O Brasil é um dos principais produtores mundiais de Eucalyptus spp., mas a produção dessa cultura tem sido comprometida por perdas causadas pelo fungo Puccinia psidii Winter, agente causal da ferrugem do eucalipto. Compreender os mecanismos moleculares da patogenicidade desse fungo, conhecer a composição química de variedades de Eucalyptus spp. resistentes e suscetíveis ao fitopatógeno e ter em mãos uma ferramenta de diagnóstico precoce da doença são conhecimentos de fundamental importância para o desenvolvimento de estratégias de controle do fitopatógeno. Uma das principais barreiras que limitam o estudo molecular de P. psidii é o fato dessa espécie ser biotrófica obrigatória, tendo seu desenvolvimento in vitro limitado. Estudos de investigação a respeito de fungos biotróficos obrigatórios são realizados principalmente in planta e em estágios tardios da doença, deixando grande parte do conhecimento dos processos iniciais de infecção desconhecidos. Informações a respeito dos estágios iniciais da infecção, nos quais diversas estruturas típicas são formadas e podem indicar importantes características sobre fungos biotróficos, são de difícil acesso em estudos in planta em função da grande quantidade de material vegetal em relação à quantidade de material do fitopatógeno, que não é passível de ser removido completamente das amostras analisadas. Dessa forma, o presente projeto de pesquisa foi realizado com os objetivos de desenvolver um protocolo para induzir a germinação e a morfogênese estrutural in vitro de P. psidii, identificar genes candidatos relacionados à diferenciação das estruturas de infecção e de fatores de virulência, caracterizar os metabólitos presentes nas ceras cuticulares de folhas de Eucalyptus grandis resistentes e suscetíveis à ferrugem do eucalipto e desenvolver uma metodologia sensível e eficaz para detectar, quantificar e monitorar a presença de P. psidii em folhas de Eucalyptus grandis assintomáticas. Os dados obtidos no presente trabalho podem auxiliar a compreensão da interação planta-patógeno durante os estágios iniciais de infecção da ferrugem e colaboram para o entendimento da biologia do fitopatógeno para que no futuro sejam desenvolvidas melhores estratégias de controle de P. psidii em plantios de eucalipto. / Brazilian production of Eucalyptus spp. is one of the greatest in the world but it has been affected by Puccinia psidii Winter, the causal agent of eucalyptus rust. The comprehension of molecular mechanisms of pathogenicity and chemical composition of resistant and susceptible eucalyptus plants as well as having a molecular tool for early detection of the disease in field can be used for the development of improved control strategies against this phytopathogen. Molecular studies of P. psidii is limited because it is an obligate biotrophic fungus with limited in vitro development. Biotrophic fungi investigations are made mainly in planta at late developmental stages of the disease. This way, most information of early stages of infection as the development of specialized structures of biotrophic fungi are little understood. The study of early stages of the infection process of biotrophic fungi in planta is hampered by the high amount of plant material in relation to fungi material which is difficult to be obtained in an isolated form for analysis. In this work we developed a protocol to increase in vitro germination and structural differentiation of P. psidii and used this protocol to obtain isolated fungi material for the identification of candidate genes related with virulence factors and initial structural morphogenesis. Moreover, we analyzed the composition of metabolites present in the cuticular wax of leaves from resistant and susceptible E. grandis plants and developed a methodology for the detection of P. psidii in asymptomatic leaves of Eucalyptus grandis. Data obtained in this work help the comprehension of E. grandis-P.psidii interaction at early stages of the infection process and can be used for the development of improved control strategies of eucalyptus rust.

