Student Number : 0405740V - MSc (Eng) dissertation - School of Chemical and Metallurgical Engineering - Faculty of Engineering and the Built Environment / Silicon carbide ceramics have many attractive properties, one of which is their high degree of corrosion resistance. Even though corrosion is slow, it does occur. Standard procedures for corrosion testing such as the immersion method is limited due to the low corrosion rates of most of these materials: it does not elucidate the mechanism of corrosion, but only gives the rate and degree of dissolution. Electrochemical techniques offer the possibility to further elucidate corrosion mechanisms and establish the resistance stability of conducting or partially-conducting ceramic materials, thus enhancing the understanding of ceramic material behaviour. In conjuction with microstructural changes, the electrochemical corrosion behaviour of solid state sintered silicon carbide (SSiC) and liquid phase sintered silicon carbide (LPSSiC) have successfully been studied at room temperature in acidic and alkaline environments by using potentiodynamic polarisation measurements. Several hypotheses were proposed to assist in establishing the effect of silicon and carbon on the corrosion mechanisms of these materials. The effect of the secondary phase on the electrochemical corrosion of the LPSSiC was also investigated. Corrosion current densities of the LPSSiC materials were much lower than the SSiC materials in all test solutions. The SSiC materials showed pseudo-passive behaviour in HCl and HNO3, due to the formation of thin layer of SiO2 on the surface. The carbon in the SiC compound increased the corrosion current densities in all test solutions for SSiC materials. The electrochemical corrosion of LPSSiC is due to the dissolution of SSiC and not the oxides; the chemcial attack on the oxide phases is mainly by acid-base type of reactions, rather than electrochemical corrosion involving redox reactions.

A simple method for increasing the stable temperature range of the liquid crystalline blue phase is demonstrated, by mixing a non-mesogenic polymer of low molecular weight into the blue phase material. In a mixture of cholesteryl benzoate and cholesteryl nonanoate the addition of polystyrene increased the stable blue phase range from 0.5K to 12K. This was measured strictly on heating from the chiral nematic phase through the blue phase in order to minimise non-equilibrium effects, and is one of the largest ranges so measured. The stability range can be closely tuned by changing the polymer concentration and molecular weight. The maximum range found by adding a particular compound seems only to depend on its saturation point in the liquid crystal, and the dependence of the range on concentration is non-linear. These features were explained by a numerical model of a blue phase unit cell incorporating the mean field Flory-Huggins and Maier-Saupe theories where the polymer could fill the high energy defect regions. Two of the oligomers which are shown to stabilise the blue phase are fluorescent, at 450nm and 500nm respectively, and it is proposed that tests on these mixtures could reveal photonic effects caused by the concentration of the fluorophores in the blue phase defect regions. The twist-grain boundary (TGB) phase is present in mixtures of cholesteryl oleyl carbonate and cholesteryl nonanoate over a range of up to 0.3K. The addition of polystyrene has no effect on the stability of the TGB phase. Conventional, in situ UV-initiated polymer stabilisation does not appear to stabilise the TGB phase, but is capable of stabilising over at least 30K the micron-size filaments which appear in the TGB phase when it is heated from the smectic phase in a cell with homeotropic alignment. Some notes are made on the causes and structure of this filament texture, and it is observed that the filaments tend to grow with a characteristic curvature. It is shown theoretically that the correct material could stabilise the TGB phase similarly to the polymers in the blue phase, by extending the previous model to include the Kobayashi-McMillan theory of smectic ordering. A second theoretical model of chirality around the transition to the smectic phase is then presented which takes account of fluctuations, based on an analogy with the state of a smectic-forming material infiltrated into an aerogel. A phase resembling the TGB phase emerges from this model. The model gives two first order transitions in accordance with experiments on the TGB phase, and reflects other experimental pitch and calorimetry measurements too. The electrochemical polymerisation of an acrylate monomer in the nematic and smectic-C* phases is investigated. 30-100V is applied across a cell containing the liquid crystal-monomer mixture, with no additional initiating compound. In both phases, the texture during polymerisation is frozen in by the polymer formed. In a nematic phase in a cell with initially planar alignment, the director in the field off state can be observed to tilt toward the homeotropic over a number of hours. In the ferroelectric case, as well as the textural freezing there is a somewhat reversible agglomeration of polymer strands into micron-scale structures. Scanning electron microscopy reveals a range of structures on both electrode surfaces, including in the nematic case corrugations with a periodicity of 500-750nm. There is no evidence of a polymer network spanning the thickness of the cell - rather the liquid crystal seems to be realigned by a polymer film at the electrode surfaces.