This thesis describes the experimental investigations of the structural properties of the conductive polymer, poly aniline. These studies have been performed on free-standing film samples, solution cast using the solvent N- methyl-2-pyrrolidinone (NMP). Such specimens have enabled a wealth of detailed information about polyaniline to be derived. The polymer itself was synthesised in the emeraldine base form using a chemical route optimised at Durham. The product was then assessed for its chemical structure and molecular weight using (^13)c NMR, elemental analysis and gel permeation chromatography. The process of fabricating the polymer into free-standing films is discussed and assessed. It has been shown that such films may be oriented by the application of uniaxial stress at elevated temperatures and this procedure has been described and analysed in detail. This stretching process aligns the polymer chains on a molecular level and hence produces changes in the physical properties of films. In particular, upon doping to the conducting emeraldine salt form by protonation in aqueous HCl, stretch oriented films display a remarkable increase in conductivity (parallel to the stretch direction) over their unstretched, doped counterparts. Various thermal analysis techniques, including dynamic mechanical thermal analysis, dielectric thermal analysis, thermomechanical analysis and infrared spectroscopy have been used to probe the physical properties of polyaniline films. Using these techniques a number of important thermal transitions have been observed and furthermore the stretch alignment process has been rationalised. Infrared orientational analysis has revealed detailed information about the molecular orientation produced during macroscopic stretching of a film. The type and degree of chain orientation has been analysed as well as the geometrical structure of a single chain. X-ray diffraction has probed the crystalline fraction of polyaniline films. Various aspects concerning the crystalline fraction of film samples has been derived along with an orientational analysis which has been contrasted with the infrared results. An even greater amount of structural information has been revealed by neutron diffraction and this technique has enabled a detailed examination of the structure of the crystalline phases of polyaniline to be made
