Conducting polymers corrosion protection

The use of electronic conducting polymers for protection against corrosion is a topic which has considerably progressed in the last years. From the analysis of the published work it is obvious that much effort has been made to understand the protection mechanisms but, also, many new metal systems have been tested and, at this time, we consider that some results are very promising and already compare well with the prohibited chromating processes. 

There is a large potential for conducting polymers as corrosion-inhibiting coatings. For instance, the corrosion protection ability of polyaniline is pH-dependent. At lower pH polyaniline-coated steel corrodes about 100 times more slowly than noncoated steel. By comparison, at a pH of about 7 the corrosion protection time is only twice for polyaniline-coated steel. Another area of application involves creation of solid state rechargeable batteries and electrochromic cells. Polyheterocycles have been cycled thousands of times with retention of over 50% of the electrochromic activity for some materials after 10,000 cycles. IR polarizers based on polyaniline have been shown to be as good as metal wire polarizers. 

Ionically conducting polymers and their relevance to lithium batteries were mentioned in a previous section. However, there are several developments which contain both ionically conducting materials and other supporting agents which improve both the bulk conductivity of these materials and the properties of the anode (Li)/electrolyte interface in terms of resistivity, passivity, reversibility, and corrosion protection. A typical example is a composite electrolyte system comprised of polyethylene oxide, lithium salt, and A1203 particles dispersed in the polymeric matrices, as demonstrated by Peled et al. [182], By adding alumina particles, a new conduction mechanism is available, which involved surface conductivity of ions on and among the particles. This enhances considerably the overall conductivity of the composite electrolyte system. There are also a number of other reports that demonstrate the potential of these solid electrolyte systems [183],... 

Since the appearance of the redox [ii, iii] and conducting [iv] polymer-modified electrodes much effort has been made concerning the development and characterization of electrodes modified with electroactive polymeric materials, as well as their application in various fields such as -> sensors, actuators, ion exchangers, -> batteries, -> supercapacitors, -> photovoltaic devices, -> corrosion protection, -> electrocatalysis, -> elec-trochromic devices, electroluminescent devices (- electroluminescence) [i, v-viii]. See also -> electrochemically stimulated conformational relaxation (ESCR) model, and -> surface-modified electrodes. 

Major polymer applications materials having electric conductivity, protection against static electricity, EMI shielding, corrosion protection... 

FIGURE 1.35 SVET map showing electrochemical potential of a metal coated with conducting polymer for corrosion protection—the metal has been scribed. 

This diol was mixed with other diols, then reacted with diisocyanates to form polyurethanes. The electrically conducting polymers, polyaniline and polypyrrole, prevent corrosion of steel.105 One of the best formulations uses polyaniline with zinc nitrate, which is then covered with an epoxy resin topcoat. Polyorganosiloxanes have been grafted to starch using the sol-gel method with alkoxysi-lanes. These materials have been complexed with cerium ions to provide corrosion protection for aircraft that is expected to be 50% cheaper than conventional coatings.106... 

Conducting polymers such as polyacetylene, polypyrrole, polyaniline, polythiophene, etc. have been actively studied for use in various fields due to their interesting properties batteries,46 electrochromic displays,47 materials for supercapacitors,48 corrosion protection,49 protecting layers for static electricity,50 materials for organic electroluminescence displays,51 sensing materials,52 etc. Polypyrrole is reported to be extremely rigid, with a semi-crystalline structure. 

Since protection of electrodes against corrosion in the photoelectrolysis cells is a question of vital importance, many attempts have been made to use protective films of different nature (metals, conductive polymers, or stable semiconductors, eg., oxides). Of these, semiconductive films are less effective since they often cause deterioration in the characteristics of the electrode to be protected (laying aside heterojunction photoelectrodes specially formed with semiconducting layers of different nature [42]). When metals are used as continuous protecting film (and not catalytical "islands" discussed above), a Schottky barrier is formed at the metal/semiconductor interface. The other interface, i.e., metal/electrolyte solution is as if connected in series to the former and is feeded with photocurrent produced in the Schottky diode upon illuminating the semiconductor (through the metal film). So, the structure under discussion is but a combination of the "solar cell" and "electrolyzer" within the photoelectrode Unfortunately, light is partly lost due to absorption by the metal film. 

One application brings the conducting polymer as a dispersion coating to the surface [66]. A powder of polyaniline (with a particle size in the range of some tens of nanometers) is dispersed in a conventional paint, and this is painted onto the metal surface. The authors use a very low powder concentration of 4% and explain the corrosion-protection properties with a percolation model. 

Mechanism of Corrosion Protection by Intrinsically Conducting Polymers... 

The first explanation of the corrosion protection of conducting polymers was based on the idea that the typical noble character of the conducting polymers (compare the redox potentials given in Table 19) simply transforms the coated metal into a noble one. This of course requires compact films, free of pores, which is not observed in practice. Also, the stability of the polymer film against the atmospheric degradation is not sufficient. 

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