Les mémoires à changement de phase (PRAM) développées par l’industrie de la microélectronique utilisent la capacité d’un materiau chalcogénure à passer rapidement et de façon réversible d’une phase amorphe à une phase cristalline. Le passage de la phase amorphe à la phase cristalline s’accompagne d’un changement de la résistance électrique du matériau. La transition amorphe vers cristallin est obtenue par un chauffage qui porte la cellule mémoires au delà de la température de transition du verre. Le verre ternaire de chalcogène Ge2Sb2Te5 (GST-225) est probablement le matériau amené à être le plus utilisé dans la prochaine génération de dispositifs de stockage de masse. La thermoréflectométrie résolue en temps (TDTR) et la radiométrie photothermique modulée (MPTR) sont utilisées ici pour étudier les propriétés thermiques des constituants des PRAM déposés sous forme de couche mince sur des substrats de silicium. Les diffusivités thermiques et les résistances thermiques de contact des films PRAM sont estimées. Ces paramètres sont identifiés en utilisant un modèle d’étude des transferts de chaleur basé sur la loi de Fourier et utilisant le formalisme des impédances thermiques. Ces mesures ont été effectuées pour des températures allant de 25 à 400°C. Les modifications de structure et de compositions chimiques causées par les hautes températures au cours des expériences sont aussi étudiées via des analyses par les techniques de DRX, MEB, TOF-SIMS et ellipsométrie.Les propriétés thermiques des GST - 225, isolants, électrodes de chauffage et électrodes métalliques mise en œuvre dans ce type de dispositif de stockage sont ainsi mesuré a l’échelle submicrométrique. / The Phase change Random Access Memories (PRAM), developed by semiconductor industry are based on rapid and reversible change from amorphous to crystalline stable phase of chalcogenide materials. The switching between the amorphous and the crystalline phase leads to change of the electrical resistance of material. The amorphous-to-crystalline transition is performed by heating the memory cell above the glass transition temperature (~130°C). The chalcogenide ternary compound glass Ge2Sb2Te5 (GST-225) is probably the candidate to become the most exploited material in the next generation of mass storage architectures. The Time Domain ThermoReflectance (TDTR) and the Modulated PhotoThermal Radiometry (MPTR) have been implemented to study the thermal properties of constituting element of PRAM deposited as thin layer (~100 nm) on silicon substrate. The thermal diffusivity and the Thermal Boundary Resistance of the PRAM film are retrieved. These parameters are identified using a model of heat transfer based on Fourier’s Law and the thermal impedance formalism. The measurements were performed in function of temperature from 25°C to 400°C. Structural and chemical changes due to the high temperature during the experimentation have been also investigated by using XRD, SEM, TOF-SIMS and ellipsometry techniques. The thermal properties of GST-225, insulator, heating and metallic electrode involved in these kind of storage devices were thus measured at a sub micrometric scale.

The process of milling drugs to obtain samples with a desirable particle size range has been widely used in the pharmaceutical industry, especially for the production of drugs for inhalation. However by subjecting materials to milling techniques surfaces may become thermodynamically activated which may in turn lead to formation of amorphous material. Polymorphic conversions have also been noted after milling of certain materials. Salt and cocrystal formation is a good way of enhancing the properties of an API but little or no work has been published which investigates the stability of these entities when subjected to milling. Different milling techniques (ball and jet) and temperatures (ambient and cryogenic) were used to investigate the milling behaviour of polymorphs, salts and cocrystals. All materials were analysed by XRPD and DSC to investigate any physical changes, i.e. changes in melting point and by inverse gas chromatography (IGC) to investigate whether any changes in the surface energetics occurred as a result of milling. Another aim of this thesis was to see if it was possible to predict the milling behaviour of polymorphs by calculating the attachment energies of the different crystal facets using Materials Studio 4.0. These results were compared to the IGC data to see if the predicted surface changes had occurred. The data collected in this study showed that different milling techniques can have a different effect on the same material. For example ball milling at ambient temperature and jet micronisation of the SFZ tosylate salt caused a notable increase in the melting point of the material whereas ball milling at cryogenic temperatures did not cause this to happen. The IGC data collected for this form also showed a contrast between cryomilling and the other two techniques. The study also showed that the formation of salts and cocrystals does not necessarily offer any increased stability in terms of physical properties or surface energetics. Changes in melting point were observed for the SFZ tosylate salt and the IMC:Benzamide cocrystal. Changes in the specific surface energies were also observed indicating that the nature of the surfaces was also changing. The materials which appeared to be affected the least were the two stable polymorphs, gamma IMC and SFZ III. The computational approach used has many limitations. The software does not allow for conversion to the amorphous form or polymorphic conversions. Such conversions were seen to occur, particularly for the metastable polymorphs used, meaning that this computational approach may only be suitable for stable polymorphs.

[ES] The automotive industry represents one of the most important sectors in the world. Given its socio-economic influence, research is aimed at reducing fuel consumption and emissions. Turbochargers provide several benefits including increased power for a given engine size, improved fuel economy and reduced emissions. The turbocharger is an important piece for the new generation of engines that must comply with the Euro 6 or in the U.S. Tier 3 vehicle emissions and fuel standard program. As more effort is made to increase efficiencies and reduce emissions, the complexity of the system increases. The high rotational speeds, pulsating flow conditions and high temperature differences between working fluids (exhaust gases, compressed air, lubricating oil, coolant fluids) make the turbo-charging a challenging task. Numerical simulation opens a range of possibilities to study the performance, efficiency and design of components in the turbocharger, but requires continued accuracy refinements. In this thesis, a great effort has been made to improve the overall understanding of the different physical phenomena that occur inside the turbocharger. Both, experimental and modelling efforts have been made to understand the thermal behaviour of the turbocharger under engine start/stop conditions. After state-of-the-art review of thermal studies and heat transfer simulation codes, this work presents an extensive experimental testing campaign that includes a thermal characterization of the turbocharger in stationary and transient conditions. Subsequently, several turbochargers were measured to assess the consequences that degraded oils can generate in the bearing system during endurance tests of oil-coking. To minimize the possibilities of coke formation, some theoretical studies were done. First, a 1D turbocharger model was used in GT-PowerTM for a detailed study of the temperature rise in the central housing during an engine hot-stop. The simulated cooling strategies aims to find an optimal in terms of minimizing extra energy consumption per K housing temperature reduction. After, a 2D radial model is proposed as improvement of an existing one-dimensional model developed at CMT - Universitat Politècnica de València. Aiming for a low computational cost, the radial model was developed to be compatible with fast one-dimensional engine simulations. Later, a detailed solution of heat fluxes was made by means of CFD using a 3D design of the turbocharger's central housing. The 3D model improved the results when temperature of the bearings/shaft is required. Additionally, thermal properties within the turbocharger can be obtained and therefore a reduction of the experimental tasks in the thermohydraulic test bench. Both 2D and 3D models were validated using experimental data, demonstrating predictive accuracy improvements on the results of previous models. / [CAT] La industria automotriz representa uno de los sectores más importantes del mundo. Dada su influencia socioeconómica, la investigación está destinada a reducir el consumo de combustible y las emisiones. Los turbocompresores ofrecen varios beneficios, entre ellos, mayor potencia para un tamaño de motor determinado, mejor economía de combustible y reducción de emisiones. El turbocompresor es una pieza importante para la nueva generación de motores que deben cumplir con la normativa Euro 6 o en el programa estándar de emisiones y combustible de los EE. UU. Tier 3. A medida que se hacen más esfuerzos para aumentar la eficiencia y reducir las emisiones, la complejidad del sistema aumenta. Las altas velocidades de rotación, las condiciones de flujo pulsante y las altas diferencias de temperatura entre los fluidos de trabajo (gases de escape, aire comprimido, aceite lubricante, fluidos refrigerantes) hacen que la turbocarga sea una tarea desafiante. La simulación numérica abre un rango de posibilidades para estudiar el rendimiento, la eficiencia y el diseño de los componentes en el turbocompresor, pero requiere continuos refinamientos de precisión. En esta tesis, se ha hecho un gran esfuerzo para mejorar la comprensión global de los diferentes fenómenos físicos que ocurren al interior del turbocompresor. Se han hecho esfuerzos experimentales y de modelado para comprender el comportamiento térmico del turbocompresor en condiciones de arranque/parada del motor. Luego de una revisión de los estudios térmicos y de los códigos de simulación de transferencia de calor, éste trabajo presenta una extensa campaña de pruebas experimentales que incluye una caracterización térmica del turbocompresor en condiciones estacionarias y transitorias. Posteriormente, se midieron varios turbocompresores para evaluar las consecuencias que los aceites degradados pueden generar en el sistema de rodamientos durante pruebas de resistencia de coque de aceite. Para minimizar las posibilidades de formación de coque, se realizaron algunos estudios teóricos. En primer lugar, se usó un modelo de turbocompresor 1D en GT-PowerTM para un estudio detallado del aumento de temperatura de la carcasa central del turbocompresor durante un paro en caliente del motor. Las estrategias de enfriamiento simuladas apuntan a encontrar un óptimo en términos de minimizae el consumo de energía extra por reducción de la temperatura de la carcasa en Kelvin. Posteriormente, se propone un modelo radial 2D como mejora de un modelo unidimensional existente desarrollado en la CMT - Universitat Politècnica de València. Con el objetivo de conseguir un bajo costo computacional, el modelo radial 2D se