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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Liquid crystal-polymer composites and the stabilisation of defect phases

Kasch, Nicholas January 2015 (has links)
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.
2

Diffusion moléculaire d'un dopant hydrosoluble dans une phase lamellaire lyotrope. Transition smectique-cholestérique dans un mélange de molécules amphiphiles

MOREAU, Patrick 22 November 2004 (has links) (PDF)
L'étude des propriétés de diffusion moléculaire d'un dopant dans une phase lamellaire lyotrope orientée nous permet de mettre en évidence les caractéristiques de diffusion dans un milieu fortement anisotrope. En particulier, l'effet de la dilution du système met en évidence deux régimes : un régime dilué où les molécules diffusent comme dans un solvant et un nouveau régime, très confiné, dans lequel les molécules diffusent comme des dopants membranaires. Le développement d'un modèle prenant en compte la fluidité des membranes nous permet d'interpréter ces résultats dans la majorité des cas étudiés et révèle aussi l'importance de l'anisotropie des diffuseurs. Dans la seconde partie, nous nous intéressons à l'étude du mécanisme microscopique mis en jeu dans la transition smectique – cholestérique dans les cristaux liquides lyotropes. En utilisant un système déjà connu au laboratoire (DMPC/C12E5/eau), nous validons expérimentalement le scénario de transition par débouclage de boucles de défauts proposé théoriquement depuis plusieurs années. Nous proposons ainsi un système expérimental de choix pour l'étude de ce genre de transition, prédites dans différents domaines de la physique de la matière condensée. La visualisation directe des défauts, la mise en évidence de leur structure en boucle, l'observation de leur différentes organisations nous permet également de proposer l'existence de nouvelles phases dans le domaine des cristaux liquides lyotropes (phase smectique biaxe, phase TGB).

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