In this thesis, we present a theoretical investigation of reactive processes involving the HeH$^+$ molecular ion, with applications in laboratory and astrophysical plasma physics. We consider in particular two processes, which are the charge transfer in H + He$^+$ collisions at low energy from a molecular approach and the photodissociation of HeH$^+$.<p><p>At the molecular level, the cross section is the basic quantity that has to be determined in order to achieve an understanding of reactive processes. Its calculation will be based on the description of the reactions using an emph{ab initio}, quantum mechanical approach. In this work, we will rely on the Born-Oppenheimer approximation, which allows the molecular motion to be separated into an electronic and a nuclear motion. The evaluation of cross sections then follows two steps.<p>The first is the determination of the electronic structure of the molecule. We will calculate the adiabatic potential energy curves of the excited electronic states as well as the dipole matrix elements between these states. The non-adiabatic radial and rotational couplings, which result from the breakdown of the Born-Oppenheimer approximation, are also estimated. The second step is to solve the nuclear motion, which we achieve using a time-dependent method based on the propagation of wave packets on the coupled electronic states. <p><p>A particular emphasis will be put on the importance of the excited states and of the non-adiabatic couplings in the description of reactive processes. <p>In the treatment of the charge transfer reaction between H and He$^+$ in excited states, it is well known that the non-adiabatic radial couplings cannot be neglected. However, we will show that the inclusion of the non-adiabatic rotational couplings is also necessary in order to obtain accurate state-to-state cross sections.<p>In the description of the photodissociation of HeH$^+$ from its ground state, we will show the influence of the excited states on the rate constant and the role of the non-adiabatic radial couplings in the determination of partial cross sections.<p>We will also consider the possible astrophysical applications of the first triplet state of HeH$^+$. We will show that this state is metastable by evaluating its lifetime, and calculate the cross sections and rate constants for the photodissociation and radiative association of HeH$^+$ in this state.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Research in local fracture processes and micro-machining of polymers and polymer-based composites has attracted increasing attention, in development of composite materials and miniaturisation of polymer components. In this thesis, sectioning (machining) of a glassy polymer and a carbon nanotube based composite at the nanoscale was performed by an instrumented ultramicrotome. The yield stresses and fracture toughness of these materials were determined by analysing the sectioning forces. Fractographic analysis by atomic force microscopy was conducted to characterise the topographies and elastic properties of the sectioned surfaces to explore the deformation and fracture behaviour of the polymer during nanosectioning. The study reveals that a transition from homogenous to shear localised deformation occurred as the uncut chip thickness (depth of cut) or sectioning speed increased to a critical value. Analytical and finite element methods were used to model the nanosectioning process. The shear localised deformation was caused by thermal softening due to plastic dissipation. Although not considering sectioning, the tensile properties of a polymer nanocomposite were additionally investigated, where the degree of nanofibrillation and polyethylene glycol (PEG) content had significant effects.

The attention for materials displaying high magnetocaloric effect (MCE) has grown during the past 30 years. One of the most important properties of MCE is the adiabatic temperature change ( ). The main aim of this work was to develop a method to measure the temperature change ( ) for magnetocaloric materials in a changing magnetic field.  A technique was developed where maximum reached  for Gadolinium was 1.19 K in a changing magnetic field of 1.3 T, however, this is lower value in comparison with previous studies (3.3 K in a changing magnetic field of 1 T, Bjørk, et al., 2010) which makes the developed method not sufficient enough to measure . Furthermore, finding novel materials displaying high MCE is of great interest. MnFePSiB alloys display promising MCE properties but processing method is expensive and time consuming. Therefore, a MnFePSiB compound was simply remelted several times and heat treated to enhance its properties. The MnFePSiB alloy was remelted 1, 2 and 3 times after initial casting. Melting the material 3 times resulted improvement in both the magnetic and magnetocaloric properties due to enhanced homogeneity. The material melted 3 times was further heat treated to improve its magnetic magnetocaloric properties. Heat treating the material for 5 hours at 1373K improved the magnetic entropy change more than 10 times compared to the as cast sample,  was moved closer to room temperature and maximum  of 0.71 K was obtained.

