Electrodeposition polymers

Recent developments on metal, metal oxide, and conductive polymer electrodeposition for energy device applications... 

In Chapter 3, by Shaigan, electrodeposition for electrochemical conversion and storage devices is presented. This chapter discusses the latest developments on metal, metal oxide, and conductive polymer electrodeposition processes developed and studied for the applications in the fields of fuel cells, batteries, and capacitors. The importance of electrodeposited materials, which are used or may have the future potential applications in the energy conversion or storage, is clearly shown. 

A remarkable recent example of the influence of electropolymerization temperature on the properties of PAn products is observed in the potentiostatic polymerization of aniline in the presence of chiral (+)-HCSA to give optically active PAn/(+)-HCSA films. The CD spectra of the polymers electrodeposited at < 25°C were inverted compared to the spectra of analogous emeraldine salts deposited at > 40°C, indicating an inversion of the preferred helical hand for PAn chains.38 The observations may be rationalized in terms of a temperature-induced interconversion between two initially (kinetically) formed diastereomeric PAn products. 

Electrochemical polymerization is a fast and simple, widely used method to synthesize different conducting polymers. Electrodeposition enables film formation on surfaces with complicated patterns as well as control of film thickness [5]. Furthermore, the subsequent growth of the polymer film and the charging reactions can be followed in situ [6]. Parameters such as solvent media, electrolyte, electrochemical method used for polymerization and monomer material, all have a profound effect on film morphology, charge transfer and transport properties. Different from the powdery products prepared through chemical approaches, this method enables an easy one-step deposition of the film directly at the surface of the electrode substrate that can be further applied for electrochemical purposes. 

One can also mention the case of composites-based conducting polymers electrodeposited and characterized on anodes of platinum- or carbon black- filled polypropylene from a stirred electrolyte with dispersed copper phthalocyanine. The electrolytic solution contained, besides the solvent (water or acetonitrile), the monomer (pyrrole or thiophene) and a supporting electrolyte. Patterned thin films were obtained from phthalocyanine derivatives, as reported in the case of (2,3,9,10,16,17,23,24-oktakis((2-benzyloxy)ethoxy)phthalocyaninato) copper . Such films were prepared by means of capillary flow of chloroform solutions into micrometer-dimension hydrophobic/hydrophilic channels initially created by a combination of microcontact printing of octadecylmercaptan (Cig-SH) layers on gold electrodes. These latter gave birth to a hydrophobic channel bottom while oxidative electropolymerization of w-aminophenol (at pH 4) led to hydrophilic channel walls. 

Electrodeposition. Electro deposition, the most important of the unit processes in electrorefining, is performed in lead- or plastic-lined concrete cells or, more recently, in polymer—concrete electrolytic cells. A refinery having an aimual production of 175,000 t might have as many as 1250 cells in the tank house. The cells are multiply coimected such that anodes and cathodes are placed alternately and coimected in parallel. Each cell is a separate unit and electrically coimected to adjacent cells by a bus bar. 

Conducting polymer composites have also been formed by co-electrodeposition of matrix polymer during electrochemical polymerization. Because both components of the composite are deposited simultaneously, a homogenous film is obtained. This technique has been utilized for both neutral thermoplastics such as poly(vinyl chloride) (159), as well as for a large variety of polyelectrolytes (64—68, 159—165). When the matrix polymer is a polyelectrolyte, it serves as the dopant species for the conducting polymer, so there is an intimate mixing of the polymer chains and the system can be appropriately termed a molecular composite. 

Hundreds of baths exist for electrodeposition of gold and its alloys . The latter are more wear resistant, so better for contacts . Polymers incorporated in cyanide-bath deposits affect wear and contact resistance . 

Industry, however, favours electrodeposited palladium-nickel alloy since it is cheaper than palladium, harder and less prone to cracking, fingerprinting and formation of polymer films Its wear resistance is poor, so it is usually given a thin topcoat of hard (sometimes, soft) gold. ... 

