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A research report submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in partial fulfillment of the requirements for the degree of Master of Science, 2017 / Over the years, epidemiological research has seen differing levels of the prevalence of hypertension across socio-economic strata. However in Sub-Saharan Africa, the patterns of association and underlying risk factors have often been poorly understood. In this study, we examined the extent to which socio-economic factors affect systolic and diastolic blood pressure across gender. Furthermore we explored whether certain risk factors associated with hypertension mediate this relationship. We used data from the third phase of the National Income Dynamic Study conducted in South Africa in 2012 on more than 18,000 adult individuals. Structural equation modelling and multiple linear regression were used to estimate the relationship between blood pressure and various behavioural, demographic and socio-economic variables. These results were then compared to determine which technique provides more meaningful results. A higher socio-economic status was associated with a higher systolic and diastolic blood pressure in both males and females. Furthermore, body mass index was a mediator of the indirect effect of socio-economic status on blood pressure. Smoker status, alcohol consumption, physical exercise, emotional well-being and resting heart rate were also mediators; however their role was modest in comparison to BMI. One of the findings of this study is that a reduction in the BMI of an individual will have an impact on lowering hypertension. Furthermore, the promotion of healthy behaviours that target higher income groups need to be established so that these groups can make rational decisions in choosing their behaviours. / XL2018

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<p>This thesis aims to measure the rate of radon loss from water in a systematic way. The dependence on surface area, temperature and concentration will be investigated. The experiments were done at UWC by creating radon using radium sources and then measuring the radon concentrations inside a vacuum chamber to obtain the speed of radon escape from the water. The results are compared to a model [Cal 2002] where the radon concentration in the air and hence the transfer rate is measured using a RAD7 radon detector. Since the equations cannot be solved analytically, a numerical solution is employed. The radon transfer velocity coefficient is found to be (1.9&plusmn / 0.5)&times / 10-6m/s. This value indicates that the escape of radon should not be a problem when a sample is open to the air for a minute or two.</p>

In this work, numerical and experimental methods are used to characterise the effects of convective transport in an anode-supported tubular solid oxide fuel cell (SOFC). To that end, a computational fluid dynamics (CFD) model is developed to compare a full transport model to one that assumes convection is negligible. Between these two approaches, the variations of mass, temperature, and electrochemical performance are compared. Preliminary findings show that convection serves to reduce the penetration of hydrogen into the anode, and becomes more important as the thickness of the anode increases. The importance of the permeability of SOFC electrodes on the characterization of convection is also investigated. Experiments performed on Ni-YSZ anodes reveal that permeability is a function of the cell operating conditions, and increases with increasing Knudsen number. An empirical Klinkenberg relation is validated and proposed to more accurately represent the permeability of electrodes in a CFD model. This is a departure from an assumption of constant permeability that is often seen in the literature. It is found that a varying permeability has significant effects on pressure variation in the cell, although according to the electrochemical model developed in this work, variation in permeability is only found to have minor effects on the predicted performance. Furthermore, it is revealed that an electrochemical model which makes the simplifying assumption of constant overpotential is in error when predicting current and temperature variation. In this work, this is found to predict an unrealistic spatial variation of the current. It is suggested that this approach be abandoned for the solution of a transport equation for potential which couples the anodic and cathodic currents. This will lead to a more realistic prediction of temperature and performance. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2008-11-04 13:54:35.743

<p>This thesis aims to measure the rate of radon loss from water in a systematic way. The dependence on surface area, temperature and concentration will be investigated. The experiments were done at UWC by creating radon using radium sources and then measuring the radon concentrations inside a vacuum chamber to obtain the speed of radon escape from the water. The results are compared to a model [Cal 2002] where the radon concentration in the air and hence the transfer rate is measured using a RAD7 radon detector. Since the equations cannot be solved analytically, a numerical solution is employed. The radon transfer velocity coefficient is found to be (1.9&plusmn / 0.5)&times / 10-6m/s. This value indicates that the escape of radon should not be a problem when a sample is open to the air for a minute or two.</p>

Time-lapse seismic is a modern technology for monitoring production-induced changes in and around a hydrocarbon reservoir. Time-lapse (4D) seismic may help locate undrained areas, monitor pore fluid changes and identify reservoir compartmentalization. Despite several successful 4D projects, there are still many challenges related to time-lapse technology. Perhaps the most important are to perform quantitative time-lapse and to model and interpret time-lapse effects in thin layers. The former requires one to quantify saturation and pressure effects on rock elastic parameters. The latter requires an understanding of the combined response of time-lapse effects in thin layers and overcoming seismic vertical resolution limitation. / This thesis presents an integrated study of saturation and pressure effects on elastic properties. Despite the fact that Gassmann fluid substitution is standard practice to predict time-lapse saturation effects, its validity in the field environment rests upon a number of assumptions. The validity of Gassmann equations, ultimately, can only be tested in real geological environments. In this thesis I developed a workflow to test Gassmann fluid substitution by comparing saturated P-wave moduli computed from dry core measurements with those obtained from sonic and density logs. The workflow has been tested on a turbidite reservoir from the Campos Basin, offshore Brazil. The results show good statistical agreement between the P-wave elastic moduli computed from cores using the Gassmann equations and the corresponding moduli computed from log data. This confirms that all the assumptions of the Gassmann theory are adequate within the measurement error and natural variability of elastic properties. These results provide further justification for using the Gassmann theory to interpret time-lapse effects in this sandstone reservoir and in similar geological formations. / Pressure effects on elastic properties are usually obtained by laboratory measurements, which can be affected by core damage. I investigated the magnitude of this effect on compressional-wave velocities by comparing laboratory experiments and log measurements. I used Gassmann fluid substitution to obtain low-frequency saturated velocities from dry core measurements taken at reservoir pressure, thus mitigating the dispersion effects. The analysis is performed for an unusual densely cored well from which 43 cores were extracted over a 45 m thick turbidite reservoir. These computed velocities show very good agreement with the sonic-log measurements. This is encouraging because it implies that core damages that may occur while bringing the core samples to the surface are small and do not adversely affect the measurement of elastic properties on these core samples. Should core damage have affected our measurements, we would have expected a systematic difference between properties measured in situ and on the recovered. This confirms that, for this particular region, the effect of core damage on ultrasonic measurements is less than the measurement error. Consequently, stress sensitivity of elastic properties as obtained from ultrasonic measurements are adequate for quantitative interpretation of time-lapse seismic data. / In some circumstances, stress sensitivity may not be obtained by ultrasonic measurements. Cores may be affected by damage, bias in the plugging process and scale effects and therefore may not be representative of the in situ properties. Consequently it is desirable to obtain this dependence from an alternative method. This other approach ideally should provide the pressure - velocity dependence from an intact rock. Few methods can sample the in situ rock. Seismic, for instance, provides in situ information, but lacks vertical resolution. Well logs, on the other hand, can provide high vertical resolution information, but usually are not available before and after production changes. I propose a method to assess the in situ pressure - velocity dependence using well data. I apply this method to a reservoir made up of sandstone. I used 23 wells drilled and logged in different stages of development of a hydrocarbon field providing rock and fluid properties at different pressures. For each well logged at a specific time, pore pressure, velocity and porosity, among other properties, are known. Pore pressure is accessed from a Repeat Formation Tester (RFT). As a field depletes and new wells are drilled and logged, similar data sets related to different stages of depletion are available. I present an approach expanding Furre et al. (2009) study incorporating porosity and obtaining a three dimensional relationship with velocity and pressure. The idea is to help to capture rock property variability. / Quantitative time-lapse studies require precise knowledge of the response of rocks sampled by a seismic wave. Small-scale vertical changes in rock properties, such as those resulting from centimetre scale depositional layering, are usually undetectable in both seismic and standard borehole logs (Murphy et al., 1984). I present a methodology to assess rock properties by using X-ray computed tomography (CT) images along with laboratory velocity measurements and borehole logs. This methodology is applied to rocks extracted from around 2.8 km depth from offshore Brazil. This improved understanding of physical property variations may help to correlate stratigraphy between wells and to calibrate pressure effects on velocities, for seismic time-lapse studies. / Small scale intra-reservoir shales have a very different response from sands to fluid injection and depletion, and thus may have a strong effect on the equivalent properties of a heterogeneous sandstone reservoir. Since shales have very low permeability, an increase of pore pressure in the sand will cause an increase of confining pressure in the intra-reservoir shale. I present a methodology to compute the combined seismic response for depletion and injection scenarios as a function of net to gross (NTG or sand – shale fraction). This approach is appropriate for modelling time-lapse effects of thin layers of sandstones and shales in repeated seismic surveys when there is no time for pressure in shale and sand to equilibrate. I apply the developed methodology to analyse the sand - shale combined response to typical shale and sandstone stress sensitivities for an oil field located in Campos Basin, Brazil. For a typical NTG of 0.6, there is a difference of approximately 35% in reflection coefficient during reservoir depletion from the expected value if these shales are neglected. Consequently, not considering the small shales intra-reservoir may mislead quantitative 4D studies. / The results obtained in this research are aimed to quantify pressure and saturation effects on elastic properties. New methodologies and workflows have been proposed and tested using real data from South America (Campos Basin) datasets. The results of this study are expected to guide future time-lapse studies in this region. Further investigations using the proposed methodologies are necessary to verify their applicability in other regions.

Magister Scientiae - MSc / This thesis aims to measure the rate of radon loss from water in a systematic way. The dependence on surface area, temperature and concentration will be investigated. The experiments were done at UWC by creating radon using radium sources and then measuring the radon concentrations inside a vacuum chamber to obtain the speed of radon escape from the water. The results are compared to a model [Cal 2002] where the radon concentration in the air and hence the transfer rate is measured using a RAD7 radon detector. Since the equations cannot be solved analytically, a numerical solution is employed. The radon transfer velocity coefficient is found to be (1.9±0.5)×10-6m/s. This value indicates that the escape of radon should not be a problem when a sample is open to the air for a minute or two. / South Africa

Les composés à transition de spin forment une classe spécifique de matériaux pour lesquels la commutation de l’état de spin du centre métallique peut être pilotée par divers stimuli (T, P, irradiation lumineuse, …) et s’accompagne de changements remarquables des propriétés physiques (magnétiques, optiques, structurales ou encore vibrationnelles). Ils se distinguent des autres matériaux commutables par l’observation, pour un certain nombre d’entre eux, de processus coopératifs à l’état solide, donnant lieu à l’ouverture d’une hystérèse thermique (bistabilité) particulièrement intéressante pour le stockage de l’information. Un des challenges technologiques actuels est de réduire la taille des matériaux susceptibles d’application et de les mettre en forme au sein de dispositifs sans altérer pour autant leurs propriétés. Les objectifs de la thèse ont été d’élaborer des micro- et nanoparticules à conversion de spin à partir de composés moléculaires présentant une transition de spin du premier ordre à l’état massif, puis d’étudier et analyser l’influence de la taille et de la matrice dispersante sur les processus de transition de spin. Après un premier chapitre introductif portant sur les matériaux à transition de spin, les méthodes de nanochimie et de mise en forme, le deuxième chapitre décrit l’élaboration de particules des composés FeII(phen)2(NCX)2 (X = S, Se) et [FeIII(3-OMeSalRen)2]PF6 (R = Me, Et). Comme la technique de précipitation rapide convient pour des composés ioniques, son application à FeII(phen)2(NCX)2 composé neutre, a nécessité la mise au point d’une synthèse indirecte de particules, basée sur l’extraction de ligand de précurseurs solubles, et le contrôle via des paramètres expérimentaux, des étapes de nucléation-croissance. De nouvelles particules de composés ioniques de Fe(III) [FeIII(3-OMeSalRen)2]PF6 (R = Me, Et) et des films minces contenant ces particules dispersées dans un polymère (PVP) ont été préparées. Les études magnétique et optique de ces films montrent que la matrice et la mise en forme modifient toujours les caractéristiques de la transition de spin des particules.La deuxième partie des travaux a été consacrée à l’étude des effets d’environnement. L’interaction entre des microparticules de Fe(phen)2(NCS)2 et des matrices vitreuses (Tg > T1/2; T1/2, étant la température de transition) peut conduire à l’ouverture d’un large cycle d’hystérésis, déplacé vers les plus basses températures. Cette zone de bistabilité a été examinée à l’aide de la méthode FORC (First-Order Reversal Curves). L’analyse a permis d’établir l’existence de composantes réversibles attribuées aux interactions élastiques à l’interface matrice/particule et au changement de volume de la particule à transition de spin.L’étude des effets de matrice et de taille a été poursuivie avec des micro- et nanocristaux de [FeIII(3-OMeSalEen2]PF6 dispersés dans des polymères ou des liquides moléculaires formant des verres à basse température. L’encapsulation dans des verres rigides de particules haut-spin (T1/2 < Tg) ou bas-spin (T1/2 > Tg) donnent lieu à des conversions de spin déplacées respectivement vers les plus basses ou plus hautes températures, éventuellement des processus coopératifs avec hystérésis. Le renforcement de la coopérativité et la bistabilité observées dans le second cas ont été interprétés comme résultant des contraintes mécaniques vis-à-vis du changement de volume BS-HS de la particule. Enfin, le changement d’état de la matrice induit par des étapes de trempe (ou recuit) en-dessous (au-dessus) de la température de transition vitreuse, a été exploité pour moduler ces effets. Dans la perspective d’une application, de nouvelles études de composites ont été engagées avec des complexes présentant une transition de spin proche de la température ambiante. Le choix de la matrice dispersante selon certains critères (nature chimique, température de transition vitreuse) a permis de retrouver certains effets. / Spin-transition compounds are a class of materials for which the spin-state switching of the metal center can be controlled by various stimuli (T, P, light irradiation,...) and produces dramatic changes of physical properties (magnetic, optical, structural or vibrational). With respect to the set of switchable materials, a number of spin-transition compounds exhibit at solid-state cooperative processes and thermal hysteresis loops (bistability), particularly suitable for information storage. One of the current technological challenges is to integrate in devices such potentially interesting materials without altering their properties. The goal of the research, recently developed by several teams, is to determine the smaller size of object in which an information can be stored, and thus to understand the effect of downsizing on cooperativity and bistability. Therefore, the objectives of the Ph-D thesis were (i) to synthesize spin-crossover nano- and microparticles from molecular materials that in the form of bulk undergo a first-order phase transition; (ii), to investigate the importance of particles size and matrix effects on the spin-transition process.After a first chapter in which the spin crossover materials are introduced, the second chapter describes the synthesis of particles of FeII(phen)2(NCX)2 (X = S, Se) and [FeIII(3-OMeSalRen)2]PF6 (R = Me, E) compounds. As the fast precipitation technique essentially suits for ionic compounds, its application to neutral ones like FeII(phen)2(NCX)2, has been made possible by an indirect syntheses based on the ligand extraction from soluble precursors and the control of nucleation and growth processes of neutral products via experimental parameters. New particles of [FeIII(3-OMeSalEen)2]PF6 and thin films containing them after their dispersion in a polymeric matrix (PVP) have been prepared. The study of these films with UV-vis and magnetic measurements has raised the issue of the impact of the polymeric matrix and processing on the spin transition properties of these particles.The second part of the manuscript focuses on the interaction between the spin-crossover particles and the dispersing medium. This interaction between microparticles of Fe(phen)2(NCS)2 and glassy matrices (Tg > T1/2, T1/2, being the transition temperature) may result in the observation of large hysteresis loops shifted towards lower temperatures. This bistability has been examined with the FORC (First-Order Reversal Curves) method, magnetic measurements and a theoretical model. This analysis has shown the existence of reversible components associated to the particles/matrix interactions and the change of volume of spin-crossover particles.In a third part, the study of matrix and size effect has been pursued with micro- and nanocrystals of [FeIII(3-OMeSalEen2]PF6 encapsulated in polymeric or molecular liquids which form glasses at sufficiently low temperature. The encapsulation in rigid glasses of high spin (T1/2 < Tg) or low spin (T1/2 > Tg) particles give rise to transitions shifted towards lower or higher temperature respectively, possibly with cooperativity and hysteresis. The reinforcement of cooperativity and the bistability observed in the second case have been accounted for by the effect of the mechanical stress exerted by the glassy matrix on the particle volume. In addition, it has been shown that a thermal treatment of matrices (quenching or annealing steps below or above the glass transition) results in the modulation of the matrix effects. Finally, in the last chapter, a few composites including compounds undergoing a spin transition close to room temperature have been shortly investigated in presence of dispersing matrices. The choice of the matrices characteristics (chemical nature, glass transition temperature) has allowed some of these effects to be observed.

Quantifying the influence of pressure on the effective elastic rock properties is important for applications in rock physics and reservoir characterization. Here I investigate the relationship between effective pressure and seismic velocities by performing inversion on the laboratory-measured data from a suite of clastic, carbonate and igneous rocks, using different analytic and discrete inversion schemes. I explore the utility of a physical model that models a natural fracture as supported by asperities of varying heights, when an effective pressure deforms the tallest asperities, bringing the shorter ones into contact while increasing the overall fracture stiffness. Thus, the model is known as the ?asperity-deformation? (ADM) or ?bed-of-nails? (BNM) model. Existing analytic solutions include one that assumes the host rock is infinitely more rigid than the fractures, and one that takes the host-rock compliance into account. Inversion results indicate that although both solutions can fit the data to within first-order approximation, some systematic misfits exist as a result of using the rigid-host solution, whereas compliant-host inversion returns smaller and random misfits, yet out-of-range parameter estimates. These problems indicate the effects of nonlinear elastic deformation whose degree varies from rock to rock. Consequently, I extend the model to allow for the pressure dependence of the host rock, thereby physically interpreting the nonlinear behaviors of deformation. Furthermore, I apply a discrete grid-search inversion scheme that generalizes the distribution of asperity heights, thus accurately reproduces velocity profiles, significantly improves the fit and helps to visualize the distribution of asperities. I compare the analytic and numerical asperity-deformation models with the existing physical model of elliptical ?pennyshape? cracks with a pore-aspect-ratio (PAR) spectrum in terms of physical meaning and data-fitting ability. The comparison results provide a link and demonstrate the consistency between the use of the two physical models, making a better understanding of the microstructure as well as the contact mechanism and physical behaviors of rocks under pressure. ADM-based solutions, therefore, have the potential to facilitate modeling and interpretation of applications such as time-lapse seismic investigations of fractured reservoirs.