Devido à sua baixa solubilidade em água, os pirrolidinoditiocarbamatos poderiam produzir eletrodos livres do problema de lixiviação do modificador, os quais poderiam ser usados como detectores amperométricos, em análises em fluxo e outros procedimentos hidrodinâmicos. O complexo poderia agir como um intermediário de transferência de elétrons entre o analito e a superfície eletródica, aumentando a sensibilidade da resposta analítica do sensor. Desta forma, eletrodos de pasta de carbono modificados (EPCM) com complexos de pirrolidinoditiocarbamatos anidros de diversos metais foram preparados e testados quanto à sua aplicação em técnicas voltamétricas. Os complexos de manganês(II), [MnPyr2] e cobalto(II), [CoPyr2], foram os que apresentaram os melhores resultados em termos de estabilidade e reprodutibilidade de resposta, escolhendo-se o EPCM-[MnPyr2], para uso neste trabalho. O desempenho do eletrodo foi avaliado usando voltametria cíclica, cronoamperometria e análise em fluxo, com detecção amperométrica de peróxido de hidrogênio apresentando regiões lineares de 1,25-14,8; 0,5-41; 1,0-75 x 10-4 mol L-1 e limites de detecção de 11,2; 2,98; 5,40 x 10-5 mol L-1 respectivamente para cada técnica. Na determinação de peróxido de hidrogênio em amostra de alvejante comercial observou-se concordância nos resultados obtidos em voltametria cíclica e análise em fluxo, usando o eletrodo proposto em comparação com a permanganometria clássica, com 95 % de intervalo de confiança. Estes resultados foram obtidos após otimização de parâmetros como velocidade de varredura, pH, eletrólito suporte, entre outros. A oxidação ocorre por meio de um processo eletrocatalítico. O desempenho do pirrolidinoditiocarbamato de vanadila hidratado também foi avaliado como alternativa aos ditiocarbamatos anidros, na preparação de eletrodos modificados com esta classe de complexos, considerando que os complexos hidratados seriam mais fáceis de preparar. Entretanto uma baixa estabilidade e reprodutibilidade de resposta foi observada. O [MnPyr2] mostrou comportamento no qual ocorre oxidação, concordando com a proposta de Schrauzer para ligantes do tipo ímpar, apesar de que a oxidação só ocorreu na presença de oxidantes fortes, como o peróxido de hidrogênio. / Considering their low solubility in water, the dithiocarbamate complexes should produce electrodes without problems of modifier leaching. Such electrodes could be used as amperometric detectors in flow injection analysis and hydrodynamic methods. The complex should act as an electron transfer mediator between the analyte and the electrode surface, improving the response sensitivity of the sensor. Considering these statements carbon paste electrodes modified (EPCM) with anhydrous pyrrolidinedithiocarbamates of several metals were prepared and evaluated in relation to their possible application in voltammetric techniques. Best results regarding response stability and reproducibility were obtained with manganese(II), [MnPyr2] and cobalt(II), [CoPyr2] complexes. The first one was chosen to develop the present work. The electrode performance was evaluated in cyclic voltammetry, chrono amperometric and flow injection analysis with amperometric detection. Linear dynamic ranges of 1,25-14,8; 0,5-41; 1,0-75 x 10-4 mol L-1 and limits of detection of 11,2; 2,98; 5,40 x 10-5 mol L-1 were found respectively for each technique in the determination of hydrogen peroxyde. The methods were used for the determination of H2O2 in bleaching formulation and presented agreement with the classical titration with potassium permanganate within 95% confidence level. Such results have been obtained after optimization of experimental parameters such as scan rate, pH, supporting electrolyte, and others. The oxidation occurred by an electrocatalytic process. Finally the performance of a carbon paste electrode modified with a hydrated vanadyl pyrrolidinedithiocarbamate complex was evaluated as an alternative to the anhydrous complex in the preparation of the modified electrode, since the hydrated complexes are easier to prepare. However a low response stability and reproducibility have been observed. The [MnPyr2] presented an oxidation behavior in agreement with Schrauzer’s predictions, although the oxidation of the metal center occurred only in the presence of strong oxidative agents as the hydrogen peroxide.

Pasta de cimento é um material comum em repositórios para rejeitos radioativos, atuando como material estrutural e de imobilização. Sua utilização como material de preenchimento em um repositório tipo poço tubular profundo para fontes seladas, no entanto, requer um maior tempo de vida útil do material. O conhecimento de seu comportamento em longo prazo é necessário para garantir a segurança da instalação em milhares de anos. O presente trabalho avaliou as alterações na pasta de cimento induzidas por fatores de degradação, como ataque de agentes agressivos, alta temperatura e presença de campo de radiação. Corpos de prova (cps) de pasta de cimento foram submetidos a ensaios acelerados de degradação e os efeitos deletérios foram avaliados por meio de ensaios de resistência mecânica, variação dimensional, lixiviação/penetração de íons, DRX, TGA e MEV. Observou-se que a hidratação dos cps foi beneficiada pela imersão (em água destilada ou em solução salina) e alta temperatura, resultando em uma resistência maior. O armazenamento à seco prejudicou a hidratação, mantendo a resistência mais baixa. O tempo de imersão e a irradiação não foram capazes de alterar a mineralogia e a resistência da pasta de cimento. / Cement paste is widely used in repositories for radioactive wastes, acting as structural and immobilization material. However, its use as backfill material in boreholes for sealed sources requires a longer service life of this material. The assessment of the cement paste behavior in long term is needed to improve the confidence that the material will perform as required during the service life of the facility. This research evaluated the changes in cement paste induced by degradation parameters. Portland cement paste specimens (cps) were submitted to accelerated degradation tests and the damage effects was evaluated by mechanical strength, variation of sample mass and volume, leaching/penetration of ions, XRD, TGA and SEM. It was observed that cps hydration was benefited by immersion (in distilled water or salt solution) and high temperatures, resulting in a higher strength. Dry storage, however, influenced the hydration process and maintained strength lower. Time of treatment and irradiation were not able to alter mineralogy and durability of cement paste.

O metacaulim é um material pozolânico que vem sendo pesquisado e adotado em vários países. O metacaulim é constituído basicamente de sílica (SiO) e alumina (Al2O3) na fase amorfa, capaz de reagir com o hidróxido de cálcio Ca(OH) gerado durante a hidratação do cimento Portland, formando produtos hidratados similares aos decorrentes da hidratação direta do clinquer Portland. Esta pozolana acelera o processo de hidratação do cimento, formando silicato de cálcio hidratado (C-S-H) adicional. O conhecimento das características do metacaulim que influenciam a interação com a cal, se faz necessário para subsidiar medidas preventivas com relação ao consumo de portlandita. O presente trabalho visa determinar as características físico-químicas relevantes para o entendimento da atividade pozolânica, avaliando as reações propiciadas pelo metacaulim em sistemas binários. Para este propósito, realizaram-se estudos experimentais em pasta e concreto, usando as técnicas de difratometria de raios X e de termogravimetria. As etapas experimentais consistiram: na caracterização do metacaulim, com ênfase na determinação do teor da fase amorfa; a avaliação da cinética da reação em sistema metacaulim/hidróxido de cálcio e análise da evolução da hidratação de cimento com alto teor de metacaulim. Nos sistemas cimenticios de concretos com diferentes teores de substituição de metacaulim com e sem cal hidratada, foi avaliado o comportamento da resistência à compressão. No metacaulim estudado, o teor da fase amorfa foi de 74,60% e o restante (25,40%) atua como material inerte, e o consumo máximo por atividade pozolânica, foi de 1,34 gr de Ca(OH)/grama de fase amorfa de metacaulim. Na evolução das reações, por atividade pozolânica o C-S-H foi formando gradativamente. A adição de 15% de metacaulim e 5% de cal hidratada em concretos proporcionou um ganho de resistência de 17% a mais em função do concreto de referência. / The metakaolin is a pozzolanic material that has been investigated and adopted in several countries. The metakaolin consists primarily of silica (SiO) and alumina (Al2O3) in the amorphous phase, and can react with calcium hydroxide Ca (OH) generated during hydration of Portland cement to form products similar to those obtained during Portland clinker basic hydration. This pozzolana could accelerate the hydration of cement, forming calcium silicate hydrate (C-S-H) additional. The knowledge of the characteristics of metakaolin that influence the interaction with lime provides the necessary subsidize to prevent excessive consumption of portlandite. This paper aims to determine the physical and chemical relevant characteristics in order to understand the pozzolanic activity, evaluating the responses provided by the metakaolin in binary systems. For this purpose, experimental studies were conducted in paste and concrete, using the techniques of X-ray diffraction and thermogravimetry. The experimental steps consisted of: the characterization of metakaolin, with emphasis on determining the amorphous phase content, this evaluation of the kinetics of the reaction system metakaolin and calcium hydroxide; The analysis of the evolution of the cement hydration with high content of metakaolin. In cementitious systems of concrete with different metakaolin replacement levels with and without hydrated lime, was rated the behavior of the compressive strength. The content of amorphous phase In the studied metakaolim was 74.60% and the remainder (25.40%) acts as an inert material, and the máximum consumption by pozzolanic activity was 1.34 g of Ca (OH)/g amorphous phase of metakaolin. During the evolution of pozzolanic reactions, the C-S-H was gradually formed. The addition of 15% metakaolin and 5% hydrated lime in concrete has a strength gain of 17% more depending on the reference concrete.

