Thermal degradation of polyaniline films prepared in solutions of strong and weak acids and in water - FTIR and Raman spectroscopic studies

Polyaniline (PANI) films were prepared in situ on silicon windows during the oxidation of aniline with ammonium peroxydisulfate in aqueous solutions of strong (0.1 M sulfuric) or weak (0.4 M acetic) acid or without any acid. In solutions of sulfuric acid, a granular PANI is produced, in solutions of weak acids or without any acid, PANI nanotubes are obtained. The thermal stability and structural variation of the corresponding films produced on silicon windows during treatment at 80 degrees C for three months were studied by FTIR and Raman spectroscopies. The morphology of the films is preserved during the degradation but the molecular structure changes. The results indicate that the spectral changes correspond to deprotonation, oxidation and chemical crosslinking reactions. The films of PANI salts loose their protonating acid. PANI bases are more stable than the salt forms during thermal ageing. The films obtained in water or in the presence of acetic acid are more stable than those prepared in solutions of sulfuric acid. The protonated structure is more prone to crosslinking reactions than deprotonated one. The molecular structure corresponding to the nanotubular morphology, which contains the crosslinked phenazine- and oxazine-like groups, is more stable than the molecular structure of the granular morphology. (C) 2008 Elsevier Ltd. All rights reserved.