The continuous escalation of intermittent energy added to the grid and forecasts of peaking power demand increments are rising the effort spent for evaluating the economic feasibility of energy storages. The aim of this research is the techno-economic analysis of Compressed Air Energy Storage (CAES) systems, capable of storing large quantities of off-peak electric energy in the form of high-pressure air, as an ―energy stock‖ which allows the production of high-profit on-peak electricity when required by the grid. Several studies of both conventional and innovative adiabatic concepts are carried out in order to identify and improve the parameters that mostly affect the plant performances. Technical models, that consider the effect of time, are developed to evaluate the parameters that reduce the electric energy spent for compressing the air and that maximize the electric energy produced. In the conventional plant, particular attention is put on the understanding of the effects of air storage pressure range, recuperator, reheating and Turbine Inlet Temperature. For the adiabatic instead, a thorough analysis of the challenging Thermal Energy Storage (TES) is performed for understanding the advantages and drawbacks of this novel efficient concept of CAES. In a further step the economic analyses are aimed at evaluating the different configurations proposed in the technical investigation and the effects that variations of generation train and storage characteristics have on the profitability. After an analysis of the TES impact on the profits, a final comparison is carried out against two existing technologies: Pumped Hydro Energy Storage and gas turbine. The results of these studies confirm, from a technical and economic point of view, the reasons of the growing interest toward CAES as a feasible solution to manage the intermittent energy production. In particular they underline the conventional CAES as promising technology to undertake.

The purpose of the work presented in this thesis was to explore and understand the mechanisms governing toughness, ductility and ballistic performance in a class of nanostructured carbide-free bainite-austenite steels, sometimes known as ‘superbainite’. The mechanical properties of these alloys have been extensively reported, but their interpretation is not clear. The thesis begins with an introduction to both the relevant nanostructures and some of the difficulties involved in explaining observed properties, alongside a summary of the role of mixed- microstructures in alloy development. An overview of the debate regarding the mechanism of bainite formation is pre- sented in Chapter 2, in the form of a literature survey encompassing the period of explicit recognition of the bainite microstructure. Of note is the role played by the displacive theory of formation in the development of the alloy structures investigated in this thesis. A characterisation of a commonly available bainitic alloy forms the basis for Chapter 4. Observations confirm the nanoscale nature of the structure, although additional phases are found to be present, namely: cementite and martensite. This is explained as resulting from relatively low alloying additions and chem- ical segregation effects, which are modelled using thermodynamic and kinetic approaches. Chapters 5 and 6 contain a comprehensive study of the response of this alloy to the stress concentration present at the notch root of a Charpy impact sample. The work provides evidence of notch root embrittlement due to stress-induced martensite transformation. Results from synchrotron and laboratory X-ray experiments in particular reveal that machining, as well as applied stress, can initiate the austenite-martensite transformation, and methods to mitigate this effect are suggested. An innovative approach is harnessed in Chapter 7, in order to identify exper- imentally the volume fraction at which three-dimensional connectivity (‘percolation’) of austenite is lost in a superbainitic steel. Hydrogen thermal desorption techniques are applied to this problem, inspired by the tendency of such alloys to undergo tensile failure with limited or zero necking. The striking result sheds light on the importance of austenite morphology in restricting the diffusion of hydrogen into a mixed structure. The final set of experimental work is directed towards understanding the damage mechanisms that occur during projectile penetration of a coarser bainitic armour- plate alloy. The formation of adiabatic shear bands is found to be a dominant factor governing the ballistic failure of the plate. The sheared material undergoes severe high-temperature deformation, but does not change phase upon cooling, leading to the proposal of certain methods that could be implemented to improve ballistic resistance of the steel. The totality of the research presented herein is summarised in Chapter 9, which draws attention to new areas of interest that have arisen from the current work, proposing several future directions of investigation. The broader issue of understanding, common to all studies performed thus far, is that of the causes, effects, and extent, of stress-induced transformation to martensite experienced by the retained austenite that is a key feature of superbainite and similar steels.