Le transport des bruts paraffiniques, et tout particulièrement leur remise en écoulement après un arrêt, dans de longues conduites sous-marines soumises à de basses températures, peut être difficile du fait de l'augmentation de leur viscosité. Le comportement rhéologique d´une huile paraffinique modèle, possédant des propriétés macroscopiques d'écoulement analogues à celles des bruts paraffiniques, est d'abord analysé en utilisant la vélocimétrie par imagerie par résonance magnétique associée à des mesures de contrainte de cisaillement au sein d'une géométrie Couette. Nous montrons que lors d'un écoulement forcé à température constante le matériau subit une déstructuration irréversible qui dépend de l'intensité du cisaillement. Ainsi la contrainte apparente critique permettant l'écoulement du matériau dépend de l'histoire thermique et d'écoulement subie par le matériau. Nous étudions ensuite le comportement rhéologique complet de deux bruts réels à partir de différents types de tests rhéométriques (fluages, redémarrage, régime permanent, changement brusque de vitesse) pour différentes histoires d'écoulement, notamment pendant la période de refroidissement. Le comportement détaillé du matériau en régime transitoire ainsi observé peut alors être modélisé. De plus les variations du seuil de contrainte en fonction de l'histoire thermique et de l'écoulement sont aussi décrites, ce qui nous donne le champ de contrainte seuil dans la conduite à l'état initial. Le modèle dans son ensemble est finalement implémenté dans un code de calcul pour simuler le redémarrage de l´écoulement d'un brut paraffinique dans une conduite réelle / Transporting waxy crude oils through long pipelines at low temperatures may be challenging, particularly its flow restart after a pipeline shut-in, due to its viscosity increase. The rheological behavior of a model waxy oil with macroscopic flow properties analogous to waxy crude oils is first analyzed using Magnetic Resonance Imaging velocimetry associated to stress measurements in a Couette geometry. While flowing at constant temperature, major irreversible structure break depending on shear intensity are observed. Thus, the critical apparent shear stress beyond which the material flows depends on the thermal and flow histories of the oil. Next, the rheological behavior of two waxy crude oils is studied using rheometrical tests (creep tests, flow restarts, abrupt changes of shear rate and steady flow) after different flow histories, notably during the cooling process. Then, those experimentally observed trends are modeled. Additionally, a comprehensive study of the yield stress in function of flow and temperature histories is presented. It provides an approach for describing the yield stress field inside the pipeline at the flow restart moment. Finally, the entire rheological model is implemented in the computational code for simulating waxy crude oils flow restart of a real scale pipeline

O Brasil é um dos principais produtores mundiais de Eucalyptus spp., mas a produção dessa cultura tem sido comprometida por perdas causadas pelo fungo Puccinia psidii Winter, agente causal da ferrugem do eucalipto. Compreender os mecanismos moleculares da patogenicidade desse fungo, conhecer a composição química de variedades de Eucalyptus spp. resistentes e suscetíveis ao fitopatógeno e ter em mãos uma ferramenta de diagnóstico precoce da doença são conhecimentos de fundamental importância para o desenvolvimento de estratégias de controle do fitopatógeno. Uma das principais barreiras que limitam o estudo molecular de P. psidii é o fato dessa espécie ser biotrófica obrigatória, tendo seu desenvolvimento in vitro limitado. Estudos de investigação a respeito de fungos biotróficos obrigatórios são realizados principalmente in planta e em estágios tardios da doença, deixando grande parte do conhecimento dos processos iniciais de infecção desconhecidos. Informações a respeito dos estágios iniciais da infecção, nos quais diversas estruturas típicas são formadas e podem indicar importantes características sobre fungos biotróficos, são de difícil acesso em estudos in planta em função da grande quantidade de material vegetal em relação à quantidade de material do fitopatógeno, que não é passível de ser removido completamente das amostras analisadas. Dessa forma, o presente projeto de pesquisa foi realizado com os objetivos de desenvolver um protocolo para induzir a germinação e a morfogênese estrutural in vitro de P. psidii, identificar genes candidatos relacionados à diferenciação das estruturas de infecção e de fatores de virulência, caracterizar os metabólitos presentes nas ceras cuticulares de folhas de Eucalyptus grandis resistentes e suscetíveis à ferrugem do eucalipto e desenvolver uma metodologia sensível e eficaz para detectar, quantificar e monitorar a presença de P. psidii em folhas de Eucalyptus grandis assintomáticas. Os dados obtidos no presente trabalho podem auxiliar a compreensão da interação planta-patógeno durante os estágios iniciais de infecção da ferrugem e colaboram para o entendimento da biologia do fitopatógeno para que no futuro sejam desenvolvidas melhores estratégias de controle de P. psidii em plantios de eucalipto. / Brazilian production of Eucalyptus spp. is one of the greatest in the world but it has been affected by Puccinia psidii Winter, the causal agent of eucalyptus rust. The comprehension of molecular mechanisms of pathogenicity and chemical composition of resistant and susceptible eucalyptus plants as well as having a molecular tool for early detection of the disease in field can be used for the development of improved control strategies against this phytopathogen. Molecular studies of P. psidii is limited because it is an obligate biotrophic fungus with limited in vitro development. Biotrophic fungi investigations are made mainly in planta at late developmental stages of the disease. This way, most information of early stages of infection as the development of specialized structures of biotrophic fungi are little understood. The study of early stages of the infection process of biotrophic fungi in planta is hampered by the high amount of plant material in relation to fungi material which is difficult to be obtained in an isolated form for analysis. In this work we developed a protocol to increase in vitro germination and structural differentiation of P. psidii and used this protocol to obtain isolated fungi material for the identification of candidate genes related with virulence factors and initial structural morphogenesis. Moreover, we analyzed the composition of metabolites present in the cuticular wax of leaves from resistant and susceptible E. grandis plants and developed a methodology for the detection of P. psidii in asymptomatic leaves of Eucalyptus grandis. Data obtained in this work help the comprehension of E. grandis-P.psidii interaction at early stages of the infection process and can be used for the development of improved control strategies of eucalyptus rust.

[pt] O petróleo é uma mistura complexa de hidrocarbonetos e pode conter em sua composição parafinas que, quando submetidas a baixas temperaturas, podem precipitar e gelificar, apresentando uma Tensão Limite de Escoamento. O estudo do comportamento do petróleo nesta condição é importante para a indústria porque, uma vez que o petróleo esteja gelificado, o reinício do escoamento pode demandar a adição de energia ao sistema, cujo dimensionamento para operação com altas pressões envolve custos elevados. Os valores de pressão de reinício de escoamento do petróleo gelificado encontrados no campo são frequentemente menores em relação aos valores calculados. O presente trabalho simulou o processo de reinício de escoamento através de uma bancada experimental que reproduz o resfriamento estático sofrido pelo petróleo parafínico em um duto submarino. Além disso, são apresentados dois métodos para cálculo da contração que resulta do resfriamentoe gelificação dos óleos parafínicos, objetivando verificar se existe uma relação entre a contração do fluido e a diferença entre a Tensão Limite de Escoamento e a tensão efetiva para iniciar o seu escoamento. O primeiro método proposto é o método da Pipeta, que consiste na utilização de uma pipeta, acoplada a um recipiente com controle de temperatura, para medição do volume de líquido. O segundo método proposto é o da célula PVT, que consiste na utilização de um sistema fechado de volume conhecido em que a medição da variação do volume de líquido é estimada pela variação do volume do gás à baixa pressão com a adoção da hipótese de gás ideal. Foram utilizados fluidos sintéticos, visando representar o petróleo parafínico, com diferentes concentrações de parafina, óleo mineral e querosene. A determinação da Tensão Limite de Escoamento foi feita a partir de testes de Creep. Os resultados mostraram que a contração do fluido é uma grandeza de difícil medição, com um alto grau de incerteza, mas que é possível estimar ordem de grandeza dessa contração para os fluidos estudados. / [en] Petroleum, as it is a complex mixture of hydrocarbons, may contain paraffinic compounds which, when subjected to low temperatures, can deposit and gel. The study of the behavior of petroleum in this condition is very important for the industry because, once the waxy crude oil gels, the restart process may demand extra energy addition to the system, whose dimensioning is expensive for high operation required pressures. Restart pressure values of the gelled oil found from laboratory tests often show a significant difference from the real values found in the field. In order to compare the yield stress and the effective stress, the present work simulated the flow restarting process through an experimental rig to reproduce the static cooling applied to a pipeline with waxy crude oil. In addition, two methods are presented for calculating the thermal shrinkage formed during the cooling and gelation of the waxy crude oils, in order to verify if there is a relationship between the shrinkage and the difference between the yield stress and the effective stress to start flowing. The first method proposed is the Pipette method, which consists of the use of a pipette, coupled to a container with temperature control, to measure the volume of liquid. The second method proposed is the PVT cell method, which consists of the use of a closed system of known volume in which the measurement of the liquid volume variation is estimated by the variation of the gas volume at low pressure with the adoption of the Ideal gas hypothesis. The fluids selected for the studies to represent paraffinic oil were laboratory-synthesized fluids with different concentrations of paraffin, mineral oil and kerosene, and they were characterized rheologically by stress ramp and creep tests for the determination of the yields stress. The results showed that thermal shrinkage is a difficult quantity to measure, which gives it a high degree of uncertainty, but it is possible to estimate the magnitude order of the thermal shrinkage for the fluids studied.

