Increased understanding of plasma-polymer interactions is required to further the technological use of such processes, and elucidates heterogeneous physico-chemical reactions which occur under bombardment by complex combinations of energetic species. This thesis presents a systematic investigation into the effect of exposing organic and inorganic polymeric surfaces to controlled non-isothermal plasmas. Concurrently, a novel process is presented by which metal oxide gas barrier coatings are synthesized on polymer substrates by non- isothermal plasma treatment. Organic polymers exhibiting a range of structures were modified using non-isothermal plasmas at atmospheric and low pressure. The extent of atmospheric discharge oxygenation, measured by X-ray photoelectron spectroscopy (XPS), correlated with the polymers' ozonolysis rate constants. Surface physical disruption, studied using atomic force microscopy (AFM), after atmospheric discharge treatment was more pronounced than after low pressure plasma treatment. During low pressure oxygen plasma treatment, polymers containing phenyl groups were oxygenated to an extent which varied with the strength of π-π* valence band excitation in XPS C(1s) spectra of the untreated polymers, suggesting a dominance of reaction of plasma atomic oxygen at polymer radical sites excited by plasma vacuum ultraviolet radiation. The size of globules, observed by AFM, on the plasma modified surfaces correlated with the extent of surface chemical modification, inkeeping with a mechanism of chemically driven agglomeration of plasma oxidized low molecular weight polymer material. Oxygen plasma was more effective than water plasma in chemically modifying the surface of films of zirconium-normal-butoxide spin coated on polyester substrates, and the resulting optimized treatment produced a significant reduction in gas permeation of the substrate. XPS studies showed that oxygen plasma treatment of a polyphenylsilsesquioxane film on polyester film created a SiO(_2) layer less than 8 nm thin, which reduced O(_2) and Ar permeation of the coated film by 37.5 % and 31.6% respectively.

国立情報学研究所で電子化したコンテンツを使用している。

Zugl.: Trier, Univ., Diss., 2007

Bachelor-Arbeit Univ. St. Gallen, 2007.

Thesis (M.Arch.)--University of Hong Kong, 1995. / Includes bibliographical references (leaves 29-30) Also available in print.

No description available.

The geometries of the sandstone-hosted calcite concretions of the Jurassic Valtos Sandstone Formation and Bearreraig Sandstone Formation are described and related to the processes operating during concretion growth. As concretionary bodies analogous to those studied form potential permeability barriers within some North Sea petroleum reservoirs; the relationship between the growth processes and permeability barrier formation is examined. The growth times for model spherical concretions are calculated for the complex carbonate-water system. Two growth processes are modelled, solute transport and surface reaction. Growth times for a 1m diameter concretion forming under geologically reasonable conditions are predicted to be 22.3Ma, which reduces to 8.8Ma in porewaters flowing at 1m/year. The depth of formation of the concretions is assessed, through an examination of depth dependent properties of both the host-sediment and the calcite cement, and is found to be less than 500m. Concretion formation preceeded the Paleocene igneous activity which affected the Hebrides. The majority of the concretions examined formed at burial depths which were too great to allow effective contact between the concretions and seawater. The major source of carbonate was the dissolution of aragonitic shell material from within the host sandbody. The nature of the porewaters from which the concretions formed is assessed. The majority were meteoric in origin, though some marine influence is noted. The minor element contents of the cements cannot be used to calculate porewater compositions, as disequilibrium between the porewaters and the cements can be demonstrated. A model is proposed to account for the minor element patterns. Crystal breeding can be demonstrated to have occurred during concretion growth. A hypothesis is presented to explain the petrographic features of a typical Valtos Sandstone Formation concretion.

Loss-of-function mutations in the filaggrin gene(FLG) have recently been shown to be strongly associated with atopic dermatitis (AD). The overall aim of this study was to explore the role of filaggrin in skin barrier function and AD. There were two main focuses in this study. The first was a functional study whose primary objective was to determine if FLG mutations correlated with skin barrier dysfunction in AD. Fifty-five mild to moderate AD individuals were recruited, genotyped and had their skin barrier assessed using three different measures - transepidermal water loss (TEWL), skin capacitance and the number of tape strips required to abrogate skin barrier. A secondary aim of this functional study was to test the hypothesis that corneocytes were less adherent to one another in filaggrin-related AD compared to wild-type AD skin. The second main focus of this thesis was a structural study aimed at interrogating the structure-function relationship of filaggrin. Filaggrin protein was extracted and purified from a total of 21 AD and non-AD subjects and analysed using mass spectrometric techniques. Specifically, matrix assisted laser desorption/ionisation time-of-flight(MALDI-TOF)mass spectrometry (MS) and nano liquid chromatography tandem MS(LC-MS/MS) were utilised. Part of this structural study also involved developing and optimising the extraction and purification of filaggrin protein, including a novel way of extracting filaggrin from skin using tape stripping. In addition, novel filaggrin-specific enzyme-linked immunosorbant assay (ELISA) was also developed, which could serve as a useful screening test for the protein. In this study, FLG mutations were found to correlate with higher TEWL and fewer number of tape strips required to abrogate skin barrier, but not with skin capacitance. FLG mutations were also not shown to correlate with AD severity. The mean amount of protein extracted from filaggrin-related AD skin was also significantly higher compared to wild-type AD skin, supporting the hypothesis that corneocytes were less adherent to one another (and therefore, densely packed) in filaggrin-related AD skin. MS analysis of filaggrin confirmed the heterogeneic nature of filaggrin protein, even within a single individual. Interestingly, this structural study also showed that filaggrin was only minimally expressed in the skin of all the AD individuals studied, whether or not they possessed any FLG mutation. Due to the limited amount of filaggrin extracted from AD skin, it was not possible to conduct comparative structural analysis between filaggrin from AD and non-AD skin.

New methods in the fabrication of top coat and bond coat have been introduced to improve the efficiency and performance of advanced thermal barrier coatings (TBCs).i. Top coat. Thick yttria-stabilized-zirconia (YSZ) coatings (300-400 μm) have been fabricated by using electrophoretic deposition (EPD) method. The EPD coatings have more favorable microstructures with uniformly distributed porosity and stronger bonding, in comparison with conventional air-plasma spray (APS) coatings. ii. Bond coat. Pt-diffused single γ’-phase bond coat has been fabricated by applying selective etching prior to the electroplating of Pt on CMSX-4 single crystal superalloys. The concern on the compromised scale adhesion caused by the depletion of Pt is effectively avoided, as Pt remains stable in a coherent γ’-phase layer after long-term diffusion and oxidation. Considerable cost of Pt could also be reduced. Commercial TBCs, comprising an electron beam physical vapour deposition (EBPVD) top coat, a Pt-enriched intermetallic bond coat and a CMSX-4 single crystal superalloy, have also been investigated focusing on the failures that typically occurred at the scale/alloy interface. Advanced characterization techniques have been used to study the chemical factors (Al, Pt, S, Hf, etc.) that determine the durability of TBCs. Mechanisms have been discussed that control the TBCs behaviours of diffusion, oxidation, and adhesion. i. Diffusion. A depletion of Pt near the scale/alloy interface inevitably occurs at high temperatures, which significantly weakens the scale adhesion. Mechanisms controlling the diffusion of Pt in Ni-based single crystal superalloys at high temperatures have been investigated focusing on the evolution of phase, microstructure, and composition. It was found that Pt has negative chemical interactions with Al, Ti and Ta, all of which could stabilize Pt in β- and γ’-phases, and therefore avoid the depletion of Pt. ii. Oxidation. Selective oxidation behaviour of Ni-based superalloys has been studied by using thermodynamic calculations, which is mainly affected by alloy compositions, oxygen partial pressures and temperatures. It was found that the formation of a protective α-Al2O3 scale is more favoured under lower oxygen partial pressures and higher temperatures. The additions of Al and Pt in Ni-based superalloys could also promote the formation of Al2O3 and the exclusion of NiO and spinel. The additions of reactive elements (RE), however, are less effective and may even cause severe internal oxidations due to a competitive oxidation between Al and RE.iii. Adhesion. Sulphur effect in TBCs mainly refers to a segregation of sulphur at the scale/alloy interface, which significantly deteriorates the scale adhesion to alloys. High resolution secondary ion mass spectrometry (Nano-SIMS) was employed to trace sulphur in commercial TBCs. The undesired “sulphur effect” on scale adhesion was suggested to be caused by the formation of residual sulphides beneath the scale with weaker ionic bonding to alloy cations, rather than a segregation of sulphur atoms. Possible solutions have been suggested to alleviate the sulphur effect in TBCs.

Recent advances in growth techniques have lead to the production of high quality GaN and this has played a vital role in the improvement of GaN based devices. A number of device types can be produced from GaN. Spectrally selective devices can be produced by creating ternary or quaternary material systems by partially substituting either Al or In for Ga in GaN. This allows a wide spectral range that can be achieved ranging from the visible to the ultraviolet. The applications of detectors based on these material systems are vast and include areas such as biological, military, environmental, industrial and scientific spheres. In front illuminated Schottky barrier photodetectors, two major factors influencing the sensitivity of the device are the reverse leakage current and the transparency of the Schottky contact. In order to reduce the reverse current of semiconductor based devices, increase the barrier height, and enhance the adhesion of a metal on a semiconductor it is important to subject the contact to annealing. Annealing studies have been performed on AlGaN based photodiodes to investigate the evolution of the optical and electrical properties. In this study, the electrical and optical characteristics of AlGaN based Ni/Au and Ni/Ir/Au Schottky photodiodes were investigated. The electrical properties of the photodiodes were optimised by annealing in an Ar ambient. An increase in the Schottky barrier height and a decrease in the reverse leakage current were observed with increasing annealing temperature up to 500 oC. This effect was observed for both the Ni/Au and Ni/Ir/Au photodiodes. The optical characteristics of the photodiodes, which include the responsivity and the quantum efficiency, were also investigated. UV/visible rejection ratios of as high as 103 were obtained. The transmittance of Ni/Au and Ni/Ir/Au metal layers deposited on a quartz substrate were optimised by annealing. This was under the same ambient conditions as the Schottky photodiode. The transmittance increased with annealing temperature for the Ni/Au metal layer whereas it decreased at higher temperatures for the Ni/Ir/Au layer. The transmittance of the Ni/Au metal layer reached as high as 85 % after 500 oC annealing. The transmittance of the Ni/Ir/Au only reached a high of 41 % after 400 oC annealing. / Dissertation (MSc)--University of Pretoria, 2013. / Physics / unrestricted