For more than 50 years total hip replacements have been a common and successful procedure to increase patient mobility and quality of life. The 10-year implant survival rate is 97.8%. However, for longer implantation times there are limitations linked to the negative biological response to wear and corrosion products from the currently used biomaterials. In this thesis silicon nitride (SiNx) coatings were evaluated for use in total hip replacements, on the articulating bearing surface and modular taper connections. Homogeneous, dense SiNx coatings were deposited using reactive high power impulse magnetron sputtering (HiPIMS) up to a thickness of 8 µm. The N/Si atomic ratios ranged from 0.3 to 1.1 and the coatings showed a low surface roughness. The wear rate of a SiNx coated cobalt chromium molybdenum alloy (CoCrMo) was similar to that of bulk Si3N4, and less than one 46th of uncoated CoCrMo, an alloy that is commonly used in joint replacements. Wear debris generated from SiNx coatings was round in shape, with a mean size of 40 nm, and ranged between 10 and 500 nm. Model particles, similar in size and shape as the wear debris, were soluble in simulated body fluid. The dissolution rate was higher than the expected rate of debris generation. Along with the size of the debris, which is not in the critical range for macrophage activation, this dissolution may limit negative biological reactions. The SiNx coatings also dissolved in simulated body fluid. The coating with the highest N/Si ratio exhibited the lowest dissolution rate, of 0.2 to 0.4 nm/day, while CoCrMo under the same condition dissolved at a rate of 0.7 to 1.2 nm/day. SiNx-coated CoCrMo exhibited a reduced release of Co, Cr and Mo ions into the solution by two orders of magnitude, compared to uncoated CoCrMo. Si3N4 evaluated under micro-displacement in a corrosive environment, replicating the modular taper, showed a lower corrosion current compared to common biomedical alloys. SiNx coatings may also act beneficially to reduce issues associated with this type of contact. SiNx coatings have shown several properties in a laboratory environment that are hypothesised to increase the longevity of joint replacements. The promising results encourage further evaluation closer to the clinical application of total hip replacements, in particular in the articulating bearing surface and in modular tapers.

No description available.

The scalable syntheses of functional, porous nanostructures with tunable three-dimensional morphologies is a significant challenge with potential applications in chemical, electrical, electrochemical, optical, photochemical, and biochemical devices. As a result, several bio-enabled and synthetic approaches are explored in this work (with an emphasis on peptide-enabled deposition) for the generation of aligned nanotubes of nanostructured titania for application as electrodes in dye-sensitized solar cells and biofuel cells. As part of this work, peptide-enabled deposition was used to deposit conformal titania coatings onto porous anodic alumina templates under ambient conditions and near-neutral pH to generate aligned, porous-wall titania nanotube arrays that can be integrated into dye-sensitized solar cells where the arrays displayed improved functional dye loading compared to sol-gel-derived nanotubes. A detailed comparison between synthetic and bioorganic polyamines with respect to titania film properties deposition rate provided valuable information for future titania coating experimental design given specific applications. The development of template-based approaches to single-wall titania nanotube arrays led to the development of a new synthetic method to create aligned, multi-walled titania nanotube arrays. Lastly, peptide-enabled deposition methods were extended beyond inorganic mineral and used for enzyme immobilization by cross-linking the peptide with the multicopper oxidase laccase. Peptide-laccase hybrid enzyme coatings improved both the amount of enzyme adsorbed onto carbon nanotube “buckypaper” and allowed the enzyme to retain more activity upon immobilization onto the surface.

