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Bismuth ferrite (BiFeO₃) is a magneto-electric material which exhibits simultaneously ferroelectric and antiferromagnetic properties. We have used high-field electron spin resonance (ESR) as a local probe of the magnetic order in the magnetic range of 0-25 Tesla. With increasing magnetic field, an induced transition has been found between incommensurately modulated cycloidal antiferromagnetic and homogeneous magnetized spin state. The data reveal a number of interesting changes with increasing field, including: (i) significant changes in the ESR spectra; (ii) hysteresis in the spectra near the critical field. We have analyzed the changes in the ESR spectra by taking into account the magnetic anisotropy of the crystal and the homogeneous anti-symmetric Dzyaloshinsky-Moria exchange. We have also investigated phase induced transition by epitaxial constraint, and substituent and cystalline solution effects. Variously oriented BiFeO₃ epitaxial thin films have been deposited by pulsed laser deposition. Dramatically enhanced polarization has been found for (001)c, (110)c, and (111)c films, relative to that of BiFeO₃ crystals. The easy axis of spontaneous polarization lies close to (111)c for the variously oriented films. BiFeO₃ films grown on (111)c have a rhombohedral structure, identical to that of single crystals. Whereas, films grown on (110)c or (001)c are explained in terms of an epitaxially-induced transition between cycloidal and homogeneous spin states, via magneto-electric interactions. Finally, lanthanum modified BiFeO₃-xPbTiO₃ crystalline solutions have been found to have a large linear magneto-electric coefficient, ∝p. The value of ∝p (2.5x10⁻⁹ s/m or C/m²-Oe) is ∼10x greater than that of any other material (cg., Cr₂O₃ ∼2.5x10⁻¹⁰ s/m), and many order(s) of magnitude higher than unmodified BiFeO₃ crystals. The data also reveal: (i) that ∝p is due to a linear coupling between polarization and magnetization; and (ii) that ∝p is independent of dc magnetic bias and ac magnetic field. We show that the ME effect is significantly enhanced due to the breaking of the transitional invariance of a long-period spiral spin structure, via randomly distributed charged imperfections. / Master of Science

The work within this thesis focuses on the study of alloy formation using an active liquid metal electrode for fundamental analysis and for the extraction and separation of the lanthanides and actinides in a pyroprocessing system. The electrochemical work herein is performed in a molten salt of lithium chloride and potassium chloride at its eutectic point (LKE). This salt is a likely candidate for pyroprocessing due to its relatively low melting point and resistance to degradation on exposure to high levels of radiation. The active electrode material under examination is bismuth due to its propensity to alloy with other elements, its relatively low melting point, high density and non-toxicity. The alloying processes studied are those of bismuth-lithium and bismuth-cerium. Lithium is the limiting reduction reaction defining the negative solvent limit in LKE. As a result, understanding the processes that would occur if the electrode were to be pushed to such negative potentials is of significant importance. Cerium is a commonly-used surrogate for plutonium, which is an element of relatively high concentration in waste nuclear fuel and is of significant interest to the nuclear international community in waste fuel recycling. This work examines the alloying processes in terms of which intermetallic compounds are formed and by what mechanisms. This is achieved through the use of co-deposition on a macro tungsten rod, employing a number of electrochemical techniques to extract pertinent information. Lithium electrodeposition and alloying with bismuth (at the negative solvent limit) was found to form BiLim alloy with increasing m at more reducing potentials, followed by the deposition of near pure lithium. Mixing of these two then gave rise to specific bismuth-lithium alloys and the apparent ejection of a lithium metal fog into the molten salt, which resulted in the chemical reduction of Bi3+ and the loss of the bismuth electrodeposition current. When electrodepositing cerium on, and alloying with, bismuth, the formation of intermetallic compounds is governed by potential with a maximum BiCem stoichiometry of m = 1 with equimolar Bi3+ and Ce3+. However, at concentrations of cerium greater than that of bismuth, alloys much richer in cerium were also deposited at more negative potentials. There is evidence that deposited cerium may also escape into solution and chemically react with Bi3+. In-house microelectrodes are also developed and used for this purpose, both through co-deposition and direct alloy formation on a liquid bismuth thin-film microelectrode. This work demonstrates that these devices provide a richness of information due to their highly beneficial microelectrode properties. A means of controllably depositing bismuth from an aqueous plating bath, without dendrite formation, on both platinum and tungsten microelectrodes was devised. This was followed by electrodeposition of bismuth films on these devices in LKE. Platinum was found to be an active electrode material, alloying with bismuth, while tungsten remained inert. Nonetheless, both electrode types produced characteristic microelectrode behaviour, which was successfully used to determine the diffusion coefficient of bismuth in LKE. A comparison of bismuth-cerium and cerium alloying on a thin film liquid bismuth microelectrode found that the latter indicated the formation of BiCe2 where only BiCe had been seen previously during co-deposition in an equivalent salt. This is thought to be due to the thin film liquid bismuth microelectrode configuration with enhanced Ce3+ mass transport. This response was also used to calculate the diffusion coefficient of cerium inside the bismuth film, which was found to be slightly slower than for Ce3+ in LKE.

