Étude des propriétés optiques et électriques dans les verres P₂O₅-Na₂O-Nb₂O₅ en vue de leur intégration dans des systèmes de détection de gaz à haute température

Authors: Landry, Annie-Kim
Advisor: Messaddeq, Younès
Abstract: The incorporation of niobium oxide, a mixed valency transition metal, in phosphate glasses would allow their integration in high temperature gas detection systems because they have optical and electrical properties that can be modulated according to the temperature and the atmosphere. In this study, the glasses (60-x)P₂O₅-xNa₂O-40Nb₂O₅ where x = 23, 27, 30 and 33 mol% were studied to evaluate the influence of the composition and the temperature on the oxidation state of niobium. In the oxide form, niobium is generally found in an oxidation state Nb(V) of composition Nb₂O₅, a colorless compound. When the niobium oxide is reduced, it is found in NbO2 composition with Nb(IV) oxidation state, which exhibits a dark-blue coloration. The glasses were heat-treated in air and hydrogenated atmosphere (90Ar/10H₂) between 450 and 630 °C. The transmittance properties were measured by UV-visible spectrophotometry resulting in a broad absorption band in the visible range up to the near-infrared following reductive thermal treatments. Electron paramagnetic resonance analysis revealed the presence of Nb⁴⁺ species responsible for the dark-blue coloration of glasses. Raman analyzes show that niobium is found in octahedral sites NbO₆ for all the compositions and a decrease in Na⁺ ions makes it possible to increase the number of bridging oxygens and thus favors the reduction of niobium. In addition, the glasses have a mixed electrical ion-electron conductivity between 10⁻¹⁰ and 10⁻³ S·cm⁻¹ over a temperature range between 25 and 575 °C. The ionic conductivity is due to the mobility of the Na⁺ ions in the vitreous lattice and is more important when the concentration of this charge carrier increases. Electronic conductivity is due to the presence of Nb⁵⁺ and Nb⁴⁺ species. The dark-blue coloration of the glasses and the electronic conductivity can be explained by interatomic charge transfer phenomenons, respectively know as intervalence charge transfer and the small polaron hopping. Moreover, XRD, DSC, density, refractive index and TGA analyzes were also performed on theses glasses.
Document Type: Mémoire de maîtrise
Issue Date: 2017
Open Access Date: 24 April 2018
Permalink: http://hdl.handle.net/20.500.11794/28147
Grantor: Université Laval
Collection:Thèses et mémoires

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