Dissertations / Theses on the topic 'Vapour expansion'

La maitrise de la composition et de la ségrégation chimique est essentielle lors de l’élaboration de matériaux à forte valeur ajoutée, comme les alliages de zirconium à destination de l’industrie nucléaire. L’élaboration sous vide permet d’obtenir des lingots d’une très grande pureté mais elle présente aussi une contrainte supplémentaire concernant la maitrise de la teneur en éléments d’alliage volatiles. Les travaux présentés dans ce document visent à améliorer la prédiction de la cinétique d’appauvrissement en espèces métalliques volatiles lors de l’élaboration sous vide et en particulier lors de la refusion VAR (Vacuum Arc Remelting ou refusion à l’arc sous vide) du Zircaloy-4, un alliage de Zr. Dans un premier temps, nous étudions la cinétique d’évaporation et l’expansion de la vapeur métallique produite lors de la fusion sous vide. L’étude est effectuée par une combinaison d’expériences en four à bombardement électronique et de la simulation numérique du comportement de la vapeur par une méthode particulaire (FPM). Nos études sur l’évaporation de métaux purs, Ti et Zr, montrent l’importance des collisions au-dessus du liquide sur l’expansion de la vapeur et sa recondensation. La caractérisation de l’expansion de la vapeur de Fe et Sn lors de la fusion sous vide de Zy4, combinée à la simulation particulaire, nous a permis de déterminer la valeur des coefficients d’activité thermodynamique de ces éléments dans le Zy4 liquide. Dans un second temps, nous présentons la simulation de l’expansion de la vapeur métallique dans les conditions du procédé VAR en nous intéressant particulièrement aux flux de condensation sur les différentes surfaces. L’application de ce modèle au Zircaloy-4 montre que la composition du dépôt sur la paroi interne de la lingotière est très différente de celle de l’alliage. Enfin, le modèle particulaire est couplé à une modélisation de la croissance du lingot et nous étudions l’influence de l’évaporation, condensation et réincorporation de la collerette sur la composition et la ségrégation des éléments d’alliage volatils. Le couplage offre aussi une première prédiction de l’épaisseur et de la composition de la collerette que nous comparons pour la refusion du Zyrcalloy-4 avec des prélèvements industriels
Composition and chemical segregation control is primordial when producing high value-added materials, such as zirconium alloys for nuclear industry. Vacuum processing allows production very high purity ingot, however it also presents an additional problematic concerning control and prediction of alloy elements evaporation. This PhD dissertation aims at improving prediction of volatile metallic species evaporation during vacuum elaboration, especially during Zircaloy 4 VAR (Vacuum Arc Remelting).First, the evaporation kinetics and the expansion of the metal vapour produced during vacuum melting is investigated. The study is done with a combination of volatilisation experiments using an experimental electron beam furnace and particle based numerical simulation (FPM) of vapour behaviour. Our volatilisation studies on pure metals, Ti and Zr, show the importance of collisions above the liquid on the vapour expansion and its recondensation. Determination of Fe and Sn vapour expansion during Zy4 vacuum melting combined with particle simulation, allowed us to determine thermodynamic activity coefficients values for these elements in liquid Zy4.Then, metallic vapour expansion under VAR conditions is studied, with particular interest shown to condensation flows on the different surfaces. Application of our numerical model to Zy4 shows that the vapour deposited on the mould has a very different composition compared to the alloy. Finally, the particle model is coupled to an ingot growth model and we study the influence of evaporation, condensation and crown reincorporation with regard to volatile solute segregation and depletion. This coupling also provides a first prediction of crown thickness and composition and we compare them to industrial crown samples

La vaporisation rapide du sodium liquide surchauffé est supposée être à l’origine des arrêts automatiques pour réactivité négative du réacteur Phénix.Un dispositif expérimental a été mis en œuvre pour reproduire la détente d'un gaz pressurisé, repoussant un liquide dans un canal de section rectangulaire très allongée.L’interface qui sépare les deux fluides, initialement plate, ondule du fait d'instabilités de Rayleigh-Taylor dont le caractère 2D est garanti par le rapport d'aspect de la section du canal. L’aire interfaciale augmente d'un facteur 50.L’expansion du gaz peut être divisée en deux phases principales : une phase dite « de Rayleigh-Taylor » (linéaire et non-linéaire) et une phase dite « à multi-structures » (transitionnelle et chaotique). La première est caractérisée par la dynamique de l'interface et l’aire interfaciale qui en résulte est proportionnelle à l’amplitude des ondulations. La deuxième est influencée par le comportement des structures liquides, dispersées dans la matrice gazeuse et l’aire interfaciale est alors proportionnelle au nombre de structures.La distribution de fraction volumique suggère un modèle d’écoulement composé de trois régions : une région où la frontière des bulles est clairement définie et régulière, une région compartimentée par des membranes liquides issues des frontières des bulles, une région diphasique formée de la queue de ces structures. L’analyse de sensibilité à la tension superficielle confirme que plus la tension est faible, plus les interfaces sont instables. Les ondes sont plus prononcées et plus de structures sont produites, ce qui conduit à une majoration du taux de production de l’aire interfaciale
The sharp vaporization of superheated liquid sodium is investigated. It is suspected to be at the origin of the automatic shutdown for negative reactivity, occurred in the Phénix reactor at the end of the eighties.An experimental apparatus has been designed and operated to reproduce the expansion of overpressurized air, superposed to water in a narrow vertical rectangular section channel.When expansion begins, the initial flat interface separating the two fluids becomes corrugated under the development of two-dimensional Rayleigh-Taylor instabilities. The interface area increases significantly and becomes even 50 times larger than the initial value. Since the channel is very narrow, instabilities along the channel depth do not develop.The gas expansion in a narrow channel can be divided into two main phases: Rayleigh-Taylor (linear and non-linear) and multi-structures (transition and chaotic) phases. The former is characterized by the dynamic of corrugated profile and the interface area results proportional to the amplitude of corrugation The latter is influenced by the behavior of the liquid structures dispersed in gas matrix and the interface area is mainly proportional to the number of liquid structures.The distribution of volume fraction suggests a model of channel flow consisting of three regions: the regular profile of peaks, the spike region and the structures tails. The analysis of sensibility to surface tension confirms that, with a lower surface tension, the fluids configuration is more unstable. The interface corrugations are more pronounced and more structures are produced, leading to a higher increment of the interface area

