Submitted by HILTON RIQUIERI null (hilton.riquieri@terra.com.br) on 2018-01-11T19:29:07Z No. of bitstreams: 1 Tese Impressão 11-01-18.pdf: 5465220 bytes, checksum: 6c44956d0ac81de9008cdd4833458455 (MD5) / Approved for entry into archive by Silvana Alvarez null (silvana@ict.unesp.br) on 2018-01-18T15:27:03Z (GMT) No. of bitstreams: 1 riquieri_h_dr_sjc.pdf: 5445301 bytes, checksum: bf194667a00b4990a467e32526c3cdb9 (MD5) / Made available in DSpace on 2018-01-18T15:27:03Z (GMT). No. of bitstreams: 1 riquieri_h_dr_sjc.pdf: 5445301 bytes, checksum: bf194667a00b4990a467e32526c3cdb9 (MD5) Previous issue date: 2017-12-04 / O objetivo deste trabalho foi avaliar o silicato de lítio reforçado por zircônia quanto a sua microestrutura e as mesmas propriedades mecânicas em diferentes fases de cristalização. Cento e vinte amostras de discos de silicato de lítio reforçado por zircônia foram usinados de acordo com as normas ISO 6872 (12x1,2mm) para o ensaio de flexão biaxial. Foram separados em 4 grupos de acordo com a fase de cristalização. Grupo I: 30 amostras de Celtra pré cristalizado (CNC); Grupo II: 30 amostras de Celtra cristalizado (CC); Grupo III: 30 amostras de Suprinity Não Cristalizado (SNC) e Grupo IV: 30 amostras de Suprinity Cristalizado (SC). Os corpos de prova foram submetidos ao ensaio mecânico de flexão biaxial e em seguida realizadas análises qualitativas e quantitativas. Por meio microscopia eletrônica de varredura, microscopia eletrônica com emissão de campo MEV-FEG, EDS e difração de raios X (n=4), foi realizada a caracterização completa dos materiais e análise morfológica da microestrutura para todos os grupos. Para as análises estatísticas foram utilizados o módulo Weibull (m) e resistência característica (σ0). / The objective of this work was to evaluate the lithium silicate reinforced by zirconia as to its microstructure and the same mechanical properties in different phases of crystallization. One hundred and twenty samples of zirconia-reinforced lithium silicate discs were machined according to ISO 6872 (12x1,2mm) standards for the biaxial flexural test. They were separated into 4 groups according to the crystallization step. Group I: 30 samples of Pre-Crystallized Celtra (CPC); Group II: 30 samples of Crystallized Celtra (CC); Group III: 30 samples of Uncrystallized Suprinity (SNC) and Group IV: 30 samples of Crystallized Suprinity (SC). The specimens were submitted to the mechanical biaxial flexion test and qualitative and quantitative analyzes were performed. Scanning Electron Microscopy, Electron Microscopy with Field emission SEM-FEG, EDS and X-ray diffraction (n = 4) were carried out to characterize the materials and morphological analysis of the microstructure for all groups. The Weibull (m) and characteristic resistance (σ0) were used for the statistical analysis.

Made available in DSpace on 2014-12-17T14:06:53Z (GMT). No. of bitstreams: 1 YankelBFC.pdf: 3745387 bytes, checksum: 0a72ac9538c533fa074f31beeeb3660d (MD5) Previous issue date: 2008-12-29 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Ceramics materials have good properties including chemical stability, high hardness and wear resistance. Moreover, due to its fragility, can suffer failure under relatively low levels of tension. Actually zirconia is the material of choice in metal free dental prostheses used in dentistry due its inertia in physiological environment, good bending strength, hardness and fracture toughness. The alumina and mixed tungsten and titanium carbides additions, acting as reinforcement elements in the zirconia matrix, have as their main objective the improvement of mechanical properties of this material. In this work, samples of zirconia, zirconia with 30% wt of alumina and zirconia with 30% wt mixed carbides were analyzed. The samples were sintered by uniaxial hot pressing on 30 MPa pressure, for 1 hour in an argon atmosphere. They were physically characterized by porosity and density measurements, and mechanically by 3-points bending strength and Vickers microhardness. The X-ray diffraction was used for the phase identifications and microstructure was examined by scanning electron microscopy (SEM). The addition of mixed carbides as reinforcement elements in zirconia matrix provides improvements in all properties analyzed in this work. The alumina addition has dropped the zirconia strength, although it caused improvement in other properties / Materiais cer?micos apresentam boas propriedades incluindo estabilidade qu?mica, elevada dureza e resist?ncia ao desgaste. Por outro lado, devido a sua fragilidade, podem sofrer falha sob n?veis de tens?es relativamente baixos. A zirc?nia ? hoje o material de escolha em odontologia para o uso em pr?teses dentais do tipo metal free por ser inerte em meio fisiol?gico, apresentar boa resist?ncia ? flex?o, dureza e tenacidade ? fratura. A adi??o da alumina e dos carbetos mistos de tungst?nio e tit?nio ,atuando como elementos de refor?o na matriz de zirc?nia, t?m como principal objetivo o aperfei?oamento das propriedades mec?nicas deste material. No presente trabalho, foram analisadas amostras de: zirc?nia, zirc?nia com 30% em peso de alumina e zirc?nia com 30% em peso de carbetos mistos. Os corpos de prova foram sinterizados por prensagem a quente uniaxial, sobre press?o de 30 MPa, durante 1 hora em atmosfera de arg?nio. Os mesmos foram caracterizados fisicamente por meio de medidas de porosidade e de densidade, e mecanicamente por resist?ncia a flex?o em 3 pontos e microdureza Vickers. A difra??o de raios X foi utilizada para a identifica??o das fases presentes e a microestrutura foi analisada por microscopia eletr?nica de varredura (MEV). A adi??o dos carbetos mistos como elemento de refor?o da matriz de zirc?nia ocasionou uma melhoria em todas as propriedades analisadas neste trabalho. A adi??o da alumina proporcionou uma queda na resist?ncia mec?nica da zirc?nia, apesar de ter ocasionado melhora nas demais propriedades

Depuis plus de dix ans les capacités MIM (Métal Isolant Métal) sont des composants passifs largement intégrés au niveau des interconnections des puces de microélectronique. A cause de la miniaturisation et de la réduction de la surface des puces, la densité de capacité des capacités MIM doit être constamment augmentée. Une solution est l'utilisation d'un isolant avec une constante diélectrique élevée dit « high-k ». Pour les prochaines générations de condensateurs, des densités de capacité supérieur à 30 fF/µm² sont visées. L'oxyde de zirconium (ou zircone) a été sélectionné pour remplacer de l'oxyde de tantale actuellement utilisé. Il possède une constante diélectrique qui dépend de sa structure cristalline. Elle est respectivement de 17, 47 et 37 dans les phases monoclinique, quadratique et cubique. Il est donc nécessaire de déposer la zircone dans la phase quadratique. Cependant, les couches minces de zircone ne sont pas entièrement cristallisées dans la phase quadratique. De plus, elles ne répondent pas aux critères de fiabilité requis par la microélectronique. L'objectif de cette thèse est la stabilisation de la zircone dans la phase quadratique par le dopage. Le tantale et le germanium sont les deux dopants choisis grâce à une étude de sélection de matériaux. Des couches minces d'environ 8 nm de zircone dopée à différentes concentrations ont été réalisées par PEALD (Plasma Enhanced Atomic Layer Deposition). Après les dépôts, des recuits à 400°C pendant 30 min ont été effectués afin de reproduire les traitements thermiques subis par les couches lorsqu'elles sont intégrées dans des puces de microélectronique. Plusieurs types de caractérisations ont été effectuées afin d'étudier l'influence des dopants sur la structure cristalline de la zircone mais aussi sur ses propriétés physico-chimiques. Des tests électriques sur des capacités MIM intégrées ont permis de mesurer les propriétés électriques des couches et la fiabilité de la zircone dopée a été évaluée. Ce travail a pour but la fabrication d'une capacité MIM planaire à base d'oxyde de zirconium dopée dont la densité de capacité sera supérieure à 30 fF/µm² pour des applications de découplage. / For more than ten years Metal-Insulator-Metal capacitors (MIM) have been integrated at the level of copper interconnections. All new technology nodes have led to a decrease of the surface of chips; capacitance density must be thus enhanced. The best solution is to use a material with a high dielectric constant commonly named “high-k”. For the next MIM capacitor generation, capacitance density has to be higher than 30 fF/µm². Tantalum oxide, currently used, has reached its limits and it must be replaced. Zirconium dioxide has a high dielectric constant of 47 in the tetragonal phase with a sufficient band gap for MIM applications. When deposited in thin films, zirconia is not fully crystalized in the tetragonal phase. Moreover, this pure zirconium oxide does not fulfill the reliability criteria. The aim of this work is to stabilize zirconia in its tetragonal phase by alloying it with other elements. Tantalum and Germanium are the two dopants selected thanks to a bibliographic study. Thin layers of zirconia of 8 nm alloyed with Tantalum and Germanium have been deposited by Plasma Enhanced Atomic Layer Deposition (PEALD). Samples were annealed at 400°C during 30 minutes after deposition to reproduce the thermal conditions that microelectronic chips are submitted to. Different characterization technics have been used to study the effect of dopants on zirconia's crystalline structure and its physic-chemical properties. Tests have been made on integrated MIM capacitors with Titanium Nitride electrodes to determine the electrical properties of the layers. Reliability of zirconia doped layers was also evaluated. The purpose of this work is the production of zirconia based planar MIM capacitor with a capacitance density of 30 fF/µm².