Le transport des bruts paraffiniques, et tout particulièrement leur remise en écoulement après un arrêt, dans de longues conduites sous-marines soumises à de basses températures, peut être difficile du fait de l'augmentation de leur viscosité. Le comportement rhéologique d´une huile paraffinique modèle, possédant des propriétés macroscopiques d'écoulement analogues à celles des bruts paraffiniques, est d'abord analysé en utilisant la vélocimétrie par imagerie par résonance magnétique associée à des mesures de contrainte de cisaillement au sein d'une géométrie Couette. Nous montrons que lors d'un écoulement forcé à température constante le matériau subit une déstructuration irréversible qui dépend de l'intensité du cisaillement. Ainsi la contrainte apparente critique permettant l'écoulement du matériau dépend de l'histoire thermique et d'écoulement subie par le matériau. Nous étudions ensuite le comportement rhéologique complet de deux bruts réels à partir de différents types de tests rhéométriques (fluages, redémarrage, régime permanent, changement brusque de vitesse) pour différentes histoires d'écoulement, notamment pendant la période de refroidissement. Le comportement détaillé du matériau en régime transitoire ainsi observé peut alors être modélisé. De plus les variations du seuil de contrainte en fonction de l'histoire thermique et de l'écoulement sont aussi décrites, ce qui nous donne le champ de contrainte seuil dans la conduite à l'état initial. Le modèle dans son ensemble est finalement implémenté dans un code de calcul pour simuler le redémarrage de l´écoulement d'un brut paraffinique dans une conduite réelle / Transporting waxy crude oils through long pipelines at low temperatures may be challenging, particularly its flow restart after a pipeline shut-in, due to its viscosity increase. The rheological behavior of a model waxy oil with macroscopic flow properties analogous to waxy crude oils is first analyzed using Magnetic Resonance Imaging velocimetry associated to stress measurements in a Couette geometry. While flowing at constant temperature, major irreversible structure break depending on shear intensity are observed. Thus, the critical apparent shear stress beyond which the material flows depends on the thermal and flow histories of the oil. Next, the rheological behavior of two waxy crude oils is studied using rheometrical tests (creep tests, flow restarts, abrupt changes of shear rate and steady flow) after different flow histories, notably during the cooling process. Then, those experimentally observed trends are modeled. Additionally, a comprehensive study of the yield stress in function of flow and temperature histories is presented. It provides an approach for describing the yield stress field inside the pipeline at the flow restart moment. Finally, the entire rheological model is implemented in the computational code for simulating waxy crude oils flow restart of a real scale pipeline

Twenty years ago, Chang et al. (1998) introduced the three-yield stresses concept (dynamic, static and elastic limits) to describe yielding of waxy crude oils cooled below the wax appearance temperature (WAT). At the time, the limits in rheological instruments were such that they never actually measured the elastic-limit, a key fundamental property. Using modern instruments, this research succeeds in recording for the first time the entire yielding process down to stresses of 10-7 Pa and shear rate of 10-6 min-1 as a function of temperature, cooling rate and stress loading rate using two waxy oils of different origins and wax content. A four-yield stress model is established using derivative data (dynamic fluidity and failure acceleration). In addition, calorimetry (DSC) and microscopy (CPM) helped extract WAT, the gel and pour points and link gel crystal structure and its yielding and breakage to rheological properties. The yielding stresses measured rheologically were tested in laboratory pipelines at two diameter scales, 6.5mm and 13.5mm to compare stresses in uniform and non-uniform cooling. It is demonstrated that rheological instruments can only predict gel breaking pressure when the cooling rate is low, i.e. yielding at the pipe wall. A complementary heat transfer study was performed on a section of pipe statically cooled, both experimentally and theoretically to predict the gel front-liquid oil interface that develops in industrial pipeline where gel breaking occurs. This key information together with rheological data provide the means to predict accurately restart pressures of shut gelled pipelines that have eluded previous research. / Ministry of Higher Education of the Libyan Government

<p>Maize is one of the top sources of food starch. Industrial use of starch is mostly in its native form and used due to their functional and structural properties. Native starch properties and functionalities have been altered using chemical. An alternative for the development of native starch substituents with desirable starch properties is the use of mutagenesis techniques to increase genetic variation in maize kernels. With this approach, a highly diverse library of native starches with different properties are produced. Traditional analysis of the functional and structural properties requires generous amounts of material as well as a time-consuming and costly breeding process to obtain enough kernels. To address this difficulty, high-throughput techniques are proposed for studying starch properties and functions which includes a 1) single kernel sampling method for the isolation of milligrams of starch, and techniques for studying starch based on functional properties, 2) retrogradation and 3) shear resistance, using low-volume low-concentration starch pastes.</p><p>First, three mechanical approaches were evaluated for the collection of endosperm samples from individual kernels: razor blade, 1.5 mm drill bit, and trephine bur. Furthermore, two methods for the isolation of crude starch from endosperm samples (steeping method and combination of proteases and sonication) were compared. In this study, the mechanical approaches were evaluated using the recovery rate, throughput, and germination rate of sampled kernels. Moreover, yield determination, particle size distribution, and morphological evaluation using a light microscope were performed on crude starch isolated from the endosperm samples. The use of trephine bur to collect endosperm samples and isolation of crude starch using protease digestion and sonication showed the best combination for a high-throughput setting. </p><p>Second, a high-throughput technique using milligram sample for the screening of retrogradation-resistant starch was evaluated by comparing two spectrophotometric techniques: turbidity method and molecular rotor (MR). MRs are fluorescent probes with high sensitivity to the viscosity of their environment, polarity of the media, molecular crowding, and free volume. After excitation, MRs relax through rotational movement and reduces the emission of fluorescence. In this study, hydroxypropylated waxy corn starch (WCS) and hydroxypropylated normal corn starch (NCS) were used and their retrogradation kinetics was compared with retrogradation kinetics of native WCS and NCS. </p><p>It was found that the molecular rotor 9-(2-carboxy-2-cyaovinyl)-julolidine (CCVJ) was effective to sense changes during slow retrogradation of amylose-containing starch pastes. Development of elastic modulus of retrograded NCS pastes obtained from dynamical rheology showed high correlation with the development of fluorescence intensity of the CCVJ. Furthermore, rate of retrogradation using fluorescence intensity was affected by the introduction of a retrogradation inhibitor, hydroxypropyl groups. Accelerated retrogradation of low-concentration WCS pastes was measured using the turbidity method and fluorescence intensity of CCVJ in a microplate. Accelerated retrogradation was performed by subjecting the