Mechanical properties of thin sol-gel films

This thesis presents a study of the mechanical properties of thin films. The main aim was to determine the properties of sol-gel derived coatings. These films are used in a range of different applications and are known to be quite porous. Very little work has been carried out in this area and in order to study the mechanical properties of sol-gel films, some of the work was carried out on magnetron sputtered metal coatings in order to validate the techniques developed in this work. The main part of the work has concentrated on the development of various bending techniques to study the elastic modulus of the thin films, including both a small scale three-point bending, as well as a novel bi-axial bending technique based on a disk resting on three supporting balls. The bending techniques involve a load being applied to the sample being tested and the bending response to this force being recorded. These experiments were carried out using an ultra micro indentation system with very sensitive force and depth recording capabilities. By analysing the result of these forces and deflections using existing theories of elasticity, the elastic modulus may be determined. In addition to the bi-axial bending study, a finite element analysis of the stress distribution in a disk during bending was carried out. The results from the bi-axial bending tests of the magnetron sputtered films was confirmed by ultra micro indentation tests, giving information of the hardness and elastic modulus of the films. It was found that while the three point bending method gave acceptable results for uncoated steel substrates, it was very susceptible to slight deformations of the substrate. Improvements were made by more careful preparation of the substrates in order to avoid deformation. However the technique still failed to give reasonable results for coated specimens. In contrast, biaxial bending gave very reliable results even for very thin films and this technique was also found to be useful for determination of the properties of sol-gel coatings. In addition, an ultra micro indentation study of the hardness and elastic modulus of sol-gel films was conducted. This study included conventionally fired films as well as films ion implanted in a range of doses. The indentation tests showed that for implantation of H⁺ ions at doses exceeding 3x10¹⁶ ions/cm², the mechanical properties closely resembled those of films that were conventionally fired to 450°C.

Metal Contaminants in Leachate from Sanitary Landfills

The uncontrolled disposal of solid wastes poses an immediate threat to public health and a long term threat to the environmental well being of future generations. Solid waste is waste resulting from human activities that is solid and unwanted (Peavy et al., 1985). If unmanaged, dumped solid wastes generate liquid and gaseous emissions that are detrimental to the environment. This can lead to a serious form of contamination known as metal contamination, which poses a risk to human health and ecosystems. For example, some heavy metals (cadmium, chromium compounds, and nickel tetracarbonyl) are known to be highly toxic, and are aggressive at elevated concentrations. Iron, copper, and manganese can cause staining, and aluminium causes depositions and discolorations. In addition, calcium and magnesium cause hardness in water causing scale deposition and scum formation. Though not a metal but a metalloid, arsenic is poisonous at relatively high concentrations and when diluted at low concentrations causes skin cancer. Normally, metal contaminants are found in a dissolved form in the liquid percolating through landfills. Because average metal concentrations from full-scale landfills, test cells, and laboratory studies have tended to be generally low, metal contamination originating from landfills is not generally considered a major concern (Kjeldsen et al., 2002; Christensen et al., 1999). However, a number of factors make it necessary to take a closer look at metal contaminants from landfills. One of these factors relates to variability. Landfill leachate can have different qualities depending on the weather and operating conditions. Therefore, at one moment in time, metal contaminant concentrations may be quite low, but at a later time these concentrations could be quite high. Also, these conditions relate to the amount of leachate that is being generated. Another factor is biodiversity. It cannot be assumed that a particular metal contaminant is harmless to flora and fauna (including micro organisms) just because it is harmless to human health. This has significant implications for ecosystems and the environment. Finally, there is the moral factor. Because uncertainty surrounds the potential effects of metal contamination, it is appropriate to take precautions to prevent it from taking place. Consequently, it is necessary to have good scientific knowledge (empirically supported) to adequately understand the extent of the problem and improve the way waste is being disposed of

A coupled meshless technique/molecular dynamics approach for deformation characterization of monocrystalline metal

