Wax anti-settling additives (WASA) are used to mitigate against the problems caused by the settling of n-alkane wax crystals, which crystallise from petroleum diesel. This can result in the blocking of fuel filters and hence vehicle failure. However, the mode of action for such additives is not currently known and two mechanisms have been proposed: they reduce the wax crystal size to such an extent that they settle very slowly; or they induce gelation in the wax suspension. This project aims to elucidate the mechanism of WASA within the diesel system. A room temperature crystallising model diesel (10 wt% n-alkanes in dodecane) has been developed. This model system has given a good response to the additives, with the wax crystals reduced in size, and is hence suitable for mechanistic studies. Differential scanning calorimetry and infra-red spectroscopy both suggest that the WASA is incorporated in or onto the wax crystal. DSC shows that small amounts of WASA suppress the wax crystallisation temperature and change the shape of the heat flow curve. FT-IR shows the WASA amide stretch present within filtered and dried wax crystals. Intriguingly, electrophoresis experiments show that the WASA imparts a positive charge to the wax crystals, suggesting an electrostatic role in the WASA action. Rheological experiments show the presence of a weak gel in the WASA doped model diesel. However, the gel strength is not altered by the presence of an organic salt and thus cannot be purely electrostatic in origin. Small angle neutron scattering has been conducted to help locate the WASA in the system. It has shown that in solution WASA shows a collapsed polymer coil structure with a single molecule occupying a 28 Å diameter sphere and multiple WASA molecules forming a 2400 Å diameter sphere. In the presence of the wax the WASA scatter does not significantly change suggesting that the WASA is on the surface of the wax crystal. By combining these results, a mechanism of WASA action is proposed as WASA cations interactions bridging between the wax crystals causing a weak bridging flocculation gel with electrostatic and steric effects contributing to stabilisation. The WASA charges are partially dissociated thus giving the electrophoretic effect and the long chains on the cations can contribute to stability via steric stabilisation.

Considerando que a tendência atual em termos de formulações cosméticas é a veiculação de diferentes substâncias ativas num mesmo produto, visando o sinergismo de efeito, o objetivo desse trabalho foi a avaliação da estabilidade, da segurança e da eficácia clínica de formulações cosméticas, contendo extrato de Myrtus communis e um complexo vitamínico hidratante à base de D-pantenol e derivados de vitaminas C e E, bem como a avaliação da atividade antioxidante in vitro do extrato objeto de estudo. Para tal, na primeira etapa do estudo foram elaboradas 4 formulações de géis creme, F1 (veículo), F2 (veículo acrescido de extrato hidrolisado de Myrtus communis), F3 (veículo acrescido de D-pantenol) e F4 (veículo acrescido de extrato hidrolisado de Myrtus communis e D-pantenol), as quais foram submetidas a testes preliminares de estabilidade e à avaliação do comportamento reológico, da compatibilidade cutânea e da eficácia clínica, por métodos subjetivos (avaliação sensorial) e quantitativos por técnicas de biofísica e análise de imagem da pele. No estudo clínico as formulações foram aplicadas nos antebraços e na face das voluntárias, sendo realizadas medidas do conteúdo aquoso do estrato córneo, da perda de água transepidérmica (TEWL), do micro-relevo cutâneo e da anisotropia da pele, antes (basal) e após 3 horas (efeito imediato) 15 e 30 dias de aplicação das formulações (efeito em longo prazo). Os dados foram analisados estatisticamente pelo teste paramétrico análise de variância. A seguir, a formulação que apresentou melhores resultados na avaliação sensorial e estudo de eficácia, foi acrescida de Tetraisopalmitato de ascorbila (F5) ou Vitamina E - D-Alfa Tocoferol Acetato (F6) ou associação destes (F7). As referidas formulações foram submetidas aos testes de estabilidade e eficácia clínica. De acordo com os resultados obtidos, as formulações foram consideradas estáveis e seguras, sendo que a formulação de nº 4 foi a que apresentou o melhor sensorial, de acordo com as voluntárias sendo, portanto, selecionada para ser acrescida dos derivados de vitaminas objeto de estudo. Na avaliação dos efeitos imediatos, as formulações estudadas aumentaram significativamente o conteúdo aquoso do estrato córneo nas regiões dos antebraços e da face, quando comparadas com os valores basais. Em relação à TEWL, foi possível observar que as formulações nos 2, 3 e 4 provocaram melhora na função barreira da pele dos antebraços, enquanto que na face apenas as formulações nos 3 e 4 provocaram melhora neste parâmetro. Na avaliação em longo prazo, todas as formulações estudadas, proporcionaram um aumento significativo no conteúdo aquoso do estrato córneo após 15 e 30 dias de aplicação, enquanto que somente as formulações que continham as substâncias ativas objeto de estudo, ou seja, as nos 2, 3 e 4, melhoraram a função barreira da pele. No estudo de eficácia clínica onde as formulações F4 (veículo acrescido de extrato hidrolisado de Myrtus communis e D-pantenol) e F7 (veículo acrescido de extrato hidrolisado de Myrtus communis, D-pantenol e os derivados de vitamina C e E) foram avaliadas comparativamente, foi possível observar um aumento significativo nos valores do conteúdo aquoso do estrato córneo, em relação aos valores basais e a região controle (região que não recebeu aplicação de nenhuma formulação), após 15 dias de aplicação. Em relação à TEWL, apenas a formulação F4 (veículo acrescido de extrato hidrolisado de Myrtus communis e D-pantenol) provocou melhora na função barreira. De acordo com os resultados obtidos, as formulações desenvolvidas neste estudo apresentaram efeito hidratante pronunciado e, as que continham o extrato Myrtus communis e D-pantenol, protegeram a função barreira da pele. Além disso, o extrato de Myrtus communis demonstrou atividade antioxidante pronunciada, efeito