Low fuel consumption is one of the main requirement for current internal combustion engines for passenger car applications. One of the most used strategies to achieve this goal is to use downsized engines (smaller engines while maintaining power) what implies the usage of turbochargers. The coupling between both machines (the turbocharger and the internal combustion engines) presents many difficulties due to the different nature between turbomachines and reciprocating machines. These difficulties make the optimal design of the turbocharged internal combustion engines a complicated issue. In these thesis a strong effort has been made to improve the global understanding of different physical phenomena occurring in turbochargers and in turbocharged engines. The work has been focused on the 1D modelling of the phenomena since 1D tools currently play a major role in the engine design process. Both experimental and modelling efforts have been made to understand the heat transfer and gas flow processes in turbochargers. Previously to the experimental analysis a literature review has been made in which the state of the art of heat transfer and gas flow modelling in turbochargers have been analysed. The experimental effort of the thesis has been focused on measuring different turbochargers in the gas stand and the engine test bench. In the first case, the gas stand, a more controlled environment, has been used to perform tests at different conditions. Hot tests with insulated and not insulated turbocharger have been made to characterise the external heat transfer. Moreover, adiabatic tests have been made to compare the effect of the heat transfer on different turbocharger variables and for the validation of the turbine gas flow models. In the engine test bench full and partial load tests have been made for model validation purposes. For the models development task, the work has been divided in heat flow models and gas flow models. In the first case, a general heat transfer model for turbochargers has been proposed based on the measured turbochargers and data available from previous works of the literature. This model includes a procedure of conductive conductances estimation, internal and external convection correlations and radiation estimation procedure. In the case of the gas flow modelling, an extended model for VGT performance maps extrapolation for both the efficiency and the mass flow has been developed as well as a model for discharge coefficient prediction in valves for two stage turbochargers. Finally, the models have been fully validated coupling them with a 1D modelling software simulating both the gas stand and the whole engine. On the one hand, the results of the validation show that compressor and turbine outlet temperature prediction is highly improved using the developed models. This results prove that the turbocharger heat transfer phenomena are important not only for partial load and transient simulation but also in full loads. On the other hand, the VGT extrapolation model accuracy is high even at off-design conditions. / El bajo consumo de combustible es uno de los principales requerimientos de los motores de combustión interna actuales para aplicaciones de coches de pasajeros. Una de las estrategias más usadas para conseguir ese fin es el uso de motores "downsized" (motores más pequeños con la misma potencia) lo que implica el uso de turbocompresores. El acoplamiento entre ambas máquinas (el turbocompresor y el motor de combustión alternativo) presenta muchas dificultades debido a la diferente naturaleza entre las turbomáquinas y las máquinas alternativas. Estas dificultades convierten el diseño óptimo de los motores de combustión interna sobrealimentados en un asunto complicado. En esta tesis se ha realizado un importante esfuerzo para mejorar el entendimiento global de los diferentes fenómenos físicos que ocurren en los turbocompresores y en los motores sobrealimentados. El trabajo se ha centrado en el modelado 1D de los fenómenos puesto que las herramientas 1D juegan actualmente un papel principal en el proceso de diseño del motor. Se han realizado tanto esfuerzos experimentales como de modelado para el entendimiento de los procesos de transmisión de calor y de flujo de gases en turbocompresores. Previamente al análisis experimental