Les éléments de terres rares (REEs) sont de plus en plus utilisés dans une multitude d’applications, notamment la fabrication d’aimants, de batteries rechargeables et les écrans de téléviseurs. Ils sont pour la plupart des métaux trivalents peu solubles dans les eaux naturelles. Comme pour les métaux divalents, le risque écologique des REEs est très probablement étroitement lié à leurs spéciations chimiques. Cependant, le comportement du samarium (Sm) dans les matrices environnementales est très peu connu et il n'existe actuellement aucune technique pour évaluer sa spéciation chimique. Dans cette optique, la technique d'échange d'ions (IET) sur la résine Dowex a été optimisée pour mesurer le samarium libre en solution. Les temps d'équilibre ont d'abord été déterminés pour des solutions tamponnées de samarium (Sm 6,7x10-8 M ; MES 1,0 mM M ; pH 6,0) en présence du nitrate de sodium (de 0,01M à 0,5 M). Pour ces diverses forces ioniques, l’équilibre thermodynamique n’est atteint que pour NaNO3 0,5M. Un autre mode d’utilisation de la résine (mode dynamique) a donc été développé pour tenir compte des conditions environnementales et évaluer efficacement le samarium libre. Les impacts des ligands organiques tels le NTA, l’EDTA, le citrate, l’acide malique et l’acide fulvique Suwannee River Standard I (SRFA) ont été étudiés par l’IET en mode dynamique. Une grande corrélation a été trouvée plus entre les taux d’accumulation de samarium sur la résine d’échange pour différents rapports NTA : Sm, EDTA : Sm, SRFA : Sm et le samarium libre. Par contre, aucune corrélation significative n’a été observée pour les ligands citrate et acide malique compte tenu des complexes qu’ils forment avec le samarium et qui s’adsorbent aussi sur la résine Dowex. Les concentrations Sm3+ mesurées par la technique IET ont été fortement corrélées avec celles prédites par le modèle WHAM 7.0 en utilisant la constante de stabilité obtenue par titration de SRFA par extinction de la fluorescence. Par ailleurs, la formation de colloïdes de samarium en fonction du pH influe grandement sur la détermination du samarium libre et doit être prise en compte dans la spéciation du samarium. L'IET assisté par des techniques auxiliaires comme le dosage par extinction de la fluorescence et le SP-ICPMS pourrait être une technique utile pour évaluer les concentrations de Sm biodisponible dans les eaux naturelles. / Samarium is present in several high technology products such as magnets, lasers, etc., however little is known about to what extent it can pollute environmental matrices. For divalent metals such as Cd, Cu and Ni, toxicity has often been closely correlated with the free ion concentration. Unfortunately, there are currently no techniques available for evaluating the speciation of samarium in environmental matrices. In this study, an economical and easy to use ion exchange technique (IET) using a resin has been studied for use in measuring free samarium. In order to optimize the IET for free samarium determinations, equilibrium times were first determined for pH buffered solutions of samarium (6.7x10 8 M Sm, 1.0 mM MES, pH 6.0) in the presence of different concentrations of sodium nitrate (NaNO3: 0.01 M to 0.5 M). Equilibrium was only attained for the highest concentration of NaNO3. Therefore, another technique using dynamic measurements on the Dowex resin was developed. Thus, the impacts of different organic ligands such as EDTA, citrate, malic acid and Suwannee River fulvic acid Standard I (SRFA) have been investigated using IET in dynamic mode. The calibration of the technique using different concentrations of NTA, EDTA, citrate, malic acid and fulvic acid (SRFA) allowed the determination of accumulation rates. Strong correlations were found between accumulation rates and the free samarium when using EDTA and NTA to control free samarium. The correlation was very low in case of citrate and malic acid suggesting that their complexes with samarium were adsorbed on the resin. Finally, fluorescence quenching titrations (FQT) and SP-ICPMS were used to determine samarium speciation. The free samarium determined by IET is strongly correlated to that calculated by WHAM 7.0 using the stability constant from FQT and that from Sonke (2006). However, the free Sm resulted from IEC-SP-ICPMS technique has been overestimated once compared to that found using VMinteQ or WHAM 7.0 models. The Sm particulates determined by SP-ICPMS have demonstrated that pH has a great influence on Sm exchange on resin and has to be considered while measuring free samarium. Thus, the IET should be associated to other techniques such as fluorescence quenching titration and SP-ICPMS for evaluating the bioavailable Sm concentrations in natural waters.

An J=1→J=1 atomic system in Samarium with incident laser resonant radiation has been investigated. A linearly polarized laser at 686nm excites atoms from the level 4ƒ[superscript]66s[superscript]2 [superscript]7F[subscript]1 to a excited level 4ƒ[superscript]66s6p [superscript]9F[subscript]1 via the process of optical pumping. When an external magnetic field is applied to the atom-laser interaction and the decay fluorescence collected, a level-crossing profile appears. Theoretical predictions of the level-crossing profile can be made using spherically irreducible tensors to describe the density matrix which take advantage of the symmetry of the atomic system. By comparing theory with experimental data, a discussion is made of the various parameters and external factors that can affect this system, which show that Doppler broadening is the major influence. An additional investigation is made into the evolution of the J=1→J=1 atomic system with increasing laser exposure. Comparisons of the experimental data with theoretical predictions are made by analyzing the FWHM of the overall level-crossing profile, the FWHM of the dip about B = 0 and the relative depth of the dip. By charting the progress of these parameters with increasing laser exposure, it can be seen that the theory and experimental data agree qualitatively. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320338 / Thesis (Ph.D.) -- University of Adelaide, School of Chemistry and Physics, 2008

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Le SmI₂ en tant que réactif de transfert monoélectronique a été largement utilisé en chimie organique depuis les premiers travaux de Kagan. Cependant, la quantité stœchiométrique ou en excès de SmI₂ et d'additifs toxique tels que HMPA sont utilisés normalement pour améliorer la réactivité. De plus, à cause de sa sensibilité à l'oxygène, le stockage de la solution de SmI₂ dans le THF est difficile. Récemment, nous avons développé une nouvelle méthode électrocatalytique basée sur la régénération électrochimique de Sm²⁺. Par rapport à la réactivité du SmI₂ classique, notre approche utilise une quantité catalytique de Sm. Premièrement, pour la réduction de nitroarènes, la réaction a sélectivement fourni les composés aromatiques azoïques et les anilines en fonction du solvant choisi. Notamment, c'est la première fois que la réaction Sm²⁺ se produit dans le méthanol dans le cas des anilines. Deuxièmement, dans le cas de la réduction des sulfoxydes par SmI₂, en général, l'HMPA était nécessaire comme additif. Dans notre procédé électrocatalytique, les sulfoxydes ont été transformés en sulfures avec une chimiosélectivité élevée et des excellents rendements toujours à température ambiante sans besoin ni de HMPA ni d’atmosphère protectrice. Enfin, les dérivés d'isoindolinone sont des séries de produits importants en chimie organique, la réduction des phtalimides est l'approche la plus pratique pour les obtenir. Avec les alcools, l'alcoxylation réductrice de phtalimides a eu lieu pour la première fois avec le Sm²⁺ électrocatalytique dans nos conditions. Et si on ajoute d'autres sources de protons, ce procédé a fourni les ω-hydroxylactames et isoindolinones correspondants avec des rendements élevés. / The SmI₂ as a single electron transfer reagent has been widely used in organic chemistry since the pioneering works by Kagan. However, the stoichiometric or excess amount of SmI₂ and harmful additives such as HMPA are used normally to enhance the reactivity, moreover, due to the oxygen sensitive, the storage of SmI₂ solution is difficult.Recently, we have developed a new electrocatalytic method based on the electrochemical regeneration of Sm²⁺. Compared to the classic SmI₂ reaction, our process occurred with a catalytic amount of Sm. In the reduction of nitroarenes, it selectively afforded the azo aromatic compounds and anilines depending on different solvents system. Notably, it’s the first time that the Sm²⁺ reaction occurred in the methanol. Normally, the HMPA was the additive in the reduction of sulfoxides by SmI₂. Under our electrocatalytic process, the sulfoxides were converted into sulfides in high chemoselectivity and yield at room temperature without HMPA and protecting atmosphere.The isoindolinone derivatives are series of important products in organic chemistry, the reduction of phthalimides is the most convenient approach to provide them. With alcohols, the unprecedented Sm²⁺ electrocatalyzed reductive alkoxylation of phthalimides was established. Moreover, adding other proton sources, this process afforded the corresponding ω-hydroxylactams and isoindolinones.

The goal of this thesis is to study the microstrucutre and texture of Yttrium-Nickel- Borocarbide and Samarium-Cobalt thin film heterostructures prepared by Pulsed Laser Deposition and to establish structure-property relations for these materials in order to improve their properties and design new structures. Coincidence site lattice epitaxy was explored in most of these heterostructures (substrate, buffer and film) and studied in detail for each case. Epitaxial thin films of the superconducting borocarbide compound YNi2B2C were grown on single crystal MgO (100) substrates without and with Y2O3 buffer layer using pulsed laser deposition (PLD). In both cases YNi2B2C grows with [001] normal to the substrate. However, the in-plane texture depends on the starting condition. For samples without buffer layer, oxygen from the substrate diffuses into the film and forms an Y2O3 reaction layer at the interface. As a consequence, a deficiency of Y is generated giving rise to the formation of secondary phases. On the other hand, using an artificial Y2O3 buffer layer secondary phases are suppressed. The texture of the Y2O3 layers determines the texture of the YNi2B2C film. The superconducting properties of the borocarbide films are discussed with respect to texture and phase purity. To prevent the formation of an impurity phase at the interface, it was the aim of this preliminary investigation to study YNi2B2C films deposited onto single crystal MgO (100) substrates with an Ir buffer layer. The Ir buffer layer shows a strong cube-on-cube texture onto MgO(100) and also prevents the formation of an Y2O3 interlayer. However, during deposition of YNi2B2C the buffer layer disappears by Ir diffusion into the borocarbide film. The YNi2B2C film exhibits a c-axis texture consisting of four components. As a consequence of these effects, the superconducting transition Tc90 equals up to 13K, but with a transition width of 4K. In the second part of this work, hard magnetic Sm-Co/Cr films were epitaxially grown on MgO(100) and (110) substrates. They were characterized by X-ray pole figure measurements and transmission electron microscopy. For films deposited on MgO(100) at 700ºC, orientations are found with the c-axis aligned in-plane and out-of-plane. By lowering the deposition temperature to 370ºC, the out-of-plane orientations disappeared. Further lowering to 350ºC leads to the formation of amorphous regions in the SmCo5 film. For films grown on MgO(110) the Cr buffer deposition temperature plays an important role. When deposited at 700°C Cr(211) and (100) growth is observed leading to two different types of SmCo5 in-plane orientations. By lowering the Cr-buffer deposition temperature to 300ºC only one buffer and one SmCo5 orientation exists: Cr(-211)[0-11] and SmCo5(10-10)[0001]. The exact orientation relationships between substrate, buffer and films are explained and their correlation with magnetic properties are discussed.

The goal of this thesis is to study the microstrucutre and texture of Yttrium-Nickel- Borocarbide and Samarium-Cobalt thin film heterostructures prepared by Pulsed Laser Deposition and to establish structure-property relations for these materials in order to improve their properties and design new structures. Coincidence site lattice epitaxy was explored in most of these heterostructures (substrate, buffer and film) and studied in detail for each case. Epitaxial thin films of the superconducting borocarbide compound YNi2B2C were grown on single crystal MgO (100) substrates without and with Y2O3 buffer layer using pulsed laser deposition (PLD). In both cases YNi2B2C grows with [001] normal to the substrate. However, the in-plane texture depends on the starting condition. For samples without buffer layer, oxygen from the substrate diffuses into the film and forms an Y2O3 reaction layer at the interface. As a consequence, a deficiency of Y is generated giving rise to the formation of secondary phases. On the other hand, using an artificial Y2O3 buffer layer secondary phases are suppressed. The texture of the Y2O3 layers determines the texture of the YNi2B2C film. The superconducting properties of the borocarbide films are discussed with respect to texture and phase purity. To prevent the formation of an impurity phase at the interface, it was the aim of this preliminary investigation to study YNi2B2C films deposited onto single crystal MgO (100) substrates with an Ir buffer layer. The Ir buffer layer shows a strong cube-on-cube texture onto MgO(100) and also prevents the formation of an Y2O3 interlayer. However, during deposition of YNi2B2C the buffer layer disappears by Ir diffusion into the borocarbide film. The YNi2B2C film exhibits a c-axis texture consisting of four components. As a consequence of these effects, the superconducting transition Tc90 equals up to 13K, but with a transition width of 4K. In the second part of this work, hard magnetic Sm-Co/Cr films were epitaxially grown on MgO(100) and (110) substrates. They were characterized by X-ray pole figure measurements and transmission electron microscopy. For films deposited on MgO(100) at 700ºC, orientations are found with the c-axis aligned in-plane and out-of-plane. By lowering the deposition temperature to 370ºC, the out-of-plane orientations disappeared. Further lowering to 350ºC leads to the formation of amorphous regions in the SmCo5 film. For films grown on MgO(110) the Cr buffer deposition temperature plays an important role. When deposited at 700°C Cr(211) and (100) growth is observed leading to two different types of SmCo5 in-plane orientations. By lowering the Cr-buffer deposition temperature to 300ºC only one buffer and one SmCo5 orientation exists: Cr(-211)[0-11] and SmCo5(10-10)[0001]. The exact orientation relationships between substrate, buffer and films are explained and their correlation with magnetic properties are discussed.

No description available.

