This dissertation determines theoretical targets for producing biogas. Calculations were based on the relationship between the mass of substrate used (assumed to be glucose) versus the amount and composition of gas produced. Methane, hydrogen and carbon dioxide were considered as gases produced by biogas processes. The calculations undertaken to determine the production rates and environmental targets of the biogas production system were based on mass and energy balances as well as the second law of thermodynamics. These were applied to determine the limits of performance of the process. These limits are important due to the fact that they cannot be exceeded even if we genetically engineer organisms or change the equipment design or operation. Combining the results enabled us to plot an attainable region that showed the achievable composition of the gas as well as the minimum work and energy requirements for biogas production. It shows that the process is hydrogen and enthalpy (heat) limited. Furthermore the results show that a maximum of 3 moles of methane per mole of glucose are produced sustainably which in turn produces a large heat load of 142 kJ/mol of glucose. / Physics / M. Sc. (Physics)

This thesis is devoted to the study of a deformable material interface between two immiscible moving<p>media, both of them being magnetizable. The first part concerns the establishment of a complete set of dynamical equations allowing a complete description of the non equilibrium phenomena including a coupling between the internal angular momentum and the electromagnetic field. The effects of the relaxation processes are also discussed. We show that the deformation of the interface introduces a nonlinear term, proportional to the mean curvature, in<p>the surface dynamical equations of mass momentum and angular momentum. That term<p>intervenes also in the singular magnetic and electric fields inside the interface which lead to<p>the influence of currents and charge densities at the interface. In a second part, we give the expression<p>for the entropy production inside the interface as well as in the bulk phase. Using the general principles of non equilibrium thermodynamics, we compute the different thermodynamical fluxes. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Les petites machines, comme les moteurs moléculaires ou les particules actives, fonctionnent dans un environnement fortement fluctuant qui affecte leur efficacité ou leur puissance. L'objectif de cette thèse est de décrire les petites machines à l'aide de la thermodynamique stochastique et de la théorie des grandes déviations. En reliant localement puis globalement les courants aux forces thermodynamiques, on introduit une matrice de conductance hors d'équilibre, qui généralise la matrice d'Onsager pour un système stationnaire hors d'équilibre. Cela permet de majorer l'efficacité des machines par une fonction universelle qui ne dépend que du degré de couplage entre les courants d'entrée et de sortie. On obtient aussi de nouvelles relations générales entre puissance et efficacité. Du point de vue des fluctuations, la matrice de conductance hors d'équilibre est reliée à une borne quadratique pour les fonctions de grande déviation des courants. Cette borne permet d'obtenir des bornes pour les fonctions de grande déviation de l'efficacité, mais aussi de revisiter le théorème de fluctuation-dissipation comme une inégalité dans le cas des systèmes loin de l'équilibre. Pour terminer, on étudie l'effet d'une brisure d'ergodicité sur les fluctuations d'observables comme l'activité, les courants ou l'efficacité. En particulier, on calcule la fonction de grande déviation de l'efficacité pour un ensemble de nanomachines en interaction pour lesquelles un couplage fort et une brisure d'ergodicité apparaissent à la limite thermodynamique. / Small machines -- like molecular motors or active particles -- operate in highly fluctuating environments that affect their efficiency and power. This thesis aims at describing small machines using stochastic thermodynamics and large deviation theory. By relating mean currents to thermodynamic forces, locally first and then at the global level, we introduce the non-equilibrium conductance matrix that generalizes the Onsager matrix for stationary non-equilibrium systems. We use it to bound machine efficiency by a universal function depending only on the degree of coupling between input and output currents and to find new general power-efficiency trade-offs. On the fluctuations side, the non-equilibrium conductance matrix can be used to find a quadratic bound on the large deviation function of currents. This enables to revisit the fluctuation-dissipation theorem as an inequality when dealing with far-from-equilibrium systems, but also to derive bounds on the efficiency large deviation function. Finally, we study the effects of ergodicity breaking on the fluctuations of observables like activity, currents or efficiency. In particular, we derive the efficiency large deviation function for a model of interacting nanomachines, for which tight coupling and ergodicity breaking emerge in the thermodynamic limit.

