Membrane processes have received growing attention due to their low energy consumption and ease of operation. Thin-film composite reverse osmosis membranes based on polyamides are the most widely applied commercial membranes, because of their high flux and selectivity. However, their application for gas separation processes is still limited. This is the due to the presence of defects in the membrane when in the dry state. Traditionally, thin-film composite membranes are made by interfacial polymerization between a polar (aqueous) phase and a non-polar (organic) phase. The most commonly applied thin-film composite membranes are made by dissolving m-phenylene diamine in the aqueous phase and trimesoyl chloride in the organic phase. This work investigated the possibility of fabricating thin-film composite membranes when an aliphatic alcohol (methanol, ethanol or isopropanol) is used as the polar phase. This is further extended to examining the ability of a PDMS coating to plug the defects in such layers. The effects of temperature and support type on the membrane performance were also studied. Solubility tests were conducted to determine the solubility limit of commercial and in-house fabricated amine monomers in water, methanol, ethanol and isopropanol. Water-insoluble monomers were found to be soluble in ethanol and methanol. Gas permeation tests were conducted on membranes made using water, methanol, ethanol and isopropanol as the polar phase. The results showed that the membranes produced by aliphatic alcohols had higher selectivities. The highest H2/CO2 selectivity of ~ 26 was observed in the ethanol-based membranes when they were coated with PDMS and tested at 80 C. It was confirmed that PDMS is able to plug the defects in the membrane. Membranes made on the polysulfone support were found to have higher permeance and comparable selectivity relative to the membranes made on the polyacrylonitrile supports. It was also found that a change in the polar phase solvent is able to alter the morphology of the membranes. SEM micrographs showed clear differences in the surface structure of each membrane. The average thickness values obtained from ellipsometry measurements showed a correlation with the interface miscibility. The thickest membrane corresponded to the most miscible interface (IPA/Isopar).

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24443号 / 理博第4942号 / 新制||理||1706(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 若宮 淳志, 教授 依光 英樹, 教授 畠山 琢次 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Fiber sizings are used to improve the performance of fiber-reinforced polymer composites made from low-cost fiber and matrix materials. Evaluation of three sizings, poly(vinylpyrrolidone) (PVP), a carboxyl modified polyhydroxyether (PHE), and a standard industrial sizing (G'), have revealed tremendous improvements in static mechanical and enviro-mechanical properties. The focus of this work is to determine if these improvements in performance can be ascertained from a micromechanical test for interfacial shear strength (IFSS) on as-processed materials. The accomplishment of this goal would create more information with fewer experiments and a need for less experimental materials. In this study, a nanoindenter uniquely outfitted with a blunt tip is effectively used to obtain microindentation results where the debond load is extracted directly from the experimental load-deflection curve. Shear lag and finite element analyses are used to evaluate the mechanics of the system, but both methods show limitations with regard to determining interfacial stresses in an experimental system. In the results obtained, the PHE and Gâ materials outperform the PVP in IFSS, but the bulk properties for PVP and PHE outperform the Gâ material, suggesting the presence of another dominant mechanism. Despite better retention of bulk properties after hygrothermal exposure, PHE experiences degradation in IFSS that PVP does not. The PHE loses 10% of its original IFSS after 576 hours of 65ºC moisture exposure, while PVP improves by 25%. The tensile strengths for PHE and PVP decrease 7% and 10% respectively at 576 hours exposure. Finite element modeling shows that matrix swelling due to moisture absorption increases interfacial shear stresses, a finding supported by a comparison of wet and dry specimens subjected to equivalent aging times. Matrix swelling is not, however, responsible for the increase in IFSS of the PVP material. The relationship between tensile strength and IFSS proves to be small as predicted by a tensile strength model, but processing defects and other failure processes that are not included in the tensile strength model appear to have strong influences over the experimental results. IFSS is important in composite materials, but in the case of the G', PHE and PVP materials, other factors dominate fiber direction tensile performance. Therefore, this one simple micromechanical test provides significant insight into the composite material behavior, but it does not provide the same magnitude of information as from bulk composite experiments. / Master of Science

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[pt] As interações óleo/água/rocha podem ter grande influência no deslocamento do óleo em um reservatório. As forças capilares, responsáveis em parte pela retenção de óleo, são um dos parâmetros que podem ser alterados buscando a optimização do processo. Durante um processo de injeção de água, as altas tensões interfaciais água-óleo diminuem a capacidade de escoamento do óleo e deixam altas saturações deste em forma de glóbulos imóveis e desconectados, nas regiões já contatadas pelo fluido injetado. Com a injeção de surfactante, a tensão interfacial diminui e consequentemente as forças necessárias para mobilizar glóbulos de óleo. No entanto, a interação da salinidade com a solução de surfactante pode trazer importantes efeitos no escoamento bifásico dentro do meio poroso. O objetivo deste trabalho é estudar o efeito da salinidade da água e concentração de surfactante em um processo de deslocamento de óleo. Neste estudo, foram realizados testes de deslocamento em amostras de arenito de Bentheimer de alta permeabilidade, para soluções salinas com e sem surfactante não iónico Álcool Laurílico Etoxilado- 8EO (L80), submetidos a uma temperatura de 40 graus celsius. As saturações residuais bem como as permeabilidades efetivas das fases ao final do processo de embebição e drenagem foram medidas para as diferentes soluções aquosas. Os resultados obtidos mostram a variação na eficiência do processo de deslocamento, influenciada principalmente pelo comportamento de fases, a tensão interfacial, concentração de eletrólitos em solução (salinidade), e a formação de emulsão durante o escoamento bifásico no meio poroso. / [en] The interactions oil/water/rock may have strong influence in displacement of the oil in a reservoir. The capillary forces, responsible in part by the trapped oil, is one of the parameters that allow the optimization of water injection processes. During water injection, the high interfacial tension of water-oil decreases the flow capacity of oil and leave high saturations of this phase in the form of immobile and disconnected ganglia, in the regions already contacted by injected water. With the injection of surfactants, the interfacial tension decreases and some of the oil ganglia are mobilized. However, the interaction of salinity with the surfactant solution can bring important effects in the two-phase flow within porous media. The aim of this work is to study the effect of water salinity and concentration of surfactant in oil displacement process. In this study, the displacement tests were performed on Bentheimer sandstone of high permeability, for saline solution with and without non-ionic surfactant Lauryl Alcohol Ethoxylates- 8EO (L80), subjected to a temperature of 40 Celsius degree. The saturation and effective permeability of each phase at the end of imbibition and drainage were determined for the different water solutions. The results obtained show the variation in the efficiency of the displacement process, mainly influenced by the behavior of phases, the interfacial tension, concentration of electrolytes in solution (salinity) and in-situ emulsion formation.

Asphaltenic crude oil is a complex fluid containing various components with different chemical properties. When it comes in contact with water, its polar components adsorb at the oil/water interface, reducing the interfacial tension and eventually developing viscoelastic films. The interfacial films impact emulsion stability and adhere to the oil-bearing reservoirs rocks, altering their wettability and thus hindering oil mobilization. Here, we investigate the formation of crude oil/water interfacial films. We measure both the time-dependent shear and extensional interfacial rheology moduli, and we relate it to the chemical composition of the films, highlighting the role of polar aromatic molecules in film formation. Varying chemical composition of the aqueous phase, we show that the properties of the interfacial films depend not only on the concentration of ionic species in water but also on their chemical nature. In particular, we highlight the role of sulfate salt in promoting interfacial viscoelasticity and in altering the composition of fully developed films. To study the rock/fluid interaction, we fabricate mixed-wet capillaries with angular cross-sections inspired by the naturally occurring primary drainage of pore-filling brine by invading crude oil. After employing our novel coating procedure, we experimentally investigate water invasion in mixed-wet capillaries and compare it with predictions of dynamic and quasi-static (Mayer-Stowe-Princen (MSP)) meniscus-invasion models. None of the dynamic models built for uniformly-wet pores can fully describe our experimental data in mixed-wet capillaries. However, the experimental results agree with predictions of MSP theory. To our knowledge, this is the first direct experimental validation of MSP theory under mixed-wet conditions. We confirm the possibility of spontaneous piston-type imbibition with high ($> 90^{\circ}$) advancing contact angles into mixed-wet pores, given that the contact angle is lowered below a critical value that is a function of pore geometry and residual water saturation. In oil reservoirs, injection of specific brines would be required to change the contact angle to values below the imbibition threshold. Finally, we extend our study and introduce a powerful 3D high-speed laser imaging of dynamic fluid flow in angular capillaries and investigate its capability to capture non-equilibrium shapes of fluid interfaces.

Wetting behaviors influence many aspects of life and industry from consumer product goods to oil recovery to cosmetics. While the traditional solid-liquid-vapor (SLV) system has been studied for many years now, wetting transitions in the solid-liquid-liquid (SLL) system has remained relatively unexplored. The purpose of this work is to bring light to the wetting transition of the solid-liquid-liquid system and to understand the replacement rates of initially hydrocarbon-filled microscopic cavities with water and the factors affecting these rates. Factors studied were viscosity, density, diffusion related properties, and surface related properties in both hydrocarbon-saturated and hydrocarbon-non-saturated conditions. Cylindrical microscopic cavities were etched in a silicon wafer, filled with various organic solvents dyed with fluorophores, then submerged in water. Through fluorescence microscopy techniques, the transition or replacement rates of the initially hydrocarbon-filled cavities with water in both hydrocarbon-saturated and hydrocarbon-absent water conditions are observed. Among the factors we investigated, namely viscosity, density, surface chemistry, and diffusive flux (composed of solubility and diffusivity), diffuse flux dominated replacement rates in hydrocarbon-absent water conditions. By using hydrocarbon-saturated water, diffusive flux was minimized, allowing for deeper investigation of other factors. In the hydrocarbon-saturated scenario, replacement rates are largely affected by initial fluid motion, specific cavity geometry, and cavity penetration mechanisms. Image analysis reveals the geometry of the oils in the cavities and shows how the transition from hydrocarbon-fully-filled to hydrocarbon-partially-filled states occurs in the SLL system.

The effect of coatings on the interfacial strength of a hollow glass microsphere/polyester composite and their capacity to endure thermal stresses were studied by mechanical testing and an active Acoustic Emission (AE) method. AE was postulated to provide more local information at or near the glass/polyester interface due to the sensitivity of elastic waves to the rigidity of polymer chains at the glass sphere/polyester interface compared to mechanical testing. Three frequency ranges identified by multivariate statistics yet consolidated for the initial analysis into a band of 140-240 kHz, were found to be changing with the different coated glass filler for different glass content and heating state. Considering the acoustic behavior of the composites containing different levels of glass sphere content (1-10 vol%), a lower concentration (aminoethylamino)-propyl-trimethoxy silane coated glass (AS6), demonstrated the lowest attenuation after heating (associated with higher interfacial strength). As anticipated, the highest attenuation after heating was observed for uncoated glass (16K) due to expectedly weaker associations. Mechanical testing results after heating were consistent with the AE response for AS6 and 16K for this frequency range. Trends in amplitude for the three narrower, frequency ranges of 130-160 kHz, 180-220 kHz and 230-260 kHz were compared against that of 140-240 kHz and very small differences were observed. It was found that the frequency range of 130-60 kHz was more descriptive of the changes of interfacial strength in composites (at 10 vol%), being consistent with the mechanical test results. Considering the AE response at 130-160 kHz and mechanical data, higher concentration (aminoethylamino)-propyl-trimethoxy silane (AS12), better endured thermal stresses compared to other coatings. A smaller trial looked at the effect of moisture aging and subsequent thermal cycling on the glass/polymer interface strength as another method to perturb the interface. Attenuation for the band of 180-260 kHz was studied for aged versus non-aged composites. The commercial coating, L21 demonstrated a better moisture resistance before and after thermal cycling compared to uncoated glass spheres. An improved evaluation of interfacial strength in glass/polyester was expected using AE technique versus mechanical testing due to its higher sensitivity to changes in internal structure, however; no significant improvement compared to mechanical testing was observed, at least based on the analysis technique currently being used. / Thesis / Master of Applied Science (MASc) / Sheet molded compound (SMC) is a polymer material reinforced by fibers providing a combination of light weight and high mechanical properties and is used in automotive industry. Light weight fillers (hollow glass microspheres) are used to obtain further weight reduction; however, addition of these fillers leads to reduced mechanical properties and further problems during painting process known as ‘paint popping’. The former is due to uncertain interfacial state between polymer and fillers and the latter results from different thermal expansion behavior of the polymer and filler materials while the material is exposed to high temperatures for painting process. This research aims to devise a highly sensitive technique and evaluate its suitability compared to mechanical testing for investigation of the origin of aforementioned problems. Acoustic Emission (AE) is a method with high sensitivity to changes in internal structure of the material which is postulated to provide a better insight on material microstructure compared to more commonly used method i.e. mechanical testing. Use of interfacial controlling agents was examined to reduce the problems as a result of introduction of fillers. The effect of using surface modified fillers and the effect of thermal stresses on material was investigated using AE technique. Application of AE method in this study provided a good insight about the changes in material internal structure; however, it did not demonstrate a significant improvement in detecting the origins of studied problems compared to mechanical testing at least based on the analysis technique used in this study.

<p> Preparations for an investigation of interfacial momentum transfer in two-phase two-component critical flows have been completed.</p> <p> The experiments involve the measurement of flow rates, axial pressure profiles, axial and transverse void fraction profiles, and axial wall shear stress profiles of steady-state gas-liquid critical flow in a vertical diverging nozzle. A photographic study is to be initiated to record the flow structure. The results of these experiments will be used to develop constitutive relations for interfacial momentum transfer.</p> <p> An experimental loop capable of circulating a gas-liquid mixture in a vertical test section was modified to suit the requirements of this investigation. The void fraction profiles are measured with a traversing gamma densitometer using a 20 mCi Co57 source. The wall shear stress profiles are obtained using the electrochemical method to measure the mass transfer coefficients of electrodes mounted flush with the test section wall. The liquid phase is an electrolyte and the gaseous phase can be air, nitrogen or freon. The latter is used to better approximate the densities of a steam-water flow.</p> <p> This report describes the required theory, measurement techniques, design and operation of the loop, and the experimental procedures.</p> / Thesis / Master of Engineering (MEngr)