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Preparação e caracterização de vidros fluorozirconados. / Preparation and characterization of fluorozirconate glasses.Delben, Angela Antonia Sanches Tardivo 12 May 1992 (has links)
A troca de BaF2 por NaF altera as características físicas dos vidros fluorozirconados. Verificamos um aumento do índice de refração, da estabilidade frente à nnucleação e do módulo de Young com a concentração de NaF. A microdureza Vickers mostrou ser pouco afetada pelas condições de umidade, mas bastante dependente do polimento. O modelo simples, do tipo degrau, proposto para a microdureza não foi suficiente para explicar o comportamento da microdureza em função da carga. Vidros fluorozirconados dopados com Pr e Eu mostraram-se bastante estáveis, possibilitando seu emprego em fibras ópticas. Algumas composições de vidros contendo LiF mostraram uma redução do índice de refração e aumento da condutividade iônica com a concentração de LiF. A estabilidade e as propriedades de transmissão destes vidros são comparáveis às dos fluorozirconados tradicionais. Realizamos com sucesso o puxamento de fibras de vidros fluorindatos e a técnica e problemas de preparação de pré-formas são apresentados neste trabalho. / Replacing BaF2 for NaF yields physical properties modifications on fluorozirconate glasses. An increase of refraction index, thermal stability and young modulus was observed with NaF concentration. Humidity affects less Vickers microhardness than polishing conditions. A simple step model proposed for microhardness does not fit microhardness vs. load behaviors. Fluorozirconate glasses doped with Eu and Pr showed high stability allowing their use in optical fibers. Some glass compositions with LiF showed a decrease of refraction index and an increase of ionic conductivity with LiF content. Stability and transmission properties of these glasses are similar to those of traditional fluorozirconate glasses. We drew nice fibers from fluorindate glasses and the techniques and problems of perform preparation will be reported.
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Ruthenium dihydride and hydride fluoride complexes with N-heterocyclic carbenes : a route to C-F bond activationReade, Steven Peter January 2009 (has links)
No description available.
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Preparação e caracterização de vidros fluorozirconados. / Preparation and characterization of fluorozirconate glasses.Angela Antonia Sanches Tardivo Delben 12 May 1992 (has links)
A troca de BaF2 por NaF altera as características físicas dos vidros fluorozirconados. Verificamos um aumento do índice de refração, da estabilidade frente à nnucleação e do módulo de Young com a concentração de NaF. A microdureza Vickers mostrou ser pouco afetada pelas condições de umidade, mas bastante dependente do polimento. O modelo simples, do tipo degrau, proposto para a microdureza não foi suficiente para explicar o comportamento da microdureza em função da carga. Vidros fluorozirconados dopados com Pr e Eu mostraram-se bastante estáveis, possibilitando seu emprego em fibras ópticas. Algumas composições de vidros contendo LiF mostraram uma redução do índice de refração e aumento da condutividade iônica com a concentração de LiF. A estabilidade e as propriedades de transmissão destes vidros são comparáveis às dos fluorozirconados tradicionais. Realizamos com sucesso o puxamento de fibras de vidros fluorindatos e a técnica e problemas de preparação de pré-formas são apresentados neste trabalho. / Replacing BaF2 for NaF yields physical properties modifications on fluorozirconate glasses. An increase of refraction index, thermal stability and young modulus was observed with NaF concentration. Humidity affects less Vickers microhardness than polishing conditions. A simple step model proposed for microhardness does not fit microhardness vs. load behaviors. Fluorozirconate glasses doped with Eu and Pr showed high stability allowing their use in optical fibers. Some glass compositions with LiF showed a decrease of refraction index and an increase of ionic conductivity with LiF content. Stability and transmission properties of these glasses are similar to those of traditional fluorozirconate glasses. We drew nice fibers from fluorindate glasses and the techniques and problems of perform preparation will be reported.
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Metal-Carbon (Metal = Iridium(III) and Gold(III)) Bond Formation Under Transmetalation and Catalytic Conditions; Metallonucleosides as Anticancer Drugs and Bio-photonic Probes; and Synthesis of Iridium Fluoride Complexes.Maity, Ayan 06 February 2015 (has links)
No description available.