Les matériaux poreux ont une importance stratégique en génie chimique, par exemple en capturant les gaz à effet de serre, la séparation et la purification, les catalyseurs et la conception de capteurs. En raison de la diversité des matériaux poreux et des propriétés thermodynamiques des fluides confinés affectés par autant de matériaux et de propriétés des fluides, les méthodes classiques de la mécanique statistique sont encore étudiées au cas par cas, ce qui rend difficile l’offre des variables de contrôle. de fluide confiné ni pour fournir un motif régulier de fluide confiné. L'élaboration de théories thermodynamiques ou des lois d'échelle universelles permettant de décrire avec précision les fluides confinés devient de plus en plus importante. Cette thèse étudie la relation entre le fluide confiné et le fluide en vrac correspondant, les propriétés interfaciales des fluides sur une surface courbe, l'équation d'état générale des fluides confinés et l'effet de trempe.Une relation de mise à l'échelle générale relie le fluide confiné et le fluide en vrac. Cette relation d'échelle montre que la différence de propriétés thermodynamiques entre un fluide confiné et un fluide en vrac peut être décrite uniquement par la porosité, la quantité d'adsorption en excès et la pression du système en vrac équilibré. La relation intrinsèque entre la relation d’échelle et la théorie d’adsorption de Gibbs est également révélée. En combinant le SPT et la thermodynamique morphologique, nous avons d'abord proposé un SPT augmenté pour explorer les propriétés interfaciales des fluides sur une surface incurvée. En introduisant un terme de courbure d'ordre supérieur, une nouvelle équation d'état offrant une expression plus précise de la tension interfaciale d'un fluide sur une surface sphérique est obtenue. Pour construire une équation d'état générale pour des fluides confinés et explorer les variables de contrôle des fluides confinés, en combinant thermodynamique morphologique et SPT, nous avons introduit la première équation d'état pour un fluide confiné, sans rapport avec le modèle de matériau poreux. Dans cette équation d'état, quatre propriétés géométriques du matériau poreux, à savoir la porosité, l'aire de l'interface solide-fluide, la courbure moyenne et la courbure gaussienne, sont considérées comme des variables de contrôle. Les variables indépendantes sont le potentiel chimique et la température. Les résultats de cette équation d'état concordent parfaitement avec la simulation moléculaire. L'effet de confinement est lié à son potentiel chimique. Nous avons d’abord étudié l’influence des conditions confinées sur le potentiel chimique des fluides. Les résultats montrent qu’une augmentation du potentiel chimique, ce qui signifie que l’augmentation de la résistance des fluides dans les matériaux poreux peut être obtenue en réduisant la porosité, en augmentant la densité du fluide ou en augmentant la surface d’interface solide-liquide. / Porous materials have strategically important in chemical engineering, e.g., capturing Greenhouse gas, separation and purification, catalysts, and design of sensors. Due to the variety of porous materials, and thermodynamic properties of confined fluid are affected by so many materials and fluid properties, studies of classical statistical mechanic methods are still on a case-by-case way, which is hard to offer neither the control variables of confined fluid nor to provide a regular pattern of confined fluid. The development of thermodynamic theories or the universal scaling laws that can accurately describe confined fluids becomes more and more important. This thesis investigates the relation between confined fluid and the corresponding bulk fluid, interfacial properties of fluids at a curved surface, the general equation of state for confined fluids, and quench effect.With the help of scaled particle theory (SPT) and molecular simulation, a general scaling relation that connects the confined fluid and bulk fluid is found. This scaling relation shows that the difference of thermodynamics properties between confined fluid and bulk fluid can be described by only porosity, excess adsorption amount, and the pressure of equilibrated bulk system. The intrinsic relation between scaling relation and Gibbs adsorption theory is also revealed. By combining SPT and morphological thermodynamics, we first proposed an augmented SPT to explore the interfacial properties of fluids at a curved surface. By introducing a higher order curvature term, a new equation of state which offers a more accurate expression of the interfacial tension of fluid at a spherical surface is derived. To construct a general equation of state for confined fluids and explore the control variables of confined fluids, by combining morphological thermodynamic and SPT, we introduced the first equation of state for confined fluid which is irrelevant to the model of porous material. In this equation of state, four geometric properties of porous material, i.e., the porosity, the area of solid-fluid interface, integrate mean and Gaussian curvature are considered as control variables. Independent variables are chemical potential and temperature. Results from this equation of state have a great agreement with molecular simulation in a wide range. The confinement effect is related to its chemical potential. We first studied the influence of confined conditions on the chemical potential of fluids. Results show that an increase on chemical potential, which means the increase of resistance of fluids into porous materials can be led by reducing the porosity, or increasing the fluid density, or increasing the area of solid-liquid interface.

