Orientador: Carlos Manuel Giles Antunez de Mayolo / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-24T10:39:53Z (GMT). No. of bitstreams: 1 Mardegan_JoseRenatoLinares_D.pdf: 36952737 bytes, checksum: f4575564084534b7dbe8742d9ea0a7b8 (MD5) Previous issue date: 2014 / Resumo: Nesta tese foram investigados as propriedades eletrônicas e magnéticas de diversos compostos que apresentam suas estruturas formadas por gaiolas na qual estas apresentam átomos hospedes no seu interior. Os compostos estudados foram o clatrato tipo-I Eu8Ga16Ge30, o composto fase cúbica de Remeika Eu3Ir4Sn13 e por m os compostos de GdT2Zn20 com T = Fe e Co. As propriedades destes materiais foram investigadas através do uso de medidas macroscópicas como resistividade elétrica, susceptibilidade magnética e também por medidas microscópicas como técnicas de absorção e espalhamento de raios-X e difração de nêutrons. O clarão Eu8Ga16Ge30, formado por dois tipos de gaiolas (X20 - dodecaedral e X24 - tetrakaidecaedral), foi principalmente investigado por difração e absorção de raios-X. Essas técnicas foram conciliadas com a aplicação de altas pressões na qual observou-se uma transição de fase irreversível cristalina-amorfa ao redor de Pa = 18 GPa. Concomitantemente a mudança estrutural, observou-se também através do dicroísmo circular magnético um colapso do ordenamento ferromagnético (FM) sob pressão. A diminuição do sinal magnético em altas pressões pode ser explicado por um estado paramagnético ou de "spin glass\", já que o íon de Eu permanece com valência 2+. Essa transição de fase estrutural foi vinculada a uma instabilidade mecânica das gaiolas devido a anisotropia criada pelo o íon hospede de Eu que esta deslocado cerca de 0.44 A do centro da gaiola X24. Além disso, a baixa pressão para que o material se transforme amorfo (~18 GPa) em comparação com outros clatratos isoestruturais confirma que o íon hospede no interior das gaiolas tem um forte papel na instabilidade mecânica das gaiolas. A estrutura e o magnetismo do composto tipo fase cúbica de Remeika Eu3Ir4Sn13 foi investigada através do uso do espalhamento de raios-X e nêutrons. A partir dos dados de espalhamento pudemos determinar que a anomalia ocorrida em T* ~ 57.1K observada no calor especifico e na resistividade elétrica e originaria de uma mudança estrutural. Esta distorção causa uma perda de simetria fazendo com que a nova célula unitária seja dobrada em duas direções, na qual pode-se observar picos com um vetor de propagação do tipo q = (0; 1/2 ; 1/2 ) em medidas com monocristais. A distorção estrutural está relacionada com uma forte hibridização dos ons presentes na gaiola de Ir(Sn2)6 o que aumenta a densidade eletrônica mudando a banda próximo do nível de Fermi e é fortemente dependente do metal de transição presente na amostra. A estrutura magnética do composto foi investigada através da difração de nêutrons, na qual abaixo de TN = 10.1 K observaram-se picos magnéticos do tipo ? = (0; 1/ 2 ; 1 /2 ). Com o refinamento das reflexões magnéticas encontramos que os momentos magnéticos dos ons de Eu estão apontados ao longo das direções [110] e [111]. Os compostos cúbicos de GdT2Zn20 com T = Fe e Co também foram investigados a partir de técnicas de difração e absorção de raios-X. Esses materiais tem importantes propriedades e muitas delas são decorrentes das interações que ocorrem entre os elementos terras raras mediadas pelos metais de transição. Tanto os ons de Gd quanto os ons de Co e Fe têm seus primeiros e segundos vizinhos formados por Zn. O composto de GdCo2Zn20 apresentou uma transição de fase de um estado paramagnético (PM) para um estado antiferromagnético (AFM) com uma temperatura de Néel ao redor de TN = 5.72 K. Utilizando a técnica de espalhamento magnético ressonante nos determinamos que os momentos dos ons de Gd estão alinhados perpendicularmente a direção [111], i.e., a representação magnética ?5. Essa direção do momento magnético tem forte influência da simetria do cristal e do fato do Gd ter momento angular nulo. Quando o metal de transição foi substituído por T = Fe, o composto de GdFe2Zn20 apresentou um ordenamento FM com uma alta temperatura crítica ao redor de TC = 86 K. As medidas de dicroísmo circular magnético realizadas ao redor das bordas de absorção L\'s do elemento terra rara e ao redor da borda K dos metais de transição (Fe e Zn) revelaram que tanto os ons de Gd quanto os ons de Zn apresentam momento magnético, entretanto, nenhum sinal magnético foi observado nos ons de Fe. O sinal magnético na borda do Zn ocorre devido à forte polarização entre as bandas 4sp do Zn com as bandas 5spd do íon de Gd. Acreditamos que a alta temperatura de ordenamento observada no composto FM esta correlacionada com uma alta densidade de estados próximo ao nível de Fermi devido aos ons de Fe, já a indução do momento magnético nos ons de Zn se deve a uma forte interação de troca entre os ons de Gd que polariza o meio / Abstract: In this thesis we have investigated the electronic and magnetic properties of several compounds in which they have the structure compose by cages. The compounds studied in this work were the clathrate type-I Eu8Ga16Ge30, the Remeika cubic phase Eu3Ir4Sn13 and the compounds GdT2Zn20 with T = Fe and Co. The electronic and magnetic properties of these materials were investigated using macroscopic measurements such as electrical resistivity and magnetic susceptibility measurements as well as microscopic techniques, such as X-ray absorption and scattering, and also neutron diffraction. The clathrate compound Eu8Ga16Ge30 formed by two types of cages (X20 ¿ dodecahedral X24 - tetrakaidecahedral) was mainly investigated by diffraction and X-rays absorption measurements. To better understand the eletronic and magnetic properties, the compound was investigated under high pressure in which we observed an irreversible crystalline-amorphous phase transition around Pa = 18 GPa. Simultaneously with structural change, it was observed by magnetic circular dichroism a collapse of the ferromagnetic (FM) ordering. This phase transition was associated with a mechanical instability in the cages due to an anisotropy created by the Eu ions rattling and displaced o center. Furthermore, this low pressure amorphization for the Eu8Ga16Ge30 compared with other isostructural clathrate compound confirms that the guest ion inside the cages has a strong role in the electronic and magnetic properties. The structure and