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

Made available in DSpace on 2014-12-17T14:07:21Z (GMT). No. of bitstreams: 1 ClawsioRCS_TESE.pdf: 6209957 bytes, checksum: 4a85a36be678a5c36d937dd4cb67fe7c (MD5) Previous issue date: 2014-04-28 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Doped lanthanum chromite ( LaCrO3 ) has been the most common material used as interconnect in solid oxide fuel cells for high temperature ( SOFC-HT ) that enabling the stack of SOFCs. The reduction of the operating temperature, to around 800 ? C, of solid oxide fuel cells enabled the use of metallic interconnects as an alternative to ceramic LaCrO3, From the practical point of view, to be a strong candidate for interconnect the material must have good physical and mechanical properties such as resistance to oxidizing and reducing environments, easy manufacture and appropriate thermo-mechanical properties. Thus, a study on the physic-mechanical interconnects La0,8Sr0,2Cr0,92Co0,08O3 ceramics for SOFC -AT obtained by the method of combustion , as well as thermo-mechanical properties of metallic interconnects (AISI 444) covered with La0,8Ca0,2CrO3 by deposition technique by spray-pyrolysis fuel cells for intermediate temperature (IT-SOFCs). The La0,8Sr0,2Cr0,92Co0,08O3 was characterized by X -ray diffraction(XRD) , density and porosity , Vickers hardness (HV) , the flexural strength at room temperature and 900 ?C and scanning electron microscopy (SEM). The X -ray diffraction confirmed the phase formation and LaCrO3 and CoCr2O4, in order 6 GPa hardness and mechanical strength at room temperature was 62 MPa ceramic Interconnector. The coated metal interconnects La0,8Ca0,2CrO3 passed the identification by XRD after deposition of the film after the oxidation test. The oxidative behavior showed increased resistance to oxidation of the metal substrate covered by La0,8Ca0,2CrO3 In flexural strength of the coated metal substrate, it was noticed only in the increased room temperature. The a SEM analysis proved the formation of Cr2O3 and (Cr,Mn)3O4 layers on metal substrate and confirmed the stability of the ceramic La0,8 Ca0,2CrO3 film after oxidative test / A cromita de lant?nio (LaCrO3) dopada tem sido o material mais utilizado como interconector nas pilhas a combust?vel de ?xido s?lido de alta temperatura(PaCOS-AT), possibilitando o empilhamento(stack) da PaCOS. 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. Do ponto de vista pr?tico para o material ser forte candidato a interconector deve ter boas propriedades f?sicas e mec?nicas, como resist?ncia a ambientes oxidantes e redutores, f?cil fabrica??o e propriedades termo-mec?nicas adequadas. Por este motivo realizou-se um estudo sobre as propriedades fisico-mec?nicas de interconectores de La0,8Sr0,2Cr0,92Co0,08O3 cer?mico para PaCOS-AT obtido pelo m?todo da combust?o, como tamb?m sobre as propriedades termo-mec?nicas de interconectores met?licos (AISI 444) recobertos com La0,8Ca0,2CrO3 pela t?cnica de deposi??o por spray-pir?lise para Pilhas a combust?vel de temperatura intermediaria (PaCOS-TI). A La0,8Sr0,2Cr0,92Co0,08O3 foi caracterizada por meio de difra??o de raios X (DRX), densidade e porosidade, dureza Vickers (HV), resist?ncia mec?nica a flex?o na temperatura ambiente e a 900?C e microscopia eletr?nica de varredura (MEV). A difra??o de raios X comprovou a forma??o das fases LaCrO3 e CoCr2O4, dureza na ordem de 6 GPa e resist?ncia mec?nica a temperatura ambiente de 62 MPa do interconector cer?mico. A avalia??o das fases formadas no interconector met?lico recoberto com La0,8Ca0,2CrO3 tanto na deposi??o quanto ap?s o ensaio oxidativo foi realizado por DRX. O comportamento oxidativo evidenciou o aumento da resist?ncia a oxida??o do substrato met?lico recoberto por La0,8Ca0,2CrO3. Na resist?ncia mec?nica a flex?o do substrato met?lico recoberto, notou-se o aumento apenas na temperatura ambiente. Com aux?lio do MEV comprovou-se a forma??o das camadas de Cr2O3 e (Cr,Mn)3O4 sobre o substrato met?lico e confirmou-se a estabilidade do filme cer?mico de La0,8Ca0,2CrO3 ap?s o ensaio oxidativo

The UG3 at Modikwa Platinum Mine occurs as a platiniferous, planar chromitite seam. It is stratigraphically located in the Upper Critical Zone of the Eastern Bushveld Complex. Field work study comprise of underground mapping, sampling, surface mapping, borehole core logging, microprobing and microscopic investigations carried out at the Rhodes University. The UG3 at the Modikwa Platinum Mine is about 22cm thick chromitite seam underlain by a white fine grained anorthosite and overlain by a brown medium grained feldspathic pyroxenite. It is an incomplete cyclic unit consisting of chromite and feldspathic pyroxenite. The UG3 reef at the Modikwa Platinum Mine lease area represents a Platinum Group Metal resource of 300 million tons of ore at an in situ grade of 2.5g/t. Under the current market conditions the UG3 reef remains unprofitable to mine in an underground operation due to the operational cost involved. However, it has been illustrated that the UG3 chromitite seam can increase profit margins in an open pit operation provided it is mined together with the economic UG2 chromitite seam. The extraction of the UG3 as ore in the four Modikwa UG2 open pits would result in a combined operating cash profit of R330 million. The UG3 chromitite seam is platiniferous. The platinum-group minerals (PGM) range in size from less than 10μm to about 70μm. The PGMs are associated with sulphides and are both located in the interstitial silicates and are concentrated in the chromitite seam. The PGMs show a strong preference to contact boundaries of the silicate grains, the chromite grains and the sulphide phases. In some instances, they are enclosed within the chromite grains in association with sulphides. The general sulphide assemblage comprises pentlandite and chalcopyrite whereas, the PGMs assemblage comprises cooperite, ferroplatinum, laurite, FeRhS and PtRhS.

Effects of mould flux contaminant on scale-steel adhesion and hydraulic descaling of scale formed on slabs were investigated. In this investigation, stainless steel type 304 (austenitic with 18% Cr and 8% Ni) and specific mould fluxes were used when growing the scale on contaminated samples under simulated industrial reheating conditions, with subsequent high pressure water hydraulic descaling. The basic hypothesis was that the steel-scale adhesion depends on the microstructure of different phases present in the scale, the segregation of specific elements at the interface and the interfacial morphology of the scale after reheating. It was found that mould flux contaminant decreases scale-steel adhesion and therefore improved the descaling effectiveness significantly compared to non contaminated stainless steel. The descaling effectiveness of contaminated and uncontaminated slab was dependent to the presence of metal free paths (chromite layers along the austenite grains boundaries) and the presence of unoxidized metal in the scale due to nickel enrichment at the interface. Compared to the uncontaminated samples, the descaling of contaminated samples was efficient which could be due to the fact that some mechanisms which increase scale– steel adhesion (notably nickel enrichment at the interface) were considerably reduced. For all contaminated samples, the descaling effectiveness after visual observation were close to 100% and it was found that mould flux type 832 ( low basicity) gave a high descaling efficiency with better steel surface quality after descaling compared to mould fluxes type 810 and RF1. / Dissertation (MSc)--University of Pretoria, 2009. / Materials Science and Metallurgical Engineering / unrestricted

The present Diploma thesis provides an original synthesis for the preparation magnetic cobalt chromite nanoparticles (CoCr2O4 NPs) well dispersed in non-polar solvents and extensive structural, morphological, phonon and magnetic characterization. Particular emphasis is on determination of the spiral magnetic structure in CoCr2O4 NPs prepared by various procedures such as hydrothermal synthesis and sol-gel method. CoCr2O4 NPs with diameters in the range of 3.0 - 4.1 nm are prepared by high temperature hydrothermal method. For the first time, the CoCr2O4 NPs are stable in non-polar solvents and they are prepared by one-step synthesis without post treatment. The structure of prepared NPs is refined by Rietveld analysis. Size of prepared NPs is determined and compared using various techniques as powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). Magnetic measurements reveal the transition from superparamagnetic (SPM) state to super spin glass - like (SSG) state. From a.c. susceptibility measurements, the spin dynamics studies and strength of inter-particles interaction are investigated. CoCr2O4 NPs with mean diameter of 26.9(1) nm are prepared by sol-gel method. The magnetization measurements reveal the transition from superparamagnetic to...

La minéralisation platinifère étudiée dans ce travail se situe dans le grand massif ultrabasique du sud de la Nouvelle-Calédonie, à l'embouchure de la Rivière des Pirogues. La transformation exogène qui affecte les roches émergées de la ceinture intertropicale, a édifié aux dépends des péridotites de Nouvelle-Calédonie, d'épais manteaux latéritiques enrichis en métaux. L'objectif de cette étude a été de caractériser les évolutions chimiques et minéralogiques qui affectent les phases porteuses d'Eléments du Groupe du Platine (EGP) dans cet environnement latéritique. L'étude pétrographique et pétrologique de trois profils d'altération dans la zone anomale en platine-palladium, a permis de mettre en évidence le rôle majeur de la serpentinisation hydrothermale dans l'évolution de la minéralisation platinifère. Cette altération pré-météorique a néoformé et formé des Minéraux du Groupe du Platine (MGP) par désulfuration de phases préexistantes et par précipitation de nouveaux minéraux. Au contact de l'atmosphère et de l'hydrosphère, les MGP évoluent différemment selon leur composition chimique. Les phases très riches en platine de type isoferroplatine (Pt3Fe) sont stables dans le manteau d'altération, alors que les phases plus riche en fer, cuivre et palladium, comme le tétraferroplatine (PtFe), la tulameenite (Pt2FeCu) ou les oxydes de Pt-Fe subissent une dissolution incongruente, avec une lixiviation sélective de leurs composants chimiques. La caractérisation géochimique à la microsonde électronique des cortex d'altération, révèle le gradient de mobilité suivant lors de la transformation latéritique des MGP : S > Cu > Pd > Fe > Pt. Quel que soit le minéral parental, la phase néoformée est relativement enrichie en Pt, et tend à acquérir la configuration chimique de l'isoferroplatine (Pt3Fe).

Situé au nord de la Nouvelle-Calédonie, le massif de Tiébaghi, d'où a été extraite la majeure partie de la production de chromite de l'île, fait partie de l'ensemble ultramafique calédonien, charrié à l''Eocène supérieur sur le bâti sialique calédonien. Ce massif est constitué presque exclusivement de péridotites à textures de tectonites. L'étude pétrographique et structurale de l'ensemble du massif permet de reconstituer les principales phases de déformation, et de définir l'organisation des roches ultramafiques par une série différenciée clans laquelle les faciès dominants sont successivement, de bas en haut et du Nord-Est au Sud-Ouest, les dunites et harzburgites, les harzburgites à clinopyroxènes et les lherzolites à spinelle - dans ces dernières, le plagioclase apparaît localement par rééquilibrage métamorphique de faciès riches en pyroxènes. Les principales concentrations chromifères se placent suivant un nombre réduit de "niveaux" dans la zone de transition entre les unités harzburgitique et lherzolitique. Les morphologies des gisements et leurs relations structurales avec l'encaissant ultramafique sont contrôlées principalement par les déformations plastiques subies par l'ensemble de la série, Les différents faciès ultramafiques s'intègrent dans une évolution géochimique continue et, dans le détail, séquentielle. Des évolutions, également séquentielles et sans discontinuité majeure entre les différentes unités de la série, apparaissent dans les compositions des minéraux, lesquelles ont pu être modifiées par des rééquilibrages ou des recristallisations partielles en liaison avec les déformations. La différenciation de la série de Tiébaghi peut s'expliquer par la cristallisation fractionnée d'un liquide basaltique tholéitique (pauvre en titane et en alcalins) contenant en suspension - ou imprégnant - un matériel constitué principalement d'olivines magnésiennes, et éventuellement d'orthopyroxènes et de spinelles. Au cours de cette différenciation, des diminutions de pression, accompagnées éventuellement de l'influx de liquides peu différenciés, peuvent être à l'origine des accumulations de chromite.

