Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Civil, Arquitetura e Urbanismo / Made available in DSpace on 2018-08-17T11:28:28Z (GMT). No. of bitstreams: 1 Santos_FabricioBassanidos_M.pdf: 870223 bytes, checksum: 8af2408dfd741b81353a11d68bfe345e (MD5) Previous issue date: 2004 / Resumo: A produção de concretos com elevado desempenho quanto a fluidez, propriedades reológicas e durabilidade, demanda o conhecimento das características físico-quimicas dos cimentos, intervenientes no desempenho dos mesmos. O presente trabalho estuda a influência do teor do C3A, tendo por objetivo contribuir para a compreensão dos fatores que deteiroinam o comportamento reológico das pastas de cimento. Foram selecionados três cimentos nacionais com diferentes teores de C3A e com mínimos teores de adições presentes. Efetuou-se a composição de um cimento e uma escória de alto-forao, obtendo-se também três diferentes teores de C3A. Estes materiais foram moídos em laboratório para equalização das suas áreas específicas. A avaliação do comportamento reológico embasou-se na determinação da viscosidade das pastas através de ensaios com um viscosímetro rotativo e, indiretamente, correlacionando à área de espalhamento obtida pelo ensaio do abatimento do mini-tronco de cone. O método do abatimento do mini-tronco de cone não se mostrou satisfatório para a avaliação do comportamento reológico dos materiais estudados. Através dos resultados obtidos com o viscosímetro rotativo foi possível determinar a viscosidade aparente, em função do tempo - as quais indicaram um comportamento reológico característico para as diferentes amostras e misturas avaliadas. / Abstract: The production of high performance concrete with special rheologic properties, fluidity and durability, demands the knowledge of physical and chemical characteristics of the used cement. The herein research studies the C3A influence on cement pastes, in order to add knowledge to all the aspects that can contribute to its rheologic behavior and, consequently, to mortars and concretes. It was select three Brazilian cements with different amounts of C3A and minimum additions to the clinker. It was made a composition of the cement and blast furnace granulated slag in order to obtain three different amounts of C3A. These materials were grind to have the same specific surface. The Theological behavior was studied through determination of the viscosity of the cement pastes, and correlating it with the spread surface obtained by the Kantro test. This test method was not efficient in showing the real rheologic behavior of the studied materials. It was possible to determinate the apparent viscosity with time through the use of a viscometer device, which has shown a peculiar rheological behavior to the different specimens and mixtures studied. / Mestrado / Edificações / Mestre em Engenharia Civil

A lot of technologically relevant incompressible fluids exhibit a substantial variaton of viscosity with the pressure;a falling cylinder viscometer is frequently used for the measurements, determining the viscosity indirectly from the time it takes the sinker to fall a given distance. The relation between the sinker fall velocity and the fluid viscosity is, however, derived under the constant viscosity assumption. The objective of the present thesis is to perform a numerical simulation of the viscometric experiment, assuming an explicit form of the pressure-viscosity dependence and realistic parameter values and to quantitatively assess the difference in body motion to the Navier- Stokes model. The computational method proposed, handling both the nonlinear constitutive relation and the body motion, was tested on simple problems with analytical solutions. The semianalytical relation for the Navier-Stokes model, also re-derived here, is compared to the computational results.The validity of the assumptions used in the theoretical derivation, based on the results of the numerical simulation, is discussed regarding the geometry of the viscometer. Powered by TCPDF (www.tcpdf.org)