considerado muito importante para o emprego deste extrato em cosméticos com finalidades antienvelhecimentos. Finalizando, este estudo mostrou a importância do desenvolvimento de formulações cosméticas estáveis, de sensorial adequado e com eficácia comprovada, contendo o extrato hidrolisado de Myrtus communis e o complexo vitamínico objeto de estudo, para a hidratação, proteção e melhora das condições gerais da pele. / Considering that the current trend in terms of cosmetic formulations is to vehicle different active ingredients in one single product, aiming the effect of synergism, the objective of this study was to evaluate the stability, safety and clinical efficacy of cosmetic formulations containing extract of Myrtus communis and a moisturizing vitamin complex based on D-panthenol and derivatives of vitamins C and E, as well as to evaluate the extract in vitro antioxidant activity. Thus, for the first study stage, four gel cream formulations were developed, F1 (vehicle), F2 (vehicle supplemented with Myrtus communis hydrolyzate extract), F3 (vehicle supplemented with D-panthenol) and F4 (vehicle supplemented with Myrtus communis hydrolyzate extract and D-panthenol), which were submitted to preliminary stability tests, to rheological behavior assessment, to skin compatibility test and to clinical efficacy assessment, by subjective methods (sensorial evaluation) and quantitative methods, by biophysics techniques and skin image analysis. In the clinical study, the formulations were applied on the volunteers´ face and forearms, with measurements of the stratum corneum water content, transepidermal water loss (TEWL), skin micro-relief and skin anisotropy before (baseline) and after 3 hours (immediate effects), 15 and 30 days of the formulations application (long-term effects). Data were statistically analyzed by parametric test analysis of variance. Afterwards, the formulation that showed best performance in sensory evaluation and clinical efficacy study was supplemented with ascorbyl tetraisopalmitate (F5) or Vitamin E - D-Alpha-Tocopherol Acetate (F6) or a combination of both derivatives of vitamins, C and E (F7). According to the obtained results, all the formulations were considered safe and stable, and formulation 4 was the one with the best sensorial performance, according to the volunteers perception, and, therefore, it was selected to be supplemented with the vitamin derivatives under study. The immediate effects evaluation demonstrated that all the other formulations significantly increased stratum corneum water content in the face and forearms skin, when compared to baseline values. In relation to TEWL, it was observed that the formulations 2, 3 and 4 provoked an improvement in forearm skin barrier function, while only formulations 3 and 4 provoked an improvement on this parameter on the face. In the long-term assessment, all formulations studied promoted a significant increase in stratum corneum water content after 15 and 30 days of the formulations application, while only formulations containing the studied active ingredients, i.e., formulations 2, 3, and 4 improved skin barrier function. In the clinical efficacy study when the formulations F4 (vehicle supplemented with Myrtus communis hydrolyzate extract and D-panthenol) and F7 (vehicle supplemented with Myrtus communis hydrolyzate extract, D-panthenol and derivatives of vitamin C and E) were comparatively assessed, it was possible to observe a significantly increase in stratum corneum water content, when compared to baseline values and to control areas (region which received no formulation), after 15 days of formulations application. Regarding TEWL, only formulation F4 (vehicle supplemented with Myrtus communis hydrolyzate extract and D-panthenol) provoked an improvement in skin barrier function. According to the obtained results, the formulations developed in this study demonstrated a pronounced moisturizing effect, and those containing Myrtus communis extract and D-panthenol, protected the skin barrier function. Moreover, the extract of Myrtus communis demonstrated a pronounced antioxidant activity, an effect considered very important for this extract use in cosmetics aiming anti-aging purposes. Finally, this study demonstrated the relevance of developing stable cosmetic formulations, with adequate sensory characteristics and proven effectiveness, supplemented with Myrtus communis hydrolyzed extract and with the vitamin complex under study, for skin hydration, protection and improvement of general skin conditions

Esta dissertação apresenta os resultados obtidos na caracterização reológica, utilizando ensaios rotacionais e oscilatórios, de sistemas de cristais líquidos liotrópicos nemáticos e colestéricos à base de cloreto de decilamônio (CDA). Os sistemas colestéricos foram obtidos pela adição às matrizes nemáticas de indutores quirais hidrofóbico (Colesterol) ou hidrofilico (D-(+)Manose) que conferem à estrutura liquidocristalina um arranjo helicoidal. Procuramos analisar os efeitos da concentração do indutor no comportamento reológico, bem como da sua natureza e da quantidade de solvente presentes nestes sistemas mesomórficos. Os ensaios rotacionais foram realizados utilizando-se taxas de cisalhamento constante e variadas. Os resultados obtidos mostraram que ocorre uma mudança no comportamento reológico dependente da natureza do indutor quiral. Fases com indutor hidrofóbico têm sua viscosidade diminuída com a adição de colesterol, enquanto as fases com D-(+)-Manose têm sua viscosidade aumentada. Também foram observadas mudanças no comportamento reológico segundo a quantidade de solvente presente na mesofase. Para sistemas com colesterol e com maior quantidade de água em sua composição, a viscosidade aumenta ao longo do tempo até atingir um valor máximo, seguido de uma diminuição. Este comportamento deve indicar que nestes sistemas, as fases devem primeiro sofrer uma deformação atingindo um máximo de tensão, a partir da qual começa a ocorrer uma melhor acomodação da sua estrutura, provocando a diminuição da viscosidade. Nos sistemas com indutor hidrofóbico e com menor. quantidade de solvente, a viscosidade diminui até atingir um valor mínimo. Pode-se observar que quanto maior for a concentração de indutor, maior é o tempo necessário para se atingir este mínimo. A partir deste ponto há um aumento da viscosidade até um valor constante. Isto sugere a ocorrência de uma quebra da estrutura do sistema, seguida por sua reorientação por fluxo. Em sistemas em que o indutor é D-(+)-Manose, o comportamento reológico observado é semelhante tanto em fases com maior ou menor quantidade de solvente, ou seja, aumento da viscosidade até um valor máximo, seguido pela sua diminuição. A diferença observada é que em sistemas com maior quantidade de solvente, o máximo é atingido mais cedo. O aumento da viscosidade deve caracterizar uma deformação da estn1tura que após atingir uma tensão máxima, começa a se orientar em uma direção preferencial, causando a diminuição da viscosidade sem quebra do edifício colestérico. A determinação da entalpia livre de ativação de fluxo (ΔH≠) mostra que para os sistemas em que o colesterol foi usado como indutor, a energia diminui com o aumento da concentração de indutor, quando D-(+)-Manose é utilizado, a energia aumenta. No caso do indutor hidrofóbico, a força quiral auxiliaria na orientação por fluxo das micelas, pois ao se movimentar uma micela, as outras seriam arrastadas pelas forças elásticas, diminuindo a entalpia de ativação de fluxo. Quando o indutor utilizado é hidrofílico, a entalpia de ativação aumenta, possivelmente devido à natureza do indutor, que possui uma interação maior com o solvente, agindo como uma barreira para a movimentação e orientação das micelas por fluxo. Os ensaios oscilatórios, por sua vez, mostram que a capacidade de armazenamento e devolução de energia, determinada pelo valor do módulo de armazenamento (G\') é maior que capacidade de dissipação desta por calor ou difusão das partículas, obtida pelo módulo de perda (G\"). Ambos os módulos apresentam uma dependência em relação quantidade de indutor, natureza de indutor e quantidade de água disponível, porém não foi possível se determinar nenhuma relação direta entre esses fatores. Esse sistema liotrópico pode ser descrito pelo modelo de Burger, contanto que seja levado em consideração que a componente elástica do elemento de Maxwell possua uma dependência temporal. Esse efeito provavelmente é devido à própria inércia do sistema. / This dissertation shows the results obtained on the rheological characterization, using rotation and oscillatory essays, for nematics and cholesterics lyotropic liquid crystals based on decylammonium chloride (CDA). The cholesteric systems were obtained adding chiral inductors, hydrophobic (Cholesterol) or hydrophilic (D-(+)-Mannose) to nematic matrixes, inducing a helical arrangement on the liquid crystalline stn1cture. The effect of the inductor concentration besides of its nature and the amount of solvent in these mesomorphic systems were correlated to the rheological properties obtained. The rotation essays were done using constant and varied shear rates. The obtained results showed a change in the rheological behavior dependent of the chiral inductor nature. Phases with hydrophobic inductor presented viscosity decreased with the increase of cholesterol concentration, while the increase of D-(+)-Mannose concentration leads to the viscosity increase. Changes in the rheological behavior were also observed according to the amount of solvent present on the phase. For systems with cholesterol and larger amount of water, the viscosity increases along the time until reaching a maximum value, followed by a decrease. This behavior should indicate that in these systems, the phases should suffer some kind of deformation until reaching a maximum of tension. After that, an accommodation process of the structure causes the viscosity decrease. For the systems with hydrophobic inductor and with smaller amount of solvent, the viscosity decreases until reach a minimum value, that is reached later as larger it is the inductor concentration. After that, there is an increase of the viscosity until a constant value be obtained. It suggests the occurrence of a breakdown of the stn1cture, proceeded by its reorientation by flow. For the systems with D-(+)-Mannose, the rheological behavior observed is quite similar for phases with larger or smaller amount of solvent, i.e., increase of the viscosity to a maximum value, followed proceeded by its decrease. The difference is that in systems with larger amount of solvent, the maximum is reached earlier. The increase of the viscosity should characterize a deformation of the stn1cture that after reaching a maximum tension, it will be orientated in a preferential direction, causing the decrease of the viscosity without break of the cholesteric building. The flow activation free enthalpy (ΔH≠) determination shows a decrease of energy value for increase of inductor concentration in lyotropic cholesteric liquid crystal that used cholesterol as inductor. When D-(+)-Mannose was used, the flow activation free enthalpy value increases. In the systems that hydrophobic inductor is used, the chiral forces should help in micelles flow orientation process, seemingly, after the movement of a micelle, the others would be dragged by the elastic forces, decreasing the flow activation enthalpy. When it is used a hydrophilic inductor, flow activation enthalpy increases with increases of inductor concentration, probably because the inductor nature that has a greater interaction with the solvent, acting as a barrier against the micelles flow orientation. The oscillatory essays show that the storage energy capacity, determined by the value of the storage modulus (G\') is larger than heat or diffusion dissipation capacity of the particles, obtained by the loss modulus (G\"). Both modulus (G\' and G\") decrease for the phases with smaller amount of available water and stay constant for the systems with larger amount of water. The lyotropic mesophase studied can be described by a Burger model modified by taken into account a temporary dependence to the elastic Maxwell component. This effect should be probably due to the inertia of the system.

A utilização de incorporadores de ar (AIA) em argamassas de revestimento é prática comum no setor de construção civil visto que podem ser obtidas vantajosas alterações nas propriedades no estado fresco e endurecido. Contudo, apesar do domínio da tecnologia e da química dos aditivos essa prática é ainda bastante empírica e seu uso tem sido apontado como um fator de complexidade operacional: a presença dos incorporadores de ar torna as composições muito sensíveis ao processamento, temperatura, tipo de cimento, transporte, etc., e essas variáveis afetam diretamente as características dos materiais no estado fresco e após o endurecimento. De fato, o desempenho desses materiais é dependente da quantidade, distribuição de bolhas e estabilidade do ar incorporado no estado fresco. Na prática, o difícil controle das propriedades dos materiais aerados é um dos fatores que têm desaconselhado a utilização desta tecnologia em diversas aplicações no setor construtivo. Assim, apesar das virtudes potenciais, a falta de controle no processamento dificulta o emprego de argamassas aeradas como tipos de materiais sustentáveis. Uma causa provável da falta de controle é que a velocidade de incorporação de ar é pouco compreendida, e a maioria dos estudos científicos são focados na avaliação do desempenho dos materiais no estado endurecido atentando-se, desta forma, para o efeito e não para a causa. A fim de preencher tal lacuna científico/tecnológica, o presente trabalho visa estudar os mecanismos e a velocidade de incorporação de ar em composições com cimento CPIIF durante o estado fresco e avaliar o seu impacto no estado endurecido. Para tanto, propôs-se uma abordagem de pesquisa inovadora na qual as propriedades das fases que compõem esses sistemas são avaliadas separadamente, determinando-se o impacto da utilização dos AIA em água, nas pastas de cimento e nas argamassas. Os resultados apontam que a quantidade efetiva de incorporador de ar e a qualidade da água afetam a capacidade espumante, que os aditivos não afetam a reação de hidratação do cimento, que a temperatura afeta as propriedades no estado fresco e endurecido das pastas, que é possível prever a porosidade resultante na argamassa a partir dos resultados observados na fase aquosa, que a distribuição granulométrica dos agregados é a variável de maior impacto nas propriedades reológicas e na permeabilidade das argamassas, propriedade intimamente ligada à durabilidade do revestimento. / The use of air-entraining agents (AEA) in rendering mortars is a common practice on the building sector because many advantages may be obtained in the fresh and hardened properties. However, in spite of the technology and chemistry of the admixtures knowhow, the air-incorporation in the cementitious materials is, still, very empirical and the use of AEA has being pointed out as a complex operational factor: its presence in the formulation gets the mortar very sensitive to the process, temperature, transport etc. and this variables can directly affect the hardened properties. In fact, the performance of these materials is very dependent of the quantity, size, distribution and stability of the air bubbles incorporated in the fresh state and in the practice, the difficult to control the aerated materials properties has dissuaded the utilization of this technique in many applications in the building sector. So, in spite of the potential virtues, the less of process control gets difficult the employment of the aerated mortars and concretes as sustainable materials. A probably cause of the air incorporation uncontrolled is that the rate of air generation in the cementitious materials is not correctly understand because the most researches are focused in the consequence and not in the cause. Thus, to try to eliminate such scientific/technology gap, this present PHD work was carried out to learn the kinetic of air incorporation in the pastes and mortar in the fresh state and evaluates the impact in the hardened state. For this, was proposed a innovative boarding where the phases that compound the systems will be research separately, determining the AEA impact on water, on the suspensions and on the mortars. The results show that the foaming capacity is influenced by the effective air-entraining admixture content and the water quality, that the cement hydration reaction was not influenced by AEA, that the temperature affects the rheological and hardened properties of suspensions, that it is possible to predict the mortar porosity from the results obtained in the water phase, that the fresh properties of mortars and it permeability (property closed related with rendering performance) were mainly affected by the aggregates granulometric distribution.

L’interaction d’un laser de haute énergie avec une cible fine d’hydrogène créé un plasma à l’intérieur duquel le champ électrostatique peut accélérer des protons jusqu’à des énergies de quelques dizaines de MeV. Ce domaine de la physique est appelé l’accélération laser/plasma.C’est dans ce contexte que le Service des Basses Températures (CEA, France) a développé en 2014 un prototype permettant de produire par extrusion des rubans d’hydrogène solide de un millimètre de large et de quelques dizaines de micromètres d’épaisseur.Cette thèse étudie la géométrie, la vitesse et la stabilité de ces rubans, qui sont des critères fondamentaux à l’efficacité de l’accélération laser/plasma. Les résultats des campagnes expérimentales menées avec ce prototype dans différents centres laser sont également décrits. Le deuxième et principal objectif de cette thèse consiste à caractériser et mesurer de façon précise les propriétés rhéologiques de l’hydrogène solide, afin de modéliser son écoulement à travers une buse d’extrusion d’épaisseur submillimétrique. Ce travail a consisté à concevoir un rhéomètre cryogénique innovant capable de générer un cisaillement continu d’hydrogène solide à des températures contrôlées, inférieures à 14 kelvins. La déformation de cisaillement de l’hydrogène solide est observée et décrite en détails, et sa viscosité apparente près de son point de fusion est quantifiée. Une loi régissant son écoulement est proposée, puis vérifiée par simulation numérique. / The interaction between a high-energy laser and a thin hydrogen target can generate an electrostatic field accelerating protons up to a few tens of MeV. This scientific field is called "laser/plasma acceleration". In this context, the Low Temperature Laboratory (CEA, France) has designed in 2014 a prototype extruding thin solid-hydrogen ribbon-shaped targets of onemillimeter in width and a few tens of micrometers in thickness.This Ph.D. thesis studies the geometry, the stability and the velocity of these ribbons, which are critical in the laser/matter interaction. Experimental campaigns led with this prototype in different laser facilities are described as well. The second and main objective of this Ph.D. thesisis to charaterize and measure the rheological properties of solid Hydrogen, in order to model its flow through a submillimeter-wide extrusion nozzle. This characterisation has been made possible through the design of an innovative cryogenic rheometer generating a continuous shear deformation in solid hydrogen at controled temperature, below 14 kelvins. Shear deformationof solid Hydrogen is studied and detailled, and its apparent viscosity near its melting point is measured. A deformation law is stated, then tested by numerical simulation.

