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O problema da emissão de gases de efeito estufa é uma questão que tem ganhado destaque nas recentes convenções internacionais. Adiciona-se a esta questão o fato de o setor siderúrgico ser responsável por parcela significativa nas emissões de gases de efeito estufa. O presente trabalho tem por objetivos estudar processos de redução de minérios de ferro usando hidrogênio e hidrogênio mais monóxido de carbono como redutor para o processo de redução, visando assim à diminuição nas quantidades de CO2 liberadas pelo processo de redução de minérios de ferro. Os minérios foram caracterizados por Microscopia Eletrônica de Varredura, difração de raios-X, quantificação de fases pelo método Rietveld e distribuição granulométrica. Os ensaios de redução foram realizados em balança termogravimétrica e em forno tubular horizontal. A caracterização dos produtos foi realizada usando imagens obtidas por Microscopia Eletrônica de Varredura. Foi constatado que os aumentos da temperatura de redução e do fluxo de gás redutor provocam uma maior degradação física das pelotas. Verificou-se que ocorre a formação de whiskers na superfície externa das pelotas, sendo estes mais frequentes quando do fluxo combinado de H2+CO. Verificou-se que as pelotas reduzidas por hidrogênio puro resultaram em maior porosidade tanto no corpo da pelota ou mesmo no interior das partículas. Foi constatado que ocorre a redução homogênea em todas as partículas componentes da pelota. Foi constatado também que o estudo cinético através dos métodos combinados Jump-FSIA é aplicável na redução direta de pelotas de minério de ferro por H2 e H2+CO. Nas pelotas conformadas a partir de pellet feed com maior área de superfície específica (mais ativas), tanto a cinética quanto a taxa de redução indicaram que a adição de CO ao gás redutor não influi no processo de redução. A teoria de Sestak-Berggren sugere que o mecanismo controlador na reação global é a difusão podendo estar aliado a outras etapas, compondo um mecanismo misto. / The problem of the emission of greenhouse gases is an issue that has gained prominence in recent international conventions. Is added to this question the fact that the steel industry is responsible for a significant portion of emissions of greenhouse gases. The present work aims to study ways of reducing iron ore using hydrogen and hydrogen plus carbon monoxide as a reducing agent to the reduction process, thus aiming to decrease the amounts of CO2 released by reduction of iron ores process. The ores were characterized by Scanning Electron Microscopy, X-ray diffraction, phase quantification by Rietveld method and particle size distribution. The reduction assays were performed in thermogravimetric balance and horizontal tubular oven. The characterization of the products was performed using images obtained by scanning electron microscopy. It was found that increases in temperature and reduction in the flow of reducing gas cause greater physical degradation of the pellets. It was found that the formation of whiskers on the outer surface of the pellets occurs most frequently found when combined flow of H2+CO. It was found that the pellets reduced with pure hydrogen resulted in much higher porosity in the body pellet or even within the particles. It was found that the homogeneous reduction occurs in all components of the particle pellet. It was also found that the kinetic study using the combined methods Jump- FSIA applies in the direct reduction of iron ore pellets by H2 and H2+CO. In shaped pellets from pellet feed with higher specific surface area (more active), both the kinetics as the rate of reduction indicated that the addition of CO to the reducing gas has no effect on the reduction process. The Sestak - Berggren theory suggests that the mechanism controlling the overall reaction is diffusion can be combined with other steps, forming a mixed mechanism.

Thesis (M.Sc. (Physics)) --University of Limpopo, 2008 / We present first principles structural, electronic and optical properties investigation of PdS, which are carried out using density functional theory under plane wave pseudopotential method within the local density approximation. We used ultrasoft- pseudopotentials to carry out our calculations. Calculated lattice parameters of the system show excellent agreement with the experimental values. The lattice parameters were observed to decrease linearly with increasing pressure. The density of states and optical properties of PdS have been computed under hydrostatic pressure. The actual size of the band gap remains constant with increasing pressure, whilst the peaks just below and above the Fermi energy moves to the left and to the right respectively. We also investigated the effect of compositional variation on our reflectance by calculating the reflectivity of Pd4-xPtxS4 and Pd4-xNixS4. Since we have different positions for the same concentration, we used the heats of formation to determine the most stable structures and these structures were used to study the effect of compositional variation on our reflectance spectrum. We studied the equation of state (EOS), structure under hydrostatic pressure, and deduced the bulk modulus. It is important to study these properties under such extreme conditions of pressure and temperature as they tend to occur below the earth's surface. Investigation of stability and mechanical properties of binary and ternary compounds from PtS to PdS have been carried out, were the presence of the miscibility gap is still uncertain. We investigate stability of these compounds by studying the heats of formation, elasticity and electronic properties. Our results show no miscibility gap but continuum solid solution between these compounds. A shift of the Fermi energy towards the conduction band is observed at a 50% concentration of Pd and Pt. All the information obtained on PdS is intended to assist in fitting interatomic potentials to enable studies of systems with many atoms.

