The present thesis explores the volumetric and transport properties of complex fluid mixtures under pressure in order to develop a better, more holistic understanding of the relationship between the volumetric properties, derived thermodynamic properties, and viscosity. To accomplish this broad objective, two different categories of fluid mixtures were examined using a combination of experimental data and models. These included base oils and their mixtures with polymeric additives, used in lubricants and ionic liquids, with cosolvent addition, for use in biomass and polymer processing. Experimental density data were collected using a variable-volume view-cell at pressures up to 40 MPa and temperatures up to 398 K. A unique high pressure rotational viscometer was developed to study the effect of pressure, temperature, and shear rate on viscosity while also allowing for the simultaneous examination of phase behavior. Viscosity data were collected at pressures up to 40 MPa, temperatures up to 373 K, and shear rates up to 1270 s-1. Experimental density and viscosity data were fit to a pair of coupled model equations, the Sanchez-Lacombe equation of state and the free volume theory respectively. From density, derived thermodynamic properties, namely isothermal compressibility, isobaric thermal expansion coefficient, and internal pressure, were calculated. By generating these models, viscosity could be viewed in terms of density, allowing for a direct link with thermodynamic properties. In the first part of the study, the effect of composition on density, thermodynamic properties, and viscosity was examined for base oils used in automotive lubricants. Six different base oils, four mineral oils and two synthetic oils, were studied to develop a better understanding on how the thermodynamic properties, particularly isothermal compressibility and internal pressure, vary with the concentration of cyclic molecules in the oil stock. Isothermal compressibility was found to decrease with cycloalkane content, while internal pressure increased. Additionally, the effect of two different polymeric additives on the volumetric properties and viscosity of a base oil composed of poly(α olefins) was examined. Both additives are polymethacrylate based, one with amine functionality, and are used as viscosity index modifiers in engine oils and automatic transmission fluids. The polymer with amine functionality was found to have a significant effect on internal pressure, seen as a large drop at high polymer concentration (7 mass percent), due to the addition of repulsive intermolecular interactions. In the second part of the study, six ionic liquids with the 1-alkyl-3-methylimidazolium cation and their mixtures with ethanol were examined. Two anions were used, chloride and acetate. The effect of ethanol addition on the derived thermodynamic properties and viscosity was studied in terms of chain length of the alkyl group on the cation. In addition, a method of estimating Hildebrand solubility parameter was employed, allowing for solubility parameter to be put in terms of pressure, temperature, and composition. The effect of cosolvent addition on the thermodynamic properties was changed by the length of the alkyl group on the cation. As the cation became bulkier, anion-cation interactions weakened, allowing for an increase in the anion-cosolvent interactions. / Doctor of Philosophy / The present thesis aims to understand both the density and viscosity of various fluid mixtures at high pressures and temperatures through both experiments and modeling. By studying these properties simultaneously, a more holistic view of a fluid can be developed to predict its usefulness for a specific application. This is especially important in the case of fluid mixtures, where, in addition to temperature and pressure, composition needs to be taken into account. To accomplish the experimental portion of this work, a new high pressure rotational viscometer was developed to measure viscosity as a function of temperature and pressure in conjunction with a preexisting technique for measuring density. This experimental data was used to create models, allowing for a better understanding of the effect of temperature, pressure, and composition on both density and viscosity along with certain thermodynamic properties. In the first part of the study, oils and additives used to make lubricants with automotive applications, such as engine oils and automatic transmission fluids, were studied. By studying the properties of these mixtures under pressure, a better understanding of how properties key to lubricant effectiveness are related to temperature, pressure, and composition can be developed. In the second part of the study, ionic liquids, salts with melting points below 100oC, and their mixtures with ethanol were studied. Ionic liquids have unique properties and have been studied for use in batteries, polymer processing, biomass processing, and gas capture. Due to the wide range of potential ionic liquids with various properties that can be made, these salts have been described as tailorable solvents. By adding an additional solvent, the resulting mixture can be tuned through temperature, pressure, and composition. Using the set of tools employed in the present work, important properties for process design were calculated. In particular, the Hildebrand solubility parameter was estimated as a function of temperature, pressure, and composition. The solubility parameter is a useful tool in predicting whether or not a material will dissolve in the solvent of choice.

Yes / A detailed steady-state catalytic-reforming unit (CRU) reactor process model is simulated in this work, and for the first time, different compressibility Z factor correlations have been applied using gPROMS software. The CRU has been modeled and simulated with the assumption that the gas phase behaves like an ideal gas. This is assumed for the four reactors in series and for different conditions of hydrogen–hydrocarbon ratio (HHR), operating temperature, and pressure. The results show that the Z factor varies at every point along the height of the reactors depending on reaction operating pressure, temperature, and HHR ratio. It also shows that the magnitude of deviation from ideal gas behaviour can be measured over the reactor height. The Z factor correlation of Mahmoud (J Energy Resour Technol Trans ASME 136:012903, 2014) is found to be suitable for predicting the Z factor distribution in the reactors.

Yes / Detailed design of pharmaceutical tablets is essential nowadays in order to produce robust tablets with tailor-made properties. Compressibility and compactibility are the main compaction properties involved in the design and development of solid dosage forms. The data obtained from measured forces and displacements of the punch are normally analysed using the Heckel model to assess the mechanical behaviour of pharmaceutical powders. In this paper, we present a technique for shape modelling of pharmaceutical tablets based on the PDE method. We extended the formulation of the PDE method to a higher dimensional space in order to generate a solid tablet and a cuboid mesh is created to represent the tablet’s components. We also modelled the displacement components of a compressed PDE-based representation of a tablet by utilising the solution of the axisymmetric boundary value problem for a finite cylinder subject to a uniform axial load. The experimental data and the results obtained from the developed model are shown in Heckel plots and a good agreement is found between both. / Available in full text since 5th Feb 2013 following the publisher's embargo period.

[pt] Um grande movimento de massa ocorrido em 28 de Março de 2013 no Porto de Santana, na região da foz do Rio Amazonas, no Amapá, motivou o estudo das características de compressibilidade de argilas moles a partir do material reconstituído. Os solos naturais diferem dos solos reconstituídos devido à influência da micro e macroestrutura. O conceito de linha de compressão intrínseca (ICL) proposto por Burland (1990) permite uma avaliação quantitativa da diferença no comportamento de compressão do solo nestas duas condições. Neste estudo, são analisados dois depósitos de solo mole da costa brasileira (Tijucas, SC e Porto de Santana, AP) e uma mistura artificial obtida em laboratório com caulim e bentonita na proporção de 98:2 em peso. Um total de 8 amostras são reconstituídas com teor de umidade igual a 1,25 vezes o limite de liquidez e submetidas a ensaios convencionais de adensamento (SIC - standard incremental consolidation tests). As curvas de adensamento das amostras reconstituídas apresentam boa concordância com a ICL proposta por Burland (1990), principalmente no intervalo de tensões de 100 a 1.000kPa. As análises evidenciam a presença de estrutura do solo natural, sendo encontrada uma maior influência nas argilas do Porto de Santana, as quais apresentam índice de vazios normalizado (Iv) de até 1,85. As correlações empíricas para obtenção dos parâmetros intrínsecos de compressibilidade e100 e Cc propostas por Burland (1990) não apresentaram bons ajustes para os resultados experimentais aqui reportados. / [en] A large mass movement occurred on March 28, 2013 at the Port of Santana, in the region of the mouth of the Amazon River in Amapá, motivated the study of compressibility characteristics of soft clays from the reconstituted material. Natural soils differ from reconstituted soils due to the influence of micro and macrostructure. The concept of the intrinsic compression line (ICL) proposed by Burland (1990) allows a quantitative evaluation of the difference in soil compression behavior in these two conditions. In this study, two soft clay deposits of the Brazilian coast (Tijucas, SC and Porto de Santana, AP) were analyzed and an artificial mixture made in the laboratory with kaolin and bentonite in the proportion of 98: 2 by weight. A total of 8 samples are reconstituted with moisture content equal to 1.25 times the liquid limit and subjected to conventional consolidation tests (SIC - standard incremental consolidation tests). The consolidation curves of the reconstituted samples show good agreement with the ICL proposed by Burland (1990), especially in the stress range of 100 to 1,000 kPa. The analyzes show the presence of natural soil structure, with a higher influence in the Santana Port clays which have a normalized void index (Iv) up to 1.85. The empirical correlations to obtain the intrinsic parameters of compressibility e 100 and Cc proposed by Burland (1990) did not present good adjustments for the experimental results here reported.

No Brasil, a partir do século XX, cada vez mais o transporte ferroviário foi sendo substituído pelo transporte viário. Por conta disso, a demanda por obras de infraestrutura viária é cada vez maior, tanto para transporte de pessoas, mas, principalmente, para transporte de cargas. Outro fator que indica a maior demanda por obras de infraestrutura é o crescimento da economia e da população. A fim de garantir segurança na construção e, principalmente, na operação, são necessárias investigações geológicas-geotécnicas, para caracterizar e estimar parâmetros do material que estão sendo utilizados em obra, para prever seu comportamento. Os parâmetros de resistência ao cisalhamento têm grande importância na condição de estabilidade dos aterros, tanto em fase de construção, em que também se sobressai o parâmetro de pressão neutra B?, quanto em fase de operação, enquanto os parâmetros de deformabilidade são essenciais na estimativa de recalques na fase operacional dos aterros Este trabalho tem como objetivo apresentar estimativas dos parâmetros de resistência ao cisalhamento (ângulo de atrito e a coesão), de deformabilidade de compressibilidade, expansibilidade e de pressão neutra do material utilizado nos aterros dos lotes 14 e 15 do Rodoanel Norte em São Paulo. Os materiais estudados possuem diferentes litologias, entre as quais pode-se citar materiais provenientes de filitos, granitos, ultramilonitos e metabásicas. Assim, foi feito um levantamento dos dados de ensaios de laboratório disponíveis, a saber, ensaios de caracterização, de compactação Proctor Normal, ensaios triaxiais UU não saturado, CU saturado e PN e ensaios de adensamento edométrico. Os ensaios mecânicos foram feitos em amostras compactadas com desvios de umidade em relação à ótima variando entre 0% até 4 e mesmo 5%, mantendo o grau de compactação em torno de 95%. Por fim, os parâmetros de resistência, deformabilidade, compressibilidade e pressão neutra estimados foram comparados por litologia com parâmetros encontrados na literatura técnica, podendo assim serem utilizados em outros projetos em regiões próximas ou que empreguem materiais de mesma origem ou litologia. / In Brazil, from the twentieth century, the rail transportation was replaced by road transportation. Because of that, the demand for road infrastructure is increasing, for the transportation of people and for the freight transportation. Another factor that indicates the greater demand for infrastructure is the growth of the economy and the population. To guarantee safety in the construction and in the operation, geological-geotechnical investigations are necessary to characterize and estimate parameters of the material, that is being used in the civil works to predict its behavior. The parameters of shear strength have a great importance in the condition of stability of the embankments, in construction phase, as the neutral pressure parameter, B?, and in phase of operation, while the deformability parameters are essential in the estimation of settlements in the operational phase of the embankments. The objective of this dissertation is to present estimates of the parameters of shear strength (angle of friction and cohesion), deformability, expansibility, compressibility and neutral pressure of the material used in embankments of two parts of Rodoanel Norte in São Paulo. The studied materials have different lithologies: phyllite, granitic gneisses, ultramilonites and metabasites. Thus, a data survey of the laboratory tests results was done, namely, characterization tests, Normal Proctor compaction text, triaxial UU unsaturated, saturated CU and PN and oedomometric densification tests. The mechanical tests were done on compacted samples with deviations of water content from the optimum ranging from 0% up to 4 and even 5%, maintaining the degree of compaction around 95%. Finally, the estimation of the shear strength parameters, deformability, compressibility, expansibility and neutral pressure were compared by lithology with parameters found in the technical literature so that it can be used in other projects in nearby regions or using materials of the same origin or lithology.

Este trabalho apresenta um estudo das propriedades de resistência e de deformabilidade dos resíduos sólidos urbanos (RSU). Amostras de resíduo de diferentes idades, obtidas no aterro metropolitano centro (Salvador-BA), foram submetidas a ensaios de compressão triaxial e de compressão confinada em equipamentos de grandes dimensões. Os resultados dos ensaios triaxiais demonstraram que os RSU não apresentam pico ou valor máximo de resistência, mesmo para grandes deformações. Os parâmetros de resistência foram obtidos a partir de níveis específicos de deformação. Não foi possível observar a influência do processo de decomposição na resistência ao cisalhamento do RSU, porém observou-se um aumento de resistência com o acréscimo do peso específico. Dos ensaios em resíduos sem fibras (plásticos, têxteis, etc), verificou-se uma redução nos parâmetros de resistência em comparação com os do resíduo composto, indicando a grande influência do material fibroso no comportamento mecânico do RSU. Ensaios não drenados mostraram grande desenvolvimento de pressão neutra, que provocaram distorções nas envoltórias efetivas, fazendo com que os ângulos de atrito obtidos fossem maiores que aqueles obtidos nos ensaios drenados. Duas amostras de RSU novo foram submetidas a ensaios de compressão confinada. Uma das amostras foi submetida à recirculação de chorume para avaliação do efeito da decomposição nos recalques medidos. Os resíduos apresentaram uma rápida compressão primária e deformações secundárias que se desenvolveram durante todo o ensaio, sem tendência de estabilização. A recirculação de chorume não provocou acréscimos nas deformações secundárias, provavelmente devido ao pequeno volume de chorume utilizado e ao ambiente não favorável à decomposição. / This work deals with the shear strenght and compressibility properties of municipal solid waste (MSW). Four years old end new waste samples recovered from metropolitan center sanitary landfill (Salvador, Brazil) were submitted to triaxial and confined compression tests using large dimension specimens. Triaxial test results showed that a peak or an ultimate shear stress value was not reached even for the largest deformation attained in the tests and thus, shear strength parameters were derived to different strain levels. It was shown that the shear strength was not too much affected by waste decomposition process, but increased with the waste unit weight. The waste without plastic fibres tended to show reduced shear strength as compared to the whole waste, showing the large influence of this materials on MSW mechanical behavior. Undrained tests showed large pore pressures build up and tended to yield effetive shear strength parameters larger than that obtained in drained tests. Confined compression tests were performed using samples of fresh waste with and without leachate recirculation to investigate the influence of the waste degradation on MSW compressibility. It was observed that the waste showed a quick primary compression and secondary compression that extended throughout the test period without reaching equilibrium. The leachate recirculation did not increase secondary defomation probably by the low volume of leachate used during the test and due the ambient conditions not suitable to the degradation.

Dans le cadre d’une réduction d’émission de gaz à effets de serre, la possibilité d’introduire une quantité de biodiesel dans les diesels dits « traditionnels », c’est-à-dire issus des énergies fossiles est une possibilité envisagée par les groupes pétroliers. Cependant, la connaissance des propriétés thermophysiques des fluides sous pression est mince, que ce soient des mélanges ou des corps purs, où peu de données expérimentales existent. Dans le cadre de cette thèse, une nouvelle sonde de mesures des propriétés acoustiques sous pression a été développée dans le but de réaliser des mesures de toutes les propriétés thermophysiques en utilisant un volume d’échantillon minimum grâce à la fois, à une technique de mesure de vitesse du son via l’utilisation de transducteurs piézoélectriques et de viscosité via l’utilisation de cristaux de quartz. Si cette thèse s’inscrit dans une démarche visant à travailler sur les biodiesels et leurs corps purs, la sonde développée au cours de ces trois ans est amenée à être expérimentée dans un avenir proche, sur des fluides directement issus de champs pétroliers et/ou de synthèses, sous pression afin de déterminer des propriétés thermophysiques mais également des équilibres de phase sous pression. / Key words : speed of sound, compressibility, density, viscosity, biodiesel, methyl and ethyl esters, pressure.In the context of reduction of exhaust gases, the possibility to introduce a quantity of biodiesel inside traditional diesel from fossils fuels is one of the step taken by petroleum societies. However, the knowledge of thermophysical properties of fluids is scant, for mixture and pure compounds, where few data exist. In this work, a new measurement probe under high pressure, has been developed in the aim to realize measurements of thermophysical properties using a minimum volume sample, thanks a technique of measurements of speed of sound using piezoelectric transducers and viscosity using quartz crystals. If this thesis is focused on the work on the biodiesels and their pure components, this probe will be experimented, in a near future, on fluids directly from oil fields and/or syntheses ones under pressure, in the aim to determine thermophysical properties but also phase equilibria.

No Brasil, a partir do século XX, cada vez mais o transporte ferroviário foi sendo substituído pelo transporte viário. Por conta disso, a demanda por obras de infraestrutura viária é cada vez maior, tanto para transporte de pessoas, mas, principalmente, para transporte de cargas. Outro fator que indica a maior demanda por obras de infraestrutura é o crescimento da economia e da população. A fim de garantir segurança na construção e, principalmente, na operação, são necessárias investigações geológicas-geotécnicas, para caracterizar e estimar parâmetros do material que estão sendo utilizados em obra, para prever seu comportamento. Os parâmetros de resistência ao cisalhamento têm grande importância na condição de estabilidade dos aterros, tanto em fase de construção, em que também se sobressai o parâmetro de pressão neutra B?, quanto em fase de operação, enquanto os parâmetros de deformabilidade são essenciais na estimativa de recalques na fase operacional dos aterros Este trabalho tem como objetivo apresentar estimativas dos parâmetros de resistência ao cisalhamento (ângulo de atrito e a coesão), de deformabilidade de compressibilidade, expansibilidade e de pressão neutra do material utilizado nos aterros dos lotes 14 e 15 do Rodoanel Norte em São Paulo. Os materiais estudados possuem diferentes litologias, entre as quais pode-se citar materiais provenientes de filitos, granitos, ultramilonitos e metabásicas. Assim, foi feito um levantamento dos dados de ensaios de laboratório disponíveis, a saber, ensaios de caracterização, de compactação Proctor Normal, ensaios triaxiais UU não saturado, CU saturado e PN e ensaios de adensamento edométrico. Os ensaios mecânicos foram feitos em amostras compactadas com desvios de umidade em relação à ótima variando entre 0% até 4 e mesmo 5%, mantendo o grau de compactação em torno de 95%. Por fim, os parâmetros de resistência, deformabilidade, compressibilidade e pressão neutra estimados foram comparados por litologia com parâmetros encontrados na literatura técnica, podendo assim serem utilizados em outros projetos em regiões próximas ou que empreguem materiais de mesma origem ou litologia. / In Brazil, from the twentieth century, the rail transportation was replaced by road transportation. Because of that, the demand for road infrastructure is increasing, for the transportation of people and for the freight transportation. Another factor that indicates the greater demand for infrastructure is the growth of the economy and the population. To guarantee safety in the construction and in the operation, geological-geotechnical investigations are necessary to characterize and estimate parameters of the material, that is being used in the civil works to predict its behavior. The parameters of shear strength have a great importance in the condition of stability of the embankments, in construction phase, as the neutral pressure parameter, B?, and in phase of operation, while the deformability parameters are essential in the estimation of settlements in the operational phase of the embankments. The objective of this dissertation is to present estimates of the parameters of shear strength (angle of friction and cohesion), deformability, expansibility, compressibility and neutral pressure of the material used in embankments of two parts of Rodoanel Norte in São Paulo. The studied materials have different lithologies: phyllite, granitic gneisses, ultramilonites and metabasites. Thus, a data survey of the laboratory tests results was done, namely, characterization tests, Normal Proctor compaction text, triaxial UU unsaturated, saturated CU and PN and oedomometric densification tests. The mechanical tests were done on compacted samples with deviations of water content from the optimum ranging from 0% up to 4 and even 5%, maintaining the degree of compaction around 95%. Finally, the estimation of the shear strength parameters, deformability, compressibility, expansibility and neutral pressure were compared by lithology with parameters found in the technical literature so that it can be used in other projects in nearby regions or using materials of the same origin or lithology.