magnetism of the Remeika cubic phase Eu3Ir4Sn13 was investigated by X-rays and neutrons scattering measurements. From these measurements we gured out that the anomaly at T 57.1 K observed in the specific heat and electrical resistivity measurements is related to a structural distortion. This distortion causes a loss of symmetry, in which one can observe new structural reflections with a propagation vector type q = (0; 1/2 ; 1/2 ). The structural distortion is related to a strong hybridization between the Ir and Sn2 ions in the Ir(Sn2)6 cages. This hybridization increases the electronic density of states near the Fermi level and it is strongly dependent on the transition metal. The magnetic structure was investigated by neutron diffraction, in which we observed magnetic Bragg peaks with a propagation vector type ? = (0; 1/2 ; 1/2 ) below TN = 10.1 K. Using several magnetic reflections we can determine the magnetic structure. From the refinement we found that the magnetic moments of Eu ions are pointing out along the [110] and [111] directions. The GdT2Zn20 cubic compound with T = Fe and Co were also investigated with diffraction and X-rays absorption measurements. These two compounds have interesting properties and many of them are due to the rare earth and transition metals elements are immersed in a sea of Zn ions. Both rare earth as well as the transition metals (Co and Fe) have the first and second neighbors formed by Zn ions. The GdCo2Zn20 compound showed a phase transition from a paramagnetic state (PM) to an antiferromagnetic state (AFM) with a Neel temperature around TN ~ 5.72 = K. Using x-ray resonant magnetic scattering technique we solved the magnetic structure and we found the magnetic moments of the Gd ions aligned perpendicular to the [111] direction, i.e., IR ?5. When the transition metal was replaced by T = Fe, the GdFe2Zn20 compound has a FM ordering with a remarkably high-temperature ferromagnetic (TC = 86 K) state. The X-ray magnetic circular dichroism measurements performed at the L2;3 absorption edges of the rare earth element and at the Fe and Zn K edges showed that only the Gd and Zn carry magnetic moment in this compound. The magnetic signal at the Zn K edge is due to the strong hybridization between the Zn 4sp states with the Gd 5d states. We believe that the high ordering temperature is related to a high density of states near the Fermi level and the magnetic moment induced at the Zn ions is due to the strong interaction among the Gd ions / Doutorado / Física / Doutor em Ciências

M. Tech. (Department of Metallurgical Engineering, Faculty of Engineering Technology), Vaal University of Technology. / Lonmin mining company located in the Bushveld Complex of South Africa is one of the main platinum group elements (PGEs) producers in the world. Its core operations are made up of 11 shafts and inclines. There are resources of 181 million troy ounces of 3PGE + Au, and there are reserves of 32 million ounces of 3PGE + Au. One of the ore type produced at Lonmin is UG2 ore which is dominated by the high presence of chromite. The UG2 ore is also associated with PGE assemblages divided into sulphides and non-sulphides, and it is beneficiated through the froth flotation technique. Froth flotation is a physico-chemical process that is used for separation of desired valuable minerals from the gangue minerals by utilising the difference in surface properties. The process has been achieving lower recoveries with P4 (shaft name) UG2 ore compared to Eastern Platinum Limited (EPL) UG2 ore when using similar reagents suite, this leads to loss of valuable minerals to the tailings, both ores were from Lonmin. The first step was to conduct the mineralogical analysis conducted using Scanning electron microscopy- energy dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), and optical microscopy to study the mineral composition of the two ores, and to identify any differences between them (two ores) considering that EPL UG2 ore is a blend of P1, P2, P3 (shaft names) and P4 UG2 ores while P4 UG2 ore is not blended with any other ores. The mineralogical results showed the presence of chromite, plagioclase, enstatite and sulphide minerals. The PGEs could not be detectable by any of the techniques used due to their small size and rarity. However, X-ray diffraction detected differences in concentrations of minor gangue constituents such as talc, muscovite, chlorite and actinolite and these results suggest that reagent consuming gangue mineralogy may have contributed to the differences in PGE recoveries by flotation. Batch flotation tests were also conducted. The existing reagent suite consisted of CuSO4 as an activator, Sodium n-propyl xanthate (SPNX) as a collector, carboxymethyl cellulose CMC as a depressant, and Senfroth 200 as a frother, and this was a single collector system. Therefore it was imperative to conduct flotation n investigation on alternative collector blends in order to improve the recovery of P4 UG2 ore. SNPX was used as the primary collector and it was blended with the following co-collectors: alkyl dithiocarbamates (DTC), two formulations of S-alkyl-N-butyl thionocarbamates (ABTC C1 & ABTC C2), and two formulations O-isopropyl-N-ethyl thionocarbamate (IPETC 30 & IPETC 31), one co-collector at a time. The first test incorporated the SNPX at dosage of 150 g/t without a blend and this dosage was selected based on the current optimum practice used at Lonmin and to use as a benchmark for the project. Trying to maintain the same dosage of 150 g/t of collectors, SNPX + co-collector were blended at two different dosages of 100 g/t + 50 g/t, and was also due to the fact that the co-collectors were highly concentrated and small dosages were expected to perform very well with SNPX. Lastly, the SNPX + co-collector at dosages 100 g/t + 125 g/t, here the dosage of co-collector was very high compared to 50 g/t and this was to check the effect of high dosages of highly concentrated collectors on the performance of the ore. The flotation results showed that the use of 50 g/t of co-collectors yielded optimum PGEs + Au recoveries and grades, while the dosage of 125 g/t decreased recoveries and grades. The high dosage quantities of collectors do not necessarily mean they will yield improved recoveries and grades. Different chain structures can be used to alter the behaviour of a collector, and these may increase or decrease their capabilities to cause higher recoveries. By using a collector with a longer hydrocarbon chain the flotation limit may be extended without loss of selectivity, consequently bringing about greater water repulsion, instead of increasing the concentration of a shorter chain collector. At 100 g/t of SNPX and 50 g/t of co-collector i.e. SNPX + IPETC 30 yielded improved 3PGE + Au recovery of 85.7 % at 3PGE + Au grades of 60.14 g/t, compared to the unblended SNPX (150 g/t) which yielded 3PGE + Au recovery of 81.1 % but insignificantly higher grade of 60.53 g/t. On the other hand, SNPX + IPETC C1 blend yielded low 3PGE + Au recoveries compared to SNPX + IPETC 30 and SNPX + IPETC 31 blends, but it achieved the highest grade of 76.1 g/t. Evidently, this proves that the relationship between recovery and grade is a trade-off. The results have also shown the synergic effects, especially for SNPX blended with IPETC 30, and SNPX blended with IPETC 31 at dosage of 100 g/t (SNPX) and 50 g/t (IPETCs). It can be concluded that the different interaction obtainable from the thionocarbamate (ROCSNHR), effectively complement that from the xanthate ion (ROCS2–) to achieve more collector interaction at surface sites otherwise interactable for xanthate only. Therefore the collector blends rendered the mineral of interest hydrophobic and as a result the minerals were recovered to the concentrate. On the other hand, too much of collectors may not be beneficial. At the dosage of 100 g/t of SNPX and 125 g/t of collectors, SNPX + DTC attained lower recoveries compared to SNPX, SNPX + IPETC 30, SNPX + IPETC 31, however the grade was higher than achieved SNPX + IPETC 30, SNPX + IPETC 31 and SNPX + ABTC C1. Nevertheless, comparing these results to the dosage of 50 g/t of the co-collectors, the 125 g/t did not perform well at all. The dosage of 125 g/t of co-collectors lead to loss of collecting power and selectivity, especially for SNPX + IPETC 30, SNPX + IPETC 31, and SNPX + ABTC C1 blends. It is therefore wise to conduct an optimisation test to determine the correct dosing rate. In addition, the chromite entrainment was below the smelter limit and is very beneficial since chromite is detrimental to the furnace. Therefore, it is concluded that the blends of SNPX with IPETC 30 and IPETC 31 at a dosage 50 g/t have shown satisfying recoveries and the FeCr2O4 recovery is less than 1 % meaning there will not be any smelter penalties for FeCr2O4 content. Therefore, these are the recommended collector blends. It is recommended that further mineralogical study of the ores be conducted so that it may provide deeper insight into the causes of low recoveries under SNPX only. The system of blended collectors and its optimisation would be beneficial and can be practiced. The Chemisorption studies between the minerals and co-collectors used will provide more specific insight and details into the actual interaction synergy that gave the improved recoveries.

Ce travail porte sur la cristallochimie de polymères de coordination poreux, ou Metal-Organic Frameworks (MOFs), pour la séparation et la catalyse énantiosélective. Les molécules chirales sont d'une importance capitale et jouent un rôle important dans la reconnaissance moléculaire. Il est donc nécessaire de pouvoir synthétiser un seul énantiomère ou de pouvoir séparer un mélange. La particularité des polymères de coordination à bénéficier d'une partie organique est la possibilité d'introduire des fragments chiraux dans la structure-même des matériaux. Nous avons décidé d'introduire la chiralité dans les MOFs par utilisation de ligands carboxylates originaux chiraux à cœur fluorène. Le premier chapitre de ce mémoire est consacré à l'étude bibliographique des MOFs avec une description des concepts de cette chimie qui permet de comprendre la stratégie mise en place dans cette étude. Le deuxième chapitre décrit la stratégie de synthèse des ligands ainsi que leurs caractérisations. Les trois chapitres suivants décrivent la synthèse, les structures cristallines et les caractérisations physico-chimiques de séries de MOFs regroupés par métal utilisé pour leur élaboration (Zn, Cd et Cu). Ces trois chapitres exposent les problématiques généralement rencontrées avec les MOFs, comme la perte de porosité par interpénétration des réseaux, et les stratégies mises en place pour les contourner, comme l'augmentation de la taille et de la fonctionnalité des ligands utilisés. Enfin la réactivité thermique et chimique des MOFs a été investiguée par diffraction des rayons X par la poudre afin de comprendre les mécanismes réactionnels et la création éventuelle de sites acides en vue d'applications en catalyse. Les techniques expérimentales sont détaillées dans le dernier chapitre de ce mémoire. Enfin un récapitulatif de cette étude est présenté afin de conclure sur la stratégie exposée dans ce mémoire et les perspectives offertes par cette étude. / This work deals with crystallochemistry of new porous coordination polymers or Metal-Organic Frameworks (MOFs) for enantioselective separation and catalysis. Chiral molecules are of a key role in molecular recognition as a consequence the ability to synthesize only one enantiomer or to separate a mixture is priority for chemistry. The particularity of coordination polymers to possess an organic part gives the possibility to introduce chiral fragments in the material structure. We decided to introduce chirality on MOFs by using originals chiral carboxylates ligands with fluorene core. The first chapter is devoted to the bibliographic study of porous coordination polymers. The second chapter describes the ligands synthesis strategy and characterizations. The next three chapters group the crystal structures and physicochemical characterizations of coordination polymers according to the metal used for their preparation (Zn, Cd et Cu). These three chapters explore also the general issues related to MOFs as the loss of porosity consequent to frameworks interpenetration, and strategies implemented to circumvent, such as increasing the size and functionality of the ligands used. Finally the thermal and chemical reactivity of MOFS has been investigated by powder X rays diffraction in order to understand reactions mechanisms and eventually the creation of acid sites for catalytic applications. The experimental technics are detailed in the last chapter. Finally a summary of this work closes this thesis showing the future perspectives of this work.

Les superalliages monocristallins base nickel sont largement utilisés dans les parties chaudes (aux alentours de 1000°C) des turbines aéronautiques au vu de leur bonne résistance thermomécanique. Pendant le stade II du fluage leur microstructure est formée d’une matrice/couloirs γ (CFC) et de précipités en radeaux γ’ (L12). Le but de cette étude est de mieux comprendre la plasticité de ces matériaux, en particulier celle de l’alliage de 1ère génération AM1. Afin de suivre son comportement mécanique durant des transitions rapides, une nouvelle technique expérimentale par diffraction en transmission des rayons X (synchrotron) a été développée. L’utilisation d’une caméra en champ lointain permet d’enregistrer (une acquisition prend 7 secondes) la tache de diffraction (200) de chacune des deux phases, et donc l’évolution en temps réel du désaccord paramétrique entre les deux phases. En utilisant un modèle mécanique simplifié, il est possible d’en déduire les contraintes internes et la déformation plastique de chaque phase. Une campagne d’essai sur la ligne ID11 de l’ESRF a été réalisée avec cette technique. Deux types d’échantillons présentant une microstructure initiale différente, obtenues par des traitements thermiques adaptés, ont été testés. Ils ont été soumis in situ à des essais de fluage à température constante avec des sauts de contrainte. Après essai, les échantillons ont été caractérisés par MET et MEB afin de déterminer leur microstructure, vérifier les désorientations des échantillons, cartographier la concentration de certains éléments et évaluer la densité de dislocations au sein des radeaux γ’. Dans les couloirs γ, la propagation des dislocations nécessite une contrainte de Von Mises supérieure à la contrainte d’Orowan, et la densité de dislocations mobiles augmente avec la déformation plastique. Le mécanisme limitant la déformation plastique par montée de la phase γ’ est vraisemblablement l’entrée des dislocations dans les radeaux. Les conséquences déduites de cette hypothèse sont détaillées ainsi que le comportement mécanique du matériau résultant / Nickel-based single crystal superalloys are extensively used for turbines blades (above 1000°C) of aeronautical engines because of their good thermomechanical properties. During stage II of creep, their microstructure consists of a γ matrix (fcc) and raft precipitates γ’ (L12). The aim of this work is to improve the understanding of plasticity of this type of alloy, especially the first generation AM1 superalloy. To follow his mechanical behaviour during fast transients, a new experimental setup using synchrotron radiation diffraction in transmission geometry was developed. A far field camera allows the recording of the (200) diffraction spot of each phase, i.e. the evolution of the lattice misfit in real time (one acquisition takes 7 seconds). By using a simple mechanical model, it is possible to determine the internal stresses and the plastic strains for both phases. An experimental campaign was performed at ID11 beamline of ESRF using this new technique. Two sample types with different initial microstructure (obtained with adapted heat treatments) were tested in situ. They underwent load jumps under high-temperature creep conditions. Further post mortem investigations by SEM and TEM were performed to determine their microstructure, to check on misorientations, map some elements composition and estimate the dislocation density within the γ’ rafts. In the γ channels, dislocation propagation occurred when the Von Mises stress was larger than the Orowan stress. The mobile dislocations density increases with γ plastic strain. The limiting mechanism for γ’ plastic strain is presumably the entry of dislocation within the γ’ rafts. Under this assumption we deduce the mechanisms of interactions between dislocations, vacancies, and pores within the material, and the mechanical behaviour of the γ’ rafts

A organização e a estabilidade de compostos de coordenação, no estado sólido, pode ser correlacionada com os ligantes diretamente coordenados a íons metálicos e com as interações não covalentes estabelecidas entre os ligantes e solventes de cristalização. O presente trabalho avaliou a influência dos pré ligantes ácido 2,6-dihidróxibenzoico (Hdhb), ácido benzoico (Hbzt), ácido oxálico (H2ox) e 2,2’-bipiridina (bipi), capazes de realizar interações não covalentes, em sua reatividade frente a sais de cobre(II), cobalto(II) e manganês(II). Foram avaliadas diferentes combinações de ligantes para cada íon metálico e condições de reação, gerando um total de dez produtos caracterizados por DRX de monocristal. Dentre eles, os complexos [Cu2( ox)(bzt)2(bipi)2(H2O)2] (A), [Co(H2O)6](dhb)2·2H2O (B) e [Mn(H2O)6](dhb)2·2H2O (C) são inéditos. Estes produtos foram avaliados em sua composição elementar, analisados por técnicas difratométricas (DRX de pó e de monocristal) e