Ph. D. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / A major challenge for this generation is cleaning up heavy metal pollution disposed during industrial, domestic and agricultural activities. So, to obtain clean water resources, new treatment technologies are needed that can be applied to a broad range of highly toxic heavy metals in water. In this study, metal organic frameworks (MOFs) were synthesized from 1,2,4,5-tertabenzene carboxylic acid with metal salts of; cobalt, copper, iron, antimony, strontium and lanthanum through solvothermal method. The synthesized MOFs were reacted with polyvinyl alcohol (PVA) by electrospinning. To the best of our knowledge it is for the first time that such hybrid materials are synthesized and reported. PVA/MOF materials were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and thermogravimetry analyzer (TGA). The SEM micrographs of PVA/MOFs materials showed relatively uniform nanofibers that were non-beaded and entangled. Some formed patches, while others were partially cross linked. TGA analysis revealed that PVA/MOF nanofibers exhibited higher decomposition temperature than PVA nanofibres. Thus, it confirmed the interactive force between MOF and PVA nanofibres. FTIR plots also exhibited shifts in critical functional group positions, thus it confirmed that there was a given amount of MOFs embedded in the electrospun fibrous mat. PVA/MOFs materials were used in the adsorption of lead ions in solution to study the effects of temperature, time dependant studies and concentrations. The batch adsorption experiments were performed at five different Pb(II) ion concentrations (20, 40, 60, 80 and 100 mg/L), four different temperatures (25, 40, 60 and 80 oC), time dependent studies ranged from (5, 10, 30 and 60 min) and pH of all Pb(II) solutions were recorded to be 5.05. The results indicated that the uptake performance of PVA and PVA/MOFs nanofibers significantly changed with concentration, temperature and time. The PVA/MOFs nanofiber hybrids demonstrated greater adsorption percentage and adsorption capacity for Pb(II) ions than PVA nanofibers. PVA nanofibers showed moderate adsorption percentage and capacity performance of 25.5 % and 44.13 mg/g (meaning 44.13 mg of Pb(II) per gram of PVA nanofibers) while PVA/MOFs nanofibers showed improved percentage and capacity perfomance (PVA/Cu-MOFs 76.36 % and 152.72 mg/g), (PVA/Co-MOFs 59.41 % and 99.28 mg/g), (PVA/La-MOFs 92.27 % and 184.03 mg/g), (PVA/Cd-MOFs 83.19 % and 165.94 mg/g), (PVA/Sb-MOFs 50.66 % - 91.57 mg/g), (PVA/Sr-MOFs 58.85 % - 124.82 mg/g) and (PVA/Fe-MOFs 56.76 % - 108.82 mg/g). The adsorption data of Pb(II) ions on PVA and all PVA/MOFs nanofibers showed that a pseudo-second order kinetic model was more suitable than a pseudo first order kinetic model. The adsorption rate was much faster on PVA/MOFs nanofibers. This is marked by lower activation energy compared to PVA nanofibers activation energy. The Temkin model did not correlate well with all the adsorption data. On the contrary, Freundlich and Langmuir isotherm models described the adsorption data adequately. All PVA/MOFs nanofibers followed Langmuir isotherm model, only PVA nanofibers followed Freundlich isotherm model. The PVA and PVA/MOFs nanofibers gave negative values of enthalpy change (ΔHo) and negative values of Gibbs free energy change (ΔGo) showing the adsorption processes were exothermic and spontaneous. Moreover, obtained positive entropy changes (ΔSo) on PVA, PVA/Fe-MOF, PVA/Cu-MOF, PVA/Co-MOF and PVA/Sb-MOF nanofibers showed that the sorped Pb(II) ions were not restricted on the electrospun nanofibres and physisorption mechanism was dominant, while negative entropy changes (ΔSo) on PVA/Sr-MOF and PVA/La-MOF nanofibers indicated that chemisorption was more dominant. The influence of ubiquitous cations such as Ca(II) and Mg(II) on the adsorption of Pb(II) ions onto PVA and PVA/MOF nanofibers was also assessed. The results showed that the ubiquitous ions had no significant influence on the sorption of Pb(II) ions. Current investigation provides a method to develop novel PVA/MOFs nanofibers hybrid adsorbents for water purification system. The adsorption capacities and removal achieved with the PVA/MOFs nanofibers sorbent were higher than those for PVA sorbent. The electro spun nanofiber sorbents presents an efficient alternative for pre-treating lead ions in aqueous solutions. Results from this research demonstrated that higher performance novel nanofibers, which possessed higher adsorption percentages and capacity capabilities were obtsained far exceeding some of the commonly used adsorbents, were obtained.