O morfolinoditiocarbamato (Mor); o piperidinoditiocarbamato (Pip) e o pirrolidinoditiocarbamato (Pyr) de rutênio derivados respectivamente da morfolina, piperidina e pirrolidina, três aminas alifáticas cíclicas foram preparados e caracterizados por análise elementar, espectroscopia vibracional na região do infravermelho, espectrometria de massa e análise térmica (termogravimetria – TG e análise térmica diferencial – DTA). A análise elementar mostrou que os compostos de fórmula geral Ru2DTC5.XH2O foram obtidos (DTC = Mor, Pip e Pyr e X = 4, 1,5 e 2 respectivamente); assim como a IV revelou que os complexos são monodentados, com duas bandas de absorção em torno de 1000 cm-1. A espectrometria de massas mostrou as estruturas moleculares e a estabilidade dos complexos, pois requerem alta energia de colisão para fragmentarem-se; alguns fragmentos puderam ser identificados. A análise térmica mostrou que após desidratação os DTC decompõem-se gerando sulfato e óxido de rutênio (III), dependendo da temperatura. Após caracterização, os complexos foram usados com modificadores na preparação de eletrodos de pasta de carbono modificados e seu desempenho avaliado por voltametria cíclica em diferentes meios e intervalos de potencial e em diferentes composições do material do eletrodo. Com base na melhor definição dos picos referentes aos processos anódicos e catódicos, assim como pela menor corrente residual, optou-se em usar como modificador o Ru2Pip5.1,5H2O, na proporção de 10% (m/m) na pasta. Eletrodos preparados com este modificador foram usados na determinação voltamétrica de carbamazepina (CBZ), usando CV. Na presença do analito a corrente do modificador aumenta proporcionalmente à concentração de CBZ no intervalo de 1,30 x 10-8 e 6,62 x 10-6 mol L-1, com limite de detecção de 3,18 x 10-7 mol L-1. O método foi aplicado na determinação de CBZ em urina sintética, usando procedimento de adição de padrão com recuperação da ordem de 97 – 104% e concordância com o método espectrofotométrico recomendado pela farmacopéia brasileira no intervalo de confiança de 95%. / The morpholinedithiocarbamate (Mor); piperidinedithiocarbamate (Pip) and pirrolidinedithiocarbamate (Pyr), three cyclic amines derived respectivelly from morpholine, piperidine and pirrolidine complex of Ruthenium (III) were synthesized and characterized by elemental analysis, infra-red spectroscopy, mass spectrometry and thermal analysis (thermogravimetry – TG – and differential thermal analysis – DTA). Elemental analysis showed that complexes of general formula Ru2DTC5.XH2O ((DTC = Mor, Pip e Pyr e X = 4, 1,5 e 2 respectively) were obtained. IR spectra revelead that the ligant behaves as a monodentate one with a duplet around 1000 cm-1. Mass spectrometry showed the molecular structures and the stability of the complexes, therefore they require high energy of collision to be broken up; some fragments could have been identified. Thermal analysis showed that after dehydration the complexes decomposed generating Ru2(SO4)3 and Ru2O3 as residues depending on the temperature, according to XDR analysis. After characterization the complexes were used as modifiers in the preparation of carbon paste electrodes. The performance of the modified electrodes (MCPE) was evaluated by cyclic voltammetry at different electrode composition and supporting electrolytes and potential intervals. On basis of peak definition and background current, the MCPERu2Pip5.1,5H2O, containing 10% of the complex, was chosen for further studies. The electrode was used in the determination of carbamazepine (CBZ) cyclic voltammetry. In the presence of CBZ the modifier current increased proportionally, to the analyte concentration in the 1,30 x 10-8 and 6,62 x 10-6 mol L-1. The method was applied in the determination of CBZ in synthetic urine sample spikes with the analyte with recoveries of 97 – 104%. Whem compared with a standart spectrophotometric procedure the results of the prposed method agreeded within 95% of confidence, according to the t-Student test.