desarrolló para ser compatible con simulaciones unidimensionales rápidas de motor. Después, se realizó una solución detallada de los flujos de calor mediante CFD utilizando un diseño 3D de la carcasa central del turbocompresor. El modelo 3D mejora los resultados cuando se requiere la temperatura de los cojinetes/eje. Además, con ésta campaña de CFD se pueden obtener propiedades térmicas dentro del turbocompresor y, por lo tanto, una reducción de las tareas experimentales en el banco de pruebas termohidráulico. Ambos modelos 2D y 3D fueron validados utilizando datos experimentales, demostrando mejoras de precisión de predicción sobre los resultados de modelos anteriores. / [EN] La indústria automotriu representa un dels sectors més importants del món. Donada la seua influència socioeconòmica, la investigació està destinada a reduir el consum de combustible i les emissions. Els turbocompressors oferixen diversos beneficis, entre ells, major potència per a una grandària de motor determinat, millor economia de combustible i reducció d'emissions. El turbocompressor és una peça important per a la nova generació de motors que han de complir amb la normativa Euro 6 o en el programa estàndard d'emissions i combustible dels EE. UU. Tier 3. A mesura que es fan més esforços per a augmentar l'eficiència i reduir les emissions, la complexitat del sistema augmenta. Les altes velocitats de rotació, les condicions de flux polsen-te i les altes diferències de temperatura entre els fluids de treball (gasos de fuga, aire comprimit, oli lubricant, fluids refrigerants) fan que la turbocarga siga una tasca desafiador. La simulació numèrica obri un rang de possibilitats per a estudiar el rendiment, l'eficiència i el disseny dels components en el turbocompressor, però requerix continus refinaments de precisión. En aquesta tesi, s'ha fet un gran esforç per a millorar la comprensió global dels diferents fenòmens físics que ocorren a l'interior del turbocompressor. S'han fet esforços experimentals i de modelatge per a comprendre el comportament tèrmic del turbocompressor en condicions d'arranque/parada del motor. Després d'una revisió dels estudis tèrmics i dels codis de simulació de transferència de calor, este treball presenta una extensa campanya de proves experimentals que inclou una caracterització tèrmica del turbocompressor en condicions estacionàries i transitòries. Posteriorment, es van mesurar uns quants turbocompressors per a avaluar les conseqüències que els olis degradats poden generar en el sistema de rodaments durant proves de resistència de coc d'aceite. Per a minimitzar les possibilitats de formació de coc, es van realitzar alguns estudis teòrics. En primer lloc, es va usar un model de turbocompressor 1D en GT- Power \textsuperscript{TM} per a un estudi detallat de l'augment de temperatura de la carcassa central del turbocompressor durant una desocupació en calent del motor. Les estratègies de refredament simulades apunten a trobar un òptim en termes de minimizae el consum d'energia extra per reducció de la temperatura de la carcassa en Kelvin. Posteriorment, es proposa un model radial 2D com a millora d'un model unidimensional existent desenrotllat en la CMT - Universitat Politècnica de València. Amb l'objectiu d'aconseguir un baix cost computacional, el model radial 2D es va desenrotllar per a ser compatible amb simulacions unidimensionals ràpides de motor. Después, es va realitzar una solució detallada dels fluxos de calor per mitjà de CFD utilitzant un disseny 3D de la carcassa central del turbocompressor. El model 3D millora els resultats quan es requerix la temperatura dels cojinetes/eje. A més, amb esta campanya de CFD es poden obtindre propietats tèrmiques dins del turbocompressor i, per tant, una reducció de les tasques experimentals en el banc de proves termohidráulico. Ambdós models 2D i 3D van ser validats utilitzant dades experimentals, demostrant millores de precisió de predicció sobre els resultats de models anteriores. / Rodriguez Usaquén, YT. (2019). Experimental study of oil coking problem and contribution to the modelling of heat transfer in turbochargers [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/117314 / TESIS

The process of milling drugs to obtain samples with a desirable particle size range has been widely used in the pharmaceutical industry, especially for the production of drugs for inhalation. However by subjecting materials to milling techniques surfaces may become thermodynamically activated which may in turn lead to formation of amorphous material. Polymorphic conversions have also been noted after milling of certain materials. Salt and cocrystal formation is a good way of enhancing the properties of an API but little or no work has been published which investigates the stability of these entities when subjected to milling. Different milling techniques (ball and jet) and temperatures (ambient and cryogenic) were used to investigate the milling behaviour of polymorphs, salts and cocrystals. All materials were analysed by XRPD and DSC to investigate any physical changes, i.e. changes in melting point and by inverse gas chromatography (IGC) to investigate whether any changes in the surface energetics occurred as a result of milling. Another aim of this thesis was to see if it was possible to predict the milling behaviour of polymorphs by calculating the attachment energies of the different crystal facets using Materials Studio 4.0. These results were compared to the IGC data to see if the predicted surface changes had occurred. The data collected