As a result of increasing cost, efficiency and environmental pressures ferrochrome producers strive towards lower overall energy consumption. Increases in local electricity prices have placed particular pressure on South African ferrochrome producers. Pelletised chromite pre–reduction is likely the currently applied ferrochrome production process option with the lowest specific electricity consumption. In this process fine chromite, together with a carbonaceous reductant and a clay binder is milled, pelletised and pre–reduced. In this dissertation it is demonstrated that the functioning of the clay binder in this process is not as straightforward as in conventional metallurgical pelletisation processes, since the cured pre–reduced pellets are characterised by an oxidised outer layer and a pre–reduced core. Conventional performance characteristics of clay binders (e.g. compressive strength and abrasion resistance) therefore have to be evaluated in both oxidative sintering and reducing environments. Two clay samples, i.e. attapulgite and bentonite, were obtained from a local ferrochrome producer and investigated within the context of this study. Results indicated that the compressive and abrasion resistance strengths of oxidative sintered pellets for both clays were substantially better than that of pre–reduced pellets. Thus, although the objective of the chromite pre–reduced process is to achieve maximum pre–reduction, the strength of pre–reduced chromite pellets is significantly enhanced by the thin oxidised outer layer. The strength of the bentonite–containing pellets was found to be superior in both pre–reducing and oxidative sintering environments. This is significant, since the attapulgite clay is currently the preferred option at both South African ferrochrome smelting plants applying the pelletised chromite pre–reduction process. Although not quantitatively investigated, thermo–mechanical analysis indicated that the hot strength of the attapulgite pellets could be weaker than the bentonite–containing pellets. The possible effects of clay binder selection on the level of pre–reduction were also investigated, since it could have substantial efficiency and economic implications. For both case study clays investigated, higher clay contents resulted in lower pre–reduction levels. This has relevance within the industrial process, since higher clay contents are on occasion utilised to achieve improved green strength. The average pre–reduction of the bentonite–containing pellets were also consistently higher than that of the attapulgite–containing pellets. Again, this is significant, since the attapulgite clay is currently the preferred option. In general the case study results presented in this dissertation indicated that it is unlikely that the performance of a specific clay binder in this relatively complex process can be predicted; based only on the chemical, surface chemical and mineralogical characterisation of the clay. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In the present work, we performed a study of the structural, electrical and optical properties of the compound LaCr1-xAlxO3 (x = 0.0, 0.05, 0.5, 0.95 and 1.0) produced by the combustion method. The structural analyzes were performed by X-ray diffraction (XRD) and Rietveld refinement, the electrical measurements using impedance spectroscopy and IV measurements, and optical measurements using UV-Vis spectroscopy. The results of XRD allied to the Rietveld method of refinement indicate that the samples with x = 0.0 and 0.05, have an orthorhombic structure belonging to the space group Pnma (62), and for x = 0.5, 0.95 and 1.0, a rhombohedral structure belonging to the space group R-3c (167), thus taking place a structural transition in the material. The impedance spectroscopy measurements associated to the IV curves show that the samples with higher concentration of Al present higher resistance, and the samples with lower concentration of Al present less resistance. We observe that for high frequencies a decrease of dielectric constant with frequency occurs. In addition, the appearance of only a semicircle establishes the presence of non-Debye type relaxation, where an equivalent circuit composed of two resistors (R1 and R2) and a constant phase element (CPE) were used. By means of the absorption measurements in the ultraviolet to visible region (UV-Vis), we estimated the optical gap of the samples, through the tauc equation, which vary between 3.27 - 3.43 eV. Still, we observed that the increase in Al concentration favors the increase in transmittance in the material. / No presente trabalho, realizamos um estudo das propriedades estruturais, elétricas e ópticas do composto LaCr1-xAlxO3 (x=0,0; 0,05; 0,5; 0,95 e 1,0) produzido pelo método da combustão. As análises estruturais foram realizadas por meio de difração de raios-X (DRX) e refinamento Rietveld, as elétricas por meio de espectroscopia de impedância e medidas IV, e ópticas por meio de espectroscopia de UV-Vis. Os resultados de DRX aliados ao método de refinamento Rietveld indicam que as amostras com x = 0,0 e 0,05, apresentam uma estrutura ortorrômbica pertencente ao grupo espacial Pnma (62), e para x = 0,5; 0,95 e 1,0, uma estrutura romboédrica pertencente ao grupo espacial R-3c (167), ocorrendo assim uma transição estrutural no material. As medidas de espectroscopia de impedância associadas às curvas IV mostram que as amostras com maior concentração de Al apresentam maior resistência, e as amostras com menor concentração de Al apresentam menor resistência. Observamos que para altas frequências ocorre uma diminuição da constante dielétrica com a frequência. Além disso, o aparecimento de apenas um semicírculo estabelece a presença do relaxamento do tipo não-Debye, onde foi utilizado um circuito equivalente composto por duas resistências (R1 e R2), e um elemento de fase constante (CPE). Através das medidas de absorção na região do ultravioleta ao visível (UV-Vis) estimamos o gap óptico das amostras, através da equação de tauc, os quais variam entre 3,27 - 3,43 eV. Além disso, observamos que o aumento da concentração de Al favorece o aumento da transmitância no material. / São Cristóvão, SE

Neste trabalho estuda-se o comportamento de redução para a obtenção da liga FeCrAC a partir da pelota auto-redutora feita de minério de cromita, coque de petróleo, ferro-silicio, cal hidratada, sílica e cimento portland ARI. As principais variáveis consideradas são: teor de redutor na composição da pelota, quantidade do redutor, temperatura e tempo. Inicialmente os materiais (cromita, ferro-silício, coque de petróleo, cal hidratada, sílica e cimento Portland ARI), foram caracterizados por: análise química e análise granulométrica. Após a caracterização os materiais (cromita, ferro-silício, coque de petróleo e cimento Portland ARI) foram aglomerados na forma de pelotas juntamente com cal hidratada e sílica para ajuste da basicidade quaternária da escória. A redução das pelotas foi feita num forno de indução que pode atingir temperaturas de até 1973K (1700oC). Todos os experimentos de redução foram realizados no aparato experimental utilizando-se cadinhos de grafite nas temperaturas de 1773K (1500oC), 1823K (1550oC) e 1873K (1600oC). Após os ensaios de redução os produtos obtidos (escória e metal) foram analisados por microscopia ótica, por microscopia eletrônica de varredura (MEV) e análise por EDS. O efeito do aumento da temperatura na redução da cromita é significativo. Houve aumento na velocidade de redução de 4 a 6 vezes com o aumento de 1773K (1500oC) para 1873K (1600oC). Os resultados indicam um efeito marcante de pequenas adições de Fe-Si na velocidade de redução da cromita. Na temperatura de 1773K (1500oC) as adições até ~2% de Fe-Si são benéficas e para adições maiores praticamente não há vantagens técnicas e econômicas. Os tempos necessários para atingir a fração unitária de redução foram 12, 7,5 e 5 minutos para adições de Fe-Si de 0, ~1%, e ~2%, respectivamente; a temperatura de 1823K (1550oC). À temperatura de 1873K (1600oC) as adições de Fe-Si na pelota apresentam também efeitos significativos na velocidade de redução, porém adições de ~1%, e ~2% mostraram os mesmos resultados, indicando que o teor ótimo de adição de Fe- Si na pelota deve estar em torno de 1%. Verificou-se que a utilização de pelotas auto-redutoras contendo 26% em excesso, sobre o estequiométrico, de coque de petróleo aumentou o rendimento de recuperação de Cr de 96% para 98%. O rendimento e a eficiência do processo de auto-redução supera aos processos convencionais de produção de FeCrAC, obtendo-se altas recuperações de cromo na faixa de 96% até 98% para Cr. / The reduction behaviors, at high temperature, of the self-reducing pellets of chromites for production of high carbon ferro-chromium are studied in this work. The influences of the temperature, of the excess of reductant and the small addition of the Fe-Si were analyzed. The materials used (chromites, petroleum coke, Portland cement, hydrated lime and silica) were characterized chemically and by size distribution. The composite pellets (self-reducing) were produced aiming a quaternary basicity of 0.91. The reductant was calculated considering a stoichiometry of reduction and dissolution of 4wt%C in the final metallic phase. The reduction experiments were made in a special system, in argon atmosphere, heated by induction and at temperatures of 1773, 1823 and 1873K. The dried pellets were placed into a pre-heated graphite crucible and left there along up to no gas evolution was observed. The results of the reacted fraction with time were plotted and the obtained product (metallic and slag phases) after experiments were analyzed by optical and by electron micrograph. The chemical estimations were made by micro-analysis (EDS) The effect of increasing the temperature of reduction was sensitive, such that, the reduction rate increased 4 to 6 times with increase of temperature from 1773 to 1873. The small additions, up to 2% of Fe-Si, for substituting the equivalent fixed carbon of the petroleum coke showed to improve substantially the reduction rate, almost doubling it in comparison with pellets without any addition. The use of excess of 26%, over the stoichiometry, of the petroleum coke decreased around 50% of the chromium content in the slag, with relation to pellet without excess. The chromium recovery yield reached 98%. This result coupled with very high reduction rate of self-reducing pellets show the potential for self-reducing processes for ferro-chromium production.

