Ce travail de recherche consiste à étudier les relations structure-propriétés de mélanges biopolymères à base de poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) et poly(butylène succinate) (PBS). Il est divisé en trois parties. La première partie est consacrée à l'étude des propriétés des mélanges PHBV/PBS préparés par voie fondue en fonction de la composition en termes de morphologie et de propriétés rhéologiques, mécaniques, thermiques et barrières. Les résultats obtenus ont été discutés par rapport aux polymères de base. La deuxième partie est consacrée à la compatibilisation des mélanges PHBV/PBS et l'amélioration des interactions à l'interface. Les effets de l'incorporation de la sépiolite à 5% en masse et du PHBV greffé par de l’anhydride maléique (PHBV-g-MA) à 5% en masse ont été étudiés en termes de changements morphologiques montrant un effet synergique entre le compatibilisant et la nanocharge sur les l’ensemble des propriétés des mélanges PHBV/PBS. Enfin, une étude sur le recyclage a été menée à travers une évaluation des effets du nombre de cycles d'extrusion sur les propriétés des matériaux. Elle révèle qu'après 6 cycles d'extrusion, la dégradation thermo-mécanique du PHBV est significativement réduite en présence du PBS. / The main objective of this work was to study the structure-properties relationships of biopolymerblends based on poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and polybutylene succinate (PBS). The work was devised into three parts. The first part was devoted to the study of the properties of PHBV/PBS blends prepared by melt compounding at different weight ratio in terms of morphology and properties. The results obtained were discussed in terms of properties and compared with the neat polymers. The second part was devoted to the study of compatibility of PHBV/PBS blends aiming to improve the interactions at the interface between the two components. The effects of both sepiolite (5% wt.) and PHBV-g-MA (5% wt.) were studied in terms of properties. The results showed a synergistic effect between the compatibilizer PHBV-g-MA and the nanofiller sepiolite though an increase in thermal, mechanical and rheological properties. The last part dealing with the recyclability of PHBV/PBS through the study of the effects of repeated extrusion cycles on the properties of materials. The results showed that after 6 reprocessing cycles the thermo-mechanical degradation of PHBV is significantly reduced in the presence of PBS.

[pt] Após a perfuração de poços de petróleo, a lama utilizada na remoção de cascalho, lubrificação e resfriamento da broca deve ser removida e substituída por uma mistura de cimento. Essa substituição se dá pelo deslocamento de um fluido por outro no espaço anular entre a formação rochosa e a coluna de completação ou revestimento. A mistura de cimento tem a função de garantir a estabilidade estrutural do poço evitando danos ambientais e prejuízos econômicos. Para melhores resultados do processo de cimentação, utilizam-se fluidos intermediários, também chamados de colchões lavadores e espaçadores, entre os fluidos principais. A boa qualidade do deslocamento dos fluidos pode ser avaliada pela forma da interface entre eles. Perfis mais acentuados sugerem um atravessamento indesejável do fluido deslocante (cimento) através do deslocado (fluido de perfuração). Por outro lado, perfis achatados indicam um deslocamento mais eficiente. Neste trabalho foi feita uma análise experimental e numérica do processo de cimentação, investigando a forma da interface e a eficiência do deslocamento dos fluidos. Uma planta experimental vertical foi construída, simulando um processo de deslocamento de fluidos em anulares excêntricos de poços. Com uma câmera digital CCD foram filmadas as interfaces entre os fluidos durante o escoamento e com essas imagens puderam-se comparar os resultados com as simulações numéricas realizadas num softw are comercial, usando o método de volumes finitos. Foram analisados os efeitos de diferentes parâmetros como a excentricidade, o regime de escoamento, e, principalmente o comportamento mecânico dos fluidos envolvidos (reologia) na eficiência do deslocamento. Com base nesses resultados é possível prever quais parâmetros operacionais otimizam o processo de deslocamento. / [en] In cementing processes of oil wells, the mud formerly used to drag the gravel, to lubricate and to cool the drill is removed and substituted by a cement mixture. This substitution is obtained by the displacement of a fluid by another in the annulus between the rock formation and the casing. For best results of cementing process, intermediate fluids, also called spacers, are used between the drill mud and the cement mixture. The displacement process is very complex due to geometry and fluids characteristics. The annular space is eccentric in most cases, and both drilling mud and cement mixtures are non-Newtonian fluids. In this work, an experimental and numerical study is performed to analyze this process. A vertical experimental plant was constructed to simulate the fluid displacement through eccentric annuli. The interface shapes between two adjacent fluids were visualized using a digital CCD camera. The images were compared with the results obtained in the numerical simulations. The numerical solution was obtained via the Finite Volume technique and using the Volume-of-Fluid method. The effects of eccentricity, displacement velocity and rheological parameters on the displacement e± ciency were investigated. Based on these results we can predict the liquid characteristics and the operational parameters that optimize the displacement process.

La cellulose est l’une des bio-ressources les plus abondantes sur terre ; elle forme des microfibrilles où alternent régions cristallines, de taille nanométrique, et régions amorphes. L’utilisation des nanocristallites de cellulose, appelés nanowhiskers, comme renforts dans des composites à matrice polymère thermoplastique a fait l’objet de nombreuses publications. En revanche, l’utilisation de nanowhiskers comme éléments structurants d’hydrogels n’a pas été vraiment explorée, en dépit d’un intérêt potentiel pour la formulation d’hydrogels verts innovants. L’objectif de la thèse était d’étudier les relations entre état structural à différentes échelles et propriétés rhéologiques de systèmes hydrocolloïdaux constitués d’hydrogels d’agarose chargés de nanowhiskers de cellulose issus de tunicier, un animal marin. Les travaux expérimentaux menés au cours de cette thèse ont montré que l’effet renfort apporté par les nanowhiskers à la matrice agarose pouvait être marqué, et qu’il pouvait être modulé en faisant varier la densité de charges électriques à la surface des nanowhiskers. Aux fractions volumiques étudiées, inférieures à 0,2%, les résultats ont montré que les nanowhiskers ne percolaient pas et l’effet renfort a été attribué à des modifications topologiques du réseau d’agarose, et à un transfert des contraintes efficace entre la matrice et les charges, qui interagissent via des liaisons hydrogène. Les résultats obtenus au cours de cette thèse permettent d’améliorer la connaissance des mécanismes qui gouvernent les propriétés renfort apportées par l’ajout de nanocharges cellulosiques à une matrice hydrogel, et donnent des pistes réalistes pour une formulation maîtrisée d’hydrogels verts innovants ayant de bonnes propriétés mécaniques. / Cellulose is the most abundant organic compound on Earth; it is composed of microfibrils, containing nanocrystalline regions, and amorphous regions. Cellulose nanocrystallites, called nanowhiskers, have been studied as reinforcement agents in polymer composites with thermoplastic matrix in numerous publications. However, the use of nanowhiskers to reinforce hydrogels has not really been explored up to now, despite potential interest in the formulation of green innovative hydrogels. The aim of this PhD thesis was to study the relationship between the structural state, on different length scales, and the rheological properties of hydrocolloid systems consisting of agarose hydrogels filled by cellulose nanowhiskers from tunicate, amarine animal. The experimental work performed in this thesis has shown that the reinforcing effect provided by the nanowhiskers could be marked, and could also be modulated by varying the density of electrical charges on the surface of nanowhiskers. Within the volume fraction range studied, that is less than 0.2%, the results have shown that the nanowhiskers could not percolate, and reinforcement effect was attributed to topological modifications of the agarose network, and to an efficient stress transfer between the matrix and the fillers, which interact via hydrogen bonds.The results obtained in this thesis improve the understanding of the mechanisms that govern there inforcement effect provided by the addition of cellulose nanofillers in a hydrogel matrix; they could also help to design innovative green hydrogels having good mechanical properties.

