Os objetivos deste trabalho foram avaliar o efeito da aplicação de sete soluções de tingimento e de três diferentes pós de partida comerciais (TZ-3YSB-E, Zpex, TZ-3Y20AB), sobre o parâmetro de translucidez, a resistência à flexão e análise de citotoxicidade de cerâmicas policristalinas à base de zircônia. As seguintes hipóteses foram testadas: (1) não há efeito da solução de tingimento ou do pó de partida nas propriedades ópticas das cerâmicas policristalinas; (2) não há efeito da solução de tingimento, do pó de partida e do envelhecimento hidrotérmico nas propriedades mecânicas das cerâmicas policristalinas; (3) não há efeito da solução de tingimento ou do pó de partida na citotoxicidade das cerâmicas policristalinas. Material e métodos: foi realizada a análise química das soluções de tingimento (FRX), caracterização dos pós cerâmicos (MEV-FEG), estudo de compactação e sinterização e análise térmica. As pastilhas cerâmicas foram confeccionadas utilizando os três pós cerâmicos. A compactação foi feita uniaxialmente com posterior prensagem isostática a frio. Após pré-sinterização, as pastilhas foram imersas nas diferentes misturas das soluções de tingimento comerciais (de acordo com a especificação do fabricante), com posterior secagem e sinterização final. Os materiais foram testados quanto às propriedades ópticas (parâmetro de translucidez (PT) e coordenadas colorimétricas), quanto à resistência à flexão em três pontos antes e após tratamento para degradação hidrotérmica (5 horas a 134°C, sob pressão de 2 bar) e análise de citoxicidade. (Resultados: Com relação ao efeito da aplicação das soluções de tingimento e de diferentes pós de partida sobre o parâmetro de translucidez, foi possível notar que o material interfere nos parâmetros de translucidez, sendo que o Zpex (PT = 11,2 ± 5,4) foi o material mais translúcido. Para o efeito do uso das soluções de tingimento, a mistura das soluções para a obtenção das cores B1 (9,5 ± 7,0) e B3 (8,7 ± 9,7) resultaram em espécimes mais translúcidos e a cor D3 (1,9 ± 0,7) apresentou espécimes com menor translucidez. Com relação ao efeito da aplicação das soluções de tingimento, dos três pós de partida e do envelhecimento sobre a resistência à flexão, foi possível notar que o material interfere na resistência à flexão das cerâmicas policristalinas, sendo que a maior média de resistência foi obtida para o TZ-3YB-E (605,8 ± 106,4 MPa). O envelhecimento causou uma diminuição dos valores de resistência, porém ao se observar cada grupo individualmente, essa queda não foi estatisticamente significativa para nenhum deles. O uso das soluções de tingimento afetou as médias de resistência, sendo que as cores A2 (614,9 ± 120,2 MPa) e C2 (625,0 ± 97,6 MPa) resultaram em resistência maior do que aquelas medidas para as cores A3 (497,0 ± 109,1 MPa) e C3 (529,5 ± 134,9 MPa). Com relação ao efeito da aplicação das soluções de tingimento e dos três diferentes pós de partida sobre a citotoxicidade, foi possível notar que ambos os fatores afetaram os valores de viabilidade celular. Entretanto, para todos os grupos analisados, a viabilidade celular obtida ficou acima de 90% e, portanto, todos os grupos apresentaram uma excelente biocompatibilidade. Conclusão: o material e as soluções de tingimento afetaram o parâmetro de translucidez e as coordenadas colorimétricas permitindo rejeitar a primeira hipótese testada. As soluções de tingimento e os materiais influenciaram a resistência à flexão das cerâmicas policristalinas, entretanto a queda de resistência no envelhecimento não foi significativa, portanto, a hipótese de que não haveria efeito do pó de partida, solução de tingimento e envelhecimento sobre a resistência à flexão foi parcialmente rejeitada A hipótese de que não haveria efeito do pó de partida e da solução de tingimento sobre a citotoxicidade foi rejeitada, mas todos os grupos testados não se apresentaram citotóxicos. / The objectives of this study were to evaluate the effect of the application of seven coloring solutions and three different starting powders (TZ 3YSB-E, Zpex, TZ-3Y20AB) on the translucency parameter, flexural strength and cytotoxicity of zirconia-based polycrystalline ceramics. The following hypotheses were tested: (1) there is no effect of the coloring solution or the starting powder on the optical properties of the ceramics tested; (2) there is no effect of the coloring solution, of the starting powder and of hydrothermal aging on the mechanical properties of the materials; (3) there is no effect of the coloring solution or the starting powder in the cytotoxicity of the ceramics tested. Material and methods: we performed