Several disequilibrium textures are found to occur within the hanging wall and footwall of the UG2 chromitite layer of the Bushveld Complex, South Africa. These textures include plagioclase chadacrysts found included within orthopyroxene and clinopyroxene as well as the orthopyroxenes exhibiting round crystal boundaries that appear to be resorbed. Textures found within the UG2 stratigraphy such as linear boundaries and 120° triple junctions at interfaces of adjacent plagioclase or pyroxene grains also suggest that recrystallization has taken place. The presence of both disequilibrium textures and recrystallization textures would suggest that a complex emplacement history has occurred. Ideally, this would be expected to be manifested by minerals of the same type but which are texturally distinct showing different composition. However this has been found not to be the case; minerals that suggest disequilibrium textures show similar compositions to the minerals which appear to have formed in equilibrium. This is also the same for recrystallized crystals which show the same compositions as crystals that have not been recrystallized. For example tabular clinopyroxene, which has a compositional range of En 44.6 to En 50.5, is indistinguishable from clinopyroxene occuring as discontinuous rims, En 44.3-48.2, and as intergranular necking connecting primocrysts of orthopyroxene ( En 44.3-50.4). Similarly, plagioclase occurring as inclusions with An 66.3-76.0 is indistinguishable from plagioclase occurring as zoned or recrystallized interstitial grains ( An 69.0- An 77.4). Compositional variation has however, been found to be controlled to an extent by stratigraphy in that minerals show different compositions within one layer to the same minerals within another layer, consistent with an evolving magma composition. It is concluded therefore that while composition is not texturally controlled it is to an extent stratigraphy controlled and that the evidence collected within the study supports two models for the formation of chromite within the Bushveld complex. The evidence is consistent with a combination of the magma mixing model and magma injection model to account for the textures and compositional variations found within the study. The evidence may also show support for models involving late modification of minerals by magmatic fluids but not as prominently as for the models mentioned above / Microsoft� Word 2010 / Adobe Acrobat 9.53 Paper Capture Plug-in

A neutron activation analysis procedure for the simultaneous determination of Au, Pd and Ir, and separate determination of Os is described and applied to the determination of these metals in the Mount Albert ultramafic pluton, Quebec. The Mount Albert is an alpine-type ultramafic body whose petrography, geology and geochemistry has been discussed in some detail by MacGregor (1962, 1964). It consists mainly of serpentinized dunite and peridotite. However, it is distinguished by the presence of an eastern lobe which is essentially unserpentinized. In addition to ferromagnesians, two varieties of spinel including disseminated accessory chrome spinel and massive, discordant chromite veins or schlieren are important mineralogical constituents. Twenty samples were analyzed including 5 fresh dunites and peridotites, 8 serpentinized equivalents, 4 disseminated chrome spinels, 1 clinopyroxenite, and 2 massive chromite. The concentrations (in p. p. b.) of average fresh ultramafics and their serpentinized equivalents are:-------------------------------------- ---------------------Pd----Os----Ir----Au------------------------------------------- Fresh rocks------------7.7----7.2--2.5--0.99------------------------------------------- Serpentinized rocks---10----6.6--2.2---2.4-------------------------------------------- The piuton was intruded as a nearly solid mass of olivine and some orthopyroxene with about 15 weight per cent melt. A small concentration of the precious metals, a factor of 2 to 3, in the melt relative to crystalline phases appears to have occurred. The disseminated chrome spinel and massive chromite appear to concentrate the precious metals. In particular, Os and Ir content of the massive chromite is approximately 10 times that of fresh or serpentinized whole rocks. There is little change in average precious metal content with serpentinization. Pd shows a slight increase, and Ir and Os slight decreases in concentration with degree of serpentinization. Only Au appears significant to be enriched in serpentinized rocks where a twofold increase occurs. The variation in precious metal content of all four metals increase when the rocks are serpentinized: When normalized to chondrite meteorites, the precious metal data give fractionation trends similar to that of average chondrite. These trends are compatible with a model in which alpine ultramafics are regarded as residua from the partial melting of parental material of approximately chondritic composition. / Thesis / Master of Science (MSc)

