The work presented in this thesis provides a new route to a colloidal form of polyaniline, which uses colloidal silica as a dispersant. We obtained stable colloidal dispersions of polyaniline-silica composite particles with a 'raspberry' morphology. Compressed pellets of these particles exhibit solid-state conductivities of 1O-!_10-2 S crrr l, which is approximately 1-2 orders of magnitude lower than that of polyaniline bulk powder. This novel colloidal form of polyaniline has significantly improved processability compared to conventionally synthesised polyaniline. The synthesis and chemical characterisations are presented for various polyaniline-silica colloidal nanocomposites. The quantity of polyaniline incorporated into the nanocomposite particles can be controlled by varying the diameter of the silica dispersant, approximately 20% and 60 % polyaniline content being obtained using 120 nm and 10 nm diameter silica respectively. The average particle size ranges of nanocomposites was found to be 150 to 700 nm and 330 to 560 nm, as determined by transmission electron microscopy (TEM) and disc centrifuge photosedimentometry (DCP) respectively. The nanomorphology and surface composition of the polyanilinesilica particles were determined by small angle X-ray scattering (SAXS) and X-ray photoelectron spectroscopy (XPS) respectively. The average inter-particle separation distance of the silica particles within the polyaniline-silica raspberries was determined by SAXS to be 4 nm, a dimension equivalent to molecular polyaniline. The XPS data suggests that the surface of the particles is silica rich, this is consistant with their long term colloidal stability in 1.2 mole dm-3 HCl. The kinetics of polymerisation was studied using 1H NMR spectroscopy to monitor the disappearance of aniline monomer. Polymerisation rates during the synthesis of polyaniline-silica nanocomposites were appreciably faster than the corresponding precipitation polymerisations carried out in the absence of silica dispersants, due primarily to an increase in the second auto-catalytic step of the reaction. Rate constants were determined for both these types of synthesis; the values obtained for the precipitation polymerisations were in reasonably good agreement with literature values.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:239632 |
| Date | January 1995 |
| Creators | Gill, Michael |
| Publisher | University of Sussex |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
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