Este trabalho apresenta a quantificação da expansão e suas características, principalmente a influência da sucção, em amostras de materiais sedimentares argilosos provenientes da Formação Corumbataí, aflorantes no interior do estado de São Paulo. Foram testadas amostras indeformadas, e amostras destorroadas e compactadas em diferentes umidades, em ensaios de pressão de expansão a volume constante por inundação, e também, com sucção controlada por meio da técnica da transferência de vapor. Foram ensaiadas, ainda, misturas compactadas desse material com bentonita em diferentes proporções, e misturas de bentonita com material não expansivo arenoso oriundo da Formação Botucatu. O controle de sucção foi realizado pelo uso de soluções salinas de NaCl em concentrações preparadas para impor sucções de 40.000, 25.000, 10.000 e 5.000 kPa. Para a realização dos ensaios, construiu-se um sistema de aplicação de cargas e de aquisição automática dos dados de pressão. Para acelerar o processo de umedecimento por vapor, utilizou-se um reservatório externo ligado em uma bomba de ar adaptada para promover a circulação do vapor de ar para dentro da célula edométrica, especialmente construída para esta pesquisa. Os resultados de expansão nos ensaios com inundação mostraram pressões de expansão crescentes com a diminuição dos teores de umidade, e consequente aumento da sucção inicial das amostras ensaiadas, bem como crescentes com o aumento na proporção de bentonita nas misturas, com valores máximos em torno de 700 kPa para o ensaio com a bentonita pura compactada seca. A análise da microestrutura das amostras por meio da porosimetria por intrusão de mercúrio permitiu constatar que as amostras indeformadas apresentaram variação, apenas, nos macroporos após a expansão; e as compactadas na umidade ótima e, posteriormente secas ao ar, não mostraram evolução significativa após a expansão. Na microscopia eletrônica de varredura (MEV) foi possível verificar a mudança nos vazios das amostras, bem como, visualizar a variação na estrutura e na textura. Além disso, no MEV foram confirmados, também, os argilominerais determinados na caracterização mineralógica. Os resultados dos ensaios de expansão com sucção controlada mostraram ausência de pressão de expansão para as amostras da Formação Corumbataí nas condições indeformada, e na condição compactada na umidade ótima e posteriormente seca ao ar. No entanto, esse material, quando compactado seco na forma de pó, e também, compactado seco misturado com bentonita em diferentes proporções, revelou pressões de expansão com a transferência de vapor, assim como, as misturas de bentonita com material não expansivo da Formação Botucatu. A ausência de expansão foi justificada pela forma lenta de umedecimento proporcionada pela transferência de vapor que, apesar de promover o aumento do teor de umidade das amostras, não mobilizou variação volumétrica suficientemente capaz de transmitir como pressão de expansão. Portanto, os ensaios de expansão, com a utilização da técnica de transferência de vapor, foram efetivos para avaliar a expansão somente nos casos em que argilominerais com potencial expansivo estavam presentes em proporções consideráveis.
This thesis presents the quantification and characterization of expansion, especially the influence of suction on samples of sedimentary materials from Corumbatai Formation that occurs in Sao Paulo. Undisturbed and compacted samples with different moisture contents were tested with swelling pressure tests at constant volume method by flooding, and also with suction control by vapour transfer technique. Compacted mixtures of this material with bentonite in differents proportions, and mixtures of bentonite with sandy non-expansive material from the Botucatu Formation were also tested. The suction control was performed by the use of NaCl salt solutions at concentrations prepared to perform 40,000, 25,000, 10,000 and 5,000 kPa suctions. For the tests, it was developed a system for load application and automatic retrieval of pressure. To accelerate the wetting process by vapour, we used an external reservoir connected to an air pump adapted to promote air circulation inside the edometric cell, specially made for this study. The expansion results in flooding tests showed increasing swelling pressure with decreasing moisture content. Consequently there was an increase in the initial suction of the tested samples, which kept increasing as the rate of bentonite was raised in the mixtures, with a peak of ca. 700 kPa for the test with dry pure bentonite compacted. In the microstructure analysis of the samples by mercury intrusion porosimetry, the samples showed variation only in macropores after swell; and the ones compacted at optimum moisture, and subsequently air dried, showed no significant change after the swell. In scanning electron microscopy (SEM) it was possible to verify the change in the voids of the samples, as well as to visualize the variation in the structure and texture. In addition, the SEM confirmed clay minerals deterninated in mineralogical characterization. The results of controlled suction with swell tests showed absence of swell pressure for Corumbatai samples tested in undisturbed conditions, and compacted condition at optimum moisture content, and then air dried. However, when compacted in the form of dry powder, as well as when compacted dry, mixed with different proportions of bentonite, this material showed swelling pressures with vapor transfer technique, as well as mixtures of bentonite with non-expansive material of Botucatu Formation. The absence of swell was explained by the slow damping provided by the vapor transfer that although promoting increasing dampen, did not sufficiently mobilized volume variation capable of transmitting blowing pressure. Therefore, the swell tests with the vapor transfer technique were effective to evaluate the swelling just in cases where clay minerals with swell potential were present in significant proportions.

Metal clusters have been produced by condensation of metal atoms on or inside small argon clusters and by collision of supersonic atomic argon beams with atomic metal vapours. A key parameter in both processes is the metal atom particle density. For iron, metal particle densities above a thermal open crucible-type evaporator were determined using quartz-micro-balance mass flux measurements, revealing a point-source-like dependence on the distance from the crucible. For silver atoms the particle densities were also determined using scattering from small argon clusters. Formation and soft-deposition of iron nanoparticles was first attempted using a supersonic beam of argon atoms that was blown into a vapour of iron atoms. Transmission electron microscopy showed the presence of iron nanoparticles whose size depended on the deposition time, showing that aggregation takes place after deposition. The deposition rates were of the order of 0.01 nm/s. In the second part of the study argon clusters containing on average 21 atoms were directed through vapours of xenon or silver atoms. Time-of-flight mass spectrometry showed the presence of xenon and silver clusters when the xenon or silver particle densities were increased. The xenon clusters contained up to four atoms whereas silver would only formdimers. The mass spectra also showed argon atoms attached to the xenon clusters, but not to the silver dimers, which was attributed to the high temperature of the silver dimers.

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Dissertacao (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

La creciente demanda del confort humano está obligando a la comunidad científica a buscar nuevas técnicas que permitan aprovechar al máximo los recursos disponibles. Gran parte de esta demanda es consumida por sistemas de producción de frío basados en la compresión de vapor, por tanto, constituye uno de los sectores estratégicos a tener en cuenta para contribuir al desarrollo sostenible mediante la optimización energética de las instalaciones frigoríficas. Además de la búsqueda de soluciones eficientes desde un punto de vista energético, la comunidad científica dirige sus esfuerzos en la búsqueda de nuevas sustancias refrigerantes cuyo efecto no sea nocivo para el medio ambiente.

Con el fin de contribuir y fomentar el uso del fluido natural CO2 como refrigerante, se ha elaborado la presente tesis doctoral que está centrada en estudios teóricos y posterior análisis experimental del funcionamiento de una planta frigorífica de compresión de vapor que emplea CO2 como refrigerante en condiciones supercríticas. Esta nueva iniciativa permite minimizar al máximo el impacto medioambiental generado por las emisiones de refrigerantes artificiales, aunque requiere de una tecnología completamente nueva debido a las propiedades físicas del propio refrigerante. El objeto de este análisis se centra en continuar buscando aquellas configuraciones que logren mejorar el rendimiento energético de las instalaciones que empleen R744 como refrigerante.

En la presente tesis doctoral se ha efectuado un estudio experimental de una configuración con un sistema de expansión en una única etapa, donde se ha analizado la influencia del aceite en la masa de refrigerante a cargar en la instalación y en el comportamiento de la misma. Este funcionamiento se compara con el comportamiento que adopta un ciclo que cuenta con un sistema de doble etapa de expansión y depósito intermedio entre ambas etapas, que le proporciona la masa que necesita en todo momento. Además, se estudia el comportamiento de la instalación al insertar en ambas configuraciones un IHX. Por otro lado, en este trabajo también se ha llevado a cabo un análisis experimental de la instalación operando en régimen supercrítico frente al modo de operación en régimen subcrítico cuando las condiciones externas lo permiten. De esta forma, se evalúa la posibilidad de operar con ambos sistemas a partir de una instalación dimensionada para operar en régimen supercrítico. El último análisis experimental realizado se basa en la búsqueda de nuevas configuraciones para mejorar el rendimiento energético del equipo, donde se estudia la extracción de vapor en el depósito de acumulación y la posterior inyección ó recompresión en diferentes puntos de la instalación.

Estos análisis experimentales se han complementado con estudios de carácter teórico. El primer estudio teórico se ha basado en el modelado de la instalación frigorífica para analizar la energía calorífica generada en el foco caliente y destinada a activar otras aplicaciones. El segundo estudio ha consistido en el modelado matemático de dos tipos diferentes de intercambiadores de calor, uno de tubo concéntrico y flujo paralelo y otro de flujo cruzado con tubos aleteados externamente.

Le développement d’un médicament pour une cible thérapeutique donnée passe par plusieurs étapes qui se résument en une étape de criblage, une phase préclinique et plusieurs phases cliniques. Ces étapes permettent de sélectionner une substance active et de démontrer son efficacité thérapeutique et sa sécurité toxicologique. Ces deux critères définissent la qualité du médicament qui, une fois démontrée, doit être garantie pendant toute sa durée de validité. La qualité est évaluée au moyen d’études de stabilité qui sont réalisées d’abord sur la matière première de la substance active au cours de la phase de pré-développement du médicament, ensuite sur le produit fini. La stabilité intrinsèque de la substance active concerne à la fois ses propriétés chimiques et ses propriétés physiques qui sont liées à la nature de la substance. L’étude de stabilité repose d’abord sur la caractérisation de ces propriétés, et ensuite sur l’étude de la sensibilité de la substance à l’égard des facteurs environnementaux pouvant modifier les propriétés intrinsèques de la substance. L’approche adoptée dans ce travail repose d’une part sur l’évaluation de la stabilité chimique c’est à dire de la réactivité chimique des substances à usage pharmaceutique au travers des études de pureté chimique et des études de dégradation forcée de ces substances en solution, et d’autre part, sur l’évaluation de la stabilité physique. Dans ce cadre, l’étude du polymorphisme cristallin revêt une grande importance, tout comme l’aptitude à la formation d’hydrates ou de solvates. Cette étude, basée sur la thermodynamique, consiste pour l’essentiel à construire un diagramme de phases pression-température permettant de définir les domaines de stabilité relative des différentes formes cristallines. Cinq substances actives, existant à l’état solide et entrant dans la composition de médicaments administrés par voie orale, ont été étudiées dans le cadre de ce travail. L’analyse chimique du tienoxolol, présentant un effet anti-hypertenseur, a montré qu’il est très sensible à l’hydrolyse et à l’oxydation. Sept produits de dégradation ont été identifiés pour ce produit dont un schéma probable de fragmentation a été établi. Des diagrammes de phases pression-température ont été construits pour le bicalutamide et le finastéride, médicaments du cancer de prostate, en utilisant une approche topologique basée simplement sur les données disponibles dans la littérature. Cette étude a montré que la relation thermodynamique (énantiotropie ou monotropie) entre les formes cristallines sous conditions ordinaires peut être modifiée en fonction de la température et de la pression. Ce résultat est important pour la production des médicaments car il montre comment une telle information peut être obtenue par des mesures simples et accessibles aux laboratoires de recherche industrielle, sans que ces derniers soient contraints d’expérimenter sous pression. La méthode topologique de construction de diagramme de phases a été validée ensuite en la comparant à une méthode expérimentale consistant à suivre, par analyse thermique, des transitions de phases en fonction de la pression. La méthode expérimentale a été appliquée à deux composés, la benzocaine, anesthésique local, et le chlorhydrate de cystéamine, médicament utilisé pour les cystinoses. Les deux formes étudiées de benzocaine présentent une relation énantiotrope qui se transforme en relation monotrope à haute pression. Une nouvelle forme cristalline (forme III) du chlorhydrate de cystéamine a été découverte au cours de ce travail. La relation thermodynamique entre cette forme III et la forme I est énantiotrope dans tout le domaine de température et de pression. De plus, le chlorhydrate de cystéamine, classé hygroscopique, a fait l’objet d’une étude quantitative de sa sensibilité à l’eau, montrant qu’il devient déliquescent sans formation préalable d’hydrate (...)
The development of a drug for a given therapeutic target requires several steps, which can be summarized by drug screening, a preclinical phase and a number of clinical phases. These steps allow the selection of an active substance and a verification of its therapeutic efficacy and toxicological safety. The latter two criteria define the quality of the drug, which once demonstrated, must be guaranteed throughout its shelf life. Quality is assessed through stability studies that are carried out with the raw material of the active substance (preformulation phase) and with the final product. The intrinsic stability of the active substance depends on its chemical and physical properties and their characterization is the core of the stability studies, which in addition consists of sensitivity studies of the active pharmaceutical ingredient (API) for environmental factors that can modify the intrinsic properties of the substance. The approach presented in this work is based on the one hand on the assessment of the chemical stability, i.e. the reactivity of APIs through chemical purity studies and forced degradation in solution, and on the other hand on the assessment of the physical stability. For the latter, crystalline polymorphism is of great importance, as is the ability of the API to form hydrates or solvates. The study of crystalline polymorphism is based on the construction of pressure-temperature phase diagrams in accordance with thermodynamic requirements leading to the stability condition domains of the different crystalline forms. The stability behavior of five APIs used or meant for oral applications has been studied as part of this work. The chemical analysis of tienoxolol, an antihypertensive drug, has demonstrated its sensitivity for hydrolysis and oxidation. Seven degradation products were identified and patterns of fragmentation have been established. Pressure-temperature phase diagrams have been constructed for bicalutamide and finasteride, drugs against prostate cancer, using a topological approach based on data available in the literature. The study demonstrates that the thermodynamic relationship (enantiotropy or monotropy) between crystalline forms under ordinary conditions can change depending on the pressure. This is important for drug development as it demonstrates how stability information can be obtained by standard laboratory measurements accessible to industrial research laboratories without the necessity to carry out experiments under pressure. The topological approach for the construction of phase diagrams has subsequently been validated by measuring transition temperatures as a function of pressure. Experiments have been carried out with benzocaine, a local anesthetic, and with cysteamine hydrochloride, a drug used against cystinosis. Two crystalline forms were observed in the case of benzocaine. They exhibit an enantiotropic relationship that becomes monotropic at high pressure. For cysteamine hydrochloride, a new crystalline form (form III) was discovered. The thermodynamic relationship between the new form III and the known form I is enantiotropic for the entire temperature and pressure range. Cysteamine hydrochloride’s sensitivity to water has been studied, as it is hygroscopic. It has been demonstrated that it becomes deliquescent in the presence of water and no trace of a hydrate has been found. Finally, a study combining thermal and chromatographic methods showed that, under the effect of temperature, cysteamine hydrochloride turns into cystamine in the solid as well as in the liquid state, The latter is known to be an important impurity of cysteamine hydrochloride. In conclusion, the approach developed in this work allowed to characterize the stability properties of a number of APIs and to determine the factors that may change these properties and influence the intrinsic stability (...)