Abstract When producing ferrochrome, a submerged arc furnace (SAF) is used. The charge of an SAF consists of chromite pellets, coke, lumpy ore and quartzite as a slag modifier. The charge is pre-heated before it descends into the SAF where the charge eventually reduces and melts. The electrical conductivity of the charge is important because, among other things, it affects the productivity of the furnace. The electrical conductivity of the charge should ideally be low on the higher parts of the furnace and high near the electrode tip. This is to ensure that the electric current path travels through the metal bath via arcing, which provides the most effective heat transfer. Another option for the current path would be through the solid feed material via ohmic conduction, but since this zone is less reactive, the heat energy would be mostly wasted. This work brings forth new information about the electrical behaviour of coke and chromite pellet is produced. The electrical conductivity was measured at room temperature for different simulated process conditions (different coke textures, different reduction degrees of chromite pellets, sulphur in atmosphere and replacing the coke used in chromite pellet production with charcoal). It was found out that unlike gasification with a CO/CO2 mixture, heat treatment at 950°C increased the degree of graphitization and changed the electrical behaviour of coke. Furthermore, it was observed that increasing the chromite pellets’ reduction degree reduced the electrical conductivity measured at room temperature. In the case of chromite pellets and sulphur in the atmosphere it was found that sulphur has an effect on the pellets’ electrical behavior and structure during reduction, which - in turn - has an effect on the SAF performance when raw materials with varying sulphur contents are used. Lastly, it was found that substituting coke with charcoal when producing chromite pellets affects the sintering behaviour, cold compression strength, and electrical conductivity of the chromite pellets. / Tiivistelmä Uppokaariuuni on osa ferrokromin valmistusprosessia. Uppokaariuuniin panostetaan kromiittipellejä, koksia, palarikastetta ja kvartsiittia. Etukuumennusuunista panos laskeutuu uppokaariuuniin, jossa se pelkistyy ja lopulta sulaa. Uppokaariuunin panoksen sähkönjohtavuus on tärkeää uunin toiminnan kannalta, koska se vaikuttaa suoraan esimerkiksi tuottavuuteen. Jotta virran kulku tapahtuisi optimaalisesti sulan metallin kautta, panoksen sähkönjohtavuuden tulee olla pieni uunin yläosissa ja suuri alaosassa lähellä elektrodien päitä. Mikäli virran kulku tapahtuu uunin yläosassa, hukataan lämpöenergiaa ja uunin toiminta hankaloituu. Tässä työssä on selvitetty koksin ja kromiittipellettien sähköisiä ominaisuuksia. Sähkönjohtavuutta on tutkittu useilla simuloiduilla prosessiolosuhteilla (koksin eri tekstuurit, kromiittipellettien eri pelkistysasteet, rikin pitoisuus atmosfäärissä ja kromiittipellettien valmistuksessa on korvattu koksi puuhiilellä). Nämä mittaukset on tehty huonelämpötilassa. Huomattiin, että toisin kuin koksin kaasutus, koksin lämpökäsittely (950°C) nosti grafitoitumisastetta ja vaikutti sähköisiin ominaisuuksiin. Kromiittipelletin pelkistymisasteen noustessa huonelämpötilassa mitattu sähkönjohtavuus laski. Kun kromiittipelletit altistetaan atmosfäärille, jossa on rikkiä, pellettien sähköiset ominaisuudet muuttuvat samoin kuin rakenne pelkistyksen aikana. Tämä vaikuttaa uppokaariuunin toimintaan, kun käytetään raaka-aineita, joissa rikkipitoisuus vaihtelee. Kun kromiittipellettien valmistuksessa käytettävä koksi korvataan puuhiilellä, tämä vaikuttaa sintrausprosessiin, kylmälujuuteen ja sähköisiin ominaisuuksiin.