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-10-17T20:04:39Z No. of bitstreams: 1 DIVANIRA FERREIRA MAIA - TESE PPGEP 2006..pdf: 9063307 bytes, checksum: 4a8a7f017dc5bdd4ff2e4624de86ba98 (MD5) / Made available in DSpace on 2018-10-17T20:04:39Z (GMT). No. of bitstreams: 1 DIVANIRA FERREIRA MAIA - TESE PPGEP 2006..pdf: 9063307 bytes, checksum: 4a8a7f017dc5bdd4ff2e4624de86ba98 (MD5) Previous issue date: 2006-04-20 / A presença de óleo na água produzida durante a extração de petróleo, causa sérios problemas tanto ao ser descartada no meio ambiente como ao ser reinjetada nos poços produtores de petróleo. Os métodos convencionais utilizados na separação óleo/água não conseguem limpar toda a água com eficiência e baixo custo. Assim sendo, a busca por novas alternativas para solucionar este problema foi a motivação principal deste trabalho, sendo este parte integrante de uma série de pesquisas, financiadas pela Agência Nacional de Petróleo (ANP), que visa otimizar todas as etapas de produção de petróleo. Assim o objetivo deste trabalho foi produzir membranas cerâmicas visando a sua aplicação na separação óleo/água. Inicialmente foram obtidos dois tipos de membranas tubulares de alumina, denominadas tipo 1 e tipo 2, com diferentes tamanhos de poros de aproximadamente 0,9\im e 15,5nm e com eficiências mínimas de aproximadamente 97,5% e 93,8%, respectivamente. Porém a membrana tipo 2 apresentou um fluxo 40 vezes maior que a membrana tipo 1. Assim, visando melhorar mais ainda o desempenho da membrana tipo 2 depositou-se sobre a mesma uma camada fina de zircônia, de forma que pudesse melhorar sua eficiência sem alterar significativamente seu fluxo. O pó de zircônia foi obtido com sucesso pelo método Pechini. Com este método foi possível a obtenção da zircônia cristalina cujos tamanhos de aglomerados indicaram que este material pode ser usado na obtenção de membranas de ultrafiltração. Para obtenção da camada de zircônia foi preparada uma suspensão com a zircônia obtida e esta foi depositada na parte interna da membrana de alumina tipo 2 usando a técnica de deposição "dip coating". A camada de zircônia formada apresentou uma espessura de 23,9 ^im, um fluxo superior a membrana de alumina tipo 1 e uma eficiência mínima de 97,8%. Para todas as membranas obtidas, a concentração de óleo no permeado foi abaixo de 7 ppm, usando concentração máxima de 1000 ppm na alimentação. A água permeada através das membranas estudadas se enquadraram nas especificações para uso na reinjeção e no descarte. / The presence of oil in water produced during the petrol extraction can cause serious problems during the discharge in the environment as well as in the re-injection in the oil well. The conventional methods used to remove oil from water can not clean with efficiency and low cost. So, the search for new alternatives to solve this problem is the motivation of this work. This study is part of a series of researches supported by Agência Nacional de Petróleo (ANP), with the aim to optimize ali the steps in the oil production. The aim of this work is to make ceramic membrane to be applied in the oil/water separation. Firstly, it was prepared two types of tubular alumina membranes, called type I and type 2, with different pore size of approximately 0.9nm and 15, 48nm, respectively. The minimal efficiency of these membranes was approximately 97.5% and 93.8% for membrane type I and type 2, respectively. However, the membrane type 2 shown a flux 40 times greater than the membrane type 1. To improve the use of the membrane type 2 it was coating the internai surface with a thin layer of zircônia to get better efficiency without to decrease the flux. The zircônia powder was prepared with success by Pechini method and it was obtained a crystalline zircônia with agglomerates that indicate the use to make ultrafiltration membranes. To obtain the zircônia layer it was prepared dispersion and deposited in the internai surface of the membrane type 2 by dip coating technique. The zircônia layer presented a thickness of 23.88}im, a flux grater than the alumina type 1 and a minimal efficiency of 97.8%. Ali studied membrane presented oil content in permeate below 7ppm, using a maximum concentration of lOOOppm in the feed tank. The permeate water through the studied membranes is in agreement with the norms to be discharge in the environment or to be re-injected in the oil well. / PRH 25.