Systematické řízení tepelných a elektrických toků v plně elektrických automobilech se stává velmi důležitým, protože v těchto typech automobilů není k dispozici dostatek odpadního tepla pro vytápění kabiny. Aby v zimním období nedocházelo ke snížení dojezdu, je nutné použití technologií, které umožní snížení spotřeby energie nutné k vytápění kabiny (např. tepelné čerpadlo, zásobník tepla). Je také zapotřebí vytvořit řídicí algoritmy pro tato zařízení, aby byl zajištěn jejich optimální provoz. V letním období je nezbytné řídit tepelné toky v rámci elektromobilu tak, aby nedocházelo k nadměrnému vybíjení baterie kvůli chlazení kabiny a dalších částí. Tato práce řeší jak návrh řídicích algoritmů, tak i vývoj rozhodovacího algoritmu, který zajistí směřování tepelných toků.

The HSE (Hard Sphere Expansion) theory calculates the thermodynamic properties of a mixture by separating its properties into contributions from molecular repulsion, which are calculated directly from a hard sphere mixture equation of state, and other contributions from various types of intermolecular attraction, which are obtained by corresponding states from known values of similar contributions in a pure reference fluid. Shape factors are used to establish conformality between individual constituents and the reference fluid. This theoretically based approach represents composition dependence better than the empirical mixing rules used in the traditional mixture equations of state. By applying the first and second order variational principles, a procedure is developed to determine the optimal repulsion contribution and rigid core dimensions. The procedure requires an equation of state capable of predicting accurate second derivatives for the reference fluid. A 32 constant modified Benedict-Webb-Rubin (MBWR) equation with exceptional accuracy is used for this purpose. Engineering equations of state are permissible for constituents other than the reference. The new development allows an accurate analytical approach to be applicable to the differentiation of the mixture Helmholtz free energy property with respect to component moles involved in the phase equilibrium calculations. The importance of the reference fluid selected for phase equilibrium calculations is discussed. The reference fluids used are the three hydrocarbons: methane, ethane, and propane. For mixtures containing polar fluids, such as carbon dioxide or hydrogen sulfide, the total attraction contribution may be evaluated entirely from the attraction in a pure nonpolar reference fluid by means of shape factors. An alternate method is to evaluate separate symmetrical and asymmetrical attraction terms, in which the multipole expansion is used to account for the polar contributions. Both approaches are discussed and compared. The HSE theory are applied to gaseous and liquid phases of binary hydrocarbon mixtures containing high concentrations of hydrogen sulfide or carbon dioxide. Calculations of densities and the vapor-liquid composition ratios (K-values) are presented. Good agreement with experimental data is achieved over a wide range of pressure and temperature. The computational procedure is detailed in this work.

