Os minerais do grupo do pirocloro (A2B2X6Y1) apresentam grande interesse econômico, principalmente como fonte de nióbio e tântalo, metais que possuem importantes aplicações tecnológicas como a fabricação de aço e a confecção de componentes eletrônicos. Apesar de seu interesse científico e econômico, a maioria das ocorrências brasileiras de minerais do grupo do pirocloro está apenas parcialmente caracterizada ou não dispõe de nenhum estudo mineralógico. Adicionalmente, o atual sistema de classificação dos minerais do grupo do pirocloro, apesar de aprovado pela IMA, não segue as regras gerais de nomenclatura de minerais da própria IMA. Na posição A, não há diferenciação na ocupação por Ca e por Na, e se um ou mais cátions diferentes de Na ou Ca compuserem mais de 20 % total de átomos na posição A, então a espécie é nomeada pelo átomo mais abundante em A (exceto Na e Ca). Por outro lado, a espécie fluornatromicrolita foi aprovada com base na predominância de Na na posição A. Com relação à ocupação da posição B, a divisão entre os grupos não é feita com uma classificação tripartite: as espécies com Nb + Ta >2Ti e Nb > Ta são consideradas como do subgrupo do pirocloro; se Nb + Ta > 2Ti e Ta ≥ Nb, o mineral irá pertencer ao subgrupo da microlita; e se 2Ti ≥ Nb + Ta, o mineral irá pertencer ao subgrupo da betafita. Espécies isoestruturais com outros cátions predominantes na posição B não são incluídas no grupo do pirocloro (por exemplo, romeíta com Sb dominante). Os ânions não são levados em consideração na classificação, mas o flúor foi usado na aprovação da espécie fluornatromicrolita. Neste trabalho, são apresentados novos esquemas de nomenclatura para os minerais do grupo do pirocloro, que levam em consideração os íons ocupantes das posições A, B e Y. Os prefixos são sempre escritos por extenso (\'hidroxi\', \'fluor\', \'calcio\', \'natro\' etc), enquanto os sufixos são representados por símbolos químicos (Na, F, H2O etc) ou por [] (vazio). Os nomes raízes relacionam-se aos cátions predominantes na posição B, levando a termos como pirocloro, microlita, betafita e romeíta. São apresentados novos dados químicos por MEV-EDS e WDS (incluindo análises de Si, normalmente negligenciado na maioria dos dados da literatura). Foram analisados minerais de seis ocorrências em pegmatitos e uma em carbonatito. Os resultados obtidos permitem separar as espécies em três \'famílias\'. A primeira delas poderia ser denominada \'microlita\', envolvendo fluornatromicrolita, fluorcalciomicrolita, oxinatromicrolita e oxicalciomicrolita. Esta família foi identificada nas ocorrências da lavra do Morro Redondo, Coronel Murta, MG; lavra do Jonas, Conselheiro Pena, MG; mina Quixabá, Frei Martinho, PB; Pegmatito Volta Grande, Nazareno, MG; lavra do Ipê, Marilac, MG; e Pegmatito Ponte da Raiz, Santa Maria de Itabira, MG. A primeira das espécies, fluornatromicrolita, parece ser bem mais comum do que se imaginava, tendo sido descrita previamente no Brasil apenas em Quixabá, e agora verificada em diversas das ocorrências estudadas nesta tese. Apesar de usados os prefixos natro e cálcio, todas as amostras parecem tender para um termo de fórmula final (NaCa)Ta2O6F, ou seja, com Na=Ca em apfu, que poderia ser denominado, por exemplo, fluormicrolita-NaCa ou CaNa. O oxigênio é, algumas vezes, superior ao flúor (em apfu) na cavidade Y, dando origem a espécie oxi-. A segunda família poderia ser denominada \'hidromicrolita\', tendendo a [ [](H2O)]Ta2O6(H2O). Esta fórmula, entretanto, não é eletricamente neutra, necessitando que na cavidade A, (H2O) seja parcialmente substituído por cátions (Ba, U etc), ao mesmo tempo que parte do O da posição X seja substituído por (OH). Minerais desta família foram verificados no Pegmatito Volta Grande, Nazareno, MG. A terceira família, do \'pirocloro\', verificada apenas no carbonatito da mina Jacupiranga, Cajati, SP, inclui as espécies fluorcalciopirocloro e oxicalciopirocloro. Os novos nomes sugeridos parecem discriminar melhor as espécies, com base em cátions, vazios ou H2O predominantes nas posições A, B eY, permitindo inclusive uni-las em \'famílias\'. Esta nova nomenclatura apresenta também como vantagem não dar ênfase a componentes menores da cavidade A, bem como verificar nela a predominância de Ca ou Na. Adicionalmente, os cátions Ta, Nb e Ti passam a ter a mesma importância na cavidade B. Por outro lado são criados nomes \'exóticos\', como hidrohidromicrolita, ou \'impronunciáveis\', como hidro-[]-microlita. / Pyrochlore group minerals are important sources of niobium and tantalum and these metals are used in important technological applications such as steel manufacturing and eletronic components development. However, the majority of Brazilian occurrences are only partially characterized or there is no mineralogic study available. In addition, the official pyrochlore-group minerals classification system does not follow the IMA mineralogical nomenclature rules although this system is approved by IMA. In the A site, it does not differentiate between occupation by Ca and Na, and if there is one or more cation other than Na or Ca composing more than 20% of total A-atoms, then the species must be named according to the most abundant A-atom, other than Na or Ca. In spite of this, the species fluornatromicrolite was approved based on the predominance of Na in the A-site. Regarding the B-site occupation, the division among the subgroups is not made with a tripartite symmetrical classification: the species with Nb + Ta >2Ti and Nb > Ta are considered as pyrochlore subgroup minerals; if Nb + Ta > 2Ti and Ta ≥ Nb, the mineral will belong to the microlite subgroup; and if 2Ti ≥ Nb + Ta, the mineral will belong to the betafite subgroup. Isostructural species with other predominant cations in the B-site are not included in the pyrochlore-group (for example, romeite, with dominant Sb). The anions are not taken into account in the classification but the predominance of fluorine was used for the approval of the species fluornatromicrolite. In this present work new nomenclature schemes, based on the ions in A, B and Y sites, are presented. Prefixes are, for example, \'hidroxi\', \'fluor\', \'calcio\', \'natro\' etc., while sufixes are represented by chemical symbols (Na, F, H2O etc) or [] (vacancies). The root names (pyrochlore, microlite, betafite, romeite) are related to the dominant-constituent cations in the B position. New chemical data by MEV-EDS and WDS (including Si analysis, hardly ever mentioned in litetarature) were obtained. Six occurrences from pegmatites and one from carbonatite were analysed. The results allow the species to be grouped in three \'families\'. The first could be named as \'microlite\', and includies fluornatromicrolite, fluorcalciomicrolite, oxinatromicrolite and oxicalciomicrolite. This family was identified in Morro Redondo quarry, Coronel Murta, MG; Jonas quarry, Conselheiro Pena, MG; Quixabá mine, Frei Martinho, PB; Volta Grande pegmatite, Nazareno, MG; Ipê quarry, Marilac, MG and Ponte da Raiz pegmatite, Santa Maria de Itabira, MG. Fluornatromicrolite seems to be more common than was previously thought. It was previously described only in Quixabá but now many other occurrences are known. Although \'natro\' and \'calcio\' prefixes were used, all the formulae seem to approach the term (NaCa)Ta2O6F. As Na approximately equals Ca (apfu) it could be used the name fluornatromicrolite-Na-Ca or CaNa could be used. The oxigen content is sometimes greater than F content in the Y position. This generates the oxi- species. The second family could be named \'hidromicrolite\', becoming [ [] (H2O)]Ta2O6(H2O). This formulae is not eletrically neutral so the H2O is replaced by cations (Ba, U etc) in the A cavity while the O is replaced by (OH) in the X position. Minerals from this family were identified in the Volta Grande pegmatite, Nazareno, MG. The third family, \'pyrochlore\', was only verified in the Jacupiranga mine, Cajati, SP, including fluorcalciopyrochlore and oxicalciopyrochlore species. The suggested new names, based on cations, vacancies or H2O dominant constituents of A, B and Y sites, seem to better describe the species, allowing their grouping in families. This new nomenclature has the advantage of not emphasize minor constituents in the A cavity, and verify the dominance of Ca or Na. Furthermore, Ta, Nb and Ti cations have the same balance in B cavity. On the other hand, exotic names were created such as hydrohydromicrolite or unpronounceable as hydro-[]-microlite.

Made available in DSpace on 2014-12-17T15:01:54Z (GMT). No. of bitstreams: 1 FranciscoWBL_TESE.pdf: 1361043 bytes, checksum: 47b3dc32f3c2abd6fdeb92f28f440080 (MD5) Previous issue date: 2011-12-16 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Rare earth elements have recently been involved in a range of advanced technologies like microelectronics, membranes for catalytic conversion and applications in gas sensors. In the family of rare earth elements like cerium can play a key role in such industrial applications. However, the high cost of these materials and the control and efficiencies associated processes required for its use in advanced technologies, are a permanent obstacle to its industrial development. In present study was proposed the creation of phases based on rare earth elements that can be used because of its thermal behavior, ionic conduction and catalytic properties. This way were studied two types of structure (ABO3 and A2B2O7), the basis of rare earths, observing their transport properties of ionic and electronic, as well as their catalytic applications in the treatment of methane. For the process of obtaining the first structure, a new synthesis method based on the use of EDTA citrate mixture was used to develop a precursor, which undergone heat treatment at 950 ? C resulted in the development of submicron phase BaCeO3 powders. The catalytic activity of perovskite begins at 450 ? C to achieve complete conversion at 675 ? C, where at this temperature, the catalytic efficiency of the phase is maximum. The evolution of conductivity with temperature for the perovskite phase revealed a series of electrical changes strongly correlated with structural transitions known in the literature. Finally, we can establish a real correlation between the high catalytic activity observed around the temperature of 650 ? C and increasing the oxygen ionic conductivity. For the second structure, showed clearly that it is possible, through chemical processes optimized to separate the rare earth elements and synthesize a pyrochlore phase TR2Ce2O7 particular formula. This "extracted phase" can be obtained directly at low cost, based on complex systems made of natural minerals and tailings, such as monazite. Moreover, this method is applied to matters of "no cost", which is the case of waste, making a preparation method of phases useful for high technology applications / Elementos terras raras t?m sido recentemente envolvido em uma ampla gama de tecnologias avan?adas, como a microeletr?nica, membranas para a convers?o catal?tica e aplica??es em sensores de g?s. Na fam?lia de terras raras, elementos como o c?rio pode desempenhar um papel chave em tais aplica??es industriais. No entanto, o alto custo desses materiais e do controle e efici?ncias dos processos associados necess?rios para sua utiliza??o em tecnologias avan?adas, s?o um obst?culo permanente ao seu desenvolvimento industrial. No presente trabalho, foi proposto a obten??o de duas fases baseadas em elementos de terras raras que podem ser utilizados devido o seu comportamento t?rmico, condu??o i?nica e propriedades catal?ticas. Desta maneira, foram estudados dois tipos de estrutura (ABO3 e A2B2O7), a base de terras raras, observando suas propriedades de transporte i?nico e eletr?nico, bem como suas aplica??es catal?ticas no tratamento do metano. Durante o processo de obten??o da primeira estrutura, um novo m?todo de s?ntese baseado no uso da mistura EDTA citrato foi usado para desenvolver um precursor, que submetidos a tratamento t?rmico a 950?C, resultou no desenvolvimento de p?s submicrom?tricos da fase BaCeO3. A atividade catal?tica desta perovskita come?a a 450?C para alcan?ar a convers?o completa em 675?C, onde nesta temperatura, a efici?ncia catal?tica da fase ? m?xima. A evolu??o da condutividade em fun??o da temperatura para a fase perovskita revelou uma s?rie de mudan?as el?tricas fortemente correlacionada com transi??es estruturais conhecida na literatura. Finalmente, pode-se estabelecer uma correla??o real entre a alta atividade catal?tica observada em torno da temperatura de 650?C e o aumento da condutividade i?nica de oxig?nio. Para a segunda estrutura, mostrou-se claramente que ? poss?vel, atrav?s de processos qu?micos otimizados, separar os elementos terras raras e sintetizar uma fase pirocloro espec?fica de f?rmula TR2Ce2O7. Esta fase extra?da" pode ser obtida diretamente, de baixo custo, baseado em sistemas complexos feitos de minerais naturais e res?duos, como a monazita. Al?m disso, este m?todo ? aplicado a mat?rias de "custo zero", que ? o caso dos res?duos, tornando um m?todo de prepara??o de fases ?til para aplica??es de alta tecnologia

Os minerais do grupo do pirocloro (A2B2X6Y1) apresentam grande interesse econômico, principalmente como fonte de nióbio e tântalo, metais que possuem importantes aplicações tecnológicas como a fabricação de aço e a confecção de componentes eletrônicos. Apesar de seu interesse científico e econômico, a maioria das ocorrências brasileiras de minerais do grupo do pirocloro está apenas parcialmente caracterizada ou não dispõe de nenhum estudo mineralógico. Adicionalmente, o atual sistema de classificação dos minerais do grupo do pirocloro, apesar de aprovado pela IMA, não segue as regras gerais de nomenclatura de minerais da própria IMA. Na posição A, não há diferenciação na ocupação por Ca e por Na, e se um ou mais cátions diferentes de Na ou Ca compuserem mais de 20 % total de átomos na posição A, então a espécie é nomeada pelo átomo mais abundante em A (exceto Na e Ca). Por outro lado, a espécie fluornatromicrolita foi aprovada com base na predominância de Na na posição A. Com relação à ocupação da posição B, a divisão entre os grupos não é feita com uma classificação tripartite: as espécies com Nb + Ta >2Ti e Nb > Ta são consideradas como do subgrupo do pirocloro; se Nb + Ta > 2Ti e Ta ≥ Nb, o mineral irá pertencer ao subgrupo da microlita; e se 2Ti ≥ Nb + Ta, o mineral irá pertencer ao subgrupo da betafita. Espécies isoestruturais com outros cátions predominantes na posição B não são incluídas no grupo do pirocloro (por exemplo, romeíta com Sb dominante). Os ânions não são levados em consideração na classificação, mas o flúor foi usado na aprovação da espécie fluornatromicrolita. Neste trabalho, são apresentados novos esquemas de nomenclatura para os minerais do grupo do pirocloro, que levam em consideração os íons ocupantes das posições A, B e Y. Os prefixos são sempre escritos por extenso (\'hidroxi\', \'fluor\', \'calcio\', \'natro\' etc), enquanto os sufixos são representados por símbolos químicos (Na, F, H2O etc) ou por [] (vazio). Os nomes raízes relacionam-se aos cátions predominantes na posição B, levando a termos como pirocloro, microlita, betafita e romeíta. São apresentados novos dados químicos por MEV-EDS e WDS (incluindo análises de Si, normalmente negligenciado na maioria dos dados da literatura). Foram analisados minerais de seis ocorrências em pegmatitos e uma em carbonatito. Os resultados obtidos permitem separar as espécies em três \'famílias\'. A primeira delas poderia ser denominada \'microlita\', envolvendo fluornatromicrolita, fluorcalciomicrolita, oxinatromicrolita e oxicalciomicrolita. Esta família foi identificada nas ocorrências da lavra do Morro Redondo, Coronel Murta, MG; lavra do Jonas, Conselheiro Pena, MG; mina Quixabá, Frei Martinho, PB; Pegmatito Volta Grande, Nazareno, MG; lavra do Ipê, Marilac, MG; e Pegmatito Ponte da Raiz, Santa Maria de Itabira, MG. A primeira das espécies, fluornatromicrolita, parece ser bem mais comum do que se imaginava, tendo sido descrita previamente no Brasil apenas em Quixabá, e agora verificada em diversas das ocorrências estudadas nesta tese. Apesar de usados os prefixos natro e cálcio, todas as amostras parecem tender para um termo de fórmula final (NaCa)Ta2O6F, ou seja, com Na=Ca em apfu, que poderia ser denominado, por exemplo, fluormicrolita-NaCa ou CaNa. O oxigênio é, algumas vezes, superior ao flúor (em apfu) na cavidade Y, dando origem a espécie oxi-. A segunda família poderia ser denominada \'hidromicrolita\', tendendo a [ [](H2O)]Ta2O6(H2O). Esta fórmula, entretanto, não é eletricamente neutra, necessitando que na cavidade A, (H2O) seja parcialmente substituído por cátions (Ba, U etc), ao mesmo tempo que parte do O da posição X seja substituído por (OH). Minerais desta família foram verificados no Pegmatito Volta Grande, Nazareno, MG. A terceira família, do \'pirocloro\', verificada apenas no carbonatito da mina Jacupiranga, Cajati, SP, inclui as espécies fluorcalciopirocloro e oxicalciopirocloro. Os novos nomes sugeridos parecem discriminar melhor as espécies, com base em cátions, vazios ou H2O predominantes nas posições A, B eY, permitindo inclusive uni-las em \'famílias\'. Esta nova nomenclatura apresenta também como vantagem não dar ênfase a componentes menores da cavidade A, bem como verificar nela a predominância de Ca ou Na. Adicionalmente, os cátions Ta, Nb e Ti passam a ter a mesma importância na cavidade B. Por outro lado são criados nomes \'exóticos\', como hidrohidromicrolita, ou \'impronunciáveis\', como hidro-[]-microlita. / Pyrochlore group minerals are important sources of niobium and tantalum and these metals are used in important technological applications such as steel manufacturing and eletronic components development. However, the majority of Brazilian occurrences are only partially characterized or there is no mineralogic study available. In addition, the official pyrochlore-group minerals classification system does not follow the IMA mineralogical nomenclature rules although this system is approved by IMA. In the A site, it does not differentiate between occupation by Ca and Na, and if there is one or more cation other than Na or Ca composing more than 20% of total A-atoms, then the species must be named according to the most abundant A-atom, other than Na or Ca. In spite of this, the species fluornatromicrolite was approved based on the predominance of Na in the A-site. Regarding the B-site occupation, the division among the subgroups is not made with a tripartite symmetrical classification: the species with Nb + Ta >2Ti and Nb > Ta are considered as pyrochlore subgroup minerals; if Nb + Ta > 2Ti and Ta ≥ Nb, the mineral will belong to the microlite subgroup; and if 2Ti ≥ Nb + Ta, the mineral will belong to the betafite subgroup. Isostructural species with other predominant cations in the B-site are not included in the pyrochlore-group (for example, romeite, with dominant Sb). The anions are not taken into account in the classification but the predominance of fluorine was used for the approval of the species fluornatromicrolite. In this present work new nomenclature schemes, based on the ions in A, B and Y sites, are presented. Prefixes are, for example, \'hidroxi\', \'fluor\', \'calcio\', \'natro\' etc., while sufixes are represented by chemical symbols (Na, F, H2O etc) or [] (vacancies). The root names (pyrochlore, microlite, betafite, romeite) are related to the dominant-constituent cations in the B position. New chemical data by MEV-EDS and WDS (including Si analysis, hardly ever mentioned in litetarature) were obtained. Six occurrences from pegmatites and one from carbonatite were analysed. The results allow the species to be grouped in three \'families\'. The first could be named as \'microlite\', and includies fluornatromicrolite, fluorcalciomicrolite, oxinatromicrolite and oxicalciomicrolite. This family was identified in Morro Redondo quarry, Coronel Murta, MG; Jonas quarry, Conselheiro Pena, MG; Quixabá mine, Frei Martinho, PB; Volta Grande pegmatite, Nazareno, MG; Ipê quarry, Marilac, MG and Ponte da Raiz pegmatite, Santa Maria de Itabira, MG. Fluornatromicrolite seems to be more common than was previously thought. It was previously described only in Quixabá but now many other occurrences are known. Although \'natro\' and \'calcio\' prefixes were used, all the formulae seem to approach the term (NaCa)Ta2O6F. As Na approximately equals Ca (apfu) it could be used the name fluornatromicrolite-Na-Ca or CaNa could be used. The oxigen content is sometimes greater than F content in the Y position. This generates the oxi- species. The second family could be named \'hidromicrolite\', becoming [ [] (H2O)]Ta2O6(H2O). This formulae is not eletrically neutral so the H2O is replaced by cations (Ba, U etc) in the A cavity while the O is replaced by (OH) in the X position. Minerals from this family were identified in the Volta Grande pegmatite, Nazareno, MG. The third family, \'pyrochlore\', was only verified in the Jacupiranga mine, Cajati, SP, including fluorcalciopyrochlore and oxicalciopyrochlore species. The suggested new names, based on cations, vacancies or H2O dominant constituents of A, B and Y sites, seem to better describe the species, allowing their grouping in families. This new nomenclature has the advantage of not emphasize minor constituents in the A cavity, and verify the dominance of Ca or Na. Furthermore, Ta, Nb and Ti cations have the same balance in B cavity. On the other hand, exotic names were created such as hydrohydromicrolite or unpronounceable as hydro-[]-microlite.

Made available in DSpace on 2016-08-18T18:19:31Z (GMT). No. of bitstreams: 1 Dissertacao Rosivaldo.pdf: 5677549 bytes, checksum: c7bd4948b673714e051ecd08adc24eeb (MD5) Previous issue date: 2012-03-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work we investigated the vibrational, structural and dielectric properties of pyrochlore Bi2Sn2O7 (BSO) by Raman spectroscopy, differential scanning calorimetry (DSC) and infrared specular reflectance. The Raman spectrum of BSO was obtained as a function of temperature in the range from 23°C to 427°C. It was observed 18 broad Raman bands at room temperature (α phase) which have been classified according to the literature. The investigation of the evolution of the position, width, integrated area and intensity on the Raman modes depending on the temperature allowed estimating the temperature of the structural transition BSO α ( ) → β ( ) by approximately 127°C. The thermogram obtained by DSC under heating rates of 10K/min and 20K/min showed a peak with onset enthalpy at 98°C. Such peak was associated with the loss of structural domains discussed in the literature. Furthermore, theoretical calculations indicate that the observed peak is related to a displacive phase transition. The infrared reflectance spectrum was obtained at room temperature in the range 60 4000 cm-1, whose setting allowed us to identify the frequencies of transverse and longitudinal optical phonons which were also classified based on the literature. It was estimated the static dielectric constant, the dielectric losses tanδј and quality factor Q for the BSO in the microwave region. The dispersion parameters numerically obtained by Kramers - Kronig show to be in agreement with results obtained from the reflectance fitting. / Neste trabalho investigamos as propriedades vibracionais, estruturais e dielétricas do pirocloro Bi₂O₂Sn₇ (BSO) através das técnicas de espectroscopia Raman, calorimetria diferencial por varredura (DSC) e reflectância especular no infravermelho. O espectro Raman do BSO foi obtido em função da temperatura na faixa de 23°C até 427 °C. Foram observados 18 modos largos Raman à temperatura ambiente (fase α) que foram classificados com base na literatura. A investigação da evolução da posição, largura, área integrada e intensidade relativa dos modos Raman em função da temperatura permitiu estimar a temperatura de transição estrutural do BSO α ( ) → β ( ) em aproximadamente 127°C. Os termogramas obtidos por DSC sob taxas de aquecimento de 10 K/min e 20 k/min exibiram um pico entálpico com onset em 98°C. Tal pico foi associado ao desaparecimento de domínios estruturais discutidos na literatura. Além disso, cálculos teóricos indicam que o pico observado está relacionado a uma transição de fase displaciva. O espectro de reflectância no infravermelho foi obtido à temperatura ambiente na faixa de 60 a 4000 cm⁻¹, cujo ajuste nos permitiu identificar as frequências transversais e longitudinais ópticas dos fônons que também foram classificados com base na literatura. Foram estimadas a constante dielétrica estática, as perdas dielétricas tanδј e o fator de qualidade Q para o BSO na região de microondas. Os parâmetros de dispersão dielétrica obtidos numericamente via relação de Kramers Kronig mostraram estar em acordo com resultados obtidos a partir do ajuste da curva de reflectância.

No description available.

En raison de la résistance élevée à l’irradiation de certaines compositions, les oxydes de structure pyrochlore A₂B₂O ₇ sont considérés comme des matrices potentielles d’immobilisation des actinides produits en réacteur nucléaire. Dans ce contexte, l’étude de la stabilité structurale sous irradiation de ces oxydes est particulièrement importante. Ce travail concerne donc l’étude de l’influence de la composition des pyrochlores et de leur microstructure sur leur comportement vis-à-vis de l’irradiation.Dans ce but, quatre compositions d’oxydes pyrochlores de formule générale A₂B₂O ₇ avec A = Gd, Nd et B = Zr, Ti ont tout d’abord été élaborées. Différentes voies de synthèse (réaction à l’état solide, chimie douce par la méthode Pechini) de poudres pyrochlores ont été explorées afin de maîtriser in fine la taille de grains des céramiques densifiées par frittage classique ou par frittage SPS. Les résultats obtenus par chimie douce sont prometteurs : des poudres fines (<100 nm) de structure pyrochlore ont été élaborées. Enfin, selon les conditions de frittage SPS choisies, des céramiques denses ont été obtenues, avec une taille de grains de 700 nm pour Y₂Ti₂O ₇ et de 300 nm pour Nd₂Zr₂O ₇ , ce qui, à notre connaissance, correspond aux plus petites tailles de grains pour ce type de composé.Afin d’étudier le comportement sous irradiation, les oxydes élaborés de compositions Gd₂Ti₂O ₇ , Y₂Ti₂O ₇ , Gd₂Zr₂O ₇ et Nd₂Zr₂O ₇ , ont été irradiés avec des ions lourds de basse énergie (Au 4MeV délivrés par l’installation JANNuS à Orsay) pour déterminer les modifications structurales produites par les effets nucléaires et par des ions lourds d’une centaine de MeV (ligne IRRSUD) ou de l’ordre du GeV (ligne SME) du GANIL à Caen afin d’étudier les effets induits par les excitations électroniques. Les transformations induites par irradiation ont été caractérisées par Diffraction des Rayons X (parfois in situ avec le dispositif ALIX du GANIL), Microscopie Electronique à Balayage et en Transmission (MEB, MET) et spectroscopie Raman. La spectroscopie d'absorption (XANES et EXAFS effectuées au synchrotron SOLEIL) a été utilisée pour caractériser l'ordre local dans la phase amorphe induite par irradiation dans les titanates. Dans le domaine du ralentissement nucléaire, les résultats principaux sont que les titanates s’amorphisent sous irradiation alors que seule une transition pyrochlore-fluorine est observée pour les zirconates. Dans le domaine du ralentissement électronique, les titanates s’amorphisent par un mécanisme d’impact direct et Gd₂Zr₂O ₇ subit uniquement une transition pyrochlore-fluorine. Par contre, contrairement à son comportement observé sous irradiation avec des ions de basse énergie, Nd₂Zr₂O ₇ s’amorphise avec des ions lourds de haute énergie, avec une cinétique d’endommagement complexe qui met en jeu des transitions pyrochlore-amorphe, pyrochlore-fluorine et fluorine-amorphe. La structure interne des traces induites par excitations électroniques a été étudiée par MET. Les analyses par spectroscopie Raman en coupe transverse des échantillons irradiés ont permis la détermination de l’épaisseur de la phase amorphe ainsi que du pouvoir d’arrêt électronique seuil pour la formation des traces. Les conductivités thermiques des échantillons irradiés sont plus faibles que celles obtenues dans les composés non irradiés. Enfin, l’étude de la restauration thermique des composés irradiés avec des ions lourds de haute énergie montre que les transformations de phases ainsi que les températures auxquelles se produisent ces transformations dépendent de la composition. / Due to the high resistance to irradiation of some compositions, pyrochlore-type oxides with A₂B₂O ₇ structure are considered as potential matrices for the immobilization of actinides produced in nuclear reactor. In this context, the study of the structural stability after irradiation of these oxides is particularly important and should be investigated. This work aims at studying the effects of both the composition and the microstructure on the behavior of pyrochlores upon irradiation. For this purpose, four compositions of pyrochlore oxides of general formula A₂B₂O ₇ (with A = Gd, Nd and B = Ti, Zr) were first elaborated. Powders were prepared using different routes (solid state reaction, soft chemistry with Pechini process) in order to control the grain size of the ceramics densified either by conventional sintering or by SPS. The results obtained by soft chemistry are promising: fine powders (<100 nm) with the pyrochlore structure were prepared. Finally, according to the selected SPS conditions, dense ceramics were obtained with a grain size of 700 nm for Y₂Ti₂O ₇ and 300 nm for Nd₂Zr₂O ₇ , which, to our knowledge, corresponds to the smaller grain size for these compositions. Pyrochlore oxides with the compositions Gd₂Ti₂O ₇ , Y₂Ti₂O ₇ , Gd₂Zr₂O ₇ and Nd₂Zr₂O ₇ were irradiated with low energy heavy ions (4 MeV Au ions delivered by the JANNuS platform in Orsay) to determine the structural modifications produced by nuclear collisions. The same ceramics were also irradiated with swift heavy ions (hundreds of MeV on the IRRSUD beamline or of the order of GeV on the SME beamline) at the GANIL accelerator in Caen to study the effects induced by electronic excitations. The transformations induced by irradiation were characterized by XRD (in situ with the ALIX set up of the GANIL or ex situ after irradiation), scanning and transmission electron microscopy (SEM, TEM) and Raman spectroscopy. Fine absorption spectroscopy (XANES and EXAFS performed at the synchrotron Soleil) was implemented in order to characterize the local order in the amorphous phase induced by irradiation in the titanates. In the ballistic process regime, the main results are the amorphization of the titanates, while only an anion-deficient fluorite phase is formed for zirconates. The phase transformations induced by electronic excitation show that titanates become amorphous by a direct impact mechanism whereas a pyrochlore-fluorite transition occurs for Gd₂Zr₂O ₇ . However, in contrast to the behavior observed upon irradiation with low energy ions, Nd₂Zr₂O ₇ becomes amorphous upon high energy ion irradiations, with a complex damage kinetics involving pyrochlore-amorphous, pyrochlore-fluorite and fluorite-amorphous phase transitions. The internal structure of tracks induced by electronic excitation was studied by TEM. Raman spectroscopy analyses performed on cross-sectioned irradiated samples allowed the determination of the amorphous phase thickness and the electronic stopping power threshold for the formation of tracks.The thermal conductivities of the irradiated samples are lower than those obtained for unirradiated compounds. Finally, a specific study concerning the thermal recovery of irradiated pyrochlores with swift heavy ions shows that the phase transitions and the temperature at which these transformations occur depend on the composition.