Approximately 70% of the western world's known nickel reserves are contained in laterite ores, but only 30% of the world's nickel production comes from these ores. This is due to the lack of economically viable technology to extract the nickel from these ores. However, recent advances in pressure acid leaching technology have resulted in new commercial attempts to extract nickel and its valuable by-product, cobalt, from laterite ores. The commissioning of three nickel laterite projects in Western Australia in the late 1990s represents the first of these new generation nickel operations, with several other projects; in Australia and overseas, in various stages of development. Unfortunately, several technical issues have hindered full production in these new refineries. Some of these problems are directly attributable to the mixer-settler contactors used in the solvent extraction process. This has highlighted a need to develop alternative contactors for industrial use. Electrostatic Pseudo Liquid Membrane (ESPLIM) is an alternative, novel technique to conduct the solvent extraction process. It combines the basic principles of solvent extraction, liquid membrane and electrostatic dispersion into a simple, compact reactor that utilises many advantages of each technique. The aim of this study w as to develop a method of extracting and separating cobalt from an acidic nickel laterite leach solution using ESPLIM. Bench scale tests using synthetic and actual leach solutions have shown that: the design and construction materials of the baffle plate and electrodes have a significant effect on the performance of the reactor; an AC power supply provided better droplet dispersion than a DC power supply; an increase in the applied electric field strength above a critical value resulted in a decrease in the aqueous droplet size and an increase in residence tune. / These effects increased the extraction efficiency and the concentration of the loaded strip solution. However, further increases in applied electric field strength decreased efficiency due to excessive levels of swelling and leakage; the known extraction isotherms for cobalt and nickel apply in the ESPLIM technique; salts of soluble organic acids influence extraction efficiency by changing the aqueous pH and interfacial tension; the use of ammonia was found to be effective as a replacement for salts of soluble organic acids; the ESPLIM reactor can cope with large changes in the flow rates of both feed and strip solutions. However, an increase in the feed flow rate should be accompanied by a relative increase in the ship flow rate to maintain high extraction efficiencies; the baffle design has a significant impact on the levels of swelling and leakage; provided the electrostatic field strength is maintained and flow rates are increased proportionately to the size of the reactor, no significant scale-up issues were observed, indicating that the data generated in bench scale studies could be applied to plant scale contactors. The optimum conditions, devised as a result of this investigation, to extract cobalt from an acidic nickel laterite leach solution using the ESPLIM technique are as follows: an applied electric field strength of 5.5 kV/cm. a raffinate pH of 5.5, a solvent containing 10% Cyanex 272 with 5% TBP in Solvent HF diluent, a feed to strip flow ratio of approximately 5 and a 1 M H[subscript]2S0[subscript]4 strip solution. At these conditions, almost complete cobalt extraction is achieved after only two extraction stages. A comparable extraction using conventional mixer-settlers could only be achieved after five stages.

Acid leaching of different natural chrysocolla samples under ambient conditions demonstrated that the chemical and chrystallographic inhomogenity significantly affects the rate and that it is virtually impossible to use the mineral as a model for the kinetics of hydrometallurgical processing of copper ores.Dissolution experiments, stability diagrams,and X-ray powder diffraction studies are undertaken and studied in this research and results are given.It is found that a complete solid solution series exists in Nature with most tungstenian wulfenites and molybdenum stolzites containing a range of compositions. The first occurrence of a molybdenum stolzite from Broken Hill, Australia, which also contains small amounts of chromium is noted.Raman microprobe spectroscopy has proven to be a very quick and effective non-destructive method for semi-quantitative analysis of the wulfenite-stolzite and powellite-scheelite solid-solution series and in detecting very small amounts of substituted chromate in wulfenite, stolzite and anglesite / Doctor of Philosophy (PhD)