Zinc is electrodeposited from the sodium zincate electrolyte during charge. As in the zinc/bromine battery, two separate electrolytes loops ("posilyte" and "nega-lyte") are required. The only difference is the quality of the separator The zinc/ bromine system works with a microporous foil made from sintered polymer powder, but the zinc/ferricyanide battery needs a cation exchange membrane in order to obtain acceptable coulombic efficiencies. The occasional transfer of solid sodium ferrocya-nide from the negative to the positive tank, to correct for the slow transport of complex cyanide through the membrane, is proposed [54],... 

Although the mechanisms discussed above are still topics of debate, it is now firmly established that the electrodeposition of conducting polymers proceeds via some kind of nucleation and phase-growth mechanism, akin to the electrodeposition of metals.56,72-74 Both cyclic voltammetry and potential step techniques have been widely used to investigate these processes, and the electrochemical observations have been supported by various types of spectroscopy62,75-78 and microscopy.78-80... 

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. 

Takahashi et al. [220] first reported the formation of Bi-Te alloy films with varying chemical composition by means of cathodic electrodeposition from aqueous nitric acid solutions (pH 1.0-0.7) containing Bi(N03)3 and Te02. The electrodeposition took place on Ti sheets at room temperature under diffusion-limited conditions for both components. In a subsequent work [221], it was noted that the use of the Bi-EDTA complex in the electrolyte would improve the results, since Bi " is easily converted into the hydrolysis product, Bi(OH)3, a hydrous polymer, thus impairing the reproducibility of electrodeposition. The as-produced films were found to consist of mixtures of Te and several Bi-Te alloy compounds, such as Bi2Tc3, Bi2+xTe3 x, Bi Tee, and BiTe. Preparation of both n- and p-type Bi2Te3 was reported in this and related works [222]. 

Within the scope of thermoelectric nanostructures, Sima et al. [161] prepared nanorod (fibril) and microtube (tubule) arrays of PbSei. , Tej by potentiostatic electrodeposition from nitric acid solutions of Pb(N03)2, H2Se03, and Te02, using a 30 fim thick polycarbonate track-etch membrane, with pores 100-2,000 nm in diameter, as template (Cu supported). After electrodeposition the polymer membrane was dissolved in CH2CI2. Solid rods were obtained in membranes with small pores, and hollow tubes in those with large pores. The formation of microtubes rather than nanorods in the larger pores was attributed to the higher deposition current. 

Electrochemical oscillation during the Cu-Sn alloy electrodeposition reaction was first reported by Survila et al. [33]. They found the oscillation in the course of studies of the electrochemical formation of Cu-Sn alloy from an acidic solution containing a hydrosoluble polymer (Laprol 2402C) as a brightening agent, though the mechanism of the oscillatory instability was not studied. We also studied the oscillation system and revealed that a layered nanostructure is formed in synchronization with the oscillation in a self-organizational manner [25, 26]. 

Folonari, C. V. and Garlasco, R., Ion-paired HPLC characterization of cathodic electrodeposition paint polymers, /. Chromatogr. Sci., 19, 639, 1981. 

Building on the success of 37 in recognition of barium ions, this unit was incorporated into monomer units derived from pyrrole and EDOT (42, 43 and 44).113 Electrodes modified by the corresponding electrodeposited polymers showed an electrochemical response in the presence of Ba2+ which was similar to 37, albeit of a lesser magnitude. 

Manufacture of Printed Wiring Boards. Printed wiring boards, or printed circuit boards, are usually thin flat panels than contain one or multiple layers of thin copper patterns that interconnect the various electronic components (e.g. integrated circuit chips, connectors, resistors) that are attached to the boards. These panels are present in almost every consumer electronic product and automobile sold today. The various photopolymer products used to manufacture the printed wiring boards include film resists, electroless plating resists (23), liquid resists, electrodeposited resists (24), solder masks (25), laser exposed photoresists (26), flexible photoimageable permanent coatings (27) and polyimide interlayer insulator films (28). Another new use of photopolymer chemistry is the selective formation of conductive patterns in polymers (29). 

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. 

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