Este trabalho traz a aplicação de alta pressão e alta pressão/temperatura (4.0 GPa e 400º C), em amostras de nanotubos de carbono de paredes múltiplas (NTCPM) comerciais para a obtenção de amostras compactas. Os NTCPM foram funcionalizados com ácido nítrico e ácido nítrico/ácido sulfúrico e, também foram usados nanotubos de carbono dopados com nitrogênio. Foram também processadas amostras contendo nanotubos de carbono de paredes múltiplas incorporados em matriz de zircônia obtida pelo método sol-gel. Para aplicação da alta pressão foi usado um sistema com câmaras do tipo toroidal, utilizando grafite como meio transmissor de pressão. Foram obtidas amostras macroscópicas autossuportadas e com resistência ao manuseio principalmente nas amostras de nanotubos de carbono funcionalizados com ácido nítrico/ácido sulfúrico incorporados em zircônia. Para a caracterização das amostras foram utilizadas as técnicas de Microscopia Eletrônica de Transmissão, Espectroscopia Raman, Difração de Raios X e isotermas de adsorção/dessorção de nitrogênio com as quais foi possível determinar que mesmo após a aplicação de alta pressão/temperatura os nanotubos de carbono não sofrem significativas modificações na sua estrutura e nas suas propriedades morfológicas e texturais, confirmando então que os NTCPM mantém suas características originais, apresentando condições para aplicações em dispositivos. As amostras macroscópicas contendo nanotubos de carbono de paredes múltiplas incorporados em zircônia apresentaram ainda resistência à carga de milhares de vezes o seu peso e comportamento de materiais semi-condutores. / This work presents the application of high pressure and/or high pressure/temperature (4.0 GPa and 400 ° C), on different samples of commercial multi-walled carbon nanotube (MWCNT) to obtain compacted samples. MWCNT were functionalized with nitric acid and nitric acid/sulfuric acid, and also carbon nanotubes doped with nitrogen. MWCNT incorporated in a zirconia matrix obtained by sol-gel method were also processed. For high pressure application it was used a system with the toroidal-type chamber, using graphite as a pressure transmitting medium. Self-supported macroscopic samples were obtained, easy to handle, especially in samples of functionalized carbon nanotubes with nitric and sulfuric acid and also incorporated in zirconia. To characterize the samples it was used Transmission Electron Microscopy, Raman Spectroscopy, X-ray diffraction and nitrogen adsoption/desorption isotherms and it was determined that even after application of high pressure/temperature carbon nanotubes do not suffer significant changes in their structure and in their morphological and textural properties, confirming that the CNT keeps its original characteristics and providing conditions for device applications. The macroscopic samples containing MWCNT incorporated in zirconia also exhibited resistance to load of thousands times its own weight and behavior like semiconductor materials.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo deste estudo foi avaliar a resistência de união a microtração de cimentos resinosos autoadesivos a cerâmicas de zircônia policristalina. Dezoito blocos cerâmicos de zircônia 3Y-TZP (9 LAVA e 9 LAVA Plus) foram jateados com partículas de 50 m de Al2O3por 20 s com pressão de 28 psi a uma distância de 10 mm. Os blocos cerâmicos foram duplicados em resina composta (Point 4, Kerr) por moldagem com silicone. Os blocos de resina composta foram cimentados à superfície jateada da zircônia usando três diferentes cimentos resinosos autoadesivos: (1) RelyX Unicem 2 (3M ESPE); (2) SmartCem 2 (Dentsply); (3) Speedcem (Ivoclar Vivadent). Após 24 h imersos em água destilada a 37oC, os blocos cimentados foram cortados em palitos para testes de microtração,com área da interface adesiva de 1 mm2 0,2 mm, e tensionados até a fratura. Os resultados foram analisados pelo teste de análise de variância de dois fatores e pelo teste de comparações múltiplas LSD (&#945;=0.05). As amostras fraturadas foram analisadas com microscopia eletrônica de varredura (MEV) e o modo de falha foi registrado. A topografia das superfícies cerâmicas antes e após o jateamento foi comparada por microscopia de força atômica (AFM). A resistência de união do cimento Speedcem à zircônia foi estatisticamente superior àquela reportada pelos cimentos RelyX Unicem 2 e SmartCem 2, independentemente da cerâmica usada (p<0,05). O fator cerâmica não teve influência estatística na resistência de união. A interação entre os dois fatores se mostrou significativa (p<0,05). O modo de fratura associado ao SmartCem 2 foi quase exclusivamente adesiva, enquanto oRelyX Unicem 2e o Speedcem exibiram um maior percentual de falhas mistas. Não foram observadas falhas coesivas. O AFM não revelou diferença no padrão de topografia de superfície entre as duas cerâmicas antes ou após o jateamento. Concluiu-se que o cimento Speedcem foi superior na adesão a cerâmicas de zircônia policristalina. / The aim of this study was to evaluate the microtensile bond strength of self-adhesive resin cements to polycrystalline zirconia. Eighteen 3Y-TZP ceramic blocks (9 LAVA and 9 LAVA Plus) were sandblasted with 50 m Al2O3 powder for 20 s with a pressure of 28 psi at a working distance of 10 mm. The ceramic blocks were duplicated in composite resin (Point 4, Kerr) using a silicon mold. Composite blocks were bonded to sandblasted zirconia using different self-adhesive resin cements: (1) RelyX Unicem 2 (3M ESPE); (2) SmartCem 2 (Dentsply); (3) Speedcem (Ivoclar Vivadent). After 24 h immersed in distilled water at 37oC the bonded specimens were cut into microtensile bond sticks of 1 mm2 0,2 mminterface areaand loaded in tension until failure. Data were analyzed by two-way ANOVA and LSDtest for multiple comparisons (&#945;=0.05). The fractured surfaces were observed using a scanning electron microscope (SEM) and the failure mode was recorded. Surface topography of the sandblasted and the as sintered zirconia materials were analyzed under an atomic force microscope (AFM).Bond strength of Speedcem cement to zirconia was significantly higher than that of RelyX Unicem 2 and SmartCem 2, irrespective of the ceramic used (p<0,05). Bond strength was not significantly influenced by the ceramic factor. Interactions were significant (p<0,05). The mode of failure of SmartCem 2 was almost exclusively adhesive, while RelyX Unicem 2 and Speedcem exhibited a good percentage of mixed fractures. No cohesive fractures were observed. AFM did not reveal differences in the topography pattern of the two ceramics before or after sandblasting. It was concluded that Speedcem presented superior adhesion to polycrystalline zirconia ceramics.

Dans ce travail, nous nous sommes tout d’abord intéressés à l’influence du traitement de la mésophase hybride sous ammoniac et des conditions de cristallisation sur les propriétés d’oxydes de titane mésoporeux. Le protocole de synthèse de ces matériaux a été mis au point auparavant au laboratoire à l’aide d’une méthode combinant le mécanisme transcriptif à partir des cristaux liquides du copolymère bloc P123 et la méthode EISA. Une cristallisation sous atmosphère oxydante, augmente le degré de cristallinité et favorise une croissance des particules d’anatase. En conséquence, la photodégradation du méthylorange, utilisé comme molécule modèle est augmentée. Lorsque la cristallisation est réalisée sous azote pur, l’anatase n’est pas favorisée et la photoactivité est alors gouvernée par la surface spécifique des matériaux. Nous avons également montré qu’au cours de la synthèse, l’interaction de NH3 avec le titane amorphe promeut la formation de la structure rutile de TiO2 et défavorise par conséquent la cristallisation sous forme anatase. Par conséquent lorsque le traitement sous ammoniac de la mésophase hybride est prolongé ou lorsqu’ il est réalisé à pression élevée, l’activité photocatalytique des oxydes de titane, obtenus après cristallisation du TiO2 amorphe sous air synthétique, diminue. L’introduction d’un second niveau de mésoporisité permet d’accroitre l’efficacité des photocatalyseurs, car la diffusion et l’accès aux sites actifs des molécules de colorant sont améliorés. Les matériaux à double mésoporisité présentent une activité photocatalytique deux fois et demie supérieure à celle des oxydes de titane mésoporeux monomodaux. Des catalyseurs pour l’hydrodésulfuration des gazoles ont également étés conçus en dispersant la phase active MoS2 à la surface des oxydes de titane mésoporeux mono- et bimodaux. Le dibenzothiophène (DBT) et le 4,6-diméthylbenzodiophène (46DMDBT) ont été utilisées comme molécules modèles. Contrairement au catalyseur conventionnel MoS2/Al2O3, pour lequel l’hydrodésulfuration se produite selon la voie hydrogénante, grâce à la présence de sites acides de Brönsted, les catalyseurs supportés sur TiO2 mésoporeux favorisent la désulfurisation directe du 46DMDBT. Pour terminer, la méthode de synthèse mise au point pour TiO2 a été transposée à l’oxyde de zirconium. Toutefois, dans ce cas seul un arrangement vermiforme des canaux est obtenu. Ce phénomène est probablement lié à la présence du propanol contenu dans la source du précurseur inorganique. L’incorporation d’étain au sein des zircones mésoporeuses a également été réalisée et nous avons mis en évidence que cet élément est favorable à la cristallisation de ZrO2 / In this work, we have first investigated the effect of both the crystallization conditions and of the hybrid mesophase treatment under ammonia atmosphere on the properties of mesoporous TiO2, for which the preparation was developed previously via a method combining Liquid Crystal Templating (LCT) and EISA mechanisms, using P123 as template. The photocatalysis efficiency of the materials crystallized under oxidizing conditions increases with the calcination temperature thanks to the enhancement of crystallinity and the growth of anatase particles. By contrast, when the crystallization is performed under pure nitrogen the anatase is not favored and the photocatalytic activity is governed by the materials’ specific surface area. We have also shown that during the mesoporous TiO2 synthesis, interactions between ammonia and amorphous titania promote the formation of rutile, which is a drawback for the transformation of amorphous titania into anatase. Consequently, when the treatment under ammonia is prolonged or when it is performed at high NH3 pressure, the activity of the photocatalysts recovered after crystallization under synthetic air decreases. The introduction of a second mesoporosity level enhances the degradation rate. In that case the diffusion and the accessibility of the dye molecules to the active sites are favored. Catalysts for gazole hydrodesulfurization have also been designed by dispersing the active MoS2 phase onto the surface of the mono and dual mesoporous titania. The obtained catalysts have been tested for the hydrodesulfurization of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (46DMDBT), used as model molecules. We highlight that thanks to the intrinsic Brönsted acidity, the CoMoS/mesoporous TiO2 catalysts favor the direct desulfurization route of 46DMDBT, in contrary to the conventional CoMoS/alumina catalyst. The synthesis procedure developed for mesoporous TiO2 has also been adapted for the preparation of mesoporous ZrO2. However, only mesoporous materials with a wormhole-like structure have been obtained. This phenomenon is likely due to the presence of propanol contained in the source of the inorganic precursor. We have also incorporated tin into the zirconia framework. The presence of thin favors the crystallization of ZrO2

Submitted by Fabricio Malheiros de Miranda Monteiro (drfabriciomalheiros@hotmail.com) on 2018-07-18T02:33:45Z No. of bitstreams: 2 Dissertação final Fabricio - Após defesa PDF.pdf: 2296763 bytes, checksum: ed270b35065a6429cbde4e2e753d6939 (MD5) Verso - Contra capa.pdf: 2579 bytes, checksum: 284cd58d1fec7c9b0fd7c0cc97473d8b (MD5) / Approved for entry into archive by Silvana Alvarez null (silvana@ict.unesp.br) on 2018-07-18T18:10:35Z (GMT) No. of bitstreams: 1 monteiro_fmm_me_sjc.pdf: 2237869 bytes, checksum: 8ae93eb96970a513787047d5630ce786 (MD5) / Made available in DSpace on 2018-07-18T18:10:35Z (GMT). No. of bitstreams: 1 monteiro_fmm_me_sjc.pdf: 2237869 bytes, checksum: 8ae93eb96970a513787047d5630ce786 (MD5) Previous issue date: 2018-06-25 / O intuito deste estudo in vitro e in silico, foi analisar as microdeformações, geradas pela aplicação de carga vertical, sobre coroas de 3 tipos de materiais restauradores diferentes (Zircônia, Dissilicato de Lítio e Cromo Cobalto), que foram selecionadas, através da biblioteca do software SMART DENT/Exocad (Darmstadt - Germany) e confeccionadas, através da tecnologia cad/cam, suportadas por implantes curtos (8mm), conexão cone morse, com diversos diâmetros (3,5 mm; 4,0 mm e 5,0 mm). Os implantes foram instalados 2mm infraósseo para análise através de elementos finitos e da extensometria. Foram confeccionados 3 blocos de poliuretano: bloco 1 (grupo experimento) no qual foi colocado um implante Titamax CM Neodent 3,5 X 08 mm, bloco 2 (grupo controle) no qual foi colocado um implante titamax CM Neodent 4,0 X 08 mm e bloco 3 (grupo controle) no qual foi colocado um implante titamax CM Neodent 5,0 X 08 mm. Pilares protéticos retos (Base de Titânio 4,5 - Neodent) foram instalados sobre os respectivos implantes sendo instalados 4 extensômetros, na região superior dos blocos ao redor dos implantes. Foi aplicada uma carga vertical de 300N ao redor da abertura de acesso do parafuso protético das coroas. Para a análise por elementos finitos (FEA), o mesmo bloco foi modelado e analisado sob a mesma carga de 300N. Os valores de tensão e deformação foram analisados quanto à correlação com a extensometria. A estatística inferencial consistiu no teste de análise de variância de Friedmann, um fator efeito fixo. Para o nível de significância, foi escolhido o valor convencional de 5%. Os resultados demonstraram haver diferença estatística significante para o fator diâmetro (p = 0,0001) no qual os implantes, com 3,5 mm de diâmetro apresentaram os maiores picos de microdeformações. Quando se analisa o material restaurador, observa-se que não houve diferenças estatísticas significativas (p = 0,783). Dentro das limitações deste estudo, pode-se concluir que a utilização de implantes unitários, curtos e estreitos com conexão cone morse instalados 2 mm infraósseo, são uma opção viável para reabilitações em regiões posteriores independente do material restaurador escolhido. / The aim of this in vitro and in silico study was to analyze the microdeformations generated by the application of vertical load on crowns of 3 different types of restorative materials (Zirconia, Lithium Dissilicate and Cobalt Chromium) that were selected through the software library SMART DENT / Exocad (Darmstadt - Germany), and made using cad / cam technology, supported by short implants (8 mm), cone morse connection with various diameters (3.5 mm, 4.0 mm and 5.0 mm). These were installed 2 mm subcrestal for finite element analysis and extensometry. Three blocks of polyurethane were made; block 1 (experimental group) in which a Titamax CM Neodent 3.5 X 08 mm implant, block 2 (control group) was implanted in which a CM Neodent 4.0 X 08 mm titamax and block 3 (control group) were implanted in which an implant was placed titamax CM Neodent 5.0 X 08 mm. Straight prosthetic abutments (Titanium Base 4.5 - Neodent) were installed on the respective implants and 4 extensometers were installed, in the upper region of the blocks around the implants. A vertical load of 300N was applied around the access opening of the crown prosthetic screw. For the finite element analysis (FEA), the same block was modeled and analyzed under the same 300N load. The stress and strain values were analyzed for correlation with extensometry. The inferential statistics consisted of Friedmann's analysis of variance, a fixed effect factor. For the level of significance, the conventional value of 5% was chosen. The results showed a statistically significant difference for the diameter factor (p = 0.0001) where 3.5 mm diameter implants presented the highest peaks of microdeformations. When analyzing the restorative material, we observed that there were no significant statistical differences (p = 0.783). Within the limitations of this study, we can conclude that the use of short, narrow unit implants with cone morse connection installed 2 mm subcrestal are a viable option for rehabilitation in posterior regions independent of the restorative material chosen.

Dans le domaine des piles SOFC, un des principaux objectifs actuels est la réduction de latempérature de fonctionnement des cellules en deçà de 700°C, afin de garantir une plusgrande durabilité des systèmes électrochimiques et des matériaux de cellules. En outre, leprocédé d’élaboration d’une cellule complète comprend actuellement deux voire trois étapesde frittage; une seule opération de frittage pourrait conduire à une diminution conséquente ducoût de production de la cellule. Le but de ce travail de thèse est d’apporter une contribution àces deux problématiques en proposant un procédé d’élaboration d’une cellule de pile àcombustible SOFC en une seule opération dite de cofrittage et avec une sélection dematériaux à hautes performances électrochimiques.Cette thèse a été abordée selon trois thématiques principales : mécanique, microstructurale etélectrochimique.Après la caractérisation du comportement en frittage des matériaux retenus pour l’étude, uncycle de frittage conduisant à une microstructure d’électrolyte acceptable (porosité fermée) aété sélectionné. Le cofrittage a ensuite été étudié selon un aspect mécanique. Les phénomènesde courbure engendrés par le cofrittage ont été expliquées à l’aide d’une modélisationanalytique et confrontées à des observations in situ. Le travail s’est ensuite orienté dans uneapproche microstructurale avec l’optimisation de la microstructure de la cathode en utilisantune modélisation numérique basée sur la méthode des éléments discrets. Les composants de lacellule complète ont finalement été caractérisés par spectroscopie d’impédanceélectrochimique afin d’optimiser leurs performances. Enfin, une cellule complète exempt defissure a été réalisée par cofrittage et ses performances électrochimiques ont été estimées. / In the field of SOFCs, a major objective is the reduction of the cell operating temperaturebelow 700°C, in order to ensure greater durability of electrochemical systems and cellmaterials. In addition, the fabrication process of a complete cell currently includes two orthree stages of sintering. Thus one sintering process could lead to a consequent decrease in theproduction cost of the cell. The purpose of this thesis is to contribute to these two issues byproposing a method for manufacturing a SOFC fuel cell in a single operation called cofiringand with a selection of high electrochemical performance materials.This thesis is addressed in three main areas: mechanical, microstructural and electrochemical.After sintering behavior characterization of the selected materials, a sintering cycle leading toan acceptable electrolyte microstructure (closed porosity) was selected. The cofiring was thenapproached by a mechanical aspect. The curvature Phenomena caused by of cofiring wereexplained using an analytical model and compared with in situ observations. The work is thencontinued with a microstructural approach. The optimization of the cathode microstructurewas done using a numerical modeling based on the discrete element method. Cell componentswere finally characterized by electrochemical impedance spectroscopy to optimize theirperformances. Finally, a free crack complete cell was obtained by co-sintering process and herelectrochemical performance was estimated.

Devido a crescente preocupação com relação ao efeito estufa e com o objetivo de obter produtos de maior valor agregado a partir dos gases CH4 e CO2, este trabalho estudou catalisadores de níquel suportados em diferentes óxidos (Al2O3, CeO2, MgO e ZrO2) promovidos com ZnO aplicados na reação de reforma seca de metano para obter gás de síntese (H2 + CO). Primeiramente foram estudados catalisadores de níquel suportados em ZrO2 dopados com diferentes teores de zinco: 0%, 5%, 12,5% e 25% a fim de selecionar o catalisador mais promissor para estudos posteriores. Também foram utilizados dois métodos de preparo: impregnação e co-precipitação. Os resultados de DRX mostraram que a adição de zinco estabilizou a fase tetragonal da zircônia em todos os teores de zinco e em ambos os métodos de preparo. As análises de RTP mostraram que os catalisadores impregnados sofreram maior redução do que os co-precipitados e para maiores teores de zinco foram necessárias maiores temperaturas de redução. Os testes catalíticos mostraram que o aditivo zinco não exerceu efeito sobre os catalisadores impregnados, porém para as amostras co-precipitadas notou-se um teor ótimo com relação à conversão de reagentes na reação e o catalisador 5Ni12ZZc apresentou os melhores resultados. A deposição de carbono também foi menor nos catalisadores co-precipitados. No estudo dos diferentes suportes, as análises de DRX sugerem a dopagem de todos os óxidos com zinco, pois houve mudanças no parâmetro de rede em todas as amostras. As análises de RTP mostraram que a adição de zinco diminui a temperatura de redução do catalisador suportado em alumina e, no suporte CeO2 o efeito é o contrário. Nos testes catalíticos observaram-se efeitos distintos: nos catalisadores Ni-ZnO-CeO2 e Ni-ZnO-MgO o efeito da adição de zinco causou diminuição na conversão dos reagentes, por outro lado, causou diminuição na deposição de carbono e inibição da formação do carbono grafite; nos catalisadores Ni-ZnO-Al2O3 a conversão de reagentes não se alterou com a adição de zinco porém houve uma diminuição na deposição de carbono. Os melhores resultados, portanto, foram apresentados pelo catalisador 5NiZnAl que converteu acima de 80% dos reagentes e não sofreu desativação pela deposição de carbono. / Due to the increasing concern related to the greenhouse effect and aiming to obtain products with higher added-value from CH4 and CO2 gases, nickel catalysts supported on different oxides (Al2O3, CeO2, MgO and ZrO2) promoted with ZnO were studied and applied to the dry reforming of methane reaction to obtain syngas (H2+CO). Firstly, ZrO2 supported Nickel catalysts doped with different zinc content: 0, 5, 12,5 and 25% molar ratio were used to identify and select the best amount of zinc to further studies. Two preparation methods were investigated: impregnation and co-precipitation. The XRD results showed that the zinc addition stabilized the zircon tetrahedral phase of all catalysts from both preparation methods. The TPR analyses showed that the impregnated catalysts reduced more than the co-precipitated ones and higher reduction temperature was needed for the catalysts with higher zinc content. The catalytic tests indicated that the zinc content did not have any effect over the impregnated catalysts, whilst for the co-precipitated samples, a great content was noted and the 5Ni12ZZc catalyst showed the best results. The co-precipitated catalysts also had lower carbon deposition. In the study of different supports, the XRD analyses showed that the zinc interacts with all the used oxides, because there were changes of the cell parameter of all samples. The TPR analyses indicated that the zinc addition lowers the reduction temperature of the alumina supported catalyst and the effect is opposite for the CeO2 support. Different effects were observed during the catalytic tests: for the CeO2 and MgO supported catalysts the effect of zinc addition caused a decrease in the conversion of reactants, but it lowered the deposition of carbon and inhibited the formation of graffiti carbon; for the Al2O3 supported catalysts, the reactant conversion was the same with the addition of zinc, however there was a reduction on the carbon deposition. Therefore, the best results were obtained for the 5NiZnAl catalyst, which converted over 80% of the reactants and wasn\'t deactivated by carbon deposition.