espectroscópicas (IV, Raman, RPE e Uv/Vis). Os dados estruturais foram correlacionados com as propriedades espectroscópicas, termogravimétricas e magnéticas. O produto A foi obtido em 90 % de rendimento a partir da reação de Cu(CH3COO)2·H2O com os pré-ligantes Hbzt, H2ox e bipi, em metanol a 70 °C. A análise por DRX de monocristal revelou que em A todos os ligantes contribuem para a manifestação de interações não covalentes do tipo ligações de hidrogênio e interação . A análise por RPE e medidas de susceptibilidade magnética à temperatura ambiente indicaram a existência de interação magnética entre os centros de cobre(II). Medidas de susceptibilidade magnética com variação de temperatura revelaram uma interação ferromagnética (J = 3,26 cm-1) mais forte que a apresentada por complexos análogos. Medidas termogravimétricas mostraram que a decomposição de A se inicia em 55 °C com a perda de 2 H2O, seguida da perda dos ligantes orgânicos entre 136 e 900 °C. Os produtos B e C, de estruturas análogas, foram obtidos em 97 e 99 % de rendimento, respectivamente, a partir da reação de CoCl2·6H2O ou MnCl2·4H2O com o pré-ligante Hdhb, em água a 70 °C. A análise por DRX de monocristal revelou que não ocorreu a coordenação do íon dhb, provavelmente devido a estabilização do carboxilato livre por duas ligações de hidrogênio intramoleculares assistidas por carga. A rede cristalina de B e C também é estabilizada por interações  e por ligações de hidrogênio intermoleculares formadas a partir das águas coordenadas e de cristalização. A decomposição térmica de B e C se inicia com a perda de moléculas de água a temperaturas inferiores a 55 °C e a perda total da parte orgânica ocorre acima de 600 °C. Os compostos obtidos neste trabalho evidenciaram que a estrutura e o grau de agregação dos compostos são dependentes da habilidade de coordenação do ligante ao íon metálico e das interações não covalentes nos ligantes livres e nos complexos formados. / The organization and stability of coordination compounds could be correlated to structural features, as the number and nature of ligands coordinated to the metallic ions and with noncovalent interactions established between the ligands and with crystallization solvents. The present work evaluated the influence of the pre-ligands 2,6-dihydroxybenzoic acid (Hdhb), benzoic acid (Hbzt), oxalic acid (H2ox), and 2,2' bipyridine (bipi), capable to perform noncovalent interactions, in its reactivity to copper(II), cobalt(II) and manganese(II) salts. For each metallic ion, and reaction condition were evaluated with different combinations of ligands, producing 10 different structures characterized by single crystal XRD. Among them, the complexes [Cu2( ox)(bzt)2(bipi)2(H2O)2] (A), [Co(H2O)6](dhb)2·2H2O (B), and [Mn(H2O)6](dhb)2·2H2O (C) were synthesized for the first time in this work. Those products were characterized by elemental analysis and diffractometric (powder and single crystal XRD) and spectroscopic (IR, Raman, EPR and Uv/Vis) techniques. Moreover, spectroscopic, thermogravimetric and magnetic properties of A, B and C, were attempt correlated with their structural features. Product A was obtained with 90% of yield from the reaction of Cu(CH3COO)2·H2O with the pre-ligands Hbzt, H2ox, and bipy, in methanol at 70 °C. Single crystal XRD analysis of A evidenced that all ligands interact through noncovalent interactions, as hydrogen bonds and  interaction. EPR and magnetic susceptibility measurements strongly suggest the existence of magnetic interaction between the copper(II) centres. In addition, magnetic susceptibility measurement varying temperature revealed a ferromagnetic exchange (J = 3.26 cm-1) stronger than those observed for analogous complexes. Thermal decomposition of A starts at 55 °C with the loss of two water molecules, succeed by the loss of the organic ligands (136 – 900 °C). Product B and C showed similar structures and were obtained in 97 and 99 % of yield, respectively, from the reaction of CoCl2·6H2O or Mn2Cl2·4H2O with Hdhb, in water at 70° C. Single crystal XRD analysis revealed that dhb ion remains as counterion of the aqua complexes, probably due the stabilization of the free carboxylate by two intramolecular charge-assisted hydrogen bonds. The crystal lattice of B and C is also stabilized by  interactions and intermolecular hydrogen bonds from both coordinated and crystallization water molecules. According to TGA curves, the thermal decomposition of B and C starts with the loss of water molecules below 55° C, and a complete weight-loss of organic ligands occurs above 600° C for both complexes. The correlation between the nature of all products obtained with synthetic conditions revealed that the structure and degree of aggregation depends on the coordination ability of the ligand to the metallic ion and on the noncovalent interactions in the free ligands and complexes formed.