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Nano-sized Transition Metal Fluorides as Positive Electrode Materials for Alkali-Ion BatteriesMartin, Andréa Joris Quentin 02 November 2020 (has links)
Übergangsmetallfluoridverbindungen sind sehr vielversprechende Kandidaten für die nächste Generation von Kathoden für Alkaliionenbatterien. Dennoch verhindern einige Nachteile dieser Materialklasse ihre Anwendung in Energiespeichermedien. Metallfluoride haben eine stark isolierende Wirkung, außerdem bewirken die Mechanismen beim Lade-/Entladevorgang, große Volumenänderungen und somit eine drastische Reorganisation des Materials, welche nur geringfügig umkehrbar ist. Um diese Nachteile zu reduzieren, werden in dieser Arbeit innovative Syntheserouten für die Umwandlung von Metallfluoridverbindungen sowie deren Anwendung in Alkaliionenbatterien vorgestellt. Im ersten Teil werden MFx Verbindungen (M = Co, Fe; x = 2 oder 3) untersucht. Diese Materialien zeigen eine hohe Ausgangskapazität aber nur bei sehr geringen C-Raten und zudem sehr geringe Zyklisierbarkeiten. Ex-situ-XRD und -TEM zeigen, dass die geringe Umkehrbarkeit der Prozesse hauptsächlich aus der Umwandlungsreaktion während des Be-/Entladens resultieren. Im zweiten Teil werden sowohl die Synthesen als auch die elektrochemischen Eigenschaften von Perowskiten aus Übergangsmetallfluoriden vorgestellt. NaFeF3 zeigt hierbei exzellente Leistungen und Reversibilitäten. Die Untersuchung der Mechansimen durch ex-situ und operando XRD während der Be- und Entladeprozesse hinsichtlich verschiedener Alkalisysteme zeigt, dass das kristalline Netzwerk über den Zyklus erhalten bleibt. Dies führt zur hohen Reversibilität und hohen Leistung selbst bei hohen C-Raten. Der Erhalt der Kristallstruktur wird durch elektrochemische Stabilisierung der kubischen Konformation von FeF3 ermöglicht, welche normalerweise erst bei hohen Temperaturen (400 °C) beobachtet wird und durch geringere Reorganisationen innerhalb des Kristallgerüsts erklärt werden kann. Ähnliche elektrochemische Eigenschaften können für KFeF3 und NH4FeF3 beobachtet werden, wobei erstmalig von Ammoniumionen als Ladungsträger in Alkaliionensystemen berichtet wird. / Metal fluoride compounds appear as very appealing candidates for the next generation of alkali-ion battery cathodes. However, many drawbacks prevent this family of compounds to be applicable to storage systems. Metal fluorides demonstrate a high insulating character, and the mechanisms involved during the discharge/charge processes atom engender large volume changes and a drastic reorganization of the material, which induces poor reversibility. In order to answer these problematics, the present thesis reports the elaboration of innovative synthesis routes for transition metal fluoride compounds and the application of these fluoride materials in alkali-ion battery systems. In a first part, MFx compounds (M = Co, Fe; x = 2 or 3) are studied. Those compounds exhibit high initial capacity but very poor cyclability and low C-rate capabilities. Ex-situ X-ray diffraction and transmission electron microscopy demonstrate that the low reversibility of the processes is mainly due to the conversion reaction occurring during their discharge/charge. In the second part, the syntheses of transition metal fluoride perovskites are reported, as well as their electrochemical properties. NaFeF3 demonstrates excellent performances and reversibility. The study of the mechanisms occurring during its charge/discharge processes towards different alkali systems by ex-situ and operando X-ray diffraction reveals that its crystalline framework is maintained along the cycles, resulting in high reversibility and excellent C-rate performance. This retention of the crystal framework is possible by an electrochemical stabilization of a cubic conformation of FeF3, which is usually only observable at high temperature (400 °C), and can be explained by lower reorganizations within the crystal framework. Similar electrochemical properties could be observed for KFeF3 and NH4FeF3, where ammonium ions are reported for the first time as a charge carrier in alkali-ion systems.
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Electron Transfer and Other Reactions Using Atomic Metal AnionsButson, Jeffery M. 04 February 2014 (has links)
The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-.
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Electron Transfer and Other Reactions Using Atomic Metal AnionsButson, Jeffery M. January 2014 (has links)
The atomic metal anions Rb-, Cs-, Cu-, Ag- and Fe- have been generated in the gas phase and reacted with various neutral reactants in a triple quadrupole mass spectrometer. The metal anions were formed via electrospray ionization of the metal-oxalate solutions and form in gas phase between the capillary and the first quadrupole. Neutral gas phase reactants investigated include NO, NO2, SO2, C6F5OH, C6F5NH2, C6F6, E-octafluoro-butene and 1,2,3/1,2,4/1,3,5 trifluoro-benzene. When possible, CBS-4M methods were used to suggest the lowest energy products based on relative energy. Observed reactions of atomic metal anions with the aforementioned neutral species include electron transfer and dissociative electron transfer to the neutral gas phase reactants. In addition, hydrogen abstraction and fluorine abstraction forming a neutral metal hydride or fluoride as well as the formation of multiply substituted metal-oxide/fluoride anions was also observed. Metal-complex anions observed from the gas phase reactions include CuF-,CuF2-,CuO-,CuO2-, FeO-, FeO2-, FeO3-, FeF-, FeF2-, FeF3-, CsF- and CsF2-.
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