se ha realizado una revisión de la literatura disponible en la que se ha analizado el estado del arte del modelado de transmisión de calor y flujo de gases en turbocompresores. El esfuerzo experimental de la tesis se ha centrado en la medida de diferentes turbocompresores en el banco de gas y en el banco motor. En el primer caso, se ha utilizado el banco de gas, un ambiente más controlado, para realizar ensayos en diferentes condiciones. Se han realizado ensayos calientes con y sin aislamiento del turbocompresor para caracterizar el flujo de calor externo. Además, se han realizado ensayos adiabáticos para comparar el efecto de la transmisión de calor sobre diferentes variables del turbocompresor y para la validación de los modelos de flujo de gases de la turbina. En el banco motor se han realizado ensayos a plena carga y a cargas parciales para usarlos en la validación. Para la tarea del desarrollo de los modelos, el trabajo se dividió en modelos de flujo de calor y modelos de flujo de gases. En el primer caso, se ha propuesto un modelo general de transmisión de calor para turbocompresores basado en los turbocompresores medidos y en datos disponibles de trabajos previos de la literatura. Este modelo incluye un procedimiento para la estimación de las conductancias conductivas, correlaciones de convección interna y externa y un procedimiento de estimación de la radiación. En el caso del modelado de flujo de gases, se ha desarrollado un modelo extendido para la extrapolación de mapas de funcionamiento de TGV tanto para el rendimiento como para el gasto másico además del modelo de predicción de coeficientes de descarga en válvulas de turbocompresores de doble etapa. Finalmente, los modelos han sido completamente validados con su acoplamiento a un software de modelado 1D simulando tanto el banco de turbos como el motor completo. Por un lado, los resultados de la validación señalan que la predicción de las temperaturas de salida de compresor y turbina mejora notablemente usando los modelos desarrollados. Este resultado demuestra que los fenómenos de transmisión de calor son importantes no sólo en simulaciones de cargas parciales y de transitorios sino también en plenas cargas. Por otro lado, la precisión del modelo de extrapolación de TGV es alta incluso en condiciones fuera de diseño. / El baix consum de combustible és un dels principals requeriments dels motors de combustió interna actuals per a aplicacions de cotxes de passatgers. Una de les estratègies més usades per a aconseguir eixe fi és l'ús de motors "downsized" (motors més xicotets amb la mateixa potència) el que implica l'ús de turbocompressors. L'adaptament entre ambdues màquines (el turbocompressor i el motor de combustió alternatiu) presenta moltes dificultats degut a la diferent naturalesa entre les turbomàquines i les màquines alternatives. Estes dificultats convertixen el disseny òptim dels motors de combustió interna sobrealimentats en un assumpte complicat. En esta tesi s'ha realitzat un important esforç per a millorar l'enteniment global dels diferents fenòmens físics que ocorren en els turbocompressors i en els motors sobrealimentats. El treball s'ha centrat en el modelatge 1D dels fenòmens ja que les ferramentes 1D juguen actualment un paper principal en el procés de disseny del motor. S'han realitzat tant esforços experimentals com de modelatge per a l'enteniment dels processos de transmissió de calor i de flux de gasos en turbocompressors. Prèviament a l'anàlisi experimental s'ha realitzat una revisió de la literatura disponible en què s'ha analitzat l'estat de l'art del modelatge de transmissió de calor i flux de gasos en turbocompressors. L'esforç experimental de la tesi s'ha centrat en la mesura de diferents turbocompressors en el banc de gas i en el banc motor. En el primer cas, s'ha utilitzat el banc de gas, un ambient més controlat, per a realitzar assajos en diferents condicions. S'han realitzat assajos calents amb i sense aïllament del turbocompressor per a caracteritzar el flux de calor extern. A més, s'han realitzat assajos adiabàtics per a comparar l'efecte de la transmissió de calor sobre diferents variables del turbocompressor i per a la validació dels models de flux de gasos de la turbina. En el banc motor s'han realitzat assajos a plena càrrega i a càrregues parcials