Alloys of Lead and Tellurium

Prior to the last few years little practical use was made of the element tellurium, which is obtained from gold and silver tellurides and from the slimes of electro­lytic copper refineries. Lately, however, more study has been made of its properties when alloyed with other metals. It was the purpose of this thesis to study the effects of the addition of tellurium to lead, particularly in small amounts.

Biotransformações na obtenção de hidróxi-selenetos e hidróxi-teluretos quirais

Neste trabalho foi estudado o comportamento de hidróxi-calcogenetos (Se e Te) frente a biotransformações, empregando enzimas isoladas em meio orgânico ou aquoso e empregando microorganismos (fungos). Estudos comparativos sobre a influência de diversas variáveis, como solvente, temperatura, imobilização enzimática e estrutura do hidróxi-calcogeneto, foram realizados. Inicialmente os compostos foram sintetizados utilizando métodos descritos na literatura, em seguida foi estudada a resolução de hidróxiselenetos em meio orgânico empregando lipases isoladas (Esquema 1), (ver arquivo), incluindo um estudo de imobilização da PSL em diversos suportes, além do estudo da influência da variação do solvente, da temperatura, da lipase, etc. Na resolução em meio aquoso empregando enzimas isoladas, primeiramente os hidróxi-selenetos foram acetilados quimicamente e depois realizado uma triagem (com dez enzimas de diferentes fontes) empregando indicador de pH colori métrico. Posteriormente os acetatos dos hidróxi-selenetos (Esquema 2) (ver arquivo) foram submetidos à resolução enzimática em meio aquoso empregando as enzimas que foram selecionadas na triagem enzimática. As biotransformações utilizando fungos foram realizadas empregando células inteiras de algumas linhagens de Aspergillus terreus. Na seqüência foi realizada a resolução de hidróxi-teluretos em meio orgânico utilizando lipases isoladas (Esquema 3)(ver arquivo). Nessas resoluções também foi estudada a influência da variação do solvente, da lipase, do tempo, etc. De forma a demonstrar a importância dos compostos resolvidos, um hidróxi-seleneto quiral e dois hidróxi-teluretos quirais foram usados para preparar compostos pertencentes a classes de unidades estruturais de vasta ocorrência em produtos naturais: um álcool alílico e duas lactonas (Esquema 4)(ver arquivo).

Formação de ligação carbono-carbono através de compostos orgânicos de telúrio

Diversas classes de compostos orgânicos de telúrio foram exploradas neste trabalho. Inicialmente foi estudada a transmetalação entre teluretos alílicos e dibutil cianocupratos de lítio de ordem superior, levando aos respectivos cianocupratos alílicos de lítio. Estes, por sua vez, foram acoplados com triflatos vinílicos, importantes intermediários sintéticos preparados previamente a partir de teluretos vinílicos, levando a sistemas altamente insaturados em ótimos rendimentos (Esquema 1). (Ver no arquivo em PDF) Em seguida, foi explorada a reatividade de teluretos aromáticos frente a reagentes organometálicos. Cianocupratos arílicos, gerados a partir da transmetalação entre teluretos aromáticos com cianocupratos de lítio de ordem superior, foram adicionados a cetonas α,β -insaturadas, levando aos produtos de adição 1,4 em bons rendimentos (Esquema 2). (Ver no arquivo em PDF) Teluretos vinílicos funcionalizados de configuração Z também foram alvo de estudo visando a formação de ligação carbono-carbono. Reações de substituição entre estes teluretos e cianocupratos de lítio de ordem inferior levaram a cetonas e ésteres α,β- insaturados com estereoquímica defInida em ótimos rendimentos (Esquema 3). (Ver no arquivo em PDF) De agosto/20OJ a março/2004, a aluna realizou um estágio sanduíche na University of California, Santa Barbara, sob a orientação do Prof. Bruce H. Lipshutz, onde realizou estudos sobre a ciclização de Bergman, visando a síntese do fragmentobiarílico A-B da vancornicina. Diversas condições para a ciclização foram estudadas com um composto modelo (Esquema 4) (Ver no arquivo em PDF) e parte da síntese total do fragmento da vancomlcma, onde a ciclização seria a etapa-chave, foi realizada com sucesso (Esquema 5). (Ver no arquivo em PDF)

Chemical reactions at nuclear fuel-clad interfaces

This thesis presents a study of the chemical reactions that may occur at the fuel- clad interfaces of fuel elements used in advanced gas-coooled reactors (A.G.R.) The initial investigation involved a study of the inner surfaces of irradiated stainless steel clad and evidence was obtained to show that fission products, in particular tellerium, were associated with reaction products on these surfaces. An accelerated rate of oxidation was observed on the inner surfaces of a failed A.G.R. fuel pin. It is believed that fission product caesium was responsible for this enhancement. A fundamental study of the reaction between 20%Cr/25%Ni/niobium stabilised stainless steel and tellerium was then undertaken over the range 350 - 850 degrees C. Reaction occurred with increasing rapidity over this range and long term exposure at ≤ 750 degrees resulted in intergranular attack of the stainless steel and chromium depletion. The reaction on unoxidised steel surfaces involved the formation of an initial iron-nickel-tellerium layer which subsequently transformed to a chromium telluride product during continued exposure. The thermodynamic stabilities of the steel tellurides were determined to be chromium telluride > nickel telluride > iron telluride. Oxidation of the stainless steel surface prior to tellerium exposure inhibited the reaction. However reaction did occur in regions where the oxide layer had either cracked or spalled.

Gold mineralisation in the Caledonides of the British Isles with special reference to the Dolgellau Gold-belt, North Wales and the Southern Uplands, Scotland. Available in 2 volumes.

Two aspects of gold mineralisation in the Caledonides of the British Isles have been investigated: gold-telluride mineralisation at Clogau Mine, North Wales; and placer gold mineralisation in the Southern Uplands, Scotland. The primary ore assemblage at Clogau Mine is pyrite, arsenopyrite, cobaltite, pyrrhotine, chalcopyrite, galena, tellurbismuth, tetradymite, altaite, hessite, native gold, wehrlite, hedleyite, native bismuth, bismuthunite and various sulphosalts. The generalised paragenesis is early Fe, Co, Cu, As and S species, and later minerals of Pb, Bi, Ag, Au, Te, Sb. Electron probe micro-analysis (EPMA) of complex telluride-sulphide intergrowths suggests that these intergrowths formed by co-crystallisation/replacement processes and not exsolution. Minor element chemical variation, in the sulphides and tellurides, indicates that antimony and cadmium are preferentially partitioned into telluride minerals. Mineral stability diagrams suggest that during gold deposition log bf aTe2 was between -7.9 and -9.7 and log bf aS2 between -12.4 and -13.8. Co-existing mineral assemblages indicate that the final stages of telluride mineralisation were between c. 250 - 275oC. It is suggested that the high-grade telluride ore shoot was the result of remobilisation of Au, Bi, Ag and Te from low grade mineralisation elsewhere within the vein system, and that gold deposition was brought about by destabilisation of gold chloride complexes by interaction with graphite, sulphides and tellurbismuth. Scanning electron microscopy of planer gold grains from the Southern Uplands, Scotland, indicates that detailed studies on the morphology of placer gold can be used to elucidate the history of gold in the placer environment. In total 18 different morphological characteristics were identified. These were divided on an empirical basis, using the relative degree of mechanical attrition, into proximal and distal characteristics. One morphological characteristic (a porous/spongy surface at high magnification) is considered to be chemical in origin and represent the growth of `new' gold in the placer environment. The geographical distribution of morphological characteristics has been examined and suggests that proximal placer gold is spatially associated with the Loch Doon, Cairsphairn and Fleet granitoids. Quantitative EPMA of the placer gold reveals two compositional populations of placer gold. Examination of the geographical distribution of fineness suggests a loose spatial association between granitoids and low fineness placer gold. Also identified was chemically heterogeneous placer gold. EPMA studies of these heterogeneities allowed estimation of annealing history limits, which suggest that the heterogeneities formed between 150 and 235oC. It is concluded, on the basis of relationships between morphology and composition, that there are two types of placer gold in the Southern Uplands: (i) placer gold which is directly inherited from a hypogene source probably spatially associated with granitoids; and (ii) placer gold that has formed during supergene processes.

Mineralogy, mineral chemistry, and genesis of precious metal-bearing volcanogenic massive sulfide deposits in the Newfoundland Appalachians, Canada: the Ming deposit as example

The Ming deposit, Newfoundland Appalachians, is a metamorphosed (upper greenschist to lower amphibolite facies), Cambro-Ordovician, bimodalmafic volcanogenic massive sulfide (VMS) deposit that consists of several, spatially-associated, elongated orebodies composed of stratabound semimassive to massive sulfides and/or discordant sulfide stringers in a rhyodacitic footwall. Copper is the main commodity; however, the deposit contains precious metal-bearing zones with elevated Au grades. In this study, field observations, microscopy, and micro-analytical tools including electron microprobe, laser ablation inductively coupled plasma mass spectrometry, and secondary ion mass spectrometry were used to constrain the relative timing of precious metal emplacement, the physico-chemical conditions of hydrothermal fluid precipitation, and the sources of sulfur, precious metals, semi-metals and metals. The ore mineral assemblage is complex and indicates an intermediate sulfidation state. Pyrite and chalcopyrite are the dominant ore minerals with minor sphalerite and pyrrhotite, and trace galena, arsenopyrite and cubanite. Additional trace phases include tellurides, NiSb phases, sulfosalts, electrum, AgHg±Au alloys, and oxides. Silver phases and precious metals occur predominantly in semi-massive and massive sulfides as free grains, and as grains spatially associated with arsenopyrite and/or sulfosalts. Precious metal phases occurring between recrystallized pyrite and within cataclastic pyrite are rare. Hence, the complex ore assemblage and textures strongly suggest syngenetic precious metal emplacement, whereas metamorphism and deformation only internally and locally remobilized precious metal phases. The ore assemblage formed from reduced, acidic hydrothermal fluids over a range of temperatures (≈350 to below 260ºC). The abundance of telluride and Ag-bearing tetrahedrite, however, varies strongly between the different orebodies indicating variable ƒTe₂, ƒSe₂, mBi, and mSb within the hydrothermal fluids. The variations in the concentrations of semi-metals and metals (As, Bi, Hg, Sb, Se, Te), as well as Au and Ag, were due to variations in temperature but also to a likely contribution of magmatic fluids into the VMS hydrothermal system from presumably different geothermal reservoirs. Sulfur isotope studies indicate at least two sulfur sources: sulfur from thermochemically-reduced seawater sulfate and igneous sulfur. The source of igneous sulfur is the igneous footwall, direct magmatic fluid/volatiles, or both. Upper greenschist to lower amphibolite metamorphic conditions and deformation had no significant effect on the sulfur isotope composition of the sulfides at the Ming deposit.

Energy level decay and excited state absorption processes in erbium-doped tellurium glass

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)