Orientadores: Roberto Perez Xavier, Carlos Roberto de Souza Filho, Lena Virginia Soares Monteiro / Tese (doutorado) -Universidade Estadual de Campinas, Instituto de Geociencias / Made available in DSpace on 2018-08-12T19:03:21Z (GMT). No. of bitstreams: 1 Carvalho_EmersondeResende_D.pdf: 11938678 bytes, checksum: fdc3794a3948e2508d41b33690dcf01d (MD5) Previous issue date: 2009 / Resumo: O depósito de óxido de ferro-cobre-ouro de Sossego na Província Mineral de Carajás (PMC), região norte do Brasil, consiste de três corpos de minério principais, denominados Sossego-Curral, Sequeirinho-Baiano e Pista, envolvidos por zonas de alteração hidrotermal sódica, sódico-cálcica, potássica, clorítica e hidrolítica. Essas zonas de alteração hidrotermal mostram diferentes graus de desenvolvimento em cada corpo de minério. Os estágios iniciais de alteração foram controlados pelo fluxo de fluido em zonas de cisalhamento regionais, enquanto a mineralização cupro-aurífera corresponde a uma fase tardia e se formou em um ambiente estrutural rúptil. Salmouras hipersalinas, quentes (> 500 oC) e compostas essencialmente por NaCl-CaCl2-H2O podem estar associadas com o desenvolvimento inicial do sistema hidrotermal Sossego. As brechas sulfetadas Sequeirinho e Sossego mostram um enriquecimento em Cu-Fe-Au-(Ag)- Ni-Co-Se-Y-V-P-La-Ce e baixo conteúdo de Ti, semelhante a outros depósitos de óxido de Fe-Cu-Au em Carajás e em termos mundiais. O alto conteúdo de Ni, Co, Se, V e Pd, especialmente no corpo Sequeirinho, possivelmente é decorrente da lixiviação de metais a partir de fontes como o gabro, que tem relação espacial com os corpos de magnetitito e as zonas mineralizadas, e lente de rochas metaultramáficas do Supergrupo Itacaiúnas. Os processos de interação fluido-rocha devem ter resultado em significativa lixiviação de metais da seqüência de rochas hospedeiras, que foi acentuado por fluidos hidrotermais inicialmente de alta temperatura (>500 oC) e alto conteúdo de cloreto no sistema hidrotermal Sossego, movido pelo calor dos vários episódios de intrusões registrados na PMC. As inclusões fluidas de amostras dos estágios finais da evolução do sistema hidrotermal Sossego, indicam a participação de (1) salmouras hipersalinas; (2) salmouras salinas, de baixa temperatura (~150 oC) e ricos em CaCl2; e (3) fluidos de baixa salinidade e baixa temperatura (< 250 oC) e compostos por NaCl-H2O, representativos, respectivamente dos estágios inicial, principal e final da mineralização de Cu-Au. As salmouras salinas ricas em CaCl2 poderiam refletir uma evolução contínua a partir de um fluido hipersalino magmático ou envolver fluidos bacinais de baixa temperatura, incluindo um componente derivado de evaporitos. Os fluidos portadores de NaCl e de baixa salinidade predominam nos estágios finais do evento mineralizante e podem representar o influxo de fluidos meteóricos. A transição para um regime estrutural dominantemente rúptil e o resfriamento do sistema favorecem o influxo desses fluidos meteóricos oxidados. A mistura de fluidos pode ter sido o mecanismo principal que desencadeou a precipitação da maior parte do Cu e Au nos diferentes corpos de minério do depósito de Sossego. / Abstract: The Sossego iron oxide-copper-gold deposit in the Carajás Mineral Province (CMP), northern Brazil, consists of three main orebodies, named Sossego-Curral, Sequeirinho-Baiano and Pista, enveloped by sodic, sodic-calcic, potassic, chloritic, and hydrolithic hydrothermal alteration zones. These alteration zones display different degrees of development in these orebodies. The early alteration stages were controlled by fluid-flow in large-scale regional shear zones, whereas bulk copper-gold mineralization was late and formed in a brittle structural environment. Hypersaline NaCl-CaCl2-H2O hot (>500 oC) brines could be associated with the initial development of the hydrothermal system. Sequeirinho and Sossego sulfide ore breccias are marked by enrichment in Cu-Fe-Au-(Ag)-Ni-Co-Se-Y-V-P-La-Ce and low contents of Ti, which also occur in other IOCG deposits of CMP and worldwide IOCG deposits. The high contents of Ni, Co, Se, V and Pd, particularly in Sequeirinho orebody, possibly were originated by metal leaching from sources such as intrusive gabbro, which have spatial relationship with massive magnetite bodies and mineralized zones, and metaultramafic lenses of Itacaiúnas Supergroup. Fluid-rock interaction process might have resulted in significant metal leaching from host sequences, enhanced by early high temperature (>500 oC) and high chloride concentrations of hydrothermal fluids in the extensive Sossego hydrothermal system driven by heat from several intrusive episodes recorded in the CMP. Fluid inclusions of the samples from the final stages of evolution of the Sossego hydrothermal system in brittle conditions, indicated participation of hot hypersaline brines, low temperature (~150 oC) CaCl2-rich saline brines and low-temperature (<250 oC) low salinity NaCl-H2O fluids in early, main and late mineralization stages. The CaCl2-rich saline brines could reflect continuum evolution from magmatic hypersaline fluids or involve low temperature basinal, including evaporite-derived fluids. Low salinity, NaCl-bearing fluids, predominates in late stages and reflect channelized influx of meteoric fluids. The transition to a dominantly brittle structural regime and cooling of the system favors the influx of these oxidized meteoric-derived fluids. Fluid mixing could have represented a major influence on ore precipitation in different orebodies from the Sossego IOCG deposit and could have had fundamental importance to trigger the bulk of copper deposition. / Doutorado / Metalogenese / Doutor em Ciências

O objetivo do presente projeto é a combinação de abordagens experimentais e teóricas para o desenvolvimento de bancos de dados termodinâmicos, visando o modelamento de aços e ligas de alto desempenho. Entre esses materiais estão as superligas fundidas por centrifugação para aplicações em fornos de reforma e pirólise, bem como aços-ferramenta reforçados por fases intermetálicas. Os métodos teóricos mencionados correspondem à combinação de cálculos de estrutura eletrônica e modelamento termodinâmico em temperaturas finitas, através do protocolo Calphad. Esta metodologia vem sendo aplicada com sucesso por vários grupos de pesquisa brasileiros e internacionais. Utilizando-nos de dados experimentais para o sistema Fe-Cr-Mo-C, obtidos recentemente em nosso laboratório, e cálculos de primeiros princípios para o sistema Ni-Nb-Si, aliados a outros resultados experimentais da literatura, aperfeiçoamos os bancos de dados termodinâmicos existentes para estes dois sistemas, minimizando as inconsistências quanto às evidências experimentais em relação aos campos de estabilidade e equilíbrio entre fases. No sistema Fe-Cr-Mo-C, utilizamo-nos de dados experimentais para uma reotimização da descrição termodinâmica. Adotamos novas descrições para os binários Cr-Fe, C-Cr e C-Fe, com novos modelos para as fases cementita no sistema C-Fe e sigma no sistema Cr-Fe. Com essas alterações, fomos levados a reavaliar todas as descrições dos ternários, reotimizando-os quando necessário (C-Cr-Fe) ou apenas revalidando os modelamentos pré-existentes (C-Cr-Mo). Por fim, reotimizamos o quaternário como um todo, chegando a resultados satisfatórios quando comparados a resultados experimentais. As propriedades termodinâmicas do sistema Nb-Ni-Si são pouquíssimo conhecidas. Por este motivo, não há dados suficientes na literatura para realizar um assessment completo deste sistema. Por isto, decidimos realizar cálculos de primeiros princípios de estrutura eletrônica, para a determinação de energias de formação dos compostos ternários presentes neste sistema. Os sistemas binários Nb-Ni, Nb-Si e Ni-Si, por outro lado, são bem conhecidos, cada um deles contando com diversas descrições termodinâmicas publicadas ao longo dos últimos anos. Por esta razão, adotamos as mais recentes descrições termodinâmicas dos binários como ponto de partida para o modelamento do sistema ternário. O resultado do modelamento, quando comparado aos poucos dados experimentais disponíveis, é bastante satisfatório. / The aim of this project is the combination of advanced experimental and theoretical approaches for the development of thermodynamic databases dedicated to modelling steels and high performance alloys. Examples of materials are centrifugally-cast superalloys designed for use in reforming and pyrolisis furnaces, as well as intermetallic-reinforced tool steels. The theoretical methods are the combination of electronic structure calculations and thermodynamic modeling at finite temperatures using the CALPHAD method. This methodology has been used by different scientific groups, both in Brazil and around the world. Using experimental data in the Fe-Cr-Mo-C sytem, recently determined in our laboratory, and first principles calculations in the Nb-Ni-Si system, together with other experimental results from the literature, we improved the existing thermodynamic databases for these two systems, minimizing discrepancies regarding the experimental evidence about phase stability fields and phase equilibria. In the Fe-Cr-Mo-C system, we employed experimental data for a reoptimization of the thermodynamic description. We adopted new descriptions for the binary Cr-Fe, C-Cr, and C-Fe systems, with new models for cementite in the C-Fe system, and sigma in the Cr-Fe system. Because of these alterations, a reevaluation of the ternary descriptions was necessary, reassessing them when required (C-Cr-Fe) or just revalidating existing models (C-Cr-Mo). After that, we re-optimized the quaternary system, arriving at satisfactory results, in comparison with experimental data. The thermodynamic properties of the Ni-Nb-Si system is almost completely unknown. For that reason, there are not enough data in the literature to perform a complete assessment of the system. With that in mind, we decided to perform first-principles electronic structure calculations, in order to determine the formation energies of the ternary compounds. The binary systems, on the other hand, are very well-known, each one of them with several published thermodynamic assessments during the last few years. For this reason, we adopted the most recent thermodynamic descriptions of the binaries as a starting point for the modelling of the ternary system. The result of the modelling is very satisfactory, in comparison with the few experimental information available.

