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This dissertation presents the first reported identification and analyses of the phase relations in the YBa2Cu3O7-x (YBCO)-SiO2 system at elevated temperatures. In this regard, a rigorous characterization study of the reaction phases within YBCO glass fibers, heat-treated YBCO+SiO2 pellets, rapid thermally annealed YBCO+SiO2 rods and rapid thermally annealed YBCO powder inside a fused silica tube is provided. These analyses are based on a vast set of generated novel results obtained using energy dispersive spectroscopy analyses on an environmental scanning electron microscope, X-Ray diffraction analyses, Raman spectroscopy, X-ray photoelectron spectroscopy analyses and a cross-polarized light study. First, original drawings of YBCO into glass fibers using the molten-core approach on a fiber draw tower in air and oxygen atmospheres are presented and analyzed. The performed analyses reveal the occurrence of reactions between the YBCO core and the silica cladding in as-drawn fibers as well as after additional heat-treatments. A detailed analysis and characterization of the occurring dissolution and diffusion based reaction processes is, then, provided along with the identification of the arising phase separation. Moreover, in order to analyze drawing YBCO glass fibers at lower temperatures, the use of borosilicate as the preform material is also investigated. This varied set of experiments and associated analyses reveal that the as-drawn YBCO fibers contain an amorphous core and that cuprite (Cu2O) is the first phase to crystallize out of the amorphous silicate matrix upon heat-treatment. Furthermore, the obtained results demonstrate the dissolution of the fused silica cladding into Si4+ and O2- ions and their subsequent diffusion into the molten YBCO core, leading to phase separation due to an occurring miscibility gap in the YBCO-SiO2 system as well as to silicate formation and amorphization of the YBCO core. This, as a result, prohibits the formation of the superconductive YBCO (Y-123) phase upon annealing. In addition, heat-treatment analyses show that higher temperatures or prolonged dwelling times at lower temperatures lead to the formation of barium copper and yttrium barium silicates. The analysis focusing on the use of borosilicate as the preform material reveals that drawing at lower temperatures reduces the dissolution and diffusion based reactions, but does not prevent them. Furthermore, the analysis on YBCO glass fibers with a fused silica cladding drawn in oxygen atmosphere shows that a higher oxygen content increases the dissolution of the fused silica cladding into its ions and their subsequent diffusion into the molten YBCO core. In addition, the performed heat-treatments on YBCO+SiO2 pellets in air and oxygen atmospheres demonstrate the gradual decomposition of the Y-123 phase with an increase in SiO2 content. Moreover, the rapid thermal annealing experiments with a subsequent quenching step on YBCO+SiO2 rods and on YBCO powder inserted inside a fused silica tube show the decomposition of the Y-123 phase and the formation of phases similar to the phases obtained in the YBCO glass fiber study, thus corroborating the results thereof. In summary, this dissertation enables the determination of the phase relations and reaction processes within the YBCO-SiO2 system, the identification of the direct effects of the silicon content on the Y-123 phase decomposition, as well as a rigorous characterization of the dissolution and diffusion based reactions within the YBCO-SiO2 glass-clad fiber system. The generated results and drawn conclusions build a fundamental understanding of phase relations in the YBCO-SiO2 system, which enables a definite assessment of the feasibility of manufacturing long-scale purely superconductive YBCO glass fibers using the molten-core approach and introduces advanced contributions to general glass-clad fiber systems manufactured using this method. / Doctor of Philosophy / This dissertation provides the first reported identification and analysis of the phase relations in the YBa2Cu3O7-x (YBCO)-SiO2 system at high temperatures. In this regard, a thorough characterization study of the reaction phases within YBCO glass fibers drawn using the molten-core approach on a fiber draw tower is provided. In addition, heat-treatment analyses considering YBCO+SiO2 pellets, rapid thermally annealed YBCO+SiO2 rods and rapid thermally annealed YBCO powder inside a fused silica tube are performed to gain further fundamental insights. The performed analyses are based on a wide set of characterization methods including energy dispersive spectroscopy on an environmental scanning electron microscope, X-Ray diffraction analyses, Raman spectroscopy, X-ray photoelectron spectroscopy and a cross-polarized light study. Our experimental results and performed analyses identify the phase relations and reaction processes within the YBCO-SiO2 system at elevated temperatures, demonstrate the direct effects of the silicon content on the superconductive YBCO phase decomposition, enable drawing definite conclusions regarding the feasibility of manufacturing long-scale purely superconductive YBCO glass fibers using the molten-core approach, and, characterize the dissolution and diffusion based reactions occurring within the YBCO-SiO2 glass-clad fiber system. In a nutshell, this dissertation provides a fundamental understanding of phase relations in the YBCO-SiO2 glass-clad system as well as key insights covering general glass-clad fibers drawn using the molten-core approach, paving the way for improved glass-clad fiber manufacturing using this method.