A organização e a estabilidade de compostos de coordenação, no estado sólido, pode ser correlacionada com os ligantes diretamente coordenados a íons metálicos e com as interações não covalentes estabelecidas entre os ligantes e solventes de cristalização. O presente trabalho avaliou a influência dos pré ligantes ácido 2,6-dihidróxibenzoico (Hdhb), ácido benzoico (Hbzt), ácido oxálico (H2ox) e 2,2’-bipiridina (bipi), capazes de realizar interações não covalentes, em sua reatividade frente a sais de cobre(II), cobalto(II) e manganês(II). Foram avaliadas diferentes combinações de ligantes para cada íon metálico e condições de reação, gerando um total de dez produtos caracterizados por DRX de monocristal. Dentre eles, os complexos [Cu2( ox)(bzt)2(bipi)2(H2O)2] (A), [Co(H2O)6](dhb)2·2H2O (B) e [Mn(H2O)6](dhb)2·2H2O (C) são inéditos. Estes produtos foram avaliados em sua composição elementar, analisados por técnicas difratométricas (DRX de pó e de monocristal) e espectroscópicas (IV, Raman, RPE e Uv/Vis). Os dados estruturais foram correlacionados com as propriedades espectroscópicas, termogravimétricas e magnéticas. O produto A foi obtido em 90 % de rendimento a partir da reação de Cu(CH3COO)2·H2O com os pré-ligantes Hbzt, H2ox e bipi, em metanol a 70 °C. A análise por DRX de monocristal revelou que em A todos os ligantes contribuem para a manifestação de interações não covalentes do tipo ligações de hidrogênio e interação . A análise por RPE e medidas de susceptibilidade magnética à temperatura ambiente indicaram a existência de interação magnética entre os centros de cobre(II). Medidas de susceptibilidade magnética com variação de temperatura revelaram uma interação ferromagnética (J = 3,26 cm-1) mais forte que a apresentada por complexos análogos. Medidas termogravimétricas mostraram que a decomposição de A se inicia em 55 °C com a perda de 2 H2O, seguida da perda dos ligantes orgânicos entre 136 e 900 °C. Os produtos B e C, de estruturas análogas, foram obtidos em 97 e 99 % de rendimento, respectivamente, a partir da reação de CoCl2·6H2O ou MnCl2·4H2O com o pré-ligante Hdhb, em água a 70 °C. A análise por DRX de monocristal revelou que não ocorreu a coordenação do íon dhb, provavelmente devido a estabilização do carboxilato livre por duas ligações de hidrogênio intramoleculares assistidas por carga. A rede cristalina de B e C também é estabilizada por interações  e por ligações de hidrogênio intermoleculares formadas a partir das águas coordenadas e de cristalização. A decomposição térmica de B e C se inicia com a perda de moléculas de água a temperaturas inferiores a 55 °C e a perda total da parte orgânica ocorre acima de 600 °C. Os compostos obtidos neste trabalho evidenciaram que a estrutura e o grau de agregação dos compostos são dependentes da habilidade de coordenação do ligante ao íon metálico e das interações não covalentes nos ligantes livres e nos complexos formados. / The organization and stability of coordination compounds could be correlated to structural features, as the number and nature of ligands coordinated to the metallic ions and with noncovalent interactions established between the ligands and with crystallization solvents. The present work evaluated the influence of the pre-ligands 2,6-dihydroxybenzoic acid (Hdhb), benzoic acid (Hbzt), oxalic acid (H2ox), and 2,2' bipyridine (bipi), capable to perform noncovalent interactions, in its reactivity to copper(II), cobalt(II) and manganese(II) salts. For each metallic ion, and reaction condition were evaluated with different combinations of ligands, producing 10 different structures characterized by single crystal XRD. Among them, the complexes [Cu2( ox)(bzt)2(bipi)2(H2O)2] (A), [Co(H2O)6](dhb)2·2H2O (B), and [Mn(H2O)6](dhb)2·2H2O (C) were synthesized for the first time in this work. Those products were characterized by elemental analysis and diffractometric (powder and single crystal XRD) and spectroscopic (IR, Raman, EPR and Uv/Vis) techniques. Moreover, spectroscopic, thermogravimetric and magnetic properties of A, B and C, were attempt correlated with their structural features. Product A was obtained with 90% of yield from the reaction of Cu(CH3COO)2·H2O with the pre-ligands Hbzt, H2ox, and bipy, in methanol at 70 °C. Single crystal XRD analysis of A evidenced that all ligands interact through noncovalent interactions, as hydrogen bonds and  interaction. EPR and magnetic susceptibility measurements strongly suggest the existence of magnetic interaction between the copper(II) centres. In addition, magnetic susceptibility measurement varying temperature revealed a ferromagnetic exchange (J = 3.26 cm-1) stronger than those observed for analogous complexes. Thermal decomposition of A starts at 55 °C with the loss of two water molecules, succeed by the loss of the organic ligands (136 – 900 °C). Product B and C showed similar structures and were obtained in 97 and 99 % of yield, respectively, from the reaction of CoCl2·6H2O or Mn2Cl2·4H2O with Hdhb, in water at 70° C. Single crystal XRD analysis revealed that dhb ion remains as counterion of the aqua complexes, probably due the stabilization of the free carboxylate by two intramolecular charge-assisted hydrogen bonds. The crystal lattice of B and C is also stabilized by  interactions and intermolecular hydrogen bonds from both coordinated and crystallization water molecules. According to TGA curves, the thermal decomposition of B and C starts with the loss of water molecules below 55° C, and a complete weight-loss of organic ligands occurs above 600° C for both complexes. The correlation between the nature of all products obtained with synthetic conditions revealed that the structure and degree of aggregation depends on the coordination ability of the ligand to the metallic ion and on the noncovalent interactions in the free ligands and complexes formed.

