Title:
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Colloidal rods, plates and their mixtures : preparation,
characterisation, and phase behaviour
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Hard rod and plate particles have previously shown an interesting range of liquid
crystalline phase behaviour in experiments, simulation and theory. Under certain
conditions a biaxial phase has been proposed but this has not been shown experimentally
yet.
The phase behaviour of hard rods in a non-aqueous solvent was studied in the first
experimental chapter. Onsager theory predicts an isotropic-nematic transition for
infinitely long, thin rods. In practice colloidal rods have a finite aspect ratio and it
is shown that the midpoint of the coexistence boundaries agree well with computer
simulations. The width of the transition, however, is increased noticeably due to
polydispersity in aspect ratio and this is found to be in broad agreement with theoretical
predictions for infinitely thin, polydisperse rods.
The second experimental chapter of this thesis showed that it is possible to adsorb
sodium polyacrylate on to the clay surface of sepiolite clay rods in order to
electrostatically stabilise the particles in water. It was possible to disrupt the formation
of a gel phase and observe isotropic - nematic phase behaviour. The isotropic - nematic
phase boundaries increased with salt concentration.
The final chapters of this thesis investigated mixtures of rod and plate particles. Firstly
aqueous sepiolite rods stabilised with sodium polyacrylate were mixed with various
concentrations of montmorillonite plates. For low concentrations of the plates, the
sepiolite underwent phase separation as previously seen but at a much lower rod
concentration with a broader coexistence range. It was found that it was possible to
obtain 3 phases in coexistence for a number of samples but the montmorillonite-rich
phase, despite observations of slight birefringence, was not considered a nematic. Yet,
the montmorillonite-rich phase did contain a higher concentration of particles than seen
in the pure samples.
Lastly mixtures of sepiolite rods and gibbsite plates in both aqueous and non-aqueous
solvents were explored. It was found in both cases that the opposite charge on the
particles led to gelation of the particles which inhibited any demixing. For the aqueous
system it was found that adsorption of sodium poly acrylate to the surface of the gibbsite
particles was able to reverse the sign of the particle which reSUlting in a stable dispersion
of the rod and plate particles similar to that seen for the mixtures of sepiolite and
montmorillonite.
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