Le futur site de stockage géologique des déchets MAVL français intègre, dans sa conception, des éléments de structure en béton armé (alvéole et conteneurs). Prédire leur durabilité à l'échelle de la phase d'exploitation (environ 100 ans) est décisif. En conditions de service, le système de ventilation assurerait un approvisionnement constant de CO2, soumettant le béton à des phénomènes de séchage et de carbonatation. L'effet de la température (dû à l'exothermie des déchets) et du séchage sur la carbonatation a été évalué par le passé. Les données acquises à ce jour se doivent cependant d'être complétées. Dans ce sens, la prise en compte des transferts hydriques simultanés à la carbonatation est indispensable. D'une part, car la carbonatation est une pathologie courante du béton armé qui mène, à terme, à une corrosion généralisée des armatures. D'autre part, car la durabilité des structures en béton armé est conditionnée par l'évolution de leur état hydrique tout au long de leur période de service. L'évaluation des propriétés de transport d'eau dans les matériaux carbonatés, en milieu insaturé, constitue un enjeu important pour l'Andra chargée de la gestion des déchets radioactifs.Des essais de carbonatation accélérée sont conduits sur quatre pâtes de ciment durci (CEM I, CEM III/A, CEM V/A et un mélange Bas-pH) à une teneur en CO2 de 3%. Les propriétés hydriques des matériaux carbonatés sont évaluées à partir d'une approche simplifiée nécessitant la connaissance de 3 paramètres physiques accessibles par l'expérience : (i) porosité, (ii) isotherme de désorption de la vapeur d'eau et (iii) perméabilité.Les résultats mettent en évidence des modifications minéralogiques et microstructurales majeures engendrées par la carbonatation : décomposition des hydrates et précipitation de carbonate de calcium (CaCO3) selon différents polymorphes. La décalcification forte des C S H et la polymérisation des chaines silicatées, menant à la formation d'un gel de silice enrichi en calcium, sont constatées. La conséquence directe est l'apparition d'un retrait de carbonatation, lui-même à l'origine d'un phénomène de microfissuration. D'autre part, une réduction du volume poreux et de la surface spécifique des matériaux sont observées. Les carbonates formés obturent les pores, réduisant ainsi la porosité totale. Dans ce sens, plus la teneur initiale en portlandite est élevée, plus la quantité de CaCO3 formée est importante et, par conséquent, plus la chute de porosité résultante est marquée. La structure d'un matériau carbonaté n'a alors plus rien à voir avec son état initial. Ces changements se traduisent par une baisse significative de la teneur en eau à l'équilibre et un changement de morphologie des isothermes, en lien direct avec les évolutions microstructurales. Une baisse de la perméabilité est obtenue dans le cas du ciment Portland (CEM I), en raison du large colmatage de la porosité. Par contre, elle augmente dans le cas des ciments avec ajouts (CEM III/A, CEM V/A et Bas-pH), fait directement imputé à l'effet de la microfissuration, qui prédomine devant la chute de porosité. Le cortège minéralogique initial (teneurs en portlandite et C-S-H) joue donc un rôle déterminant vis-à-vis du comportent des matériaux cimentaires face à la carbonatation. La représentativité de la carbonatation accélérée vis-à-vis de la carbonatation naturelle a, par ailleurs, été vérifiée. Le jeu de données récolté au cours de ces travaux peut être étendu et, appliqué avec confiance, en condition de carbonatation réelle / The French design of deep geological repository involves the use of cement-based materials (vault cell and containers). The durability assessment over the operational phase (supply 100 years) is decisive. In operating conditions, a ventilation system would maintain the CO2 partial pressure within the disposal, subjecting concrete to drying and carbonation. The temperature (due to the waste thermal output) and drying effects on carbonation have been studied in the past. The data acquired must however be complemented. In this sense, taking into account the water transfers simultaneously to carbonation is essential. On the one hand, because carbonation is a common pathology of reinforced concrete that leads to rebar corrosion. On the other hand, because the durability of reinforced concrete structures is dependent on their water content evolution all along their service life. The assessment of water transport properties in carbonated materials, under unsaturated conditions, is an important issue for Andra in charge of the management of radioactive waste in France.Accelerated carbonation test are performed on four hardened cement pastes (CEM I, CEM III/A, CEM V/A and a Low-pH mix) at 3% CO2 content. The water transport properties of carbonated materials are evaluated using a simplified approach, requiring the knowledge of 3 physical parameters, accessible through experimental way: (i) porosity, (ii) water vapour desorption isotherm and (iii) permeability.The results highlight mineralogical and microstructural changes induced by carbonation: hydrates decomposition and calcium carbonate precipitation (CaCO3) according to various polymorphs. The high decalcification of C-S-H and the polymerisation of silicates chains, leading to the formation of a calcium-enriched silica gel, are found. This results in carbonation shrinkage, responsible of microcracking. On the other hand, the reduction