Master of Science / Department of Biological & Agricultural Engineering / Donghai Wang / Gums are water-soluble polysaccharides used in many industrial and food applications because of their functions such as thickening, gelling, emulsification, adhesion, and encapsulation. Interactions between gums are conducted to enhance functional properties of finished products and reduce processing costs. In this study, camelina gum, from the oil-seed plant Camelina sativa, is characterized by carbohydrate composition and morphological, thermal, and rheological properties. Interactions with xanthan gum, galactomannans guar gum, and locust bean gum (LBG) are also studied. Camelina gum is composed of arabinose, rhamnose, galactose, glucose, xylose and mannose; according to high-performance anion exchange chromatography analysis. Scanning electron microscopy and transmission electron microscopy images showed camelina gum with fibrillar structure and intermeshed network. Camelina gum solutions exhibited a shear thinning flow behavior in a range of concentrations (0.1% to 2.0% w/w) and shear rate (0.001 sˉ¹ to 3000 sˉ¹). Camelina gum is temperature independent at temperature ranges from 4 °C to 90 °C. The apparent viscosity increased as gum concentration increased. Mechanical properties of camelina gum demonstrated viscoelastic behavior with entangled molecular chains. Interaction of camelina gum with monovalent salt NaCl significantly reduced the viscosity of camelina gum solution at 1% when NaCl concentration increased. Camelina gum is soluble in water up to 60% ethanol content, in which the rheological properties do not significantly differ from camelina gum in water solution only. A synergy with xanthan and galactomannans was determined. All mixtures exhibited shear-thinning flow behavior, solid-like behavior at low frequencies, and liquid-like behavior at high frequencies. For camelina-galactomannans mixtures, synergistic interactions occurred in LBG-camelina mixtures at ratios of 1:1 and 3:1. For xanthan-camelina mixture, maximum synergy was observed at the ratio 1:1. Synergistic effects of gum mixtures suggest dependency on the ratios and chemical structures of the gums. The effect of temperature on apparent viscosity of mixtures is not significant. Results showed that camelina gum can be used for commercial applications.

The films formed by tetradecylamine (TDA) at the water-dodecane interface in the presence of hydrogen phosphate ions have been studied. Between pH 5 and 8, tetradecylammonium cations bind to hydrogen phosphate anions to form needle-shaped crystallites of tetradecylammonium hydrogen phosphate (TAHP). Fourier Transform Infrared Spectroscopy (FTIR) shows that these films consist of two tetradecylammonium cations and one hydrogen phosphate anion. Light microscopy and Small Angle Neutron Scattering (SANS) results show that these crystallites self-assemble into films with a hierarchical structure. On the molecular level, the TAHP has lamellar order. On a mesoscopic level, these lamellae assemble into needle-shaped crystallites with a size on the order 0.1-100 μm. These crystallites assemble into interfacial films with a range of morphologies; below pH 7 they form continuous sheets, at pH 8 they form lace-like networks. The films have both unusually high elastic shear moduli (G's ≈ 10 N/m) and a structure that can be directly imaged using light microscopy. Varying the structure of the films affects their rheology. The lace-like networks deform plastically when sheared, whilst the continuous sheets are highly brittle. The films are temperature-responsive: when the system is heated the film thins and its rheological moduli drop. The temperature response is caused by dissolution of the film into the bulk fluid phases. The TAHP film also stabilises water-in-oil emulsions. The rheological properties of the film are directly related to the stability of the TAHP-stabilised droplets: the droplets coalesce upon being heated, suggesting potential applications in controlled release of active molecules. TAHP and colloidal PMMA particles stabilise emulsions by compatible mechanisms, and can be used to synthesise ('patchy') droplets with an inhomogeneous particle coverage, and ('hairy') droplets, from which long, tendril-like aggregates extend. Finally, the temperature-responsive nature of TAHP is applied to the composite interfaces. As the droplets are heated the lipid film dissolves, and the PMMA particles become mobile at the interface. The electrostatic interactions between the particles lead to competition between the ordering that the electrostatics would favour, and the defect structure favoured by the topology of the spherical surface. I investigate the freezing transition on a spherical surface, and show the emergence of hexagonal order as particle density is increased.

O colágeno possui características que fazem com seja amplamente utilizado como biomaterial. A termo-estabilidade do colágeno está diretamente relacionada a mudanças na sua estrutura (hélice tripla) via de regra quanto mais estável termicamente uma matriz, mais estável biologicamente será. Vários poliálcoois incluindo o glicerol têm apresentado um aumento na estabilidade térmica do colágeno tipo I, embora o tipo de interação não seja evidente. Este trabalho tem como objetivo estudar o efeito da adição de glicerol sobre o colágeno aniônico obtido por tratamento alcalino (24 H) em três diferentes tecidos: pericárdio e tendão bovinos e serosa porcina. Para isto são utilizados a espectroscopia na região do infravermelho (FTIR), termogravimetria e reologia. Os espectros mostraram que o tratamento alcalino e a adição de glicerol não causam desnaturação da proteína de colágeno. A partir dos resultados das curvas termogravimétricas foi observado que o glicerol aumenta a temperatura de decomposição térmica do colágeno. Os resultados dos ensaios de reologia mais precisamente a varredura de deformação mostrou que as soluções de colágeno apresentam G\' maior que G\'\' independente do tecido de origem, e a adição de glicerol não causa mudanças nesta propriedade das soluções. A varredura de freqüência mostrou que as amostras têm características de um gel, sendo G\' maior que G\'\' nas condições de estudo. O ensaio de escoamento a temperatura constante determinou o comportamento pseudoplástico das soluções, e a adição de glicerol causou aumento na viscosidade das soluções sem alterar tal característica. Os ensaios de escoamento com variação de temperatura permitiram determinar a temperatura de desnaturação do colágeno. A adição de glicerol aumentou apenas a temperatura de desnaturação do colágeno obtido por serosa porcina, sugerindo que esta solução é a mais sensível à adição de glicerol. / Several characteristics make collagen widely applied as a biomaterial. The collagen thermal stability is directly related with its structure changes (triple helix), generally, the better is the thermal stability the better is the biological stability. Several polyols including glycerol, has shown a increasing on type I collagen denaturation. The objective of this work is to study the effect of glycerol when mixed with anionic collagen. Type I anionic collagen was obtained after alkaline treatment (24h) of bovine pericardium, bovine tendon and porcine serosa. FT-IR, thermogravimetry and rheology were used. The results of thermal analysis showed that glycerol indeed increases the collagen decomposition temperature. The reologycal tests, precisely strain sweep, revealed that collagen samples have modulus G\' prevailed on modulus G\'\' independent of tissue origin, and glycerol addiction did not change these. The frequency sweep revealed that collagen and collagen:glycerol samples behave like a gel-like substance since both the storage and loss modulus showed dependence with frequency sweep and G\' > G\'\' in all cases. Flow tests at constant temperature revealed that collagen solution behave like a pseudoplastic substance, and glycerol addiction increase solution viscosity and did not change the pseudoplastic characteristic. Flow tests in function of temperature revealed collagen denaturation temperature, but glycerol addiction alters thermal stability (increase of denaturation temperature) only for collagen obtained from porcine serosa.

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2009. / This study investigated water-in-oil (WIG) super-concentrated emulsions used as pumpable explosives. The aqueous phase of the emulsions is a supersaturated nitrate salt solution (at room temperature), with a volume fraction usually greater than 0.8. Aqueous phase droplets are deformed by packing and contact with neighbouring droplets. Compounds of this kind are thermodynamically unstable and their instability is related to the coarsening of emulsions (droplet coalescence) and phase transition (crystallisation) in the dispersed phase. However, it was demonstrated that the dominating mechanism is slow crystallisation inside the supercooled droplets. The main goal of this thesis therefore concerned a phenomenological study of the dependence of type and concentration of surfactant, as well as the ageing processes, on the rheological properties of these emulsions. The bulk rheological measurements were carried out using a rotational dynamic rheometer MCR 300 (Paar Physica). Samples of different types of surfactant (Pibsa-MEA, Pibsa-UREA, Pibsa-IMIDE, SMO and SMO/Pibsa-MEA) and different concentrations of surfactants were studied. The results of the measurements include the flow and viscoelastic properties of the materials. The rheological parameters have been correlated with the kinetics of structural changes during ageing as a function of emulsion formulation content. The emulsions under study were non-Newtonian liquids. It was demonstrated that different surfactant types yield different interfacial properties. In fact, both the interfacial tension and the interfacial elastic modulus were found to decrease according to the sequence MEA-UREAMEAlSMG- IMIDE-SMG. It was established that the surfactant type and surfactant concentration affected the bulk rheological properties of explosive emulsions. Indeed, both the elastic modulus and the yield stress as function of surfactant type decreased in the following order: MEA-IMIDE-UREA-MEAlSMG, whereas they also decreased as the surfactant concentration increased. However the sensitivity of the rheological parameters to the type or concentration of surfactant was found to decrease as the droplet size increased. Moreover, the changes in rheological parameters were more strongly expressed than any changes in interfacial tension. This last finding is considered as rather important. It seems reasonable to assume that it provides proof of an active role of a surfactant not only as a compound responsible for the interfacial tension, but also creating additional sources of elasticity.

Thesis (MTech (Mechanical Engineering))--Cape Peninsula University of Technology, 2016. / This dissertation presents how material properties (solids densities, particle size distributions, particle shapes and concentration) of gold tailings slurries are related to their rheological parameters, which are yield stress and viscosity. In this particular case Bingham yield stresses and Bingham plastic viscosities. Predictive models were developed from analysing data in a slurry database to predict the Bingham yield stresses and Bingham plastic viscosities from their material properties. The overall goal of this study was to develop a validated set of mathematical models to predict Bingham yield stresses and Bingham plastic viscosities from their material properties. The interaction of the non-Newtonian material properties is very complex at varying mass solids concentrations. The evaluation of these interactions in terms of constitutive equations is almost impossible and the relationship between material properties, mass solids concentration and rheology can only be modelled in a statistical manner. The validity of each model is checked to ensure that predictions and interpretations are unbiased and efficient. This is done by comparing the resulting models to experimental data generated from test work. An in-depth analysis was conducted to see the interrelationship between the material properties and how they affect the yield stress and viscosity values.

Orientador: Raul Cesar Evangelista / Banca: Raul Cesar Evangelista / Banca: Osvaldo de Freitas / Banca: Ana Dóris de Castro / Resumo: Os polissacarídeos naturais vêm sendo extensamente usados no desenvolvimento de formas farmacêuticas sólidas para liberação prolongada de fármacos, fato demonstrado na literatura por inúmeros estudos de utilização de polissacarídeos como quitosana, pectina, sulfato de condroitina, ciclodextrinas, dextranas, inulina, amilose e galactomananas de goma de guar e de alfarroba. Neste trabalho, os polímeros de galactomananas de flamboyant (Delonix regia) e de Carolina (Adenanthera pavonina), que são vegetais pertencentes à família Leguminosae, foram estudados após serem reticuladas por reação com trimetafosfato de sódio, um agente reticulante adequado para o uso farmacêutico e alimentício e avaliou-se os diferentes graus de reticulação das gomas em função da variação do tempo de reação (30 min. a 4 horas) e da concentração de base no meio reacional( 2% e 4%). As técnicas analíticas empregadas mostraram-se úteis na avaliação do grau de reticulação das amostras, exceto a espectroscopia na região do infravermelho, que não permitiu estabelecer diferenças entre as estruturas obtidas com diferentes graus de reticulação. A técnica da reologia apresentou-se como uma ferramenta importante na análise dos polímeros. Através das análises de viscoelasticidade foi possível observar mudanças significativas no comportamento viscoelástico dos polímeros reticulados quando comparados aos polímeros não-reticulados, oriundos do flamboyant ou da carolina. Para todos os tempos de reticulação, o módulo G' apresentou valores maiores para os polímeros reticulados em comparação aos polímeros não reticulados, para todos os tempos de reticulação. A análise do grau de intumescimento das partículas aliada à reologia mostrou ser útil para a caracterização dos polímeros, permitindo observar que os produtos reticulados de ambas as origens tiveram sua capacidade... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The natural polysaccharides have been extensively used in the development of solid dosage forms for sustained release of drugs, a fact demonstrated by countless studies in the literature about the use of polysaccharides such as chitosan, pectin, chondroitin sulphate, cyclodextrins, dextran, syrup, starch and gum galactomannans of guar and carob. In this work, the polymers of galactomannans of Flamboyant (Delonix regia) and Carolina (Adenanthera pavonina), which are plants belonging to the family Leguminosae, were studied after a cross-linked reaction with sodium trimetaphosphate, which is a cross-linked agent suitable for pharmaceutical and food use. Then, from this study, the different cross-linked degrees of gum depending on the variation of the reaction time (30 minutes to 4 hours) and the concentration of base in the middle reaction (2% and 4%) were analyzed. The analytical techniques employed have proved useful in assessing the cross-linked degree of the samples, except in the infrared spectroscopy, which failed to establish differences between the structures obtained with different degrees of cross-linkage action. The rheology technique presented itself as an important tool in the analysis of polymers. Through the viscoelasticity analysis it was possible to see significant changes in the viscoelastic behavior of cross-linked polymers when compared to non-cross-linked polymers, from the Flamboyant or the Carolina. For all times of reticulation, the module G had higher values for the cross-linked polymers when compared to non-cross-linked polymers, for all times of cross-linkage actions. The analysis of the degree of swelling of the particles combined with rheology has shown to be useful for the characterization of polymers, enabling the observation that the cross-linked products of both origins had their ability to absorb water increased significantly in relation to non-cross-linked... (Complete abstract click electronic access below) / Mestre

Sistemas multifásicos reativos, como as argamassas, vêm sendo bastante estudados e explorados das mais diversas formas ao longo dos anos. A mistura é uma das etapas do processamento (mistura, transporte e aplicação) desses sistemas que, devido à aparente simplicidade operacional tem sido de certa forma negligenciada. A qualidade da mistura exerce influência direta no comportamento reológico e nas propriedades no estado endurecido. Nesse contexto, os objetivos da pesquisa consistem em avaliar a influência de parâmetros que interferem no comportamento de mistura (tempo, taxa de adição de água e velocidade de mistura do equipamento), no intuito de entender o fenômeno físico envolvido, sugerindo técnicas de análise para estudá-los e propor procedimentos (sequência de introdução dos materiais) mais adequados para a mistura de argamassas em laboratório. O trabalho de pesquisa compreende duas etapas. A primeira trata da avaliação dos parâmetros que influenciam a mistura de argamassas (cimento, cal, filer e areia) com e sem aditivo dispersante (policarboxilato de sódio) e, estabelece técnicas de análise da curva de mistura, obtida no reômetro rotacional tipo planetário desenvolvido na POLI-USP. A segunda etapa estuda diferentes procedimentos de mistura de argamassas em laboratório, na Hobart, e os compara com o procedimento da ABNT NBR13276/2005. No estado fresco emprega-se a reometria rotacional (curva de mistura + ciclos de cisalhamento) e squeeze-flow (na segunda etapa do trabalho) para avaliação do comportamento reológico. No estado endurecido, as propriedades mecânicas são verificadas por meio de resistência à tração por compressão diametral, módulo de elasticidade dinâmico e porosidade. Os resultados obtidos na primeira etapa, indicam que a técnica empregada na análise das curvas mostra ser apropriada para avaliar o fenômeno físico envolvido na dispersão e homogeneização das partículas do sistema durante a mistura. Na segunda etapa, o estudo de diferentes procedimentos de mistura em laboratório, aponta que introduzir o líquido nos materiais sólidos, nas condições analisadas, tende a produzir sistemas mais fluidos. Dependendo da composição dos sistemas, estes podem ser mais ou menos suscetíveis ao processo de mistura. E, por fim, no estado endurecido, as propriedades avaliadas indicam que um processo de mistura adequado conduz a resultados satisfatórios no material endurecido, com redução da porosidade e melhor desempenho do produto final. / Multiphase reactive systems, such as mortars, have been extensively studied in many different ways over the years. The mixture is one of the processing steps (mixing, transport, application) of these systems that due to its apparent operational simplicity, has been somewhat neglected. The quality of the mixing process has a direct influence on the rheological behavior and on the properties in the hardened state. In this context, the objectives of the research are to assess the influence of experimental parameters that affect the mixing behavior (time, water addition rate and rotation speed) in order to understand the physical phenomena involved, and to develop analysis methodology and propose procedures (sequence of mixing) best suited for mixing mortar in the laboratory. The research comprises two steps; the first part is the evaluation of the influence of experimental parameters on mixing behavior of mortars (cement, lime, filler, sand) with and without additive (sodium polycarboxylate) and the establishment of a methodology to analyze the mixing curve obtained in planetary rotational rheometer developed on POLI-USP, and the second stage studies different procedures for mixing mortars in laboratory, on Hobart, and compares them with the current ABNT NBR13276/2005 standard procedure. In the fresh state rotational rheometer (mixing curve + shear cycles) and squeeze-flow (in the second stage of research) are used for rheological characterization, while mechanical properties were verified by splitting tensile strength, dynamic modulus of elasticity and porosity. The results obtained in the first step indicates that the technique employed for the analysis of the curves is suitable for evaluating the physical phenomena involved in the dispersion and homogenization of the particles during mixing. In the second step, the study of different mixing procedures in the laboratory indicates that introducing the water in the solids tends to produce more fluid systems. The mixing behavior of the systems depends on their mix design (composition). Finally, in the hardened state, properties evaluated indicated that a suitable mixing process leads to satisfactory results with reduced porosity and better final performance of the products.

O desenvolvimento de novos materiais tem sido baseado na mistura de dois ou mais polímeros ou biopolímeros, onde soluções destes são misturadas em diferentes proporções na tentativa de se obter materiais com propriedades distintas das de seus precursores. Neste trabalho foram analisadas blendas colágeno:PVA. O colágeno utilizado foi o tipo I, porem proveniente de duas formas diferentes, o colágeno comercial que foi cedido pela Novaprom Food Ingredients Ltda e o colágeno obtido a partir de tendão bovino por meio de hidrólise alcalina em diferentes tempos (24h e 96h). As blendas e os colágenos foram caracterizados por análise térmica (DTG e DSC), microscopia eletrônica de varredura (MEV), espectroscopia de absorção no infravermelho (FT-IR) e analises reológicas. As curvas DSC mostraram que o colágeno comercial é o de maior temperatura de desnaturação e que a adição de PVA não altera essa temperatura. Já as curvas TG mostraram que o PVA, seja qual for sua massa molecular, aumenta a estabilidade térmica do colágeno. A microscopia eletrônica mostrou que os colágenos com tratamento alcalino apresentam uma estrutura fibrilar e pouco desorganizada, enquanto o colágeno comercial apresenta uma estrutura uma pouco mais compacta. Através do FT-IR foi possível observar que a presença de PVA nas blendas não influencia na presença dos picos, sugerindo que não há interação química entre os mesmos. A análise reológica permitiu comparar os módulos elástico (G\') e viscoso (G\") dos géis em diferentes proporções, tendo todos eles valores de G\' maior do que G\", ou seja, podemos concluir que os materiais são mais elásticos do que viscosos. Observa-se também a influência na viscosidade dos géis com a adição de PVA ao mesmo, sendo a viscosidade maior com o aumento da massa de PVA adicionado. / The development of new materials has been based on the mix of two or more polymers or biopolymers where solutions are mixed in different portions trying to get materials with distinct properties from their precursors. In this work different collagen solutions and collagen-PVA blends were analyzed. The used collagen was the type I, however obtained from two different forms, the commercial collagen that was provided by Novaprom Food Ingredients Ltda and the collagen obtained from bovine tendon by alkaline hydrolysis in different times (24h and 96h). The blends and collagen were characterized by thermal analysis (DTG and DSC), electronic scan microscopy (ESM), infrared absorption spectroscopy (FT-IR) and rheological analysis. DSC curves showed that the commercial collagen has the highest denaturing temperature and that the addition of PVA does not change this temperature. In other hand, TG curves showed that PVA, in any given molecular weight, increases collagen thermal stability. Electronic microscopy shows that collagen with alkali treatment have a fibrillar and little disorganized structure, insofar, the commercial collagen have a little more compact structure. By FT-IR it was to possible observe that the presence of PVA on blends have no influence on the peaks, suggesting that there is no chemical interaction between then. Rheological analysis allow to compare the elastic module (G\') and the viscous module (G\'\') from blends in different proportions. All the obtained values for G\' are higher than G\'\', so it can be conclude that samples are more elastic than viscous.