La première partie de la thèse comporte l’étude des machines à froid, en tenant compte de la vitesse finie des processus. L’approche est basée sur une nouvelle méthode d’optimisation des processus et cycles à vitesse finie, la Méthode Directe d’étude et évaluation des irréversibilités. Les performances de ces cycles sont évaluées en prenant en compte les irréversibilités internes générées par la vitesse finie, notamment (1) les pertes de pression dues au laminage, (2) les pertes de pression dues à la vitesse finie du piston, (3) les pertes de pression dues aux frottements interne et mécanique et (4) l’irréversibilité due aux pertes de chaleur. On obtient ainsi directement l'expression du rendement ou du coefficient de performance et de la génération d’entropie en fonction de la vitesse des processus et d'autres paramètres géométriques et fonctionnels. Le travail proposé pour cette partie de thèse analyse la génération des irréversibilités dans une machine thermique fonctionnant selon le cycle inverse quasi-Carnot (Machine Frigorifique à compression mécanique des vapeurs), en proposant un schéma de calcul complètement analytique. A l’aide de ce schéma de calcul on peut développer des études de sensibilité et d’optimisation de ces machines, sans avoir besoin d’utiliser de tableaux des vapeurs saturés.La deuxième partie du mémoire présente l’application des modèles thermodynamiques (la Méthode Directe, la Méthode de la Thermodynamique en Dimensions Physiques Finies (TDPF), la méthode isotherme de Schmidt, la méthode adiabatique de Finkelstein) dans l’étude des machines Stirling – moteurs et récepteurs et confrontation avec l’expérience.La Méthode de la TDPF est une méthode qui regroupe les techniques de la thermodynamique en temps, vitesse et dimensions géométriques finies. Cette méthode introduit les exo-irréversibilités dues aux transferts de chaleur finis entre les réservoirs (source chaude, puits froid, régénérateur) et le fluide de travail et, de plus, considère les contraintes qui se présentent à l’ingénieur (la pression maximale, le volume maximum, les températures des réservoirs chaud et froid, la vitesse de rotation). La méthode isotherme de Schmidt est une méthode zéro-dimensionnelle qui permet l’étude de la machine divisée en trois volumes isothermes. Elle permet de décrire l’évolution de paramètres, comme le volume instantané (chaud, froid ou de régénération) ou la pression en fonction du temps. L’analyse des processus de transfert de la chaleur et d’écoulement du gaz de travail, ayant lieu dans le moteur Stirling d’un micro-cogénérateur, est effectuée en utilisant un model adiabatique monodimensionnel. Cette analyse repose sur la division du moteur Stirling en 5 volumes de control auxquels on applique les équations des gaz parfaits et les équations de conservation de masse et d’énergie.Les résultats expérimentaux seront confrontés à ceux obtenus par les quatre méthodes de calcul, ce qui permettra de définir les paramètres d’ajustage afin de valider les modèles thermodynamiques. Cette confrontation permettra le développement d’une autre méthode, une combinaison des trois approches utilisées afin de modéliser au mieux le fonctionnement du système, préservant les avantages de chacune sur des intervalles de vitesse de rotation donnés.Des études de sensibilité et d’optimisation de paramètres géométriques et fonctionnels seront effectuées afin de proposer des améliorations de mise au point système pour fournir puissance et de rendement plus élevés. / This paper presents the author's overall results obtained in his doctoral thesis, on: The analysis of entropy generation and the evaluation of the performances of the inversed cvasi-Carnot cycle; The application of the Direct Method, Finite Physical Dimensions Thermodynamics method (TDFF), Schmidt’s isotherm method and Finkelstein’s adiabatic model in the study of Stirling engines – engines and machines that function on reversed cycles (receivers) and the confrontation of analytical results with the experimental ones. The first part of the thesis covers the study of the refrigeration machines, considering the finite speed of the processes. The study is based on a new method to optimize the processes and the cycles with finite speed, the Direct Method of study and the evaluation of the irreversibilities. The performance of these cycles are evaluated using analytical relations, considering internal irreversibilities generated by finite speed, especially the pressure losses due to (1) throttling (2) finite speed of the piston (3) internal and mechanical friction (4) irreversibilities due to heat losses. These irreversibilities are introduced in the expression of the First Principle of Thermodynamics for processes with finite speed, and its application leads directly and through analytical means to the expressions of efficiency or coefficient of performance and entropy generation, function of the finite speed of the processes and other geometrical and functional parameters of the machine. The proposed study for this first part of the thesis analyzes the generation of thermal irreversibilities in a thermal machine functioning on a cvasi-Carnot reversed cycle (refrigerating machine with mechanical compression of vapor-IFV) proposing a completely analytical calculation scheme. With this calculation scheme sensitivity studies and optimization of these types of machines were developed, without having to use saturated vapor tables.The second part of the thesis presents the application of thermodynamic models (Direct Method, Finite Physical Dimension thermodynamics method, Schmidt's isotherm model and Finkelstein’s adiabatic model) in the study of Stirling engines – engines and machines that function on reversed cycles (receivers) and the confrontation of analytical results with the experimental ones. The Direct Method consists in the study and assessment of the irreversibilities generated in thermal machines by analyzing the cycle step by step (progressive) and the direct integration of the equation the First Principle of Thermodynamics combined with the Second Principle of Thermodynamics with finite speed, for each process of the cycle. This provides analytical expressions for power and efficiency or coefficient of performance COP, function of the speed of the processes and other geometric and functional parameters.

A ratchet is an asymmetric, non-equilibrated system that can produce a directed current of particles without the need for macroscopic potential gradients. In rocked quantum electron ratchets, tunnelling and wave-reflection can induce reversals in the direction of the net current as a function of system parameters. An asymmetric quantum point contact in a GaAs/GaAlAs heterostructure has been studied experimentally as a realisation of a quantum electron ratchet. A Landauer model predicts reversals in the direction of the net current as a function of temperature, amplitude of the rocking voltage, and Fermi energy. Artifacts such as circuit-induced asymmetry, also known as self-gating, were carefully removed from the experimental data, which showed net current and net differential conductance reversals, as predicted by the model. The model also predicts the existence of a heat current where the net electron current changes sign, as equal numbers of high and low energy electrons are pumped in opposite directions. An idealised quantum electron ratchet is studied analytically as an energy selective electron heat engine and refrigerator. The hypothetical device considered consists of two electron reservoirs with different temperatures and Fermi energies. The reservoirs are linked via a resonant state in a quantum dot, which functions as an idealised energy filter for electrons. The efficiency of the device approaches the Carnot value when the energy transmitted by the filter is tuned to that where the Fermi distributions in the reservoirs are equal. The maximum power regime, where the filter transmits all electrons that contribute positively to the power, is also examined. Analytic expressions are obtained for the power and efficiency of the idealised device as both a heat engine and as a refrigerator in this regime of operation. The expressions depend on the ratio of the voltage to the difference in temperature of the reservoirs, and on the ratio of the reservoir temperatures. The energy selective electron heat engine is shown to be non-endoreversible, and to operate in an analogous manner to the three-level amplifier, a laser based quantum heat engine. Implications for improving the efficiency of thermionic refrigerators and power generators are discussed.

1. There is a crisis in economics. The discipline evolved in nineteenth century Europe and is difficult to adapt to modern conditions, even in the West, and particularly in alien cultures. Application of conventional economic analysis to economic activity in a culture as alien as traditional China highlights the biases in assumptions of the paradigm. 2. The concepts, models and vocabulary evolved over one hundred years ago predate important developments in the natural sciences. It is now necessary for economists to concede no goods can ever be 'produced', and they are not 'consumed' either. In clear terms matter is transformed, but is not created or destroyed (First Law of Thermodynamics). 3. When people transform matter, in lay language we say energy is 'used'. In a simple cottage industry, 'raw material' is transformed into a commodity in front of our eyes by the use of human energy and the release of energy from a 'fuel'. In modem complex economic activity, it is difficult or impossible to keep track of the processes from raw matter to transformed 'product' although the principle is the same. 4. The Second Law of Thermodynamics states that in any transformation, energy is not created or destroyed, but becomes 'less available'. In short, entropy increases. This appears to work well for pure physics and chemistry, but its application to analysis of economic activity has only been notional. 5. There is a reason why economists borrowing terms from hard science experience difficulty. It is because physicists and chemists have addressed specific laboratory and engineering problems, but not the broader economic issues. The hypothesis gradually evolved in this research program that not only economic concepts and terms needed reworking, but those in physics as well. The definitions of energy as 'ability to do works and of entropy as 'unavailable energy' jar the logic of our commonsense. 6. The notion of 'available energy' was traced back to the phenomenon in physical chemistry known as exothermicity, or the release of energy during a chemical reaction. It was reasoned that while scientists had focussed on this phenomenon and measured it carefully they saw no need to ask where the energy came from, or to measure its transformation. From the perspective of analysing economic activity, the question was important. 7. It was hypothesised that the energy released from a fuel as electromagnetic radiation (mainly heat) was the residual of the set of coulombic forces within atoms that maintain the structure of shells of electrons around the protons. This idea in turn came from the presumption that molecular bonding is a residual of vectors of the set of coulombic forces within atoms, and the likelihood that in an exothermic reaction, after the reactants are said (by scientists) to 'seek equilibrium', product molecules have a portion of the coulombic forces 'left over' and not required to maintain their structures. An estimate was made of the coulombic forces extant in various fuels, and compared with the known data for their release of energy. 8. The idea was developed in detail. The concept we call in economics, 'production', and should call 'transformation' can only occur when forces locked within atoms are released as electromagnetic forces. (Gravitational forces exist because matter has been put 'there' by electromagnetic radiation). When 100 grams of dry grass fuel is burnt, about 2 megajoules of electromagnetic radiation are released. It was estimated that the coulombic forces between each electron and proton in that amount dry grass total 150 gigajoules (or giganewtons, since the reference is to forces). 9. Within the boundary of a simple economic activity, the ratio of aggregated coulombic forces locked up within atoms to the electromagnetic forces radiated out was estimated at the beginning of the activity, and then after a duration. The ratio of forces always tends towards 'evening out'. This measurement captures the entropy phenomenon which has been said by Georgescu-Roegen to be the basis of all economic activity. 10. At the roots of the economic paradigm founded by Adam Smith is the premise that the material world, as a set of substances, is a stage on which economic actors 'add value', bid prices up and down, and by their rational perception manage their livelihoods and surroundings well. From the findings of this research program it is contended that the surroundings of economic actors can be classed into two categories: locked up (coulombic) electromagnetic forces, and radiated electromagnetic forces. The former has a tendency to convert to the latter. All action, including all economic activity, and all life can be traced to a point in space and time where this conversion is (naturally) occurring. The phenomenon is analogous to a slope where water cascades, and gravitational potential energy converts to other (either useless or useful) forms of energy. To appreciate the nature of this phenomena, and to attempt to fathom its dimensions, sets our perceptions of ourselves as economic actors in a quite different and very humbling context.

