A method for the determination of platinum group elements (PGEs) in natural tree samples was developed. An alumina column in-line with inductively coupled plasma mass spectrometry (ICP-MS) achieves the separation of interferents as well as pre-concentration of the analytes. The application of this proposed method on tree top samples displayed an effective separation of Ru, Rh, Re, Pd, Ir and Pt from the interferents, Ni, Cu and Zn for quantitative analysis of the analytes. The concentration data was compared to ICP-HRMS data and while it was difficult to determine whether the concentrations were in agreement or not, as both methods have a large degree of error. However, both methods displayed elevated concentrations of PGEs in areas over geological conductors in Rock Lake, Manitoba. This proposed method offers distinct advantages over previous on-line methods, as it is extended to include multiple PGEs as well as reduces sample consumption to a more suitable volume for natural samples. While the detection limit is higher than previous methods due to the lowered sample volume, it is still lower than the detection limits reported in commercial laboratories. / Thesis (Master, Chemistry) -- Queen's University, 2008-01-30 19:40:54.673 / Anglo American

No description available.

Indium tin oxide (ITO) and molybdenum are substrates of choice in the manufacture of the CdS-CIS photovoltaic cell, which is the base for the leading thin-film solar cell technology. Substantial advancement in this technology is expected if these devices can be made in nanoporous alumina (AAO) templates. The first step to this endeavor is to learn to form AAO templates on molybdenum and ITO substrates. This was accomplished, and the results are reported in this thesis. Starting substrates were glass, coated with either a thin molybdenum layer or a thin ITO layer. Aluminum was deposited on top of this conducting substrate. Oxalic acid was used as the electrolyte for anodization. In the case of molybdenum substrates, average pore diameter was 45 nm when an anodization voltage of 40 volts was used for approximately 46 minutes; current density was approximately 23 amps/sq. m. In the case of ITO substrates, pores of 45 nm diameter were obtained for approximately 20 minute anodization at 40 V; current density was 40 amps/sq. m; annealing of aluminum layer prior to anodization, at 550 oC (degrees Centigrade) for 90 minutes was needed to obtain good pores. A one micrometer thick CdS layer was electrodeposited inside the AAO pores on top of the ITO substrate. In preliminary experiments, CdS/Cu2S photovoltaic heterojunctions with an open circuit voltage of 242 mV were formed inside the nanopores.

No description available.

The objective of this study was to determine how Al2O3 nanoparticle concentration affected the specific heat, heat of fusion, melting point, thermal diffusivity and thermal conductivity of Alumina-Nitrate nanofluids. Al2O3 nanoparticles were dispersed in a eutectic of sodium nitrate and potassium nitrate (60:40 for mole fraction) to create nanofluids using a hot plate evaporation method and an air dryer method. The nominal Al2O3 (alumina) mass fraction was between 0 and 2%, and was determined as the ratio of the mass of Al2O3 nanoparticles to the total mass of the nanofluid. After the preparation of the nanofluids, Neutron Activation Analysis (NAA) was used to measure the actual Al2O3 mass fraction in the nanofluids. The specific heat, heat of fusion, and melting point were measured with a Modulated Differential Scanning Calorimeter (MDSC). The thermal diffusivity and thermal conductivity were measured with Laser Flash Analysis (LFA). The MDSC results showed that the addition of Al2O3 nanoparticles enhanced the specific heat of the nanofluids synthesize from both methods. There was a parabolic relation between the specific heat and the Al2O3 mass fraction for the nanofluids synthesized from the hot plate evaporation method, with a maximum 31% enhancement at 0.78% Al2O3 mass fraction. The nanofluids synthesized from the air dryer method also resulted in enhanced specific heats which were higher at the same Al2O3 mass fraction than those of the nanofluids synthesized from the hot plate evaporation method. It was not determined why this enhancement occurred. The results also showed that the introduction of Al2O3 nanoparticles had no significant effect on the heat of fusion and melting point of the nanofluids synthesized from either method. The LFA results showed that adding Al2O3 nanoparticles decreased the thermal diffusivity and the thermal conductivity of the nitrate eutectic.

In this study, a new arranged catalyst support with distinct open pore morphology has been fabricated via thermal oxidation of an FeCrAl alloy with an aim to address mass transfer limitations that conventional supports have due to their internal porosity. Subsequent characterization tests including, drop shape analysis, X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy revealed that the support formed upon thermal oxidation for 1 hour at 930C, 1 hour at 960C and 2 hours at 990C embodies advantageous support characteristics. Preliminary tests were performed using palladium (active component) deposited on the new support in representative three phase hydrogenation reactions of 2-methyl-3-butyn-2-ol or 2-methyl-3-buten-2-ol. Absence of mass transfer limitations was verified for 2-methyl-3-buten-2-ol hydrogenation at 35-50C, 1200 rpm stirring speed and 0.46 MPa pressure of hydrogen in a 300 ml semi-batch reactor using ethanol as solvent. The study paves the way to the development of arranged catalysts based on FeCrAl alloy fibers for structured reactors. / Chemical Engineering

Inkjet printing is a mature technique for colourful graphic arts. It excels at customized, large area, high resolution, and small volume production. With the developments in conductive, and dielectric inks, there is potential for large area inkjet electronics fabrication. Passive radio frequency devices can benefit greatly from a printing process, since the size of these devices is defined by the frequency of operation. The large size of radio frequency passives means that they either take up expensive space “on chip” or that they are fabricated on a separate lower cost substrate and somehow bonded to the chips. This has hindered cost-sensitive high volume applications such as radio frequency identification tags. Substantial work has been undertaken on inkjet-printed conductors for passive antennas on microwave substrates and even paper, yet there has been little work on the printing of the dielectric materials aimed at radio frequency passives. Both the conductor and dielectric need to be integrated to create a multilayer inkjet printing process that is capable of making quality passives such as capacitors and inductors. Three inkjet printed dielectrics are investigated in this thesis: a ceramic (alumina), a thermal-cured polymer (poly 4 vinyl phenol), and a UV-cured polymer (acrylic based). For the conductor, both a silver nanoparticle ink as well as a custom in-house formulated particle-free silver ink are explored. The focus is on passives, mainly capacitors and inductors. Compared to low frequency electronics, radio frequency components have additional sensitivity regarding skin depth of the conductor and surface roughness, as well as dielectric constant and loss tangent of the dielectric. These concerns are investigated with the aim of making the highest quality components possible and to understand the current limitations of inkjet-fabricated radio frequency devices. An inkjet-printed alumina dielectric that provides quality factors of 200 and high density capacitors of 400 pF/mm2 with self-resonant frequencies into the GHz regime is developed in this thesis. A multilayer fully printed process is demonstrated using PVP dielectric and dissolving type vias, giving better than 0.1 ohm resistance. In the multilayer process, capacitors and inductors have self-resonant frequencies around 1GHz. These fully printed devices have quality factors less than 10. Finally, 3D inkjet-printed UV-cured material is utilized with a novel silver organo-complex ink at 80oC providing conductivity of 1x107 S/m. A lumped element filter is demonstrated with an insertion loss of only 0.8 dB at 1GHz. The combination of inkjet printing 3D polymer and conductive metal together allows for complex shapes. A fully printed antenna with 81% radiation efficiency is shown. With these promising results and future advances in conductive inks and low-loss dielectrics, the performance of inkjet passives could one day overcome conventional fabrication methods.

The present thesis focuses on characterisation of microstructure and the resulting mechanical and tribological properties of CVD and PVD coatings used in metal cutting applications. These thin and hard coatings are designed to improve the tribological performance of cutting tools which in metal cutting operations may result in improved cutting performance, lower energy consumption, lower production costs and lower impact on the environment.  In order to increase the understanding of the tribological behaviour of the coating systems a number of friction and wear tests have been performed and evaluated by post-test microscopy and surface analysis. Much of the work has focused on coating cohesive and adhesive strength, surface fatigue resistance, abrasive wear resistance and friction and wear behaviour under sliding contact and metal cutting conditions. The results show that the CVD deposition of accurate crystallographic phases, e.g. α-Al2O3 rather than κ-Al2O3, textures and multilayer structures can increase the wear resistance of Al2O3. However, the characteristics of the interfaces, e.g. topography as well as interfacial porosity, have a strong impact on coating adhesion and consequently on the resulting properties.  Through the deposition of well designed bonding and template layer structures the above problems may be eliminated. Also, the presence of macro-particles in PVD coatings may have a significant impact on the interfacial adhesive strength, increasing the tendency to coating spalling and lowering the surface fatigue resistance, as well as increasing the friction in sliding contacts. Finally, the CVD-Al2O3 coating topography influences the contact conditions in sliding as well as in metal cutting. In summary, the work illuminates the importance of understanding the relationships between deposition process parameters, composition and microstructure, resulting properties and tribological performance of CVD and PVD coatings and how this knowledge can be used to develop the coating materials of tomorrow.

abstract: The release of organophosphorus compounds (OPs) and subsequent exposure to these compounds is of concern to humans and the environment. The goal of this work was to control the concentrations of gaseous OPs through interaction with sorbent oxides. Experimental and computational methods were employed to assess the interactions of dimethyl phosphite (DMHP), dimethyl methylphosphonate (DMMP), dimethyl ethylphosphonate (DMEP), diethyl ethylphosphonate (DEEP), and triethyl phosphate (TEP) with amorphous silica (a-silica), ã-alumina, and monoclinic zirconia (m-zirconia) for applications in air pollution control. Interactions of the selected OPs with a-silica were chosen as a baseline to determine the applicability of the computational predictions. Based on the a-silica results, computational methods were deemed valid for predicting the trends among materials with comparable interactions (e.g. -OH functionality of a-silica interacting with the phosphonyl O atoms of the OPs). Computational evaluations of the interactions with the OPs were extended to the oxide material, m-zirconia, and compared with the results for ã-alumina. It was hypothesized that m-zirconia had the potential to provide for the effective sorption of OPs in a manner superior to that of the a-silica and the ã-alumina surfaces due to the surface charges of the zirconium Lewis acid sites when coordinated in the oxidized form. Based on the computational study, the predicted heats of adsorption for the selected OPs onto m-zirconia were more favorable than those that were predicted for ã-alumina and a-silica. Experimental studies were carried out to confirm these computational results. M-zirconia nanoparticles were synthesized to determine if the materials could be utilized for the adsorption of the selected OPs. M-zirconia was shown to adsorb the OPs, and the heats of adsorption were stronger than those determined for commercial samples of a-silica. However, water interfered with the adsorption of the OPs onto m-zirconia, thus leading to heats of adsorption that were much weaker than those predicted computationally. Nevertheless, this work provides a first investigation of m-zirconia as a viable sorbent material for the ambient control of the selected gaseous OPs. Additionally, this work represents the first comparative study between computational predictions and experimental determination of thermodynamic properties for the interactions of the selected OPs and oxide surfaces. / Dissertation/Thesis / Ph.D. Chemical Engineering 2011

Neste trabalho foram estudadas estruturas cerâmicas laminares formadas por lamelas de alumina de alta pureza e lamelas do compósito alumina/zircônia parcialmente estabilizada. Estas estruturas foram conformadas por colagem de barbotina sequencial. Nas lamelas constituídas pelo compósito alumina/zircônia foi investigado o efeito do teor de zircônia parcialmente estabilizada nas propriedades do compósito laminar. Depois de dominada a técnica de produção dos compósitos, as propriedades mecânicas destas cerâmicas foram caracterizadas e otimizadas. Foi verificada a influência da espessura relativa entre as camadas no campo de tensões residuais formado. Um estudo sistemático foi desenvolvido para relacionar as propriedades mecânicas dos compósitos laminares com mecanismos microscópicos existentes neste tipo de cerâmicas. Neste estudo foram realizados testes instrumentados de dureza, ensaios de flexão, medidas de fluorescência de rubi para avaliação do nível de tensionamento interno, ensaios de dureza, análises por microscopia eletrônica de varredura e microscopia óptica, e simulações computacionais por elementos finitos. Os resultados mostraram que, além da influência da espessura relativa entre as lâminas, há uma forte influência da razão de aspecto (RA=L/d, onde L é a largura da lâmina e d seu comprimento). / In this study, laminar ceramic structures formed by layers of high purity alumina and alumina/partially stabilized zirconia composite layers were investigated. These structures were formed by sequential slip casting. In the alumina/zirconia layers it was investigated the effect of partially stabilized zirconia content on the composite properties. After mastering the experimental technique to produce the laminar ceramic composites, their mechanical properties were characterized and optimized. The influence of the thickness of adjacent layers on the residual stress fields formed was investigated. A systematic study was settled to correlate the mechanical properties of laminar composites with microscopic mechanisms peculiar of this type of ceramics. The samples were characterized by hardness instrumented tests (HIT), bending tests, fluorescence measurements, hardness tests, scanning electron microscopy and optical microscopy, and computational simulations using finite elements. The results showed that, besides the influence of the relative thickness between the layers there was a strong influence of the aspect ratio (AR = W / d, where W is the width of the layer and d its length).