Este trabalho tem por objetivo a caracterização de filmes finos de óxido de alumínio produzidos por deposição assistida por feixe de íons Ar+. Tal caracterização consiste em estabelecer a relação entre os parâmetros de produção (energia do feixe e uxo relativo de Ar), a composição e a estrutura dos lmes. Para tanto, utiliza-se técnicas de microscopia de força atômica, difração de raios-x, reetividade de raios-x e análise por feixe iônico. Resultados mostram que amostras produzidas à temperatura ambiente e à 450 oC são amorfas independentemente da energia do feixe iônico. Filmes formados com assistência de feixe possuem qualidade superior àqueles formados por deposição física de vapor. O bombardeamento de íons Ar+ mostra-se capaz de controlar a concentração de hidrogênio, a estequiometria, a rugosidade, o tamanho dos grãos e a densidade dos lmes nos. Amostras com excelente qualidade baixa rugosidade, estequiometria próxima da ideal e boa densidade foram produzidas utilizando íons com energia dentre 300 eV e 600 eV. / The scope of this work is the characterization of aluminum oxide thin films produced by Ar+ ion beam assisted deposition. This characterization consists in establishing the relationship between production parameters (ion beam energy and argon relative ux), structure and composition of these lms. In order to undertake this task, the following techniques were used: atomic force microscopy, x-ray diraction, x-ray reectivity and ion beam analysis. Results show that samples produced at room temperature and at 450 oC are amorphous regardless the ion beam energy. Films grown under ion assistance have better characteristics than the ones deposited by physical vapor deposition. The ion beam bombardment is capable of controlling hydrogen concentration, stoichiometry, roughness, grain size and density of alumina samples. High quality lms at surface and increased density lms with near ideal stoichiometry were produced with 300 eV and 600 eV ion beam energy.

Objetivos: verificar a influência da técnica de microinfiltração, pressão pulpar simulada, armazenamento e fadiga cíclica na microinfiltração e integridade marginal das coroas In-Ceram alumina. Material e métodos: Dentes pré-molares superiores humanos de dimensões semelhantes receberam preparos para coroa total com 4mm de altura, 6 graus de convergência e 2mm de desgaste axial e oclusal. Coroas de In-Ceram alumina com 0,5mm de espessura foram obtidas e cimentadas com Panavia F/Clearfil SE Bond (PAN-SE) e/ou Rely XARC/Adper Single Bond 2 (REL-SB). Quatro hipóteses foram testadas: 1) Ausência de diferença na microinfiltração entre uma nova técnica sugerida para verificar a microinfiltração, quando comparada à técnica convencional, 1.1) Verificar se a nova técnica é adequada para estudos laboratoriais de microinfiltração, 2) A pressão pulpar simulada (15cmH2O) não altera a microinfiltração; 3) O armazenamento (90 dias) / fadiga cíclica (500.000 ciclos, 2Hz, 5kg) não têm influência na microinfiltração marginal e 4) O armazenamento/fadiga cíclica não influenciam a integridade marginal das coroas. Grupos controle foram constituídos em todos os experimentos. Resultados: 1) Nenhuma diferença estatisticamente significante foi detectada entre as duas técnicas testadas para analisar a microinfiltração dentro de cada conjunto cimento/adesivo (p>0,05); 2) A pressão pulpar simulada alterou significativamente a microinfiltração nos conjuntos PAN-SE (Mann-Whitney, p=0,025) e REL-SB (Mann-Whitney, p=0,014); 3) O armazenamento em água (Mann-Whitney, p=0,032) e armazenamento/fadiga cíclica (Mann-Whitney, p=0,008) aumentaram significativamente a microinfiltração no conjunto PAN-SE; 4) A perda de integridade marginal foi de 4% e 10% nos conjuntos REL-SB e PAN-SE, respectivamente. Conclusões: 1) não houve diferença na microinfiltração entre uma nova técnica sugerida para verificar a microinfiltração, quando comparada à técnica convencional, 1.1) A nova técnica parece adequada para estudos laboratoriais de microinfiltração; 2) O uso da pressão pulpar alterou significativamente os valores de microinfiltração para os dois cimentos/adesivos; 3) O armazenamento/fadiga cíclica mostrou influência na microinfiltração para o cimento Panavia F; 4) O armazenamento/fadiga cíclica não tiveram influência estatisticamente significante na integridade marginal dos cimentos/adesivos testados. / Objectives: To verify the influence of microleakage technique, simulated pulpal pressure, water storage and cyclic fatigue on marginal integrity and microleakage of In-Ceram alumina crowns. Material and methods: Human premolar teeth of similar dimensions received complete crown preparation with a 6 convergence degree, 4mm-height and 2mm of axial and occlusal reduction. In-Ceram alumina copings 0.5mm-thick were obtained and cemented either with Panavia F/Clearfil SE Bond (PAN-SE) or Rely XARC/Adper Single Bond 2 (REL-SB). Four hypotheses were made: 1) No difference between a new technique and a standard one to verify microleakage, 1.1) To verify if a new microleakage technique is adequate for laboratorial studies; 2) Simulated pulpal pressure (15cmH2O) does not alter microleakage; 3) Water storage (90 days) / cyclic fatigue (500.000 cycles, 2Hz, 5kg) does not have influence on microleakage and 4) Water storage/cyclic fatigue does not influence marginal integrity of crowns. Control groups were established for all experiments. Results: 1) No statistically significant difference was detected between the two techniques to assess microleakage in each cement/adhesive combination; 2) Simulated pulpal pressure significantly altered microleakage for PAN-SE (Mann-Whitney, p=0.025) and REL-SB (Mann-Whitney, p=0.014); 3) Water storage (Mann-Whitney, p=0.032) and water storage/cyclic fatigue (Mann-Whitney, p=0.008) significantly increased microleakage only in PAN-SE groups. These parameters were not decisive in REL-SB groups even with higher microleakage values, and 4) Loss of marginal integrity was of 4% and 10% in REL-SB and PAN-SE groups, respectively. Conclusions: 1) No differences on microleakage were observed when a new technique suggest to assess microleakage was compared to a standard one. 1.1) This new technique seems adequate for laboratorial microleakage studies; 2) Simulated pulpal pressure significantly altered microleakage values for both adhesives/cements; 3) Water storage/cyclic fatigue influenced on microleakage of Panavia F and 4) Water storage/cyclic fatigue did not have influence on marginal integrity of both adhesives/cements tested.

Neste trabalho foram produzidas molas cerâmicas através do processo de moldagem por injeção em baixa pressão, utilizando-se como matéria-prima alumina submicrométrica, aditivada com ligantes a base de ceras. Dentro do tanque de uma injetora Pelstman, estes materiais foram homogeneizados e resultaram em uma suspensão de baixa viscosidade. Entre os objetivos deste trabalho estão a produção de molas cerâmicas helicoidais com perfil circular, a extração dos ligantes orgânicos utilizados durante a moldagem, a pré-sinterização das molas a 1000°C, o acabamento e a sinterização das molas em diferentes temperaturas e a medida de algumas de suas propriedades. A mudança na temperatura de sinterização é uma maneira simples de alterar as propriedades das molas cerâmicas, sem alterar sua composição ou suas dimensões. Foram produzidos três lotes de molas de alumina, que foram sinterizadas a 1550°C, 1600°C e 1650°C, com o objetivo de verificar os efeitos da temperatura sobre a constante de mola e a tensão de fratura. As molas de alumina sinterizada foram obtidas com densidades variando de 94,0% para 97,5% do limite teórico. As constantes de mola foram medidas desde a temperatura ambiente até 1100°C. Os dados obtidos nos ensaios de fratura sob compressão foram analisados de acordo com a estatística deWeibull e o método da máxima verossimilhança. Com o aumento da temperatura de sinterização, de 1550°C até 1650°C, foi observado que a constante de mola e a resistência característica de Weibull das molas de alumina aumentaram em 15% e 32%, respectivamente. Por outro lado, a temperatura de sinterização não teve muita influência sobre o módulo de Weibull. Isso acontece porque as bolhas internas e os defeitos superficiais introduzidos na fase de conformação das molas cerâmicas, possuem um efeito pronunciado na fratura das molas, mais importante do que a redução da porosidade com o aumento da temperatura de sinterização, e são fundamentais para determinar a resistência à compressão das molas cerâmicas. / In this work, ceramic coil springs was prepared by low-pressure injection molding using alumina submicrometer-sized powder. The powder are mixed with organic binders in the Pelstman machine tank for several hours resulting in a mixture with low viscosity. This work include the production of helical ceramic springs, thermal debinding, sintering in different temperatures and measure some properties. Sintering temperature was shown to be a simple way to change the spring constant and resistence to compression of ceramics without having a significant impact in the spring´s physical dimensions. Three sets of springs were sintered at different temperatures, from 1550°C to 1650°C, in order to observe the effects on spring constant and fracture stress. Sintered alumina springs were obtained with densities ranging from 94.0% to 97.5% of the theoretical limit. Springs constants were measured from room temperature up to 1100°C. Fracture stress data was analyzed according to Weibull statistics and the maximum likelihood method. Upon increase of sintering temperature from 1550°C to 1650°C, the spring constant and the Weibull characteristic strength of the alumina springs increases by 15% and 32%, respectively. On the other hand, sintering temperature has a negligible influence on Weibull modulus. This is because internal bubbles and surface defects introduced in the production stage of the ceramic springs - more than the reduction in porosity with increasing sintering temperature - are critical in determining the compression resistance of the ceramic springs.

Solar cells based on organohalide perovskites (PSCs) have made rapid progress in recent years and are a promising emerging technology. An important next evolutionary step for PSCs is their up-scaling to commercially relevant dimensions. The main challenges in scaling PSCs to be compatible with current c-Si cells are related to the limited conductivity of the transparent electrode, and the processing of a uniform and defect-free organohalide perovskite layer over large areas. In this work we present a generic and simple approach to realizing efficient solution-processed, monolithic solar cells based on methylammonium lead iodide (CH₃NH₃PbI₃). Our devices have an aperture area of 25 cm² without relying on an interconnected strip design, therefore reducing the complexity of the fabrication process and enhancing compatibility with the c-Si cell geometry. We utilize simple aluminum grid lines to increase the conductivity of the transparent electrode. These grid lines were exposed to an UV-ozone plasma to grow a thin aluminum oxide layer. This dramatically improves the wetting and film forming of the organohalide perovskite junction on top of the lines, reducing the probability of short circuits between the grid and the top electrode. The best devices employing these modified grids achieved power conversion efficiencies of up to 6.8%.

Indiana University-Purdue University Indianapolis (IUPUI) / Repair is an alternative treatment option in many cases to replacement of resin matrix composite restoration. However, aged resin matrix composites have a limited number of carbon-carbon double bonds to adhere to a new layer of rein. Therefore, surface treatments of the aged resin matrix composite surface prior to repairing could improve the repair bond strength. The objectives of this study were to: 1) To evaluate various surface treatments on shear bond strength of repair between aged and new microhybrid resin matrix composite, and 2) To assess the influence of applying a silane coupling agent after surface treatments. Eighty disk-shaped resin matrix composite specimens were fabricated and thermocycled 5000 times prior to surface treatment. Specimens were randomly assigned to one of the three surface treatments (n = 20): 1) Airborne abrasion with 50 μm aluminum oxide, 2) Tribochemical silica coating (CoJet), or 3) Er,Cr:YSGG laser and control group (n = 20). Specimens were cleaned with 35-percent phosphoric acid, rinsed, and dried. Each group was assigned into two subgroups (n =10): a) no silanization, and b) with silanization. Adhesive agent was applied and new resin matrix composite was bonded to each conditioned surface. Bond strength was evaluated by shear test. Data were analyzed with a two-way ANOVA model. The interaction between conditioning and silanization was significant(p = 0.0163), indicating that comparisons of silanization must be evaluated for each conditioning method, and that comparisons of conditioning methods must be evaluated separately with and without silanization. Airborne particle abrasion showed significantly higher repair bond strength than Er,Cr:YSGG laser without silanization (p < 0.0001) and with silanization(p = 0.0002), and higher repair bond strength than the control without silanization (p < 0.00001) and with silanization (p < 0.00001). Airborne particle abrasion did not have significantly different in repair bond strength than Tribosilica coating without silanization (p = 0.70) or with silanization (p = 0.33). Tribosilica coating had significantly higher repair bond strength than Er,CR:YSGG laser without silanization (p < 0.0001) and with silanization (p < 0.0001), and significantly higher repair bond strength than control without silanization (p < 0.0001), but not with silanization (p =0.16). Er,CR:YSGG laser and control did not have significantly different repair bond strength without silanization (p = 1.00) or with silanization (p = 0.11). There was no effect of silanization on repair bond strength overall (p = 0.34) for any of the surface conditioning methods (p = 0.76 for airborne particle abrasion; p = 0.39 for tribosilica coating; p = 1.00 for Er,Cr:YSGG laser, or p = 0.39 for control). Airborne particle abrasion with 50-μm aluminum oxide particle and tribochemical silica coating followed by the application of bonding agent provided the highest shear bond strength values, suggesting that they might be adequate methods to improve the quality of the repairs of resin-matrix composites.

Indiana University-Purdue University Indianapolis (IUPUI) / Provisional restorative treatment is an essential part of fixed prosthodontics. Incorporation of adequately constructed provisional restorations will enhance the success rate of definitive restorations. Repairing or replacing failed provisional restorations is a concern for both clinicians and patients. The objective of this investigation was to study the effects of alumina nanofibers reinforcement on the mechanical properties of commercially available provisional fixed partial denture PMMA material. The hypothesis was that the addition of alumina nanofibers to commercially available PMMA resin will significantly increase its flexural strength, fracture toughness, and microhardness. Alumina nanofibers at 0.0 wt %, 0.5 wt %, 1.0 wt %, and 2.5 wt % were added to commercially available provisional fixed partial material (Jet Tooth Shade). A quaternary ammonium acetate dispersant (CC-59, Goldschmidt, Janesville, WI) was added to the acrylic monomer at 0.0 wt %, 1.0 wt %, 2.0 wt % and 5.0 wt % of the nanofiber weight (12 test groups, 1 control). Samples from each group were evaluated for flexural strength, flexural modulus, fracture toughness, and microhardness. The samples were tested after storing in distilled water for 24 hours and 7 days at 37ºC. Two-way analysis of variance (ANOVA) was used to test the effects of storage time and combinations of alumina nanofiber level and quaternary ammonium acetate dispersant level on the flexural strength, fracture toughness, and microhardness of the provisional PMMA resin. Pair-wise comparisons between groups were performed using Tukey’s multiple comparisons procedure to control the overall significance level at 5 percent. Three fracture toughness samples/group were randomly selected for Energy Dispersive Spectrometry (EDS) to qualitatively evaluate the dispersion of the fibers. The data obtained from this study showed that control sample values were in the acceptance range compared with previous research. The experimental samples did not reinforce the provisional resin in the flexural strength, modulus, fracture toughness, or microhardness. There are several factors may attribute to these results, such as poor bonding at the filler/matrix interface. The more homogeneous the mixture of PMMA and fiber, the stronger the acrylic resin. In fact, the presence of poorly bonded fibers, to which little load is transferred, can be almost equivalent to voids. In addition, as seen with EDS images, alumina nanofibers had a tendency to agglomerate. The use of a magnetic stirrer was not effective in physically separating nanofibers agglomerates. Direct dispersion of alumina nanofibers in methyl methacrylate monomer and quaternary ammonium acetate dispersant was not effective in separating the nanofibers into nano-scaled single crystals. The presence of fiber agglomerates acts as a structural defect that detrimentally affects the mechanical properties. Further studies are needed to evaluate the effectiveness of fibers, dispersion techniques, and coupling agents to enhance the mechanical properties of the provisional PMMA resin.

Цель магистерской диссертации состояла в изучении влияния режимов анодирования и условий последующей температурной обработки на структурные и люминесцентные свойства нанопористого оксида алюминия. Рассмотрены основные структурные особенности анодированного оксида алюминия (АОА) и методики получения его упорядоченных структур, его области применения и люминесцентные свойства. Успешно синтезирована серия из 20 образцов АОА в условиях варьирования электрохимических, временных и температурных режимов. Проведена аттестация полученных образцов методами сканирующей электронной микроскопии и рентгеноструктурного анализа. Проведена статистическая обработка полученных снимков с помощью анализатора изображений SIAMS 700. Проанализированы зависимости среднего диаметра пор от напряжения анодирования и толщины оксидного слоя от времени анодирования. Рассчитана средняя скорость роста АОА для гальвано- и потенциостатических режимов. Изучены особенности и трансформация спектров диффузного отражения, фото- и катодолюминесценции образцов АОА в зависимости от условий электрохимического окисления и последующей термообработки. На основе сравнительного анализа литературных данных проведена идентификация активных центров свечения собственной (F-, F+-центры) и примесной (комплексы C2O42- и HC2O4-, ионы Cr3+ и Mn4+) природы. Рассмотрены перспективы дальнейших исследований и возможных применений синтезируемых мембран анодированного оксида алюминия. / The aim of this Master paper is to study the effect of anodizing modes and subsequent temperature treatment on structural and luminescent properties of nanoporous anodic alumina. Structural features of anodic aluminum oxide (AAO), its ordered structures obtaining methods, fields of application and luminescent properties were discussed. A series of twenty samples varying electrochemical, time and temperature regimes was obtained. Obtained samples were characterized by scanning electron microscopy and X-ray diffraction analysis techniques. Images of structures were quantitavely analyzed using SIAMS 700 software package. It was studied how average pore diameter and oxide layer thickness depend on anodizing voltage and duration accordingly. Average AAO growth rate for galvanostatic and potentiostaic modes was calculated. Features and transformation of diffuse reflection, photo- and cathodoluminescence of AAO samples obtained under various electrochemical oxidation conditions and after subsequent temperature treatment were studied. Active emission centers of intrinsic (F-, F+-centers) and impurity (C2O42- and HC2O4- complexes, Cr3+ и Mn4+ ions) nature were identified on the basis of literature data comparative analysis. Further promising directions of studies and possible applications of synthesized AAO membranes were discussed.

Due to the study basic structural features of ultrafine ceramics, using the scanning electron microscopy method, were identified. Dependency of particle sizes on thermal treatment modes was determined, and average size of the sample grains was determined due to statistical processing of the SEM images, using hardware and software image analysis package SIAMS 700. It has been established that photoluminescent properties of single-crystalline samples under the study correspond to the publicly available literature data. Photoluminescence spectra were measured after sample finishing and dependence of optical absorption on exposure dose was identified. The ultrafine ceramic FL was examined and comparison study of the resulting parameters with a single-crystalline sample was carried out. Excitation and emission spectra under various modes of ceramic synthesis were also produced. This study makes it possible to consider ultrafine ceramics as a non-conventional material for high-dose measurements. / В результате исследования были выявлены основные структурные особенности ультрадисперсной керамики методом растровой электронной микроскопии. Определена зависимость размеров частиц от режимов термической обработки, а так же найден средний размер зерен образцов за счет проведения статистической обработки изображений РЭМ на программно-аппаратном комплексе анализа изображений SIAMS 700. Установлено, что фотолюминесцентные свойства исследуемых монокристаллических образцов соответствуют общеизвестным литературными данными. Измерены спектры фотолюминесценции после полировки образцов и найдена зависимость оптического поглощения от дозы облучения. Рассмотрена ФЛ ультрадисперсной керамики и проведен сравнительный анализ полученных параметров с монокристаллическим образцом. Так же получены спектры возбуждения и излучения при различных режимах синтеза керамики. Данные исследования позволяют рассматривать ультрадисперсную керамику как перспективный материал для высокодозных измерений.

Anhand von theoretischen Untersuchungen wird eine umfassende Beschreibung von kleinen Metalloxidclustern gegeben. Bei den untersuchten Systemen handelt es sich um Aluminium- und Eisenoxid-Ionen sowie entsprechende Oxid-Cluster, die beide Metalle enthalten. Neben der Bestimmung der geometrischen Struktur der Cluster werden auch die allgemeinen elektronischen Eigenschaften der eisenhaltigen Verbindungen untersucht. Alle Vorhersagen werden durch Vergleich mit verfügbaren experimentellen Ergebnissen -- hauptsächlich aus der Infrarot-Photodissoziations- und der Photoelektronenspektroskopie -- überprüft und bewertet. Soweit möglich werden die Bewegungen von Atomen oder kleinen Gruppen innerhalb der Cluster einzelnen experimentellen Signalen zugeordnet. Besondere Aufmerksamkeit wird dem Eisendioxidmolekül und seinem Anion gewidmet. Es wird mit spezialisierten Wellenfunktionsmethoden untersucht, mit denen ab initio Franck-Condon-Simulationen einschließlich nicht-adiabatischer und Spin-Orbit-Kopplungen für die Photoionisation des Anions erstellt werden. Sie liefern Erklärungen für die komplizierte Schwingungsstruktur des experimentellen hochauflösenden Photoelektronenspektrums. / By means of theoretical investigations, a comprehensive description of small metal oxide clusters is given. The studied systems are aluminum and iron oxide ions as well as respective bi-metallic oxide clusters. Besides the determination of the geometrical structure of the clusters, the general electronic properties of the iron-containing compounds are investigated. All predictions are checked and assessed by comparison with available experimental results, mainly infrared photodissociation and photoelectron spectroscopy measurements. As far as possible, motions of atoms or small groups within the clusters are assigned to distinct experimental vibrational features. Particular attention is paid to the iron dioxide molecule and its anion. It is studied with sophisticated wave function methods based on which ab initio Franck-Condon simulations for the photodetachment from the anion, including non-adiabatic and spin-orbit couplings, are generated. They provide explanations for the complicated vibrational structure of the experimental high-resolution photoelectron spectrum.

No description available.