in this study showed that different milling techniques can have a different effect on the same material. For example ball milling at ambient temperature and jet micronisation of the SFZ tosylate salt caused a notable increase in the melting point of the material whereas ball milling at cryogenic temperatures did not cause this to happen. The IGC data collected for this form also showed a contrast between cryomilling and the other two techniques. The study also showed that the formation of salts and cocrystals does not necessarily offer any increased stability in terms of physical properties or surface energetics. Changes in melting point were observed for the SFZ tosylate salt and the IMC:Benzamide cocrystal. Changes in the specific surface energies were also observed indicating that the nature of the surfaces was also changing. The materials which appeared to be affected the least were the two stable polymorphs, gamma IMC and SFZ III. The computational approach used has many limitations. The software does not allow for conversion to the amorphous form or polymorphic conversions. Such conversions were seen to occur, particularly for the metastable polymorphs used, meaning that this computational approach may only be suitable for stable polymorphs.

The doctoral research revolves around a comparative study of timber modern methods of construction for low-rise, residential buildings in Scotland. The building techniques studied involve both timber-frame panel construction (open-panel and closed-panel systems and structural insulated panels) and massive-timber construction (cross-laminated and nail-laminated timber panels). A non-timber technique is also included in the study: more traditional, load-bearing masonry (blockwork). These different building techniques have been analysed from two complementary aspects: environmental impacts and thermal performance. The environmental study is based on the life-cycle assessment methodology and embraces various aspects: environmental impacts (e.g., climate change, acidification, eutrophication, ozone depletion, etc.), consumption of energy (renewable and non-renewable resources) and production of waste (from non-hazardous to radioactive). The assessment takes a cradle-to-gate approach and, in its structure and method, is informed by the current recommendations of the international standards in the field (i.e., ISO 14040 series). Various environmental trade-offs between construction methods have been identified. In terms of global-warming potential (excluding biogenic carbon sequestration), results suggest that timber-frame buildings show a better performance than masonry buildings; this is particularly true for the open-panel system, which emits about 10% less carbon than the masonry counterpart. Massive-timber buildings tend to cause more carbon emissions than masonry ones. In terms of consumption of non-renewable primary energy, timber buildings do not generally show significant advantages with respect to blockwork-based masonry. In particular, structural-insulated panel systems tend to show very high energy requirements. Timber-based buildings show a tendency to cause increased acidification, eutrophication and creation of low ozone than their masonry counterpart. The level of offsite fabrication that is employed for the erection of the buildings plays an important role in the magnitude of most environmental impacts, which show an average decrease between 5% and 10% when some of the operations are shifted from the construction site to the factory. v The thermal study investigates the performance of the building envelope, and, in particular, of external walls, by means of tests whereby the thermal behaviour of a sample of walls (of full-size section) has been observed and measured over time. On the outside, the walls were exposed to real, natural weather variations throughout the summer. The study especially focuses on the time-dependent response of three different walling systems (which results from their individual cross-sectional arrangements of building components and the associated combination of heat-storage capacity and thermal resistance): a timber-framed wall, a cross-laminated-timber wall and a masonry wall. Thus, the main goal of the study was to characterise the thermal-inertia parameters of these walls. This type of thermal behaviour is related to the repercussions of global climate change at UK level, especially in terms of increase in solar irradiance and temperature, which requires an adaptation of the building-envelope such that it can perform well both during wintertime and summertime, by providing maximum indoor comfort with minimum economic and environmental costs from the construction and operation of buildings. The timber-framed wall possesses the greatest capacity to slow down the propagation of temperature waves from the outer surface to the inner surface (time lag), whereas the masonry wall performs best with respect to reducing the amplitude of temperature oscillation on the inner surface (decrement factor). The cross-laminated-timber wall exhibits intermediate values of both time lag and decrement factor, relative to the other two walls. Both the thermal and life-cycle assessment of the construction alternatives aim at assisting the design and decision-making process in the residential field and at suggesting areas that need to be addressed and improved, towards a coherent evolution of the building techniques included in this study and a step forward in the realisation of sustainable, low-rise dwellings.