Liquefied Natural Gas (LNG) is flammable when it forms a 5 – 15 percent volumetric concentration mixture with air at atmospheric conditions. When the LNG vapor comes in contact with an ignition source, it may result in fire and/or explosion. Because of flammable characteristics and dense gas behaviors, expansion foam has been recommended as one of the safety provisions for mitigating accidental LNG releases. However, the effectiveness of foam in achieving this objective has not been sufficiently reported in outdoor field tests. Thus, this research focused on experimental determination of the effect of expansion foam application on LNG vapor dispersion and pool fire. Specifically, for evaluating the use of foam to control the vapor hazard from spilled LNG, this study aimed to obtain key parameters, such as the temperature changes of methane and foam and the extent reduction of vapor concentration. This study also focused on identifying the effectiveness of foam and thermal exclusion zone by investigating temperature changes of foam and fire, profiles of radiant heat flux, and fire height changes by foam. Additionally, a schematic model of LNG-foam system for theoretical modeling and better understanding of underlying mechanism of foam was developed. Results showed that expansion foam was effective in increasing the buoyancy of LNG vapor by raising the temperature of the vapor permeated through the foam layer and ultimately decreasing the methane concentrations in the downwind direction. It was also found that expansion foam has positive effects on reducing fire height and radiant heat fluxes by decreasing fire heat feedback to the LNG pool, thus resulting in reduction in the safe separation distance. Through the extensive data analysis, several key parameters, such as minimum effective foam depth and mass evaporation rate of LNG with foam, were identified. However, caution must be taken to ensure that foam application can result in initial adverse effects on vapor and fire control. Finally, based on these findings, several recommendations were made for improving foam delivery methods which can be used for controlling the hazard of spilled LNG.

Like the hard sphere expansion (HSE) theory, the hard convex body expansion (HCBE) theory separates any residual thermodynamic property into a contribution from molecular repulsion, which is calculated directly from a hard convex body (HCB) equation of state, and other contributions from molecular attraction, which are obtained by the corresponding states principle (CSP) using pure reference fluids. The HSE theory yields good agreement with the experimental thermodynamic data for light hydrocarbon mixture systems. However, there is a limit to molecular size and shape difference in mixtures where the intermolecular repulsion can be represented by hard sphere mixture. A HCB equation of state developed by Naumann and Leland (1984) is applicable to pure components and their mixtures. The HCB equation of state for a pure component is characterized by two dimensionless geometrical parameters, $\alpha$ and $\tau\sp{-1},$ which are combinations of three molecular dimensions of a convex body--volume(V), surface area(S), and mean radius(R). Two dimensionless geometrical parameters are determined directly from Pitzer's acentric factor. The molecular volume is evaluated by equating the HCB equation of state to the optimal repulsion evaluated by the expansion method. The surface area and the mean radius are obtained from known dimensionless geometrical parameters and molecular volume. Four kinds of convex bodies are considered in this work. These are prolate spherocylinders, oblate spherocylinders, prolate ellipsoids, and oblate ellipsoids. Better results for the vapor-liquid equilibrium constants (K-values) for mixtures containing molecules as nonspherical as n-decane in the prolate models and cyclohexane in the oblate models are obtained with this method than with ordinary equations of state using empirical mixing rules. This HCBE theory can also be applied to predict thermodynamic properties of pure components using two reference fluids as in the Lee-Kesler method (1975).

In recent years, heat pumps and refrigeration systems are widely used in both residential and industrial applications. The possibility of recovering the large throttling losses by using an expander could give a substantial contribution to the performance improvement. In this thesis, a reciprocating expander developed from a hydraulic motor was numerically and experimentally analyzed. A numerical model was developed to identify the needed small modifications to be made on the expander without change its architecture. Successively, an extensive experimental activity on the modified expander has been carried out to characterize it in detail and evaluate the effective performance. With this aim, a dedicated test rig and a measurement system have been developed. The expander was tested in a R134a heat pump cycle and in a CO2 refrigeration cycles. Despite of the mechanical losses due to the different original application of the machine, the thermodynamic cycles showed very promising results with the adoption of this solution. For this reason, a redesign and manufacturing of the machine was done in order to improve the efficiency in HFC cycles and to decrease the mechanical losses. The new version of the expander was tested in a "hot-gas bypass cycle", which has been designed and manufactured. The aim of this cycle is to obtain high stability and flexibility, and lower size due to the lack of the evaporator. The results showed improvement in both the thermodynamic behavior and mechanical losses. Finally, a 1D thermal conduction model has been developed to study the two-phase expansion with R134a with an improved accuracy.