low-concentration WCS pastes to six freeze-thaw cycles of -20 ºC for 1 hour and 30 ºC for 1 hour. Overall, development of turbidity resulted in the more sensitive technique to detect rate of retrogradation of amylopectin-containing starch. </p><p>The last part of this research studied the use of CCVJ as a technique to identify shear-resistant starch in starch slurries using milligram sample. For this purpose, WCS was cross-linked with sodium trimetaphosphate (STMP) and phosphoryl chloride (POCl₃). Low-volume starch slurries having CCVJ were prepared ranging from 0.5% to 1% starch concentration in a 96-well PCR plates and subjected to heat and shear treatments. It was found that fluorescence intensity measured in native WCS pastes were the lowest. Furthermore, fluorescence intensity of the CCVJ in the gelatinized starch increased as the amount of cross-linker increased in the cross-linked WCS. After shear treatments, the same trend in fluorescence intensity increase was recorded in all the crosslinked WCS. Results obtained using fluorescence intensity were compared with rapid viscosity analyzer (RVA) and images from microscope. Results obtained from both techniques corroborated the findings using fluorescence intensity.</p><p>In general, the findings of this research provide new insights into the possibilities of developing a high-throughput screening platform of milligram starch sample based on their physical properties. </p>

[pt] Esta tese é sobre a reologia de óleos parafínicos crus. Um protocolo baseado na literatura relevante é desenvolvido para garantir que históricos térmico e de cisalhamento bem definidos sejam impostos em amostras que serão submetidas à medições reológicas. Com este protocolo, uma caracterização reológica quase completa de um óleo parafínico cru brasileiro é executada . Quatro experimentos reométricos são realizados, a saber, escoamento em estado estacionário, taxa de cisalhamento constante, tensão constante e rampa oscilatória de amplitude de tensão. Propriedades reológicas importantes, tais como, viscosidade, tensão limite de escoamento e módulos elástico e viscoso são medidos com o auxílio de técnicas diferentes em uma ampla faixa de condições. Além disso, uma comparação entre essas técnicas de medição é realizada. O processo de quebra da microestrutura do óleo parafínico brasileiro, assim como os efeitos na reologia do histórico do material e do tempo de repouso isotérmico são estudados. Fenômenos interessantes são observados, incluindo bifurcação da taxa de cisalhamento, dependência da tensão limite com os históricos térmico e de cisalhamento e independência dos resultados de regime permanente com relação à condição inicial após o resfriamento. Por fim, oportunidades para futuros desenvolvimentos e investigações são enfatizadas. / [en] This thesis deals with the rheology of waxy crude oils. A protocol based on the relevant literature is developed to guarantee well defined shear and thermal histories to waxy crude oil samples to be submitted to rheological measurements. With this protocol, a fair complete rheological characterization of a Brazilian waxy crude oil is performed. Four rheometric experiments, namely steady-state flow, constant shear rate, constant shear stress, and dynamic-stress-amplitude sweep are carried out. Important rheological properties, such as, viscosity, yield stress, and storage and loss moduli are measured with di↵erent techniques in a wide range of conditions and a comparison between the techniques is presented. The yielding as well as the history effects and the e↵ects of isothermal holding time on the microstructure and rheology of a Brazilian waxy crude oil are investigated. Interesting phenomena are observed, including bifurcation of shear rate, dependence of the yield stress with thermal and shear histories, and independence of the steady-state results with the post-cooling initial condition of the experiment. At last, opportunities for further developments are highlighted.