O objetivo deste trabalho foi desenvolver e caracterizar um cimento endodôntico experimental a base de resina epóxica com a adição de diferentes proporções de três sais de bismuto, seguindo os requisitos das normas ISO 6876 e ISO 4049 em busca da composição que atendesse estas normas. Para isto, foram formulados dezoito grupos com resina epóxica e adição de 20%; 40%; 60%; 80%; 100% e 120% em massa de três diferentes sais de bismuto. Foram realizados ensaios de escoamento, tempo de trabalho, tempo de presa, espessura de película, alteração dimensional, sorção e solubilidade, radiopacidade e citotoxicidade. Os resultados foram comparados com requisitos das normas ISO 6876 e 4049 e submetidos a ANOVA de duas vias (tipo de carga e concentração) e teste de Tukey com nível de significância de 5%. Os cimentos com subnitrato e subcarbonato de bismuto demonstram-se promissores, com especial destaque às formulações contendo subnitrato de bismuto por apresentarem resultados superiores. A adição de carga a partir de 80% conferiu radiopacidade satisfatória para os cimentos com subnitrato e subcarbonato de bismuto. Para os cimentos com subsalicilato de bismuto a única concentração que atendeu à norma foi de 120%. No ensaio de citotoxicidade nenhuma das formulações apresentou diferença estatística significativa quando comparado ao controle. Conclui-se que o subnitrato de bismuto e subcarbonato de bismuto apresentam características para utilização como carga e radiopacificante em cimentos endodônticos a base de resina epóxica. / The aim of this study was the development and evaluating of an experimental endodontic sealer epoxy based after addition of three different bismuth salts, according to the requirements of ISO 6876 and 4049 searching for the composition with better performance. Eighteen groups were formulated with the inclusion of 20%, 40%, 60%, 80%, 100% and 120% of three different bismuth salts, by weight, on epoxy resin. Then, flow tests, working time, setting time, film thickness, dimensional change, sorption and solubility, radiopacity and cytotoxicity were performed. Data were analyzed by two-way ANOVA (type of filler and concentration) and Tukey at a level of significance of 5%. The formulations with bismuth subsalicylate did not show suitable properties. However, cements with bismuth subnitrate and subcarbonate shown to be promising, particularly with regard to formulations containing bismuth subnitrate, wich presented superior results. The addition of 80% salt generated satisfactory radiopacity to subcarbonate and bismuth subnitrate sealers, bismuth subsalicylate had only reached satisfatory radiopacity at 120%. In the cytotoxicity assay none of the formulations showed statistical significance when compared to control. It is concluded that the formulations containing bismuth subnitrate and bismuth subcarbonate have potential use as filler in endodontic sealers.

O objetivo deste trabalho foi desenvolver e caracterizar um cimento endodôntico experimental a base de resina epóxica com a adição de diferentes proporções de três sais de bismuto, seguindo os requisitos das normas ISO 6876 e ISO 4049 em busca da composição que atendesse estas normas. Para isto, foram formulados dezoito grupos com resina epóxica e adição de 20%; 40%; 60%; 80%; 100% e 120% em massa de três diferentes sais de bismuto. Foram realizados ensaios de escoamento, tempo de trabalho, tempo de presa, espessura de película, alteração dimensional, sorção e solubilidade, radiopacidade e citotoxicidade. Os resultados foram comparados com requisitos das normas ISO 6876 e 4049 e submetidos a ANOVA de duas vias (tipo de carga e concentração) e teste de Tukey com nível de significância de 5%. Os cimentos com subnitrato e subcarbonato de bismuto demonstram-se promissores, com especial destaque às formulações contendo subnitrato de bismuto por apresentarem resultados superiores. A adição de carga a partir de 80% conferiu radiopacidade satisfatória para os cimentos com subnitrato e subcarbonato de bismuto. Para os cimentos com subsalicilato de bismuto a única concentração que atendeu à norma foi de 120%. No ensaio de citotoxicidade nenhuma das formulações apresentou diferença estatística significativa quando comparado ao controle. Conclui-se que o subnitrato de bismuto e subcarbonato de bismuto apresentam características para utilização como carga e radiopacificante em cimentos endodônticos a base de resina epóxica. / The aim of this study was the development and evaluating of an experimental endodontic sealer epoxy based after addition of three different bismuth salts, according to the requirements of ISO 6876 and 4049 searching for the composition with better performance. Eighteen groups were formulated with the inclusion of 20%, 40%, 60%, 80%, 100% and 120% of three different bismuth salts, by weight, on epoxy resin. Then, flow tests, working time, setting time, film thickness, dimensional change, sorption and solubility, radiopacity and cytotoxicity were performed. Data were analyzed by two-way ANOVA (type of filler and concentration) and Tukey at a level of significance of 5%. The formulations with bismuth subsalicylate did not show suitable properties. However, cements with bismuth subnitrate and subcarbonate shown to be promising, particularly with regard to formulations containing bismuth subnitrate, wich presented superior results. The addition of 80% salt generated satisfactory radiopacity to subcarbonate and bismuth subnitrate sealers, bismuth subsalicylate had only reached satisfatory radiopacity at 120%. In the cytotoxicity assay none of the formulations showed statistical significance when compared to control. It is concluded that the formulations containing bismuth subnitrate and bismuth subcarbonate have potential use as filler in endodontic sealers.

O objetivo deste trabalho foi desenvolver e caracterizar um cimento endodôntico experimental a base de resina epóxica com a adição de diferentes proporções de três sais de bismuto, seguindo os requisitos das normas ISO 6876 e ISO 4049 em busca da composição que atendesse estas normas. Para isto, foram formulados dezoito grupos com resina epóxica e adição de 20%; 40%; 60%; 80%; 100% e 120% em massa de três diferentes sais de bismuto. Foram realizados ensaios de escoamento, tempo de trabalho, tempo de presa, espessura de película, alteração dimensional, sorção e solubilidade, radiopacidade e citotoxicidade. Os resultados foram comparados com requisitos das normas ISO 6876 e 4049 e submetidos a ANOVA de duas vias (tipo de carga e concentração) e teste de Tukey com nível de significância de 5%. Os cimentos com subnitrato e subcarbonato de bismuto demonstram-se promissores, com especial destaque às formulações contendo subnitrato de bismuto por apresentarem resultados superiores. A adição de carga a partir de 80% conferiu radiopacidade satisfatória para os cimentos com subnitrato e subcarbonato de bismuto. Para os cimentos com subsalicilato de bismuto a única concentração que atendeu à norma foi de 120%. No ensaio de citotoxicidade nenhuma das formulações apresentou diferença estatística significativa quando comparado ao controle. Conclui-se que o subnitrato de bismuto e subcarbonato de bismuto apresentam características para utilização como carga e radiopacificante em cimentos endodônticos a base de resina epóxica. / The aim of this study was the development and evaluating of an experimental endodontic sealer epoxy based after addition of three different bismuth salts, according to the requirements of ISO 6876 and 4049 searching for the composition with better performance. Eighteen groups were formulated with the inclusion of 20%, 40%, 60%, 80%, 100% and 120% of three different bismuth salts, by weight, on epoxy resin. Then, flow tests, working time, setting time, film thickness, dimensional change, sorption and solubility, radiopacity and cytotoxicity were performed. Data were analyzed by two-way ANOVA (type of filler and concentration) and Tukey at a level of significance of 5%. The formulations with bismuth subsalicylate did not show suitable properties. However, cements with bismuth subnitrate and subcarbonate shown to be promising, particularly with regard to formulations containing bismuth subnitrate, wich presented superior results. The addition of 80% salt generated satisfactory radiopacity to subcarbonate and bismuth subnitrate sealers, bismuth subsalicylate had only reached satisfatory radiopacity at 120%. In the cytotoxicity assay none of the formulations showed statistical significance when compared to control. It is concluded that the formulations containing bismuth subnitrate and bismuth subcarbonate have potential use as filler in endodontic sealers.

L'objectif de ce travail est d'améliorer les performances photocatalytiques de deux oxydes mixtes de bismuth, Bi2WO6 et BiOBr, présentant une activité sous lumière visible. Leurs activités photocatalytiques sont en effet majoritairement limitées par un taux de recombinaison des charges photoinduites élevé. Deux stratégies différentes ont été respectivement appliquées pour chaque matériau. La première consiste à former une hétérostructure entre Bi2WO6 et un métal noble, le platine, pour assurer une séparation efficace des charges. La seconde consiste à réduire la taille des particules de BiOBr afin d'augmenter la surface spécifique et de diminuer le parcours moyen des charges jusqu'à la surface du photocatalyseur. Les synthèses ont été réalisées par chimie douce. La répartition et la quantité de platine déposé sur Bi2WO6 a ainsi pu être modulée et des particules de BiOBr sous forme de microfleurs ou de plaquettes de différentes tailles ont été obtenues. La dégradation de la rhodamine B en solution sous irradiation bleue a permis d'évaluer les propriétés photocatalytiques des matériaux. La dégradation de molécules non photosensibles a également été réalisée afin de confirmer l'activité photocatalytique observée. Dans le but d'évaluer la potentialité de Bi2WO6 et BiOBr pour la purification de l'air intérieur, des tests de dégradation photocatalytique de polluants modèles gazeux ont été effectués. L'ensemble de ces tests ont mis en évidence les relations entre les paramètres physico-chimiques des matériaux et leurs performances photocatalytiques et ont souligné les potentialités et les limitations de Bi2WO6 et BiOBr pour la dépollution de l'air et de l'eau. / The aim of this work is to improve photocatalytic performance of two mixed bismuth oxides, Bi2WO6 and BiOBr, which have an activity within visible range of the electromagnetic spectrum. Two different strategies have been developed for each material. First one consists in designing a heterostructure between Bi2WO6 and a noble metal, platinum, which ensures an efficient charge separation at the interface. Second one aims at lowering BiOBr particle’s size in order to boost specific surface and shrink mean free path of charges to the surface of the photocatalyst. Syntheses of the materials were carried out using soft chemistry method. Platinum particle distribution and quantity on Bi2WO6 were thus successfully tuned and BiOBr microspheres or plates with different size were obtained. Photocatalytic properties of our materials were characterized by rhodamine B degradation in solution under blue light (λ = 445 nm). Degradation test of non-photosensitive compounds were also performed to show their photocatalytic activity. In order to evaluate Bi2WO6 and BiOBr potential in purifying indoor air photocatalytic degradation tests of model gaseous pollutant were performed. All these photocatalytic tests highlight the relationship between physicochemical and photocatalytic properties of the materials. They also enable us to determine the potentials and limitations of Bi2WO6 and BiOBr as photocatalysts for water and air depollution.

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published_or_final_version / Physics / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy