Micropores can constitute up to 100% of the total porosity within carbonate hosted hydrocarbon reservoirs, usually existing within micritic fabrics. There is, however, only a rudimentary understanding of the contribution that these pores make to reservoir performance and hydrocarbon recovery. To further our understanding, a flexible, object-based algorithm has been developed to produce 3D computational representations of end-point micritic fabrics. By methodically altering model parameters, the state-space of microporous carbonates is explored. Flow properties are quantified using lattice-Boltzmann and network modelling methods. In purely micritic fabrics, it has been observed that average pore radius has a positive correlation with single-phase permeability and results in decreasing residual oil saturations under both water-wet and 50% fractionally oil-wet states. Similarly, permeability increases by an order of magnitude (from 0.6md to 7.5md) within fabrics of varying total matrix porosity (from 18% to 35%) due to increasing pore size, but this has minimal effect on multi-phase flow. Increased pore size due to micrite rounding notably increases permeability in comparison to original rhombic fabrics with the same porosity, but again, multi-phase flow properties are unaffected. The wetting state of these fabrics, however, can strongly influence multi-phase flow; residual oil saturations vary from 30% for a water-wet state and up to 50% for an 80% oil wet fraction. flow when directly connected. Otherwise, micropores control single-phase permeability magnitude. Importantly in these fabrics, recovery is dependent on both wetting scenario and pore-network homogeneity; under water-wet imbibition, increasing proportions of microporosity yield lower residual oil saturations. Finally, in grain-based fabrics where mesopores form an independently connected pore network, micropores do not affect permeability, even when they constitute up to 50% of the total porosity. Through examination of these three styles of microporous carbonates, it is apparent that micropores can have a significant impact on flow and sweep characteristics in such fabrics.

Microneedle (MN) enhanced drug delivery is a safe, effective and efficient enhancement method for delivery of drug molecules across the skin. The “poke (press) and patch” approach employs solid stainless steel MN to permeablize the skin prior to application of a regular drug patch over the treated area. It has been previously shown that MN can be used to deliver naltrexone (NTX) at a rate that provides plasma concentrations in the lower end of the therapeutic range in humans. The drug delivery potential of this technique is, however, limited by the re-sealing of the micropores in a 48-72h timeframe. The goal of the current research was to optimize the formulation for a 7 day MN enhanced delivery system for NTX either by adding a second active pharmacological moiety or by optimizing formulation characteristics alone. Three different formulation strategies were explored: formulation pH optimization with NTX; a codrug approach with NTX and a nonspecific cyclooxygenase inhibitor, diclofenac (DIC); and a topical/transdermal approach with NTX and an enzyme inhibitor of the cholesterol synthesis pathway, fluvastatin (FLU). The results indicated that formulation pH cannot be used to extend micropore lifetime, although formulation optimization leads to enhanced transport and thus drug delivery across MN treated skin. The codrug approach was successful in extending the micropore lifetime and further screening of codrug structures and formulation optimization helped in selection of a codrug candidate suitable for evaluation in animal pharmacokinetic studies. Local treatment with FLU helped to keep the micropores open and enabled delivery of NTX for an extended period. The pores re-sealed on removal of treatment within a 30-45 minute timeframe, indicating that infection/irritation should not be a major issue, as in the case of other topical chemical enhancers. Thus, overall it can be concluded that different formulation strategies can be utilized to extend micropore lifetime and enhance delivery of drug molecules across the skin.

This dissertation outlines the research and development of ground-breaking nanometer sized openings (nanopores) integrated with an on-chip optofluidic platform. This platform represents a significant advancement for single nanoparticle sensing. In this work specifically, the integrated optofluidic platform has been used to electrically and optically filter and detect single nanoparticles using ionic current blockade and fluorescence experiments. The correlation of electrical and optical signal has provided the highest sensitivity single nanoparticle measurements ever taken with integrated optofluidic platforms. The particular optofluidic platform used for this work is an antiresonant reflecting optical waveguide (ARROW). ARROW hollow and solid core waveguides are interference based waveguides that are designed to guide light in low index media such as liquids and gases. Because of this unique guiding property, ARROW hollow cores can be used to sense and analyze low concentrations of single particles. Additionally, because ARROW platforms are based upon standard silicon processing techniques and materials, they are miniature sized (~1 cm2), inexpensive, highly parallelizable, provide a high degree of design flexibility, and can be integrated with many different optical and electrical components and sources. Finally, because of the miniature, integrated nature of the ARROW platform, it has the potential to be incorporated into hand held devices that could provide quick, inexpensive, user-friendly diagnostics. The ARROW platform has been through many revisions in the past several years in an attempt to improve performance and functionality. Specifically, advanced fabrication techniques that have been used to decrease the production time, increase the yield, and improve the optical quality of ARROW platforms are discussed in the first part of this work. These advancements were all developed in order to facilitate the production of high quality integrated nanopores and ARROW platforms. The second part of this work then focuses on the actual integration of micrometer sized openings (micropores) and nanopores in the hollow waveguide section of ARROW platforms for filtering, detecting, and analyzing single nanoparticles. The successes and attempts at achieving these results are the basis of this dissertation of work.

L'objectif de ce travail est de contribuer à l'amélioration des mécanismes d'imprégnation d'un renfort fibreux par une résine polymère dans les procédés de mise en œuvre de matériaux composites de type LCM (Liquid Composite Molding). Les études théoriques et expérimentales réalisées se sont focalisées sur les anomalies d'imprégnation pouvant apparaître lors des écoulements. Les défauts couramment observés sont des vides pouvant s'assimiler à des bulles et provenant, en partie, d'une compétition entre les régimes gouvernant les écoulements intra-mèche et inter-mèches. L'analyse de la formation et du transport des bulles au sein d'une structure fibreuse demeure délicate à réaliser du fait de l'architecture complexe de la préforme. Afin de s'exonérer des difficultés rencontrées lors de la visualisation au sein du renfort et pour répondre à cette problématique de vide créé, nous avons fait le choix d'étudier les mécanismes d'imprégnation ainsi que la formation et le transport de bulles dans des réseaux modèles. Une analyse multi-échelles a été adoptée pour nos expérimentations faisant appel à une approche micro et millifluidique où les forces de mouillabilité sont prépondérantes. Les résultats obtenus montrent, dans un premier temps, l'influence de ces forces dans les mécanismes de génération et de transport de bulles et permet de justifier certaines observations proposées dans ce sujet. Un modèle simple basé sur des configurations d'inter-connectivités micropore/macropore a été proposé. Ce modèle permet d'envisager différentes analyses paramétriques selon des configurations géométriques et des régimes d'écoulement variés. Sur cette base, il est possible de prendre en compte différents facteurs et de les comparer à certaines contributions de la littérature dans le domaine de l'imprégnation des milieux fibreux et de la mise en œuvre des composites.

This thesis is dedicated to the exploration of fluid phases confined in nanoporous materials using Nuclear Magnetic Resonance (NMR) techniques, with an aim to benefit catalysis research. Included in this report are studies of pure fluids and their mixtures, confined in titania and silica catalyst supports. These investigations are conducted at industrially-relevant, high-temperature (≥ 180 °C) and high-pressure conditions (up to 13 bar), made possible by a pilot-scale chemical reactor unit, designed to operate inside the strong magnetic fields of an NMR spectrometer. NMR spectroscopy, relaxation and pulsed field gradient (PFG) diffusion experiments were performed on each of the systems discussed in this report. Cyclohexane was initially studied inside a porous titania catalyst support at 188 °C and various pressures up to 13 bar. The adsorption and desorption processes of the cyclohexane were observed, revealing a number of previously unobserved phenomena. In addition to an overall, averaged diffusion coefficient, a slow diffusion coefficient was observed within the PFG NMR data attributable to surface diffusive processes occurring within the material. Additionally, T1 relaxation studies were found to provide experimental evidence for the differing configurations of adsorbed layers on the adsorption and desorption branch of the isotherm. Cyclohexane was subsequently studied alongside fluorobenzene in a series of silica catalyst supports of 6 nm, 10 nm and 20 nm pore size. In doing this, it was hoped that the multiple phenomena observed in the titania experiments might be deconvoluted, allowing a greater level of insight. The diffusivities of the fluids were found to differ significantly between the materials, and greater evidence was found of the slow-diffusing surface phase in each of the materials. Additionally, concentrations of cyclohexane and fluorobenzene in the gas and adsorbed layers inside the pore space were calculated via the results of the PFG NMR experiments, providing a map of confined phase behaviour. Competitive adsorption effects were found to become more significant, the smaller the pore size of the material. The results of the cyclohexane and fluorobenzene in silica studies were modelled, using approaches available in the literature, which were found to give varying levels of prediction. The data set acquired in this thesis was found to provide a useful standard, against which current and future models of confined phase behaviour might be verified.

No description available.

Nanopore technology has introduced new techniques for single particle detection and analysis. A nanopore consists of a small opening in a membrane on the nanometer scale. Nanopores are found in nature and are utilized for transporting molecules through biological membranes. Researchers have been able to mimic naturally forming biological nanopores and utilize them for a variety of sensing applications. Nanopores, fabricated either organically or inorganically, can be used for detecting biomarkers such as proteins, nucleic acids, and metabolites that translocate the membrane by way of the nanopore. Constant ionic current flow is measured through the nanopore by way of a sensitive ammeter. In the presence of a biomarker, the ionic current flow will be impeded, causing the electrical signal to drop. This drop uniquely corresponds to the type of particle passing through the nanopore. In this work, the thin membrane on which the nanopore resides is created through a newly developed meniscus shaped sacrificial technique. The sacrificial polymer material starts as a liquid and is confined to the microfluidic channel through the capillary effect, giving it the meniscus profile. It is used as a structural support on which a thin silicon dioxide layer is grown. The layer of oxide takes on the same natural meniscus shape as the sacrificial material. The polymer is subsequently etched, resulting in a hollow core liquid channel with a suspended meniscus membrane. This process allows a thin membrane to be fabricated on top of a microfluidic channel that ranges from 50-200 nm in thickness. The meniscus membrane is crucial to the success of nanopore formation. The nanoscale membrane allows for smaller, more precise nanopores to be created. Reduced nanopore dimensions are advantageous for the detection of smaller biomarkers. The platform described in this dissertation integrates solid-state naturally forming meniscus membranes with solid-core and optofluidic waveguides for nanopore detection applications. The waveguides allow for a particle trap to be introduced to the system. The ability to trap particles directly under the nanopore is critical to the speed of which the nanopore can operate. This dissertation focuses on the fabrication, characterization, and testing of an optofluidic platform that features a nanopore for rapid single molecule detection and analysis.