Este trabalho propõe contribuir no desenvolvimento do processo de extrusão para a produção de compósitos cimentícios, mediante metodologia que possibilite a obtenção de formulações extrudáveis utilizando cimento Portland de alta resistência inicial, sílica ativa, calcário, polpa de celulose de eucalipto, fibras de polipropileno e aditivos. Para isso, foram caracterizadas as matérias-primas como subsidio para as discussões. O efeito dos diferentes componentes da formulação no comportamento reológico da mistura foi avaliado utilizando reômetro extrusor. As propriedades físicas e mecânicas dos compósitos elaborados com combinações de calcário, sílica ativa e cimento foram modeladas estatisticamente com o propósito de estimar o comportamento das matrizes. A demanda de água dos sistemas cimentícios foi determinada experimentalmente e utilizada na extrusão das matrizes. Selecionada uma matriz, suas propriedades mecânicas e físicas foram modeladas, estatisticamente, com diferentes teores de polpa celulósica de eucalipto e fibras de polipropileno. As formulações com características desejadas foram avaliadas ao envelhecimento acelerado por 200 ciclos de imersão-secagem. Finalmente foi analisada a reprodutibilidade utilizando o módulo de Weibull para as formulações selecionadas. O estudo reológico constatou que as fibras de polipropileno apresentam os maiores aumentos nos valores dos parâmetros reológicos se comparados com os efeitos do calcário, sílica ou celulose de eucalipto, repercutindo em maiores pressões de extrusão. O incremento do modificador reológico hidroxipropilmetilcelulose reduz no compósito cimentício o módulo de ruptura mesmo que durante o processamento, promova o incremento da pressão de extrusão. Os modelos estatísticos empregados para modelar a matriz reforçada foram de maior complexidade e com menor coeficiente de determinação se comparados com os utilizados na modelagem das matrizes. O preço de mercado do fibrocimento é aproximadamente 64% menor do que os determinados utilizando unicamente os valores das matérias-primas e aditivos do fibrocimento extrudado no presente estudo. / This work intends to contribute in the development of the extrusion process for the production of cementitious composites, through methodology that makes it possible to obtain formulas using high resistance Portland cement, silica fume, limestone, eucalyptus pulp, polypropylene fibers and admixtures. With this intention, the raw materials were characterized as a support for the discussions. The effects of the different components of the formula on the rheological behavior of the mixture were evaluated using an extrusion rheometer. The physical and mechanical properties of the composites elaborated with the combinations of limestone, silica fume and cement were modeled statistically with the purpose of estimating the behavior of the matrix. The water demand of the cementitious systems was determined experimentally and used in the matrixes extrusion. After the Matrix Selection, their mechanical and physical properties were modeled statistically, with different pulp eucalyptus and polypropylene fibers quantities. The formulas with the expected characteristics were evaluated to the accelerated aging for 200 wet-drying cycles. Finally the reproducibility was analyzed using the Weibull module for the selected formulas. The rheological studies verified that the polypropylene fibers demonstrate the largest increase in the values of the rheological parameters when compared with the effects of the limestone, silica fume or eucalyptus pulp, inducing larger extrusion pressures. The increment of the rheological modifier hydroxypropyl methylcellulose decreases the module of rupture in the cementitious composite, and simultaneously during the process it promotes the increment of the extrusion pressure. The statistical models used to reinforce the matrix modeling were of large complexity and with smaller coefficient determination when compared to matrixes used for modeling. The fiber cement market price is approximately 64% smaller than the raw materials and admixtures used in extruded fiber cement in this study.

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