Toward an understanding of the formation of conducting polymer nanofibers.

Introducing small amounts of additives into polymerization reactions to produce conducting polymers can have a profound impact on the resulting polymer morphology. When an oligomer such as aniline dimer is added to the polymerization of aniline, the nanofibers produced are longer and less entangled than those typically observed. The addition of aniline dimer can even induce nanofiber formation under synthetic conditions that generally do not favor a nanofibrillar morphology. This finding can be extended to both the synthesis of polythiophene and polypyrrole nanofibers. The traditional oxidative polymerization of thiophene or pyrrole only produces agglomerated particles. However, when minute amounts of thiophene or pyrrole oligomers are added to the reaction, the resulting polymers possess a nanofibrillar morphology. These results reveal important insights into a semirigid rod nucleation phenomenon that has hitherto been little explored. When polyaniline nucleates homogeneously, surface energy requirements necessitate the formation of ordered nuclei which leads to the directional polymerization of aniline. This ultimately leads to the one-dimensional nanofibrillar morphology observed in the final product. The synthetic procedures developed here are simple, scalable, and do not require any templates or other additives that are not inherent to the polymer.