<div><div><div><p>Interfacial rheology describes the functional relationship between the deformation of an interface, the stresses exerted in and on it, and the resulting flows in the adjacent fluid phases. These interfacial properties are purported to influence emulsion stability. Protein emulsifiers tend to adsorb to the interface of immiscible phases, reduce interfacial tension as well as generate repulsive interactions. A magnetic interfacial shear rheometer was used to characterize the surface pressure-area isotherms as well as interfacial rheological properties of two proteins- sodium caseinate and b-lactoglobulin. Then, sodium caseinate was used as a carrier for b-carotene encapsulation.</p><p>b-carotene is a carotenoid that exhibits pro-vitamin A activity, antioxidant capacity and is widely used as a food colorant. It is however, highly hydrophobic and sensitive to heat, oxygen and light exposure. Thus b-carotene as food ingredient is mainly available as purified crystals or as oil-in-water emulsions. In this study, b-carotene stability, and solubility in water for application as a natural colorant was improved by preparation of a sodium caseinate/ b-carotene powder using high pressure homogenization, solvent evaporation and spray drying. The powders thus prepared showed good solubility in water and yielded an orange coloration from b-carotene. The effect of medium chain triglyceride concentration (1%, 10%) and incorporation of a natural antioxidant (Duralox, Kalsec) on powder stability was studied as a function of storage time and temperature.b-carotene stability was reduced at higher storage temperature (4oC> 21oC> 50oC) over 60 days and followed first order degradation kinetics at all temperatures. Incorporation of natural antioxidant improved b-carotene stability and resulted in a second first order degradation period at 50oC. As b-carotene content decreased, Hunter Lab color values denoting lightness increased, while those for redness and yellowness of the powder decreased. This sodium caseinate based b-carotene powder could be used as a food ingredient to deliver natural b-carotene to primarily aqueous food formulations.</p><div><div><div><p>In the last part of this work, an engagement workshop was developed as a means to educate young consumers about the function of emulsifiers in foods. Food additives are important for food product development, however to consumers, a discord between their objective purpose and subjective quality has led to confusion. Food emulsifiers, in particular, are associated with lower healthiness perception due to their unfamiliar names. In collaboration with the 4H Academy at Purdue, a workshop high school student was conducted to develop an increased understanding of emulsions and emulsifiers. A survey was conducted with the participants who self-evaluated their gain in knowledge and tendency to perform certain behaviors with regards to food ingredient labels. The participants reported a gain in knowledge in response to four key questions on emulsions and emulsifiers, as well as an increased likelihood to read ingredients on a food label and look up information on unfamiliar ingredients.</p></div></div></div></div></div></div>

Fondue de chocolate é um produto derivado de chocolate consumido fundido com frutas e bolos sob aquecimento. É crescente o interesse dos consumidores em alimentos que tragam algum tipo de benefício à saúde. Óleo de castanha do Brasil, aveia e ácido graxo ômega-3 são alguns dos ingredientes funcionais mais comentados da atualidade. Assim, o objetivo desse trabalho foi desenvolver formulações enriquecidas desses ingredientes e avaliar a reologia, através de análises de textura, comparando-as com os produtos de mercado. Avaliou-se a textura, com probe back extrusion, avaliando-se os resultados através da equação Herschel-Bulkley, e por análise de consistência. O resultado da composição centesimal indicou que três (das seis) formulações apresentaram alto conteúdo de proteína bruta, comparado às amostras comerciais. As amostras enriquecidas com aveia apresentaram alto teor de fibra total e mostraram-se bons substitutos para a gordura do leite e sacarose. Na avaliação de textura por back extrusion, dentre as amostras comerciais, a amostra contendo leite condensado e chocolate amargo apresentou os maiores valores para os parâmetros de firmeza, coeficiente de consistência, coesividade e índice de viscosidade. Os fondues foram classificados como fluidos pseudoplásticos (n < 0) e os chocolates do tipo cobertura, fluidos dilatantes (n > 1). O ponto de fluidez foi semelhante para todas as amostras. O resultado do ensaio back extrusion para as formulações apontou que as amostras que contêm extrato de aveia apresentaram valores bem mais baixos frente às outras formulações. A avaliação da consistência revelou que a 10 ºC a amostra D apresenta bom potencial para aplicação como spread; enquanto à 20 ºC, as amostras C e D são as que apresentam melhor potencial. Assim, sugeriu-se a qualidade superior dos produtos desenvolvidos frente aos comerciais, que contêm estabilizantes e espessantes artificiais, bem como prolongada vida de prateleira e potencial emprego como spread. / Chocolate fondue is a chocolate product which is consumed melted with fruits and cakes. There is a growing interest by consumers in foods that brings some healthy benefits. Brazilian nut oil, oats and omega-3 are some of the most famous functional ingredients nowadays. Thus, the aim of this work was developing enriched formulations containing these ingredients and evaluating rheology through textural analysis, comparing to brand products. Texture was evaluated by probe back extrusion, results being evaluated through Herschel-Bulkley equation, and by consistency test. Chemical analysis pointed that three (of six) formulations showed high content of protein, comparing to brand products. Samples enriched with oats showed a high fiber content. Oat extract was suggested as a good milk fat + sucrose replacer. Among brand products, sample comprising condensed milk and dark chocolate showed the higher values for firmness, consistency coefficient, cohesiveness and viscosity index on back extrusion analysis. Fondues were classified as thinning fluid (n < 0) and chocolate bars are thickening fluids (n > 1). Break point was alike for all samples. Back extrusion for developed samples pointed that samples containing oat extract showed an overall lower results comparing to the others. Consistency test showed that when conditioned at 10 ºC, sample D shows a good potential for application as chocolate spread; while at 20 ºC, samples C and D perform better. Thus, it was suggested a major quality of enriched samples when compared to brand products, which contains stabilizers, artificial thickener, as a longer shelf life and potential use as spread.

