Dynamic mechanical thermal and infrared analyses of polyacrylonitrile "electrografted" onto a metal

Polyacrylonitrile (PAN) films have been grafted onto copper electrodes by cathodic polarization and analyzed by infrared spectroscopy and dynamic mechanical thermal analysis (DMTA). The dynamic mechanical response shows two or three transitions depending on the film thickness and the potential deposition. The viscoelastic properties of ungrafted PAN films, e.g., solvent cast films of commercially available PAN, are deeply different from those of electrografted films. The experimental data support that ungrafted chains are paracrystalline in contrast to the grafted ones which are essentially amorphous. Moreover, the irreversible transformation of the grafted PAN chains observed beyond 225°C is confirmed by Fourier transform infrared (FTIR) analysis and ascribed to an intramolecular cyclization of PAN into polyimine. This reaction occurs rapidly and at a comparatively low temperature with respect to ungrafted PAN, which suggests that the grafted chain configuration might be predominantly isotactic. The isotacticity and the amorphous structure appear to decrease as the thickness of the PAN film is increased. Literature data and the herein reported observations would suggest a dependence of the amorphous structure of PAN on the chain isotacticity.