<p>Apstrakt je obrađen tehnologijama za optičko prepoznavanje teksta (OCR).</p><p>Maltodekstini, hidrolizati skroba niskog stepena konverzije (dekstrozni ekvivalent manji od 20), imaju &scaron;iroku upotrebu u prehrambenoj, kozmetičkoj i farmaceutskoj industriji. U prehrambenoj industriji koriste se u niskoenergetskim prehrambenim emulzijama (majonez, salatni prelivi, namazi) kao zamena za masne materije da bi obezbedili viskozitet, poželjne senzorne osobine i smanjenje energetske vrednosti proizvoda.<br />Viskozitet razblaženih rastora maltodekstrina različitog dekstroznog ekvivalenta i botaničkog porekla meren je kapilarnim viskozimetrom i izračunate su vrednosti unutra&scaron;njeg viskoziteta za pojedine maltodekstrine. Vrednosti untra&scaron;njeg viskoziteta i molekulske mase pokoravaju se zavisnosti &Scaron;taudingerove jednačine, iako su molekuli maltodekstrina relativno kratki i ne spadaju u grupu polimera. Utvrđena je mogućnost odredivanja DE- vrednosti viskozimetrijskin putem i izvedene su jednačine za dva opsega DE (5-10 / 10-20).<br />Da bi se ispitalo pona&scaron;anje emulzija sa maltodekstrinima (emulgovanje) u procesnim uslovima, kao i osobine fmalnih proizvoda (tečljivost, mazivost) ispitivana je dinamika emulgovanja, veličina kapljica i reolo&scaron;ko pona&scaron;anje, tj. uticaj različitih faktora na disperzione karakteristike emulzija suncokretovog ulja u vodi stabilizovanih prehrambenim emulgatorom, sa dodatkom maltodekstrina u kontinualnoj fazi.<br />Utvrđeno je da osobine maltodekstina kao &scaron;to je stepen konverzije (DE-vrednost) tj. veličina molekula maltodekstrina, utiču na dispezione i reolo&scaron;ke osobine emulzija. Uticaj koncentracije ulja i maltodekstrina, kao i delimična zamena ulja maltodekstrinom, na osobine emulzija su takode ispitivane. Sa povećanjem koncentracije ulja, pri istoj koncentraciji maltodekstrina u kontinualnoj fazi, emulzije menjaju tip proticanja od pseudoplastičnog preko tiksotropnog do antitiksotrpnog. Atitiksotropija izazvana smicanjem rezultat je formiranja unutra&scaron;nje strukture emulzije usled povezivanja kapljica ulja preko molekula maltodekstrina kao i orijentacije i deformacije kapljica ulja i maltodekstrina.<br />Dodatkom maltodekstrina za pri istoj koncentraciju ulja i vremenu emulgovanja dobijene su se emulzije sitnijih kapi.<br />Emulzije sa niskom koncentracijom ulja (30%) sa maltodekstrinom u kontinualnoj fazi bile su nestabilne i pokazivale efekat isplivavanja na povr&scaron;inu (creaming), &scaron;to je posledica interakcija molekula maltodekstrina i molekula emulgatora Tween 80 u kontinualnoj fazi i na povr&scaron;ini kapi.</p> / <p>Abstract was processed by technology for Optical character recognition (OCR).</p><p>Maltodextrins, low converted products of starch hydrolysis (dextrose equivalent less than 20), have been subject of various investigations due to their wide application in food industry, cosmetics and pharmaceuticals. They are used in various low energy food emulsions (mayonnaise, salad dressing, spreads) as fat replacer to provide desirable viscosity, texture and sensory fat-like mouthfeel.<br />Viscosity of diluted maltodextrin solutions of different dextrose equivalent and botanical origin were determined by capillary visometer and intrinsic viscosity [q] of each tested maltodextrin was calculated. The values of [q] together with molecular mass M have shown applicability of Staudinger equation, regardless maltodextrin molecules are rather short. The possibility for the determination of DE-values of maltodextrins by viscometric method has been deduced and the equation was calculated for two ranges of DE (5-10/ 10-20).<br />In order to assess behavior of sunflower oil in water emulsions stabilized with food grade emulsifier with addition of maltodextrins in continuous phase in processing (emulsification), as well as end products in application (pouring, spreading) the emulsification dynamics, globule size changes and rheological behavior, as well as, the influence of different factors on dispersion characteristics of such emulsions were studied.<br />Dispersion and viscous properties of emulsions were influenced by certain specific maltodextrin characteristics such as degree of conversion (DE value) i.e. size of maltodextrin molecules. Influence of oil and maltodextrin concentration and partial substitution of oil with equivalent quantity of maltodextrin were investigated too. With increase of oil concentration at the same concentration of maltodextrin in continuous phase, emulsions undergo changes in flow type from shear-thinning to thixotropic and antithixotropic. Antithxotropy induced by shear, was result of formation of network due to two competing factors; linking of oil droplets through maltodextrin molecules as well as orientation of deformed oil droplets and maltodextrin molecules.<br />Addition of maltodextrin, at the same oil concentration and emulsification time, resulted in formation of emulsions with smaller oil droplets.<br />Emulsions with low oil concentration (30%) with maltodextrin in continuous phase were unstable, showing so called creaming effect. This was mainly due to interactions between maltodextrin and emulsifier Tween 80 molecules which took place in continuous phase and on droplet surfaces.</p>

Rhéologie des résidus agricoles pour un procédé de méthanisation par voie sèche multi-étapes.Le procédé Arkométha® utilise à profit l’injection de biogaz pour mélanger les résidus agricoles (fumier, lisier, ensilage, etc…) lors d’un procédé de méthanisation en voie sèche dans lequel la matière est épaisse. La connaissance des propriétés rhéologiques de ces matériaux, rarement étudiés dans la littérature, notamment à l’échelle industrielle, est un élément indispensable pour maitriser et contrôler le processus de mélange. Cette thèse a pour objectif de développer la compréhension des évolutions physiques et rhéologiques de ces matériaux lors de la méthanisation. La revue bibliographique détaillée dans le deuxième chapitre, a montré la nécessité de disposer d’un rhéomètre capable de mesurer les propriétés rhéologiques de ces produits à l’échelle industrielle. Pour cela, un cahier de charge a été établi à partir des contraintes scientifiques et techniques imposées par ces matériaux considérés comme des suspensions concentrées en fibres de dimensions importantes. Sur cette base, un rhéomètre de grandes dimensions pour les substrats, nommé RGDS, a été construit, validé et mis en service sur site industriel. La technique de scissométrie était utilisée pour mesurer le seuil d’écoulement et des pales type mélangeur, étalonnées en utilisant l’analogie de Couette, permettent de mesurer les propriétés sous écoulement. Dans le troisième chapitre nous avons montré la limite de l’utilisation du taux de matière sèche (MS%) traditionnellement utilisé comme un paramètre contrôlant la rhéologie, comme par exemple, le seuil d’écoulement de ces matériaux. Nous avons montré qu’il est plus pertinent de maitriser la répartition de l’eau dans la suspension pour contrôler les propriétés rhéologiques en prenant en compte le caractère spongieux de la matière lignocellulosique. Nous avons montré comment déterminer les concentrations critiques qui séparent les régimes semi-concentré, concentré, milieu triphasique non saturé en liquide jusqu’à un milieu granulaire humide et leurs relations avec le seuil d’écoulement. Dans le quatrième chapitre nous avons étudié l’effet de l’évolution des paramètres opératoires du procédé de méthanisation comme la taille des fibres, la température et le taux de matière sèche sur les propriétés rhéologiques des matériaux. Plusieurs modèles et lois ont été proposés pour quantifier l’intérêt d’effectuer des modifications des paramètres opératoires sur la rhéologie de ces matériaux. / The Arkometha® process uses biogas injections to mix agricultural residues (manure, slurry, silage, straw) in a dry anaerobic digestion process. Knowledge of the rheological properties of these materials, rarely studied in the literature, and especially not on an industrial scale, is an essential element to supervise and control the mixing process. This thesis aims to improve the understanding of the physical and rheological evolutions of these materials along the anaerobic digestion process. The literature showed the need for a rheometer able to measure the rheological properties of these products at the industrial scale. For this purpose, specifications were established based on the scientific and technical constraints imposed by these materials, which are considered as fiber concentrated suspensions. On this basis, a large rheometer for substrates, called RGDS for (Rheometer Grand Dimensions for the Substrate), was built, validated and commissioned on an industrial site. The van test technique was used to measure the yield stress and mixer blades, calibrated using the Couette analogy, were used to measure shear stresses. In the third chapter we have shown the utilization limits of the total solids (TS%), traditionally used as the main parameter for rheology controlling. In this chapter we treated the yield stress of these materials as a rheological parameter example. We have shown that it is more appropriate to control the water distribution in order to control the rheological properties of theses suspensions by taking into account the spongy nature of the lignocellulosic material. We have shown how to determine the critical concentrations separating the semi-concentrated, concentrated, triphasic and the wet granular behaviors and their relationship with yield stress. In the fourth chapter, we studied the effect of changes in the anaerobic digestion operating parameters, such as fiber size, temperature and TS on the rheological properties of materials. Several models and empirical equations have been proposed to quantify the advantage of making changes in the operating parameters on the rheology of these materials.

Dans le contexte actuel d'une prise de conscience environnementale générale, concernant plus particulièrement la gestion des polymères en fin vie, la thèse se propose d'étudier la substitution d'une matrice non biodégradable (Polyéthylène) par une matrice biodégradable (Polybutylene Succinate) dans le cadre de la propriété singulière de thermorétraction mise à profit dans le secteur de l'emballage.Ce travail de thèse, cofinancé par un industriel du secteur de l'emballe et par l'Agence de l'Environnement et de la Maitrise de l'Energie (ADEME) a donc consisté à :- Mettre en évidence l'influence des branchements longs contenus dans certains polymères, ainsi que leurs mélanges avec des polymères linéaires sur le comportement rhéologique en cisaillement et en élongation,- Proposer une modélisation de la contrainte interne stockée lors de l'étape de mise en forme par extrusion de film à plat (extrusion dite « cast ») en vue de prédire la contrainte de thermorétraction,- Etablir le lien entre la structure des matériaux, ses conditions de mise en œuvre et la morphologie du film final afin d'établir une corrélation avec le taux de rétraction.Dans un premier temps, cette étude a été réalisée sur des matrices modèles de polyéthylènes et ensuite transposée à une matrice biodégradable de Polybutylène Succinate. / Due to environmental concerns growth including the management of the end of life of polymer wastes, the present work proposes to study the feasibility of a substitution of conventional non-biodegradable polyethylene by a biodegradable matrix of Polybutylene Succinate in order to produce heat shrinkable films with equivalent properties. This property is mostly used in the packaging industry to wrap product such as six packs bottles, cans or other food products together.This work half-financed by a packaging company based in France and by the French environment and energy management agency consisted on:- Highlight the impact of the macromolecular architectures of the polymers and their blends on the rheological behavior under shear and elongational flow,- Developing a modeling approach of the stress stored in the molten polymer during the cast film extrusion process in order to predict the shrinkage stress,- Correlate the structure of the materials with their processing conditions and the morphology(ies) of the final film in order to correlate them with the shrinkage rate.The first part of this work was dedicated to the understanding of the shrinkage mechanism and to develop an approach on polyethylenes matrices used as models and then to transpose this approach to a biodegradable matrices of Polybutylene Succinate and therefore conclude on the feasibility of the use of such a matrices for heat shrinkable films for packaging application.

The main contribution of the present work is the proposition of a framework for analysis of active suspensions using the Caenorhabditis elegans nematode as the living model. To do so, five different perspectives are used: kinematics, macro-reological, numerical, theoretical and micro-reological. First, a theoretical and experimental analysis of the kinematic motion of the nematodes suspended in a biological fluid is presented. Two different populations are examined: starving and well fed nematodes. We show that the relationship between the length of an individual nematode and the wavelength of its movement is linear and can be adjusted by a theoretical prediction proposed in this work. A deep discussion on propulsive mechanics based on a scale analysis that identifies three major forces acting on an individual nematode is made. In addition, we investigated the shear viscosity of Caenorhabditis elegans suspensions. The oscillatory shear experiments revealed an anomalous viscosity behavior with the variation of the volumetric fraction of suspension, ?. The effective viscosity of the suspension decreased with increasing nematode volumetric fraction at low concentrations. Based on the experimental data, a phenomenological equation for the effective viscosity of the suspension as a function of the volumetric fraction of particles is proposed. The collective behavior of the nematodes is also observed in linear regime through the difference of normal stresses. Finally, step strain tests are conducted to obtain the relaxation times. The presence of a negative active stress due to the nematoid driving behavior persists for a period of time, leading to a negative undershoot and an oscillatory behavior in the relaxation function. In order to propose a rheological model, simplifications are made in the model and immersed boundary method simulations are conducted in a flexible filament, varying the type of movement that it performs. It is observed that the presence of asymmetries in its undulating movement generates drastic changes on its kinematic responses. A rheological model as a function of filament orientation is proposed and validated with experimental data in linear regime. After validation of the proposed constitutive equation, the model is observed under the nonlinear regime of oscillatory shear, in which the rheological characterizations are made based on existing frameworks using Lissajous-Bowditch curves and Pipkin diagrams. Finally, a protocol for analysis of suspensions in a microrheometer is presented. Particles are added and tracked as unidirectional oscillatory shear (pulsatile flow) is applied. The velocity and shear rate profiles are obtained, as well as the rheological signals equivalent to the strain rate and stress. Signal analysis tools are used and an artificial intelligence system is proposed to remove the component added to the signal by unidirectional shear, aiming to reconstruct the signal with null temporal average and allowing the application of well known rheological theories, such as the decomposition of stresses in coefficients of Chebyshev, for the calculation of viscommetric quantities of compliances and fluidities. The major contribution of the study concerns the observation, characterization, modeling and simulation of a microsized animal that moves in different fashion, depending on the environment, and the surrounding fluid. The rheological properties analyzed, simuations performed and model proposed can be used for both production of artifitial microorganisms and control of living organisms. Moreover, this combination of analyses and techniques can be used to study any type of passive and active suspension providing new and conclusive results regarding the rheological characterization and the physical behavior of the particles. / A principal contribuição do presente trabalho é a proposição de um framework de análise de suspensões