In this article a Novikov engine with fluctuating hot heat bath temperature is presented. Based on this model, the performance measure maximum expected power as well as the corresponding efficiency and entropy production rate is investigated for four different stationary distributions: continuous uniform, normal, triangle, quadratic, and Pareto. It is found that the performance measures increase monotonously with increasing expectation value and increasing standard deviation of the distributions. Additionally, we show that the distribution has only little influence on the performance measures for small standard deviations. For larger values of the standard deviation, the performance measures in the case of the Pareto distribution are significantly different compared to the other distributions. These observations are explained by a comparison of the Taylor expansions in terms of the distributions’ standard deviations. For the considered symmetric distributions, an extension of the well known Curzon–Ahlborn efficiency to a stochastic Novikov engine is given.

The present thesis is conducted in the frame of a research project involving the ‘von Karman Institute (VKI Belgium)’ and the ‘Ecole des mines d’Alès (EMA France) with the support of the CEA Gramat. This project is about theoretical study, experimental characterization and modeling of hazards from pressurized or atmospheric reservoirs, containing liquids, flammable or not. <p><p>The objective of this thesis is to study the apparition criteria and the consequences of an accident involving a container of pressure liquefied gas (BLEVE phenomenon) or liquid fuels (Boilover phenomenon). After a bibliographic research on the two phenomena, an experimental study in laboratory scale is conducted and from the results, the phenomena and their hazards are modeled. Small scale experiments are performed in the BABELs facility (Bleve And Boilover ExperimentaL setup) that consists of a cylindrical chamber of 2m diameter and 3m high, with round shape flanges, made out of steel with a rated pressure of 0.5 MPa. It has 3 series of 7 optical accesses, an entrance door, and an optional air venting system. <p><p>A Boilover is a violent ejection of fuel due to the vaporization of a water sublayer, resulting in an enormous fire enlargement and formation of fireball and ground fire. Small scale experiments with cylindrical reservoirs of 0.08 to 0.3m diameter in glass or metal, filled with a mixture of diesel and oil have been performed. Instrumentation of the measurements consists of thermocouples rake, Medtherm radiometers, load cell and CCD or high-speed camera with a fisheye. During the quasi-steady combustion prior the Boilover, the typical variables describing a pool fire like burning rate, flame size, puffing frequency and radiation can be predicted with semi-empirical correlations available in the literature. At Boilover onset, high speed visualizations in glass reservoir show that the growth of one big bubble leads to a boiling front that propagates radially all along the fuel-water interface, ejecting the upper fuel layer and leading to the increase of flame size. LS-PIV technique applied to high-speed camera images shows that the flame enlargement is directly linked to the velocity of the flame.<p><p>A BLEVE (or Boiling Liquid Expanding Vapour Explosion) is an explosion resulting from the catastrophic failure of a vessel containing a liquid at a temperature significantly above its boiling point at normal atmospheric pressure. Small scale experiments are performed with cylinders of 42g of propane, laid horizontally and heated from below by an electrical resistor. A groove of the reservoirs on the upper part allows better reproducibility of the rupture. High speed visualization and shadowgraphy are helping in visualizing the rupture and the content release. Thermocouples and PCB are also used to measure respectively the temperature and the blast wave overpressure. These experiments show that the fluid behavior during rupture differs with the size of the weakened part and therefore with the rupture pressure. The internal pressure measurement showed that the rupture pressure and temperature are supercritical, leading to the definition of a new type of BLEVE since there is no distinction between liquid and vapor phases prior rupture.<p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished