The course of aniline oxidation with ammonium peroxydisulfate in aqueous solutions has been investigated. The reaction was terminated at various times and the intermediates collected. Besides the precipitates, the films deposited in situ on silicon windows have also been studied. The kinetic course of polymerization is controlled by the acidity level, which changes during the polymerization from pH 8 to a final value close to pH 1. It has two distinct exothermic phases. Gel-permeation chromatography indicates that aniline oligomers are produced at first at high pH, while polyaniline follows after the pH becomes sufficiently low. The growth of polyaniline nanotubes was observed by optical microscopy and confirmed by electron microscopy. The molecular structure of the reaction intermediates was studied in detail by FTIR spectroscopy. Oxidation products are markedly sulfonated, and they contain phenazine units. Aniline oligomers are more soluble in chloroform than the polymer fraction, which contains nanotubes.

The courses of aniline oxidation with ammonium peroxydisulfate in aqueous solutions of strong (sulfuric) and in weak (acetic) acids, followed by temperature and acidity changes, are different. In solutions of sulfuric acid, granular polyaniline (PANI) was produced; in solutions of acetic acid, PANI nanotubes were obtained. The external diameter of the nanotubes was 100-300 nm, the internal cavity 20-100 nm, and the length extended to several micrometres. The morphology of PANI, granular or tubular, depends on the acidity conditions during the reaction rather than on the chemical nature of the acid. PANI nanotubes were also produced when aniline was oxidized in the absence of any acid. The bulk conductivity of PANI prepared in solutions of acetic acid was 0.08-0.27 S cm −1 , depending on the acid concentration. Protonated PANI prepared in sulfuric and acetic acids were deprotonated with ammonium hydroxide to obtain PANI bases and the ammonium salt of the protonating acid. FTIR spectroscopy showed the differences in the molecular structure of the PANI bases. Irrespective of whether the polymerization was performed in solutions of sulfuric or acetic acid, PANI had hydrogen sulfate counter-ions only. The PANI morphology is thus not controlled by the nature of counter-ions. The acidity of the reaction medium determines the protonation of monomer, oligomer and polymer species. The chemistry of aniline oxidation is likely to be affected especially by the protonation of an intermediate in the pernigraniline form. It is proposed that, in the course of aniline oxidation, pH-dependent self-assembly of aniline oligomers predetermines the final PANI morphology.

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Any surface immersed in the aqueous reaction mixture used for the preparation of polyaniline becomes coated with a polyaniline film of submicrometre thickness. In this way, various materials can be modified by an overlayer of conducting polymer. The present review illustrates the role of infrared, Raman, and UV-VIS spectroscopies in the studies of polyaniline film growth. Spectroscopic methods are crucial in the evaluation of the performance of polyaniline films alone or in combination with nanoparticles of noble metals. The assessment of film ageing and stability can be followed conveniently by these methods. Carbonization of polyaniline films to nitrogen-containing carbon analogues is also discussed.

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