This thesis presents the results of investigations of the synthesis, structure and physical properties of multiferroic materials. Multiferroics are materials in which two or all three of ferroelectricity, ferromagnetism and ferroelasticity occur in the same phase. Such materials have the potential applications of their parent materials, as well as new ones because of the interaction between the order parameters. The thesis is organized into four sections. Section 1 gives an overview of multiferroics, explaining the origin of mul-tiferroicity , occurrence of magnetoelectric coupling, their possible technological ap-plications and the challenges involved. Section 2 gives the scope of the investigations. The specific objectives of the present research on yttrium chromite, heavy rare earth chromites, solid solutions of yttrium chromite, rare earth manganites doped with alkaline earth metals, charge-ordered rare earth ferrites and indium manganite are outlined. Experimental aspects of the work carried out are discussed in section 3. It gives details of the experimental set up and the basic operation principles of various structural and physical characterizations of the materials prepared. In section 4, results of the investigations are discussed. Magnetic and di-electric properties of yttrium chromite (YCrO3), heavy rare earth chromites and YCr1-xMnxO3 are reported in section 4.1. These materials show canted antiferro-magnetic behavior below the Nel transition temperatures and dielectric transitions at high temperatures. Role of local non-centrosymmetry is discussed based on high-resolution neutron powder diffraction data. In 4.2 we discuss the results of charge-ordered rare earth ferrites which show good magnetoelectric effect. Magnetic, dielectric and magneto-dielectric properties of YCr1-xMnxO3 (Ln = rare earth) are discussed in 4.3. These materials show magneto-dielectric effect. In 4.4 we discuss the near normal incidence far infrared reflectivity spectra of a single crystal of TbMnO3, in the spectral range of 50cm−1 to 700 cm−1 from 10 K to 300 K. Finally in 4.5, magnetic and dielectric properties of bulk and thin films of indium manganite are discussed.

The recent discovery of the 31-km-wide Hiawatha impact crater has raised unanswered questions about its age, impactor and highly unusual organic carbon component. Previous research suggests a fractionated iron meteorite impactor, a probable maximum 3–2.4 Ma impact age and a possible Younger Dryas impact age. The first objective in this study has been to investigate a possible link between the Cape York meteorites and the Hiawatha impact crater by comparing the chromium isotopic signature in chromite from a Cape York meteorite with the chromium isotopic signature in potential chromite from the Hiawatha impactor. The second objective has been to investigate a possible Hiawatha signature in the Younger Dryas deposits from Baffin Bay. The third objective has been to study the organic carbon component in impactites derived from the Hiawatha impact crater. Heavy mineral grains were separated from glaciofluvial sediment which contains Hiawatha impactite grains. Not a single chromite grain was found and the possible link to the Cape York meteorites could not be tested. The petrographic examination of Younger Dryas marine deposits resulted in absence of impact-related Hiawatha grains. A petrological investigation revealed that organic carbon was likely found in five of six variably shocked impactites derived from the Hiawatha impact crater. The character of the organic carbon varies between the samples and also within individual samples. Vitrinite reflectance measurements of the organic carbon in two impactites yielded low reflectance values compared to charcoalification experiments of wood. Organic particles with different reflectance in the same sample suggest that the particles had different impact histories prior to settling and becoming a rock. Diagnostic conifer cellular texture was found in at least one of the samples. The character of the organic particles in the impactites supports the suggestion in a previous study that the sources of the Hiawatha organic carbon component are unmetamorphosed surficial deposits containing dead conifer tree trunks and fine-grained layered clay and organic matter.  In this study it is concluded that the apparent absence of chromite in the examined glaciofluvial sediment sample corroborates the significance of previous research which suggests that the Hiawatha impactor was an iron meteorite. The apparent absence of impact related grains in the Younger Dryas deposits suggests that although a Younger Dryas age for the Hiawatha impact crater is less likely now, the possibility remains open. The organic carbon with diagnostic conifer cellular texture in the Hiawatha impactites corroborates the conclusion in a previous study that the Hiawatha impact-related organic carbon component stems from local, thermally degraded conifer trees with a probable age of ca. 3–2.4 Ma. It is also concluded that the relatively low reflectance values of the organic carbon in the Hiawatha impactites seem to be related to the short duration of the high-temperature excursion during the hypervelocity impact event.

The project elaborated in frame of engineering studies is submitting the study of thermal properties of holding mixtures using different types of sand. Were tested a total of 5 sands: zirkon, ŠH22, chromite, olivine and dunite. Molding compounds were tested for thermal capacity, thermal conductivity and heat accumulation. The highest heat capacity was achieved in dunite sand. The largest heat accumulation had mixture with chromite sand and the best thermal conductivity was found in a mixture with olivine sand.