In the search for novel magnetic materials, systems with strong spin-orbit coupling are a focus. 5d Ir-oxides and 4d Ru-halide, in particular, are associated in this context with a flurry of new theoretical concepts, models, and predictions, and more recently to various exotic topological states. In this thesis, we use computational quantum-chemistry methods to determine nearest-neighbor (NN) magnetic interactions in such systems. We also explore different routes to tune NN exchange couplings and provide guidelines for material design. In the first chapter, an introduction to concepts of electron correlations, spin-orbit coupling and magnetic interactions is provided. Many-body quantum chemistry methods used to determine electronic and magnetic properties of the transition metal systems in this work are outlined in the second chapter. In chapter 3, we determine multiplet-structure, magnetic g factors as well as NN magnetic interaction for the edge-shared 4d5 honeycomb lattice-based system, i.e., α-RuCl3. We find that the the magnetic anisotropy shows up in the form of bond-dependent Kitaev couplings, which defines the largest superexchange energy scale in this system. Magnetic couplings obtained by mapping the ab initio data onto an effective spin Hamiltonian are then used in the the subsequent exact diagonalization calculation to retrieve the magnetic phase diagram as a function of second and third NN coupling. Further, in chapter 4, we investigate the effects of uniform pressure and strain on the magnetic interactions in honeycomb and related lattice-based systems. We find that the Heisenberg and Kitaev terms are affected differently: for strain, in particular, the Heisenberg component decreases more rapidly than the Kitaev counterpart. This suggests a scenario where strain can stabilize a spin liquid state in such materials. In chapter 5, we discuss another factor that allows to modify magnetic couplings, i.e., the electrostatics between layered stackings with different metallic species. We examine magnetic interactions between Ir moments in H3LiIr2O6, a recently proposed Kitaev spin liquid candidate, and clarify the effect of interlayer electrostatics on the anisotropic Kitaev exchange . We show that the precise position of H+ cations between magnetically active [LiIr2O6]3− honeycomb-like layers has a strong impact on the magnitude of Kitaev interactions. In the last chapter, we examine Ir-oxides on the pyrochlore lattice. In these corner-sharing systems the NN anisotropic exchange occurs in the form of antisymmetric exchange, also known as Dzyaloshinskii-Moriya (DM) coupling. Our calculations predict that a highly unusual regime can be realized in such systems due to the vanishing NN Heisenberg interaction, making the antisymmetric DM exchange to be the dominant interaction in the oxides where the Ir-O-Ir links show bond-angles less than 125◦. We also confirm the accuracy of the employed quantum-chemistry methods by reproducing experimental data for Sm2Ir2O7.:Table of contents 1 Introduction 1 1.1 Electronic correlations 2 1.2 Crystal fields and d-level splitting 5 1.3 Spin-orbit Coupling 8 1.4 Magnetic interactions 10 1.5 Conclusions 13 2 Quantum Chemistry Methods 15 2.1 Introduction 15 2.2 Motivation for using quantum chemical approach 17 2.3 The Hartree-Fock approach 19 2.4 Multiconfigurational approach 22 2.5 Multireference configuration interaction 26 2.5.1 Recent developments towards performing FCI 27 2.6 Embedded cluster approach 28 2.7 Conclusions 30 3 Anisotropic spin interactions in α-RuCl3 31 3.1 Introduction 31 3.2 Spin-orbit ground state and excitations 33 3.2.1 Structural details .34 3.2.2 Computational details 37 3.2.3 Results and Discussions 40 3.3 Intersite exchange interactions for j=1/2 moments 44 3.3.1 Kitaev-Heisenberg model and symmetric anisotropies 45 3.3.2 Computational details 49 3.3.3 Results and Discussion 53 3.4 Conclusions 61 x Table of contents 4 Strain and pressure tuned magnetic interactions in Kitaev materials 63 4.1 Introduction 64 4.2 Qualitative analysis: Kitaev-Heisenberg model 65 4.3 Quantitative analysis: ab initio results 66 4.3.1 Computational approach 69 4.3.2 Results and discussion 70 4.4 Experimental results for pressurized α-RuCl3 74 4.4.1 Pressure induced dimerization 75 4.4.2 Ab initio calculations 76 4.5 Conclusions 78 5 Impact of inter-layer species on in-plane magnetism in H3LiIr2O6 79 5.1 Introduction 79 5.2 Structural details 81 5.3 Computational approach 82 5.4 Results and discussion 85 5.4.1 Magnetic couplings 85 5.4.2 Phase diagram and longer-range interactions 86 5.4.3 Position of H cations and effect on in-plane interactions 88 5.4.4 Angle dependence, the Kitaev limit 91 5.5 Conclusions 92 6 Anisotropic spin interactions in pyrochlore iridates 95 6.1 Introduction 95 6.2 Structural details 97 6.3 Computational details 98 6.3.1 Embedded cluster and basis sets 98 6.3.2 Quantum chemistry calculations 99 6.3.3 Effective spin model Hamiltonian 99 6.4 Results and Discussion 101 6.4.1 Magnetic couplings 101 6.4.2 Spin Dynamics 103 6.4.3 Magnetic ground state 105 6.5 Conclusions 109 Summary 111

Pyrochlore iridates have received considerable attention for the past few years as they possess strong electron correlations and spin orbit coupling, giving rise to a finite temperature metal-insulator transition (MIT). The nature of this MIT transition is related to the magnetic order of the Ir atoms which also experience frustration as they are part of a pyrochore structure. The aim of this study is to elucidate the magnetic configuration of the magnetic iridium ions by doping Y2Ir2O7 with Bi. Here we present a study on the magnetic properties of the Y2−xBixIr2O7 (x = 0, 0.2, 0.4, 0.9, 1.3, 2) system using μSR and DC susceptibility. Our results show that pure Y2Ir2O7 has a magnetic transition to a long- range ordered state. Substituting Bi by Y results in a lower temperature transition with increasing amount of bismuth. When the system goes into the ordered state a weak ferromagnetic moment is seen. This is in agreement with the belief that the system orders in an canted antiferromagnetic fashion with all-in all-out spins in the tetrahedron of the pyrochlore structure. However the addition of bismuth into the sample does not change the internal magnetic field measured at low temperatures with μSR, but only changes the transition temperature and the ordered volume fraction. For the Bi2Ir2O7 system two magnetic transitions had been measured previously counter to the belief that this material did not order magnetically. In this work, our μSR measurements show no evidence of such a transition. In the transverse field μSR set up a small Knight shift is measured due to the local susceptibility of Bi2Ir2O7. / Thesis / Master of Science (MSc)

Frustrated magnets realize exotic forms of quantum matter beyond conventional order. Due to a lack of controlled and unbiased methods to study frustration in three dimensions, many questions remain unanswered. While most established numerical techniques have limited applicability, approaches based on cluster expansions are promising alternatives. By design, they do not suffer from dimensionality or frustration and generate reliable insights into the thermodynamic limit without any restriction in the parameter space. This thesis makes significant methodological progress in controlled numerical approaches tailored to study frustration in three dimensions. It covers (i) an automatic detection algorithm for symmetries in generic clusters, (ii) a general approach to the numerical linked cluster algorithm to study finite - and zero - temperature properties, and (iii) an expansion method based on the linked cluster theorem to obtain a suitable dressing for valence-bond crystals. In particular, we study one of the archetypal problems of frustrated magnetism in three dimensions: the pyrochlore Heisenberg antiferromagnet. For the first time, we are able to unbiasedly resolve its thermodynamic quantities to a temperature far beyond the scale on which the Schottky anomaly occurs. The broad applicability of the numerical linked cluster algorithm allows for the systematic investigation of different spin-liquid candidate materials such as the Cerium-based pyrochlores Ce₂Zr₂O₇ and Ce₂Sn₂O₇. Despite a similar chemical composition, the algorithm finds fundamental differences in their quantum mechanical nature by constraining their microscopic exchange parameters. Zero temperature properties are even less accessible: Neither the nature of the ground state nor an estimate of its energy are known for the pyrochlore antiferromagnet. Large-scale density matrix renormalization group calculations pushed to three dimensions provide the first reliable estimate of its ground-state energy and yield robust evidence for a spontaneous inversion symmetry breaking manifesting itself as an energy density difference on the tetrahedral sublattice. The symmetry-breaking tendency of the model is further observed in the presence of an external magnetic field where similar calculations suggest a stable 1/2-magnetization plateau. Continuing the investigation of low-energy states, we propose a new family - exponentially numerous in the linear system size - of valence-bond crystals as potential ground states. Understanding the stability of the previously overlooked family of states suggests a remarkable change of perspective on frustration with a focus on unfrustrated motifs. In sum, these discoveries present significant progress towards resolving long-standing questions regarding the nature of the ground state of the quantum pyrochlore S=1/2 antiferromagnet. / Frustrierte Magnete realisieren exotische Formen von Quantenmaterie, welche gewöhnliche Ordnungen übersteigen. Viele etablierte numerische Methoden versagen bei Frustration in drei Dimensionen, da sie entweder nicht anwendbar sind, unkontrolliert sind oder bestimmte Zustände vorziehen. Clusteralgorithmen bilden eine vielversprechende Alternative. Sie erfahren keine Einschränkung durch die Dimensionalität oder die Frustration des Problems und erlauben daher zuverlässige Einblicke in den thermodynamischen Limes. Diese Arbeit präsentiert methodische Fortschritte von kontrollierbaren Ansätzen, welche auf frustrierte Systeme in drei Dimensionen zugeschnitten sind. Sie beinhaltet (i) die Entwicklung eines Algorithmus zur automatischen Detektion räumlicher Symmetrien für allgemeine Cluster, (ii) einen allgemeinen Zugang zum 'numerical linked cluster algorithm'', um Eigenschaften bei endlicher Temperatur und dem absoluten Nullpunkt zu studieren und (iii) einen Clusteralgorithmus zur Optimierung des Zustands eines 'valence-bond' Kristalls. Die methodischen Fortschritte dieser Arbeit tragen zur Lösung eines archetypischen Problems von frustriertem Magnetismus in drei Dimensionen bei: dem Pyrochlor Heisenberg Antiferromagnet. Sie erlauben zuverlässige Einblicke in die Thermodynamik bis hin zu nicht-trivialen Temperaturen weit unter der Schottky-Anomalie. Die weiten Anwendungsmöglichkeiten des Clusteralgorithmus macht die systematische Untersuchung von Spinflüssigkeitskandidaten, wie die auf Cer basierenden Pyrochlore Ce₂Zr₂O₇ und Ce₂Sn₂O₇, möglich. Trotz einer ähnlichen chemischen Komposition, findet der Algorithmus fundamentale Unterschiede in ihrer quantenmechanischen Struktur. Frustration in drei Dimensionen ist am absoluten Nullpunkt ähnlich unzugänglich wie bei endlicher Temperatur und weder der Grundzustand, noch Schätzungen der Grundzustandsenergie des Pyrochlor Antiferromagneten sind bekannt. Groß angelegte Dichtematrixrenomierungsgruppenrechnungen in drei Dimensionen ermöglichen erstmals eine verlässliche Schätzung der Energie und finden eine spontan gebrochene Inversionssymmetrie, welche durch einen Unterschied in der Energiedichte auf dem tetraedrischen Untergitter ausgedrückt ist. Die Tendenz, die Symmetrie des Systems zu brechen, ist auch in der Präsenz eines externen magnetischen Feldes zu beobachten. Rechnungen deuten die Stabilität des 1/2-Magnetisierungsplateaus an. Einen signifikanten Beitrag zum Verständnis des Heisenberg-Models auf dem Pyrochlor wird durch eine Familie von potentiellen Grundzuständen geleistet, welche als harte Hexagone im Gitter visualisiert werden können. Ihre Anzahl skaliert exponentiell in der linearen Systemgröße und ihre niedrige Energie eröffnet eine neue Sichtweise auf frustrierte Magnete, welche den Fokus auf unfrustrierte Geometrien lenkt. Im Widerspruch zu der prominenten Spinflüssigkeitsannahme deuten die Ergebnisse dieser Arbeit auf Ordnung im Pyrochlor Antiferromagneten hin.

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