La connaissance de la viscosité est un défi majeur dans les technologies de pointe (biomédical, pétrochimie, imprimerie, cosmétique, agroalimentaire, etc). Cette étude présente un capteur de viscosité qui exploite la vibration transversale forcée d’une poutre mince. L’amortissement induit par le fluide permet d’évaluer sa viscosité et sa masse volumique par la seule connaissance des caractéristiques à la résonance de la poutre (amplitude et fréquence). Cette mesure est réalisée par un circuit électromagnétique. Dans ce travail, la simulation numérique et l’étude expérimentale du viscosimètre sont réalisées en vue de mieux cerner les paramètres influençant le fonctionnement du capteur. Les différentes investigations menées dans ce travail sont d’une grande importance pour l’optimisation du viscosimètre d’une part. D’autre part, c’est une contribution à l’ensemble des études qui traitent de l’aspect du couplage fluide-structure-électromagnétisme. / Knowing the viscosity becomes increasingly a major challenge in leading-edge technologies (biomedical, petrochemical, printing, cosmetic, food industry, etc). This study presents a viscosity sensor based on a thin beam immersed in a newtonian fluid and subjected to transverse vibrations due to an electromechanical excitation system. The damped vibration can be used to evaluate the fluid viscosity and density by measuring the beam’s resonance characteristics (amplitude, frequency). This measurement is done by an electromagnetic feedback circuit. In this work, numerical model and experimental studies of the vibrating viscometer are conducted to better understand the influencing factors of the sensor’s operation. The different investigations carried out in this work are of great importance for the viscometer optimization on one hand. On the other hand, it’s a contribution to all studies dealing with the aspect of fluid-structure-electromagnetism coupling.

Polymer nanocomposites (PNCs) are hybrid materials incorporating organic or inorganic nanoparticles (NPs) with at least one dimension in the submicron scale. Over the last two decades, these materials have drawn a remarkable attention due to their central role in industrial formulations and technological applications, extending from food packaging to smart coatings. Incorporating nanoparticles (NPs) to a polymer matrix can significantly alter the conformation and the mobility of the polymer chains in their proximity. Moreover, understanding the delicate balance between the enthalpic and entropic interactions is crucial to control and predict the ability of NPs to diffuse and disperse in the polymer matrix. The impact of these interactions on the structure and the dynamics of polymer chains and NPs is fully revealed in how a number of macroscopic properties changes, justifying the high interest on these materials for industrial applications. In this thesis, the impact on the structure, dynamics, viscosity and thermal conductivity of a number of microscopic properties is investigated by performing Molecular Dynamics (MD) simulations. Specifically, the PNC is represented by a coarse-grained model of a melt of linear homopolymer chains containing spherical NPs. Throughout this work, a number of parameters are modified in order to unveil possible patterns in the PNC’s performance. To this end, this work focuses on the consequences of modifying the NP size dispersity, NP-polymer chain relative size, and chains’ degree of stiffness. Four theoretical models describing the diffusivity of NPs, three of which include nano-scale corrections, have been averaged to study the dependence of dilute NPs’ diffusivity on the NP polydispersity index. By comparing these models to the simulation results at different degrees of polydispersity, it is possible to obtain a more complete picture of their validity as compared to the monodisperse case. Regarding the diffusion of polymer chains, simulation results were in good agreement with the experimental results previously obtained by Composto and coworkers (Soft Matter 2012, 8, 6512), which relate the chains’ diffusivity to the average interparticle distance. As far as the transport properties are concerned, they show a weaker dependence on the polydispersity index. By contrast, results on viscosity and thermal conducitivity show that they are conditioned by the polymer-NP specific interfacial area and the inverse average mass, respectively. These results are in good agreement with previous experimental results. A deeper examination of this intriguing deviation from viscosity predictions in traditional composites, reveals a non-trivial combination of thickening and thinning effects contributing to the final viscosity of the PNC. This thesis also address the influence of the chains’ stiffness on the dynamical and viscous behaviour. An isotropic-to-nematic phase transition is observed, regardless of the NP-monomer interactions, below which a monotonic increase of both properties is observed, whereas orientationally ordered systems dramatically modify them, resulting into a steep increase or a smooth decrease depending on the direction in which they are measured.

Radicals are core reactive species that occur in almost every subfield of chemistry. In particular, solution phase radicals find their way into biochemistry (e.g. vitamin B12), and in polymer chemistry (e.g. radical polymerizations) just to name a few. Yet, given the proliferation of radical chemistry, there are still fundamental aspects of it that are poorly understood. This dissertation probed factors that influence the solvent cage effect. The solvent cage effect is where two radicals are held in close proximity to one another and prevented from easily escaping (to form free radicals) by a cage of solvent molecules. A convenient metric of the solvent cage effect is the radical recombination efficiency (FcP). Typically, FcP correlates with the bulk viscosity of the solution, however, this parameter only produces qualitative assessments. This dissertation outlines a method to quantitatively predict FcP using the microviscosity. This microviscosity dependence holds for non polar, aromatic, polar, and hydrogen-bonding solvents, along with solutions that contain polymers. Microviscosity is a great metric because it addresses an underlying reason for the solvent cage effect, the strength of the cage. Not only does the strength of the solvent cage around the radical pair affect FcP, but so does the identity of the radicals themselves. That is, the strength of the solvent cage is one piece to forming a total predictive model. FcP for the Cp'2Mo2(CO)6 dimer also varies with the wavelength of irradiation. Identifying the mechanism by which this wavelength dependence occurs may also provide another factor to include in an overall model of the solvent cage effect. Also, an attempt at synthesizing an asymmetric molybdenum dimer was performed. This asymmetric dimer would allow the study of solvent caged radical pairs that are different from each other. Predicting the photochemical cage pair recombination efficiency (FcP) is the major topic of this dissertation. However, there is also the collisional cage recombination efficiency (Fcʹ). This is where free radicals come together in what is called a collisional solvent cage pair. A method and values of Fcʹ are detailed later in this dissertation. This dissertation contains previously published and unpublished co-authored material.

[pt] Este trabalho descreve experimentos relacionamentos com o movimento relativo entre partículas sólidas e fluido não-newtoniano, confinados no interior de um duto circular. Medições da pressão dinâmica adicional, devida unicamente à presença da partícula (fonte de perturbação no escoamento) e do arrasto viscoso foram conduzidas de forma a se verificar a validade da Teoria de Brenner (1962). Esta teoria, já confirmada para fluidos newtonianos, permite que parâmetros característicos do escoamento perturbado sejam determinados, convenientemente, através de parâmetros do escoamento não-perturbado (ausência de partícula). Para o caso de fluido não-newtoniano, denominados puramente viscosos, do tipo Power-law, a teoria se mostrou perfeitamente aplicável. O valor da razão Delta P mais A/D descrito por Brenner foi confirmado com uma precisão de 3 por cento, num total de 70 experimentos realizados. Para fluidos não-newtonianos, viscoelásticos, com função viscosidade tipo Power-law, a validade da teoria parece, entretanto, depender de um parâmetro capaz de descrever na natureza constitutiva do fluido utilizado. Experimentos realizados com três diferentes fluidos viscoelásticos (expoentes power-law n igual 0,303; 0,343; 0,483) conduziram à identificação deste parâmetro, o Segundo Número Elástico, El2. Para valores de El2, inferiores a 14, caracterizando um escoamento predominantemente viscoso, o valor da razão Delta P mais A/D novamente é confirmado com precisão inferior a 4 por cento. Para valores de El2 superiores a 40 a razão Delta P mais A/D não mais pode ser avaliada com base em parâmetros do escoamento perturbado, analogamente ao que havia sido proposto por Brenner para o caso de fluidos newtonianos. Neste trabalho incluem-se também registros contínuos dos experimentos enfatizando os efeitos viscoelásticos envolvidos, bem como uma análise dos efeitos de parede associados ao movimento relativo entre fluidos não-newtonianos e partículas sólidas. Todos os experimentos foram realizados num regime de Reynolds variando de 0,1 a 90 e num regime de Weissenberg (calculando com base no modelo de Powell-Eyring) variando de 850 a 3800. / [en] This work describes experiments related to relative motion between solid particles and mon-newtonian fluid, inside a circular duct. Measurements of the aditional dynamic pressure, due to the presence of the particle (a source of disturbance in the flow) ando f the viscous drag, were conducted to verify the validity of Brenner’s Theory (1962). This theory, already confirmed for newtonian fluids, allows the determination of the characteristic parameters of the disturbed flow using parameters of non-disturbed flow (without particle). In the case of purely viscous non-newtonian fluids, of the power-law type, the theory was confirmed. The value of the ratio Delta P plus A/D, described by Brenner, was confirmed. The value an accuracy of 3 per cent, in a total of 70 experiments. For viscoelastic fluids, with Power-law viscosity function, it appears that the validity of the theory depends on the Second Elastic Number, El2. Experiments conducted with three different viscoelastic fluids (power-law exponents, n equal 0,303; 0,343 and 0,483) shows that for values of El2 bellow 14, which characterizes a predominantly viscous flow, the value of of the ratio Delta P plus A/D is agair confirmed, with na accuracy of 4 per cent. For values of the El2, parameter above 40, the ratio Delta P plus A/D cannot be determined using parameters of the non-disturbed flow, as proposed by Brenner for newtonian fluids. In this work are also included graphic registers of the experiment, showing the complex viscoelastic effects, as well as na analysis of the wall effects associated with the relative motion between non- newtonian fluid and solid particles. All the experiments were conducted with Reynolds number between 0,1 and 90 and a Weissenberg number (based in Powell-Eyring model) between 850 and 38.00.

Há uma demanda por competitividade entre as indústrias de aços, a fim de alcançar a excelência definida pelo termo clean steel. O processo de desgaseificação a vácuo (VD) ocorre durante o Refino Secundário de aços especiais. Sua principal função é remover gases indesejáveis, especialmente o hidrogênio. Entretanto, durante este processo, o fenômeno de flotação e a absorção de inclusões são reportados. O objetivo do presente trabalho foi estudar a viscosidade de escórias e a capacidade da estação de desgaseificação a vácuo do tipo tanque na limpeza de aços sob uma perspectiva industrial. Para realizar este objetivo, foram coletadas amostras de escória e aço antes e após a etapa de vácuo. Os resultados em limpeza de aço foram relacionados à energia de agitação durante o tratamento a vácuo (associada a um parâmetro cinético - βs) e ao efeito da viscosidade de escórias. É possível observar um decréscimo expressivo na população de inclusões entre as condições antes e após tratamento de desgaseificação a vácuo. A remoção de inclusões durante o vácuo atinge 64, 75 e 78% para as faixas de diâmetro de 2,5-5, 5-15 e ≥ 15 μm, respectivamente. Após o processo de desgaseificação, a composição das inclusões não-metálicas aproxima-se da composição química da escória. O processo de agitação na estação de desgaseificação a vácuo promove uma diminuição significativa na densidade de inclusões na faixa de diâmetro de 2,5-15 μm. Além disso, ao aumentar a intensidade do parâmetro cinético, a composição química de inclusões não-metálicas foi afetada e o teor de enxofre presente no aço líquido foi reduzido. Quanto às viscosidades efetiva das escórias, conclui-se que, para valores mais baixos (0,20 Pa.s) aumenta-se a capacidade da escória na remoção de inclusões, enquanto que valores mais altos (> 0,40 Pa.s) aparentaram ser prejudiciais à limpeza do aço. / There is a demand in competitiveness within the steel industry towards achieving excellence defined by clean steel term. The process of vacuum degassing (VD) occurs during the secondary refining of special steels. Its main function is to remove undesirable gases, primarily hydrogen. However, during this process, flotation phenomenon and inclusions absorption are reported. The aim of the present work was to study the slag viscosity and vacuum degassing (tank type) capacity in steel cleanliness from an industry perspective. To achieve this objective, slag and steel samples were taken before and after vacuum stage. The results in steel cleanliness were related to the stirring energy of the vacuum station (associated to a kinetic parameter – βs) and to the effect of slag viscosity. It is possible to observe an expressive decrease in the population of inclusions between the conditions before and after vacuum degassing treatment. The removal of inclusions during the vacuum stage reaches 64, 75 and 78% in the diameter ranges of 2,5-5, 5-15 and ≥ 15 μm, respectively. After the degassing process, the composition of non-metallic inclusions seemed to approach the slags’ chemical compositions. The stirring process in the vacuum degassing station promotes a significant decrease in the inclusion density with 2,5-15 μm diameter range. Also, by increasing the kinetic parameter intensity, the composition of non-metallic inclusions was affected. The sulfur content present in liquid steel was reduced. Regarding the effective viscosities of slags, it was concluded that lower values (0,20 Pa.s) increased slag capacity in inclusion removal, whereas higher values (> 0,40 Pa.s) was detrimental to steel cleanliness.

This diploma thesis deals with questions of the present meat products market, meat products quality and the relevant legislation with focus on steamed ham. According to the present legislation ham is divided into three categories based on the content of pure muscle protein. The categories are as follows: top-grade quality ham, choice ham and standard ham. Use of starch, food colouring ingredients, fibrous additives, vegetable protein and different animal protein is not allowed with top-grade quality ham and choice ham. Within the practical part of the diploma work twenty samples of ham from all categories were examined. The tests showed that starch was not added to any top-grade quality ham or choice ham. Starch was found only in two samples of standard ham, in which starch addition is allowed by legislation.

Submitted by MARÍLIA SBRAGIA DEL BEM null (msbragia@gmail.com) on 2016-04-11T17:40:10Z No. of bitstreams: 1 Dissertação Marília Sbragia Del Bem.pdf: 4218662 bytes, checksum: 6a79164a0b53df57f2a07e3084e7fa8e (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-04-12T18:04:49Z (GMT) No. of bitstreams: 1 delbem_ms_me_bot.pdf: 4218662 bytes, checksum: 6a79164a0b53df57f2a07e3084e7fa8e (MD5) / Made available in DSpace on 2016-04-12T18:04:49Z (GMT). No. of bitstreams: 1 delbem_ms_me_bot.pdf: 4218662 bytes, checksum: 6a79164a0b53df57f2a07e3084e7fa8e (MD5) Previous issue date: 2016-02-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / No presente trabalho, objetivou-se avaliar os efeitos de parâmetros variáveis na fosfatação do amido nativo de mandioca sobre as propriedades físicas dos amidos modificados e avaliar o uso do amido fosfatado na produção de emulsão tipo maionese. O amido de mandioca nativo e o amido de milho comercial foram analisados quanto à composição físico-química, amilose aparente, difração por raios-X e cristalinidade relativa, morfologia geral, tamanho e distribuição dos grânulos, poder de inchamento e solubilidade, propriedades de pasta e térmicas. O amido de mandioca nativo foi fosfatado pela mistura de fosfato de sódio monobásico anidro (NaH2PO4) e fosfato de sódio dibásico anidro (Na2HPO4) totalizando sete tratamentos com diferentes quantidades em mol de fosfato. Todas as análises realizadas nos amidos de mandioca nativo e no amido de milho comercial foram também realizadas nos amidos fosfatados de mandioca, com exceção da composição físico-química. Além dessas análises, os amidos fosfatados foram analisados quanto ao teor de fósforo e grau de substituição (DS). Foram realizados testes de aplicação do amido de milho comercial (P), amido nativo de mandioca (T1) e dos amidos de mandioca fosfatados (T2 e T3) em maioneses com 30 % (m/m) de óleo. As maioneses foram submetidas às análises de pH, acidez titulável, textura, estabilidade da emulsão, microscopia óptica e análise sensorial. Nos amidos de mandioca nativo e milho comercial foram observadas diferenças significativas tanto na composição físico-química, quanto na caracterização morfológica, estrutural e física. Nos amidos modificados houve aumento nos teores de fósforo e no DS com o aumento das concentrações de fosfato, sendo que nas maiores concentrações testadas os valores finais ultrapassaram o permitido pela legislação. O aumento das concentrações ocasionou aumento aproximado de 4 vezes no diâmetro médio e menor uniformidade dos grânulos, intensificando-se a partir da quinta concentração, ou seja, 5,20 milimol de fosfato g-1 de amido. No primeiro tratamento, ou quantidade em mol de fosfato igual a 0, o teor de amilose aparente era de 23,21 %, mas na maior concentração de fosfato esse valor teve uma diminuição aproximada de 12 vezes. A fosfatação provocou o rompimento das ligações de hidrogênio das duplas hélices de amilopectina, responsáveis pela formação dos cristais, reduzindo a cristalinidade relativa. O poder de inchamento e a solubilidade do amido aumentaram com o aumento das concentrações, assim como a viscosidade inicial a 25 °C. Houve redução nos picos, na quebra, na viscosidade final e na tendência à retrogradação. A adição de fosfato também reduziu as temperaturas de gelatinização e a variação da entalpia (ΔHgel), enquanto a porcentagem de retrogradação aumentou até a concentração estimada de 3,96 milimol de fosfato g-1 de amido, diminuindo com as próximas concentrações. As maioneses testadas com o amido de milho comercial (P), amido de mandioca nativo (T1) e amidos de mandioca fosfatados com teores de fósforo aceitáveis pela legislação para uso em alimentos (T2 e T3) apresentaram resultados de pH, acidez titulável e estabilidade da emulsão dentro do esperado. O amido de mandioca modificado T2 mostrou-se mais estável frente às forças mecânicas em relação aos demais amidos. O aumento das concentrações de fosfato reduziu a firmeza das maioneses, no entanto, todas foram bem aceitas na avaliação sensorial em todos os atributos, inclusive em relação à textura e à intenção de compra. O amido de mandioca fosfatado, obtido no presente trabalho, pode ser utilizado como substituinte do amido de milho comercial na produção de maionese, sendo o tratamento T2 (0,88 milimol de fosfato g-1 de amido) o mais recomendado. / This study aimed to evaluate the effects of the variable parameters of chemical modification of on the phosphating of cassava starch and the influence of this modification on the physical properties of the starch, as well as studying the application of the phosphate cassava starch in mayonnaise. The cassava starch and commercial corn starch were analyzed for physical-chemical composition, apparent amylose, diffraction X-rays, relative crystallinity, general morphology, size and distribution of the granules, swelling power and solubility, paste and thermal properties. Native cassava starch was phosphated by the mixture of anhydrous sodium monobasic phosphate (NaH2PO4) and anhydrous dibasic sodium phosphate (Na2HPO4), with a total of seven treatments with different amounts of mol phosphate. All analyzes performed on starches of cassava and commercial corn starches were also carried out in phosphate starch cassava, except for the physical and chemical composition. In addition to these analyzes, the phosphate starches were analyzed for phosphorus content and degree of substitution (DS). Tests of application were conducted with commercial corn starch (P), native cassava starch (T1) and phosphate cassava starches (T2 and T3) on mayonnaise with 30 % (w/w) of oil. The mayonnaises were analyzed for pH, titratable acidity, texture, emulsion stability, optical microscopy and sensory analysis. Significant differences in the physical and chemical composition as well as the morphological, structural and physical characteristics were observed between the starches of cassava and maize. The analysis of modified cassava starches showed that there was increase in phosphorus content and degree of substitution with increasing phosphate doses used, whereas in conditions of higher concentrations tested the final values of phosphorus in starches were greater than allowed by legislation. Increased concentrations led to an increase in about four times the average diameter of the starch granules and promoted a lower uniformity of the granules, intensifying from the fifth concentration or phosphate or 5.20 millimoles g-1 of starch. In the first treatment, or quantity in moles of phosphate 0, the apparent amylose content was 23.21 %, but in higher phosphate concentration, this value had an approximate decrease of twelve times. The phosphating caused the rupture of hydrogen bonds of amylopectin double helices, responsible for the formation of crystals, reducing the relative crystallinity. The swelling power of the starch and solubility increased with the increasing concentrations, and the initial viscosity at 25 °C (cold viscosity). There was a reduction in the peaks, breakdown, final viscosity and retrogradation tendency. The addition of phosphate also reduced gelatinisation temperatures and the variation of enthalpy (ΔHgel), while the percentage of retrogradation increased up to an estimated concentration of 3.96 millimoles phosphate g-1 of starch, decreasing with higher concentrations. The mayonnaise tested with commercial corn starch (P), starch native tapioca (T1) and phosphate cassava starch with phosphorus levels acceptable by law for food use (T2 and T3) showed pH results, titratable acidity and stability the emulsion as expected. The cassava modified starch T2 was more stable compared to the mechanical forces than the other starches. The increase in phosphate concentrations reduced the firmness of mayonnaise, however, all were well accepted in the sensory evaluation in all attributes, including with respect to texture and purchase intent. The tapioca starch phosphate obtained in the present study may be used as the substituent of commercial corn starch in the production of mayonnaise and the treatment T2 (0.88 millimoles phosphate g-1 of starch) as recommended.

Made available in DSpace on 2014-06-11T19:31:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-07Bitstream added on 2014-06-13T19:20:42Z : No. of bitstreams: 1 oliveira_rb_dr_botfca.pdf: 2430018 bytes, checksum: 83351333d3d9c8a67f6e396d9780730d (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / A alta demanda por agrotóxicos pelos sistemas de produção agrícola, aliada ao possível uso inadequado desses produtos, torna a deriva um dos maiores problemas potenciais da agricultura atual, e a escolha correta de adjuvantes pode ser uma das alternativas para minimizar os impactos negativos causados pela deriva nas pulverizações. Este trabalho foi desenvolvido com o objetivo de avaliar o efeito proporcionado por diferentes grupos de adjuvantes nas propriedades físicas e químicas das soluções, no espectro de gotas, bem como no potencial do risco de deriva quantificado em túnel de vento, como forma de auxiliar na escolha correta desses produtos para melhor utilização nas aplicações de agrotóxicos. Foram selecionados 18 adjuvantes comumente utilizados em misturas com agrotóxicos em pulverizações agrícolas, avaliando-se as propriedades físicas e químicas dos mesmos em soluções aquosas (viscosidade, densidade, tensão superficial e condutividade elétrica), o espectro de gotas e o potencial de deriva medido em túnel de vento. O experimento foi composto de 33 tratamentos, tendo a água como testemunha adicional, resultantes da diluição dos adjuvantes em diferentes concentrações, com três repetições. Para os ensaios em túnel de vento e análise de espectro de gotas foi utilizada uma ponta de pulverização XR8003 VK na pressão de 200 kPa, gerando um padrão de gotas médias. A deriva foi coletada no túnel de vento com fluxo de ar na velocidade de 2 m s-1. O corante Azul Brilhante a 0,6% (m v-1) foi utilizado como marcador para todas as soluções pulverizadas visando a quantificação da deriva por espectrofotometria. Os resultados mostraram que a adição de adjuvantes alterou as propriedades físicas e químicas das soluções aquosas em diferentes magnitudes, dependendo da concentração utilizada. Os surfatantes organosilicones... / Due to the high demand for pesticide by the agricultural systems and the possible inadequate use of the products, drift became one of the biggest concerns of the modern agriculture, and the correct use of adjuvants may be one of the possible alternatives to minimize the negative impact of spray operations. This study was developed to evaluate the effect of different adjuvants on physical and chemical properties of spray solutions, droplets spectra as well as drift potential measured in wind tunnel, aiming the correct choice of adjuvants to improve efficiency in pesticide application. For this purpose 18 commercially available agricultural spray adjuvants were selected including products usually mixed up with pesticides in the sprayer tank. The evaluation included physical and chemical properties of spray solutions (viscosity, density, surface tension and electric conductivity), droplets spectra and drift risk potential measured in wind tunnel. The experiment was set up with 33 treatments (solutions) obtained from 18 adjuvants used in different concentrations with 3 replications, including pure water as a standard. For wind tunnel tests and droplet spectra analysis it was used a Teejet XR8003 flat fan nozzles at 200 kPa (medium droplets) and all solutions were mixed up with a food color dye (Blue FDC) at 0,6% m v-1 for spectrophotometry analysis of drift deposits on the wind tunnel. The results showed that the addition of adjuvants changed physical and chemical properties of spray solutions in different magnitudes according to the product concentration. The organosilicon surfactants (Silwet 0.1% e 0.2% and BreakThru 0,1%) had the lowest values for surface tension, while the drift retardant based polymers (Define 0,06% e 0,12%) had the highest values for viscosity and density. There was high correlation between the Volume Median Diameter (VMD) and percentage of droplets smaller... (Completo abstract click electronic access below)

abstract: The need for sustainability in construction has encouraged scientists to develop novel environmentally friendly materials. The use of supplementary cementitious materials was one such initiative which aided in enhancing the fresh and hardened concrete properties. This thesis aims to explore the understanding of the early age rheological properties of such cementitious systems. The first phase of the work investigates the influence of supplementary cementitious materials (SCM) in combination with ordinary Portland cement (OPC) on the rheological properties of fresh paste with and without the effect of superplasticizers. Yield stress, plastic viscosity and storage modulus are the rheological parameters which were evaluated for all the design mixtures to fundamentally understand the synergistic effects of the SCM. A time-dependent study was conducted on these blends to explore the structure formation at various time intervals which explains the effect of hydration in conjecture to its physical stiffening. The second phase focuses on the rheological characterization of novel iron powder based binder system. The results of this work indicate that the rheological characteristics of cementitious suspensions are complex, and strongly dependent on several key parameters including: the solid loading, inter-particle forces, shape of the particle, particle size distribution of the particles, and rheological nature of the media in which the particles are suspended. Chemical composition and reactivity of the material play an important role in the time-dependent rheological study. A stress plateau method is utilized for the determination of rheological properties of concentrated suspensions, as it better predicts the apparent yield stress and is shown to correlate well with other viscoelastic properties of the suspensions. Plastic viscosity is obtained by calculating the slope of the stress-strain rate curve of ramp down values of shear rates. In oscillatory stress measurements the plateau obtained within the linear visco-elastic region was considered to be the value for storage modulus. Between the different types of fly ash, class F fly ash indicated a reduction in the rheological parameters as opposed to class C fly ash that is attributable to the enhanced ettringite formation in the latter. Use of superplasticizer led to a huge influence on yield stress and storage modulus of the paste due to the steric hindrance effect. In the study of iron based binder systems, metakaolin had comparatively higher influence than fly ash on the rheology due to its tendency to agglomerate as opposed to the ball bearing effect observed in the latter. Iron increment above 60% resulted in a decrease in all the parameters of rheology discussed in this thesis. In the OPC-iron binder, the iron behaved as reinforcements yielding higher yield stress and plastic viscosity. / Dissertation/Thesis / Masters Thesis Civil Engineering 2016

Orientador: Vânia Regina Nicoletti Telis / Banca: José Roberto Delalibera Finzer / Banca: Maria Aparecida Mauro / Resumo: O comportamento reológico de suspensões de cristais de sacarose em soluções aquosas saturadas de sacarose foi avaliado usando um reômetro acoplado a um agitador, mais conhecido como reômetro de turbina. Foram analisadas suspensões formadas por soluções aquosas saturadas de sacarose a diferentes temperaturas (e, portanto, com diferentes concentrações de sacarose), às quais foram adicionadas diferentes frações de cristais de sacarose de tamanho conhecido. As frações de cristais de sacarose usadas na composição das suspensões foram separadas, através de peneiramento, a partir de três diferentes tipos de açúcares comerciais: açúcar granulado, refinado e de confeiteiro. As soluções aquosas saturadas de sacarose, consideradas como meio dispersante das suspensões, foram caracterizadas reologicamente utilizando-se um reômetro rotacional de cilindros concêntricos. Todas as soluções analisadas apresentaram comportamento Newtoniano nas faixas de concentração e temperatura avaliadas. Já as suspensões de cristais de sacarose em soluções aquosas saturadas de sacarose foram avaliadas reologicamente com o auxílio do reômetro de turbina, o qual foi montado na base do reômetro rotacional de cilindros concêntricos e cujo agitador foi acoplado ao eixo originalmente destinado ao cilindro interno. O agitador usado no equipamento foi do tipo âncora e teve suas constantes determinadas através de metodologia específica. As suspensões analisadas também apresentaram comportamento reológico do tipo Newtoniano. Os resultados obtidos foram utilizados para a obtenção de modelos relacionando a viscosidade das suspensões à fração das partículas cristalinas presentes no sistema, bem como às características reológicas do meio líquido. / Abstract: Rheological properties of suspensions of sucrose crystals in saturated sucrose aqueous solutions were investigated using a rheometer coupled to an agitator, also known as mixer-type rheometer. Suspensions formed by saturated solutions were analyzed at different temperatures (and, therefore, at different sucrose concentrations), and with different added fractions of sucrose crystals of known size. Three different types of commercial sugars (granulated, refined, and confectioner) were sieved in order to obtain fractions of sucrose crystals of different sizes. Saturated sucrose aqueous solutions, considered as a suspension dispersant mean, were rheologically characterized using a concentric cylinders rheometer. In the studied ranges of concentration and temperature, all analyzed solutions showed Newtonian behavior. The crystals suspensions in saturated sucrose aqueous solutions were rheologically evaluated by using the mixer-type rheometer, which was coupled to the concentric cylinders rheometer. The impeller was an anchor type agitator and had their constants determined by means of a specific methodology. The analyzed suspensions also showed Newtonian behavior. The experimental results were used to obtain mathematical models relating the suspensions viscosity to the dispersant liquid phase viscosity and to the volumetric fraction of crystals. / Mestre