The solid state, hydrothermal and flux methods were used for the investigation of alkaline earth and transition metal borophosphate compounds. The products and the phase relations were investigated by XRD, IR, DTA, and EDX methods. The solid state reactions of several boron compounds with different phosphating agents have been studied in the temperature range of 400-1200 oC. Hydrothermal and flux techniques were performed at 150 oC and 1200 oC, respectively. On the other hand, an attempt has been made to prepare a novel borophosphate compound MIIMIV[BPO7] (where MIV= Zr4+, Si4+, and MII= Sr2+, Ca2+) by solid state reactions and to investigate intermediate and final products. (NH4)2HPO4 and NH4H2PO4 were used as a phosphating agent. For the synthesis of these new compounds, the following reaction was predicted using the stoichiometric amount of the reactants: 2MIVO2 + 2MIICO3 + B2O3 + 2(NH4)2HPO4 &amp / #8594 / 2MIIO.MIVO2.B2O3.P2O5 + 4NH3 + 3H2O + 2CO2 (According to IUPAC formulation for the compounds composed of oxides) In the case of MIV=Zr4+ and MII=Sr2+, the formation of ZrSr[BPO7] was observed together with ZrO2 and SrBPO5. The formation of a new phase was proved by indexing the XRD pattern of the product after separating ZrO2 and SrBPO5 lines. Its crystal system was found to be orthorhombic and the unit cell parameters are a=11.85&Aring / , b=12.99 &Aring / , c=17.32 &Aring / . IR analysis shows that there is [BPO7]6- bands in the spectrum. At higher temperatures, Sr7Zr(PO4)6 was obtained. In the case of MIV=Si4+, SrBPO5 was the main product together with unreacted SiO2. At 1100 oC, Si4+ entered SrBPO5 structure and the product was indexed in orthorhombic system with a=8.9243 &Aring / , b=13.1548 &Aring / , and c=5.4036 &Aring / . Several other M:B:P ratios were tried for solid state systems. For compositions with different cations (such as Al3+, Ca2+, Na+), reactions generally pass through metal phosphates and BPO4. The X-ray diffraction powder pattern and infrared spectrum of several intermediate products obtained at different temperatures were presented and the several phase relations were investigated. The DTA and EDX analyses of some products were also reported.

Au cours de la dernière phase d’accrétion, les planètes terrestres ont connu des impacts géants violents et très énergétiques. A la suite du chauffage causé par les impacts, la Terre primitive était partiellement ou totalement fondue, et un océan magmatique a été formé dans la couche externe de la Terre. Le refroidissement successif de l’océan magmatique a causé la cristallisation fractionnée du manteau primitif. Cependant, il reste beaucoup d’incertitudes à propos de l’accrétion de la Terre primitive, comme la profondeur et la durée de vie d’un (ou plusieurs) océan(s) magmatique(s), l’effet de la recristallisation du manteau sur la ségrégation chimique entre les différents réservoirs de la Terre et ainsi de suite. La connaissance des propriétés de fusion du manteau profond est important aussi pour examiner la possibilité d’une fusion partielle actuellement. L’objectif était d’aborder quelques problèmes concernant le manteau inférieur terrestre : Quelle est la séquence de fusion entre les phases dominantes dans le manteau inférieur ? Est-ce qu’on peut expliquer la zone à ultra-basse vélocité (ULVZ) avec la fusion partielle d’un manteau pyrolytique (ou chondritique) ? Quel est le partage du fer entre les phases silicatées liquides et solides dans le manteau profond ? Est-ce qu’on peut donner des informations nouvelles sur les propriétés d’un océan magmatique profond à partir des courbes de fusion du manteau primitif ? Dans cette étude les courbes de fusion et les relations de fusion ont été analysées en utilisant la cellule à enclume de diamant chauffé au laser (LH-DAC) pour des pressions entre 25 et 135 GPa et des températures jusqu’à plus que 4000 K, i.e. pour des conditions de P-T qui correspondent au manteau inférieur terrestre entier. Les compositions utilisées ont été le raccord entre MgO et MgSiO3 et une composition de type chondritique pour le manteau terrestre. J’ai utilisé deux techniques in-situ de radiation-synchrotron pour déduire les propriétés de fusion à hautes pressions ; la diffractométrie au rayons-X et la fluorescence au rayons-X. Les nouveaux résultats obtenus dans cette étude sont : (...) / During the final stage of accretion, terrestrial planets experienced violent and highly energetic giant impacts. As a consequence of impact heating, the early Earth was partially or wholly molten, forming a magma ocean in the outer layer of Earth. Subsequent cooling of the magma ocean has led to fractional crystallization of the primitive mantle. Many unknowns remain about accretion of the early Earth, such as extension depth and life time of the magma ocean(s), role of mantle recrystallization on the chemical segregation between the different Earth reservoirs, and so on. The knowledge of melting properties of the deep mantle is also important to investigate the possibility of partial melting at the present time. The aim of this study was to tackle a few major questions concerning the Earth lower mantle : What is the melting sequence between the main lower mantle phases ? Can we explain the ultra-low-velocity zones (ULVZ) by partial melting of pyrolitic (or chondritic) mantle ? How does iron partition between liquid and solid silicate phases in the deep mantle ? Can we provide new information on the properties of the deep magma ocean based on the melting curve of the primitive mantle ? Melting curves and melting relations have been investigated using the laser-heated diamond anvil cell (LH-DAC) for pressure between 25 and 135 GPa and temperature up more than 4000 K, i.e. at P-T conditions corresponding to the entire Earth’s lower mantle. Compositions investigated were the join between MgO and MgSiO3 and a model chondritic-composition for the Earth mantle. Two different in situ synchrotron radiation techniques have been used to infer melting properties at high pressures ; X-ray diffraction and X-ray fluorescence spectroscopy. The new results obtained in this study include : (...)