The aim of the study was to investigate if methane emission in a constructed wetland changed in a diurnal pattern correlating to temperature, humidity or light conditions. The gas measurements were carried out with a static chamber technique. The wetland (in Nykvarn outside of Linköping, Sweden) takes care of wastewater to reduce the nitrogen loads. Measurements were carried out at three different occasions in the summer of 1998 on two sites in the wetland. One site was close to the inflow, inhabited by Lemnaceae, and another site was located further downstream inhabited by the emergent macrophyte Typha latifolia. The results showed a variation, but no discernible diurnal pattern. The Typha site had a methane emission rate of 166 mg CH4 m-2d-1 and the Lemnaceae site had an methane emission rate of 712 mg CH4 m-2d-1. In all experiments at the Typha site, the highest methane emission rate was obtained at sunrise.

Dissociation of gas hydrates has been the primary concern of the oil and gas industry for flow assurance, mainly in an offshore environment. There is also a growing interest in the rapid formation of gas hydrates for gas storage, transport of natural gas and carbon sequestration. In this thesis, we experimentally measure the kinetics of formation and dissociation of methane hydrates and the effect of various anionic and cationic surfactants such as sodium dodecyl sulfate (SDS), cetyl trimethylammonium bromide (CTAB) and alpha olefin sulfonate (AOS) on the association/dissociation rate constants. The importance and necessity of micelle formation in these surfactants has been studied. The effect of foam generation on the rate of formation of these hydrates has also been measured. SDS was found to significantly decrease the induction time for hydrate formation. There was an added decrease in the induction time when a foamed mixture of water and SDS was used. On the other hand CTAB and AOS had an inhibiting effect. The contribution of micelles towards promoting hydrate formation was demonstrated with a series of experiments using SDS. The micelles formed by these surfactants appear to serve as nucleation sites for the association of hydrates. New experimental data is presented to show that some surfactants and the use of foam can significantly increase the rate of hydrate formation. Other surfactants are shown to act as inhibitors. A new experimental setup is presented that allows us to distinguish between surfactants that act as promoters and inhibitors for hydrate formation. / text

Die grundlegenden Aspekte chemischer Reaktionen auf Oberflächen können anhand von geeigneten Modelsystemen unter Vakuumbedingungen untersucht werden. Siliciumdioxid (SiO2) als wichtiges Material für hochmoderne Technologieanwendungen in der Mikroelektronik, Photonik und Katalyse, war Gegenstand zahlreicher Studien, um die Beziehungen zwischen der atomaren Struktur und funktionalen Eigenschaften von Silizium-basierten Materialien zu erklären. Diese Arbeit untersucht die Wechselwirkung von Gasen mit epitaktisch gewachsenen Silikat-Dünnschichten auf einem Ru(0001) Einkristall. Unter Verwendung von Infrarot-Reflexions-Absorptions-Spektroskopie (IRAS) und temperaturprogrammierter Desorptionspektroskopie (TPD) konnten die Hydroxy-Spezies auf reinen Silikatfilmen als isolierte Silanole (Si-OH) identifiziert werden. Isotopenexperimente haben gezeigt, dass sich thermisch stabile Oberflächenhydroxylate hauptsächlich aus der Adsorption von Wassermolekülen bilden. Ein Austausch der Silanole mit Sauerstoffatomen im Kristallgitter während des Dehydroxylierungsprozesses wurde nicht beobachtet. Durch die Adsorption von Gasen wie CO, H2 und O2 bei erhöhtem Druck, lässt sich auf komplexere Prozesse schließen. Dies beinhaltet Gastransport durch Poren im Film, was mit strukturellen Defekten in dem Silikatfilm verbunden ist, sowie nachfolgende Adsorption und Diffusion auf dem unterliegenden Ru(0001)-Substrat. Während der Einlagerung der Moleküle in die Silikatschicht bleibt der Oxidfilm auch unter hohem Druck (~ 10 mbar) sowie hoher Temperatur (~900 K) intakt. Solch ein Hybridsystem, welches eine robuste Siliciumdioxidmembran mit einem sich darunter befindlichen, chemisch aktiven Metall kombiniert, könnte ein interessantes Materialsystem für technische Anwendungen darstellen, insbesondere zur Herstellung von Katalysatoren und Sensoren sowie für Korrosionsanwendungen. / The fundamental aspects of the chemical reactions at surfaces can be elucidated by using well-defined model systems under the controlled conditions provided by vacuum-based techniques. Silicon dioxide (SiO2) as one of the crucial materials in modern technological applications, including microelectronics, photonics, and catalysis, has been subjected to numerous studies in order to rationalize relationships between the atomic structure and functional properties of silica-based materials. This work marks the attempt to understand interaction of ambient gases with a well-ordered, ultrathin silicate film grown on a Ru(0001) substrate. Using infrared reflection absorption spectroscopy (IRAS) and temperature programmed desorption (TPD), hydroxo species, primarily in the form of isolated silanols (Si-OH), were identified on pristine silicate films. Isotopic experiments demonstrated that surface hydroxyls form primarily from the water molecules. Silanols do not undergo scrambling with the lattice oxygen atoms upon dehydroxylation. Steps on a silicate sheet and/or “holes” in these ultrathin films are proposed as active sites for hydroxylation. Adsorption of gases such as CO, H2 and O2 at elevated pressures revealed a more complex behavior. It involves gas transport through the pores, associated with structural defects in the silicate film, subsequent adsorption, and diffusion across the Ru(0001) surface underneath. During this intercalation, the silicate film stays intact even under high pressure (~10 mbar) and high temperature conditions (~900 K). The silicate layer does however strongly passivate the Ru surface towards RuO2(110) formation that readily occurs on bare Ru(0001) under the same conditions. Such a hybrid system, which combines a robust silica “membrane” and a chemically active metal underneath, could become an interesting material for technological applications, in particular in catalysis, sensors and anti-corrosion applications.

