Please read the abstract in the 00front part of this document / Dissertation (M Eng (Metallurgical Engineering))--University of Pretoria, 2007. / Materials Science and Metallurgical Engineering / unrestricted

Cadmium sulphide (CdS) films were electrodeposited from an aqueous electrolytic solution onto indium tin oxide and fluorine doped tin oxide substrates, commonly used in photovoltaic applications. The CdS films were deposited for between 1 minute and 4 hours at temperatures ranging from 30°C to 90°C and a deposition potential of 600 mV with respect to a Ag/AgCI reference electrode. Some films were annealed in an argon atmosphere at temperatures of 300°C, 400°C and 460°C for 15 minutes and 30 minutes with and without CdCh2 treatment. The cleaning efficiency of the substrates by several solvents was determined using atomic force microscopy (AFM), surface roughness and scanning electron microscopy (SEM). It was found that the cleaning of the substrates could be monitored by the RMS roughness of the surfaces, and that the efficiency of the cleaning methods was substrate dependent. The microstructure, composition and optical properties of the films were determined using SEM, transmission electron microscopy, transmission electron diffraction, AFM, x-ray photoelectron spectroscopy (XPS), transmittance and Raman spectroscopy. All films, including those formed at the lowest deposition temperature of 30°C, were crystalline with the hexagonal (wurtzite) structure. At deposition temperatures ≤50°C the crystallites were extremely small as evidenced by broad diffraction rings and Raman peaks. At higher deposition temperatures (≥60°C) the deposition rate increased and the crystalline quality improved significantly. At the very early stages of deposition the deposits consisted of isolated, three-dimensional particles. Rapid lateral growth of these particles dominated the initial stages of deposition. Field emission SEM and AFM showed that ostensibly single particles consisted of agglomerates of elongated and plate-like grains with no preferred orientation. The final films had a columnar structure with good contact between the substrate and the film. XPS results showed that there was no significant compositional change in the deposition temperature range used and the films were all slightly cadmium rich. Carbon, oxygen and chlorine were detected mainly on the surface of the films. After annealing, the composition of the CdS films were close to stoichiometric once the surface layer had been removed. There was an improvement in the crystallinity of the films after annealing. / Thesis (PhD (Physics))--University of Pretoria, 2006. / Physics / unrestricted

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<p> The effects of engineering operating variables in the sulphide precipitation of Cu+2, Cd+2 and Zn+2 have been examined with a statistical experimental design. The independent (operating) variables studied were 1) the level of sulphide added, 2) the level of Fe+2 added as scavenger for excess HS- ion and 3) the pH level. The dependent variables were the concentrations of dissolved, suspended and total metals in the supernatant after treatment and the zone settling velocities of the suspensions.</p> <p> The major effect of the operating variables was to yield a precipitate which was either a stable colloid or a suspension which coagulated and settled. Stable colloid formation was associated with an excess of HS- ion. For those conditions which produced coagulant suspensions, 1) ten of the thirteen correlations between dependent and independent variables were not statistically significant at the 95% confidence level, 2) for practical purposes, variations in engineering operating variables did not alter the levels of dissolved and suspended Cu+2, Cd+2 and Zn+2 .</p> <p> When the precipitates coagulated and settled, concentrations of approximately 100 mg/l of each of Cu+2, Cd+2 and Zn+2 were reduced to mean values of 0.41, 0.33 and 0.62 mg/l total metals and 0.03, 0.01 and 0.37 mg/l dissolved metals respectively.</p> / Thesis / Master of Engineering (MEngr)

Orientador: Oswaldo Luiz Alves / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-11T15:46:56Z (GMT). No. of bitstreams: 1 Vieira_LucianaLima_M.pdf: 10012169 bytes, checksum: 3526b70650ff03af91d229d38c75c1e4 (MD5) Previous issue date: 2008 / Resumo: Esta dissertação visa à obtenção de nanoestruturas de sulfeto de molibdênio e sulfeto de tungstênio partindo dos respectivos óxidos com morfologia de nanobastões. Os óxidos precursores foram preparados via rota hidrotérmica (MoO3 e W18O49) via rota térmica (WO3). Os sulfetos foram preparados a partir da reação sólido-gás dos óxidos em atmosfera de H2S. Os nanobastões de óxido de molibdênio foram preparados através do tratamento hidrotérmico do MoO3·2H2O em solução aquosa de ácido acético a 180 °C durante 7 dias. Os nanobastões de MoO3 com diâmetro médio de 150 nm foram submetidos à atmosfera de H2S e H2 5% / N2 95% a 800 °C, obtendo-se como produto nanobastões de sulfeto de molibdênio. Nanobastões de W18O49 foram preparados pelo tratamento hidrotérmico do ácido túngstico (WoO3·nH2O) na presença de sulfato de sódio (0-30 g) e possuem diâmetro de 5- 15 nm. Foi observado que o sulfato de sódio possui um papel importante como direcionador de fase e morfologia do óxido de tungstênio. A sulfidização dos nanobastões de W18O49 foi realizada na presença e na ausência de atmosfera redutora. Em ambos os casos foram obtidos como produto WS2 com morfologia de nanobastões e/ou nanopartículas. Por ser uma fase parcialmente reduzida, não foi necessária a presença de gás hidrogênio para a preparação de nanoestruturas de WS2 através desta rota. Nanobastões de WO3 triclínico foram obtidos através do tratamento térmico de óxido de tungstênio não cristalino (proveniente da reação entre WCl6 e metanol) em atmosfera de nitrogênio a 600-1000 °C. Os nanobastões foram sulfidizados a 800 °C em atmosfera de H2S obtendo-se como produto nanotubos de WS2 com diâmetro entre 20 e 180 nm. Tal rota se mostrou eficiente quanto ao rendimento morfológico, e também interessante na medida que temos um número menor de etapas de síntese envolvidas na obtenção da morfologia e fase desejada. Também foram feitos experimentos de sulfidização alternativa para óxidos de molibdênio e tungstênio sobre condições hidrotérmicas. Tais reações foram realizadas em meio aquoso e utilizando agentes sulfidizantes (compostos que podem gerar H2S ou íons S2-), tais como enxofre, tioacetamida e tiouréia. A sulfidização do óxido de molibdênio foi efetiva, formando sulfeto de molibdênio. Os sulfetos apresentam uma interessante mudança de morfologia do agregado dependendo do tipo de preparação de amostras para microscopia eletrônica, apresentando-se na forma de flores quando a preparação é feita através do tratamento da suspensão aquosa do sólido em ultrassom. A sulfidização alternativa do óxido de tungstênio, por sua vez, não foi efetiva, uma vez que não produz sulfeto de tungstênio, mas apenas a redução parcial do óxido. Porém, nanoestruturas unidimensionais de W18O49 são formadas quando este óxido é submetido a tratamento térmico sob atmosfera inerte. Este óxido mostrou-se bastante interessante para as reações de sulfidização em H2S, uma vez que também pode ser utilizado para a preparação de nanoestruturas cilíndricas de WS2 / Abstract: The main of this Dissertation is the preparation of nanostructured WS2 and MoS2 from a template reaction with the respective nanorods oxides. Molybdenum oxide nanorods with diameters around 100 nm and microscale lengths were prepared from MoO3·2H2O via a one step solvothermal reaction. The formation of MoO3 rods proceeds in acidic media at 180 °C. The oxide was converted in quantitative yield to MoS2 nanorods by H2S in a reducing atmosphere. TEM and SEM analysis reveals that the rod-like morphology of the oxide precursor is preserved during the H2S treatment. Monoclinic W18O49 nanorods of 5¿15 nm in diameter have been synthesised by a low temperature hydrothermal route using sodium sulfate as structural and morphological modifier. The important role of Na2SO4 salt in the synthesis has been demonstrated. These nanorods were found suitable as a precursor for the synthesis of nanostructured WS2 by reducing them with H2S at 800 °C for 30 min. This reaction can work out without a reducing atmosphere. The morphological and structural features of WS2 nanotubes, generated from WO3 nanorods, by an in situ heating process, have been studied. The nanorods were prepared by a simple annealing method of a low-crystalline tungsten oxide (from a sol-gel reaction between WCl6 and methanol) at 600-1000 °C. Finally, an alternative route to molybdenum and tungsten sulfide by solution chemical reactions was also explored. The reaction was carried out from the respective oxides and sulfurization reagents such as S, CH3CSNH2 and CSN2H4 through hydrothermal method. MoS2 nanostructures including flower-like particles have been synthesized. The hydrothermal reaction with tungsten has not produced WS2 but W18O49 nanorods after thermal annealing. These oxides were converted in nanostructured WS2 by solid-gas reaction in H2S atmosphere at 800°C / Mestrado / Quimica Inorganica / Mestre em Química

This project was compiled in co-operation with the Royal Institute of Technology, Stockholm and Veolia Environmental Services (Australia) at the Woodlawn Bioreactor in NSW, Australia. Hydrogen sulphide is an unwanted component of landfill gas, raising occupational health and safety concerns, whilst leading to acid gas corrosion of power generation equipment and increased emissions of SOx, a primary constituent of acidification. Australian governmental requirements to place a periodic cover over the unused proportion of the tipping surface of landfills and bioreactors create an interesting opportunity for the removal of the hydrogen sulphide component of landfill gas. Using waste materials containing a high concentration of metals as waste cover can enhance the precipitation of sulphur in the form of metal sulphides. The reduction of sulphate via sulphate reducing bacteria is prevalent in sites that have a sizeable inflow of sulphate. The Woodlawn Bioreactor is located in an area where the influence of sulphate has a critical influence of bioreactor performance and production of hydrogen sulphide. Through a series of experimental bioreactors it was established that from the use of metalliferous periodic waste covers, the hydrogen sulphide component of landfill gas was maintained at an extremely low level when compared to the levels of hydrogen sulphide produced in waste under the influence of high sulphate loads with no waste cover. / www.ima.kth.se

Gossans, the brightly coloured oxidation products of sulphide mineralised rocks, have acted as an exploration target for base and precious metals and sulphur for thousands of years. They are easily identified from remote sensing and field-based reconnaissance, and once found may be drilled to determine the character of mineralisation below. The number of targets drilled could potentially be reduced if gossans overlying significant mineralisation can be discriminated from their field relations, mineralogy and geochemistry. Previous such studies have focussed on porphyry-type systems, with less attention on the generally much lower tonnage volcanogenic massive sulphide (VMS) deposits. However, VMS continue to provide an economically important source of metals in Europe and elsewhere. The Troodos Massif in Cyprus was chosen for this study as it hosts a currently active Cu mine along with historically worked VMS, is little deformed and has a relatively well understood geological framework. Of particular interest are secondary Cu deposits (SCUD) which form due to weathering of primary massive sulphides (PMS). These can be worked at relatively lower financial and environmental cost, and at much lower grades (down to around 0.1 % Cu). The only currently mined SCUD in Cyprus is the Phoenix ore body at Skouriotissa, which lies immediately adjacent to, and structurally below the Phoukasa PMS. The questions addressed in this study are: 1) Do Cypriot PMS that were mined for Cu show original Cu enrichments, or is their elevated Cu content a result of supergene enrichment to form an SCUD? This was addressed by comparing the mineralogical, chemical and S isotopic compositions of PMS mined for Cu with those mined for pyrite only from across the Troodos; 2) Do gossans formed from Cu-rich sulphides show distinctive mineralogical and chemical signatures? The characteristics of gossans known to overlie prospective sulphide bodies were compared with those from barren PMS; 3) What circumstances promote the formation of SCUDs? In particular, did sulphide oxidation occur on the sea floor or in a terrestrial environment? It was considered likely that SCUD formation may require sea floor oxidation because this will result in limited Cu dispersion, due to both sharp pH and redox gradients and limited fluid flow when compared with terrestrial weathering, where the depth to the water table can be considerable. The question was addressed by comparing the field relations, chemistry and S and O isotope compositions of gossans thought to have formed on the sea floor (Skouriotissa - Phoenix) with those generated in a terrestrial setting (Kokkinopezoula, Mathiati and Sia). The remnants of primary VMS deposits mined for Cu in Cyprus (Phoukasa, Sia and Troulli) almost exclusively contain primary Cu sulphides such as chalcopyrite. Secondary Cu sulphides, mainly chalcocite and covellite, are only present in significant concentrations at Phoukasa and Troulli, with Cu oxides being found in Phoenix. At Phoukasa, secondary Cu sulphides have a mean δ34S = 3.69±0.08 ‰ similar to primary pyrite and chalcopyrite (mean δ34S = 3.78±0.08 ‰) suggesting formation from Cu-rich fluids that scavenged S from primary sulphides. Sulphide material collected from copper mines has Cu = 840 to > 10,000 ppm at Phoukasa; 167 to 3573 ppm at Sia; 288 to > 10,000 ppm at Troulli, while the Cu-barren deposits have generally lower Cu grades (Cu = 170 to 433 ppm at Kokkinopezoula; 327 to 1303 ppm at Mathiati north). There are no systematic differences in the S isotope compositions of pyrite between deposits mined for Cu and those not (average δ34S = 1.68, 3.74 and 7.1 ‰ for Cu-rich Sia, Lysos and Phoukasa, and 5.03 and 3.70 ‰ for Cu-poor Kokkinopezoula and Mathiati North sulphides, respectively). No consistent chemical differences (including chalcophile elements) could be identified between gossans overlying Cu-rich as opposed to barren PMS. Gossans overlying the Lysos and Sia Cu-rich PMS, however, show an enrichment in Pb and Zn not observed in other gossans, and umbers, which are chemical sediments associated with VMS systems, often overlying gossans, show strong Cu enrichments in the vicinity of Cu-rich PMS. Umber samples from near the Cu-rich Phoukasa sulphide body contain > 10,000 to 35,400 ppm Cu, while those around Cu-poor Mathiati North contain 669 to 819 ppm Cu. There were no differences in the S isotope compositions of gypsum from sulphide bodies which were Cu-rich (δ34S = 5.9 to 6.9 ‰ for Sia, Phoukasa and Troulli) and Cu-poor (δ34S = 5.0 to 7.3 ‰ for Kokkinopezoula, Mathiati North). Regarding the environment of formation of SCUDs, an initial submarine oxidation of the Phoukasa VMS is considered likely as it is immediately overlain by marine pelagic sediments, while all other deposits studied are overlain by volcanics. In addition, volcanics in the vicinity of Phoukasa show large negative Ce anomalies (Ce/Ce* = 0.90 to 0.38, average = 0.71), consistent with sea floor alteration, compared with other localities such Kokkinopezoula (Ce/Ce* = 0.89 to 1.08, average = 0.97) and Sia (Ce/Ce* = 0.92 to 1.03, average = 0.99). Unfortunately, the S isotope composition of gypsum could not be used to determine the nature of the gossan-forming environment. Gypsums from all locations (average δ34S = 6.74±0.08 ‰) have δ34S values similar to, but slightly 34S enriched compared with their associated sulphides (average δ34S = 2.9±0.08 ‰) which indicates that their S isotope signature largely reflects that of S released during sulphide oxidation, as opposed to evaporation of sulphate-rich waters or direct precipitation from a similar solution (i.e., seawater). However, the oxygen isotope composition of gypsum (average δ18O = 6.2 ‰) from Sia (average δ18O = 2.4 ‰) reflects a mixture of atmospheric O (δ18O = 23.6 ‰) and Mediterranean meteoric water O (δ18O ≈-5.0 ‰), indicating a terrestrial environment of formation. Gypsum from Skouriotissa has an average δ18O = 6.6 ‰ which most likely indicates a combination of seawater and seawater-dissolved O (δ18O ≈23.5 ‰), despite some overlap with the composition of meteoric water and atmospheric O. In summary, it is proposed that the currently unique nature of Skouriotissa as hosting the only major SCUD in Cyprus is due largely to initial sea water alteration of the Phoukasa PMS resulting in limited Cu dispersion and localised Cu enrichment within the primary ore body. Subsequent uplift and alteration of the Phoukasa PMS led to the formation of a relatively high grade SCUD in the Phoenix deposit. The main outcomes of the study are a series of models for the development of gossans and associated lithologies in terrestrial and seafloor weathering environments in Cyprus. These incorporate a new term (retali) for acid leached volcanics in the footwall of PMS, and exploration-relevant field, mineralogical and chemical criteria for their discrimination from gossans, which overlie PMS. In agreement with an existing model, the formation of the Phoenix SCUD is interpreted as having been due to the downward migration of Cu-bearing acid fluids from the seafloor oxidation of the upper parts of the Phoukasa deposit. Secondary Cu mineralisation is thought to have taken place within the relatively reducing environment below the water table in lavas stratigraphically below the Phoukasa deposit. That the formation of SCUDs may require seafloor sulphide oxidation, and that this can be recognised in the mineralogy and chemical compositions of associated volcanics and gossans, provides new exploration criteria for SCUDs. However, it should be noted that the Phoenix deposit was the only SCUD examined in this study, and that this model should therefore be tested elsewhere.