per a usar-los en la validació. Per a la tasca del desenvolupament dels models, el treball es va dividir en models de flux de calor i models de flux de gasos. En el primer cas, s'ha proposat un model general de transmissió de calor per a turbocompressors basat en els turbocompressors mesurats i en dades disponibles de treballs previs de la literatura. Este model inclou un procediment per a l'estimació de les conductàncies conductivas, correlacions de convecció interna i externa i un procediment d'estimació de la radiació. En el cas del modelatge de flux de gasos, s'ha desenvolupat un model estés per a l'extrapolació de mapes de funcionament de TGV tant per al rendiment com per al gasto màssic a més del model de predicció de coeficients de descàrrega en vàlvules de turbocompressors de doble etapa. Finalment, els models han sigut completament validats amb el seu adaptament a un software de modelatge 1D simulant tant el banc de turbos com el motor complet. D'una banda, els resultats de la validació assenyalen que la predicció de les temperatures d'eixida de compressor i turbina millora notablement usant els models desenrotllats. Este resultat demostra que els fenòmens de transmissió de calor són importants no sols en simulacions de càrregues parcials i de transitoris sinó també en plenes càrregues. D'altra banda, la precisió del model d'extrapolació de TGV és alta inclús en condicions fora de disseny. / Dombrovsky, A. (2017). Synthesis of the 1D modelling of turbochargers and its effects on engine performance prediction [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/82307 / TESIS

C’est dernières années, les progrès des techniques expérimentales combinées avec les simulations théoriques ont données un accès à l’étude et le contrôle des réactions photochimiques dans des systèmes moléculaires de grande taille. Ceci ouvre des portes à de nouvelles applications technologiques. Par exemple, les molécules de la famille du 3-hydroxychromone et de l’aminobenzonitrile sont des types de systèmes où les spectres de fluorescences vont présentés des différences importantes suivant l’environnement du système ou même suivant les substituants utilisés. Ce type de propriété est crucial dans le domaine des matériaux organique, afin de pouvoir comprendre et designer des matériaux qui présentent des propriétés optiques choisis tells que les marqueurs fluorescents dans le domaine médical par exemple.Notre stratégie pour étudier la réactivité photochimique est la suivante: *Explorer la surface d’énergie potentielle et optimiser les points spécifiques avec des calculs de chimie quantiques. Dans un premier temps, on a utilisé des méthodes CASSCF/CASPT2 et la méthode PCM pour décrire les effets de solvant. * Génération des surfaces d énergies potentielles exprimer sous la forme de fonctions analytiques des coordonnées nucléaires. * Résolution de l’équation de Schrödinger dépendant du temps pour les noyaux et pour tout les derges de libertés de la molécule. Cette étape est faite à l’aide de la méthode multilayer multiconfiguration time-dependent hartree (ML-MCTDH). / Over the last decades, progress in experimental techniques combined with theoretical simulations has given access to studying and controlling the photochemical reactivity of large molecular systems with numerous technological applications. 3-hydroxychromone and aminobenzonitrile-like molecules are an example where different fluorescence patterns are observed, depending of the solvent or its substituents. Such properties are crucial in the field of organic materials to understand and design materials with specific optical properties such as fluorescent markers.Our strategy to study the photochemistry reactivity is summarised as follows: * Exploring the potential energy surfaces and optimising specific points with quantum chemistry calculations. In a first stage, these are run at the CASSCF/CASPT2 level of theory with a polarised extended basis set, and the solvent effect is described implicitly with the PCM model. * Generating the full dimension potential energy surfaces as analytical functions of the nuclear coordinates.* Solving the nuclear time-dependent Schrödinger equation for all the degrees of freedom. This is achieved with the multilayer Multi-Configuration Time-Dependent Hartree method (ML-MCTDH).