Aneurysms are a deadly asymptomatic cardiovascular disease that may occur especially where there are bends and bifurcations in the cerebral vasculature. A region where these features are especially prominent is the Circle of Willis (COW) in the brain, where aneurysms are known to occur. In the carotid artery, which feeds into the COW, the Reynolds number of blood flow is typically around 200-500. Even with such a low Reynolds number, turbulent-like flow, or tortuous flow, can occur due to bends, bifurcations and highly pulsatile flow which lower the effective Reynolds number where tortuous flow can occur. Highly pulsatile flow is unsteady flow that is high in magnitude and changes over time. Endothelial cells (ECs) line the inner wall of the blood vessel and experience the friction force of blood flow. This work is focused on designing a device that can expose ECs to forces they would undergo in an aneurysm-susceptible site. This is accomplished by exposing ECs to physiologically relevant Wall Shear Stress (WSS) and vibrations simultaneously. Vibrations in the body occur due to flow separation at the vessel wall, which leads to pressure changes. These pressure changes induce vibrations onto ECs. The fluid flow in the designed Parallel Plate Flow Chamber (PPFC) is laminar to induce a predictable WSS onto the cells, while the vibrations will induce a rapid cyclical force to simulate pressure fluctuations that may occur in vivo. The aneurysm-susceptible flow will simulate a more turbulent-like flow in the carotid artery; higher maximum WSS (around 2.2 Pa) with vibrations. The aneurysm-protective flow will have a lower WSS maximum (around 0.5 Pa). The PPFC, made of polycarbonate, is small and light enough to be conveniently vibrated using an electromagnetic vibration stage. The PPFC can be driven by a syringe or peristaltic pump, allowing for either steady or transient waveforms. The PPFC’s fluid domain will not change upon vibration, isolating the effect of vibration on the cells. Also, two side-by-side glass slide slots were included to allow for both protein and mRNA quantification from the same experiment, increasing experimental efficiency and flow-related consistency between the two cell areas. Simulations using ANSYS Fluent verified the flow field and WSS waveform on the cells for the designed geometry for 3D and 2D cases, as well as verified equal WSS values throughout all areas of ECs. Then, Particle Image Velocimetry (PIV) was done to verify the predicted flow rate in the machined PPFC given a steady flow rate driven by a syringe pump. Preliminary cell experiments were performed in an incubator under flow and vibration conditions to demonstrate cell survivability.

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<p>This dissertation describes an investigation into the free radical batch polymerization of methyl methacrylate to high conversion. The overall objective was to develop a kinetic model to accurately predict conversion and molecular weight distribution for the polymerization. The dissertation is divided into three self-contained parts.</p> <p>Part I describes the development and testing of the kinetic model. New gel permeation chromatograph (GPC) data interpretation methods (developed in Part I I), the free volume concept of diffusion theory, and newly obtained isothermal kinetic data, are combined with computer implemented optimization techniques, to show that classical kinetics apply to high conversions.</p> <p>Part II details the development of three new GPC interpretation techniques. The two most recent are evaluated in Part I.</p> <p>The third has been used by other workers. Other interpretation methods are also evaluated and discussed. Part I I I describes the development of a high shear concentric cylinder viscometer and its use with Newtonian standards. This is a prelude to future studies in polymer rheology and polymerization under shear conditions.</p> / Doctor of Philosophy (PhD)

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.