This paper presents a multiscale study using the coupled Meshless technique/Molecular Dynamics (M2) for exploring the deformation mechanism of mono-crystalline metal (focus on copper) under uniaxial tension. In M2, an advanced transition algorithm using transition particles is employed to ensure the compatibility of both displacements and their gradients, and an effective local quasi-continuum approach is also applied to obtain the equivalent continuum strain energy density based on the atomistic poentials and Cauchy-Born rule. The key parameters used in M2 are firstly investigated using a benchmark problem. Then M2 is applied to the multiscale simulation for a mono-crystalline copper bar. It has found that the mono-crystalline copper has very good elongation property, and the ultimate strength and Young's modulus are much higher than those obtained in macro-scale.

Ultrafast near infrared sintering of TiO2 layers on metal substrates for dye-sensitized solar cells

A limiting step to roll-to-roll production of dye-sensitized solar cells on metals is TiO2 sintering (10-30 min). Near infrared (NIR) heating is a novel process innovation which directly heats titanium substrates giving rapid binder removal and sintering. NIR heating (for 12.5 s) at varying power gave titanium temperatures of 545, 685 and 817 degrees Celsius yielding cells with efficiencies of 2.9, 2.8 and 2.5%. Identical cells prepared in a conventional oven (1800 s) at 500, 600 and 800 degrees Celsius gave 2.9, 2.6 and 0.2% efficiency. NIR sintering is ultrafast and has a wide process window making it ideal for rapid manufacturing on metals.

Nanostructured metal oxides as adsorbents and photocatalysts

This research underlines the extensive application of nanostructured metal oxides in environmental systems such as hazardous waste remediation and water purification. This study tries to forge a new understanding of the complexity of adsorption and photocatalysis in the process of water treatment. Sodium niobate doped with a different amount of tantalum, was prepared via a hydrothermal reaction and was observed to be able to adsorb highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ions. This study facilitates the preparation of Nb-based adsorbents for efficiently removing toxic radioactive ions from contaminated water and also identifies the importance of understanding the influence of heterovalent substitution in microporous frameworks. Clay adsorbents were prepared via a two-step method to remove anionic and non-ionic herbicides from water. Firstly, layered beidellite clay was treated with acid in a hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted onto the acid treated samples to prepare the adsorption materials. In order to isolate the effect of the clay surface, we compared the adsorption property of clay adsorbents with ƒ×-Al2O3 nanofibres grafted with the same functional groups. Thin alumina (£^-Al2O3) nanofibres were modified by the grafting of two organosilane agents 3-chloropropyltriethoxysilane and octyl triethoxysilane onto the surface, for the adsorptive removal of alachlor and imazaquin herbicides from water. The formation of organic groups during the functionalisation process established super hydrophobic sites along the surfaces and those non-polar regions of the surfaces were able to make close contact with the organic pollutants. A new structure of anatase crystals linked to clay fragments was synthesised by the reaction of TiOSO4 with laponite clay for the degradation of pesticides. Based on the Ti/clay ratio, these new catalysts showed a high degradation rate when compared with P25. Moreover, immobilized TiO2 on laponite clay fragments could be readily separated out from a slurry system after the photocatalytic reaction. Using a series of partial phase transition methods, an effective catalyst with fibril morphology was prepared for the degradation of different types of phenols and trace amount of herbicides from water. Both H-titanate and TiO2-(B) fibres coated with anatase nanocrystal were studied. When compared with a laponite clay photocatalyst, it was found that anatase dotted TiO2-(B) fibres prepared by a 45 h hydrothermal treatment followed by calcination were not only superior in performance in photocatalysis but could also be readily separated from a slurry system after photocatalytic reactions. This study has laid the foundation for the development of the ability to fabricate highly efficient nanostructured solids for the removal of radioactive ions and organic pollutants from contaminated water. These results now seem set to contribute to the development of advanced water purification devices in the future. These modified nanostructured materials with unusual properties have broadened their application range beyond their traditional use as adsorbents, to also encompass the storage of nuclear waste after concentrating from contaminated water.