Este trabalho apresenta um estudo das propriedades de resistência e de deformabilidade dos resíduos sólidos urbanos (RSU). Amostras de resíduo de diferentes idades, obtidas no aterro metropolitano centro (Salvador-BA), foram submetidas a ensaios de compressão triaxial e de compressão confinada em equipamentos de grandes dimensões. Os resultados dos ensaios triaxiais demonstraram que os RSU não apresentam pico ou valor máximo de resistência, mesmo para grandes deformações. Os parâmetros de resistência foram obtidos a partir de níveis específicos de deformação. Não foi possível observar a influência do processo de decomposição na resistência ao cisalhamento do RSU, porém observou-se um aumento de resistência com o acréscimo do peso específico. Dos ensaios em resíduos sem fibras (plásticos, têxteis, etc), verificou-se uma redução nos parâmetros de resistência em comparação com os do resíduo composto, indicando a grande influência do material fibroso no comportamento mecânico do RSU. Ensaios não drenados mostraram grande desenvolvimento de pressão neutra, que provocaram distorções nas envoltórias efetivas, fazendo com que os ângulos de atrito obtidos fossem maiores que aqueles obtidos nos ensaios drenados. Duas amostras de RSU novo foram submetidas a ensaios de compressão confinada. Uma das amostras foi submetida à recirculação de chorume para avaliação do efeito da decomposição nos recalques medidos. Os resíduos apresentaram uma rápida compressão primária e deformações secundárias que se desenvolveram durante todo o ensaio, sem tendência de estabilização. A recirculação de chorume não provocou acréscimos nas deformações secundárias, provavelmente devido ao pequeno volume de chorume utilizado e ao ambiente não favorável à decomposição. / This work deals with the shear strenght and compressibility properties of municipal solid waste (MSW). Four years old end new waste samples recovered from metropolitan center sanitary landfill (Salvador, Brazil) were submitted to triaxial and confined compression tests using large dimension specimens. Triaxial test results showed that a peak or an ultimate shear stress value was not reached even for the largest deformation attained in the tests and thus, shear strength parameters were derived to different strain levels. It was shown that the shear strength was not too much affected by waste decomposition process, but increased with the waste unit weight. The waste without plastic fibres tended to show reduced shear strength as compared to the whole waste, showing the large influence of this materials on MSW mechanical behavior. Undrained tests showed large pore pressures build up and tended to yield effetive shear strength parameters larger than that obtained in drained tests. Confined compression tests were performed using samples of fresh waste with and without leachate recirculation to investigate the influence of the waste degradation on MSW compressibility. It was observed that the waste showed a quick primary compression and secondary compression that extended throughout the test period without reaching equilibrium. The leachate recirculation did not increase secondary defomation probably by the low volume of leachate used during the test and due the ambient conditions not suitable to the degradation.

Composite materials have traditionally been used in high-end aerospace parts and low-end consumer parts. The reason for this separation in markets is the wide gap in technology between pre-preg materials processed in an autoclave and chop strand fiberglass blown into an open mold. Liquid composite molding has emerged as a bridge between inexpensive tooling and large, technical parts. Processes such as vacuum infusion have made it possible to utilize complex layups of reinforcement materials in an open mold style set-up, creating optimal conditions for composites to penetrate many new markets with rapid innovation. Flow simulation for liquid composite molding is often performed to assist in process optimization, and requires the permeability of the reinforcement to be characterized. For infusion under a flexible membrane, such as vacuum infusion, or for simulation of a part with non-uniform thickness, one must test the permeability at various levels of compaction. This process is time consuming and often relies on interpolation or extrapolation around a few experimental permeability measurements. To accelerate the process of permeability characterization, a small number of methodologies have been previously presented in the literature, in which the permeability may be tested at multiple fiber volume contents in a single test. Some of the methods even measure the permeability over a continuous range of thicknesses, thus requiring no later interpolation of permeability values. A novel method is presented here for the rapid measurement of permeability over a continuous range of fiber volume content, in a single unidirectional vacuum infusion flow experiment. The thickness gradient across the vacuum bag, as well as the fluid pressure at several locations in the mold, were concurrently measured to calculate the fabric compressibility. An analytical flow model, which accounts for the compressibility, is then used by iterating the fitting constant in a permeability model until the predicted flow front progression matches empirical measurement. The method is demonstrated here for two reinforcement materials: 1) a fiberglass unbalanced weave and 2) a carbon bi-ax non-crimped fabric. The standard deviation of calculated permeabilities across the multiple infusion experiments for each material and flow orientation ranged from 12.8% to 29.7%. Validation of these results was performed by comparing the resulting permeability with multiple non-continuous permeability measurement methods.