Seventeen novel osmium cymene complexes with O,O′- and P,P′-chelating ligands as well as N- and P-monodentate ligands are reported. The osmium cymene complexes were synthesised and characterised by spectroscopic techniques (NMR, IR and Raman), elemental analysis, thermal analysis, conductivity studies and X-ray crystallography. The molecular structures of complexes 1(b), 2, 4, 6, 7(a)-(d) and 11 in this study are reported. The cymene rings of these complexes show different conformations due to loss of planarity influenced by the ancillary ligands as a result of ML back bonding. Osmium cymene complexes of the type [Os(η6-p-cymene)BrL2]+ (where L2 = chelating P,P′ ligand) and binuclear [{Os(η6-p-cymene)Br2}2 L2] (where L2 = bridging P,P′ ligand) were evaluated for anticancer activity against renal, melanoma, breast and HeLa cancer cells. The chelated-diphosphine osmium cymene complexes exhibited significant anticancer activities relative to the bridged-diphosphine osmium analogues. A series of O,O′-chelated osmium complexes exhibited moderate and poor anticancer activities. / Chemistry / M. Sc. (Chemistry)

The semiconducting silicides offer significant potential for use in optoelectronic devices. Full implementation of the materials, however, requires the ability to tailor the energy gap and band structure to permit the synthesis of heterojunctions. One promising approach is to alloy the silicides with Ge. As part of an investigation into the synthesis of semiconducting silicide heterostructures, a series of β-Fe(Si1−xGex)2 epilayer samples, with nominal alloy content in the range 0 < x < 0.15, have been prepared by molecular beam epitaxy on Si(100). I present results of the epitaxial and crystalline quality of the films, as determined by reflection high-energy electron diffraction, Rutherford backscattering spectroscopy, and double crystal x-ray diffraction, and of the band gap dependence on the alloy composition, as determined by Fourier transform infrared spectroscopy. A reduction in band gap was observed with increasing Ge content, in agreement with previous theoretical predictions. However Ge segregation was also observed in β-Fe(Si1−xGex)2 epilayers when x > 0.04. Osmium silicide films have been grown by molecular beam epitaxy on Si(100). The silicides have been grown using e-beam evaporation sources for both Os and Si onto Si(100) substrates at varying growth rates and temperatures ranging from 600-700ºC. The resulting films have been analyzed using reflection high-energy electron diffraction, Raman spectroscopy, reflectivity measurements, in-plane and out of plane X-ray diffraction and temperature dependent magnetotransport. A change in crystalline quality is observed with an increase in Si overpressure. For a lower silicon to osmium flux ration (JSi/JOs=1.5) both OsSi2 and Os2Si3 occur, whereas with a much larger Si overpressure (JSi/JOs>4), crystalline quality is greatly increased and only a single phase, Os2Si3, is present. The out-of-plane X-ray diffraction data show that the film grows along its [4 0 2] direction, with a good crystal quality as evidenced by the small FWHM in the rocking curve. The in-plane X-ray diffraction data show growth twins with perpendicular orientation to each other.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Nanostructured noble metals exhibit novel physical, mechanical and chemical behavior, and hold promise for applications such as gas sensing and electron emission. A strong emphasis was placed on the processing and characterization of these materials, in the form of nanoporous or nanocrystalline thin films. Palladium-based and osmium-ruthenium alloys were investigated in this dissertation research and will be presented as follows: (1) Preparation and Characterization of Nanoporous Metal Thin Films (2) Characterization of Osmium-Ruthenium Coatings Nanoporous palladium (np-Pd) thin films were prepared by dealloying co-sputtered palladium-nickel precursor alloys. Nanoporous structures were created with 3-D interconnected ligaments and open pores. Size of ligaments and pores was ~5 nm, achieved with a novel processing method developed in this study. Hydrogen cycling tests performed with np-Pd films demonstrated a significant improvement in sensitivity to hydrogen and response time for sensing. Effects of alloying element (Ni), film thickness, local stress and pore/ligament size on hydrogen cycling behavior were investigated in detail. Additionally, nanoporous gold and gold-palladium thin films were studied to clarify the evolution of microstructure during dealloying, including the formation of nanoporous structure and effects of substrate curvature on dealloying behavior. The results from this project have yielded a new understanding of dealloying as well as an ideal coating material for hydrogen sensing. Nanocrystalline osmium-ruthenium (Os-Ru) thin films were deposited on porous tungsten substrates with varied sputtering parameters. These parameters were mapped to microstructure, film texture and film composition in samples that were comparable to commercial devices. Using this map, Os-Ru films can be produced with higher stability during annealing and/or high-temperature operation. These results should lead to Os-Ru top coatings that increase the lifetime and emission performance of dispenser cathodes.

No description available.

Bibliography: leaves 317-318

Pour la première fois, nous avons utilisé les isotopes de l'osmium, comme traceurs de l'empreinte environnementale d'une aluminerie Rio Tinto Alcan située au Saguenay. La technologie « précuite » de l'entreprise permet de réduire l'alumine en aluminium métallique, grâce à des anodes de carbone. Ces anodes sont consumées au cours du procédé d'électrolyse et parce qu'elles sont constituées de coke de pétrole et de brai (résidus de matières pétrolifères à l'âge géologique important) aux rapports Re/Os élevés, l'osmium qui s'y trouve est radiogénique (riche en isotope 187Os, le produit de la désintégration radioactive du 187Re). Par conséquent, il en est de même pour l'osmium présent dans les émissions atmosphériques de ce type d'industrie. Les signatures isotopiques mesurées sur les anodes et aux cheminées de l'usine sont très radiogéniques (187Os/188Os = 2,04 à 2,86). Dans l'environnement proche de l'usine, nous avons observé une forte teneur en Os dans des dépôts de surface. Elle diminue au fur et à mesure que l'on s'éloigne de l'usine, jusqu'à atteindre 25 ppt au point d'échantillonnage le plus proche de la limite de la propriété industrielle (la valeur moyenne pour la croûte continentale est d'environ 30 ppt). La composition isotopique des émissions atmosphériques particulaires de l'usine est donc différente des autres sources d'osmium anthropogéniques usuelles, provenant de contextes géologiques ultramafiques. L'Os est donc un bon candidat pour surveiller les émissions atmosphériques d'une aluminerie; sa signature isotopique en sortie d'usine étant sensiblement distincte de celle de l'environnement naturel (croûte continentale moyenne 187Os/188Os ~ 1.2). Pour le cas particulier de l'usine étudiée ici, la charge sédimentaire régionale (mesuré sur des niveaux pré-anthropiques d'un forage dans la Baie des Ha!-Ha!) présente une composition isotopique similaire à celle du matériel anodique, rendant plus difficile la détection d'un apport en Os provenant des anodes sur la base de la composition isotopique. Par contre, l'absence d'augmentation des teneurs en Os entre les niveaux pré-industriels et actuels tend à démontrer un faible apport anthropique (toutes sources confondues) à cet environnement sédimentaire. En tentant d'établir le bilan annuel d'osmium de l'usine G-B, nous constatons une perte d'osmium en sortie d'usine, représentant près de 65% de la quantité totale entrant en usine. Cette perte d'Os particulaire dans le bilan pourrait être expliquée par les conditions thermodynamiques du procédé d'électrolyse, qui sont favorables à une liaison entre l'osmium et le fluor, favorisant ainsi une libération de l'osmium sous forme gazeuse (OsFx) aux cheminées. Globalement, cette étude démontre que les isotopes de l'Os sont de bons traceurs de matières particulaires provenant de l'industrie de l'aluminium, et illustre l'efficacité des dispositifs de réduction des émissions atmosphériques particulaires pour l'osmium. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Osmium, isotope, géochimie isotopique, aluminerie, anode de carbone, Re-Os, émissions atmosphériques particulaires.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy