based on the template of the membrane with etched pores. Polycarbonate film was also of use as the base membrane of the template, and micro- and nanopores were formed by precise control of the etching procedure. Their most resent report showed the successful formation of ultrasmall pores and electrodeposited materials of which sizes were as much as 20 nm [139]. Another attractive point of these studies is the deposited materials in the etched pores. Electrochemical polymerization of conjugated polymer materials was demonstrated in these studies, and the nanowires based on polypyrrole or polyaniline were formed with a fairly cylindrical shape reflecting the side wall structure of the etched pores. Figure 10 indicates the shape of the polypyrrole microwires with their dimension changes by the limitation of the thickness of the template. 

A second, equally powerful means to prepare such materials relies on traditional inorganic polymerization tools, most notably sol-gel polymerization.24 25 A number of excellent reviews have appeared on this subject as well.5,12,17 In sol-gel processing, the functional monomer [i.e., an organoalkoxysilane such as 3-aminopropyltrimethox-ysilane (APTMS)] is combined with the cross-linking agent [i.e., a tetrafunctional alkoxysilane such as tetramethoxysilane (TMOS) or tetraethoxysilane (TEOS)], a catalyst (such as hydrochloric acid or ammonia), and the template molecule. The resultant sol can be left to gel to form a monolith, which can then be dried, sieved, and extensively washed to remove the template. Alternatively, the sol can be spin coated, dip coated, or electrodeposited on a surface to yield a thin film, which can be subsequently washed with a solvent to remove the template and yield the imprinted cavities. 

Nanomold Replication A physical mold is produced that has nanoscales on the order of tens or a few hundred nanometers. To achieve such fine features with precision and repeatability, electrodeposition is used to produce the molds, otherwise referred to as a nanostamp [194], The stamp is then use as a master stamp to duplicate the image or object by casting or embossing the polymeric material. 

The design of the interstices filling in colloidal crystals with appropriate media and subsequently fluid-solid transformation is central to the whole synthesis. Fluid precursors in the voids of crystal arrays can solidify by polymerization and sol-gel hydrolysis. More recently, many methods have been developed including salt precipitation and chemical conversion, chemical vapor deposition (CVD), spraying techniques (spray pyrolysis, ion spraying, and laser spraying), nanocrystal deposition and sintering, oxide and salt reduction, electrodeposition, and electroless deposition. 

Oxide, flouride, and polymeric films, as well as certain others, are used as protective coatings for HTSC materials (for example, see [505]). The electrodeposition of conducting polymers such as polypyrrole [433,491, 493, 506], polythiophene and its derivatives [493, 507], and polyaniline [478] is the most effective process. Anodic electropolymerization in acetonitrile solutions proceeds without any degradation of the HTSC substrate and ensures continuous and uniform coatings. Apparently, this method is promising not only for the fabrication of compositions with special properties based on HTSC [50, 28,295] as mentioned above, but also for the creation of junctions with special characteristics [507]. 

The processability of certain CEPs has been utilized in the construction of microsystems, particularly miniature sensor systems. For example, simply dip-coating connecting platinum wires with a polyaniline formulation produces a useful humidity sensor.133 CEPs can also be screen-printed or ink-jet-printed to produce the complex shapes needed for various devices. Electrodeposition of CEPs is also a popular processing method, and this technique is compatible with conventional MEMS fabrication, where lithography and etching can be used to prepattern metal electrodes. Subsequent deposition of CEP by electrochemical polymerization produces the CEP microdevice.129... 

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