Sharp leading edges required for hypersonic vehicles improve the maneuverability as well as reduce aerodynamic drag. However, due to the sharp design, increased surface temperatures require materials that can withstand these extreme conditions. Ultra-high temperature ceramics are a material group being considered for the leading-edge material, specifically ZrB₂/SiC (ZBS) which has a high thermal shock resistance, melting temperature, and thermal conductivity. Studies done by Tan et. al. has shown that adding samarium (Sm) as a dopant to ZBS has an emittance of 0.9 at 1600^oC and develop oxide scales that have excellent ablation performance. However, it remained unknown how the Sm doped oxide scale formed as well as how the emittance and ablation performance are affected by the microstructure. This study investigates the oxide scale development of 3 mol% doped Sm-ZBS billets as well as how differences in microstructure affect the emittance and ablation performance. Samples were prepared via chemical infiltration of samarium nitrate into spray-dried powders of 80 vol.% ZrB₂/20 vol.% SiC; powders were then pressed into billets and pressureless sintered. Samples cut and polished from these billets were then oxidized for 10, 60, or 300 s, respectively, using an oxyacetylene torch. X-ray diffraction was used to determine the sequence of oxidation of Sm-ZBS, beginning with the formation of ZrO₂ and Sm₂O₃. The final oxide scale was determined to be c₁-Sm_0.2Zr_0.8O_1.9, with a melting temperature exceeding 2500^oC. SEM and EDS were also used to investigate the microstructural formation that occurs from the bursting of convection cells. Samples with different microstructures revealed similar topographical microstructures post-ablation due to the sequence of the oxide formation. However, samples with rougher surfaces and higher porosities had a higher concentration of trapped glass in the cross-sectional oxide scale. It was also found that due to differences in heating the sample during emittance testing compared to ablation testing, the oxide developed was identical for all the samples. It was also found that variances in microstructure had no effect on the spectral emittance of Sm-ZBS at ultra-high temperatures. The fabrication of c₁-Sm_0.2Zr_0.8O_1.9 (SZO) as a bulk billet was also investigated to use as a thermal barrier coating (TBC) in replacement of Sm-ZBS.

<p>Hypersonic flight causes ultra-high surface temperatures which are most intense on sharp leading edges. One way of reducing the surface temperature is to apply a high emittance ceramic (HEC) on the leading edge, increasing the radiation component of heat transfer. An ideal HEC must have a high emittance, while also possessing a strong ablation resistance. From a scientific standpoint, it would be helpful if emittance could be tailored at different wavelengths. For example, materials with tailorable emittance could be used to improve the efficiency of engines, thermo-photo voltaic cells, and other applications. The approach used to create a ceramic with tailorable emittance was to use two different rare-earth elements, adding them to an ultra-high temperature ceramic (UHTC) in small quantities. The samarium element was added to increase the emittance of the UHTC over a large wavelength range (visible to near infrared wavelengths, consistent with the temperature range expected for hypersonic flight), and the erbium element was added to decrease the emittance at specific wavelength ranges. The goal of this study was to create an UHTC with tailorable emittance while maintaining the required ablation resistance. Therefore, ZBS billets with five different Sm to Er ratios and with a nominal total amount of 3 mol.% dopant incorporated were prepared by sintering in vacuum to 2000 °C. The ablation resistance was evaluated by using an oxyacetylene torch and observing at exposure times of 60 s and 300 s, whereas the emittance was evaluated at the Air Force Research Lab facilities via a laser heating testing. The results for the ablation testing showed that ZrB₂-SiC (ZBS) billets co-doped with Sm and Er formed a beneficial <i>c₁</i>-(Sm/Er)_0.2Zr_0.8O_1.9 oxide scale as the majority phase, which is more thermally stable than the <i>m</i>-ZrO₂ oxide scale typically formed in oxidized ZBS systems, resulting in a more adherent oxide scale to the unreacted material. The crystalline oxide scale and the amorphous phase were formed by a convection cell mechanism where the <i>c₁</i>-(Sm/Er)_0.2Zr_0.8O_1.9 crystalline islands precipitate, grow, and coalesce. Moreover, differences in surface temperatures between ZBS samples with different dopant ratios suggest differences in spectral absorptance/emittance between each of the five compositions evaluated. Despite that the emittance profiles with varying Sm:Er molar ratios were similar because <i>m</i>-ZrO₂ was formed as the major oxide phase, the emittance study showed that the erbium oxide influences the emittance profile, as can be noted by the maximum and minimum emittance peaks. Furthermore, results showed that the emittance varies as a function of dopant(s) molar ratios and temperature at shorter wavelength ranges. These changes in the emittance are caused by the different Sm and Er concentration on the surface. Future work should be focused on producing the beneficial <i>c₁</i>-(Sm/Er)_0.2Zr_0.9O_1.8phase directly from the manufacturing process, and therefore, maximize the effect of varying the Sm:Er molar ratios to tailor the emittance. Nonetheless, this study represents the first generation and reported emittance data of UHTC doping ZBS systems with both Sm and Er elements. </p>