O objeto desta pesquisa consiste em investigar as propriedades estruturais, magnéticas e hiperfinas dos compostos pseudobinários de fases de Laves: Hf(Fe(1-x)Cr(x))2 e (Nb(1-x)Zr(x))Fe2. Para o Hf(Fe(1-x)Cr(x))2, preparamos as amostras como ligas policristalinas e as fundimos por síntese nas concentrações: x = 0,0; 0,1; 0,2; 0,3; 0,4; 0,5; 0,6; 0,7; 0,8; 0,9 e 1,0. O mesmo foi feito para as amostras de (Nb(1-x)Zr(x))Fe2 nas concentrações x = 0,0; 0,1; 0,2; 0,3; 0,4 e 0,5. Todas as amostras fundiram-se num forno de fusão de arco, sob atmosfera de argônio ultrapuro (99.999%). Em seguida investigamos a estrutura cristalina das ligas pelo método do pó, com a técnica de difratometria de Raios X (XRD), obtendo-se os parâmetros de rede e confirmando-se a estrutura de fase hexagonal C14 para as amostras Hf(Fe(1-x)Cr(x))2 nas concentrações 0,0 <= x < 0,9, bem como em todas as outras amostras de (Nb(1-x)Zr(x))Fe2. Depois, determinamos as propriedades magnéticas das ligas Hf(Fe(1-x)Cr(x))2 pela técnica de magnetização a baixas temperaturas em baixos campos magnéticos aplicados de 0 a 7 T e em altos campos magnéticos aplicados de 0 a 16 T. As suscetibilidades AC e DC a baixos campos magnéticos com temperaturas de 4,2 K a 300 K, FC e ZFC, nos indicaram que as ligas de concentrações 0,4 <= x < 0,8 apresentam comportamento \'vidro de spin\', sendo que em x <= 0,3 são aglomerados magnéticos com interação de curto alcance e em x = 0,9 é um superparamagnético. Por tanto, os valores dos momentos magnéticos por átomo de Fe foram calculados para todas as amostras. As medidas de spectroscopia Mössbauer das mesmas amostras de Hf(Fe(1-x)Cr(x))2, na temperatura ambiente, apresentam dois sextetos para a mostras com x = 0,2 e dois dubletos quadrupolares para as demais composições, atribuídos aos sítios cristalográficos 2a e 6h do Fe. Por outra parte, os espectros Mössbauer das amostras de (Nb(1-x)Zr(x))Fe2 à temperatura de 4,2 K, sem campo magnético aplicado e com campo magnético aplicado de 6 e 12 T, sugerem que estes compostos se encontram em um balanço em que coexistem as fases ferromagnéticas e antiferromagnéticas. Finalmente, notamos que no composto (Nb0.6Zr0.4)Fe2 há, uma possível existência de comportamento paramagnético nos Fe do sítio cristalino 2a e, ao mesmo tempo, pouca certeza que o valor do momento magnético seja nulo neste sítio cristalino. / The object of this research consists of investigating the structural, magnetic and hiperfine properties of the pseudobinar Laves phases compounds Hf(Fe(1-x)Cr(x))2 and (Nb(1-x)Zr(x))Fe2. We prepared polycristaline samples alloys and for synthesis melting in the concentrations: x = 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 e 1.0, for the Hf(Fe(1-x)Cr(x))2 and in the concentrations: x = 0.0, 0.1, 0.2, 0.3, 0.4 e 0.5 for (Nb(1-x)Zr(x))Fe2. We melted them in an arc furnace under pure Argon (99.999%) gas atmosphere. We investigated the cristaline structure of the alloys by the powder XRD technique, obtaining lattice parameters and confirming the structure of hexagonal phase C14 for the samples Hf(Fe(1-x)Cr(x))2 in the concentrations 0.0 <= x <= 0.9 and also in all the other samples produced of (Nb(1-x)Zr(x))Fe2. We investigate the magnetic properties of Hf(Fe(1-x)Cr(x))2 alloys bye the technique of magnetization at low temperatures and low magnetic field applied until 7 T and high magnetic field applied until 16 T. The susceptibility AC and DC at low magnetic fields and temperatures of 4.2 K until 300 indicated that alloys of concentrations 0.4 <= x < 0.8 show spin glass behavior, in x <= 0.3 they are magnetic clusters with short range interactions, and in x = 0.9 is superparamagnetic. The values of the magnetic moments for atom of Fe were calculated for all samples. We measured Mössbauer spectra of the same samples of Hf(Fe(1-x)Cr(x))2 at room temperature, obtaning two sextets for the samples with x < 0.2 and two quadrupolar doublets for the other compositions, that would be attributed to the cristalographic sites 2a and 6h. Also the Mössbauer spectrum of the samples (Nb(1-x)Zr(x))Fe2 at temperature of 4.2 K without magnetic field applied and with magnetic field applied of 6 and 12 T, suggest that those compounds show coexisting ferromagnetic and antiferromagnetic phases. We could note for the compound (Nb0.6Zr0.4)Fe2 a possible existence of the paramagnetic behavior in the Fe of the cristalographic site 2a, but the magnetic moment in this site is not zero.

O desenvolvimento industrial tem, como conseqüência, a maior geração de resíduos, muitos deles tóxicos aos seres vivos. Dentre esses, benzeno, tolueno e xilenos (BTX), derivados do petróleo, estão contaminando aqüíferos por acidentes no transporte e no armazenamento. Por esse motivo, diversas pesquisas têm sido realizadas buscando formas de biodegradar BTX. Esses trabalhos indicam que os principais fatores que podem influenciar a degradação biológica dos BTX são temperatura, pH, disponibilidade de nutrientes, concentração de tóxicos e diversidade de microrganismos. Visando contribuir com o estudo desses fatores, este trabalho teve por objetivo avaliar a influência do inóculo e de aceptores de elétrons no processo de degradação anaeróbia de BTX. Neste trabalho três inóculos foram pesquisados: 1- biomassa proveniente de reator anteriormente submetido à mistura de gasolina comercial e água; 2- biomassa proveniente de reator da estação de tratamento de esgoto da USP - São Carlos; 3- biomassa proveniente de reator tratando água residuária de abatedouro de aves. Os resultados obtidos comprovaram que a origem do inóculo foi fundamental na degradação anaeróbia de BTX, pois os inóculos apresentaram diferentes períodos de adaptação e porcentagens de degradação do tóxico. Depois de 93 dias de operação os inóculos 1, 2 e 3 apresentaram eficiência de remoção de BTX da ordem de 57%, 83% e 90%, respectivamente. O reator com o inóculo 3 foi submetido a condições metanogênica, sulfetogênica com presença e ausência de Ferro (III). Os resultados demonstraram que a degradação dos BTX foi influenciada pelas diferentes condições adotadas. A adição de Fe (III) melhorou a degradação dos BTX, do reator sob condições sulfetogênicas. / The industrial development has increased the generation of residues. Some of them are toxics and impact the environment. Benzene, toluene and xylenes (BTX), petroleum sub products, are examples of such toxic compounds. These compounds may contaminate aquifers as a result of accidents during transportation or of leakages of storage tanks. Several factors are reported to affect the biodegradation of BTX, such as: temperature, pH, availability of nutrients, concentration of toxics and diversity of microorganisms. This research aimed to study some of these factors, such as different inoculum sources and different electrons acceptors during BTX degradation processes in an horizontal-flow anaerobic immobilized biomass (HAIB) reactor. In this research three inocula were studied: 1- an adapted microbial community for BTX degradation; 2 - microorganisms collected from a pilot-scale UASB reactor treating domestic wastewater; and 3 - Microorganisms collected from an UASB treating poultry slaughterhouse industry wastewater. The results have shown that the inoculum sources were fundamental to the adaptation period for the toxic biodegradation, producing different BTX removal efficiencies. After 93 days of operation, the inocula 1, 2 and 3 showed BTX removal efficiency of 57, 83 and 90%, respectively. The inoculum 3 was submitted to conditions of methanogesis and sulfetogenesis in the presence and absence of Fe (III). The results demonstrated that BTX degradation was affected by the different conditions adopted, showing that the addition of Fe (III) improved biodegradation in the reactor under sulfate reduction condition.

Orientadores: Lena Virgínia Soares Monteiro, Roberto Perez Xavier / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-08-25T01:47:31Z (GMT). No. of bitstreams: 1 Melo_GustavoHenriqueCoelhode_M.pdf: 5898704 bytes, checksum: 9979e7e61290df2fb3d52d7c2beef5b2 (MD5) Previous issue date: 2014 / Resumo: O depósito Salobo, de classe mundial, representa o maior e mais importante depósito de óxido de ferro-cobre-ouro (IOCG) da Província Carajás. O depósito é hospedado por rochas gnáissicas fortemente modificadas por processos de alteração hidrotermal espacialmente relacionados à Zona de Cisalhamento Cinzento. Idades U-Pb SHRIMP IIe em zircão obtidas nos gnaisses pemitem correlacioná-los aos granitoides sin-tectônicos da Suíte Igarapé Gelado (2.763 ± 4,4 Ma; MSWD = 1,7). Adicionalmente, idades U-Pb SHRIMP IIe em zircão de 2.950 ± 25 Ma (MSWD = 5,9) e 2.857 ± 6,7 Ma (MSWD = 0,001) foram atribuídas à cristalização dos protólitos e metamorfismo, respectivamente, de gnaisses do Complexo Xingu, que ocorrem como lascas tectonicamente imbricadas aos granitoides sin-tectônicos no depósito Salobo. Intensa alteração hidrotermal sobre as rochas gnáissicas hospeiras formou rochas ricas em hastingsita-actinolita, grunerita-almadina-biotita-(turmalina) e magnetita com bornita e calcocita disseminadas.O sistema hidrotermal evoluiu de alteração sódica-cálcica (hastingsita-actinolita) inicial seguido por estágio de enriquecimento em ferro (grunerita-almandina-faialita) e formação de turmalina. Alteração potássica com biotita subsequente foi acompanhada pela formação de magnetita, cogenética à precipitação do minério. O minério é constituído principalmente por bornita, calcocita, magnetita e quantidades menores de calcopirita, e ouro, além de exibir significativos conteúdos de Co, Ni, As, Ag, Mo e ETR. Alteração hidrotermal pós-mineralização (alteração potássica com feldspato potássico, alteração propilítica, e formação de hematita) também foi reconhecida espacialmente associada à colocação do granito Old Salobo (U-Pb SHRIMP IIe em zircão; 2.547 ± 5,3 Ma; MSWD = 0,92), sobrepondo-se à alteração hidrotermal e mineralização relacionada ao sistema IOCG. Adicionalmente, os dados geocronológicos e a sequência de alteração hidrotermal parecem evidenciar que a mineralização é mais antiga que a colocação do granito Old Salobo e não possui relação genética com o mesmo. O depósito Salobo, entretanto, foi submetido a uma complexa evolução com possível mineralização IOCG em ca. 2,7 Ga e remobilização do minério em ca. 2,57 Ga e durante o Paleoproterozoico / Abstract: The giant Salobo deposit represents the largest iron oxide-copper-gold deposit (IOCG) in the Carajás Province. The deposit is hosted by gneisses of the Igarapé Gelado suite (2,763 ± 4.4 Ma; MSWD = 1,7) and of the Xingu Complex. The latter has SHRIMP IIe U-Pb zircon ages of 2,950 ± 25 Ma (MSWD = 5,9) and 2,857 ± 6.7 Ma (MSWD = 0,001), attributed to igneous crystallization and metamorphism. Gneissic rocks underwent strong hydrothermal alteration within the Cinzento Shear Zone, resulting in hastingsite-actinolite-, grunerite-almadine-biotite-(tourmaline)- and magnetite-rich rocks with disseminated bornite and chalcocite. The hydrothermal system evolved from early sodic-calcic (hastingsite-actinolite) alteration followed by a stage of iron-enrichment (grunerite-almandine-fayalite) and tourmaline formation. Subsequent potassic alteration I with biotite was superposed by magnetite formation, coeval with ore precipitation. Ore minerals include mainly bornite, chalcocite, magnetite and minor chalcopyrite and gold, with significant enrichment in Co, Ni, As, Ag, Mo, and REE. Post-ore alteration (potassic alteration II with K feldspar, propylitic alteration, and hematite formation) was spatially related with the emplacement of the Old Salobo Granite at 2,547 ± 5.3 Ma (MSWD = 0.92), and overprints the IOCG hydrothermal alteration and mineralization. Moreover, the geochronological data and the sequence of hydrothermal alteration may evidence the mineralization is older than the emplacement of the Old Salobo Granite and has no genetic relationship with its emplacement. The Salobo deposit, however, may have undergone a complex evolution with possible IOCG mineralization at ca. 2.7 Ga and ore remobilization at ca. 2.57 Ga and during Paleoproterozoic, similarly to the IOCG deposits in the Southern Copper Belt / Mestrado / Geologia e Recursos Naturais / Mestre em Geociências

Orientadores: Lena Virginía Soares Monteiro, Roberto Perez Xavier / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-08-23T01:24:15Z (GMT). No. of bitstreams: 1 Moreto_CarolinaPenteadoNatividade_D.pdf: 13805186 bytes, checksum: 31ff869acc3883e50095008070e1e739 (MD5) Previous issue date: 2013 / Resumo: O Cinturão Sul do Cobre, Província Carajás, hospeda diversos depósitos de óxido de ferro-cobre-ouro (iron oxide-copper-gold ou IOCG), tais como Sossego (corpos Sequeirinho-Pista-Baiano e Sossego- Curral), Cristalino, Alvo 118, Bacuri, Bacaba, Castanha, Visconde e Jatobá, que estão localizados ao longo de uma zona de cisalhamento com direção WNW-ESSE, no contato sul entre a Bacia Carajás e as rochas do embasamento. Mapeamento geológico aliado a estudos geocronológicos (U-Pb SHRIMP IIe e LA-ICPMS) permitiram a caracterização dos litotipos hospedeiros de depósitos IOCG na porção centrooeste do Cinturão Sul do Cobre, incluindo: (1) unidades neoarqueanas de 2,74 Ga (Pórfiro Castanha, granito granofírico Sossego e intrusivas máficas); (2) unidades mesoarqueanas entre 2,87 Ga a 2,84 Ga (Tonalito Campina Verde, Trondhjemito Rio Verde e Granito Serra Dourada); (3) rochas metavulcânicas félsicas de 2,97 Ga associadas às lentes de rochas metaultramáficas; (4) rochas graníticas mesoarqueanas de 3,0 Ga (Tonalito Bacaba e Granito Sequeirinho). Alteração hidrotermal que afeta essas rochas consiste em alteração sódica regional (albita, escapolita e óxidos de ferro), sódico-cálcica (albita-actinolita), potássica (feldspato potássico-biotita), clorítica (clorita) e hidrolítica (sericita-muscovita-hematitaquartzo), silicificação e formação de epidoto-calcita-clorita. Os depósitos IOCG, entretanto, exibem variações dos padrões de distribuição das zonas de alteração hidrotermal, apontando para níveis crustais distintos de instalação dos sistemas hidrotermais, com formação de corpos de magnetita maciça e actinolititos em depósitos mais profundos (corpos Sequeirinho-Pista-Baiano e depósito Castanha) e zonas de alteração clorítica e hidrolítica nos mais rasos (corpos Sossego-Curral e depósito Alvo 118). Datação de cristais de monazita hidrotermal (U-Pb LA-MC-ICPMS) e molibdenita (Re-Os NTIMS) dos corpos Sequeirinho e Pista, e dos depósitos Bacuri e Bacaba, forneceram idades entre 2,71 a 2,68 Ga, enquanto que monazita hidrotermal dos corpos Sossego e Curral resultaram em idades entre 1,90 a 1,88 Ga. Adicionalmente, cristais de molibdenita do depósito Bacuri e de monazita do depósito Bacaba indicaram idades em 2,76 Ga e 2,05 Ga, respectivamente. Esses dados sugerem que múltiplos eventos hidrotermais neoarqueanos e paleoproterozóicos foram responsáveis pela alteração hidrotermal e mineralização cuprífera no Cinturão Sul do Cobre. O desenvolvimento de sistemas hidrotermais IOCG profundos (Sequeirinho-Pista, Bacaba, Bacuri, Visconde e Castanha) no Neoarqueano (2,71-2,68 Ga), associados a extensas zonas de escapolita, foi relacionado a reativações das zonas de cisalhamento em função da inversão tectônica da Bacia Carajás. No Orosiriano (1,9-1,87 Ga), a instalação de sistema(s) hidrotermal(is) IOCG em níveis crustais mais rasos resultou na formação de novos depósitos (Alvo 118) e corpos de minério (Sossego-Curral), possivelmente relacionados às fontes de calor devido à colocação dos granitos do tipo-A da província. Esse evento teria resultado em (re)mobilização do minério e sobreposição de estágios hidrotermais, tal como o desenvolvimento de alteração hidrolítica sobre alteração escapolítica preexistente. Assim, o Cinturão Sul do Cobre apresenta um notável registro de recorrência de eventos hidrotermais ao longo do tempo geológico, responsável pela formação de depósitos IOCG de classe mundial / Abstract: The Southern Copper Belt, Carajás Province, hosts several iron oxide-copper-gold (IOCG) deposits, including the Sossego (Sequeirinho-Pista-Baiano and Sossego-Curral orebodies), Cristalino, Alvo 118, Bacuri, Bacaba, Castanha, Visconde, and Jatobá deposits. These deposits are situated within a WNW-ESE shear zone in the southern contact between the Carajás Basin and basement rocks. Geological mapping combined with geochronological studies (U-Pb SHRIMP IIe and LA-ICPMS) allowed the characterization of the host rocks of the IOCG deposits in the central-west part of the Southern Copper Belt, which include: (1) 2.74 Ga Neoarchean units (Castanha Porphyry, Sossego granophyric granite and mafic intrusive rocks); (2) 2.87-2.84 Ga Mesoarchean units (Campina Verde Tonalite, Rio Verde Trondhjemite and the Serra Dourada Granite); (3) 2.97 Ga felsic metavolcanic rocks associated with metaultramafic lenses; (4) 3,0 Ga Mesoarchean granitic rocks (Bacaba Tonalite and Sequeirinho Granite). Hydrothermal alteration that affects these rocks consist in regional sodic (albite, scapolite and iron oxides), sodic-calcic (albite-actinolite), potassic (potassium feldspar and biotite), chlorite, and hydrolytic (sericite-muscovitehematite- quartz) alterations, silicification, and epidote-calcite-chlorite formation. However, the IOCG deposits display variations in the distribution of the hydrothermal alteration zones, pointing to distinct crustal levels in which the deposits were installed. Massive magnetite-rich and actinolite-rich bodies are recognized in deeper-emplaced deposits (Sequeirinho-Pista-Baiano orebodies and Castanha deposit), while chlorite and hydrolytic alteration zones are identified in shallower-emplaced deposits (Sossego- Curral orebodies and Alvo 118 deposit). Dating of hydrothermal monazite (U-Pb LA-MC-ICPMS) and molybdenite (Re-Os NTIMS) from the Sequeirinho and Pista orebodies and the Bacuri and Bacaba deposits rendered ages of ca. 2.71 to 2.68 Ga, whilst hydrothermal monazite from the Sossego and Curral orebodies yielded ages of ca. 1.90 to 1.87 Ga. Additionally, molybdenite crystals from Bacuri and monazite from Bacaba provided the ages of 2.76 Ga and 2.05 Ga, respectively. These data suggest that multiple discrete Neoarchean and Paleoproterozoic hydrothermal events were responsible for hydrothermal alteration and ore formation at the Southern Copper Belt. The development of deep IOCG hydrothermal systems (Sequeirinho-Pista, Bacaba, Bacuri, Visconde, and Castanha) at the Neoarchean (2.71-2.68 Ga), related to extensive scapolite-rich zones, was linked to the reactivation of shear zones due to the tectonic inversion of the Carajás basin. In the Orosinian (1.90-1.87 Ga), the establishment of IOCG hydrothermal system(s) in shallower crustal levels resulted in the formation of new deposits (Alvo 118) and orebodies (Sossego-Curral). This event was possibly associated with heat sources due to the emplacement of A-type granites at the province. This event would have caused ore re (mobilization) and overprint of hydrothermal alteration zones, with the formation of hydrolytic alteration over previously formed scapolite-rich zones. Therefore, the Southern Copper Belt presents an excellent example of recurrence of hydrothermal systems along the geological time, responsible for the genesis of world-class IOCG deposits / Doutorado / Geologia e Recursos Naturais / Doutora em Ciências

Memoria (licenciado en ciencias jurídicas y sociales)

Copper based alloys play important role in high heat flux applications, particularly in rocket technology, the liner of the combustion chamber, and also in other heat transfer vessels. In these applications, one needs excellent high-temperature strength without sacrificing the thermal conductivity significantly. However, it is a challenging and difficult task to significantly improve the balance between strength and conductivities (electrical and thermal) of Cu-based alloys. In general, microstructural attributes, responsible for increasing mechanical strength of the alloy, also affect the transport properties by creating scattering centers. Hence, delicate optimization is needed for developing balanced alloy system for better performance. A substantial amount of research efforts has therefore been focused on devising methodologies to synthesize copper based alloys with a good combination of strength and conductivity. The present thesis deals with the development of a newer class of high strength high conductivity copper base alloy through tuning of phase transformation and careful additions of ternary and quaternary alloying elements and ultimately by microstructural engineering. In this thesis, we report the development of novel high strength high conductivity Cu-based alloy series in the Cu-Fe-Si system through rapid solidification process using suction casting apparatus. We have also optimized the alloys by altering and fine tuning the alloy compositions in order to achieve balanced and optimum properties. The strength of copper can be increased by various strengthening mechanisms. In general, precipitation hardening, dispersion strengthening and solid solution strengthening are the three most effective mechanisms for improving the strength of copper. Among these, solid solution strengthening has the most detrimental effect on the transport properties due to the presence of solute atoms which act as prominent scattering centres. Precipitation hardened copper alloys are often unable to retain strength at high temperatures, due to the coarsening of the precipitates. Currently, efforts are being made to develop newer dispersion strengthened copper alloys. These alloys contain a fine dispersion of nanometer sized oxides or other intermetallic compounds in the copper matrix. Dispersion strengthened copper alloys show impressive mechanical strength as well as thermal stability. In this thesis, we have explored the possibility of obtaining structurally ordered intermetallic dispersions through exploiting immiscibility of solutes in copper based alloys. The immiscibility promotes precipitation and decrease the solid solubility of solute elements in the matrix which in turn minimizes the scattering process and thus offers the possibility of improved transport properties. These ordered and coherent dispersion of intermetallic particles in the continuous copper matrix, dispersed during solidification, are believed to be the main contributor to the improvement of mechanical strength of the alloy. Crystallographically ordered structure and the coherency strain associated with the intermetallic particles in the copper matrix, together contribute to the mechanical strength through the mechanism of order hardening and coherency strengthening. These also, promote a low interfacial energy between precipitates and matrix in the alloy. This low interfacial energy reduces the driving force for coarsening process and thus helps in retaining the mechanical strength at elevated temperatures. Releasing of coherency strain at the precipitate-matrix interface with increasing temperature also yields a dramatic effect on the enhancement of thermal conductivity at high service temperatures. In the current study, we have selected three alloy compositions in the Cu-Fe-Si system at the higher end of copper. These are Cu-20Fe-5Si (at%), Cu-2.5Fe-2.5Si (at%) and Cu-1.0Fe-1.0Si (at%) respectively. We have systematically increased the concentration of copper, and altered the ratio of Fe and Si in order to achieve the better combination of properties (mechanical and transport) through fine tuning the microstructure. The present sets of alloys have been chill cast by the suction casting technique. This rapid solidification process, associated with moderate undercooling, is capable of accessing the submerged metastable miscibility gap of the Cu-Fe binary system. The higher quenching rate moves the system far away from equilibrium and hence, the solidification process occurs at the non-equilibrium regime. Rapid solidification of a copper rich Fe-Cu melt promotes the precipitation of the γFe from copper solid solution due to the immiscibility of Fe and Cu. In this scenario, the addition of a small quantity of silicon as a ternary element leads to its partition to both copper and iron rich phases. However, the larger chemical affinity between Fe and Si, leads to the formation of an ordered structure. However, the FCC crystal field of the copper matrix tends to promote an FCC based novel L12 ordered structure of the Fe3Si intermetallic particles instead of the ordered DO3 structure of Fe3Si composition normally observed in the bulk alloy. This nano meter sized L12 ordered particles maintain a cube-on-cube orientation relationship with the surrounding copper matrix and are associated with large coherency strain. A good lattice matching between these L12 ordered particles and copper matrix will promote a low interfacial energy and thus, a low driving force for particle coarsening. The present thesis is divided into eight chapters. The first chapter introduces the present work and the organization of the thesis. In the second chapter, current status in the development of the copper alloys and the general principle of alloy developments has been described. This includes both experimental and theoretical developments that can be used for developing high strength Cu based alloys. Chapter three, titled as „experimental procedure‟, describes the detailed description of materials and experimental techniques, adopted for the current studies. There are three chapters that deal with the main results of the thesis. Chapter eight, describes the suggestion for future work. The fourth chapter, titled as „Chill cast Cu75Fe20Si5 alloy: Microstructural Evolution and Properties‟, explores the detailed microstructural evolution of the Cu75Fe20Si5 alloy. This chapter also discusses the microstructure-property correlations. The microstructure of the alloy exhibits a multi-scale hierarchical structure during rapid solidification. The solidified microstructure contains Fe-rich globules with DO3 ordered structure, embedded in the continuous Cu-rich matrix. The continuous copper matrix also contains nanometer sized (average diameter 12 nm) coherent particles that exhibit