a chemical analysis of the coloring solutions (FRX), characterization of ceramic powders (SEM-FEG), study of compaction, sintering and thermal analysis. The ceramic discs were made using the three ceramic powders. Compression was made uniaxiallly with subsequent cold isostactic pressure. After pre-sintering, the discs were immersed in different mixtures of commercial coloring solutions (according to manufacturer\'s specifications) with subsequent drying and final sintering. The materials were tested for optical properties (translucency parameter, TP), and biaxial flexural strength before and after hydrothermal degradation protocol (5 hours at 134°C under 2 bar pressure) and cytotoxicity analysis (evaluation cell viability). Results: With regard to the effect of applying the coloring solutions and the effect of the different starting powders on the translucency parameter, it was observed that the material interfered significantly with the light transmission parameters, and the Zpex (TP=11.2 ± 5.4) was the morst translucent material. With regards to the effect of the coloring solutions on TP, mixing the solutions to obtain the shades B1 (9.5 ± 7.0) and B3 (8.7 ± 9.7) resulted in more translucent specimens and shade D3 (1.9 ± 0.7) resulted in the lowest translucency. With respect to the effect of applying the coloring solutions, the three starting powders and aging on the flexural strength, it was observed that the material interfered with the flexural strength of polycrystalline ceramics, being the highest mean strenght obtained for the TZ-3YB-E (605.8 ± 106.4 MPa). Aging caused a decrease in resistance values, but when considering each group individually, this decrease was not statistically significant for any of them. The use of coloring solutions affected the average strength, as shades A2 (614.9 ± 120.2 MPa) and C2 (625.0 ± 97.6 MPa) resulted in greater strength than those measured for shades A3 (497.0 ± 109.1 MPa) and C3 (529.5 ± 134.9 MPa). With respect to the effect ofthe coloring solutions and the powders on the cytotoxicity, it was observed that both factors affected cell viability values. However, for all groups, the obtained cell viability was above 90% and therefore all of them showed an excellent biocompatibility. Conclusion: the material and coloring solutions affected the translucency parameter and the colorimetric coordinates allowing for rejection the first hypothesis tested. The coloring solutions and the starting powder influenced the flexural strength of polycrystalline ceramics, however, the decrease in strength after aging was not significant; therefore, the second hypothesis was partially accepted. The hypothesis that there would be no effect of the starting powder and the coloring solution on the cytotoxicity was rejected, but all tested groups were not cytotoxic.

Este trabalho visa dar uma importante contribuição à pesquisa de novos materiais, através da determinação de condições otimizadas para obtenção pela técnica LHPG de fibras monocristalinas de compostos óxidos. Com esse objetivo fibras foram obtidas com êxito para compostos que podem ser utilizados como meios ativos para lasers de estado sólido (CaNb2O6 e GdTaO4), em aplicações de óptica de raios X (cristais gradientes dos sistemas GdTaO4-ErTaO4 e GdTaO4-YbTaO4) e também compostos que apresentam supercondutividade (EuNbO3, Yb2NbO5, Sm2NbO5 e Er2NbO5). A preparação dos pedestais se mostrou uma etapa muito importante na preparação das várias fibras. A caracterização estrutural por técnicas de difração de raios X mostrou que fibras monocristalinas de CaNb2O6 e GdTaO4 podem ser obtidas rapidamente e com alta qualidade cristalina sendo altamente adequadas para aplicações em óptica. Adicionalmente resultados de medidas espectroscópicas mostraram que as fibras CaNb2O6 dopadas com Nd+3 são boas candidatas para desenvolvimento de micro-lasers. Monocristais com gradiente controlado de parâmetro de rede foram obtidos pela primeira vez para os sistemas GdTaO4- ErTaO4 e GdTaO4-YbTaO4. A estratégia aplicada aqui possibilitou a obtenção de um gradiente composicional e de parâmetros de rede com ótima linearidade. Para o sistema GdTaO4- ErTaO4 foi obtido um gradiente de espaçamento de rede de 1,24%/cm para a reflexão (4 -4 4). Para os cristais GdTaO4- ErTaO4 um gradiente de 2,9%/cm para a reflexão (6 -4 0) foi obtido, sendo este o maior valor já observado em cristais gradientes. Através de uma inovação, utilizando Nb metálico em pó na preparação dos pedestais, fibras do composto EuNbO3 foram obtidas pela primeira vez, ao nosso conhecimento, através de uma técnica utilizando fusão. A aplicação