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This thesis investigated the perception of salt taste in two novel strategies for inclusion of NaCl in liquid foods: water-in-oil (w/o) emulsions and mucoadhesive biopolymer solutions. The major factors influencing w/o emulsion stability and perception were evaluated and a response surface model was developed. The amount of dispersed aqueous phase was the most significant factor affecting stability and perception. NaCl stabilized the emulsions and depressed salt sensory perception at elevated concentrations due to its interaction with the emulsifier polyglycerol polyricinoleate. Future research should elaborate events during oral processing of w/o emulsions. Biopolymer mucoadhesive character and concentration effects were also investigated. Mucoadhesion did not enhance salt taste. Above c*, there was a significant depression of sensory intensity, enhanced in polymers with hyperentanglements in solution. The depressive concentration effect may mask the effects of mucoadhesion. Future research should also inspect the influence of thickened hydrocolloid microstructure on perception. / The Advanced Foods and Materials Network

No description available.

Orientador: Niederauer Mastelari / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-24T20:16:15Z (GMT). No. of bitstreams: 1 Casari_MatheusPuttinati_M.pdf: 7346334 bytes, checksum: 21f16ea44e6fdefa2b0445fe1a0b6b3a (MD5) Previous issue date: 2014 / Resumo: A concentração volumétrica de água na produção de óleo cru é um parâmetro constantemente monitorado para acompanhar as sempre inconstantes propriedades do reservatório assim com para razões de otimização; resumindo, o que é importante é o volume de óleo na produção. A medição da concentração volumétrica de água é geralmente feita em bancada (colhendo uma amostra da produção e analisando-a em um laboratório) ou por sensores que monitoram a concentração em tempo real. Uma das técnicas utilizadas para a medição online da concentração de água é a espectroscopia por impedância. De fato, propriedades dielétricas e condutivas formam a impedância elétrica da solução. Na presente análise foram considerados os dois tipos básicos de emulsão: água em óleo (A/O) e óleo em água (O/A). O objetivo deste trabalho foi comparar a concentração de água medida com a predição do modelo matemático baseado nas medições das propriedades dielétricas e condutivas da solução. As emulsões de água e óleo foram sintetizadas em condições de laboratório. A concentração de água variou entre 13,1% à 41,1% em volume para as emulsões A/O e de 50% à 60% em volume para as emulsões O/A à temperaturas de 25°C à 62°C e salinidade da água de 0 (água deionizada), 1Kg/m³ e 10Kg/m³ de NaCl. A constante dielétrica e condutividade das emulsões foram medidas em um sensor composto por dois cilindros concêntricos cuja área dos eletrodos é bem maior que a distância entre eles. Essa geometria favorece os efeitos polarização e é apropriada para materiais dielétricos como as emulsões A/O, além de aumentar o erro de medição em soluções condutivas. Para melhores resultados com as emulsões O/A foi utilizado em sensor de placas paralelas com uma distância entre eletrodos bem maior que a sua área o que favorece os efeitos de transporte de carga. Os dados foram medidos por uma Ponte RLC de precisão Agilent E4980A em uma faixa de frequência de 20Hz à 1MHz. Os dados obtidos nos testes foram proporcionais à concentração de água na solução e seguiram o modelo matemático de Maxwell com um erro máximo de 4%. Os resultados também mostraram que a constante dielétrica não sofre influência significativa da temperatura e salinidade da água, assim como a medida do volume de água. Já para as emulsões O/A os testes mostraram grande influência da temperatura e salinidade da água nas medições, onde o conhecimento prévio destas condições é imprescindível ao método / Abstract: The volumetric concentration of water in crude oil production is a parameter constantly monitored to access the ever changing reservoir properties as well as for economical purposes; after all what is needed is the net oil production. The measurement of water concentration is usually done in over-the-bench (sampling the crude stream and screening in a chemistry lab) or by online instruments which continuously monitor the concentration. One of the techniques for online assessment of water concentration is the impedance spectroscopy. In fact, the dielectric and conductive property of the liquid phase is proportional to the electrical impedance. In the present analysis it was considered the two basic types of emulsions: the water in oil (W/O) and the oil in water (O/W). The objective of this work was to compare the measured water concentration against model's prediction based on the measured dielectric and conductive properties of the emulsions. The water and oil emulsions were synthesized in laboratory conditions. The water concentration range was 13.1% to 41.1% (v/v) for W/O emulsions and 50% to 60% (v/v) for O/W emulsions at temperatures of 25oC to 62oC and water salinity of 0 (de-ionized water), 1Kg/m³ and 10Kg/m³ of NaCl. The emulsion dielectric constant and conductivity were measured in a sensor made by two concentric cylinders whose electrodes area is much bigger than the distance between them. This geometry favors the polarization effects and is appropriate for dielectric solution as A/O emulsions. For better results for the O/A emulsion it was used a parallel electrode sensor where the distance between the electrodes is much bigger than the electrodes area which favors the charge transport effects. The data were measured by the Precision LCR Meter Agilent E4980A in a frequency range of 20Hz to 1MHz. The experimental data was found proportional to the volumetric concentration and follows Maxwell correlation within 4%. The experimental tests also disclosed that the dielectric constant, or the volumetric concentration, were almost insensitive to the changes in temperature and in salinity and so the water concentration of W/O emulsions. For O/W emulsions the tests showed a great influence of the temperature and salinity on the conductivity measurements. So, for O/W emulsions the temperature and water salinity must be considered / Mestrado / Mecanica dos Sólidos e Projeto Mecanico / Mestre em Engenharia Mecânica

[pt] Os hidratos são compostos cristalinos semelhantes ao gelo, formados por uma combinação de água e gás. A medida que a indústria de petróleo e gás natural vem se expandindo cada vez mais para águas mais profundas e geladas, a formação de hidratos em emulsões do tipo água em óleo (A/O) é um problema a ser considerado. O problema associado a formação de hidratos reside principalmente em seu elevado potencial para interromper ou prejudicar o escoamento nos dutos, o que eleva a custos proibitivos as operações de perfuração e produção. No que diz respeito a este cenário, a indústria de óleo e gás vem investindo em métodos para gerenciar o risco de formação de hidratos, de modo a prevenir um bloqueio total do escoamento. Uma das alternativas dessa estratégia é estudar a relação entre a variação de propriedades reológicas e a formação do hidrato usando um fluido modelo. Todavia, usualmente os hidratos são formados sob baixa temperatura e alta pressão, condição esta que representa um obstáculo a este tipo de estudo. A solução para tal problema é utilizar compostos que formem hidrato a pressão atmosférica, como por exemplo, o ciclopentano, que é liquido a temperatura ambiente. O presente trabalho visou analisar diferentes métodos de preparo para formação de emulsões do tipo A/O. Foram produzidas emulsões com corte de água variando de 20 a 40 por cento, com dois tipos de óleos minerais: Morlina S2 BL 10 e Morlina S2 B 150. Para todas as emulsões, foi utilizada uma mistura de surfactantes, Span 80 e AOT, com duas diferentes concentrações: 1 e 5 por cento em peso dos tensoativos. Após a produção desses fluidos modelos, estudou-se a reologia dos mesmos, sem e com ciclopentano, sendo estes últimos submetidos a condições de formação de hidratos em testes oscilatórios. / [en] Hydrates are crystalline compounds similar to the ice formed by a combination of water and gas. Once the oil and gas industry expands into deeper and icy waters, the formation of hydrates in water-in oil (w/o) emulsions should be considered. The problem associated with hydrate formation lies mainly in its high potential to stop or damage the flow in pipelines, which increases to prohibitive costs the operations of drilling and production. Regarding this scenario, the oil and gas industry has been investing in methods to manage the risk of hydrate formation, in order to prevent a total blockage of the flow. One of the alternatives of this strategy is to study the relationship between the change of rheological properties and the formation of hydrate in a fluid model. However, usually natural gas hydrates are formed under low temperature and high pressure condition, which is a barrier to this type of study. The solution to this problem is to use certain compounds that form hydrate at atmospheric pressure, such as cyclopentane, which is liquid at room temperature. This study aimed to analyze different methods of preparation for the formation of w/o emulsions. The emulsions were prepared with water cut ranging from 20 to 40 percent and with two different mineral oils: Morlina S2 BL 10 and Morlina S2 B 150. In all cases, a surfactant blend, composed by Span 80 and AOT, was added, with two different concentrations: 1 and 5 wt percent surfactant mixture in respect to the total emulsion weight. After the production of these fluid models, it was studied the rheology of those without and with cyclopentane, which were submitted to hydrate formation conditions in oscillatory tests.

Une nouvelle famille de dérivés amphiphiles du dextrane a été obtenue par réaction du dextrane avec le 1,2-époxydodécane en milieu basique. Deux voies de synthèse ont été étudiées. La première en milieu aqueux dispersé n’a permis d’obtenir que des taux de modification faibles (< 10 %) car l’homopolymérisation de l’époxyde est prépondérante. Au contraire, la réaction en milieu organique homogène a permis la synthèse de dérivés dont le taux de modification atteint 164 %. Des émulsions huile dans eau ont été préparées par sonication en présence de plusieurs dérivés hydrosolubles (τ ≤ 25 %). La fraction volumique d’huile (hexadécane ou nujol) est comprise entre 10 % et 50 %. La taille des gouttelettes augmente avec la fraction volumique d’huile mais ne dépend pas du taux de modification du dextrane entre 10 et 25 %. Ces émulsions ont un comportement de gel d’autant plus marqué que la fraction volumique d’huile dispersée augmente. Des émulsions inverses eau : chloroforme, stables pendant au moins 2 mois, ont été obtenues par sonication en présence de dérivés organosolubles (τ = 164 %). Le processus dynamique d’émulsification sous cisaillement a été étudié pour des émulsions directes (hexadécane / eau) dont la fraction volumique d’huile était comprise entre 10 et 60 % et pour différents gradients de vitesse. Un suivi continu in situ de la viscosité des émulsions et du rayon des gouttes formées montre que le temps caractéristique d’émulsification dépend du gradient de vitesse et du rapport des viscosités mais pas de la fraction volumique d’huile dispersée. Dans le cas d’un système newtonien, la viscosité finale et la taille finale des gouttes dépendent du gradient de vitesse appliqué alors qu’elles sont invariantes dans le cas du système non newtonien sur tout l’intervalle exploré / A new family of amphiphilic dextran derivatives was obtained by reaction of 1,2-epoxydodecane on dextran in basic medium. Two reaction procedures were examined. The first one was carried out in biphasic medium but produced only low degrees of hydrophobic substitution. Epoxide homopolymerization was indeed predominant. On the contrary, the reaction in a homogeneous organic medium allowed the synthesis of dextran derivatives with substitution degrees as high as 164 %. Oil-in-water emulsions were prepared by sonication in the presence of different hydrosoluble derivatives (τ ≤ 25 %). Oil volume fraction (hexadecane or nujol) ranged from 10 % to 50 %. The size of the emulsion droplets increased with the oil volume fraction but did not depend on the substitution degree of modified dextran between 10 and 25 %. These emulsions behave like a gel which strengthened with the oil volume fraction. Water-in-oil emulsions (water in chloroform) were obtained by sonication in the presence of organosoluble derivatives (τ = 164 %). They were stable over at least two months.Furthermore, dynamic emulsification process under shear flow was investigated for oil-in-water emulsions (hexadecane in water). The volume fraction of oil ranged from 10 % to 60 % and various shear rates were applied. Simultaneous in situ measurements of viscosity of emulsions and droplet size were performed. The characteristic time of emulsification depended on shear rate and viscosity ratio but was independent of the oil volume. For the newtonian system, final shear stress and final droplet size depended on the applied shear rate while they were invariant in the non newtonian system

In the present work, a new generation opaque polymer pigment with multihollow structure was synthesized by suspension polymerization of &ldquo / Water-in-Oil-in-Water&rdquo / (W/O/W) emulsion system. Oil phase was methyl methacrylate and ethylene glycol dimethacrylate monomer mixture at 1:1 weight ratio. The dimension and distribution of hollows inside polymer particles are dependent on the size of water droplets which are encapsulated in micelles. For Water-in-Oil (W/O) assembly, a hydrophobic surfactant and hydrophilic co-surfactant (Span 80-Tween 80) combination with a hydrophilic/lipophilic balance (HLB) value between 5-8 was used. The effects of surfactant and co-surfactant composition on the stability of the W/O emulsion and also on the size of water droplets were studied. In addition, the effect of the ultrasonication on the average size of water droplets was investigated. The hollow size distribution which may possibly give the maximum scattering efficiency was predicted by a mathematical model based on the Mie scattering. The optimum size distribution for W/O emulsion was obtained at the monomer/surfactant/water ratio of 75.5/9.4/15.1 after ultrasonication for 30 seconds at 80 W power. The W/O/W emulsion was prepared by dispersing the W/O emulsion in aqueous solution of hydrophilic Triton X-405. The influence of surfactant concentration and mechanical mixing on monomer droplets was investigated by size measurement and optical microscopy. After stabilizing with 1 %w/w polyvinylpyrrolidone (PVP) solution, the W/O/W emulsion was polymerized at 55 &deg / C for 20 h. The surface morphology of synthesized polymer pigments was analyzed by scanning electron microscopy (SEM) and the inner hollow structure was confirmed by transmission electron microscopy (TEM). The analysis indicated that multihollow opaque polymer pigments were successfully synthesized. The opacity, the L*a*b* color, and the gloss properties of polymer pigments were examined by spectrophotometer and glossmeter. The opacity values were assessed by contrast ratio measurements, and the synthesized polymer pigments provided up to 97.3 % opacity (50 %v/v solid content). In addition, the pigments exhibited low gloss values, and yielded matt films.

Ces travaux entrent dans la cadre du projet européen Fundamental and Applied Studies on Emulsion Stability (FASES). L'objectif de ce projet est de comprendre les phénomènes responsables de la déstabilisation des émulsions dans le temps, en relation avec les propriétés interfaciales de ces systèmes. Les travaux de thèse décrits dans ce mémoire se divisent en deux parties : ils portent tout d'abord sur la fabrication de gouttes d'émulsions eau-dans-huile par un procédé microfluidique, puis sur l'étude de la taille et de l'état de dispersion des gouttes sur la cristallisation de l'eau dispersée. Dans un premier temps, nous avons étudié les conditions opératoires permettant de fabriquer des gouttes de taille contrôlée par microfluidique avec le système de fluides mis en œuvre dans le projet FASES. Suivant le mode d'introduction des phases liquides, soit les débits, soit les pressions appliquées, ont été modifiés pour délimiter les zones de fabrication des gouttes. Afin de mieux comprendre les différences observées entre les deux modes d'introduction des fluides, un modèle reposant sur l'analogie entre circuits électriques et circuits microfluidiques a été proposé. Dans un second temps, les émulsions obtenues avec le dispositif microfluidique ont été analysées par calorimétrie et par thermo-microscopie. Les expériences ont permis de mettre en évidence, suivant les conditions étudiées (viscosité, taille des gouttes), différents processus de cristallisation des gouttes. Ces résultats mettent en avant directement le rôle du phénomène de sédimentation, les signaux de congélation observés dépendant fortement de l'état de dispersion des gouttes d'émulsion. / This thesis takes place in the framework of the European project FASES (Fundamentaland Applied Studies on Emulsion Stability). The aim of this project is to understand the phenomena responsible for emulsions destabilization, in relation with the interfacial properties of these systems. The research work described in this thesis is divided into twoparts : the first part deals with the creation of water-in-oil emulsion droplets in a microfluidic device, and in the second part, the influence of the size and the state of dispersion of the droplets on the crystallization of dispersed water is analyzed.To begin with, the operating conditions required to create emulsion droplets by microfluidic were studied. Two modes of introduction of the liquid phases, based on flow and pressure-driven techniques, were used to create the droplets. Maps of the droplet formation regions were drawn as a function of the applied flow rates and pressures. In order to compare the two processes, a model based on the analogy between electrical and microfluidic circuits was proposed.Then, emulsions obtained with the microfluidic device were analyzed by calorimetry and thermo-microscopy. The experimental results evidenced different droplet crystallization processes, depending on the system parameters (oil phase viscosity, droplet size …). The water freezing signals strongly depend on the state of dispersion of the droplets, showing themajor role of droplet sedimentation in the emulsion destabilization process.

[pt] O aumento do fator de recuperação e o uso de métodos de recuperação avançada no atual cenário de novos patamares de preços representam um enorme desafio para a indústria do petróleo. Neste contexto, o uso de emulsões óleo-água como um método de recuperação avançada torna-se bastante atrativo. Diversos trabalhos mostraram um aumento no volume de óleo produzido através da injeção de emulsões óleo-água. Resultados de pesquisas experimentais indicam que a injeção de emulsões pode ser utilizada como agente de controle de mobilidade, bem como reduzindo a saturação residual de óleo. A aplicação do método de injeção alternada água-emulsão-água (WAE) requer o entendimento do escoamento de emulsões no meio poroso e dos mecanismos responsáveis pela melhora na recuperação. Este entendimento tanto na escala de poros como na escala de reservatórios permite incorporação destes mecanismos na modelagem para simulação de fluxo de reservatórios. No presente trabalho foi feita a incorporação dos efeitos gravitacionais no modelo desenvolvido para o escoamento de emulsões em meios porosos através da parametrização das curvas de permeabilidade relativa em função da concentração de gotas e do Número de Capilaridade. O processo WAE foi avaliado através de simulações em duas e três dimensões (2D/3D) utilizando um conjunto de camadas do segundo modelo comparativo do SPE10. Com simulações 2D e 3D foi possível realizar um estudo de sensibilidade do processo em relação ao momento da injeção de emulsão, o tamanho do banco, e as faixas de vazão e respectivos números de capilaridades de atuação da emulsão. / [en] In the current crude oil price scenario, the increase in oil recovery factor and the use of enhanced recovery methods represent a major challenge for the Oil Industry. In this context, the use of oil-water emulsion flooding as an enhanced recovery method becomes very attractive. Several studies have shown a significant potential to increase oil volume recovery by the injection of oil-water emulsions. Experimental results indicate that the emulsions injection can be used as a mobility control agent, resulting in a more uniform fluid displacement in the reservoir and lower residual oil saturation. Based on these experimental results, the most relevant parameters for emulsion injection performance effectiveness are droplet size, the local concentration of the dispersed phase of the emulsion and the local capillary number. The application of water alternating emulsion injection (WAE) method requires understanding of the flow of emulsions in porous media and the mechanisms responsible for the improved recovery. The understanding of this process in both porous scale and reservoir scale is fundamental to model emulsion injection effects in reservoir flow simulation. In this work, the gravitational effects was incorporated in the macroscopic model to represent flow of emulsions in porous media by relative permeability curves parametrization as function of emulsion concentration and of the local capillary number. The WAE process was evaluated in two and three dimensional simulations (2D / 3D) using a set of layers of the second SPE 10 comparative model. With 2D and 3D simulations, it was possible to explore a WAE injection performance sensitivity analysis considering the time at which the emulsion injection is started, the size of emulsion bank, and the injection flow rates and consequently the flow their capillary number.