ativas utilizando como modelo vivo o nematoide Caenorhabditis elegans. Para tanto, cinco perspectivas diferentes são utilizadas: cinemática, macrorreológica, numérica, teórica e microrreológica. Primeiramente, uma análise teórica e experimental do movimento cinemático das partículas ativas suspensas em um fluido biológico é apresentada. Duas populações diferentes são examinadas: na ausência de alimento e com nematoides bem alimentados. Mostramos que a relação entre o comprimento de um nematoide individual e o comprimento de onda de seu movimento é linear e pode ser ajustada por uma previsão teórica proposta neste trabalho. Uma profunda discussão sobre a mecânica de propulsão com base em uma análise de escala que identifica três forças principais que atuam em um nematoide individual é feita. Além disso, investigamos a viscosidade de cisalhamento das suspensões de Caenorhabditis elegans. Os experimentos em cisalhamento oscilatório revelaram um comportamento anômalo da viscosidade com a variação da fração volumétrica de suspensão, ?. A viscosidade efetiva da suspensão diminuiu com o aumento da fração volumétrica do nematoide para pequenas concentrações. Baseando-se nos dados experimentais, uma equação fenomenológica para a viscosidade efetiva da suspensão em função da fração volumétrica de partículas é proposta. O comportamento coletivo dos nematoides é também observado, em regime linear, pela diferença de tensões normais. Finalmente, o teste de step strain é conduzido para obter os tempos de relaxação. A presença de uma tensão ativa negativa devido ao comportamento impulsor do nematoide persiste por um certo período, levando a um undershoot negativo e a um comportamento oscilatório na função de relaxação. A fim de propor um modelo reológico, simplificações são efetuadas no modelo e simulações usando o método de fronteira imersa são conduzidas em um filamento flexível, variando o tipo de movimento que este realiza. Observa-se que a presença de assimetrias em seu movimento ondulatório gera drásticas mudanças em suas respostas cinemáticas. Um modelo reológico em função da orientação do filamento é proposto e validado com os dados experimentais em regime linear. Após a validação da equação constitutiva proposta, o modelo é observado sob o regime não-linear do cisalhamento oscilatório, no qual as caracterizações reológicas são feitas com base nos frameworks existentes, utilizando curvas de Lissajous-Bowditch e diagramas de Pipkin. Por fim, é apresentado um protocolo de análise de suspensões em um microrreômetro. Partículas são adicionadas e rastreadas à medida que um cisalhamento unidirecional (escoamento pulsátil) é aplicado. Os perfis de velocidade e taxa de cisalhamento são obtidos, assim como os sinais reológicos equivalentes à taxa de deformação e tensão. Ferramentas de análise de sinais são utilizadas e um sistema de inteligência artificial é proposto para remoção da componente constante do sinal adicionada pelo cisalhamento unidirecional, visando reconstruir o sinal com média temporal nula e possibilitando a aplicação de teorias reológicas já conhecidas, como a decomposição de tensões em coeficientes de Chebyshev para o cálculo das quantidades viscométricas de conformidade e fluidez. A principal contribuição do estudo diz respeito à observação, caracterização, modelagem e simulação de um animal microscópico que se movimenta de maneira diferente dependendo do ambiente e do fluido circundante. As propriedades reológicas analisadas, as simulações realizadas e o modelo proposto podem ser utilizados tanto para a produção de microorganismos artificiais quanto para o controle de organismos vivos. Além disso, essa combinação de análises e técnicas pode ser usada para estudo de qualquer tipo de suspensão ativa e passiva, fornecendo resultados novos e conclusivos em relação à caracterização reológica e ao comportamento físico das partículas.

L’objectif de ce travail est d’identifier les conditions et les mécanismes permettant la création d'aptitudes nouvelles ou améliorées des protéines du lactosérum à la stabilisation et texturation des mousses alimentaires.À cette fin, nous avons étudié la rhéologie interfaciale de protéines adsorbées à l’interface eau/air, les réarrangements topologiques à l’échelle de quelques films liquides, la stabilité et la rhéologie de mousses de protéines. L’étude a porté à la fois sur un mélange de protéines du lactosérum et sur sa protéine majoritaire purifiée, la ß-lactoglobuline. Pour identifier les liens avec leurs propriétés structurales et physico-chimiques, des modifications des protéines ont été générées par étuvage de poudres. Plusieurs paramètres d’étuvage ont été variés simultanément. Une large gamme de modifications structurales des protéines a été obtenue grâce au contrôle de ces paramètres. Nous avons mis en évidence que de petites modifications structurales des protéines ont des conséquences majeures sur la rhéologie interfaciale, la dynamique des réarrangements de films, la stabilité et la rhéologie des mousses.Les effets de l’étuvage des poudres sur les propriétés des mousses sont complexes, car ils dépendent étroitement de la combinaison des effets des paramètres d’étuvage, comme de la propriété de la mousse qui est mesurée. Parallèlement, l’examen de la variabilité des comportements à plusieurs échelles apporte un éclairage original sur la contribution de la rhéologie interfaciale aux propriétés de mousses de protéines. Il met notamment en évidence l’intérê / The objective of this work is to identify the conditions and mechanisms of the creation or improvement of the stability and rheology of whey proteins foams. To this aim, we studied the interfacial rheology of protein layers adsorbed at the air/water interface, the liquid films dynamics after a topological rearrangement, the stability and rheology of whey protein foams. Both a mixture of whey proteins and purified ß-lactoglobulin, used as a model protein, were studied. To study the relationships with protein structure, proteins were modified by dry-heating of whey protein powders. A wide variety of structural changes was obtained by varying simultaneously multiple dry-heating parameters.Interestingly, low-extent structural modifications have a dramatic impact on interfacial rheology, liquid film dynamics, foam stability and foam rheology. The effects of dry-heating parameters on the foam properties are complex and depend on their combination and the considered foam feature. Our original multiscale approach (interface, film dynamics and foam) sheds light on the contribution of the interfacial rheology to protein foam properties. In particular, foam dynamics have been shown to play a predominant role.