Tecnécio-99m (99mTc), o produto de decaimento do molibdênio-99 (99Mo), é um dos radioisótopos mais utilizados na medicina nuclear, abrangendo cerca de 80% de todos os procedimentos de radiodiagnóstico médico pelo mundo. Atualmente o Brasil necessita de uma quantidade de aproximadamente 450 Ci de 99Mo por semana. Devido à crise e à escassez em seu fornecimento que vem sendo observada no cenário mundial desde 2008, o IPEN decidiu desenvolver um projeto próprio para produção de 99Mo através da fissão do urânio-235. O objetivo deste trabalho de dissertação foi desenvolver cálculos neutrônicos e temo-hidráulicos para avaliar a segurança operacional de um dispositivo para produção de 99Mo a ser irradiado no núcleo do reator IEA-R1. Neste dispositivo serão alojados dez alvos do tipo dispersão de UAlx-Al com baixo enriquecimento de urânio (LEU) e densidade de 2,889 gU/cm³. Para o cálculo neutrônico foram utilizados os programas computacionais HAMMER-TECHNION e CITATION e as temperaturas máximas atingidas nos alvos foram calculadas com o código MTRCR-IEAR1. Os cálculos demonstram que a irradiação do dispositivo deverá ocorrer sem consequências adversas à operação do reator. A quantidade total de 99Mo foi calculada com o programa SCALE e considerando que o tempo necessário para o processamento químico e recuperação do 99Mo será de cinco dias após a irradiação, teremos disponível para distribuição uma atividade de 99Mo de 176 Ci para 3 dias de irradiação, 236 Ci para 5 dias de irradiação e 272 Ci para 7 dias de irradiação dos alvos. / Technetium-99m (99mTc), the product of radioactive decay of molybdenum-99 (99Mo), is one of the most widely used radioisotope in nuclear medicine, covering approximately 80% of all radiodiagnosis procedures in the world. Nowadays, Brazil requires an amount of about 450 Ci of 99Mo per week. Due to the crisis and the shortage of 99Mo supply chain that has been observed on the world since 2008, IPEN/CNEN-SP decided to develop a project to produce 99Mo through fission of uranium-235. The objective of this dissertation was the development of neutronic and thermal-hydraulic calculations to evaluate the operational safety of a device for 99Mo production to be irradiated in the IEA-R1 reactor core at 5 MW. In this device will be placed ten targets of UAlx-Al dispersion fuel with low enriched uranium (LEU) and density of 2.889 gU/cm³. For the neutronic calculations were utilized the computer codes HAMMER-TECHNION and CITATION and the maximum temperatures reached in the targets were calculated with the code MTRCR-IEAR1. The analysis demonstrated that the device irradiation will occur without adverse consequences to the operation of the reactor. The total amount of 99Mo was calculated with the program SCALE and considering that the time needed for the chemical processing and recovering of the 99Mo will be five days after the irradiation, we have that the 99Mo activity available for distribution will be 176 Ci for 3 days of irradiation, 236 Ci for 5 days of irradiation and 272 Ci for 7 days of targets irradiation.

Orientador: Ana Maria Martinez Nazar / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-07-22T16:31:39Z (GMT). No. of bitstreams: 1 Nunes_CarlosAngelo_D.pdf: 12292935 bytes, checksum: ea1a755d6645281ed644bfe2879a287c (MD5) Previous issue date: 1997 / Resumo: Em trabalhos recentes têm-se proposto que materiais formados por um metal refratário em equilíbrio com uma fase intermetálica constituem a melhor opção para aplicações estruturais em temperaturas acima de 1400°C. Baseado em informações disponíveis na literatura foi identificada a existência de um campo bifásico envolvendo as fases Mo (solução sólida) e o intermetálico 'Mo IND. 5¿ ¿Si¿ ¿B IND. 2¿ ('T IND. 2¿) A 1600 º C no sistema Mo-B-Si. Tendo em vista o limitado número de informações relacionadas a este sistema objetivamos neste trabalho uma avaliação sistemática sobre estabilidade de fases na região rica em Mo. O trabalho consistiu em: determinar a relação de fases a 1600°C; desenvolver métodos de análise via microssonda eletrônica (WDS) para determinação da composição das fases; determinação da projeção liquidus; determinação da seção vertical Mo-'T IND. 2¿.A determinação da relação de fases a 1600°C confmnou a existência do campo bifásico Mo+ 'T IND. 2¿ naquela temperatura.A fase ternária 'T IND. 2¿ é rodeada pelos campos trifásicos ... Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital / Abstract: In recent investigations it has been proposed that equilibrium microstructures constituted by a refractory metal and an intermetallicphase are the best choice for high temperature structural applications at temperatures higher than 1400°C. Based on the information available in the literature it has been identified the existence of a Mo (solid solution) + intermetallic 'Mo IND. 5¿ ¿Si¿ ¿B IND. 2¿ two-phase field in the Mo-B-Si system. Considering the limited information related to this system it was the objective of this study to systematically evaluate the phase stability in the Mo-rich region. Specific objectives were: determination of the phase relations at 1600°C; development of microprobe methods of analysis to determine phase compositions; determination of the liquidus projection; determination of the Mo-'T IND. 2¿ vertical section. The Mo+ 'T IND. 2¿ two-phase field was confirmed to exist at 1600°C. The ternary phase ('T IND. 2¿) is surrounded by the following three-phase field ... Note: The complete abstract is available with the full electronic digital thesis or dissertations / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Made available in DSpace on 2014-10-09T12:50:18Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:53Z (GMT). No. of bitstreams: 1 10885.pdf: 6800168 bytes, checksum: 564283882a42941e0a49be623bd8981e (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-02-03T12:06:00Z No. of bitstreams: 0 / Made available in DSpace on 2016-02-03T12:06:00Z (GMT). No. of bitstreams: 0 / Este trabalho apresenta a análise neutrônica do combustível a dispersão de UMo-Al em relação ao aumento da densidade de urânio e faz uma comparação com o combustível de U3Si2-Al. Neste estudo, a densidade de urânio do U3Si2-Al é variada de 3,0 à 5,5 gU/cm3 e a do UMo-Al entre 4,0 à 7,5 gU/cm3 e com a porcentagem em massa de molibdênio com 7 e 10 %. Neste trabalho também é proposta a aplicação de veneno queimável metálico no cerne do combustível de UMo-Al, uma vez que este combustível é metálico e é analisada a utilização de gadolínio (Gd) e európio (Eu) como veneno queimável. A utilização do Gd como veneno queimável foi analisada com o fator de multiplicação infinito (k∞) através do programa celular HRC desenvolvido pelo IPEN e composto pelos códigos HAMMERTECHNION para a analise de célula, ROLAIDS para o cálculo de auto blindagem dos actinídeos e CINDER-2 empregado para a fissão e transmutação dos actinídeos. O núcleo do reator simulado foi similar ao do RMB (Reator Multipropósito Brasileiro) composto por um arranjo de 5x5 posições com 23 elementos combustíveis e dois blocos de alumínio. Para o európio, foram utilizados os programas SERPENT e CITATION. Os cálculos de queima foram realizados considerando uma potência de 30 MW durante três ciclos do RMB de 97 dias. Os resultados obtidos mostram que a porcentagem em massa do molibdênio têm uma grande influência no comportamento neutrônico devido a seção de choque de absorção do molibdênio ser considerável. Portanto, foi escolhida a porcentagem de 7 % de Mo para os estudos com veneno queimável. Para o núcleo proposto, o európio mostrou-se melhor, pois apresenta uma queima mais gradual que o gadolínio. Foi realizada uma simulação com o programa SERPENT com adição de 6 % de silício, o que mostrou que a adição de Si não causa mudança significativa no ciclo de operação do reator. Para validação da metodologia de cálculo, foi elaborada uma especificação técnica e fabricadas 12 miniplacas combustíveis de UMo-Al sem veneno queimável. As miniplacas foram irradiadas no núcleo do reator IPEN/MB-01, em quatro configurações de núcleo, para obtenção da reatividade inserida. Os resultados simulados obtidos para a inserção de reatividade pelas miniplacas nos diversos núcleos analisados apresentaram alta concordância com os resultados experimentais. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T11:09:13Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T11:09:13Z (GMT). No. of bitstreams: 0 / Neste trabalho foi desenvolvido uma metodologia para a determinação de metais (Cr, Cu, Fe, Mg, Mo, Pb), em óleos lubrificantes e estes quantificados pela técnica de espectrometria de emissão optica com plasma induzido por laser (LIBS). As amostras de óleo usadas foram coletadas em oficina de troca de óleo, variando-se a quilometragem, ano, marca do carro e a marca do óleo, com o preenchimento de formulários contendo as informações necessárias à pesquisa. A preparação de amostras foi realizada com o depósito ds mesmas em substrato de papel e sequente otimização dos parâmetros instrumentais. Para a calibração, foi utilizado o padrão de óleo S-21 multielementar da Conostan (SCP Science, Champlain, NY). Para a avaliação da exatidão do método desenvolvido foi utilizado o padrão de óleos lubrificantes (SRM 1084a) obtidos junto ao Instituto Nacional de Padrões e Tecnologia (NIST, Gaithersburg, MD). O método proposto apresentou as seguintes vantagens quando comparado com métodos de análise tradicionais (espectrometria de absorção atômica ou espectrometria de emissão optica acoplado ao plasma indutivo com diluição da amostra): mais rápida, sem desgaste do equipamento (em função da não introdução de solvente), geração de resíduo praticamente nula e menor consumo de reagentes. O método desenvolvido foi aplicado em amostras reais e o tratamento de dados realizado por análise estatística (equação de Stuarges, teste não paramétrico de Kruskalwallis). / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

L'enjeu de cette thèse est d'identifier des systèmes catalytiques, actifs, sélectifs et stables pour la transformation de l'acide lévulinique (LevA) en 1,4-pentanediol (1,4-PDO) en phase aqueuse. Dans un premier temps, des catalyseurs monométalliques à base de ruthénium (Ru), palladium (Pd), platine (Pt) supportés sur charbon (C) ou sur oxyde de titane (TiO2) sont préparés et testés. Ces premiers résultats ont montré l'importance de certains paramètres sur les performances catalytiques observées. Les catalyseurs à base de Ru se sont révélés les plus actifs et sélectifs en 1,4-PDO (rendement maximal de 50%). L'utilisation de ces catalyseurs monométalliques favorise la formation importante de sous-produits et de réactions de craquage d'où des pertes de carbone transférées en phase gaz. Par imprégnation de différentes teneurs de rhénium (Re) ou de molybdène (Mo) sur ces catalyseurs monométalliques, des catalyseurs bimétalliques Re-Ru et Mo-Ru ont été préparés. L'ajout d'un promoteur permet d'augmenter la vitesse de la réaction de transformation du LevA et améliore significativement la sélectivité en 1,4-PDO (90%). Les mécanismes réactionnels mis en jeu ont été étudiés notamment en s'appuyant sur une modélisation cinétique et sur des tests de réactivité de molécules modèles identifiées comme intermédiaires réactionnels ou produits de la conversion du LevA en 1,4-PDO / The aim of our research project is the hydrogenation of the levulinic acid in aqueous phase into 1,4-pentadeniol using noble metal catalysts (Ru, Pd, Pt) supported on C or TiO2. First results have shown the effect of the metal, the method of preparation or the supports on catalytic performances. Monometallic Ru catalysts are active and selective into 1,4-PDO (maximum yield 50%). By using monometallic catalysts, an important formation of by-products and loss of carbon by cracking reactions was observed. By impregnating various amount of Re or Mo, bimetallic catalysts were prepared. Adding promoter both allows enhancing the reaction rate of LevA hydrogenation and improved the selectivity to 1,4-PDO up to 90%. In order to understand the mechanism, a kinetic modeling and stability test on intermediates or products of the reaction were realized

Les enjeux environnementaux actuels, ainsi que la hausse continue du prix du pétrole, ont incité les constructeurs automobiles du monde entier à améliorer le rendement de leurs véhicules. Les propriétés tribologiques des lubrifiants des moteurs et boîtes de vitesses ont une influence considérable sur le rendement global des véhicules. Ils réduisent en effet le frottement généré par un grand nombre de contacts, et permettent parfois la réduction de la taille de différents composants en leur conférant une meilleure résistance à l’usure. Les avancées récentes en termes de synthèse de nanoparticules ont ouvert de nouvelles perspectives en termes d’additivation de lubrifiants avec, par exemple, la découverte des excellentes propriétés tribologiques des nanoparticules inorganiques de type fullerène comme le disulfure de molybdène ou de tungstène. L’objectif de ce manuscrit est d’évaluer le potentiel tribologique des nanoparticules IF-MoS2 dans l’optique d’une application automobile. L’influence de la taille et de la structure des nanoparticules a d’abord été étudiée. Les nanoparticules peu cristallines se sont révélées être plus aptes à maintenir un tribofilm performant sur des surfaces en acier dans des conditions de lubrification limite, indépendamment de leur taille. Toutes les nanoparticules testées ont cependant atteint des performances équivalentes lorsqu’une recirculation de l’huile était imposée, permettant de maintenir une alimentation continue du contact en nanoparticules. Une fois incorporées dans une formulation d’huile complète, les nanoparticules IF-MoS2 perdent leurs propriétés tribologiques. Les dispersants contenus dans l’huile, bien que permettant une bonne dispersion des IF-MoS2, semblent responsables de leur inefficacité en empêchant la formation de tribofilms sur les surfaces antagonistes. Une fois correctement dispersées, les nanoparticules pénètrent toujours le contact et se retrouvent bien exfoliées. Une adsorption excessive des dispersants sur les feuillets de MoS2 ainsi libérés et/ou sur les surfaces en acier semble nuire à l’adhésion du tribofilm. Un équilibre entre dispersion des nanoparticules et performance tribologique a ensuite été trouvé, en utilisant de très faibles concentrations de dispersants. Le comportement des huiles dopées en nanoparticules dans des conditions plus proches d’une application automobile a finalement été exploré. Les IF-MoS2 ont permis une réduction significative du frottement et de l’usure à température ambiante et en roulement/glissement, à la fois pour des surfaces lisses et rugueuses. Les risques associés à la présence de nanoparticules dans l’huile dans les régimes de lubrification en film complet ont été partiellement levés. Aucun impact significatif n’a en effet été constaté sur le coefficient de frottement pour l’ensemble des conditions d’essais retenues. Le potentiel des nanoparticules IF-MoS2 pour la protection des surfaces soumises à la fatigue de contact a enfin été démontré. / The growing environmental concerns, along with the continuous increase in the price of fossil fuels, have highly motivated car manufacturers worldwide to improve the efficiency of their vehicles. The tribological properties of engine and gearbox lubricants have a significant impact on the global efficiency of vehicles, as they contribute to reducing friction in many contacts and allow the downsizing of various components by providing their surfaces with anti-wear protection. The recent breakthroughs in nanoparticle synthesis have opened new prospects in terms of lubricant additivation, with the discovery of the excellent friction and wear reducing properties of nanoparticles such as Inorganic Fullerene-like (IF-) molybdenum or tungsten disulfides. The tribological potential of IF-MoS2 for automobile applications was investigated in this work. The respective influences of nanoparticle size and structure were first of all studied, revealing that poorly crystalline nanoparticles were more efficient in maintaining low-friction tribofilms on steel substrates in severe boundary lubrication regimes regardless of size (for the range studied). All the nanoparticles tested however showed similar performances when proper oil recirculation was ensured, providing a continuous feeding of the contact in nanoparticles. The IF-MoS2 nanoparticles lost their lubricating abilities when added to fully-formulated lubricants. This behavior was attributed to the presence of dispersants in the oil, which dispersed the nanoparticles effectively but prevented them from forming tribofilms on the rubbing surfaces. The well-dispersed IF-MoS2 were shown to enter the contact and exfoliate, but an excessive adsorption of the dispersants on the released MoS2 platelets and/or the steel surfaces is thought to prevent tribofilm adhesion. A balance between nanoparticle dispersion and tribological performance was then found, by using very low concentrations of dispersants. The behavior of nanoparticle-doped oils in various scenarios related to automobile applications was finally explored. The IF-MoS2 provided significant friction and wear reduction at ambient temperature and in milder rolling/sliding test conditions, for smooth and rough surfaces. The risks related to the presence of nanoparticles in the oil in full-film lubrication regimes were partially lifted, with no significant influence on friction witnessed for all the test conditions considered. The ability of IF-MoS2 nanoparticles to protect steel surfaces from surface-initiated Rolling Contact Fatigue was finally shown.

No description available.

Le concept de décomposition par un faisceau électronique a été développé dans le but de créer des motifs supportés de taille inférieure à celle atteinte par les méthodes lithographiques classiques. Ce travail avait pour objectif d’appréhender ce concept à travers une séparation des mécanismes mis en jeu, de façon à mieux les comprendre pour mieux les contrôler.Un dispositif a été conçu et un protocole défini où une première étape correspond à l'adsorption à température cryogénique de composés carbonylés à cœur métallique. L’adsorbat est ensuite décomposé par un faisceau d’électrons focalisés puis les résidus de la fragmentation sont éliminés lors de recuits permettant la réorganisation du dépôt lithographié. Pour suivre les différentes étapes, une approche de type « science des surfaces » a été choisie car elle offre la possibilité d’étudier les processus mis en jeu à l’aide de techniques d'analyses sensibles à la chimie.Ainsi, ce travail a permis de mettre en évidence que l'adsorption à température cryogénique de Mo(CO)6 et W(CO)6 sur des surfaces métalliques ou oxydes n'induit pas d'important changement de leur structure moléculaire démontrant que cette étape est renversable. Par ailleurs, il a été montré que les électrons de basse énergie (< 150 eV) engendrent la dissociation de ces molécules par un processus de collision mono-électronique et qu'il est aussi possible de les décomposer à l'aide d'un faisceau d'électrons lorsqu'elles sont physisorbées, menant à la formation de dépôts stables à température ambiante. Un traitement thermique finalise la décomposition. La morphologie finale est liée à la dose d'électrons et à la quantité initiale de molécules adsorbées. / The concept of electon beam decomposition has been developed in order to create smaller patterns than those achieved by conventional lithographic methods. This work aimed to go further about this concept through a separation of the involved mechanisms in order to better understand them and thus reach a better control of process.A device was designed and a protocol was defined where the first stage is the adsorption at cryogenic temperature of metal-carbonyl compounds. The adsorbate is then decomposed by a focused electron beam and fragmentation residues are removed through annealing allowing the deposit reorganization. The study of the different steps of the elaboration method was followed through the "surface science" approach because such a way offers the opportunity to study the processes involved by analytical techniques sensitive to material chemistry.Thus, this work has highlighted that the adsorption at cryogenic temperature of Mo(CO)6 and W(CO)6 on metal or oxide surfaces does not induce any significant changes in their molecular structure demonstrating that this step is reversible. Moreover, it was shown that low energy electrons ( <150 eV ) cause dissociation of these molecules by a one-electron process. Moreover, it is possible to decompose adsorbed molecules with a focused electron beam, leading to the formation of a stable deposit at room temperature. Annealing treatment can complete the decomposition. Besides, the final morphology is related to the electron dose as well as the initial amount of adsorbed molecules.

Due to the short period that some photovoltaic technologies have taken part on the solar energy market, it is crucial to evaluate the long term stability of solar cells belonging to those technologies in order to ensure a minimum lifetime of their performance. Accelerated degradation tests are thus carried out to achieve such goals. The present study analyzes the encapsulation effects on co-evaporated manufactured Copper Indium Gallium Selenide (CIGS) solar cells under damp heat conditions, consisting in 85 °C and 85 % relative humidity, during an approximated period of 1000 hours. The experimental procedure has been carried out at Solliance Solar Research facilities. Since the encapsulation packages play a critical role as a protection to achieve long term stability of the solar cells and modules, several packaging structures and materials has been taken into study. Thus, eighteen types of mini modules were manufactured including different combinations of encapsulants, front sheet foils, thin film protective barriers and CIGS cells from different manufacturers. The design of these mini modules and the manufacturing process to obtain them is also presented in this work. Various characterization techniques were carried out in order to acquire the required information about the solar cells and encapsulants performance along the damp heat degradation process. The results exposed that encapsulation packages including thin film barriers between the encapsulant and the front sheet foil allowed a longer solar cell lifetime due to their remarkable protection against moisture ingress. Moreover, the degradation of the molybdenum layer included in the CIGS cells was found as principal cause of efficiency decrement and end of performance of solar cells protected by regular encapsulant and front sheet foils. Some other findings in relation with the evaluated components are shown along the present study.