Growing environmental concerns regarding the use of heavy metals in coating formulations have lead to a new coating strategy employing inherently conducting polymers (ICPs), such as polyaniline (PANI), as a key component. The principal potential advantage offered by the ICP coating technology is toleration of pinholes and minor scratches. This paper describes the application of the scanning reference electrode technique (SRET) to the study of PANI coatings on carbon steel. SRET results demonstrate that conductive PANI "passivates" pinhole defects in coatings on carbon steel. In addition, it is shown that phosphonic acid salts of PANI are more effective for corrosion protection than sulfonic acid salts. A model is proposed which entails passivation of the metal surface through anodization of the metal by PANI and formation of an insoluble iron-dopant salt at the metal surface.

An emulsion process has been developed for the direct synthesis of the emeraldine salt of polyaniline (PANI) that is soluble in organic solvents. The process entails formation of emulsion particles with a mean hydrodynamic diameter of 150 nm and consisting of a water-soluble organic solvent (e.g., 2-butoxyethanol), a water-insoluble organic acid (e.g., dinonylnaphthalenesulfonic acid), aniline, and water. Aniline is protonated by the organic acid to form a salt which partitions into the organic phase. As oxidant (ammonium peroxydisulfate) is added to the reaction mixture, PANI intermediates are formed in the organic phase. As the reaction proceeds, the emulsion flocculates, forming a two-phase system. The reaction features an induction period followed by an exothermic polymerization, at which time soluble PANI forms in the organic phase. The reaction progress is conveniently monitored by temperature, pH, and open circuit potential. When dinonylnaphthalenesulfonic acid (DNNSA) is employed as the organic acid, the resulting product is highly soluble in organic solvents such as xylene and toluene (not a dispersion), has high molecular weight (M w > 22 000), and forms moderately conductive (10-5 S/cm) films. We have also found that the conductivity of PANI−DNNSA films may be enhanced (up to 5 orders of magnitude) by treating the films with surfactants such as benzyltriethylammonium chloride (BTEAC) or low-molecular-weight alcohols and ketones such as methanol and acetone. Electron microscopy shows that the conductivity enhancement phenomenon observed upon treatment with surfactants is due to self-assembly of PANI−DNNSA molecules into an interconnected network morphology. In the case of alcohol or ketone treatment the film conductivity is enhanced due to extraction of excess dopant, densification of the polymer, and a concomitant increase in crystallinity.

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The electrochemical reduction of benzoate esters in aprotic media leads to relatively stable radical anions. The radical anions decompose to electroinactive products in an initial EC mechanism. At long‐time scales and/or higher concentrations, the benzoate esters begin to exhibit more complicated mechanistic behavior. The initial rates of decomposition of several benzoate ester radical anions have been determined by digital simulations of cyclic voltammograms, double potential step experiments, and rotating ring‐disk techniques. On short‐time scales, the reduction of t‐butyl p‐toluate is a good example of pure EC mechanistic behavior. The final decomposition products are many and complex for most of the esters studied, but t‐butyl benzoate cleanly gives benzoate anion and t‐butyl p‐t‐butyl benzoate.