Les sols et les activités agricoles qu’ils supportent, contribueraient à environ 2/3 des émissions globales de protoxyde d’azote (N2O), un puissant gaz à effet de serre. L’objectif de la thèse était la compréhension des déterminismes des émissions de N2O liés aux propriétés hydriques des sols. Des expérimentations de laboratoire permettant le contrôle hydrique fin d’échantillons de sol, en saturation et en désaturation, et la mesure des flux de N₂O ont été menées. Un couplage avec la tomographie par rayons-X a par ailleurs permis de caractériser la connectivité gazeuse. Enfin, une démarche de modélisation a permis de tester les hypothèses de fonctionnement émises, et de poursuivre la démarche de réflexion sur le lien entre les propriétés hydriques des sols et les émissions de N₂O. On a mis en évidence le rôle des propriétés hydriques des sols dans la variabilité des émissions de N₂O couramment observées, et la nécessité de distinguer des périodes de production/consommation de N₂O et de transport. On retiendra ainsi le fort caractère dynamique des émissions de N₂O, en lien avec la phase hydrique (saturation ou désaturation), le fonctionnement hydrodynamique des sols, le transport gazeux et la configuration spatiale de l’air et de l’eau dans le réseau de pores. Afin de décrire l’intensité et le timing des pics de N₂O, il est apparu pertinent d’observer les paramètres potentiel matriciel, coefficient de diffusion gazeuse et connectivité gazeuse, en plus de la teneur en eau. Ces observations ont des implications sur la modélisation des flux de N₂O. On recommande ainsi l’utilisation couplée de modules de transport hydrique, de transport gazeux et en solution de N₂O, en plus de modules de production microbiologique, pour prédire efficacement les émissions de N₂O. / Soils and associated agricultural activities are estimated to account for about 2/3 of the global emissions of nitrous oxide (N₂O), a potent greenhouse gas. The aim of the thesis was to understand the controls linked to soil hydric properties on N₂O emissions. Laboratory experiments were designed to control the hydric status of soil samples during wetting and drying, and to measure N₂O fluxes. Moreover, a coupling with X-ray computed tomography allowed characterizing the gaseous connectivity. Finally, a modeling approach allowed testing the hypotheses of functioning, and to further discuss the links between hydric properties and N₂O emissions. We highlighted the role of soil hydric properties on the variability of N₂O emissions which is often measured, and the need to distinguish N₂O production/consumption and transport phases. The highly dynamic nature of N₂O emissions was linked to the hydric phase (wetting or drying), soil hydrodynamic functioning, gas transport, and spatial configuration of water and air in the pore network, in addition to the water-filled pore space parameter. These observations have implications for N₂O emission modeling. We recommend thus the coupled use of hydric transport, and modules of gas and liquid transport of N₂O, in addition to microbial production modules to efficiently predict N₂O emissions.

Increasingly growing consumption of natural gas all around the world requires development of new transporting equipment and optimization of existing pipelines and gas pumping facilities. As a special case, Russian gas pumping system has the longest pipes with large diameter, which carry great amounts of natural gas. So, as reconstruction and modernization needs large investments, a need of more effective and low cost tool appeared. As a result diagnostics became the most wide-spread method for lifecycle assessment, and lifecycle extension for gas pumping units and pipelines.One of the most effective method for diagnostics of gas pumping units is parametric diagnostics. It is based on evaluation of measurement of several termo-gas dynamic parameters of gas pumping units, such as pressures, temperatures and rotational speed of turbines and compressors.In my work I developed and examined a special case of parametric diagnostics – methodic for evaluation of technical state and output parameters for gas pumping unit “Ural-16”. My work contains detailed analysis of various defects, classified by different GPU’s systems. The results of this analysis are later used in development of the methodic for calculation of output parameters for gas pumping unit.GPU is an extremely complex object for diagnostics. Around 200 combinations of Gas Turbine engines with centrifugal superchargers, different operational conditions and other aspects require development of separate methodic almost for each gas pumping unit type.Development of each methodic is a complex work which requires gathering of all possible parametric and statistical data for the examined gas pumping unit. Also parameters of compressed gas are measured. Thus as a result a number of equations are formed which finally allow to calculate such parameters as efficiency, fuel gas consumption and technical state coefficient which couldn’t be measured directly by existing measuring equipment installed on the gas compressor station.

Sustainable growth and development in a society requires energy supply that is efficient, affordable, readily available and, in the long term, sustainable without causing negative societal impacts, such as environmental pollution and its attendant consequences. In this respect, proton exchange membrane (PEM) fuel cells offer a promising alternative to existing conventional fossil fuel sources for transport and stationary applications due to its high efficiency, low-temperature operation, high power density, fast start-up and its portability for mobile applications. However, to fully harness the potential of PEM fuel cells, there is a need for improvement in the operational performance, durability and reliability during usage. There is also a need to reduce the cost of production to achieve commercialisation and thus compete with existing energy sources. The present study has therefore focused on developing novel approaches aimed at improving output performance for this class of fuel cell. In this study, an innovative combined numerical computation and optimisation techniques, which could serve as alternative to the laborious and time-consuming trial-and-error approach to fuel cell design, is presented. In this novel approach, the limitation to the optimal design of a fuel cell was overcome by the search algorithm (Dynamic-Q) which is robust at finding optimal design parameters. The methodology involves integrating the computational fluid dynamics equations with a gradient-based optimiser (Dynamic-Q) which uses the successive objective and constraint function approximations to obtain the optimum design parameters. Specifically, using this methodology, we optimised the PEM fuel cell internal structures, such as the gas channels, gas diffusion layer (GDL) - relative thickness and porosity - and reactant gas transport, with the aim of maximising the net power output. Thermal-cooling modelling technique was also conducted to maximise the system performance at elevated working temperatures. The study started with a steady-state three-dimensional computational model to study the performance of a single channel proton exchange membrane fuel cell under varying operating conditions and combined effect of these operating conditions was also investigated. From the results, temperature, gas diffusion layer porosity, cathode gas mass flow rate and species flow orientation significantly affect the performance of the fuel cell. The effect of the operating and design parameters on PEM fuel cell performance is also more dominant at low operating cell voltages than at higher operating fuel cell voltages. In addition, this study establishes the need to match the PEM fuel cell parameters such as porosity, species reactant mass flow rates and fuel gas channels geometry in the system design for maximum power output. This study also presents a novel design, using pin fins, to enhance the performance of the PEM fuel cell through optimised reactant gas transport at a reduced pumping power requirement for the reactant gases. The results obtained indicated that the flow Reynolds number had a significant effect on the flow field and the diffusion of the reactant gas through the GDL medium. In addition, an enhanced fuel cell performance was achieved using pin fins in a fuel cell gas channel, which ensured high performance and low fuel channel pressure drop of the fuel cell system. It should be noted that this study is the first attempt at enhancing the oxygen mass transfer through the PEM fuel cell GDL at reduced pressure drop, using pin fin. Finally, the impact of cooling channel geometric configuration (in combination with stoichiometry ratio, relative humidity and coolant Reynolds number) on effective thermal heat transfer and performance in the fuel cell system was investigated. This is with a view to determine effective thermal management designs for this class of fuel cell. Numerical results shows that operating parameters such as stoichiometry ratio, relative humidity and cooling channel aspect ratio have significant effect on fuel cell performance, primarily by determining the level of membrane dehydration of the PEM fuel cell. The result showed the possibility of operating a PEM fuel cell beyond the critical temperature ( 80„aC), using the combined optimised stoichiometry ratio, relative humidity and cooling channel geometry without the need for special temperature resistant materials for the PEM fuel cell which are very expensive. In summary, the results from this study demonstrate the potential of optimisation technique in improving PEM fuel cell design. Overall, this study will add to the knowledge base needed to produce generic design information for fuel cell systems, which can be applied to better designs of fuel cell stacks. / Thesis (PhD)--University of Pretoria, 2012. / Mechanical and Aeronautical Engineering / unrestricted

Ce travail a eu pour objectif la création de matériaux composites à base de nanocharges de carbonate de calcium. L'étude des phénomènes interfaciaux qui régissent ces systèmes, ainsi que leurs impacts sur les propriétés fonctionnelles du matériau et plus particulièrement des propriétés de transport, ont été réalisées. Pour ce faire, nous avons considéré deux matrices polymères de nature chimique différente : le polylactide et le polyfluore de vinylidène. Les nanocomposites ont été élaborés par deux voies de mise en œuvre : la voie fondu et la voix solvant. Une analyse fine des relations structure/morphologie/propriétés des composites a été réalisée. Nous avons mis en évidence, quelle que soit la matrice polymère choisie, l'importance du traitement de surface des charges afin d'améliorer leurs états de dispersion dans le matériau et d'augmenter la qualité de l'interface charge/polymère. Ces paramètres ont été corrélés aux propriétés de transport de ces matériaux composites. / The aim of this PhD work is to elaborate composites based on calcium carbonate nanoparticles. Polylactide and polyvinylidene fluoride were used as polymer matrix and nanocomposite were elaborated either by melting process and either by casting method. The interfacial behaviour between polymer and calcium carbonate were studied and we especially focused on their impact on the composite gas barrier properties. The importance of filler surface treatment had been highlighted on the filler dispersion state improvment and filler/polymer interface reinforcement. Both parameters were important in the improvement of composite gas barrier properties.

Diese Arbeit liefert, in den ersten beiden Kapiteln einen allgemeinen Überblick über die klassischen Ansätze zur Optimierung unter Unsicherheit mit einem Schwerpunkt auf probabilistischen Randbedingung. Anschließend wird im dritten Kapitel eine neue Klasse von sogenannten Probust Randbedingungen beim Auftreten von Modellen mit unsicheren Parametern mit teilweise stochastischem und teilweise nicht-stochastischem Charakter eingeführt. Wir zeigen dabei die Relevanz dieser Aufgabentypen für zwei Problemstellungen in einem stationären Gasnetz auf. Erstens liegen beim Gastransport probabilistische Randbedingungen bezüglich der Gasnachfrage vor sowie auch robuste Randbedin- gungen bezüglich der Rauheitskoeffizienten in den Rohren, welche in der Regel unbekannt sind, da es keine zuverlässigen Messmöglichkeiten gibt. Zweitens lösen wir ein Problem für einen Netzbetreiber, der zum Ziel hat, die angebotene Kapazität für alte und neue Kunden zu maximieren. In diesem Fall ist man mit einer ungewis- sen Gesamtnachfrage konfrontiert, die sich aus der probabilistischen Nachfrage für Altkunden und der robusten Nachfrage für Neukunden zusammensetzt. Für beide Fälle zeigen wir, wie mit probusten Randbedingungen im Rahmen der sogenannten sphärisch-radialen Zerlegung multivariater Gauß-Verteilungen umgegangen werden kann. Starke und schwache Halbstetigkeitsergebnisse werden für den allgemeinen Fall, in Abhängigkeit davon ob Strategien in Lebesgue oder Sobolev Räumen angenommen werden, erstellt. Für ein ein- faches zweistufiges Modell werden überprüfbare Bedingungen für die Lipschitz- Stetigkeit und die Differenzierbarkeit dieser Wahrscheinlichkeitsfunktion abgeleitet und mit expliziten Ableitungsformeln unterstützt. Diese Werkzeuge werden dann verwendet, um das Problem des Bäckers und zwei Probleme des Wasserkraftmanagements zu lösen. / This thesis offers, in the first and second chapter, a general overview of the classical approaches to solving optimization under uncertainty, with a focus on probabilistic constraints. Then, in the third chapter, a new class of so-called Probust constraints is introduced in the presence of models with uncertain parameters having partially stochastic and partially non-stochastic character. We show the relevance of this class of approach and solve two problems in a stationary gas network. First, in the context of gas transportation, one ends up with a constraint, which is probabilistic with respect to the load of gas and robust with respect to the roughness coefficients of the pipes (which are uncertain due to a lack of attainable measurements). Secondly, we solve a problem for a network operator, who would like to maximize the offered capacity for old and new customers. In this case, one is faced with an uncertain total demand which is probabilistic for old clients and robust for new clients. In both problems, we demonstrate how probust constraints can be dealt within the framework of the so-called spheric-radial decomposition of multivariate Gaussian distributions. Furthermore, in chapter four, we present novel structural and numerical results for optimization problems under a dynamic joint probabilistic constraint. Strong and weak semicontinuity results are obtained for the general case depending on whether policies are supposed to be in Lebesgue or Sobolev spaces. For a simple two-stage model, verifiable conditions for Lipschitz continuity and differentiability of this probability function are derived and endowed with explicit derivative formulae. These tools are then used to solve the Baker's problem and two hydro-power management problems.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.