To ensure safety regarding dust explosion hazards, it is important to study the dust lifting process experimentally and identify important parameters that will be valuable for development and validation of numerical predictions of this phenomenon. A new shock tube test section was developed and integrated into an existing shock tube facility. The test section allows for shadowgraph or laser scattering techniques to track dust layer particle motion. The test section is designed to handle an initial pressure of 1 atm with an incident shock wave velocity up to Mach 2 to mimic real world conditions. The test section features an easily removable dust pan and inserts to allow for adjustment of dust layer thickness. The design allows for the changing of experimental variables including initial pressure, Mach number, dust layer thickness and characteristics of the dust itself. A separate vacuum manifold was designed to protect existing equipment from negative side effects of the dust. A study was performed to demonstrate the capabilities of the new facility and to compare results with experimental trends formerly established in the literature. Forty-micron limestone dust with a layer thickness of 3.2 mm was subjected to Mach 1.22 and 1.38 shock waves, and a high-speed shadowgraph was used for flow visualization. Dust layer rise height was graphed with respect to shock wave propagation. Dust particles subjected to a Mach 1.38 shock wave rose more rapidly and to a greater height with respect to shock wave propagation than particles subjected to a Mach 1.22 shock wave. These results are in agreement with trends found in the literature, and a new area of investigation was identified.

Biogeochemical reactions and vadose zone transport, in particular gas phase transport, are inherently coupled processes. To explore feedback mechanisms between these processes in a quantitative manner, multicomponent gas diffusion and advection are implemented into an existing reactive transport model that includes a full suite of geochemical reactions. Multicomponent gas diffusion is described based on the Dusty Gas Model, which provides the most generally applicable description for gas diffusion. Gas advection is described by Darcy's Law, which in the current formulation, is directly substituted into the transport equations. The model is used to investigate the interactions between geochemical reactions and transport processes with an emphasis to quantify reaction-induced gas migration in the vadose zone. Simulations of pyrite oxidation in mine tailings, gas attenuation in partially saturated landfill soil covers, and methane production and oxidation in aquifers contaminated by organic compounds demonstrate how biogeochemical reactions drive diffusive and advective transport of reactive and non-reactive gases. Pyrite oxidation in mine tailings causes a pressure reduction in the reaction zone and drives advective gas flow into the sediment column, enhancing the oxidation process. Release of carbon dioxide by carbonate mineral dissolution partly offsets pressure reduction, and illustrates the role of water-rock interaction on gas transport. Microbially mediated methane oxidation in landfill covers reduces the existing upward pressure gradient, thereby decreasing the contribution of advective methane emissions to the atmosphere and enhancing the net flux of atmospheric oxygen into the soil column. At an oil spill site, both generation of CH4 in the methanogenic zone and oxidation of CH4 in the methanotrophic zone contribute to drive advective and diffusive fluxes. The model confirmed that non-reactive gases tend to accumulate in zones of gas consumption and become depleted in zones of gas production. In most cases, the model was able to quantify existing conceptual models, but also proved useful to identify data gaps, sensitivity, and inconsistencies in conceptual models. The formulation of the model is general and can be applied to other vadose zone systems in which reaction-induced gas transport is of importance.

Direct Reduced Iron (DRI) is used as an alternative feedstock in electric arc furnaces, making up 50% or more of the total iron charge. DRI produced with coal based reductants (for example in rotary kilns) make up roughly 25% of DRI produced in the world. It was found that SL/RN DRI samples from a kiln cooler had high nitrogen contents (50-250ppm, depending on particle size), higher than DRI from gas-based reduction. The higher nitrogen content of SL/RN DRI would increase the levels of nitrogen of liquid steel produced in the EAFs. The problem is exacerbated by the fact that the SL/RN DRI contains virtually no carbon (which would aid in preventing nitrogen pickup). The proposed mechanism of nitrogen pick-up by the SL/RN DRI is one where nitrogen present within the atmosphere of the rotary cooler (where hot DRI, discharged at 1000°C from the rotary kiln, is cooled to approximately 100 °C in ca. two hours) penetrates the solids bed and nitrides DRI particles. Possible rate-determining steps for nitriding in the cooler have been evaluated. Nitriding of DRI particles is predicted to be rapid: the most plausible location for rapid nitrogen pickup is the first 5 meters of the rotary cooler, where the high temperature, nitrogen-rich gas atmosphere and rapid solids bed mixing are conducive to nitriding; solid-state and pore diffusion of nitrogen into DRI particles are predicted to be rapid too. The most plausible rate determining step for nitriding of DRI particles is that of nitrogen dissociation on the DRI surface, which can be further retarded by the presence of sulphur. A strong correlation was found between the amount of “melt-in” carbon in the liquid steel and the final tap nitrogen content, with 0.3% C resulting in nitrogen levels as low as 50 ppm (80 ppm or less is desired on the plant in question) at tap, even with DRI material that is high in nitrogen and contains virtually no carbon. Proposals to increase the melt-in carbon are included. / Dissertation (MEng)--University of Pretoria, 2013. / gm2014 / Materials Science and Metallurgical Engineering / unrestricted

Des gaz vont être générés par corrosion des conteneurs de déchets radioactifs au niveau d'un stockage en couche géologique profonde. Une bulle de gaz se crée et monte en pression. Si le gaz pénètre difficilement la formation géologique, l'augmentation de pression pourra la fissurer et créer des chemins préférentiels à la migration de radionucléides. Les argilites du Callovo-Oxfordien sont ici caractérisées. Un dispositif permettant de mesurer de très faibles perméabilités à l'hydrogène/hélium a été utilisé couplé au Dusty Gas Model. Les argilites proches de la saturation ont une porosité accessible au gaz inférieure à 1% voire 0,1% de la porosité totale. A partir de l'étude de l'effet Knudsen cette porosité pourrait être due à des pores de 50 à 200 nm de diamètre mis en évidence lors de la caractérisation des réseaux. En intégrant ces résultats dans un modèle opérationnel de l'ANDRA, la pression maximale atteinte au sein d'une alvéole de stockage serait de 83 bar.

In this thesis we show how reactive processes can be affected by the presence of different types of spatial constraints, so much so that their nonlinear dynamics can be qualitatively altered or that new and unexpected behaviors can be produced. To understand how this interplay can occur in general terms, we theoretically investigate four very different examples of this situation. <p><p>The first system we study is a reversible trimolecular chemical reaction which is taking place in closed one-dimensional lattices. We show that the low dimensionality may or may not prevent the reaction from reaching its equilibrium state, depending on the microscopic properties of the molecular reactive mechanism. <p><p>The second reactive process we consider is a network of biological interactions between pigment cells on the skin of zebrafish. We show that the combination of short-range and long-range contact-mediated feedbacks can promote a Turing instability which gives rise to stationary patterns in space with intrinsic wavelength, without the need of any kind of motion.<p><p>Then we investigate the behavior of a typical chemical oscillator (the Brusselator) when it is constrained in a finite space. We show that molecular crowding can in such cases promote new nonlinear dynamical behaviors, affect the usual ones or even destroy them. <p><p>Finally we look at the situation where the constraint is given by the presence of a solid porous matrix that can react with a perfect gas in an exothermic way. We show on one hand that the interplay between reaction, heat flux and mass transport can give rise to the propagation of adsorption waves, and on the other hand that the coupling between the chemical reaction and the changes in the structural properties of the matrix can produce sustained chemomechanical oscillations. <p><p>These results show that spatial constraints can affect the kinetics of reactions, and are able to produce otherwise absent nonlinear dynamical behaviors. As a consequence of this, the usual understanding of the nonlinear dynamics of reactive systems can be put into question or even disproved. In order to have a better understanding of these systems we must acknowledge that mechanical and structural feedbacks can be important components of many reactive systems, and that they can be the very source of complex and fascinating phenomena.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished