Electrodeposition, of polymers

Conductive polymers may be synthesized via either chemical or electrochemical polymerization methods. Electrodeposition of conductive polymers from electrolytes is, thus, feasible provided that the depositing polymer is not soluble in the electrolyte.206 Conductive polymers can be deposited from the electrolytes containing the monomers via either electrooxidation or electroreduction, based on the monomer type used. Similar to that of metals, the electrodeposition of polymers is based on nucleation and growth. The deposition mechanism involves oxidation of monomers adsorbed on the electrode surface, diffusion of the oxidized monomers and oligomerization, formation of clusters, and eventually film growth.213... 

Subramanian RV, Sundaram V and Patel AK, Electrodeposition of polymers on graphite fibres Effects on composite properties, 33rd Ann Tech Conf Reinf Plast Comp Div, Section 20F, 1978. 

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. ... 

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. 

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. 

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

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. 

Although the literature on electrodeposited electroactive and passivating polymers is vast, surprisingly few studies exist on the solid-state electrical properties of such films, with a focus on systems derived from phenolic monomers, - and apparently none exist on the use of such films as solid polymer electrolytes. To characterize the nature of ultrathin electrodeposited polymers as dielectrics and electrolytes, solid-state electrical measurements are made by electrodeposition of pofy(phenylene oxide) and related polymers onto planar ITO or Au substrates and then using a two-electrode configuration with a soft ohmic contact as the top electrode (see Figure 27). Both dc and ac measurements are taken to determine the electrical and ionic conductivities and the breakdown voltage of the film. 

Most suitable for electrically conducting materials such as carbon fibers, the electrochemical processes involve deposition of polymer coatings on the fiber surface through electrodeposition or electropolymerization techniques. The major advantage of these processes is that a uniform layer of controlled thickness and variable polymer structure and properties can be obtained by controlling the current and the solution concentration. 

Q. Gao, B. Qi, Y. Sha and X. Yang, Electrodepositing redox polymer on sandwich complex for the improvement of sensitivity in sandwich enzyme-linked immunoassay, Chem. Lett., 33 (2004) 1198-1199. 

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... 

Electrodeposition experiments were carried out in the apparatus described earlier (4). The equipment is illustrated schematically in Figure 2. The circuit also included a strip chart recorder and integrator. A variety of metals were coated at the cathode using the standard condition of 200 V for 2 min. The cathode area was held constant at 7.3 cm, unless otherwise specified. After deposition, the metal test pieces were rinsed with deionized water, dried and weighed to determine the amount of polymer deposited. The number of coulombs was measured simultaneously in order to calculate current efficiencies. Results were analyzed and compiled in a simple computer program. A typical printout is shown below for a system with poor current cutoff (Table V ), and good cutoff (Table VI). The set of metals used as substrate are listed below. 

By the process described above, a plasma film could be obtained that had high enough electrical conductivity to allow direct electrodeposition of copper. The bulk resistivity of film measured by a four-point probe was 2.6 x 10 " ohm-cm for the copper-containing polymer film when deposition was stopped after 18 min at HOW. This value is critical if a uniform electrolytic deposit is to be obtained. For safety, deposition was carried out until a total film thickness of 150nm was obtained, giving a nearly pure metallic layer thick enough to allow subsequent electroplating. 

Figure 33.2 shows XPS spectra of the surfaces of the TMS plasma polymer film deposited on (Ar + H2) plasma-pretreated steel (a, b, c) and on O2 plasma-pretreated steel (d, e, f). As shown in the spectra, the surface of the plasma film is functional in nature with functional groups of C-OH, C=0, and Si-OH. Two films basically ended up with the same surface structure. This is also confirmed by XPS analysis of the film during the film aging in air after the film deposition, which indicated that the film surfaces were saturated with a fixed surface structure after a few hours of air exposure [4]. This is due to a well-known phenomenon that the residual free radicals of the plasma polymer surface reacted with oxygen after exposure to air [5]. Curve deconvolution of C Is peaks showed structures of C-Si, C-C, C-0, and C=0. The analysis clearly shows a silicon carbide type of structure, which is consistent with the IR results. The functional surfaces of TMS films provide bonding sites for the subsequent electrodeposition of primer (E-coat). 

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