of porosity and specific surface area are observed. The formed carbonates fill the pores, reducing the total porosity. In this sense, the higher the initial portlandite content, the higher the amount of CaCO3 and, consequently, the more the porosity decrease. The structure of the carbonated materials is totally different from the initial state. These changes result into a significant reduction of the water content at the equilibrium and a modification of the isotherms morphology, directly related to the microstructure evolutions. The permeability is found to decrease in the case of Portland cement (CEM I), due to porosity clogging. By contrast, it was found to increase significantly for blended cements (CEM III/A, CEM V/A and Low-pH mix), this is directly attributed to the microcracking effect which is more significant compared to porosity clogging. The initial mineralogy (portlandite and C-S-H contents) therefore plays a determinant role regarding to the carbonation impact on the cementitious materials behaviour. Furthermore, the representativeness of accelerated carbonation compared to natural one was verified. The data set acquired during this work can be extended and, applied confidently under real carbonation conditions

Made available in DSpace on 2017-07-24T19:37:59Z (GMT). No. of bitstreams: 1 Cristiane_de_Abreu_Dias.pdf: 17390080 bytes, checksum: 6e0128183854fb8cc356100b574dac1a (MD5) Previous issue date: 2009-02-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Throughout the times, new pigment systems have been gradually developed. In the nowadays, the development of ceramic pigments represents a part of the Materials Science, where there is a lack of concepts, roles and strategies, which in goal allows the developing of new rotes of preparing or pigments, in both scientific and technological areas. This work deals with the development of an innovative processing route and characterization of ceramic pigments based on the formation of solid solution of zircon silicate via doping with manganese cations being the source of manganese cations a waste of alkaline battery. In fact, an electrolytic paste of zinc-carbon batteries was used as a starting precursor of the manganese oxide, major component of the electrolytic paste, as a precursor of the chromophore agent. As a standard, Mn doped ZrSiO4 pigments were prepared via mechanical mixture of oxides process using analytical MnO2 (P.A.) oxide as a starting precursor of manganese cations. Powder mixtures exhibiting different percentages in weight of electrolytic paste were homogenized in the isopropyl alcohol via ball milling during 6 h. In the sequence, precursors were dried in furnace type oven at 110°C until the weight stabilizing giving the precursor of the pigment. Then, the precursor was calcined, desagglomerated and sieved (350 mesh).The precursor calcination was carried out in an oven furnace at 1150°C with a soaking time of 4h, in air atmosphere, heating rate of 10°C/min, cooling rate stemming from high temperature to the room temperature was carried out via natural rate of the furnace. After the calcination of precursor, powders were characterized by scanning electron microscopy, X-ray diffraction, UV-Vis spectroscopy and laser granulometry, so the crystalline phases, microstructure, the colorimetric parameters and the some spectroscopic properties of pigments were determined. Pigment exhibiting the highest color intensity was obtained using higher fraction of electrolytic paste. As a whole, pigments proved to be chemically and thermally resistant at 800°C, when applied in vitreous enamels with industrial composition directed to ceramic plating. Pigments showed excellent dispersion degree in a low-density polyethylene and a homogeneous color. / Embora se tenha descoberto novos sistemas pigmentares, os pigmentos cerâmicos constituem um dos campos da Ciência dos Materiais onde existe um maior desconhecimento, tanto em nível de centros de pesquisa como industrial. A presente pesquisa pretende desenvolver e caracterizar pigmentos cerâmicos, à base de zirconita, com incorporação de pasta eletrolítica de pilhas Zinco-carbono, descarregadas energeticamente, explorando como agente cromóforo o manganês presente na pasta eletrolítica. Paralelamente, foram obtidas e caracterizadas amostras utilizando como dopante MnO2 P.A. Amostras com diferentes proporções em peso de pasta eletrolítica de pilhas foram homogeneizadas a úmido com álcool isopropílico em moinho de bolas por um período de 6 h, e posteriormente secas em estufa à 110oC até peso constante, levadas à calcinação, desagregadas e peneiradas. O tratamento térmico foi realizado em forno à 1150oC com um tempo de patamar de 4h, ao ar, aplicando uma velocidade de aquecimento de 10ºC/min, sendo o resfriamento das amostras a temperatura ambiente. Após o tratamento térmico as amostras foram caracterizadas por microscopia eletrônica de varredura, difração de raios X, UV-Vis e granulometria à laser e as microestruturas, as fases presentes, os parâmetros colorimétricos e as propriedades físicas dos pigmentos foram determinados. Cores mais intensas foram obtidas nas amostras com maior concentração de pasta eletrolítica adicionado. Os pigmentos mostraram ser resistentes química e termicamente à 8000C, quando aplicados em esmalte vítreo em placas cerâmicas. Em polietileno de baixa densidade os pigmentos apresentaram excelente dispersão e homogeneidade de cor.

OBJECTIVES: The aims of this study are to determine the shade correlation between try-in pastes with their corresponding resin cements. Also, to investigate the effect of resin cement shades and various ceramic thicknesses, shades, and translucency in the final color outcome over tooth-shaded backgrounds. MATERIALS AND METHOD: Lithium Disilicate CAD/CAM blocks (IPS e.max CAD) were prepared, in high and low translucency, in two different shades (A1 and A3), and in 2 different thicknesses (0.53 ± 0.02 mm and 0.83 ± 0.02 mm). Four different tooth-shaded backgrounds (ND2, ND5, ND8, and ND9) were prepared from acrylic resin in a standard thickness of 6.610 mm to achieve complete opacity. RelyX veneer cement and its corresponding try-in paste in three different shades, Transparent (TR), White Opaque (WO), and Bleached Opaque (BO), in a thickness of (80 ± 5 μm) were used. For each combination, the color was measured with a spectrophotometer to calculate the color difference (ΔΕ value) in reference to ceramic veneer, and the differences of ΔΕ among the specimens were compared statistically using JMP Pro 13. Analysis was performed for 3 aims, (1) to compare the ability of ceramic to mask the aspect of the abutment in relation to its thickness (0.5 and 0.8) mm, transparency (HT and LT) and shade (A1 and A3), (2) effect of a change in cement color (TR, WO, and BO) on the final color of the ceramic; and (3) to determine the correlation between try-in pastes with their corresponding resin cements. RESULT: A significant difference was found with a p-value of <.0001 for the following factors: Stump Shade, ceramic thickness, cured cement, ceramic shade, cement type and for the interactions of cured cement with cement type, and stump shade with ceramic transparency. Also, a significant difference was found with ceramic transparency with a p-value 0.0476. While cured cement and its corresponding try-in paste showed a significant difference in color masking (p <.0001) shade White Opaque cement and shade White Opaque try-in paste exhibited insignificant color change outcome with a p-value of 0.8051. CONCLUSION: RelyX veneer cements shades (Translucent and Bleached Opaque) have lower masking ability than White Opaque cement. RelyX veneer Try in paste is much less effective in masking than its corresponding resin cement. The only correlation between RelyX veneer cements with their corresponding try-in pastes among the shades tested (White Opaque, Translucent and Bleached Opaque) is with shade White Opaque. This study demonstrated that underlying tooth abutment color, cement color, and ceramic thickness, shade and translucency all influence the resulting optical color of CAD/CAM glass-ceramic lithium disilicate-reinforced restorations. / 2020-10-24T00:00:00Z

Os efeitos terapêuticos dos sais de lítio são comprovados no tratamento de pacientes com depressão, certos tipos de câncer e transtornos bipolares de humor. A dosagem de lítio deve ser cuidadosamente controlada em cada paciente já que excessos na dosagem podem conduzir a danos irreversíveis no sistema nervoso e nos rins. Sendo assim é interessante produzir métodos de baixo custo, simples e rápidos que permitam o monitoramento desse íon. Portanto no presente trabalho foi estudado o desempenho potenciométrico de um eletrodo compósito de pasta de carbono modificado com óxido de manganês tipo espinélio dopado com cobalto (III). O eletrodo de pasta de carbono modificado foi preparado pela mistura de 55% (m/m) de pó de grafite, 20% (m/m) de aglutinante (óleo mineral) e 25% (m/m) de óxido de manganês dopado com cobalto (III) (Li1,05Co0,02Mn1,98O4.). O desempenho eletroquímico do eletrodo foi estudado através de voltametria cíclica (etapa de ativação) e cronopotenciometria (i=0) (etapas de estabilização e adição de padrão). Na caracterização eletroquímica do eletrodo estudou-se a melhor concentração de íons lítio para ativação do sensor, bem como a melhor velocidade de varredura, tempo de estabilização, pH, intervalo linear de resposta, limite de detecção e possíveis íons interferentes. Encontrou-se um limite de detecção de 3,98 x 10-6 mol L-1, intervalo linear de resposta de 1,82 x 10-4 mol L-1 a 1,62 x 10-3 mol L-1, pouca interferência dos íons estudados (Na+, K+, Rb+, Cs+, Mg+2, Ca+2 e Ba+2) sendo a interferência proporcional ao raio iônico dos íons interferentes e sensibilidade de 97,90 mV dec-1. Esse valor de sensibilidade classifica o eletrodo estudado como tendo resposta supernerstiniana o que pode ser atribuído à coexistência de sítios de troca iônica e sítios redox no processo de inserção/extração dos íons lítio na matriz do óxido de manganês. A substituição parcial dos íons Mn pelos íons Co provoca uma diminuição no parâmetro de célula unitária do óxido, o que melhora a estabilidade da estrutura durante o processo de inserção/extração de íons lítio fornecendo maior sensibilidade e propiciando maior seletividade. / The therapeutic effects of lithium salts have been proved useful, as an example given, in the treatment of patients who presents depressive behavior, bipolar disorder and certain types of cancer. The lithium dosage for each patient has to be carefully controlled because an excessive dose can produce irreversible damages to the nervous system and the kidneys. Therefore is interesting produce low cost, simple and quick methods to allow the monitoring of this ion. Hence in this work, the performance of a composite potentiometric carbon paste electrode modified with spinel type manganese oxide doped with cobalt (III) (Li1,05Co0,02Mn1,98O4) was studied. The modified carbon paste electrode was prepared by mixing 55% (w / w) of graphite powder, 20% (w / w) binder (mineral oil) and 25% (m / m) manganese oxide doped with Cobalt (III). The potentiometric performance of the electrode was studied by cyclic voltammetry (activation step) and potentiometry - zero current (stabilization and standard addition steps). The electrochemical characterization of the electrode consisted of the studies of the optimal concentration of lithium ions for activation of the sensor, as well as the best scan rate, stabilization time, pH, linear response range, detection limit and possible interfering ions. In pH = 10, the better one chosen for this study, it was found a detection limit of 3.98 x 10-6 mol L-1, a linear response range from 1.82 x 10-4 mol L-1 to 1.62 x 10-3 mol L-1, low interference from the studied ions (Na+, K+, Rb+, Cs+, Mg+2, Ca+2 e Ba+2), which is proportional to their ionic radius and sensitivity of 97,90 mV dec-1. This high sensitivity value can be attributed to the coexistence of ion exchange sites and redox sites in the insertion / extraction of lithium ions in the manganese oxide matrix process. The best working pH was around 10, as opposed to working with similar materials found in the literature. This can be explained by the substitution of manganese for cobalt (III) in the structure of the spinel type manganese oxide. This substitution causes a decrease in the unit cell parameter of the oxide, which improves the stability of the structure during the process of insertion / extraction of lithium ions and resistance to change in alkaline solutions.

Supercapacitors, also known as electrochemical capacitors, have shown great potential as energy storage devices; and 3D printing likewise as a manufacturing technique. This research progressively investigates combining these two technologies to fabricate 3D-printed, electrochemical double-layer capacitors (EDLCs). Small EDLCs were designed in a sandwich structure with an FDM-printed plastic frame and carbon electrodes. Inkjet printing was initially combined with FDM printing to produce a pilot sample with a silver ink current collector, however this performed poorly (Cs = 6 mF/g). Henceforth a paste extrusion system was added to the FDM printer to deposit the current collectors and electrodes, fabricating the entire device in a single continuous process. This process was progressively developed and tested, ultimately attaining specific capacitances of 200 mF/g. The fully integrated 3D printing process used to manufacture the EDLCs was a novel approach. Combining the FDM printer with a paste extruder allowed for a high degree of dimensional accuracy, as well as simplifying the production process. This aspect of the design functioned successfully, without significant faults, and proved a reliable fabrication method. The later designs used in this study provided the EDLCs extendable by incorporating connection jacks. This was to create the possibility to increase capacitance simply by connecting multiple EDLCs together. Tests of this feature showed that it worked well, with the extendable EDLCs delivering outputs very close to the theoretical maximum efficiency of the unit. Carbon conductive paint was applied as a current collector and electrode for the 3D printed EDLCs in an exploration of metal-free 3D printed supercapacitors. These metal-free EDLCs were found to provide around 60% of the specific capacitance of the best performing EDLC variant produced (silver paint current collectors with activated carbon and carbon paint mixture electrodes). Although considerable improvement is required to produce EDLC samples with comparable capacitances to existing commercial manufacturing techniques, this study lays important groundwork in this area, and has introduces effective and innovative design ideas for supercapacitors and integrated 3D printing processes.

Orientador: Neura Bragagnolo / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-10-03T13:46:21Z (GMT). No. of bitstreams: 1 Alves_AdrianaBarreto_D.pdf: 4493430 bytes, checksum: b528cf0688daea5421cc2af99d689e45 (MD5) Previous issue date: 2009 / Resumo: Estudos epidemiológicos têm demonstrado que o consumo de frutas e vegetais tem um efeito benéfico na redução da incidência de várias doenças como o câncer e doenças cardiovasculares. Esse efeito tem sido relacionado com a presença de compostos antioxidantes nesses alimentos, sobretudo os flavonóides. O tomate (Lycopersicum esculentum Mill.) é um dos vegetais mais consumidos no mundo, in natura ou processado, e também é rico em compostos antioxidantes como carotenóides, vitaminas e flavonóides. Os alimentos processados, frequentemente, são tidos como menos nutritivos que os alimentos in natura, devido, principalmente, ao fato de que alguns nutrientes são degradados pelas altas temperaturas empregadas. Assim, torna-se importante avaliar o efeito do processamento e da estocagem sobre os compostos antioxidantes do tomate e também sobre sua atividade antioxidante. Um planejamento experimental foi realizado para otimizar as condições de extração dos compostos fenólicos e concentração dos flavonóides em polpa de tomate concentrada. O método otimizado foi validado para as determinações de compostos fenólicos totais e flavonóides totais por espectrofotometria e também para a determinação de flavonóides por cromatografia líquida de alta eficiência (CLAE). Os métodos espectrofotométricos foram validados nos parâmetros repetibilidade e exatidão. A determinação de flavonóides por CLAE foi validada nos parâmetros seletividade, linearidade, precisão, exatidão e sensibilidade. O efeito do processamento e da estocagem sobre os compostos antioxidantes do tomate foi avaliado. Foram analisados os teores de compostos fenólicos totais, flavonóides totais, flavonóides por CLAE, ácido ascórbico, licopeno e ß-caroteno, bem como a atividade antioxidante das frações hidrofílicas e lipofílicas pelos métodos ABTS e DPPH. Verificou-se que, durante o processamento, em geral, não houve perdas dos compostos antioxidantes. Durante o armazenamento, observou-se grande degradação do ácido ascórbico, porém, os demais compostos mantiveram-se estáveis, e não foi observada nenhuma alteração na atividade antioxidante. O efeito do processamento sobre a atividade antioxidante do extrato fenólico foi também avaliado por espectroscopia de ressonância de elétron-spin (ESR) usando sal de Fremy e em sistema-modelo de lipossomas. Esses e os outros resultados de atividade antioxidante obtidos previamente foram correlacionados com os teores de compostos fenólicos totais a fim de melhor estudar os mecanismos de ação antioxidante envolvidos. A ação antioxidante das amostras de tomate, coletadas em diferentes etapas do processamento, foi testada em carne de frango processada sob alta pressão a 300, 600 e 800 MPa e armazenada sob refrigeração por 15 dias. A adição de 0,30% de subproduto (pele + semente) ou 0,10% de polpa concentrada resultou em uma fase lag de 6 dias para a formação de produtos secundários da oxidação lipídica na carne de frango processada a 600 MPa. O subproduto apresentou efeito similar também para a carne de frango processada a 800 MPa. O resultado deste trabalho mostrou que, embora o processamento e a estocagem de polpa de tomate possam ter degradado substâncias mais sensíveis como o ácido ascórbico, os demais compostos antioxidantes não sofreram alterações deletérias, e, para alguns, o processamento foi benéfico, aumentando sua disponibilidade. De forma semelhante, as atividades antioxidantes dos produtos processados foram iguais ou maiores que as das amostras in natura e se mantiveram estáveis durante o armazenamento por um ano. Além disso, o subproduto do processamento pode ter boas chances de aplicação como antioxidante em outros produtos alimentícios / Abstract: Epidemiological studies have shown that the consumption of fruits and vegetables has a beneficial effect on reducing some diseases like cancer and cardiovascular diseases. These benefits have been associated to the presence of antioxidant compounds in those foods, mainly flavonoids. Tomato (Lycopersicum esculentum Mill.) is one of the most worldwide consumed vegetables, in natura or processed. Moreover, tomato is rich in many antioxidant compounds like carotenoids, vitamins and flavonoids. Frequently, thermoprocessed foods are taken as less healthy than in natura foods, mainly because nutrient losses caused by high temperature. So, it is very important to evaluate the effect of processing and storage on tomato antioxidant compounds and on their antioxidant activity. A response surface methodology was used to optimize the phenolics extraction conditions and flavonoids concentration from concentrated tomato paste. The optimized method was validated for total phenolics and total flavonoids spectrophotometric determinations and also for flavonoids quantification by high performance liquid chromatography (HPLC). The spectrophotometric methods were validated for repeatability and recovery. Flavonoids determination by HPLC was validated for selectivity, linearity, precision, recovery and sensibility. Processing and storage effect on tomato antioxidant compounds was evaluated. Total phenolics, total flavonoids, flavonoids by HPLC, ascorbic acid, lycopene and ß-carotene were determined and also the antioxidant activity of hydrophilic and lipophilic fractions were studied using ABTS and DPPH methodologies. It was observed that during processing, in general, there was no loss of the antioxidant compounds present in tomato. During the storage time there was a great loss of ascorbic acid, but all other antioxidant compounds were stable and no changes in their antioxidant activity were observed. The effect of tomato paste processing on the antioxidant activity of phenolic extract was also analyzed through electron-spin resonance spectroscopy (ESR) using Fremy¿s salt, and in a liposome model-system. These and the other antioxidant activity results previously obtained were correlated with the total phenolics content found in the samples in order to better study the antioxidant mechanisms involved. The antioxidant action of tomato samples, collected at different processing steps, was analyzed during 15 days chill storage of high-pressure treated chicken meat balls at 300, 600, and 800 MPa. Addition of 0.30% tomato waste (skin + seeds) or of 0.10% final tomato paste to minced meat led to a lag phase of 6 days for formation of secondary oxidation products in meat treated at 600 MPa. The waste product seemed especially efficient in protecting chicken meat pressurized at 800 MPa, as a notably lower rate of formation of secondary oxidation products was found. This work showed that, although processing and storage of tomato paste might result in loss of the most labile substances like ascorbic acid, the other antioxidant compounds were not affected, and, for some of them, processing increased their availability. Similarly, the antioxidant activities of final products were equal to or greater than the in natura ones and remained unaltered during one year storage. In addition, waste material may have good chances of application as antioxidant in other foods / Doutorado / Ciência de Alimentos / Doutora em Ciência de Alimentos