Made available in DSpace on 2014-10-09T12:34:31Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:26Z (GMT). No. of bitstreams: 0 / Neste trabalho foram estudadas ligas La0,7-xPrxMg0,3Al0,3Mn0,4Co0,5Ni3,8 (x= 0 a 0,7) no estado bruto de fusão, para utilização em eletrodos negativos de baterias de níquel-hidreto metálico (Ni-HM). A caracterização das ligas foi realizada através das seguintes técnicas: microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva (EDS) e difração de raios X. Foi também determinada capacidade de absorção de hidrogênio destas ligas. A hidrogenação do material foi realizada em dois processos sendo: o primeiro denominado de baixa pressão (0,2 MPa de hidrogênio e temperatura de 500ºC) e o segundo de alta pressão (1 MPa e de hidrogênio e temperatura de 25ºC). Foi observado que com o aumento do teor de Pr a capacidade de absorção de hidrogênio diminui. Para o estudo da capacidade de descarga das baterias foi utilizado um analisador digital de quatro canais e observou-se um decréscimo na capacidade de descarga das baterias com adição de praseodímio para as composições La0,7-xPrxMg0,3Al0,3Mn0,4Co0,5Ni3,8 (x= 0 a 0,3). A maior capacidade de descarga (386 mAhg-1) e estabilidade cíclica foi obtida para a liga La0,2Pr0,5Mg0,3Al0,3Mn0,4Co0,5Ni3,8. Esta capacidade obtida pode estar relacionada com a maior proporção da fase LaMg2Ni9 encontrada na liga com adição de 0,5 % at. de Pr. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2016-12-21T16:28:43Z No. of bitstreams: 0 / Made available in DSpace on 2016-12-21T16:28:43Z (GMT). No. of bitstreams: 0 / O titanato de estrôncio (SrTiO3) possui estrutura cristalina do tipo perovsquita. Materiais com este tipo de estrutura são utilizados para diversas aplicações, tais como, sensores, atuadores, em células a combustível de óxido sólido, entre outros. Devido as suas interessantes propriedades físicas, o SrTiO3 vem sendo intensamente estudado, em especial com a introdução de dopantes. Portanto, neste trabalho foi investigada a influência de diferentes teores de Ca (1; 2,5 e 5% mol) e Pr (0,025; 0,050; 0,075 e 1% mol) na microestrutura e propriedades elétricas e dielétricas do SrTiO3, assim como o material sem aditivos (puro). Os resultados mostram que após a sinterização do SrTiO3 puro, a microestrutura consiste de grãos poligonais com tamanho médio micrométrico, além de texturas lisas e rugosas. A condutividade elétrica das amostras sintetizadas sinterizadas a 1450 e 1500ºC é máxima para 2 horas de patamar. Apenas as amostras de SrTiO3 contendo 1% em mol de Ca apresentam fase única. O tamanho médio de grãos das amostras contendo 1% em mol de Ca é 10,65 ± 0,28 µm e para teores acima deste valor ocorre crescimento significativo dos grãos. As medidas de condutividade elétrica mostraram que as amostras contendo a adição de 1% em mol de Ca possuem maior condutividade dos grãos em relação ao material puro. Para as amostras contendo teores de até 0,075% mol de Pr, pode-se observar alguns grãos lisos e outros rugosos e não há variação considerável do tamanho médio de grãos. As amostras contendo menor teor de Pr (0,025% mol) apresentam maior condutividade dos grãos e contornos de grãos. As amostras de SrTiO3 sintetizado sinterizadas a 1450ºC/10 h apresentaram permissividade elétrica colossal em temperatura ambiente em altas frequências. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

科学研究費補助金 研究種目:基盤研究(C)(2) 課題番号:07650870 研究代表者:藤澤 敏治 研究期間:1995-1996年度

科学研究費補助金 研究種目:基盤研究(C)(2) 課題番号:09650806 研究代表者:藤澤 敏治 研究期間:1997-1998年度

Ce travail est relatif à la synthèse et à la caractérisation d’oxydes mixtes Pr1-zCezO2-y et Pr1-xZrxO2-y. Différentes compositions chimiques associées à une valence mixte Pr4+/Pr3+ concomitant à un taux précis de lacunes d’oxygènes ont été isolées tant pour les composés à l’état oxydé que pour ces derniers réduits sous Ar/H2. A l’état réduit, différentes surstructures de la maille fluorine ont été caractérisées par diffraction des RX et de neutrons. Sur la base de mesures magnétiques, d’analyses par spectroscopie d’absorption X (XANES-EXAFS) aux seuils K du Zr et LIII du Ce/Pr et d’analyses thermogravimétriques et/ou TPR (Temperature Programmed Reduction), les évolutions des taux de Pr4+/Pr3+ dans cette série ont été déterminées. Enfin, des mesures in-situ sous atmosphère réductrice par diffraction de neutrons et EELS (Electron Energy Loss Spectroscopy) ont été réalisées dans l’objectif de corréler compositions chimiques- édifices structuraux et propriétés de réductibilité. / This work deals with the synthesis and the characterization of Pr1-zCezO2-y and Pr1-xZrxO2-y oxides. Various chemical compositions associated with mixed valence state Pr4+/Pr3+ concomitant to precise oxygen vacancies rate were isolated for compounds in both oxidized and reduced compounds. In the reduced state, different superstructures of the fluorine network were characterized by X-ray and neutrons diffraction. On the basis of magnetic measurements, X-ray absorption spectroscopy (XANES-EXAFS) at Zr K-edge and Pr and Ce LII/III-edges and the thermogravimetric analyses and\or TPR (Temperature Programmed Reduction), evolutions of Pr4+/Pr3+ rates in this series were estimated. Finally, in-situ measurements under reducing atmosphere by neutrons diffraction and EELS (Electron Energy Loss Spectroscopy) were realized to correlate chemical compositions- structural features and reducibility properties.

Les micro-résonateurs optiques comptent parmi les dispositifs les plus importants en photonique. Les résonateurs WGM sont assez particuliers. Il s'agit de composant présentant une symétrie circulaire comme c'est le cas des sphères, des anneaux, des disques et des tores. Les résonateurs WGM présentent un facteur de qualité exceptionnel et un volume modal très faible. Ces appareils peuvent être utilisés dans plusieurs domaines, notamment la télédétection, le filtrage optique et l'optique non linéaire. D'autres applications sont possibles en biologie, médecine, spectroscopie moléculaire, surveillance environnementale, astronomie et astrophysique grâce à l'exploitation du rayonnement moyen infrarouge. Les micro-résonateurs optiques comportent un grand nombre de transitions vibrationnelles qui agissent comme des «empreintes» pour de nombreuses molécules organiques permettant le développement d'applications spectroscopiques innovantes et de nouveaux capteurs. Il convient de noter que l'atmosphère de la terre est transparente au niveau des deux fenêtres de transmission atmosphérique. La première est comprise entre 3 et 5 μm et la seconde entre 8 et 13 μm, ce qui rend possible des applications telles que la détection d'explosifs à distance ainsi que le brouillage de communication confidentielles. La large fenêtre de transparence en verres de chalcogénures dans le domaine spectral infrarouge rend envisageable le développement de nombreuses applications. Les verres de chalcogénure sont caractérisés par une bonne résistance mécanique et une durabilité chimique suffisante dans l'eau et l'atmosphère. Par ailleurs, l'indice de réfraction élevé, le rendement quantique élevé, l'énergie de phonon faible et la solubilité importante des terres rares permettent des émissions dans le domaine spectral du moyen IR. Dans cette thèse, la conception de dispositifs innovants en chalcogénure pour des applications utilisant le moyen infrarouge est étudiée en utilisant un code d'ordinateur personnel formé de façon aléatoire. Les appareils reposent sur des trois types de micro-résonateurs : les microsphères, les micro-disques et les microbulles. Les résonateurs WGM sont efficacement excités à l'aide de fibres nervurées et de guides d'ondes optiques de forme conique. Le nouveau procédé de conception est développé en utilisant la méthode d'optimisation par essaims particulaires (PSO). Elle permet de maximiser le gain d'un amplificateur reposant sur une microsphère d'émission laser dopée à l'erbium à 4,5 μm. Une technique innovante permettant de caractériser les propriétés spectroscopiques de la terre rare intégrant la recherche électromagnétique en mode WGM grâce à l'algorithme PSO a été développée. Les valeurs récupérées sont entachées d’une erreur inférieure à celle prévue par les instruments de mesure ayant un coût élevé. Des applications intéressantes peuvent être obtenues en excitant le micro-résonateur avec une fibre conique présentant deux LPG identiques sur les côtés. En effet, les FLP peuvent sélectionner le couplage de modes de fibre avec le résonateur WGM. En utilisant différentes paires de FLP identiques, opérant dans différentes bandes de longueurs d'onde, il est possible de coupler de façon sélective différents résonateurs à l'aide de la même fibre optique. Un code informatique aléatoire a été développé et validé. Il a démontré la faisabilité d'un capteur de microbulles de glucose. Un microdisque en terre rare dopé est étudié pour obtenir une source de lumière compacte et économique dans l'infrarouge moyen. Un code informatique est développé afin de simuler un micro-disque de terre rare dopé et associé à deux guides d'ondes nervurés, un pour le signal et l'autre pour la pompe. Le modèle est validé à l'aide d'un micro-disque dopée à l'erbium émettant à 4,5 μm. Ce dispositif très prometteur pour des applications dans le moyen infrarouge est obtenu en utilisant un micro-disque de praséodyme dopé émettant à 4,7 μm. / Optical micro-resonators represent one of the most important devices in photonics. A special kind is constituted by the WGM resonators, i.e. devices with circular symmetry such as spheres, rings, disks and toroids. They are characterized by very small dimensions, exceptionally quality factor and very low modal volume becoming a valuable alternative to the traditional optical micro-resonators, such as Fabry-Pérot cavities. These devices allow applications in several fields, such as sensing, optical filtering and nonlinear optics. In particular, different applications in biology and medicine, molecular spectroscopy, environmental monitoring, astronomy and astrophysics are feasible in Mid-Infrared wavelength range. For example, it includes a lot of strong vibrational transitions that act as “fingerprints” of many bio-molecules and organic species allowing the develop of innovative spectroscopic applications and novel sensors. In addition, the earth's atmosphere is transparent in two atmospheric transmission windows at 3–5 μm and 8–13 μm and then applications such as remote explosive detection, e.g. in airports and for border control, and covert communication systems are feasible. The wide transparency window of chalcogenide glasses in Mid-Infrared makes possible the development of several devices. Chalcogenide glasses are characterized by good mechanical strength and chemically durability in water and atmosphere. Furthermore, the high refractive index, high quantum efficiency, the low phonon energy and high rare-earth solubility enables the emissions at long wavelengths.In this thesis, the design of innovative chalcogenide devices for applications in Mid-Infrared is investigated using an ad-hoc home-made computer code. The devices are based on three kinds of micro-resonators: microspheres, micro-disks and microbubbles. The WGM resonators are efficiently excited by using tapered fiber and ridge waveguides. A novel design procedure is developed using the particle swarm optimization approach (PSO). It allows to maximize the gain of an amplifier based on an erbium-doped microsphere lasing at 2.7 μm.An innovative technique in order to characterize the spectroscopic properties of rare-earth is developed integrating the WGM electromagnetic investigation with PSO algorithm. The method is based on two subsequent steps: in the first one, the geometrical parameters are recovered, in the second one, the spectroscopic parameters. The recovered values are affected by an error less than that provided by high-cost measurement instruments. Furthermore, the procedure is very versatile and could be applied to develop innovative sensing systems.Interesting applications could be obtained exciting the micro-resonator by a tapered fiber with two identical LPGs on the sides. Indeed the LPGs can select the fiber modes coupling with the WGM resonator. Using different pairs of identical LPGs operating in different wavelength bands, it is possible to selective couple different micro-resonators by using the same optical fiber. An ad-hoc computer code is developed and validated and it demonstrated the feasibility of a microbubble glucose sensor.In order to obtain a compact and cost-saving light source in Mid-Infrared, rare-earth doped micro-disk are investigated. A computer code is developed in order to simulate a rare-earth doped micro-disk coupled to two ridge waveguide, one at signal wavelength and the other one at pump wavelength. The model is validated using an erbium-doped micro-disk emitting at 4.5 μm. A very promising device for application in Mid-Infrared is obtained using a praseodymium-doped micro-disk emitting at 4.7 μm.

No description available.

In the presented thesis thin praseodymia films on non-passivated and passivated Si(111) substrates were investigated. The first part deals with PDA of praseodymia films with fluorite structure under UHV conditions in the temperature region from RT to 600°C. Here, a sophisticated model of the annealing process of praseodymia films is established. This is done by detailed analysis of XRD measurements using the kinematic diffraction theory in combination with the analysis of GIXRD, XRR and SPA-LEED measurements. It is shown that the untreated films, which are oxidized in 1 atm oxygen to obtain fluorite structure, do not exhibit pure PrO2 stoichiometry as it was assumed before. Instead, they decompose into two laterally coexisting species exhibiting a PrO2 and a Pr6O11. oxide phase, respectively. These species are laterally pinned to the lattice parameter of bulk Pr6O11. Homogeneous oxide films with Pr6O11 phase can be observed after annealing at 100°C and 150°C. Here, lateral strain caused by the pinning of the species is minimized and an increase of the crystallite sizes is determined. If higher annealing temperatures are applied, the film decomposes again into two coexisting species. Finally, after annealing at 300°C, a mixed crystalline film with both Pr2O3 and Pr2O3+Delta oxide phases is formed, where Delta denotes a considerable excess of oxygen within the sesquioxide phase. Again the lateral strain increases due to the tendency of praseodymia phases to increase their lattice parameters during oxygen loss combined with the lateral pinning. This is accompanied by a decrease of crystallite sizes, which are afterwards comparable to those of the untreated films. Further annealing at temperatures above 300°C does not significantly change the structure of the oxide film. However, the increase of the amorphous Pr-silicate interface between Si substrate and oxide at the expense of the crystalline oxide can be observed after annealing at higher temperatures. Furthermore, an increased mosaic spread of the crystallites occurs, which reduces the lateral strain caused by the oxygen loss. Nevertheless, the crystalline structure is stable against further annealing up to temperatures of 600°C. Transportation of the sample under ambient conditions after annealing at 200°C and 300°C leads to the formation of an additional crystalline structure at the surface which cannot be allocated to any praseodymia phase and may be explained by the contamination of the topmost crystalline layers with Pr-hydroxides. The results obtained from praseodymia films annealed in 1 atm nitrogen show that these films are good candidates to form homogeneous oxide films with pure cub-Pr2O3 structure by subsequent annealing in UHV. Here, a single oxide species is already observed after annealing at 300°C by SPA-LEED measurements which is in contrast to praseodymia films with fluorite structure where higher annealing temperatures (600°C) are necessary. In this case, negative effects like interface growth or increased defect density (mosaics, grain boundaries) can be minimized. Investigations on oxygen plasma-treated praseodymia films to obtain pure PrO2 stoichiometry are presented in the second part. Oxygen plasma-treated samples are compared with samples oxidized in 1 atm oxygen regarding the structure of the crystalline film. For this purpose, XRR and XRD measurements are performed to get structural information of the oxide film, which can be used to identify the corresponding oxide phases. Here, significantly smaller lattice constants of the crystalline oxide species can be observed after plasma treatment, which points to the incorporation of additional oxygen atoms. This verifies former studies, where a higher oxidation state of the oxide film was found by XPS measurements and it shows that plasma-treated films exhibit a higher oxidation state than films oxidized in 1 atm oxygen due to the availability of reactive atomic oxygen in the plasma. Furthermore, the Pr-silicate interface between crystalline film and Si substrate is not increased during plasma treatment. In the last part of the presented thesis, first results from the epitaxy of praseodymia films on Cl-passivated Si substrates are shown. The aim is to suppress the Pr-silicate formation during the growth process. Thus, praseodymia films are grown on passivated and non-passivated substrates to compare the crystallinity of both samples using XSW and LEED measurements. The structure of the oxide films on Cl-passivated Si is determined afterwards by XRR. It is shown that crystalline films with cub-Pr2O3 structure and several nanometer thickness can be successfully grown on Cl-passivated substrates. Here, the Pr-silicate interface layer are restricted to a single mono-layer. In contrast, the films grown on non-passivated substrates are completely amorphous containing Pr-silicates and Pr-silicides.

Ο αρχικός στόχος της εργασίας μας ήταν η παρασκευή ετερομεταλλικών συμπλόκων Cd(II)/Ln(III) [Ln=λανθανίδιο] για να μελετηθούν οι φωτοφυσικές τους ιδιότητες. Διάφορα συστήματα αντιδράσεων Cd(II)/Ln(III)/οργανικός υποκαταστάτης έδωσαν μόνο ομομεταλλικές ενώσεις Cd(II) ή Pr(III).Χρησιμοποιώντας διάφορα αντιδρώντα Cd(II) και Pr(NO3)3∙6H2O, παρασκευάστηκαν τα ακόλουθα σύμπλοκα: [CdCl2(PhpaoH)]n (1), [Cd(O2CMe)2(NH2paoH)2] (2), [Cd(ΝΟ3)2(tzpy)2] (3), [CdI2(tzpy)2] (4), [Pr(ΝΟ3)3(tzpy)2]∙tzpy (5∙tzpy), [Cd4(NO3)4{(py)2C(H)(O)}4] (6) [(py)2C(H)(O)- είναι το ανιόν της δι-2-πυρίδυλο μεθανόλης που σχηματίζεται in-situ από τη μεταλλο-υποβοηθούμενη αναγωγή της (py)2CO με MeOH κάτω από σολβοθερμικές συνθήκες], [Cd(ΝΟ3)2(aphz)2] (7), [CdI2(aphz)2]n (8), [Pr(ΝΟ3)3(aphz)2] (9), [CdI2(bphz)2] (10), [Cd(NO3)2(bzdhz)2] (11). Η αντίδραση του Pr(NO3)3∙6H2O με δύο ισοδύναμα bzdhz σε H2O/Me2CO οδήγησε στην απομόνωση της Ν,Ν’-δι-ισοπροπυλιδενε-βενζίλιο διυδραζόνη (L’). Οι δομές των ενώσεων 1-11 προσδιορίσθηκαν με κρυσταλλογραφία ακτίνων Χ μονοκρυστάλλου. Όλα τα σύμπλοκα χαρακτηρίσθηκαν με φασματοσκοπία IR, και επιλεγμένες ενώσεις με τεχνικές RAMAN και 1H NMR. Τα φασματοσκοπικά δεδομένα εξετάζονται σε σχέση με τις γνωστές δομές των ενώσεων και των τρόπων ένταξης των υποκαταστατών.Πιστεύουμε ότι τα αποτελέσματα που παρουσιάζονται στη Διπλωματική Εργασία συνιστούν συνεισφορά στη χημεία του καδμίου(ΙΙ) και του πρασεοδυμίου(ΙΙΙ), καθώς επίσης και στη χημεία ένταξης των οργανικών υποκαταστατών. / The original goal of this work was to prepare heterometallic Cd(II)/Ln(III) complexes (Ln=lanthanide) in order to study their photophysical properties. A variety of CdII/PrIII/organic ligand reaction schemes led to only homometallic Cd(II) or Pr(III) complexes.Employing various Cd(II) sources and Pr(NO3)3∙6H2O, as starting materials, the following complexes have been prepared: [CdCl2(PhpaoH)]n (1), [Cd(O2CMe)2(NH2paoH)2] (2), [Cd(ΝΟ3)2(tzpy)2] (3), [CdI2(tzpy)2] (4), [Pr(ΝΟ3)3(tzpy)2]∙tzpy (5∙tzpy), [Cd4(NO3)4{(py)2C(H)(O)}4] (6) [(py)2C(H)(O)- is the anion of di-2-pyridyl methanol formed in-situ by the metal ion-assisted reduction of (py)2CO in MeOH under solvothermal conditions], [Cd(ΝΟ3)2(aphz)2] (7), [CdI2(aphz)2]n (8), [Pr(ΝΟ3)3(aphz)2] (9), [CdI2(bphz)2] (10), [Cd(NO3)2(bzdhz)2] (11). The reaction of Pr(NO3)3∙6H2O and 2 equivalents of bzdhz in H2O/Me2CO led to the isolation of N,N’-di-isopropylidene-benzil dihydrazone (L’). The structures of 1-11 and L’ have been determined by single-crystal X-ray crystallography. All the complexes have been characterized by IR spectroscopy, and selected compounds by RAMAN and 1H NMR techniques. The spectroscopic data are discussed in terms of the known structures and the coordination modes of the ligands.We believe that our results contribute into the chemistry of cadmium(II) and the praseodymium(III), and into the coordination chemistry.