Cette étude apporte des données sur l'intérêt des chromites de lanthane strontium dopés au ruthénium La1-xSrxCr1-yRuyO3δ (LSCrRu) comme anode de pile à combustible ITSOFC. La synthèse sous champ micro-onde d'oxydes mixtes a permis la mise en forme de demi-cellules et cellules complètes modèles par pulvérisation cathodique magnétron et par sérigraphie. Les propriétés de reformage de CH4 ont pu être étudiées dans un dispositif mono-chambre couplé à un spectromètre de masse en collaboration avec l'Institut de REcherche Hydro-Québec. La réactivité à l'interface anode/électrolyte a été analysée par SIMS et XRD sur demi-cellules modèles vieillies sous H2 à 800°C. Elle a permis de préciser la chimie du film après traitement. Les cellules complètes, testées en condition de fonctionnement, ont mis en évidence, après dissolution sélective de LSCrRu, une modification de la microstructure à l'interface anode/électrolyte. Des analyses XPS et SEM-EDX n'ont pas montré de réactivité chimique.

L'ophiolite d'Oman montre une séquence complète qui permet de bien comprendre les modalités de l'accrétion, la dynamique des magmas et l'évolution tectonique et magmatique au niveau de la palèodorsale téthysienne. L'étude faite à partir d'une étude détaillée des lithofaciès a consisté a compléter les travaux antérieurs du massif de Fizh (partie septentrionale de l'ophiolite d'Oman)

Le massif de Tropoja est le plus septentrional des massifs de la ceinture orientale des ophiolites d'Albanie dont les caractères pétrologiques et métallogéniques s'apparentent aux produits magmatiques des arcs insulaires immatures. Quatre niveaux enrichis en chromite ont été définis d'après leur stratigraphie, leur structure et leur composition : trois dans le manteau et un dans les cumulats. D'importantes variations de la fugacité en oxygène ont accompagné la formation des chromitites et des minéralisations en élement du groupe du platine qui leur sont associées. Au Sud du massif, une forte fugacité en oxygène couplée à une faible fugacité en soufre seraient responsables de la précipitation, directement à partir du magma, d'alliages de fer et de platine, qui forment la minéralisation platinifère caractéristiques des cumulas de Tropoja. Cette minéralisation, rare dans les autres massifs ophiolitiques, est située dans un niveau bréchique, à l'interface de dunites basales et de pyroxénites. Les teneurs de platine, qui peuvent atteindre 11 grammes par tonne, sont corrélées positivement aux concentrations de chrome. Trois stades minéralisants y ont été définis, le dernier étant lié à des interactions entre minéraux et fluides tardifs. D'autres caractéristiques minéralogiques de cette minéralisation, importantes pour le traitement des minerais, ont été obtenues grâce à une étude statistique. Au Nord du massif, les minéralisations platinifères, localisées dans le manteau, sont associées à des sulfures de métaux de base.

Made available in DSpace on 2014-12-17T14:06:53Z (GMT). No. of bitstreams: 1 ClawsioRCS_DISSERT.pdf: 4688648 bytes, checksum: dd0d723d2cc3d7de35608b8ed730a95b (MD5) Previous issue date: 2010-03-29 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The cells unitaria of the solid oxide fuel cell are separated by means of interconnects, which serve as electrical contact between the cells. Lanthanum Chromite (LaCrO3) has been the most common material used as interconnect in solid oxide fuel cells. Reducing the operating temperature around 800 ? C of cells to solid oxide fuel make possibilite the use of metallic interconnects as an alternative to ceramic LaCrO3. Metallic interconnects have advantages over ceramic interconnects such as high thermal conductivity, electricity, good ductility, low cost, good physical and mechanical properties. In this work evaluate the thermo-mechanical properties of the metallic substrate and coated metallic substrate with the ceramic LaCrO3 film via spray-pyrolysis, in order to demonstrate the feasibility of using this material as a component of a fuel cell solid oxide. The materials were characterized by X-ray diffraction, oxidation behavior, mechanical strength, optical microscopy (OM) and scanning electron microscopy (SEM). The X-ray diffraction proved the formation phase of the LaCrO3 on the metallic substrate and the identification of the phases formed after the oxidative test and mechanical strength at high temperature. The oxidation behavior showed the increased oxidation resistance of the coated metallic substrate. It was noted that the mechanical resistance to bending of the coated metallic substrate only increases at room temperature. The optical microscopy (OM) has provided an assessment of both the metallic substrate and the LaCrO3 film deposited on the metal substrate that, in comparison with the micrographs obtained from SEM. The SEM one proved the formation of Cr2O3 layer on the metallic substrate and stability of LaCrO3 film after oxidative test, it can also observe the displacement of the ceramic LaCrO3 film after of mechanical testing and mapping of the main elements as chromium, manganese, oxygen, lanthanum in samples after the thermo-mechanical tests. / As pilhas unit?rias de uma pilha a combust?vel de ?xido s?lido s?o separadas por meio de interconectores, que servem como contato el?trico entre as pilhas. A cromita de lant?nio (LaCrO3) tem sido o material mais utilizado como interconector nas pilhas a combust?vel de ?xido s?lido. A redu??o da temperatura de opera??o em torno de 800 ?C das pilhas a combust?vel de ?xido s?lido, tornou poss?vel o uso de interconectores met?licos como alternativa aos LaCrO3 cer?micos. Esses materiais apresentam vantagens em rela??o aos interconectores cer?micos tais como: alta condutividade t?rmica, el?trica, boa ductilidade, baixo custo, boas propriedades f?sicas e mec?nicas. Neste trabalho foram avaliadas as propriedades termomec?nicas do substrato met?lico e substrato met?lico recoberto com o filme de LaCrO3 via spray-pir?lise, com o objetivo de demonstrar a viabilidade da utiliza??o deste materiais como componente de uma pilha a combust?vel de ?xido s?lido. Os materiais foram caracterizados por meio de difra??o de raios-X, comportamento oxidativo, resist?ncia mec?nica, microscopia ?ptica e microscopia eletr?nica de varredura (MEV). A difra??o de raios-X comprovou a forma??o da fase LaCrO3 sobre o substrato met?lico e a identifica??o das fases formadas ap?s o ensaio oxidativo e resist?ncia mec?nica a alta temperatura.O comportamento oxidativo evidenciou o aumento da resist?ncia a oxida??o do substrato met?lico recoberto. Na resist?ncia mec?nica a flex?o do substrato met?lico recoberto, notou-se o aumento apenas na temperatura ambiente. A microscopia ?ptica (MO) fez uma avalia??o pr?via tanto do substrato met?lico e do filme de LaCrO3 recoberto sobre o substrato met?lico,que em compara??o com as micrografias obtidas por MEV. Com aux?lio do MEV comprovou a forma??o da camada de Cr2O3 sobre o substrato met?lico e a estabilidade do filme de LaCrO3 ap?s o ensaio oxidativo. Observando tamb?m o descolamento do filme de LaCrO3 ap?s ensaio mec?nico e a distribui??o dos principais elementos como: cromo, mangan?s, oxig?nio, lant?nio nas amostras que foram submetidas aos ensaios termo-mec?nicos