Novel paint driers based on iron co-ordination complexes were investigated for use as stoving finishes in oil-based coatings. Cis 9, cis 12-octadecadienoic acid was employed as a model vehicle because of its high drying capacity. Iron compounds generally have low catalytic efficiency at low temperatures which however improve with rises in temperature. The catalytic efficiency of some iron compounds was compared with those of some conventional driers at room temperature; 60 C, 80 C and 1200 C. To make the results comparative, equal weights of drier (0.05%) metal were employed in one series of experiments. In another series, a much higher concentration (0.25%) metal based on the weight of 9,12-octadecadienoic acid was employed. Equal weights of drier combination(s) and variable drier weights were examined to determine synergism or antagonism in the autoxidative systems. Maximum oxygen absorption, changes in iodine and peroxide values were monitored to determine a comparative catalytic performance of the driers at the reaction temperatures used. The reactivity of iron co-ordination complexes was found to be influenced by the organic compound with which the iron is chelated. Zerovalent iron complexes can be employed as high temperature driers. For convenience some common names have been used for major chemicals of importance in this work, e. g., Linoleic acid; cis 9, cis 12-octadecadienoic acid. Ferrocene; dicyclopentadienyl iron.

This work investigates the feasibility of the use of plasma spray deposition as a method of producing high performance polymer coatings. The work concentrates on the understanding of the processing of the plasma spraying of polymers, the behaviour of polymeric materials during deposition, and the study of process-structure-properties relationships. Processing modelling for the three stages of the evolution of a polymer deposit (droplet-splat-coating) has been carried out using heat transfer theory. A theoretical model is proposed which consists of three parts: the first part predicts the temperature profile of in-flight particles within plasma jet, the second part predicts the cooling of isolated splats impacting on a substrate and the third part, the heat transfer through the coating thickness. The heat transfer analysis predicts that the development of large temperature gradients within the particle is a general characteristics of polymers during plasma spraying. This causes difficulties for polymer particles to be effectively molten within the plasma jet without decomposition. The theoretical calculations have predicted the effect of processing parameters on the temperature, the degree of melting and decomposition of in-flight polymer particles. With the aid of the model, the conditions for the preparation of high integrity thermoplastic deposits have been established by the control of the plasma arc power, plasma spraying distance, feedstock powder injection, torch traverse speed and feedstock particle size. The optimal deposition conditions are designed to produce effective particle melting in the plasma, extensive flow on impact, and minimal thermal degradation. The experimental work on optimizing processing parameters has confirmed the theoretical predictions. Examination of polymer coating structures reveals that the major defects are unmelted particles, cracks and pores. Five major categories of pores have been classified. It also revealed a significant loss in crystallinity and the presence of a minor metastable phase in the plasma deposited polyamide coatings due to rapid solidification. The study has indicated that the molecular weight of a polymer plays an important role on the splat flow and coating structure. Under non-optimal deposition condition, substantial thermal degradation occurred for which a chain scission mechanism is proposed for plasma deposited polyamide coatings. There are difficulties in achieving cross-linking during plasma spray deposition of thermosets. The theoretical calculations predict that adequate cross-linking is unlikely in a coating deposited under normal conditions, but preheating the substrate to above the cross-linking temperature improves the degree of cross-linking of the coatings substantially. In addition, the coating thickness has a major effect on the degree of cross-linking of thermosets. The calculations also predict that lowering the thermal conductivity by applying a thermal barrier undercoat and using a faster curing agent to reduce time required for the cross-linking reaction can improve the degree of cross-linking of thermoset deposits. The experimental results for the degree of cross-linking and wear resistance confirmed these predictions.

A study of thermal, structural, electrical and optical characteristics of molybdenum black surface coatings on various substrates has been made. The suitability of these coatings for use as selective absorbers for solar collector applications has been assessed. Molybdenum black (Mo black) coatings were prepared by electrodeposition (on aluminium) and a chemcial conversion method (on zinc and electroplated cobalt on nickel plated copper substrates). The solar absorptancer (αs) and thermal emittances (εth) of the coatings were determined from room temperature spectral reflectance measurements in the solar (0.3 to 2.5μm) and infrared regions (2.5 to 50 μm) respectively. The effect of different preparation parameters and substrate pretreatments on the spectral selectivity has been investigated in order to optimize the thermal performance. The spectral selectivity is related to the Mo-black coating thickness and surface roughness together with the microstructure, of the substrate and the intermediate layer. Dip coatings on polished zinc have significant selectivity (αs/ εth = 8.4 when αs = 0.76). The absorptance of the dip coatings is increased to 0.87 with εth = 0.13 by chemical etching of zinc prior to coating deposition. For coatings on electroplated cobalt on nickel plated copper (cobalt (NC) substrate), an absorptance as high as 0.94 has been obtained with an emittance value 0.3. By using an addition agent in the plating solution of cobalt the high emittance can be reduced to 0.1 with αs = 0.91 giving a coating with a relatively high efficiency (82.5%) for photo-thermal energy conversion. A study of the surface composition and microstructure of the coatings has been made using scanning and transmission electron microscopy together with electron diffraction, X-ray diffraction and X-ray photoelectron spectroscopy. The structural investigations indicate that Mo-black coatings contain polycrystals of orthorhombic Mo4O11 with a small proportion of Ni(OH)2. Presence of water and also Mo4O11 in the coatings are evident from IR spectroscopy study. The bandgap of the coating has been determined from optical transmission spectra (1.66 eV) and also from reflectance spectra (0.85 eV). The discrepancy between these two values has been discussed. The refractive indices of the coatings have also been estimated. The band gaps and refractive indices are found to be related to the spectral selectivity of the coatings. The durability test of the coatings shows that the coatings on etched zinc are more resistant to heat treatment than the coatings on unetched zinc. The coatings on cobalt (NC) substrates also show good stability for relatively short periods at temperatures ~400ºC. A study of the electrical properties of Mo-black coatings suggests that at electrical field strengths (greater than 106v/m the dominant conduction process is of the Poole-Frenkel type. The activation energy of the conduction process has been estimated to be -0.56 eV at higher temperatures. The effect of heat treatment on the electrical properties of the coatings has been examined. The dielectric constant of Mo-black has been estimated from A. C. measurements. At high frequency (20 kHz) the value of the dielectric constant is about 4.0.

No description available.

No description available.

Regular disinfection of surfaces is required in order to reduce the number of microorganisms, unable to transmit infections and maintaining the surfaces sterilized. For this purpose, antimicrobial thin film coatings on the various surfaces such as glass and ceramic surfaces, capable of killing harmful microorganisms are being investigated. Generally a semiconducting material which can be activated by UV light tends to exhibit a strong antimicrobial activity. With holes (h+) and hydroxyl radicals (OH*) generated in the valence band, electrons and the superoxide ions (O2-) generated in the conduction band, illuminated semiconductor photocatalysts can inactivate microorganisms by participating in a series of oxidation reactions leading to carbon dioxide. The aim of this current study was developing semiconductor coatings, increasing the photocatalytic activity of these coatings by metal doping, particularly palladium doping, and investigating the antimicrobial properties of these coatings. In this study, glass surfaces were coated with titanium dioxide (TiO2), tin dioxide (SnO2) and palladium doped TiO2 and SnO2 sol-gels. After achieving thin, dense and strong coatings, antimicrobial properties of the coatings were investigated by applying the indicator microorganisms directly onto the coated glasses. Different cell wall structure of microorganisms can strongly affect the photocatalytic efficiency of the coatings. Hence Escherichia coli as a Gr (-) bacteria, Staphylococcus aereus as Gr (+) bacteria, Saccharomyces cerevisiae as a yeast and Aspergilus niger spores were used in the experiments. Photocatalytic efficiency of TiO2 was better than SnO2 coatings. Palladium doping increased the antimicrobial activity of both coatings. The reduction efficiencies were found to decrease in the following order of E. coli [Gr (-)] &gt / S. aereus [Gr (+)] &gt / S.cerevisiae (yeast) &gt / A. niger spores. The complexity and the density of the cell walls increased in the same order. As a result of this study, with the coating that shows the best photocatalytic activity, 98% of Escherichia coli, 87% of Staphylococcus aereus, 43% Saccharomyces cerevisiae were killed after 2 hours illumination.

Graduation date: 2004