Hydrothermal fluid flow is spatially and genetically associated with deformation in the earth�s crust. In the Otago Schist, New Zealand, the circulation of hydrothermal fluids in the Cretaceous formed numerous mesothermal gold-quartz vein deposits. Otago schist rocks are largely L-S tectonites in which the penetrative fabric is the product of more than one deformation phase/transposition cycle. Regional correlation of deformation events allowed mineralised deposits to be related to the structural evolution of the Otago Schist. Compilation of a detailed tectonostratigraphy of New Zealand basement rocks reveals that extensional mineralisation correlates with the onset of localised terrestrial fanglomerate deposition, thermal perturbation and granitic intrusion that mark the beginning of New Zealand rifting from the Antarctic portion of Gondwana. Laminated and breccia textures in mineralised veins suggest that host structures have experienced repeated episodes of incremental slip and hydrothermal fluid flow. However, analysis of vein orientation data in terms of fault reactivation theory (Amontons Law) shows that most deposits contain veins that are unfavourably oriented for frictional reactivation. Repeated movement on unfavourably oriented structures may involve dynamic processes of strain refraction due to competency contrasts, the effect of anisotropy in the schist, or localised stress field rotation. Deposits have been classified on the basis of host structure kinematics at the time of mineralisation into low angle thrust faults, and high angle extensional fault - fracture arrays. Low angle deposits have a mapped internal geometry that is very different from conventional imbricate thrust systems. This study applied ⁴⁰Ar/�⁹Ar geochronology to selected deposits and has identified at least three distinct mineralisation events have occurred within the central axial belt during the Cretaceous. Relationships between radiometric apparent age and inferred crustal depth reveal that after metamorphism, the onset of cooling and rapid exhumation of the schist belt coincides temporally and spatially with the age of mineralisation and structural position of a regional scale low angle shear zone in Otago.

Over many years, researchers in the field of flotation have developed an in-depth understanding of processes occurring in the pulp phase of flotation machines. Until recently, however, the froth phase has received little attention. The froth phase serves to separate bubble-particle aggregates from suspended slurry in a flotation cell. The mechanism of recovery by entrainment, its relationship to water recovery and particle size dependency is well understood. Froth recovery, (the fraction of particles entering the concentrate launder that entered the froth phase attached to air bubbles), is not well understood. Up until now, there has been doubt over whether this property is dependent on particle size and hydrophobicity. Difficulties in measuring froth recovery had previously prevented researchers from gaining a deeper understanding of the transport of attached particles across the froth phase. A novel device was designed and tested to measure froth recovery by isolating bubble-particle aggregates in the pulp-phase of flotation machines through the determination of the bubble loading in the pulp phase (mass of particles attached per unit volume of air bubbles). This technique can be used with other measurements to investigate froth selectivity by directly comparing these captured particles to those found in the froth phase. Evidence was collected at Red Dog Mine, Alaska and Newmont Golden Grove Operations, Western Australia which showed that the froth phase selectively transported more hydrophobic and smaller sized particles across the froth than less hydrophobic and larger particles. Particles collected in the device were compared to those found in the concentrate stream on a size by mineral by liberation class. Froth recovery was also calculated on a size by mineral by liberation class for two valuable sulphide minerals in a continuous 3m³ flotation cell. These results show that the froth phase is responsible for the upgrading of attached particles across the froth phase as well as for the separation of bubble-particle aggregates from suspended slurry. The pulp phase is responsible for creating bubble-particle aggregates through the attachment of hdyrophobic mineral particles to air bubbles. Many complex factors affect the extent to which this occurs including the size and hdyrophobicity of the particles, the size and number of air bubbles produced by the flotation machine, the rate of collisions between particles and bubbles and the overall chemistry of the system. This measurement of bubble loading presents an opportunity to measure the impact of all these factors on the successful creation of bubble-particle aggregates. Based on a literature review suggesting that there was a high probability of particles being detached at the pulp-froth interface due to the aggregates change in momentum, a three phase description of a flotation cell was proposed. The three phases were: pulp, pulp-froth interface and upper froth zones. A second froth recovery measurement technique (changing froth depth) was used in combination with the bubble load technique to determine the recovery across each of the two froth zones. It was found that the pulp-froth interface appears to be responsible for the selectivity observed across the froth phase as a whole. These findings will enable more in-depth research into the sub-process of the froth phase as well as assisting flotation cell design through a better understanding of the roles of the pulp-froth interface and the upper froth region.

Typescript (Photocopy) Includes copies of 5 published papers co-authored by the author in back Bibliography: leaves 214-230

Graduation date: 1994

Thesis (M.Sc.)--Memorial University of Newfoundland, 2006. / Bibliography: leaves 296-319. Also available online.