Orientador: Cesar Augusto Moreira / Resumo: A área de estudo está localizada próxima a Caçapava do Sul no estado do Rio Grande do Sul, ocorrência conhecida como Colônia Santa Barbara. A ocorrência está situada na Bacia do Camaquã, alocada estruturalmente em um bloco alto, na interseção de duas falhas com direções NE-SW e NW-SE, com litologias aflorantes pertencentes ao Complexo Metamórfico Bossoroca e Formação Hilário do Grupo Bom Jardim. Descrita entre 1960 e 1970, a pesquisa foi suspensa após análise geoquímica apontar teores de cobre insatisfatórios, não ultrapassando a 1%, sem interesse econômico. Atualmente com uso de aparelhos multi-cabos de aquisição automática é possível a realização de ensaios geoelétricos de diferentes arranjos em menor tempo e maior praticidade, o que impulsionou o desenvolvimento deste trabalho. Essa dissertação apresenta a análise comparativa dos dados de tomografia elétrica em arranjo Schlumberger, Wenner e Dipolo-Dipolo, para averiguar o resultado que descreva a morfologia mais realista esperada do jazimento, baseado no modelo magmático hidrotermal com forte controle estrutural. A análise comparativa entre os arranjos de tomografia elétrica proposta neste trabalho revelou a conformação de um corpo cônico de alta cargabilidade (2,7 mV/V) que engloba o núcleo vertical de alta resistividade (438 Ω.m), além de uma zona anelar de alta cargabilidade possivelmente correlacionada ao sistema de falhas que estruturam o alto estrutural (tufo vulcânico). A estrutura cônica observada é compatível com... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The study area is located near to Caçapava do Sul, at Rio Grande do Sul State, an occurrence known as Colônia Santa Barbara. The occurrence is in the Camaquã Sedimentary Basin, structurally allocated in a high block, at the two faults intersection with NE-SW and NW-SE directions, with outcropping lithologies belonging to Bossoroca Metamorphic Complex, and Hilario Formation. Described between 1960 and 1970, the research was suspended after geochemical analysis pointed to unsatisfactory copper levels, not exceeded 1%, without economic interest. Nowadays, with the use of automatic and multicable devices, like Terrameter Ls, it is possible to perform different arrangements geometric tests in a shorter time and greater practicality, fact that support this work development. This dissertation presents the electrical tomography arrays comparative analysis to Schlumberger, Wenner, and Dipolo-Diplo, to verify the result that describes the most realistic expected deposit morphology, based in a hydrothermal magmatic metallogenetic deposit with high structural control. The comparative analysis revealed a conical body with high chargeability conformation (2,7 mV/V) that encompasses the high resistivity vertical core (438 Ω/m ), as well as an annular portion with high chargeability possibly correlated to the fault zone that structures the central and high block (volcanic tuff). The conical structure observed is compatible with the dike, vertical and cylindrical morphology described for hydr... (Complete abstract click electronic access below) / Mestre

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.

In this study the unique Magotteaux Mill® system was used to control the grinding chemical conditions, which may be adjusted by varying grinding media, purging gas and pH, during grinding. An electrochemical apparatus was used to investigate oxidation-reduction behaviour of grinding media and sulphide mineral electrodes, as well as their galvanic interaction in-situ of the Magotteaux Mill®. Galvanic interaction between the grinding media (mild steel, 15% chromium, 21% chromium and 30% chromium media) and the sulphide minerals (bornite, arsenopyrite and pyrite) was initially quantified in-situ of the mill by electrochemical techniques under different grinding atmospheres (nitrogen, air and oxygen). An innovative mathematical theoretical model was developed to describe the effect of galvanic interaction on oxidation rates of the grinding media during grinding, which was verified by the experimental data. Galvanic interaction enhanced the oxidation of the grinding media and produced more oxidized iron species in the mill discharge. It was observed that oxidized iron species (EDTA extractable iron) was linear with galvanic current between the grinding media and the sulphide minerals, in agreement with the prediction of the theoretical model. The effect of grinding conditions on pulp chemistry, surface properties and floatability was investigated by the measurement of dissolved oxygen (DO), pH, pulp potential (Eh), ethylene diamine-tetra acetic acid (EDTA) extraction, X-ray photoelectron spectroscopy (XPS) and floatation recovery. / PhD Doctorate