Neste trabalho, foram obtidos compósitos poliméricos de Óxido de Grafite (GO) incorporado em Poli(metaclilato de metila) (PMMA). A obtenção do Óxido de Grafite foi realizada por dois diferentes métodos: método de Hummers modificado e método de Staudenmaier. Em seguida, foi ainda adicionada uma etapa secundária de tratamento térmico à 1000 ºC nos GOs obtidos a fim de expandir as lamelas de grafite e remover os grupos funcionais aderidos durante o ataque ácido do grafite. As cargas obtidas foram caracterizadas com o auxílio das técnicas de Difração de Raios-X (DRX), Espectroscopia Raman, Espectroscopia Vibracional no Infravermelho (FTIR), Análise Termogravimétrica (TGA), Microscopia Eletrônica de Varredura (MEV), Microscopia Eletrônica de Transmissão (MET) e Microscopia de Força Atômica (AFM), constatando a formação do Óxido de Grafite por ambos os métodos, e ainda a expansão das folhas após o tratamento térmico. O estudo comparativo dos compósitos de matriz polimérica com 1, 3 e 5 % de concentração de GO antes do tratamento térmico e 1 e 3 % após o tratamento térmico foi realizado com o objetivo de entender a contribuição nas propriedades reológicas do polímero com a adição da carga de GO. Os compósitos poliméricos foram obtidos através de um misturador interno, variando-se o método de adição da carga na matriz polimérica via solvente ou via moinho - para estudar a melhor dispersão da carga na matriz. Os compósitos PMMA/GO foram caracterizados por Cromatografia de Permeação em Gel (GPC), Análise Termogravimétrica (TGA), Calorimetria Exploratória Diferencial (DSC), Microscopia Eletrônica de Varredura (MEV), Microscopia Eletrônica de Transmissão (MET); e por ensaios reológicos de Varredura de Deformação, Varredura de Tempo, e Cisalhamento Oscilatório de Pequenas Amplitudes (COPA). Os resultados reológicos apresentaram um aumento da viscosidade complexa tanto na Varredura de Tempo, quanto no COPA. De acordo com a metodologia adotada, ainda não foi possível verificar o aumento crescente da viscosidade complexa a baixas frequências. Este aumento de viscosidade indicaria que o Óxido de Grafite formou uma rede tridimensional, cuja percolação impede que as cadeias poliméricas relaxem completamente. / In this study, composites of graphite oxide (GO) in poly(methyl methacrylate) (PMMA) were obtained. Obtaining of graphite oxide was performed by two potential methods by literature: modified Hummers method and Staudenmaier method; Then, a secondary GOs obtained heat treatment step - at 1000° C - was added in order to expand the graphite flakes and remove functional groups attached during the acid attack of graphite. The reinforcement obtained by both methods were characterized by X-Ray Diffraction (XRD), Raman Spectroscopy, Infra Red Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM), confirming the formation of Graphite Oxide by both methods, and also the expansion of the leaves after the heat treatment. Then, a comparative study of the polymer matrix composites with 1, 3 and 5 % concentration of oxides graphite before the heat treatment and 1 and 3 % after the heat treatment was performed in order to understand the contribution to the rheological properties of the polymer with the addition of GO reinforcement. The composites were obtained by internal mixer, varying the load adding method in the polymeric matrix - via mill and via solvent - to study the best dispersion of GO in the matrix. The samples were characterized by Gel Permeation Ghromatography (GPC), Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM); and rheological measurements of Deformation Scan, Time Sweep, and Small Amplitude Oscillatory Shear (SAOS). The rheological results showed an increase in complex viscosity at both Time Sweep, as in SAOS. However, it was not possible to verify the increase of complex viscosity at low frequencies, that would indicate that graphite oxide form a three-dimensional arrangement, which prevents the percolation of the polymer chains, letting them to relax completely.

Neste trabalho, foi estudado o comportamento reológico nos regimes de viscoelasticidade linear (VEL) e não linear (VENL) da mistura polimérica de polimetacrilato de metila/poliestireno (PMMA/PS), compatibilizada ou não com os copolímeros: estatístico P(S-co-MMA) (VEL e VENL) e bloco P(S-b-MMA) (VEL). No estudo do comportamento de VEL, ensaios de cisalhamento oscilatório de pequenas amplitudes (COPA) foram realizados utilizando-se um reômetro de tensão controlada. O comportamento de VEL das misturas poliméricas foi comparado com os modelos teóricos de Bousmina[1] e generalizado de Palierne[2]. Os tempos de relaxação das misturas poliméricas foram obtidos analisando o comportamento reológico no regime de VEL utilizando o software desenvolvido por Honerkamp e Weese[3]. Os tempos obtidos foram comparados com o modelo de Jacobs et al.[4]. O estudo do comportamento de VENL foi conduzido através de ensaios de relaxação de tensão utilizando-se um reômetro de deformação controlada. Os resultados do comportamento reológico no regime de VEL indicaram a presença de quatro tempos de relaxação, para as blendas compatibilizadas com P(S-co- MMA) (composições menores de 10% de fase dispersa e concentrações maiores de 4% de copolímero): dois picos relacionados às fases puras; F, relacionado com a relaxação das gotas da fase dispersa e o relacionado com a relaxação do compatibilizante na interface entre as fases matriz e dispersa. Os valores experimentais de F e foram utilizados para os cálculos de tensão interfacial () e do módulo complexo de interface () das blendas poliméricas compatibilizadas. Os resultados indicaram uma diminuição de com o aumento da concentração de copolímero. Os resultados do comportamento reológico no regime de VEL, para as blendas compatibilizadas com P(S-b-MMA), também apresentaram a presença de quatro tempos de relaxação. Observou-se que o aumento da adição de P(S-b-MMA) proporcionou uma redução no .. Os resultados de VENL de relaxação de tensão mostraram a presença de três fenômenos de relaxação, relacionados com: 1) as fases puras, 2) a relaxação das gotas da fase dispersa e um terceiro mais rápido. A adição de P(S-co-MMA) resultou numa diminuição do processo de relaxação das gotas da fase dispersa. / In this work, the dynamic behavior of polymethylmetacrylate/polystyrene (PMMA/PS) blends to which P(S-co-MMA) was added was studied. Several blend composition and copolymer concentrations were studied. The rheological behavior of blends was compared to Bousminas[1] and Paliernes generalized[2] models. The relaxation spectra of the blends were also inferred, and the results were analyzed in light of the analysis of Jacobs et al.[4]. The relaxation spectra of the blends with smaller dispersed phase (below 10 wt%) and larger copolymer concentrations (above 0.4 wt%) showed the presence of four relaxation times, two corresponding to the blend phases, F, corresponding to the relaxation of the shape of the dispersed phase of the blend, and , that can be attributed to the relaxation of Marangoni stresses tangential to the interface between the dispersed phase and matrix. The experimental values of F and were used to infer the interfacial tension () and the interfacial complex shear modulus () for the different blends, decreased with increasing copolymer concentration. decreased with increasing blend dispersed phase concentration and decreasing copolymer concentration. The predictions of Paliernes generalized model were found to corroborate the experimental data once the values of and found analyzing the relaxation spectra were used in the calculations. Bousminas model was found to corroborate the data only for larger dispersed phase concentration. The stress relaxation behavior of PMMA/PS blends with or without random copolymer addition, submitted to step shear strain experiments in the linear and nonlinear regime was studied. The effect of blend composition, viscosity ratio and random copolymer was evaluated. All blends presented three relaxation stages, a first relaxation which was attributed to the relaxation of the pure phases, a second one which was characterized by the presence of plateau and a third fast one.

O chocolate é um dos principais produtos oriundos do cacau, sendo comercializado em sua maior parte na forma de bombons maciços ou recheados. Bombons com recheio de fruta podem conter a fruta ou pedaços da fruta distribuídos no recheio. Eles podem ser produzidos em base fondant, gordura, geléia ou com o próprio chocolate (trufas), entre outros, adicionando-se aromas e corantes ou não. O objetivo deste trabalho foi produzir preparados de frutas e recheios para bombons em base fondant, gordura hidrogenada e chocolate branco (trufa), utilizando estes preparados como substituto parcial ou total de aromas e corantes na formulação final dos recheios. Os preparados foram elaborados utilizando-se açúcar invertido, xarope de glicose e água como matriz, adicionados de morango e maracujá liofilizados e casca de laranja, para conferir o aroma da fruta in natura, reduzindo de maneira significativa o uso de aromas e corantes artificiais. Avaliou-se pH nos preparados de frutas e nos recheios; teor de sólidos solúveis nos preparados de fruta; atividade de água nos recheios base fondant, gordura hidrogenada e \"trufa\". Os valores de pH apresentaram-se menores que 4,0 para os preparados e menores que 6,0 para os recheios. A atividade de água não apresentou variação durante o período estudado. O teor de sólidos solúveis encontrado foi de 68 ºBrix, 69 ºBrix e 73 ºBrix, respectivamente para os preparados de morango, maracujá e laranja. A composição centesimal foi feita para caracterizar os bombons quanto ao teor de gordura, proteínas, umidade, cinzas e valor energético. Os bombons recheados com açúcar fondant apresentam os menores teores de lipídeos, foram encontrados valores de proteínas maiores para as trufas. O valor energético destes produtos variou de 500 a 600 kcal por 100 g de produto. O estudo da textura dos bombons recheados foi feito a 25 ºC e caracterizou os bombons quanto a sua dureza, sendo que as trufas se mostraram os bombons de menor dureza. Os dados de atividade de água e dureza foram analisados através da ANOVA e Teste de Tukey. Na análise sensorial dos bombons recheados foi aplicado teste de aceitação global aos consumidores. A análise dos dados foi feita através da ANOVA, Teste de Tukey, Mapa de Preferência e Análise de Cluster. O estudo da reologia foi feito para os preparados de fruta, para os recheios base fondant e gordura hidrogenada a 25 ºC. Para as trufas foi feito o estudo reológico através do teste rotacional à 0 ºC e 70 ºC. Os ensaios oscilatórios utilizaram varredura de freqüência. A análise sensorial apresentou resultados significativos quanto à aceitação dos produtos, sendo que as trufas foram as que obtiveram as maiores notas, seguidas dos bombons com recheio base gordura hidrogenada. Os ensaios oscilatórios demonstraram que os preparados de fruta e os recheios nos sabores morango, maracujá e laranja são estáveis quando sujeitos a uma baixa freqüência. No teste rotacional, a curva de fluxo determinou o comportamento dos preparados. As curvas de fluxo obtidas através do teste rotacional, foram avaliadas quanto ao melhor modelo reológico aplicado. A utilização de um preparado de fruta, dando aos recheios características da fruta in natura, conferindo sabor e aroma sem a necessidade de nova adição de aroma e corante, em combinação com açúcar fondant, com gordura hidrogenada e nas trufas, mostrou-se uma maneira interessante de produzir um recheio de baixo custo, com longa vida de prateleira se comparado aos produtos artesanais presentes no mercado, conferindo aos produtos atributos bem aceitos pelo consumidor. / Chocolate is one of the most important products made from cacao, being major commercialized as chocolate filled or plain. Chocolate filled with fruit can contain the fruit or parts of it mixed in the filling. The fillings could be produced using fondant, fat, jelly or the white chocolate, as the truffles, with the addition of flavor and colorants or not. The objective of this work was to produce fruit mixes and filling for chocolate, using fondant, hydrogenated fat and White chocolate (truffles), using those mixes as replacers of flavor and colorants in the final formulations. The mixes were elaborated using inverted sugar, glucose syrup and water, mainly, freeze dried strawberry and passion fruit, and orange, was added to gave flavor of in nature fruit, reducing the use of artificial flavor and colorants. The pH was evaluated for the mixes and fillings; soluble solids content in the mixes; water activity in the fillings. The pH values showed to be lower than 4,0 to the mixes , and lower than 6,0 for the fillings. Water activity didn\' t show variability during the evaluated period. The soluble solids content was 68 ºBrix, 69 ºBrix and 73 ºBrix, respectively for strawberry, passion fruit and orange mix. The centesimal composition was done to characterize the chocolates filled showing the content of fat, protein, humidity, ashes and energetic value. The chocolates filled with fondant sugar presented the lower values of fat, protein was greater for the truffles. The energetic value varied between 500 to 600 kcal per 100 g of product. The texture study of chocolates filled was done at 25 ºC and characterized the hardness of them. The truffles presented the lower values for hardness. The data of water activity and hardness were analyzed trough ANOVA and Tukey test. Sensory evaluation of chocolates filled was done applying global evaluation test to consumers. The data analysis was done trough ANOVA, Tukey test, Internal Preference Mapping and Cluster Analysis. The rheological study was done at 25 ºC for the mixes, fondant and hydrogenated fat fillings, for the truffles the rotational test was done at 0 ºC and 70 ºC. The oscillatory test was done using a frequency sweep. The sensory evaluation presented significant results, regarding product acceptance, the truffles gotten the greater grades, followed by the hydrogenated fat chocolate filled. The oscillatory study showed stability for all the mixes and fillings, when those are subjected to lower frequencies. In the rotational study, the flow curve determined the mixes behavior. The flow curves obtained trough rotational test, were evaluated for the best rheological model which fitted them. The use of a fruit mix, giving characteristics of in nature fruit, with flavor and color without the need of adding artificial ones, combined with fondant, hydrogenated fat and for the truffles, showed to be an efficient way to produce fillings with low cost, and a greater shelf life, if compared with artisanal products of the market, being well accepted by consumers.

Fondue de chocolate é um produto derivado de chocolate consumido fundido com frutas e bolos sob aquecimento. É crescente o interesse dos consumidores em alimentos que tragam algum tipo de benefício à saúde. Óleo de castanha do Brasil, aveia e ácido graxo ômega-3 são alguns dos ingredientes funcionais mais comentados da atualidade. Assim, o objetivo desse trabalho foi desenvolver formulações enriquecidas desses ingredientes e avaliar a reologia, através de análises de textura, comparando-as com os produtos de mercado. Avaliou-se a textura, com probe back extrusion, avaliando-se os resultados através da equação Herschel-Bulkley, e por análise de consistência. O resultado da composição centesimal indicou que três (das seis) formulações apresentaram alto conteúdo de proteína bruta, comparado às amostras comerciais. As amostras enriquecidas com aveia apresentaram alto teor de fibra total e mostraram-se bons substitutos para a gordura do leite e sacarose. Na avaliação de textura por back extrusion, dentre as amostras comerciais, a amostra contendo leite condensado e chocolate amargo apresentou os maiores valores para os parâmetros de firmeza, coeficiente de consistência, coesividade e índice de viscosidade. Os fondues foram classificados como fluidos pseudoplásticos (n < 0) e os chocolates do tipo cobertura, fluidos dilatantes (n > 1). O ponto de fluidez foi semelhante para todas as amostras. O resultado do ensaio back extrusion para as formulações apontou que as amostras que contêm extrato de aveia apresentaram valores bem mais baixos frente às outras formulações. A avaliação da consistência revelou que a 10 ºC a amostra D apresenta bom potencial para aplicação como spread; enquanto à 20 ºC, as amostras C e D são as que apresentam melhor potencial. Assim, sugeriu-se a qualidade superior dos produtos desenvolvidos frente aos comerciais, que contêm estabilizantes e espessantes artificiais, bem como prolongada vida de prateleira e potencial emprego como spread. / Chocolate fondue is a chocolate product which is consumed melted with fruits and cakes. There is a growing interest by consumers in foods that brings some healthy benefits. Brazilian nut oil, oats and omega-3 are some of the most famous functional ingredients nowadays. Thus, the aim of this work was developing enriched formulations containing these ingredients and evaluating rheology through textural analysis, comparing to brand products. Texture was evaluated by probe back extrusion, results being evaluated through Herschel-Bulkley equation, and by consistency test. Chemical analysis pointed that three (of six) formulations showed high content of protein, comparing to brand products. Samples enriched with oats showed a high fiber content. Oat extract was suggested as a good milk fat + sucrose replacer. Among brand products, sample comprising condensed milk and dark chocolate showed the higher values for firmness, consistency coefficient, cohesiveness and viscosity index on back extrusion analysis. Fondues were classified as thinning fluid (n < 0) and chocolate bars are thickening fluids (n > 1). Break point was alike for all samples. Back extrusion for developed samples pointed that samples containing oat extract showed an overall lower results comparing to the others. Consistency test showed that when conditioned at 10 ºC, sample D shows a good potential for application as chocolate spread; while at 20 ºC, samples C and D perform better. Thus, it was suggested a major quality of enriched samples when compared to brand products, which contains stabilizers, artificial thickener, as a longer shelf life and potential use as spread.

O dissilicato de ítrio (Y2Si2O7) por apresentar propriedades luminescentes consideráveis, é um potencial substituto dos óxidos de terras raras na tecnologia de queimadores de gás para iluminação. Em processos de conformação a partir de suspensões, o controle da estabilidade das partículas em meio líquido consiste em uma importante etapa para a produção de componentes com microestrutura homogênea e estabilidade estrutural. Neste sentido, este trabalho apresenta estudos sobre o comportamento de superfície, de estabilidade e reológico de suspensões aquosas de Y2Si2O7 e &beta;-Y1,95Dy0,05Si2O7 com o objetivo de preparar suspensões compatíveis para o processo de conformação por réplica, usando-se fibras vegetais como matriz para a confecção de componentes reticulados para queimadores de gás. Neste estudo foram avaliados parâmetros determinantes na estabilidade e comportamento de fluxo das suspensões, como também a luminescência estimulada pela temperatura desses materiais na forma de pó e a eficiência radiante do protótipo de queimador de gás. Os resultados obtidos para o &beta;-Y1,95Dy0,05Si2O7 comparados com a ítria (Y2O3) e concentrado de terras raras contento ítria (YTR) mostram-se promissores. Desenvolveu-se por processamento coloidal do &beta;-Y1,95Dy0,05Si2O7 e utilizando-se o processo de conformação por réplica a partir da esponja vegetal Lufa Cylindrica, um protótipo de lâmpada de queimador de gás com boa resistência mecânica ao manejo, emissividade espectral no visível (&lambda;=580nm) e eficiência radiante de 13%, com grande potencial para iluminação de ambientes internos de acordo com as recomendações da Comissão Internacional de Iluminação (CIE). / Yttrium disilicate (Y2Si2O7) shows luminescent proprieties and is a potential material to replace rare earth oxides in porous burner technology for lighting. In conformation process from suspensions the control of stability of particles in aqueous medium is an important step to produce ceramic components that show homogeneous microstructure and structural stability. This work presents studies about surface behavior, stability and rheological behavior of aqueous suspensions of Y2Si2O7 and &beta;-Y1,95Dy0,05Si2O7 and aims to prepare suitable suspensions for replica method, and vegetable fibers were used as template to produce porous components for gas burners. In this study key parameters on stability and rheological behavior of suspensions were evaluated, as well as the stimulated luminescence of powders by increasing temperature and radiant efficiency of gas burner prototype. The results as compared with yttria and rare earth concentrate containing yttria are very promising. By colloidal processing of &beta;-Y1,95Dy0,05Si2O7 and using replica method from Luffa Cylindrica vegetable sponge a prototype of gas burner lamp showing good handle strength, visible spectral emissivity (&lambda;=580nm), radiant efficiency of 13%, and great potential to be used for lighting internal spaces according to the International Commission on Illumination (CIE).