desta mesma inovação buscando a obtenção de fases com esta mesma estrutura para outras terras raras, proporcionou a descoberta de três fases inéditas, Yb2NbO5, Sm2NbO5 e Er2NbO5. A estrutura destas novas fases foi determinada e através de caracterizações magnéticas e elétricas iniciais observou-se que estas apresentam supercondutividade com temperaturas de transição, Tc, iguais a 12,5K, 6,5K e 14,9K respectivamente para Yb2NbO5, Sm2NbO5 e Er2NbO5 / This work aims to give an important contribution to the research of new materials, by determining optimized conditions for obtaining of single crystal fibers of oxide compounds by LHPG technique. With this objective fibers were successfully obtained for compounds which can be used as solid state lasers (CaNb2O6 e GdTaO4), for X-ray optics applications (gradient crystals of GdTaO4-ErTaO4 e GdTaO4-YbTaO4 systems) and also as superconducting compounds. The preparation of the pedestals was a very important stage in the obtaining of the various fibers, with influence in growth experiments and quality of the fibers. The structural characterization by X-ray diffraction techniques showed that CaNb2O6 and GdTaO4 single crystal fibers presenting high crystalline quality can be quickly obtained. These fibers can be highly suitable for optics applications. In addiction the results of spectroscopic measurements showed Nd+3 doped CaNb2O6 fibers are good candidates for development of micro-lasers. Single crystals with controlled lattice parameter gradient were obtained for the first time for GdTaO4- ErTaO4 e GdTaO4-YbTaO4 systems. The applied approach in here enabled to obtain a compositional and lattice parameters gradient presenting optimized linear behavior. For the GdTaO4- ErTaO4 system a lattice spacing gradient of 1.24%/cm for (4 -4 4) reflection was obtained. For GdTaO4-YbTaO4 crystals a gradient of 2.9%/cm was observed. This is the largest value of lattice spacing gradient up to this moment. By an innovation, using metallic Nb in the form of powder in preparing the pedestals, fibers of the EuNbO3 compound were obtained, being the first report by a fusion technique. The application of this innovation to obtain phases with this structure for others rare earth enabled the discovery of three new phases, namely Yb2NbO5, Sm2NbO5 and Er2NbO5. The structure of these new phases was determined and by magnetic and electric characterizations it was observed that the phases are superconductor materials with transition temperatures, Tc, equals to 12,5K, 6,5K and 14,9K respectively for Yb2NbO5, Sm2NbO5 and Er2NbO5. compounds

As restaurações monolíticas de Y-TZP (Zircônia Tetragonal Policristalina estabilizada por Itria) se apresentam como uma alternativa interessante devido a suas elevadas propriedades mecânicas, porém existe a preocupação quanto a Degradação em Baixa Temperatura (DBT). Os compósitos ZTA (Alumina reforçada por Zircônia) tem o potencial de atender a esta demanda, apesar do desafio estético uma vez que a passagem de luz pode ser limitada pela combinação de duas fases cristalinas. O presente trabalho teve como objetivo inovar na criação de um compósito ZTA sintetizado com Y-TZP translúcida, na procura de um material com alta resistência mecânica em relação à alumina, resistente à DBT quando comparada à YTZP e com propriedades ópticas melhoradas em relação ao ZTA sintetizado com Y-TZP convencional. Sessenta corpos de prova (discos de 12 mm de diâmetro por 1 mm de espessura) foram confeccionados e divididos em quatro grupos: zircônia convencional (3YSB-E), zircônia translucida (Zpex), compósito ZTA (Al2O3-70%v ZrO2-30%) sintetizado com 3YSB-E (ZTA-3YSB-E) e outro com zircônia translucida Zpex (ZTA-Zpex). Os corpos de prova foram obtidos mediante prensagem uniaxial e isostática dos pós cerâmicos. Após sinterização, o polimento das duas faces foi realizado com discos e suspensões diamantadas de até 1 m. A caracterização óptica foi realizada mediante testes de refletância sobre fundo branco e preto para determinar a razão de contraste (RC) e o parâmetro de translucidez (PT) mediante a diferença de cor (E). Difração de Raios-X (DRX) e Microscopia Eletrônica de Varredura (MEV) foram realizadas para estudo da microestrutura do material. Análise de variância ANOVA e teste de Tukey com nível global de significância de 5% foram utilizados na análises dos dados de propriedades ópticas. A RC mostrou opacidade significativamente menor para o grupo Zpex (0.77; p=0.0001), o grupo 3YSB-E mostrou valores intermediários (0.84; p=0.0001), sendo que os dois compósitos ZTA apresentaram valores maiores de opacidade (ZTA-3YSB-E = 0.99 e ZTA-Zpex = 1) sem diferença significante entre eles (p=0.7433). Para o PT os compósitos ZTA mostraram um E baixo (ZTA-Zpex = 0.22 e ZTA-3YSB-E = 0.43), sem diferença significante entre os grupos (p=0.5). O grupo 3YSB-E apresentou valores intermediários e significativamente diferentes em relação aos outros grupos (E = 7.11 p<0.0001). Já o grupo Zpex apresentou a menor capacidade de mascaramento com E =10.19 (p<0.0001). A DRX mostrou similaridade das fases cristalinas dos grupos 3YSB-E e ZPEX evidenciando que as mesmas foram preservadas na mistura nos compósitos, sem mostrar alterações da estrutura cristalina. A analise no MEV em até 1.500x de aumento evidenciou pouca alteração morfológica entre as zircônias e entre os ZTAs. As propriedades ópticas do ZTA Zpex não foram estatisticamente diferentes do compósito sintetizado com 3YSB-E, sendo que as Y-TZPs apresentaram menor opacidade. As Y-TZPs mostraram estrutura cristalina regular sem a formação de aglomerados e os compósitos ZTAs apresentaram uma mistura uniforme, mantendo as características da estrutura cristalina tanto da Y-TZP quanto da Al2O3, sem formação de aglomerados nem segregação dos grãos dos compósitos. Novos estudos são necessários para avaliar a resistência a DBT e as propriedades mecânicas destes materiais experimentais. / Monolithic Yttria stabilized Tetragonal Zirconia Polycrystals (Y-TZP) prostheses are considered an interesting treatment alternative due to their high mechanical properties. Nevertheless there is concern about the Low Temperature Degradation (LTD) process. Zirconia-Toughened Alumina (ZTA) composites seem to be capable of meeting this demand, while facing the challenge of being aesthetically suitable, since the passage of light can be limited by the combination of two polycrystalline phases. The present work aimed to innovate in the synthesis of a ZTA composite with a translucent Y-TZP for dental applications, in the search for a material with high mechanical resistance when compared to alumina, resistant to LTD when compared to Y TZP, and with improved optical properties over ZTA synthesized with conventional Y-TZP. Sixty disc shaped specimens with 12 mm diameter and 1 mm thick, were prepared and divided in four groups: a conventional zirconia (3YSB-E), a translucent zirconia (Zpex), a ZTA composite (Al2O3-70%v ZrO2-30%) synthetized with 3YSB-E (ZTA- 3YSB-E), and a ZTA composite synthetized with translucent zirconia (ZTA-Zpex). The specimens were obtained by uniaxial and isostatic pressing of the ceramic powders. After sintering, polishing of both sides was performed with diamond disks and suspensions up to 1 m. The optical characterization was performed by means of reflectance on a white and a black background to determine the contrast ratio (CR) and the translucency parameter (TP) of the experimental groups. XRD and SEM analyses were performed to study the crystalline structure. Analysis of variance ANOVA and Tukey test with a global significance level of 0.05% were used to analyze the data. CR showed significantly lower opacity for Zpex group (0.77, p = 0.0001), 3YSB-E showed intermediate values of opacity (0.84, p = 0.0001), and both ZTA composites presented higher opacity (ZTA-3YSB-E = 0.99 and ZTA-Zpex = 1) with no statistically significant difference between them (p = 0.7433). The TP showed a low E for ZTA composites (ZTA-Zpex = 0.22 and ZTA-3YSB-E = 0.43), with no statistically difference between the groups (p = 0.5). The 3YSB-E group presented intermediate and significantly different values of TP relative to the other groups (E = 7.11 p <0.0001). The Zpex group presented the lowest masking ability with E = 10.19, also significantly different from the other groups (p <0.0001). The XRD showed similarity of the crystalline phases of 3YSB-E and ZPEX, structure that were preserved in the blends in ZTA composites, without showing changes in the crystalline structure of the materials. SEM analysis (up to 1.500 x) showed low morphologic alteration between Y-TZP and ZTA composites. Optical properties of ZTA-Zpex showed no statistical difference when compared with ZTA-3YSB-E, whereas Y-TZP groups showed less opacity than other groups. The experimental Y-TZPs showed a regular crystalline structure without the formation of agglomerates, and the ZTA composites presented a uniform mixture of the phases, maintaining the characteristics of the polycrystalline structure of both Y-TZPs and Al2O3, without the formation of agglomerates or segregation of the grains in the composites. Future tests evaluating the resistance to LTD and mechanical properties of these experimental materials are warranted.

