The effect of uniaxial orientation upon the structural properties of polvaniline films

Abstract

The effects of elongation upon the structural and electronic properties of the conducting polymer polyaniline have been investigated. In particular, the properties of high molecular weight (ca. 150 000 Daltons) polyaniline have been examined, and the effects of increased molecular weight assessed. A method has been found to elongate the emeraldine base (EB) form up to 700% (l/l(_o)=8). This induces partial molecular alignment in the polymer which, upon doping, exhibits electrical conductivity of up to 700 Scm(_-1) and electrical anisotropy of almost 4.The mechanical properties of high molecular weight emeraldine base have been investigated as a function of elongation. The breaking stress has been observed to increase by almost one order of magnitude for a 500% elongated film compared with its unoriented counterpart. The breaking strain is found to decrease initially with increasing elongation, though no noticeable change is evident for samples elongated to more than 300%. Similarly, Young's modulus increases by a factor of 2 with increased elongation, but above 300% remains approximately constant. The behaviour has been interpreted in terms of the crystalline fraction of the samples. X-ray diffraction experiments have enabled the crystalline fraction of emeraldine base and emeraldine salt (ES) to be assessed. 300% elongated EB samples exhibit increased crystalhnity compared with as-cast samples. However, no further increase in crystallmity is evident for 600% elongated samples. Unoriented ES samples have a crystalline fraction of approximately 0.3. The crystallinity of 300% and 600% elongated ES samples is slightly less than for unoriented ES. The polarised reflectance spectra of EB and ES have been measured in the region 0.5- 5.6 eV. The results show increased optical anisotropy with increasing elongation for EB samples, but no change in anisotropy for ES samples above 300% elongation. A Kramers-Kronig analysis of the reflectance data reveals near metallic behaviour parallel to the dkection of elongation, and a high degree of localisation perpendicular to this direction.