Research Doctorate - Doctor of Philosophy (PhD)
Helium has the highest ionization energy of any species and is as a consequence difficult to detect by conventional means. On the other hand, it is the ideal surface probe, having no net charge or spin, a low mass and a short de Broglie wavelength. Therefore, there exists a strong incentive to develop a microscopy technique based on helium atom scattering. The purpose of this thesis is to investigate in detail how an efficient helium detector might be developed using the phenomenon of field ionization, an ionization method that relies on quantum mechanical tunneling rather than the more conventional electron impact ionization techniques. In particular, the work focusses on the potential use of a novel nanomaterial, carbon nanotubes, as the source of the high electric fields required for field ionization detection. In Chapter 1 we review the history of field ionization research and the properties and synthesis methods for carbon nanotubes. Chapter 2 describes the experimental apparatus and procedures used for the present research, and Chapter 3 introduces the theoretical framework and background for field ionization. In Chapter 4, the prototypical field ionization system is considered from a detector viewpoint. The work demonstrates that existing theory is not sufficiently quantitative for describing a field ionization detector and therefore a semi-empirical theory is advanced for that purpose. Chapter 5 considers the problem of nanotube field enhancement in detail using computational methods, leading to a complete description of the maximum field enhancement of a nanotube array based on the four fundamental array parameters. Efforts to synthesize carbon nanotubes in the Newcastle plasma-enhanced chemical vapor deposition system are described in Chapter 6. Several procedures are developed for reproducible growth of nanotube films and the chemical vapor deposition system is characterized with single parameter studies. Chapter 7 presents the results of electron field emission and helium field ionization experiments carried out using the grown nanotube films. We demonstrate for the first time the field ionization of helium using a planar film of carbon nanotubes. Finally, we conclude the investigation of field ionization detection in Chapter 8 with a discussion on how such a detection method integrates into a helium microscope and in particular we detail the design and initial calculations for the planned Newcastle helium microscope.

Research Doctorate - Doctor of Philosophy (PhD)
Helium has the highest ionization energy of any species and is as a consequence difficult to detect by conventional means. On the other hand, it is the ideal surface probe, having no net charge or spin, a low mass and a short de Broglie wavelength. Therefore, there exists a strong incentive to develop a microscopy technique based on helium atom scattering. The purpose of this thesis is to investigate in detail how an efficient helium detector might be developed using the phenomenon of field ionization, an ionization method that relies on quantum mechanical tunneling rather than the more conventional electron impact ionization techniques. In particular, the work focusses on the potential use of a novel nanomaterial, carbon nanotubes, as the source of the high electric fields required for field ionization detection. In Chapter 1 we review the history of field ionization research and the properties and synthesis methods for carbon nanotubes. Chapter 2 describes the experimental apparatus and procedures used for the present research, and Chapter 3 introduces the theoretical framework and background for field ionization. In Chapter 4, the prototypical field ionization system is considered from a detector viewpoint. The work demonstrates that existing theory is not sufficiently quantitative for describing a field ionization detector and therefore a semi-empirical theory is advanced for that purpose. Chapter 5 considers the problem of nanotube field enhancement in detail using computational methods, leading to a complete description of the maximum field enhancement of a nanotube array based on the four fundamental array parameters. Efforts to synthesize carbon nanotubes in the Newcastle plasma-enhanced chemical vapor deposition system are described in Chapter 6. Several procedures are developed for reproducible growth of nanotube films and the chemical vapor deposition system is characterized with single parameter studies. Chapter 7 presents the results of electron field emission and helium field ionization experiments carried out using the grown nanotube films. We demonstrate for the first time the field ionization of helium using a planar film of carbon nanotubes. Finally, we conclude the investigation of field ionization detection in Chapter 8 with a discussion on how such a detection method integrates into a helium microscope and in particular we detail the design and initial calculations for the planned Newcastle helium microscope.