[pt] Durante a gelificação por parafina, a rede de cristais de parafina modifica o comportamento do óleo cru. Ele muda de um material newtoniano de baixa viscosidade para um material com dependência temporal e de alta viscosidade com tensão limite do escoamento. Com isto, é totalmente desafiador descobrir a pressão minima de início do fluxo de petróleo gelificado com uma microestrutura tão complexa. Através da minha dissertação de mestrado, investigamos dois materiais viscoplásticos: um gel de cabelo com uma tixotropia desprezível e uma suspensão aquosa tixotrópica 2 por cento de laponita para imitar o início de fluxo de óleos gelificados. Para ambos os materiais, o gradiente de pressão axial mínimo necessário para o início do fluxo foi medido e os valores medidos estavam de acordo com a previsão do balanço de força convencional. Por outro lado, os casos da indústria exibiram que o balanço de força mencionado acima leva a uma superestimação da pressão mínima inicial. Em alguns estudos, uma explicação elicitada é o comportamento tixotrópico do petróleo gelificado, mas nossos resultados acima mencionados serviram para refutá-lo. Durante a primeira parte da minha tese de doutorado, buscamos verificar por laboratório porque o balanço de força não se aplica ao petróleo gelificado, em seguida, buscamos uma explicação fisicamente adequada para essa discrepância e também uma maneira confiável de prever a pressão mínima de início do escoamento. Nesta linha, mostramos o efeito do encolhimento do petróleo gelificado na discordância entre a tensão limite estática de escoamento e o gradiente de pressão mínimo necessário para iniciar o fluxo, através da reometria e do fluxo de fluido em um tubo. Em seguida, introduzimos uma equação de balanço de força modificada com o efeito de encolhimento incluído para obter o melhor estimação da pressão minima de início de escoamento. Outro elemento essencial sobre o início de escoamento de petróleo gelificado é descobrir uma estratégia confiável para modelar matematicamente a reologia do material. Na maioria dos modelos que visam prever o comportamento reológico de petróleo gelificado, as mudanças da microestrutura durante o fluxo são consideradas tixotrópicas; dependência temporal reversível. Porém, observamos em nossos experimentos com histórias de fluxo e térmicas bem controladas que o caráter irreversível da dependência temporal é bastante evidente. Assim, na segunda parte da tese, propomos um modelo baseado no desenvolvimentos anteriores de Souza Mendes e colaboradores que considera a dependência temporal irreversível observada experimentalmente para petróleo gelificado. A capacidade preditiva do modelo proposto é então avaliada através de comparações com dados experimentais. / [en] Throughout the wax gelation, the network of parafinn crystals modifies the behavior of waxy crude oil. It changes from a low viscosity Newtonian to a high viscosity time-dependent material with yield strength. Now, it is totally challenging to find out the restart pressure for gelled crude oil ow with such a complex microstructure. Through my Master s dissertation, we investigated two viscoplastic materials, namely a hair gel with a negligible thixotropy and a quite thixotropic 2 percent aqueous suspension of Laponite to mimic the startup flow of waxy crude oils. For both materials, the minimum axial pressure gradient required for the onset of flow was measured, and the measured values were in good agreement with the prediction of a conventional force balance. On the other hand, industry cases have exhibited that the just mentioned force balance leads to an overestimation of the minimum startup pressure gradient. In some studies, an elicited explanation is the thixotropic behavior of the gelled crude, but our results above-mentioned served to falsify it. Over the first part of my PhD thesis, we aimed to verify in the laboratory that why the force balance does not hold for gelled crude oil and then we sought a physically proper explanation for this discrepancy and also a reliable way to predict the minimum startup pressure gradient. Along these lines, we show the role of gelled crude oil s shrinkage in the discordance between static yield strength and required minimum pressure gradient to onset the flow, through rheometry and fluid flow in a tube. Then, we introduce a modified force balance equation with the role of shrinkage included to best estimate the minimum restart pressure gradient. Another essential element through the restart flow of gelled waxy crude is to find out a reliable strategy to mathematically model the material s rheology. In most models that aim at predicting the rheological behavior of gelled waxy crude oil, the microstructure changes during ow are assumed to be thixotropic (reversible time dependent). But, we observed in our experiments with well-controlled flow and thermal histories that the irreversible character of time dependence is quite evident. Thus, in the second part of thesis we propose a model based on previous developments by Souza Mendes and co-workers that accounts for the irreversible time dependence observed experimentally in a waxy crude oil. The predictive capability of the proposed model is then assessed via comparisons with experimental data.

Today, the focus lies on the state of the environment and how we can choose more sustainable alternatives to oil based materials. One material of interest is microfibrillated cellulose (MFC).The microfibril exhibits interesting properties, which one is its excellent barrier properties, that is expected to come in good use for the conversion to a more sustainable society. It is believed that the use of biobased barriers will increase with these new materials and MFC is showing promising results. But in order to develop the material to its full potential, it is important to investigate how MFC behaves in different situations, which can be examined with rheological measurements. The aim of the thesis is to examine how the rheological properties of suspensions containing MFC are affected by temperature and time storing and how the learning from this work can be used for influencing dispersion properties. Four samples were investigated, containing different amounts of MFC and modified waxy maize starch. The samples were analyzed with a dynamic rotational rheometer (Kinexus Pro +) with a splined cup and bob. The following steps were included in the method development used in this work: sample preparation, the repeatability, rest time and statistical analysis. An oscillatory shear and steady shear measurement was performed on the samples, and selected samples were studied with microscopy. The results show that the temperature has affected the samples. The shear viscosity of all samples decreased with increasing temperature and the samples followed the temperature dependence of Arrhenius' equation. For samples containing MFC, the structure was affected, and the initial viscosity was not recovered. The complex viscosity did also decrease at the beginning to then suggestively increase, creating a stronger network at higher temperatures. With the raised temperature the bonding between the fibrils became weaker, which in turn made the dispersion less viscous. Then, depending on the applied force, the shear viscosity and complex viscosity acted differently. To conclude, both the shear viscosity and the complex viscosity in these dispersions containing MFC are dependent on the temperature and time storing. By the learnings from this work, a method has been developed to understand how to use temperature and storing time to lower the shear viscosity and lower, or increase, the complex viscosity. / Idag ligger det ett stort fokus på miljöns tillstånd och hur vi kan välja mer hållbara alternativjämfört med oljebaserade material. Ett material av intresse är mikrofibrillerad cellulosa (MFC).Denna mikrofibrill besitter intressanta egenskaper, varav en är enastående barriäregenskaper,som förväntas komma till god användning i omställningen till ett mer hållbart samhälle. Det tros att biobaserade barriärer kommer att användas mer i dessa nya material och här visar MFC lovande resultat. Men för att kunna utveckla materialet till sin fulla potential är det viktigt att undersöka hur MFC beter sig i olika situationer, som kan undersökas genom reologiska mätningar. Syftet med arbetet är att undersöka hur de reologiska egenskaperna för suspensioner innehållande MFC påverkas av temperatur och lagringstid samt hur lärdomen från det här arbetet kan användas för att påverka dispersionsegenskaper. Fyra prover undersöktes,innehållande olika mängd MFC och modifierad majsstärkelse. Proverna analyserades med en dynamisk rotations reometer (Kinexus Pro +) med räfflad kopp och bob. Följande steg ingick i metodutvecklingen som användes i detta arbete: provberedning, repeterbarhet, vilotid och statistisk analys. En oscillerande skjuvning och jämn skjuvmätning utfördes på de olika proverna samt att utvalda prover studerades med mikroskopi. Resultatet visade att temperaturen hade påverkat proverna. Skjuvviskositeten för alla prover minskade med en ökande temperatur och proverna följde temperaturberoendet av Arrhenius ekvation. För prover innehållande MFC påverkades strukturen och startviskositeten återficks inte. Den komplexa viskositeten minskade också till en början för att sedan suggestivt öka, vilket skapade ett starkare nätverk vid högre temperaturer. Med en högre temperatur blev bindningarna mellan fibrillerna svagare, vilket bidrog att dispersionerna blev mindre viskösa. Beroende på den applicerade kraften, verkade skjuvviskositeten och den komplexa viskositeten olika. Slutsatsen var att både skjuvviskositeten och den komplexa viskositeten i dessa prover innehållande MFC beroende av temperaturen och lagringstid. Från lärdomen av arbetet har en metod tagits fram för att kunna använda temperatur och lagringstid för att sänka skjuvviskositeten och sänka, eller öka, den komplexa viskositeten.