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21585号 / 理博第4492号 / 新制||理||1645(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 谷村 吉隆, 教授 林 重彦, 教授 寺嶋 正秀 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22770号 / 工博第4769号 / 新制||工||1746(附属図書館) / 京都大学大学院工学研究科機械理工学専攻 / (主査)教授 黒瀬 良一, 教授 中部 主敬, 教授 岩井 裕 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The focus of the world is on the reduction of greenhouse gases, such as carbon dioxide, which contribute to the global warming currently experienced. Because most of the carbon dioxide emitted into the atmosphere is from fossil fuel combustion, alternative energy sources were developed and others are currently under study to see whether they will be good alternatives. One of these alternative sources of energy is the combustion of wood instead of coal. The advantages of wood are that it is a neutral carbon fuel source and that currently installed infrastructure used to combust coal can be retrofitted to combust wood or a mixture of wood and coal in an attempt to reduce the carbon dioxide emissions. Spent nuclear fuel has to be cooled so that the decay heat generated does not melt the containment system, which could lead to the unintentional release of radioactive material to the surroundings. The heat transfer mechanisms involved in the cooling have historically been analysed by assuming that the fluid and solid phases are at local thermal equilibrium (LTE) in order to simplify the analysis. The exergy destruction of the combustion of pine wood in an adiabatic combustor was investigated in this thesis using analytical and computational methods. The exergy destruction of the combustion process was analysed by means of the second law efficiency, which is the ratio of the maximum work that can be achieved by a Carnot engine extracting heat from the combustor, and the optimum work of the combustor. This was done for theoretical air combustion and various excess air combustions, with varied inlet temperatures of the incoming air. It was found that the second law efficiency reached an expected maximum for theoretical air combustion, and this held true for all varying air inlet temperatures. However, it was found that as the air inlet temperature was increased more and more, the maximum second law efficiency was the same for all excess air combustions, including the theoretical air combustion. It was also found that the results of the analytical and commercial computational fluid dynamics code compared well. Another analysis was conducted of irreversibilities generated due to combustion in an adiabatic combustor burning wood. This was done for a reactant mixture varying from a rich to a lean mixture. A non-adiabatic non-premixed combustion model of a numerical code was used to simulate the combustion process where the solid fuel was modelled by using the ultimate analysis data. The entropy generation rates due to the combustion and frictional pressure drop processes were computed to eventually arrive at the irreversibilities generated. It was found that the entropy generation rate due to frictional pressure drop was negligible when compared with that due to combustion. It was also found that a minimum in irreversibilities generated was achieved when the air-fuel mass ratio was 4.9, which corresponded to an equivalent ratio of 1.64, which was lower than the respective air-fuel mass ratio and equivalent ratio for complete combustion with theoretical amount of air of 8.02 and 1. Studieswere conducted to numerically analyse irreversibilities generated due to combustion in an adiabatic combustor burning wood. The first study analysed the effect of changing the incoming air temperature from 298 K to 400 K. The second study analysed the effect of changing the wall condition of the combustor from adiabatic to negative heat flux (that is heat leaving the system) for an incoming air temperature of 400 K. The irreversibilities generated in the combustor were calculated by computing the entropy generation rates due to the combustion, heat transfer and frictional pressure drop processes. For the first part of the study, it was found that for the minimum irreversibilities generated in the adiabatic combustor, the optimal air-fuel ratio (AF) corresponding to minimum irreversibilities slightly reduced from 4.9 to 4.8. In the second part of the study, it was found that by changing the wall condition from adiabatic to heat flux on the combustor, the AF corresponding to the minimum irreversibilities increased from 4.8 to 6. For the third part of the study, the combustor with a heat flux wall condition and a wall thickness simulated at an AF of 6, the sum of twice the wall thickness and the optimum diameter always added up to 0.32 m, resulting in the minimum irreversibilities. An analytical model was developed to minimise the thermal resistance of an air-cooled porous matrix made up of solid spheres with internal heat generation. This was done under the assumption of LTE. It was found that the predicted optimum sphere diameter and the minimum thermal resistance were both robust in that they were independent of the heat generation rate of the solid spheres. Results from the analytical model were compared with those from a commercial numerical porous model using liquid water and air for the fluid phase, and wood and silica for the solid phase. The magnitudes of the minima of both the temperature difference and the thermal resistance seemed to be due to equal contribution from the thermal conduction heat transfer inside the solid spheres and heat transfer in the porous medium. Because the commercial numerical porous model modelled only the heat transfer occurring in the porous medium, it expectedly predicted half of the magnitudes of the minima of the temperature difference and thermal resistance of those by the analytical model. / Thesis (PhD)--University of Pretoria, 2017. / Mechanical and Aeronautical Engineering / PhD / Unrestricted