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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
261

Thermoluminescence et frittage de l'alumine alpha ultra-pure dopée par le zirconium, le thorium, le calcium, ou le cérium

Ferey, Frédérique 10 January 2002 (has links) (PDF)
La thermoluminescence est une technique de caractérisation des défauts ponctuels qui apparaissent dans un solide lors de son élaboration. Les paramètres de synthèse de l'alumine alpha considérés dans cette étude sont l'atmosphère de calcination (oxydante ou réductrice) et les différents dopants : Zirconium, thorium, calcium et cérium. L'objectif de ce travail est de relier les défauts ponctuels à la réactivité de la poudre, en particulier son frittage. Les mécanismes de TL du pic dosimétrique de l'alumine alpha, situé à 200°C, ont été clarifiés : Le défaut piège est une association de 2 défauts du type Schottky (V<sub>Al</sub>-V<sub>0</sub>), et le centre de recombinaison est le Cr<sup>3+</sup>. L'effet sensibilisateur du thorium, ou du cérium sous atmosphère réductrice, est expliqué par la présence d'une large bande d'émission bleue-verte. Le chrome est l'impureté principale à l'origine du pic E' (360°C) de l'alumine alpha. Il intervient comme défaut piège et comme centre de recombinaison. Un mécanisme de transfert d'énergie entre le Cr<sup>3+</sup> et le Ti<sup>4+</sup> est également proposé pour expliquer l'augmentation du signal de TL du pic E' lors du dopage par un cation tétravalent. Dans le cas du dopage par le calcium, la TL a permis de révéler la présence de la phase CaAl<sub>12</sub>O<sub>19</sub>. Un phénomène d'extinction par concentration a été observé sur les alumines dopées calcium ou dopées cérium et préparées sous atmosphère réductrice. Ce phénomène est expliqué par une teneur élevée en lacunes d'oxygène (Ca) et par la présence de Ce<sup>3+</sup>. Les alumines calcinées sous atmosphère réductrice présentent une cinétique de frittage perturbée, ainsi qu'un grossissement anormal des grains pour les alumines dopées. Cette cinétique irrégulière s'explique par une diminution de la concentration en lacunes d'aluminium sous atmosphère réductrice, ce qui augmente indirectement la ségrégation du Si<sup>4+</sup> aux joints de grains, et conduit à l'apparition d'une phase liquide à la surface des grains. Ce phénomène est amplifié lors du dopage par le calcium.
262

Étude physicochimique des oxydes de zirconium et du dispersoi͏̈de alumine-zircone

Orlans, Patrick 30 September 1987 (has links) (PDF)
Le procédé de synthèse et les divers traitements thermiques ou mécaniques modifient les propriétés physicochimiques des zircones industrielles. Cependant, l'origine exacte de ces modifications est difficile à déterminer compte-tenu des imprécisions concernant la préparation des produits industriels. Les oxydes de zirconium sont synthétisés par précipitation de gel. Les propriétés physicochimiques de la zircone sont liées aux modifications des différents paramètres (température, ph de fin de neutralisation, séchage, conditions de calcination). L'obtention du dispersoïde alumine-zircone par coprécipitation de gels permet une bonne homogénéisation des poudres. Selon les conditions de synthèse, l'interaction entre les oxydes peut devenir un phénomène important qui dans certains cas améliore notablement les propriétés mécaniques des matériaux obtenus.
263

Thermoluminescence spectra from sulphates, fluorides and garnets doped with rare earth ions

Al-Maghrabi, Mufied Mahmoud January 2001 (has links)
Luminescence measurements have been applied to three different structures namely, sulphate, fluorides and YAG. In all cases the RE doping suppresses the intrinsic emission and results in intense luminescence characteristic of the RE dopant. Additionally, in double doped samples, or contaminated ones, the TL data show that each dopant defines a glow peak, which is displaced in temperature relative to the others. Examples of this were discussed for CaS04:Ce,Mn; YAG:Nd,Tb,Cr,Mn; BaF2:Ho,Ce and BaF2:Tm,Ce. The data are discussed in terms of an energy transfer model between different parts of extended defect complexes which encompass the RE ion and the lattice defects. Calcium sulphate doped with Dy define a TL peak near 200°C suitable for radiation measurements, but when co-doped with Ag the TL peak move to higher temperatures with minor effects on the peak sensitivity. In Ce,Mn double doped samples, the peak temperatures differ by -7°C between the Ce and Mn sites. The TL glow curves from alkaline earth fluorides are complex and contain several overlapping peaks. Curve fitting show that the peak maxima below room temperature are insensitive to the RE dopant. Additionally the host material has a modest effect on the peak positions. Above room temperature each dopant provides a TL curve specific to the added RE ion and do not show common peaks. Concentration has many effects on the resultant glow curve, and even at the lowest concentration used here (0.01%) there is evidence of cluster formation. Samples with high RE content show low values of the frequency factor consistent with the energy transfer model in that the emission from RE-RE cluster dominates over the emission from direct charge recombination within the defect complex. The effect of concentration and the TL mechanism operating below room temperature are also discussed. Luminescence signals from the near surface of YAG:Nd (via CL) were contrasted with those from the bulk material via RL. Results indicate that the outer few micron layers differ significantly in luminescence response from the bulk crystal. The differences were ascribed to result from solvents that enter the YAG lattice during the growth stage or subsequently from cleaning treatments via the dislocations caused by cutting and polishing. Additionally, the growth stage may include gases from the residual air in the growth furnace trapped into the YAG lattice. In each case there is a discontinuity in luminescence intensity and/or emission wavelengths at temperatures which mach the phase transitions of the contaminants. At the transition temperature there will be a sudden pressure change and this will induce surface expansion or bulk compression. The differences between the two cases were detected by the alternatives of CL and RL excitation, where the Nd or Er lines have moved in opposite directions. The detection of such low concentrations of solvents/trapped gases by luminescence is extremely difficult due to experimental limitations. Hence their role in luminescence generation is normally ignored.
264

Caractérisation thermique de structures de combustion par les effets de la chauffe sur les minéraux : thermoluminescence et propriétés magnétiques de foyers de la grotte des Fraux (Dordogne).

Brodard, Aurélie 29 January 2013 (has links) (PDF)
Les structures de combustion constituent un témoin de la fréquentation humaine et leur étude permet d'appréhender un aspect du mode d'occupation d'un lieu donné. Ainsi, pour compléter les approches classiques qui s'intéressent à la typologie des foyers, à la fréquence des feux, à la nature des combustibles, etc., une caractérisation thermique de ces structures a été proposée. Elle s'appuie sur les impacts thermiques enregistrés par les sédiments soumis aux feux et plus précisément sur les modifications des propriétés de thermoluminescence (TL) et de magnétisme avec la chauffe.Le site-laboratoire est celui de la grotte de Fraux (Dordogne), occupée à l'Âge du bronze, dont le statut et le mode d'occupation pose question puisqu'elle présente tant des vestiges domestiques (sols de circulation, foyers, mobiliers) que des vestiges symboliques (manifestations pariétales, dépôts de mobilier). La place importante des foyers parmi ces vestiges a induit une étude spécifique de ces structures. En effet, ce site recèle plus d'une soixantaine de structures de combustion et, aspect important pour notre approche archéométrique, présente un état de conservation exceptionnel puisque la grotte est restée fermée depuis l'occupation de l'Âge du bronze.L'étude de certains foyers de la grotte des Fraux a permis de tester le potentiel de paléothermomètres fondés sur ces deux propriétés indépendantes à savoir la TL des grains de quartz et le magnétisme des oxydes de fer contenus dans les sédiments. Le paléothermomètre TL a été élaboré en comparant les signaux TL d'échantillons provenant de foyers archéologiques à ceux de références thermiques chauffées en laboratoire. Pour le magnétisme deux pistes ont été exploitées : les températures de déblocage de l'aimantation rémanente et l'évolution de la signature magnétique -minéralogie et taille de grain) avec la chauffe. La détermination des paléotempératures atteintes par les sédiments substrats des structures de combustion apporte une première indication sur leur intensité de chauffe. Afin d'étalonner ces informations paléothermométriques en termes d'énergie mise en jeu, des feux expérimentaux ont été réalisés. Ils ont permis de comparer les impacts thermiques entre feux archéologiques et feux expérimentaux, de construire un échantillonnage d'histoire thermique connue, mais aussi d'estimer les températures atteintes, les épaisseurs de sédiments affectés, les quantités de combustibles consommés pendant un temps donné, la quantité d'énergie dégagée par la combustion... Ces expérimentations ont aussi servi de base à une modélisation de la propagation de la chaleur dans les sédiments. Les simulations effectuées dans ce modèle numérique permettent alors d'estimer un temps minimal de fonctionnement des structures de combustion.Nous disposons ainsi d'un nouvel outil pour la caractérisation thermique de foyers archéologiques.
265