Poços e super-redes delta-doping tipo são sistemas semicondutores de interesse considerável tanto para a pesquisa básica como para aplicações em dispositivos. Neste trabalho desenvolvemos um novo método para o cálculo de potenciais e estruturas de bandas deste tipo de sistemas. O método baseia-se na expansão em ondas planas da equação da massa efetiva multibandas, usa matrizes de energia cinética de qualquer tamanho e leva em conta o potencial de troca e correlação de uma maneira mais rigorosa do que em trabalhos anteriores. São calculados perfis de potencial e estrutura de minibandas e subbandas bem como a posição do nível de Fermi de uma série de poços isolados e super-redes delta-doping tipo p. São estudadas também as diferenças entre super-redes delta-doping tipo p e tipo n. A partir deste método foi desenvolvido ainda um procedimento de cálculo de espectros de fotoluminescência dos poços estudados. Este procedimento baseia-se nas forças de oscilador das transições entre os buracos confinados no interior do poço e os elétrons livres da banda de condução. Ele é utilizado para calcular funções envelope, integrais de superposição e espectros de transições diretas e indiretas. Por fim, comparamos espectros calculados teoricamente com resultados experimentais extraídos da literatura. / p-type ro-doping quantum wells and superlattices are semiconductor systems of considerable interest for basic research and device applications. In this work, a method for calculating potentials and band structures of such systems is developed. The method relies on a plane wave expansion of the multiband effective mass equation, uses kinetic energy matrices of any size, and takes exchange correlation into account in a more rigorous way than this was done before. The method is used to calculate potential profiles, subband and miniband structures as well as Fermi level positions for a series of p-type delta-doping quantum wells and superlattices. The differences between n- and p-type delta-doping structures are studied. In addition to this we developed a procedure within this method to ca1culate photoluminescence (PL) spectra of the wells studied. It depends on the oscillator strength between the holes inside the wells and the free electrons on the conduction band. We use this procedure to calculate envelope functions, overlap integrals and direct and indirect transitions spectra. Finally, we compare our theoretical calculations of PL spectra with experimental results extracted from the literature.

O objetivo do trabalho foi o de avançar na compreensão dos mecanismos envolvidos no comportamento óptico de diferentes materiais cerâmicos em função da espessura, utilizados para restauração dentária, determinar os coeficientes de absorção e espalhamento e correlacioná-los às características microestruturais de cada material. Além disso, foi avaliada a capacidade de mascaramento e a razão de contraste do material cerâmico nas formas monolítica, em duas camadas e como restauração cimentada. Para tanto, foram analisadas quatro cerâmicas odontológicas, uma porcelana de cobertura (vítrea) e três compósitos cerâmicos infiltrados com vidro do Sistema InCeram (alumina/vidro, alumina/zircônia/vidro e espinélio/vidro), além de uma resina composta odontológica empregada como substrato resinoso e um cimento resinoso para cimentação. Os coeficientes de espalhamento e absorção foram determinados por meio dos modelos de Beer-Lambert e Kubelka-Munk a partir das curvas espectrais de transmitância e reflectância (com fundos branco e preto) geradas em um espectrofotômetro na faixa de comprimento de onda entre 300 e 800 nm. A microestrutura de cada material foi analisada por meio de microscopia eletrônica de varredura com mapeamento elementar, difração de raios X e análise química por fluorescênica de raios X. O comportamento óptico dos materiais estudados foi influenciado pelas características microestruturais do material e a pela espessura. Os valores do coeficiente de espalhamento, S, das cerâmicas avaliadas foram significativamente maiores do que os valores do coeficiente de absorção, K, na região do visível. Foram propostas equações para prever as curvas espectrais de reflectância e transmitância de bilayers e de restaurações cimentadas. / The aim of this work was to advance in the understanding of the mechanisms related to the optical behavior of different ceramic materials as a function of thickness, used for dental restoration, to determine the absorption and scattering coefficients and to correlate them to the microstructural characteristics of each material. The masking ability and the contrast ratio of ceramic material as monolith, bilayer and cemented restoration were also evaluated. For this, four dental ceramics, one porcelain and three glass-infiltrated ceramic composites of InCeram System (alumina/glass, alumina/zirconia/glass, and spinell/glass), besides one dental composite resin used as resinous substrate and one resinous cement for luting. The scattering and absorption coefficients were determined by the Beer-Lambert and Kubelka-Munk models using spectral curves of transmittance and reflectance (with white and black backs) generated in a spectrophotometer in the 300 to 800 nm wavelength range. The microstructure of each material was analyzed by scanning electron microscopy with elemental mapping, X-ray diffraction, and chemical analysis by X-ray fluorescence. The optical behavior of studied materials was affected by the microstructural characteristics and thickness of the material. The values of scattering coefficient, S, of evaluated ceramics were significantly higher than the values of absorption coefficient, K, in the visible range. Equations for the prediction of reflectance and transmittance spectral curves of bilayer and cemented restorations were proposed.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2018-05-03T14:10:04Z No. of bitstreams: 1 pedrovictoralmeidapessanha.pdf: 2319111 bytes, checksum: 6718ea3032cf8200f1974eed7e9ba421 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2018-09-03T15:57:11Z (GMT) No. of bitstreams: 1 pedrovictoralmeidapessanha.pdf: 2319111 bytes, checksum: 6718ea3032cf8200f1974eed7e9ba421 (MD5) / Made available in DSpace on 2018-09-03T15:57:11Z (GMT). No. of bitstreams: 1 pedrovictoralmeidapessanha.pdf: 2319111 bytes, checksum: 6718ea3032cf8200f1974eed7e9ba421 (MD5) Previous issue date: 2018-02-26 / O PEDOT:PSS (poli(3,4-etilenodioxitiofeno):poli(estirenossulfonato)) é um polímero condutor da classe dos politiofenos amplamente utilizado como camada aceitadora de lacunas na confecção de dispositivos fotovoltaicos. Neste trabalho estudou-se via espectroscopia Raman ressonante, SERS e de absorção UV-VIS-NIR as propriedades ópticas do PEDOT:PSS puro e na presença de AuNPs. O PEDOT:PSS foi sintetizado por polimerização oxidativa com persulfato de sódio e da mistura de persulfato com sulfato férrico hidratado, seguida de purificação com resina de troca iônica ou diálise em água deionizada. A evolução das sínteses foi monitorada através de espectroscopia UV-VIS-NIR, pela qual evidenciou-se a existência de dois regimes eletrônicos distintos para o processo de síntese do PEDOT:PSS, com uma cinética de reação mais rápida para as sínteses realizadas com a mistura de sais. Os polímeros formados apresentam elevado grau de oxidação, caracterizado pela forte absorção de radiação eletromagnética pelas espécies que contém pólarons em torno de 800 nm e bipólarons em cerca de 950 nm. Verificou-se a eficiência dos métodos de purificação por agitação com resina de troca iônica e diálise em água deionizada. A purificação por diálise mostrou-se distinta da obtida por agitação com resinas de troca iônica, rendendo polímeros menos dopados que aqueles purificados com resinas, o que foi atribuído à reorganização das cadeias do polímero mediante a migração via difusão simples e pressão osmótica de íons pequenos e das menores cadeias de PSS para a solução de alimentação. A evolução do perfil vibracional foi monitorada através da espectroscopia Raman ressonante com comprimento de excitação de 633, 785 e 1064 nm. A variação para região de maior número de onda das bandas atribuídas ao grupo tiofeno, responsável pela alta deslocalização de carga das espécies condutoras, indicou que os polímeros formados possuem alto grau de oxidação, com a existência de dois regimes para a evolução do perfil vibracional. A dopagem que ocorre durante o processo de síntese favorece a formação das espécies mais oxidadas na matriz polimérica, e o processo de purificação do PEDOT:PSS altera a estrutura do polímero. Filmes finos e opacos foram obtidos, e apresentaram resistência de folha comparável àquela obtida com polímeros disponíveis comercialmente. Observou-se ainda, através da espectroscopia SERS de cadeias pequenas de PEDOT:PSS adsorvidas sobre nanopartículas de ouro, com radiação incidente de 1064 e 785 nm, a intensificação de modos vibracionais característicos das espécies oxidadas, mais próximos da superfície metálica, embora não exista evidência de interação específica entre o polímero e as nanoestruturas. / PEDOT: PSS is a conductive polymer of the polythiophene class widely used as the hole injection layer in photovoltaic devices. In this work, resonance Raman, SERS and UVVIS-NIR spectroscopies were used to study the optical properties of pure PEDOT: PSS and modified with AuNPs. PEDOT: PSS was synthesized via oxidative polymerization with sodium persulfate and with persulfate mixture with ferric sulfate hydrate, followed by purification with ion exchange resin or dialysis in deionized water. The evolution of the syntheses was monitored via UV-VIS-NIR spectroscopy, in which the existence of two distinct electronic regimes for the synthesis process was evidenced, with a faster kinetics for the syntheses performed with the mixture of salts. The polymers formed exhibited a high level of oxidation, characterized by a strong absorption of electromagnetic radiation by the species that contain polarons and bipolarons. The efficiency of purification methods with ion exchange resin compared to dialysis in deionized water was also evaluated. Purification by dialysis proved to be distinct from stirring with ion exchange resins, yielding less doped polymers than those purified with resins, which was attributed to the rearrangement of the polymer chains by migration of small ions and the small PSS chains for the feed solution. The evolution of the vibrational profile was monitored by resonant Raman spectroscopy with excitation wavelength of 633, 785 and 1064 nm. The variation for the region of high wavenumber of the bands attributed to the thiophene group, responsible for the high delocalization of charge in the conducting species, indicated that the polymers formed have a high degree of oxidation, with the existence of two regimes for the evolution of the vibrational profile. Doping that occurs during the synthesis process favored the formation of more oxidized species in the polymeric matrix, and the purification process of PEDOT: PSS changed the structure of the polymer. Thin and opaque films were obtained, and showed sheet resistance comparable to that obtained with commercially available polymers. It was also observed, through SERS spectroscopy of small chains of PEDOT:PSS adsorbed on gold nanoparticles, using incident radiation of 1064 and 785 nm, the intensification of vibrational modes characteristic of the oxidized species, probably near the metallic surface, although there was no evidence of specific interaction between the polymer and the nanostructures.

Some diagnostic methods have been used for a very long time. Congo red stain saw the light of day in 1883, and quickly became important in many fields of use. Nowadays we recognize the importance of Congo red in diagnose of amyloid diseases. However, the technique and experience needed throughout the process from a suspected case to the diagnose is of greate importance. When diagnostic difficulties appeared in a few patient cases at the local hospital in Gävle, Sweden, a solution was needed. A delayed diagnose could have a potential devastating outcome seen in the perspective of the patient. Therefore it is crucial to have both sensitive and specific diagnostic methods that are optimized against the sought pathogenesis. This study aspired to find the solution to the difficulties in diagnostic work, brought to light by a pathology doctor at the hospital. Several different methodical procedures are used throughout the process, and were evaluated with focus lying on the thickness of the tissue, the staining method and the microscopes used in diagnostics. Different thickness of the tissue was cut and stained. The results demonstrated the importance of proper techniques and methods in preparing the tissue, and the tools to analyse it with. The thickness of tissue and the lightsource in the microscope played a cruicial role in diagnostics. Additionally it showed the importance to continue to raise the quality of work and make progress in the diagnostic and scientific field, possibly by finding new applications for old methods.

The picosecond optical response of five thin germanium samples was measured following intense optical excitation using two variations of the excitation and probe technique. Seven-picosecond laser pulses of wavelength 1.054 um were used to measure the optical transmission of the samples for a variety of probe delays, excitation fluences, and sample temperatures. These parametric experiments were performed in an effort to determine if carrier cooling, carrier diffusion, or carrier recombination dominates the carrier dynamics immediately following excitation. The studies of a 5.7 um thick sample indicated that Auger recombination does not dominate the carrier dynamics, but that the carriers most likely cool immediately to within a few optical phonons of the lattice temperature. Lattice heating may also occur depending on excitation level. Neither cooling nor diffusion was ruled out as a major contributor to the transient optical response. A numerical analysis indicated that, although diffusion may be minimized in the thinner samples, the importance of surface recombination increases as the sample thickness decreases. The lattice temperature dependence of the optical transmission was found not to be in disagreement with the known temperature dependence of the low-density diffusion coefficient. Finally, new structure was observed in the data which is consistent with an increased intervalence band absorption at the highest excitation levels.

Anthropogenic gas- and particle-phase emissions affect the climate by absorbing and scattering radiation, and have been linked to adverse health effects. Black carbon (BC), a by-product of incomplete combustion, is the most potent light-absorbing component of atmospheric aerosols, with a top-of-the atmosphere direct radiative forcing estimated to be only second to CO2. However, there is a large uncertainty associated with BC’s total direct and indirect radiative forcings due to uncertain source emissions and optical properties and complex interactions with clouds. In this dissertation we investigate the direct radiative impact of two of the most important sources of BC particles: biofuel combustion and vehicles. Together these sources contribute around 40% of the global atmospheric BC burden. Recently, both of these energy sources are undergoing rapid technology changes, and the climate impacts from the emissions of these newly adopted technologies remain uncertain. We also investigate the role of atmospheric processing on the optical properties and growth rates of particles. This dissertation first assesses the climate impacts of aerosol emissions of two rapidly emerging technologies: improved cookstoves and gasoline direct injection (GDI) vehicles. We performed extensive measurements of gas- and particle emissions and optical properties of emissions from both these sources. Our data suggests that improved rocket cookstoves have, on average, a factor of two lower particulate matter (PM) emissions compared to traditional cookstoves but only a 4% climate benefits associated with their emissions. In contrast, we estimated a 30% climate benefit from switching traditional cookstoves to gasifier ones. Of all the stoves tested, charcoal stoves had the lowest emissions and climate impacts. Our data suggests the widespread deployment of improved cookstoves to replace existing, inefficient, traditional cookstoves will likely result in health and climate co-benefits. Similarly, we estimated that the rapid adoption of GDI vehicles to replace existing port fuel injection (PFI) vehicles will likely result in reduced warming from emissions. This is due to the higher fuel economy of GDI engines; we measured an average CO2 reduction of 57 g/mi, from switching engine technologies. GDI engine emissions had higher PM emissions compared to PFI engines, similar to previous findings. In addition, our data suggests that newer GDI engines have a factor of two lower PM emissions compared to older GDI engines. These improvements in emissions may enable GDI-equipped vehicles to meet the new Federal Tier 3 PM standard of 3.0 mg/mi without gasoline particulate filters (GPF, which would reduce their fuel economy). To better constrain the large uncertainty of radiative forcing associated with cookstove emissions, this dissertation examines emissions and optical properties from several cookstove and fuel combinations. We performed extensive laboratory measurements of the optical properties of fresh cookstove emissions using the newly developed firepower sweep protocol. Current model treatments of the optical properties of cookstove emissions assume: (1) complete internal mixture between BC and non-BC material and (2) absorption properties of organics based on parametrizations developed for biomass burning emissions. These assumptions do not accurately represent optical properties of fresh cookstove emissions. We developed new parametrizations of optical properties (BC-mass absorption cross section (MACBC), absorption angstrom exponent (AAE), and single scattering albedo (SSA)) of aerosol emissions from cookstoves as a function of the BC-to-PM mass ratio. These parametrizations are designed for use in climate models to more rigorously assess the global climate implications from adoption of improved stove technologies. Upon entering the atmosphere aerosol emissions undergo complex chemical transformations. Aerosol optical properties depend on their atmospheric processing which controls the amount of coating the particles accumulate and their lifetime. To assess the effects of coating on the optical properties, we performed targeted experiments using real world, size selected, BC particles emitted from a rocket improved cookstove, and coated with biogenic secondary organic aerosol (SOA) material. These experiments explicitly target to evaluate measurements and modeling using simple formulation like Mie theory. Measurements of MACBC and the mass scattering cross section (MSC) of coated BC particles were in good agreement with Mie predictions when the organic-to-BC mass ratio>5. Scattering (but not absorption) was sensitive to BC fractal-like morphology; Mie theory under-predicted measured scattering of fresh emissions. Our data suggest that Mie theory can be used in climate models to approximate the optical properties of coated BC particles emitted from cookstoves, if the mixing-state of BC particles is known. In this dissertation, we present initial evidence that particle growth rates depend on seed composition and gas-phase supersaturation. Current models do not account for seed-dependent growth rates. We conducted experiments to investigate the growth of diesel and biogenic SOA particles. Both seeds were exposed to the same gas-phase supersaturation, which allows us to accurately retrieve differences in growth rates and decouple the effects of surface activity and accommodation coefficients. We estimated that the accommodation coefficients of condensing material was 10% to 30% lower on the diesel particles compared to the SOA particles. Moreover, we measured larger surface activity of condensing material on the diesel particles, potentially due to less-miscible condensing vapors in the diesel particles compared to the SOA particles. Our data suggest that growth of BC (diesel) particles in the atmosphere is likely slower compared to SOA particles. Accurately representing these processes is important to estimate the lifetime and absorption enhancement from coated BC particles, as they compete with other particles for condensable vapors.

The varied properties of Silicon Carbide (SiC) are helping to launch the material into many new applications, particularly in the field of novel semiconductor devices. In this work, the cubic form of SiC is of interest as a basis for developing integrated optical components. Here, the formation of a suitable SiO2 buried cladding layer has been achieved by high dose oxygen ion implantation. This layer is necessary for the optical confinement of propagating light, and hence optical waveguide fabrication. Results have shown that optical propagation losses of the order of 20 dB/cm are obtainable. Much of this loss can be attributed to mode leakage and volume scattering. Mode leakage is a function of the effective oxide thickness, and volume scattering related to the surface layer damage. These parameters have been shown to be controllable and so suggests that further reduction in the waveguide loss is feasible. Analysis of the layer growth mechanism by RBS, XTEM and XPS proves that SiO2 is formed, and that the extent of formation depends on implant dose and temperature. The excess carbon generated is believed to exit the oxide layer by a number of varying mechanisms. The result of this appears to be a number of stable Si-C-O intermediaries that form regions to either depth extreme of the SiO2 layer. Early furnace tests suggest a need to anneal at temperatures approaching the melting point of the silicon substrate, and that the quality of the virgin material is crutial in controlling the resulting oxide growth.