Baigiamojo magistro darbo tikslas – ištirti cheminių įmaišų poveikį reologinėms portlandcemenčio tešlos savybėms, panaudojant skirtingų tipų cementus. Darbe išnagrinėta lietuvių, užsienio mokslinė literatūra, aprašytos naudotos žaliavos, parinktos skirtingos cementinės tešlos sudėtys, kurios skiriasi cemento ir plastifikuojančios įmaišos tipu. Tyrimams naudotos šios medžiagos: AB „Akmenės cementas“ gamyklos portlandcementis CEM I 42,5 (N ir R ankstyvojo stiprumo), klinties portlandcementis CEM II/A-LL 42,5 N, plastiklis Centrament N3, naujausios kartos superplastiklis MC-PowerFlow 3140 ir vanduo. Ištirtas plastiklio ir superplastiklio poveikis portlandcemenčio tešlos vandens ir cemento (V/C) santykio pokyčiams ir sklidumui naudojant Sutardo viskozimetrą. Buvo tiriamos vienodo vandens ir cemento santykio portlandcemenčio tešlos su cheminėmis įmaišomis ir be jų. Tyrimai atlikti naudojant rotacinį viskozimetrą Rheotest NH 4.1 su bendraašiais cilindrais. Nustatytas cheminių įmaišų portlandcemenčio tešloje veiksmingumas, esant skirtingo tipo cementui. Pastebėta, kad portlandcemenčio tešlos dinaminis klampis gali būti reguliuojamas cheminėmis įmaišomis viso indukcinio hidratacijos periodo metu. Sukurta metodika portlandcemenčio tešlos reologinėms savybėms nustatyti bei parinktas reologinis modelis, kuris geriausiai apibūdina gautus tyrimų duomenis. Atlikus portlandcemenčio tešlos su cheminėmis įmaišomis ir be jų tyrimų rezultatų regresinę analizę, gautos klampio, tekėjimo lygtys... [toliau žr. visą tekstą] / The purpose of this thesis is to analyse the influence of chemical admixtures on the rheological properties of Portland cement paste, which differ depending on the type of cement used. In addition to the literature analysis, different cement paste compositions (differing in type of cement and plasticizers) were tested. Testing materials: Portland cement CEM I 42.5 (N and R early strength), limestone Portland cement CEM II/A-LL 42.5 N, plasticizer Centrament N3, the latest generation superplasticizer MC-PowerFlow 3140 and water. Research focused on effects of plasticizer and superplasticizer on water and cement (W/C) ratio and Portland cement paste slump-flow characteristics. Portland cement pastes with the same water-cement ratio with and without chemical admixtures were tested. Tests were carried out using a Suttard viscometer and rotation viscometer Rheotest NH 4.1 with coaxial cylinders. It was observed that viscosity of Portland cement paste can be controlled by chemical admixtures during the hydration induction period. The work provides analysis of the effectiveness of the chemical admixtures on the rheological properties of the Portland cement pastes, comparing it with a control composition of the Portland cement paste. Diagrams demonstrate changes in viscosity of the Portland cement pastes depending on the type and amount of the chemical admixtures. Obtained results were compared with the same consistence paste without admixtures. We created a new methodology of... [to full text]

High-temperature, high-pressure (HTHP) conditions are exemplified in ultra-deep petroleum reservoirs and can be exhibited within diesel engines. Accurate pure component hydrocarbon data is essential in understanding the overall behavior of petroleum and diesel fuel at these conditions. The present study focuses on the HTHP properties of toluene since this hydrocarbon is frequently used to increase the octane rating of gasoline and toluene occurs naturally in crude oil. In this thesis experimental densities and viscosity are presented to 535 K and 300 MPa extending the database of toluene viscosity data to higher temperature than previous studies. The data is correlated to a Tait-like equation and a Padѐ approximate in conjunction with a single mapping of the isotherms. Free-volume theory and a superposition of the viscosity in relation to the Leonnard-Jones repulsive force are both used to model the toluene viscosity data. It was found that the data are in good agreement with the available literature data.

Modern automotive applications such as transmission clutch plates, combustion chambers, diesel fuel injector tips, and axle gears and friction plates operate at temperatures that can exceed 250°C and pressures of 40,000 psia. Industrial practice is to add homopolymers and copolymers to base oils to modify bulk fluid viscosity and frictional properties for these demanding applications. However, designing polymeric additives for lubricants and predicting their performance is limited by the lack of available high-temperature high-pressure (HTHP) viscosity and density data needed to test contemporary lubricity models. Thus, a major objective of this thesis is the design, development, and commissioning of a rolling ball viscometer/densitometer (RBVD) capable of simultaneously determining fluid densities and viscosities at temperatures in excess of 250°C and pressures of 40,000 psia. Resulting data may then be generated to directly address the fundamental need for lubricant property data at these HTHP conditions. The design and development of the RBVD is described in detail to highlight the design iterations and modifications utilized to ensure robust operation at extreme conditions. Three significant and novel features of this RBVD apparatus that distinguish and differentiate it from other apparatus of this type are: (1) specially designed metal-to-metal and sapphire-to-metal seated surfaces capable of eliminating temperature- and chemically-sensitive elastomeric seals; (2) use of a bellows piston to eliminate significant temperature and operational constraints; and (3) incorporation of a linear variable differential transducer (LVDT) to simultaneously permit determination of solution density and viscosity. A detailed analysis of initial accumulated uncertainty for the experimental viscosity and density techniques revealed the need for key RBVD modifications. Final data are presented showing that the RBVD is capable of measuring viscosities with an accuracy of ± 2 to 3 percent and densities to ± 0.7 percent, including at the extreme operating conditions targeted. A second objective of this thesis is the measurement of HTHP viscosities of star polymer-solvent mixtures to determine the impact of star polymer architecture on solution viscosity at extreme conditions similar to those that might be experienced in automotive applications. This objective is motivated by current challenges facing industry to identify polymeric additives that can be added to base oils to improve fuel economy and allow for the implementation of novel hardware technology that relies on enhanced lubricant properties. Relative to linear polymers, the unique architecture of star polymers enhances polymer solubility in base oils while having a more favorable impact on viscosity and density properties over a wide range of temperatures and pressures. Data are presented for an industrially-relevant star polymer in octane to assess the impact of the star configuration on solvent viscosity at extreme conditions. The star polymer used in this instance consists of an ethylene glycol dimethacrylate (EGDMA) core with poly(lauryl methacrylate-co-methyl methacrylate) (LMA-MMA) arms. The star polymer has a total weight averaged molecular weight (Mw) and Mw of each arm of 575,000, and 45,000, respectively. The copolymer arms of the star polymer have an LMA-to-MMA mole ratio of 0.6. The results of further viscosity studies are presented for a model system of well-characterized commercially available narrow polydispersity index (PDI) star polystyrenes (PS) in toluene. Each PS is evaluated at a two percent by weight concentration in toluene to evaluate the effect of arm molecular weigh on viscosity. Each three-arm star polymer has arm and total molecular weights ([arm Mw] total star Mw) of ([15,400] 41,200), ([36,000] 97,600), and ([108,000] 305,000). In this instance, the viscosity of toluene increased by more than a factor of three for the star with the highest Mw arms.

Self-compacting concrete (SCC) offers rational and fast casting process since it merely has to be poured, or pumped, into the formwork without any compaction work needed. But this can be at the cost of high form pressure. However, reported results show that SCC can act thixotropically, i.e., build up a structure at rest, and this can reduce the form pressure considerably. Thus, in order to utilise the favourable possibilities to increase effectiveness without risking form collapses, the need arises for deeper and broader understanding of the mechanisms behind this thixotropic behaviour. Methodologies have been developed for the characterisation and measurement of the structural build-up at rest, both for the fluid (micro mortar) phase and the concrete itself. Hypotheses state that thixotropic mechanisms originate within the colloidal domain and, thus, motivate studies on the fluid phase comprising this domain. The stress-strain methodology is based on the hypothesis stating that the magnitude of the structure is represented by the maximum elastic stress the fresh material can withstand before the structure breaks. An instrumented steel tube is used to simulate various casting heights and rates. Results show that both micro mortar and SCC are thixotropic and this behaviour is influenced by every measure taken influencing the interparticle colloidal forces. The time-dependent structural build-up of SCC is a function of an irreversible structure (slump-loss) and a reversible, thixotropic structure. There is apparently a threshold value of the structural build-up necessary to reach before obtaining any significant form pressure reduction. Housing SCC´s, with W/C = 0.58, show low degree of structural build-up and pressure decrease while civil engineering SCC´s can show the opposite, but this often at the cost of slump-loss. Recommendations are presented and for the nearest future, suggesting a conservatism regarding design of formwork systems when SCC is used. If the behaviour of a SCC is known it should be used to optimise the formwork. If not, calculating with hydrostatic pressure should be done or the knowledge missing should be gained by using this methodology. A third option is given and this is to monitor the form pressure in real time using sensors. / QC 20100812