Élaboration, caractérisation et modélisation des phénomènes de luminescence du monoaluminate de strontium dopé à l'europium et au dysprosium SrAl<sub>2</sub>O<sub>4</sub>

Beauger, Christian 02 December 1999 (has links) (PDF)
Ce travail est consacré à l'étude d'un pigment phosphorescent (luminophore), le monoaluminate de strontium dopé à l'europium et au dysprosium : SrAl<sub>2</sub>O<sub>4</sub> : Eu, Dy. Il a abouti à la modélisation de la luminescence de ce composé (fluorescence & thermoluminescence (TL)), exposée à l'aide du schéma des bandes d'énergie usuellement employé pour décrire ces phénomènes (chapitre IV). Ce système s'est révélé se comporter comme une pile, stockant, sous l'effet de la lumière du jour, de l'énergie sous forme de paires électron/trou dissociées. Chaque partie, piégée par les défauts du luminophore, est libérée par activation thermique a température ambiante. Elles se recombinent ensuite libérant le surplus d'énergie sous forme d'une émission lumineuse verte (525 nm). L'explication de ces mécanismes optoélectroniques à nécessité la compréhension du rôle de chacun des composants du système : la matrice (SrAl<sub>2</sub>O<sub>4</sub>) et les éléments dopants (Eu & Dy) identifié séparément. La première partie de ce travail (chapitre II) à pour cela été dédiée à l'étude de la matrice et a permis de mettre au point un mode de synthèse par réaction solide/solide, sous atmosphère contrôlée, entre le carbonate de strontium et l'alumine gamma. L'influence des différents paramètres de synthèse (stœchiométrie des réactants, durée, température et atmosphère de calcination) a permis de caractériser les propriétés optoélectroniques de la matrice (Emission de fluorescence bleue a 440 nm & 3 pics de TL à - 170, -70 et 0°c). Le rôle du dysprosium, puis de l'europium et enfin leur interaction ont fait l'objet d'une étude particulière (chapitre III). L'émission verte à 525 nm a ainsi pu être attribuée à l'europium divalent (Eu<sup>2+</sup>), l'interaction Eu-Dy étant quant à elle responsable du phénomène de phosphorescence.
266

Mineralogia de solos e ambientes de sedimentação em manguezais do Estado de São Paulo / Soil mineralogy and sedimentary environment in mangroves of São Paulo State

Valdomiro Severino de Souza Júnior 22 February 2006 (has links)
Manguezais são formados por grupos de árvores e arbustos que se desenvolvem na zona de intermarés de regiões tropicais. Este ecossistema ao se estabelecer na interface do ambiente marinho e continental, apresenta sua formação relacionada com as flutuações relativas do nível do mar quaternário, através do preenchimento dos vales dos rios, margens de lagunas e baías com sedimentos tanto de origem continental como marinha. O conhecimento da distribuição de partículas e dos minerais constituintes da assembléia mineralógica dos solos em ambiente de planícies estuarinas, auxilia na compreensão de processos de sedimentação e geoquímica dentro dos estuários. O trabalho foi realizado nos manguezais distribuídos ao longo do litoral do Estado de São Paulo, e objetivou-se caracterizar os ambientes de sedimentação de acordo com a granulometria e o processo de evolução quaternária, determinar qualitativamente e semiquantitativamente a assembléia mineralógica e estudar em detalhe os tipos de esmectitas presentes nesses solos. Para tanto foram coletadas amostras de solos de 14 manguezais nas camadas de 0-20 e 60-80cm e de sedimento em suspensão do Rio Ribeira de Iguape, além de amostras de diferentes profundidades para datações. Determinaram-se as frações, argila, silte, areia total e 5 frações da areia, foram realizadas datações 14C por cintilação líquida e AMS na fração humina da matéria orgânica e por termoluminescência em grãos de quartzo. As análises mineralógicas foram realizadas na fração silte e argila e no sedimento em suspensão através de DRX, IV, MET, MEV com microanálise, ATD e ATG, realizou-se também o teste de Greene- Kelly para identificar o tipo de esmectitas presentes nesses solos. De acordo com os resultados obtidos, concluiu-se que os solos dos manguezais do Estado de São Paulo podem apresentar diferentes texturas desde arenosa até muito argilosa, freqüentemente contêm altos teores de silte e todos têm idade holocênica, oscilando entre 410 anos A.P. e 3.700 anos; a distribuição de partículas está relacionada à morfologia atual do estuário e à natureza dos sedimentos costeiros adjacentes; a assembléia mineralógica da fração fina dos solos é constituída de pirita, nontronita, caulinita, illita, gibbsita, quartzo, feldspato, e localmente ocorrem goethita, vermiculita, biotita, halloysita e anatásio; os minerais alóctones são de origem continental e marinha; a distinção entre os cenários geomorfológicos ao longo do litoral condiciona a distribuição de minerais, e ainda foi inferido que ocorre neoformação de esmectita e de caulinita, e que o processo de oxidação de matéria orgânica nesses solos pode estar utilizando o Fe3+ da nontronita como receptor de elétrons. / Mangroves are formed by groups of trees and shrubs that develop in the intertidal zone of tropical regions. This ecosystem to establish in the interface of both marine and continental environment, present its formation related to the sea-level fluctuations during the quaternary period, where the terrigenous and marine sediments are deposited in rivers valleys, edges of lagoons and bays. The knowledge of both particle distribution and minerals constituent of soils in estuarines areas, can aid to understand the processes of sedimentation and geochemistry in this site. This study was carried out with mangroves distributed along the São Paulo State coast, and aims to characterize the sedimentary environments in accordance with grain size and process of quaternary evolution, to determine qualitatively and semiquantitatively the mineralogical assemblage and to identify the smectites types in these soils. Samples were collected from 14 mangroves soils at the layers 0-20 and 60-80cm, and also was collected sediment in suspension of the Ribeira de Iguape River, and samples of different depths for dating. The clay, silt and total sand sizes and 5 sand fractions were determined, radiocarbon dating were carried out by liquid scintillation counting and accelerator mass spectrometry in humin fraction of the soil organic matter and by thermoluminescence of quartz grains. The mineralogical analyses were carried out by XRD, FTIR, TEM, SEM, DTA and GTA in silt and clay sizes and in the sediment in suspension, also was made the Greene-Kelly test to identify the smectites type. According to the results we concluded that the mangroves soils from São Paulo State have different textures varying from sandy up to very clay, also occuring high silt contents. All the mangroves are holocenic, with ages varying from 410 yr B.P. to 3,700 yr; the particle distribution is related to the current geomorphological setting of the estuary and the origin of coastal sediments. The mineralogical assemblage is constituted of pyrite, nontronite, kaolinite, illite, biotite, gibbsite, quartz, feldspars, and locally occurs goethite, vermiculite, halloysite and anatase; the aloctones minerals are from both the terrigenous and marine origin; the difference between geomorphological settings along the coastal plain rules mineral distribution, and still it was inferred the neoformation of esmectita and kaolinite and that the process of organic matter mineralization in these soils may be using Fe3+ from nontronite as an electron acceptor.
267

Synthesis and characterization of long persistent phosphors using combustion method

Colen, Manaka Mmakgabo January 2015 (has links)
In this work, alkaline earth aluminate phosphors doped with rare-earth ions and manganese were synthesized using combustion method. Several characterization techniques were used to study the structural and luminescent properties of the as-synthesized phosphors, namely X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), X-ray energy Dispersive Spectroscopy (EDS), Ultraviolet-Visible (UV-Vis) Spectroscopy, Photoluminescence (PL), and Thermoluminescence (TL). The structural properties were studied by collecting the XRD patterns of the samples using an X'Pert PRO PANalytical diffractometer with CuKα at λ = 0.15405 nm. The particle morphologies of the as-synthesized powder phosphors were investigated using a JEOL JSM-7500F field-emission scanning electron microscope (FE-SEM). The optical properties of the phosphors were studied using Perkin-Elmer Lambda 750s UV-Vis spectrometer, Jobin Yvon/SPEX FluoroLog spectrofluorometer (Model FL-1040) and Riso TL/OSL reader (Model DA-20). The as-prepared SrAl2O4:Eu 2+ ; SrAl2O4:Dy 3+; SrAl2O4:Mn 2+; phosphors were synthesized at an initiating temperature of 600 oC. The XRD patterns were consistent with the low temperature monoclinic structure of SrAl2O4 for all the as-synthesized phosphor powders. SEM measurements showed nano-rod like particles. The SrAl2O4:Eu 2+ ; SrAl2O4:Dy 3+; SrAl2O4:Mn 2+ samples were excited using a 450 W Xenon light source at 364 nm, 390 nm, and 426 nm respectively. A broad blue emission peak at 500 nm shown by the SrAl2O4:Eu 2+ sample is attributed to the 6 1 7 4f 5d 4f transition of the Eu 2+ ion. Also, the red sharp emission lines due to the 4f-4f transition of the Eu 3+ were observed. SrAl2O4:Dy3+ samples exhibited blue, green, and red emissions which can be atributed to the 4 6 9/2 15/2 F  H ,4 6 9/2 13/2 F  H , and 4 6 9 11 2 2 F  H transitions of Dy 3+ ions respectively. The two broad emissions (green at 513 nm and red at 650 nm) shown by 2+ 0.98 2 4 0.02 Sr Al O :Mn sample can be atributed to the 4 4 6 6 1 1 T ( G)  A ( S) transition of the Mn 2+ ion in the sample. The SrAl2O4:Eu 2+ , Dy 3+ ; SrAl2O4:Eu 2+, Mn 2+ ; SrAl2O4:Dy 3+, Mn 2+; and SrAl2O4:Eu 2+ ,Mn 2+, Dy 3+ phosphors were synthesized by combustion method at an initiating temperature of 600 oC. The blue emissions were observed in all the samples except SrAl2O4:Eu 2+ ,Mn 2+, Dy 3+ sample. The SrAl2O4:Eu 2+ ,Mn 2+, Dy 3+ phosphor showed the longest afterglow intensity. The BaAl2O4 doped with Eu 2+ , Mn 2+ and Dy 3+ phosphors synthesized at an initiating temperature of 600 oC using combustion method. The XRD patterns confirmed the hexagonal structure of BaAl2O4 in all the as-synthesized samples. A broad blue emission of the BaAl2O4:Eu 2+ sample at 490 nm is attributed to the 6 1 7 4f 5d 4f transition of the Eu 2+ ion in the sample. A red emission peak observed at 611 nm is due to the 4f - 4f transition of un-reduced Eu 3+ ions during the combustion reaction. A blue emission at 482 nm, a green emission at 575 nm, and a red emission at 663 nm of the BaAl2O4:Dy 3+ sample can be associated with 4 6 9/2 15/2 F  H ,4 6 9/2 13/2 F  H , and 4 6 9 11 2 2 F  H transitions of the Dy 3+ ions respectively. The green emission peaks exhibited by BaAl2O4:Mn 2+ sample at 512 nm is due to the 4 4 6 6 1 1 T ( G)  A ( S) transitions of the Mn 2+ ions. Barium aluminate phosphors doped with different concentrations of Dy 3+ ion were synthesized by combustion method at an initiating temperature of 600 oC. The XRD patterns confirmed the hexagonal structure of BaAl2O4. The emission peaks observed at 482 nm, 575 nm, and 663 nm are due to4 6 9/2 15/2 F  H ,4 6 9/2 13/2 F  H and 4 6 9 11 2 2 F  H transitions of Dy 3+ ion respectively. The PL measurements also confirmed the quenching of luminescence at higher concentrations of the Dy 3+ ion. The UV-Vis measurements has confirmed the increase in the band-gap of the BaAl2O4 sample followed by a decrease and an increase again as doping concentration of the Dy 3+ increased. The X-ray diffraction patterns of the Ca0.97M0.3Al2O4:Eu 2+ , Dy 3+ (M = Ba, Mg, and Sr) powder samples prepared by combustion method confirms the monoclinic structure of CaAl2O4 in all samples. A broad emission peak at 490 nm for both Ba 2+ and Mg 2+ substituted samples and the one for Sr 2+ substituted sample at 485nm are attributed to the 6 1 7 4f 5d 4f transition of the Eu 2+ . The decay curves confirmed that the Mg 2+ substituted sample has a longer persistence (phosphorescence) than all the other samples. / Physics / M. Sc. (Physics)
268

Contribuição da dinâmica morfoestrutural e morfoescultural na estruturação da bacia do Ribeirão Entupido, complexo alcalino do Passa Quatro - SP

Arruda, Emerson Martins [UNESP] 03 April 2008 (has links) (PDF)
Made available in DSpace on 2014-06-11T19:33:21Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-04-03Bitstream added on 2014-06-13T19:04:03Z : No. of bitstreams: 1 arruda_em_dr_rcla.pdf: 9662595 bytes, checksum: 0ed9158bd4d58632c075670ed3c2f2ba (MD5) / A pesquisa analisa os eventos deposicionais, esculturadores do relevo, na bacia do Ribeirão Entupido, Complexo Alcalino do Passa Quatro, Estado de São Paulo, a partir do estudo dos depósitos recentes da área. Além da análise geomorfológica na referida unidade espacial, a pesquisa buscou estabelecer a idade absoluta de deposição de algumas unidades sedimentares estruturadoras do relevo e os mecanismos envolvidos na sua gênese. Neste contexto, utilizou-se datações por Luminescência Opticamente Estimulada (LOE) e Termoluminescência (TL). Os depósitos sedimentares foram estudados a partir da abordagem morfoestratigráfica. O cruzamento de dados morfoesculturais e morfoestruturais e de datação absoluta permitiu estabelecer quais mecanismos, atuantes ao longo do último milhão de anos, comandaram a morfogênese na bacia em foco. A determinação da morfogênese permitiu definir a susceptibilidade do relevo às mudanças ambientais, inclusive às intervenções antrópicas. Os depósitos sedimentares apresentaram idades vinculadas ao Pleistoceno Superior (61.500 anos) e Holoceno (650 anos) representando, portanto, eventos diferenciados no desenvolvimento e localização deste ambientes. A complexidade da paisagem na bacia do Ribeirão Entupido envolve justamente esta interdigitação de materiais de idades diversas que compõem o mesmo ambiente de deposição, interferindo conjuntamente a tectônica e as condições climáticas, a priori, na espacialização dos depósitos e nas características dos sedimentos. / This research of doctor’s grade analyze the depositional and sculptural events, at stream Entupido basin, Passa Quatro Alkalin Complex, Estate of São Paulo, from the study of recent deposits.Beyond the geomorphologycal analysis at referred spacial unit, this research tried to establish the absolute age of some sedimentary units that structure the relief and the mechanism involved in its genesis. The dating method of Optically Stimulated Luminescence (OSL) Thermoluminescence (TL) was used in that context.The sedimentary deposits were studied by morphostratigraphic approach. The crossing of mophosculptural and moprostructural data and absoluting dating allow establish wich mechanism, acting through the last million years, commanded the morphogenesis process at the basin.The determination of morfogenesis allowed define the susceptilidy of relief to ambiental changes, including antropic intervention. The sedimentary deposits show ages linked at Up Pleistocene (61.500 years) and Holocene (650 years), showing, therefore, differenced events in development and localization of this environment.The landscape complexity in stream Entupido basin, involves precisely this interdigitation of materials and different ages that compose the same depositional environment, interfering jointly tectonic and climatic conditions, in prior, at specialization of deposits and sedimentary characteristics.
269

Caracterização de silicatos e carbonatos de cálcio aplicados à dosimetria de doses altas / Characterization of silicates and calcium carbonates applied to high-dose dosimetry

VILA, GUSTAVO B. 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:35:56Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:32Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
270

Produção e caracterização de compostos à base de MgB4O7 para aplicação em dosimetria

Souza, Luiza Freire de 29 March 2016 (has links)
Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Many materials with luminescent properties are used for ionizing radiation dosimetry through the thermoluminescence (TL) and optically stimulated luminescence (OSL) techniques. Detectors based on lithium fluoride (LiF), calcium sulphate (CaSO4) and aluminum oxide (Al2O3), doped or codoped with various elements, are the TL or OSL commercial dosimeters most widely used currently. However, several researches are focused to the development of new TL /OSL materials aiming to enhance the dosimetric properties, since no TL/OSL dosimeter has all the ideal characteristics for monitoring radiation. In this context, magnesium tetraborate (MgB4O7), which has been presented in the literature as a material for TL dosimetry, was investigated in this work. As there are no reports on the structural characterization of this material or regarding its applicability in OSL dosimetry, the proposal of the present work was to develop compounds based on MgB4O7, with different doping, by solid state synthesis. It was made the structural, optical, TL and OSL characterization of the compound to verify its feasibility for application in radiation dosimetry. Initially, it was determined the calcination temperature and time for MgB4O7 formation, with the use of thermal analyses and x ray diffraction. We produced , in powder form, the compounds:MgB4O7, MgB4O7:Dy, MgB4O7:Dy,Li, MgB4O7:Ce, MgB4O7:Ce,Li, MgB4O7:Nd and MgB4O7:Nd,Li. For TL and OSL analyses it were produced pellets sintering at 950º C for 2 hours. The radioluminescence (RL) results from the MgB4O7:Dy and MgB4O7:Dy,Li composites shows wavelength emissions at 490, 590, 670 and 760 nm. For MgB4O7:Ce and MgB4O7:Ce,Li composites, we observed a wide emission band in the ultraviolet region. With the results obtained from the TL characterization, we also discuss aspects such as: effect of sintering and dopant concentrations in emissions, influence of doping and codoping with Li in MgB4O7 matrix, thermal treatment reuse, TL signal reproducibility, dose response curve, relative sensitivity and we analyzed the kinetic parameters of the TL emission curves. The OSL analyses of MgB4O7:Dy,Li,MgB4O7:Ce,Li and MgB4O7:Nd,Li indicate that the compounds have high cross section for photoionization to the wavelength emitted by blue LEDs, and from three compounds analyzed the MgB4O7: Ce,Li showed greater sensitivity.Partial preheating and partial cleaning methods allowed to elucidate the OSL phenomenology in compounds. / Muitos materiais com propriedades luminescentes são utilizados para dosimetria das radiações ionizantes através da técnica da termoluminescência (TL) e da luminescência oticamente estimulada (LOE). Os detectores à base de fluoreto de lítio (LiF), o sulfato de cálcio (CaSO4) e o óxido de alumínio (Al2O3), dopados ou codopados com diversos elementos, são os dosímetros comerciais TL ou LOE mais utilizados atualmente. Porém, diversas pesquisas estão focadas para o desenvolvimento de novos materiais TL/LOE com intuito de aprimorar as propriedades dosimétricas, tendo em vista que nenhum dosímetro TL/LOE possuem todas as características ideais para a monitoração da radiação. Neste contexto, o tetraborato de magnésio (MgB4O7), que tem sido apresentado na literatura como um material para dosimetria TL, foi investigado. Como não há relatos sobre a caracterização estrutural desse material nem quanto à sua aplicabilidade em dosimetria LOE, a proposta do presente trabalho foi desenvolver compostos à base de MgB4O7, com diferentes dopagens, através da síntese de estado sólido. Foi realizada a caracterização estrutural, ótica, TL e LOE do composto para se verificar a viabilidade dele para aplicações em dosimetria das radiações. Inicialmente, foi determinada a temperatura e o tempo de calcinação para a formação do MgB4O7, com uso de análises térmicas e difratometria de raio X (DRX). Foram produzidos, na forma de pó, os compostos: MgB4O7, MgB4O7:Dy, MgB4O7:Dy,Li, MgB4O7:Ce, MgB4O7:Ce,Li, MgB4O7:Nd e MgB4O7:Nd,Li. Para a análise TL e LOE, foram produzidas pastilhas sinterizadas a 950º C por 2 horas. Os resultados de radioluminescência (RL) dos compostos MgB4O7:Dy e MgB4O7:Dy,Li mostram emissões em 490, 590, 670 e 760 nm. Para o compostos MgB4O7:Ce e MgB4O7:Ce,Li foi observada uma larga banda de emissão RL na região do ultravioleta. Com os resultados obtidos da caracterização TL, também foram discutidos aspectos como: efeito das sinterizações e das concentrações de dopantes nas emissões, influência dos dopantes e do codopante Li na matriz MgB4O7, tratamento térmico de reutilização, reprodutibilidade do sinal TL, curva dose-resposta, sensibilidade relativa e foram feitas análises dos parâmetros cinéticos das curvas de emissões TL. As análises LOE dos MgB4O7:Dy,Li,MgB4O7:Ce,Li e MgB4O7:Nd,Li indicaram que os compostos apresentaram alta secção de choque para fotoionização para o comprimento de onda emitido por LEDs azuis, e que dos três compostos analisados o MgB4O7:Ce,Li apresentou maior sensibilidade LOE. Os métodos de aquecimentos parciais e limpeza parcial permitiram elucidar a fenomenologia LOE nos compostos.

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