Ashby-Brown strain contrast. Characterization of these phases has been carried out by a combination of X-ray diffraction, electron probe microanalysis and transmission electron microscopy coupled with energy dispersive spectroscopy. This multi-scale complex copper alloy (Cu75Fe20Si5 ) has achieved a remarkable yield and ultimate tensile strength at both room temperature and elevated temperatures in comparison to other copper based alloys. The yield strength and ultimate tensile strength at room temperature are 516±17 MPa and 635±14 MPa respectively whereas yield strength and ultimate tensile strength at 6000C turn out to be 95±11 MPa and 105±12 MPa respectively. In spite of achieving good mechanical strength, this alloy suffers from deterioration of electrical and thermal conductivity due to the presence of high volume fraction of the second phase and alloying elements. The room temperature electrical resistivity of this alloy shows that it is 10 times higher than that of pure copper (alloy resistivity = 1.70E-05 Ohm-cm at 250C and pure Copper- 1.68 × 10-6 Ohm-cm at 200C ). The thermal conductivity of this alloy turns out to be 88 W/m.K at 500C and 161 W/m.K at 6000C respectively which is much smaller in comparison to pure copper ( pure copper ≈ 401 W/m.K at 50 to 6000C). Attempts have been made to overcome the lowering of the transport properties by careful alteration of alloy compositions and fine tuning the microstructure. A new alloy with composition Cu-2.5Fe-2.5Si (at %) has been synthesized in order to achieve better transport properties without significantly sacrificing the mechanical strength. In this new alloy, we have reduced the volume fraction of the second phase (Fe-rich DO3 ordered globules) by lowering the addition of the alloying elements. We have also tried to alter the Fe to Si ratio in such a way that we can retain nanometer sized coherent particles in the matrix that provides strengthening. We arrived at a Fe and Si atom ratio of 1:1. The study of this alloy is presented in chapter five titled as „Chill cast Cu95Fe2.5Si2.5 alloy: Microstructural Evolution and Properties‟. Microstructural characterization indicates that the alloy contains only the nano meter sized coherent L12 ordered particles in the copper matrix. These particles show the Ashby-Brown strain contrast and are rich in iron and silicon. The absence of the high volume fraction of DO3 ordered Fe-rich globular phase and the smaller addition of the alloying elements ensure an improvement in the transport properties. The average resistivity value of this alloy at 250C is 3.5053 × 10-6 (Ohm-cm). This value represents a dramatic improvement in electrical properties in comparison to the Cu75Fe20Si5 alloy (Cu75Fe20Si5 alloy: 1.70E-05 Ohm-cm at 250C). The result is even better when we consider the temperature dependent thermal conductivity of the Cu95Fe2.5Si2.5 alloy. The thermal conductivity of this alloy turns out to be 236 W/m.K at 500C and 313 W/m.K at 6000C respectively. Though the thermal conductivity at room temperature is lower than pure copper, the gap reduces with increasing temperature (pure copper ≈ 401 W/m.K at 50 to 6000C and Cu75Fe20Si5 alloy: 88 W/m.K at 500C and 161 W/m.K at 6000C). This trend of temperature dependent thermal conductivity has made this alloy as one of the potential candidates for high-temperature applications. In situ heating experiment using transmission electron microscope (up to 4500C) and the heat treatment analysis at 6000C confirm that these L12 ordered particles are structurally stable at high temperatures and believed to be the main contributor to high mechanical strength in the alloy through the mechanism of order hardening and coherency strengthening. Coherent nature of the interface between the ordered particles and copper matrix also promotes low interfacial energy in the alloy and thus offers resistance to coarsening at elevated temperatures. Along with the attractive transport properties, this alloy also exhibits its success of retaining mechanical strength at both ambient and high temperatures as compared to the earlier alloy. The room temperature yield strength and ultimate tensile strength of this alloy are recorded as 580±18 MPa and 690±16 MPa respectively whereas the yield strength and ultimate tensile strength at 6000C of this alloy obtained as 128±8 MPa and 150±10 MPa respectively. Thus newly modified alloy exhibits an excellent balance between mechanical strength and conductivity (electrical and thermal) and can be regarded as a promising alloy for high strength high heat flux applications. The possibilities of the Cu95Fe2.5Si2.5 alloy as a potential candidate for high strength high conductivity application has provided the motivation for further optimization of the composition of this class of alloy. Mechanical strength and transport properties of a precipitation strengthened alloy always depends on the structure, shape, volume fractions and the number densities of the precipitate particles. Electrical and thermal conductivity are also sensitive to the presence of third elements and the number densities of the precipitates in the alloy. Thus, optimization of the volume fraction and the number density of the precipitates can yield a better alloy. With this objective, we have further increased the concentration of copper while keeping the Fe and Si atom ratio fixed at 1:1. Chapter six, titled as „Chill cast Cu98Fe1.0Si1.0 alloy: Microstructural Evolution and Properties‟ describes the microstructural evolution and microstructure-property correlation of this new alloy. Characterization analysis (X-ray diffraction, electron probe microanalysis and transmission electron microscopy) confirms that the microstructure of this alloy contains similar kind of nanometer sized L12 ordered particles with lower number density as compared to Cu95Fe2.5Si2.5 alloy (Relative planar number density of the particles: Cu98Fe1.0Si1.0 = 0.13 and Cu95Fe2.5Si2.5 = 0.20). This nano sized coherently ordered particles show the similar Ashby-Brown strain contrast and are rich in iron and silicon similar to the Cu95Fe2.5Si2.5 alloy. This dilute alloy exhibits slight improvement in transport properties in comparison to the earlier Cu95Fe2.5Si2.5 alloy. The electrical resistivity of this alloy at 250C is 3.438E-6 Ohm-cm (Cu95Fe2.5Si2.5 = 3.5053 × 10-6 Ohm-cm at 250C). The thermal conductivity values of this alloy are 243 W/m.K and 338 W/m.K at 500C and 6000C respectively (Cu95Fe2.5Si2.5 = 236 W/m.K at 500C and 313 W/m.K at 6000C). This increase in transport properties is associated with further compositional dilution and the presence of lower number density of the ordered particles in the copper matrix. The mechanism of strengthening is similar to the earlier alloys. The only difference lies in the fact that this present alloy contains lower number density of the L12 ordered particles in the copper matrix. This lower number density is responsible for the loss in mechanical strength of this alloy. The room temperature yield strength and the ultimate tensile strength of this present alloy are 467±16 MPa and 558±12 MPa whereas yield strength and ultimate tensile strength at 6000C are recorded as 102±13 MPa and 110±12 MPa respectively. Though the alloy exhibits some loss in mechanical strength, the values are still attractive in comparison to other commercially available copper based alloys. Both the alloy Cu98Fe1.0Si1.0 and Cu95Fe2.5Si2.5 demonstrate an excellent balance of mechanical strength and transport properties and have the potential to become a high strength and high conductivity materials for high temperature applications. Chapter seven is entitled as „Comparison between the alloy systems‟. In this chapter, we have presented a comparison of our new alloys with other commercially available Cu-base alloys. The thesis ends with a chapter titled as “Suggestions for future work”. We have included a descriptive note for possible future extension of our current work in this chapter.

Cette thèse porte sur la croissance de films minces d’oxydes de zinc/fer (ZnxFe1-xO1+δ par ablation laser pulsée (PLD) et sur la possibilité de contrôler leurs propriétés structurales et physico-chimiques en variant les conditions d’élaboration : pression d’oxygène et température de croissance, proportions respectives de zinc/fer. Pour de fortes valeurs de x (x > 65%), les films sont monophasés de structure wurtzite type ZnO (films Fe:ZnO), avec une transparence optique dans la gamme UV-visible de 80% mais sans propriété ferromagnétique ; en fonction de leur teneur en fer (1-x), ils évoluent de très bons conducteurs électriques à quasi-isolants. Pour de faibles valeurs de x (x < 15%), les films sont également monophasés de structure spinelle type Fe3O4 (films Zn:Fe3O4). Ils présentent de très bonnes propriétés ferromagnétiques dès la température ambiante ainsi qu’une bonne conductivité électrique, les effets de localisation des porteurs de charge se manifestant en dessous de la température de Verwey. Le nombre de parois d’antiphase peut être diminué par une croissance en deux étapes, comme l’atteste les mesures de magnétorésistance. Aux taux intermédiaires de zinc (15% < x < 65%), les films sont nano-composites. Dans le cas d’une coexistence des phases Fe:ZnO et Zn:Fe3O4, la bonne conductivité de Zn:Fe3O4 jointe à la multiplicité des variantes épitaxiales et donc des interfaces fournit un matériau adapté à la thermoélectricité. Dans le cas d’une coexistence de la phase ferrromagnétique Zn:Fe3O4 avec la phase Zn:FeO antiferromagnétique de type sel gemme, un fort couplage d’échange ainsi qu’une anisotropie magnétique perpendiculaire élevée sont mis en évidence. / This thesis deals with the growth of thin films of zinc/iron oxides (ZnxFe1-xO1+δ) by pulsed laser deposition (PLD) and the possibility of controlling their structural and physicochemical properties by varying the elaboration conditions: oxygen pressure and growth temperature, respective proportions of zinc/iron. For high values of x (x> 65%), the films are single-phase with a ZnO-type wurtzite structure (Fe:ZnO films), with 80% optical transparency in the UV-visible range but without ferromagnetic properties; depending on their iron (1-x) content, they evolve from very good electrical conductors to near-insulators. For small values of x (x <15%), the films are also single-phase with a Fe3O4-type spinel structure (Zn:Fe3O4 films). They exhibit very good ferromagnetic properties at ambient temperature as well as good electrical conductivity, the localization effects of charge carriers occurring below the Verwey temperature. The number of antiphase walls can be decreased by a two-step growth, as evidenced by magnetoresistance measurements. At intermediate zinc rates (15% <x <65%), the films are nano-composites. In the case of a coexistence of the Fe:ZnO and Zn:Fe3O4 phases, the good conductivity of Zn:Fe3O4 combined with the multiplicity of epitaxial variants and thus of the interfaces provides a material suitable for thermoelectricity. In the case of a coexistence of the ferrromagnetic Zn:Fe3O4 phase with the Zn:FeO antiferromagnetic rocksalt phase, strong exchange coupling as well as high perpendicular magnetic anisotropy are demonstrated.

The course of polymer film functioning has been a crucial concern in the advent of packaging technology. The thesis project aims towards obtaining an understanding of mechanical properties for a class of these materials, namely LDPE and PET. A constitutive understanding of this behavior in the case of LDPE is acquired through incorporating a plastic stress strain relationship in an iterative approach with focus put on the sensitivity of a few parameters by following a simple linear curve-fit technique in a way that the global as well as the local response are predictable. FE-models also developed in this way are validated with experimental data. An inverse analysis testing validity or usefulness of DIC technique in identifying a material model is done and some discussions are drawn towards this area. A relative numerical study with respect to experimentally obtained global response for tearing of these polymers is done through use of a similar material model developed from tensile tests and the challenges faced in this area have been addressed.