Orientador: Carlos Kenich Suzuki / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-07-22T19:32:43Z (GMT). No. of bitstreams: 1 Ogata_DanielaYuri_M.pdf: 14373801 bytes, checksum: 37390613963c28ba54f71a665d3cefb7 (MD5) Previous issue date: 1997 / Resumo: Neste trabalho procurou-se investigar a influência do tratamento da superficie (tensão/rugosidade provocado pelo processo de desbaste com pó abrasivo) na devitrificação e na dissolução da sílica vítrea. Para tanto, utilizou-se de métodos de caracterização de materiais, tais como difratometria de raios-X, espectroscopia de infravermelho, microscopia óptica e eletrônica e espalhamento de raios-X a baixo ângulo. Para o estudo da influência do tratamento superficial na devitrificação, os resultados de difração de raios-X e microscopia, mostraram que a devitrificação possui forte correlação com o tratamento superficial da sílica vítrea, onde amostras com maior rugosidade, apresentaram também uma maior devitrificação em comparação à outra com menor rugosidade. A dissolução da sílica vítrea por ácido fluorídrico ("etching") também foi estudado, e os resultados mostraram que a taxa de dissolução é dependente da rugosidade superficial, concentração do ácido e tempo de "etching". Resultados adicionais mostraram a formação de cavidades arredondadas na forma de "larvas" (padrão superficial) após "etching". Após um tempo de "etching" entre 33 e 88 horas, as amostras apresentaramum padrão superficial semelhante a "grãos" e no interior dos "grãos", outros "sub-grãos" da ordem de 4-10 'mu¿m, que denotam a existência de microtensões na estrutura amorfa. Neste trabalho, este resultado inédito foi denominado "grão ou sub-grão amorfo", que podem estar relacionados com heterogeneidades em nível atômico da estrutura da sílica vítrea / Abstract: The effect of surface stress and roughness, produced by polishing process with abrasive powder, was investigated on the devitrification and dissolution of silica glass. The characterization studies of the silica glass treated by grinding, polishing and etching and their effect on the devitrification were conducted by X-ray diffraction, optical and electronic microscopy, inftared spectroscopy and small-angle X-ray scattering. The samples were heat treated at 1250°C for a period of 15 min and 150 mino X-ray diffraction and optical microscopy observation showed more intense devitrification effect into a-cristobalite for higher degree of surface roughness, and the samples treated with HF etching presented the lowest devitrification effect. The silica glass surfaces exposed to the furnace atmosphere (air) presented a much bigger crystallization effect, inversely to the bottom surface in contact with a silica base. The dissolution of silica glass by chemical etching (HF solutions) was studied, and the results showed that dissolution rate is dependent on the surface roughness, HF concentration and etching time. For example, the dissolution rate of samples treated with SiC #320 and 'Ce IND. 2¿¿O IND. 3¿, were estimated as 0.16 'mu¿m/min and 0.14 'mu¿m/min, respectively. The results showthat sampleswith longtime etching(~1000 min) revealed grain-like etch pattern of 4 to 10 11min diameter, which suggests reveals the existence of micro-stress in the amorphous structure. This "amorphous grains or sub-grains" might be correlated with atomic into inhomogeneities of amorphous silica structure / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Orientador: Carlos Kenichi Suzuki / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-11T16:06:32Z (GMT). No. of bitstreams: 1 Nunes_ClaudiaCarvalho_M.pdf: 7074659 bytes, checksum: 4dec2d1e75a640341af023ba7541f5cb (MD5) Previous issue date: 2008 / Resumo: O sistema binário sílica titânia, SiO2-TiO2,apresenta grande interesse tecnológico devido as suas propriedades: ultra-baixo coeficiente de expansão térmico e alto índice de refração. As propriedades são dependentes da quantidade de dopante presente no material. A SiO2-TiO2 é usada na indústria de componentes fotônicos, tais como, lentes, micro-lentes, espelhos e fibras ópticas especiais. Um importante material óptico para litografia no extremo ultravioleta (EUVL) é caracterizado por concentrações próximas a 8 % em peso de TiO2, com estrutura amorfa e transparente num amplo espectro da região UV, visível e IV. A indústria óptico-eletrônica necessita de fibras ópticas sensoras com alto índice de refração. Este tipo de fibra pode ser obtido através da fabricação de uma fibra de SiO2-TiO2. Amostras com concentrações que variam de 1 a 14 % em peso TiO2 fabricadas pelo método do aerosol em chama foram caracterizadas quanto a suas propriedades estruturais e ópticas. As amostras com concentrações superiores a 7,5 % em peso apresentaram-se translúcidas ou opacas, e com estrutura octaédrica segundo dados de XANES (Absorção de Raios-X próximo à estrutura da borda). A difração de raios-X identificou a fase anatásio da titânia como estrutura octaédrica. Através de tratamentos térmicos a altas temperaturas em chama (> 1500 ºC) obtivemos amostras transparentes no visível, amorfa, contendo 8,2 % em peso. Foi obtido um material com índice de refração de 1,48 para concentração de 10 % em peso de TiO2. Portanto a SiO2-TiO2 é viável para a fabricação de uma fibra com alto índice de refração / Abstract: The binary SiO2-TiO2 system presents a great technological importance due to its special properties: ultra low thermal expansion and high refractive index. The properties depend on the amount of dopant present in material. The SiO2-TiO2 is used for the components of photonic industries, such as lenses, mirrors and special fiber optics. As an important optical material for extreme ultraviolet lithography (EUVL), it is characterized by concentrations of ~ 8 wt. % of TiO2, with amorphous structure and transparent for a large UV, visible and IR spectra. The optoelectronic industries needs optical fiber sensor that presents high refractive index. This kind of fiber can be produce by SiO2-TiO2 fiber production. Samples with concentrations varying in the range 1 to 14 wt. % TiO2 made by flame aerosol technique were characterized in terms of structural and optical properties. As-consolidated samples with concentrations up to 7.5 wt. % TiO2 presented itself translucent or opaque with octahedral structure, according to XANES data (X-ray absorption near-edge structure). The anatase phase of titania was identified by X-ray diffraction patterns. However, by high temperature flame heat treatments (> 1500 ºC), it was possible to obtain transparent SiO2-TiO2 materials in the visible range with concentration up to 8.2 wt. % TiO2. The material presents refractive index 1.48 with concentration about 10 wt. % TiO2. Therefore SiO2-TiO2 is feasible to fibers fabrication with high refractive index / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Le grenaillage est souvent utilisé sur les pieds d’aube de turbine haute pression afin de retarder l’apparition des fissures dans les zones de concentration de contraintes. Ce traitement de surface génère des contraintes résiduelles et de l’écrouissage en surface de la pièce, ce qui influe sur sa durée de vie. L’enjeu de cette thèse est de mettre en place une méthodologie permettant de prendre en compte cet état mécanique initial, ainsi que son évolution en service, dans l’analyse de durée de vie d’une aube élaborée en superalliage monocristallin à base de nickel (AM1). Tout d’abord, cet état mécanique (contraintes résiduelles et écrouissage) est déterminé expérimentalement. Les contraintes résiduelles sont notamment évaluées par diffraction des rayons X en utilisant la méthode d’Ortner. Cet état mécanique est ensuite introduit dans les calculs de structure. Pour cela, on s’inspire de la méthode connue de l’introduction directe du champ d’eigenstrains qui est, ensuite, étendue afin d’introduire également les variables d’écrouissage ainsi que l’état mécanique anisotrope complet dans toute la structure. L’étape suivante a visé à suivre expérimentalement et à modéliser l’évolution de ces quantités sous sollicitations thermique, d’une part et cycliques à température constante (650°C), d’autre part. Enfin, la chaîne complète de calcul de durée de vie de l’AM1 est appliquée afin d’analyser la durée de vie des éprouvettes grenaillées. Les résultats obtenus sont discutés en regard des essais de fatigue effectués sur éprouvettes représentatives / Shot-peening is widely used on roots of high pressure turbine blade to postpone crack initiation in stress concentration area. This pre-stressing introduces compressive residual stress and strain hardening in a surface layer which will influence lifetime. The aim of this thesis is to propose a methodology which allows taking into account the impact of such pre-stressing and their evolution on the fatigue behaviour of a single crystal nickel-based superalloy (AM1) used for high pressure turbine blades. Firstly, the experimental work is devoted to the determination of the initial mechanical state (residual stresses and strain hardening). Residual stresses are namely determined using X-ray diffraction involving the use of a specific method developed by Ortner. This experimental initial mechanical state is then introduced as an input in structure calculation. The well-known method involving the direct introduction of eigenstrain profiles is used and improved to also introduce strain hardening variables and the complete anisotropic mechanical state in all the integration points of the structure. The next step consist in following experimentally and modeling the evolution of these quantities under thermal and mechanical loads under an uniform temperature (650°C). Finally, the complete lifetime assessment is carried out on representative shot-peened samples. Results are discussed with respect to experimental fatigue tests

Liquid crystalline materials forming columnar mesophases are of importance for both the fundamental research and technological applications due to their supramolecular architecture allowing for one-dimensional charge transport. The potential applications of these materials include light emitting diodes, solar cells, field effect transistors and photovoltaic cells. However, to design a LC material suitable for a particular application, a fundamental understanding of the structure-property relationships is needed.<p>In the present thesis, a variety of systems forming columnar mesophases have been explored. They include small molecular weight compounds (triphenylene, phthalocyanine derivatives and star-shaped mesogens) and polymer materials. The research was focused on the study of the influence of the molecular architecture and specific interactions such as hydrogen bonding on the supramolecular organization in the mesophase, as well as on the influence of columnar mesophase on crystal growth. The main results of the thesis are summarized below.<p>The influence of hydrogen bonding on the structure and charge carrier mobility was investigated for a triphenylene derivative, hexaazatriphenylene, having lateral alkyl chains linked to the core via amide groups. These linking groups provide the possibility to form inter- and intra-molecular hydrogen bonds. Acting as “clamps”, the inter-molecular hydrogen bonds are found to enforce the attractive interactions between the molecules in the column. Thus, the columnar mesophase formed by this system is characterized by the smallest inter-disk distance ever found in columnar mesophases (3.18 Å). The improved intra-columnar order brings about a higher charge carrier mobility (0.02 cm2/Vs) as compared to other triphenylene derivatives without hydrogen bonds. <p>Phthalocyanine derivatives, which are liquid crystalline at ambient temperature, could be suitable for opto-electronic applications due to their improved processibility and self-healing of structural defects. Our interest in these systems was inspired by the fact that, in spite of numerous studies performed to date, only very a few phthalocyanine derivatives were found to exhibit columnar mesophases at ambient temperature. We observed that by introducing branches in alkyl chains close to the core, we were able to render the material LC at ambient temperature. Analysis of X-ray diffraction patterns measured on oriented samples showed that these systems form hexagonal and rectangular ordered columnar mesophases. This finding is in contradiction with the general view stating that non-hexagonal mesophases can be only disordered. Since the absolute majority of applications require fabrication of films, it was very important to achieve the visualization of the organization of the phthalocyanine derivatives at the nanometer scale. AFM images on thick spin-coated films with columnar resolution are presented for the first time. They allowed the examination of columnar curvatures and breaks at the boundaries between different single crystal-like domains. <p>The possibility of templating columnar crystal growth was studied for a star-shaped mesogen using a combination of direct- and reciprocal-space techniques. AFM images with columnar resolution showed that the crystal growth initiated in the monotropic columnar mesophase occurs almost in register with the mesomorphic template. In the final crystalline structure, the placement of the crystalline columns is controlled by the mesomorphic tracks at the scale of an individual column, i.e. at the scale of approximately 3.5 nm. <p>The mesophase-assisted crystallization was also studied for the case of a polymer material forming columnar mesophase, poly(di-n-propylsiloxane). X-ray diffraction on oriented fibers allowed us to correct the previous indexation and solve the structure of the unit cell. The crystallization process was studied on samples crystallized in different conditions. It was found that, depending on crystallization conditions, both folded-chain and extended-chain crystals can be obtained. Thus, crystallization of the material from the mesophase results in the formation of 100-150nm thick crystals, which corresponds to a nearly extended-chain conformation. By contrast, when crystallized from a dilute solution, folded-chain crystals result. The mechanisms of chain unfolding was studied by variable temperature atomic force microscopy on PDPS single crystals. It was found that crystals rapidly thicken above the initial melting point, up to 80 nm. / Doctorat en sciences, Spécialisation physique / info:eu-repo/semantics/nonPublished