Geo-energy piles and walls have long been recognized as a promising way to reduce carbon dioxide emissions while providing renewable energy. However, enhancing the thermal performance of these structures has remained a signif-icant challenge. This thesis evaluated five different approaches to improving the thermal performance of geo-energy piles and walls, through a series of experiments using a fully instrumented testing rig. The first approach involved adding graphTHERM powder to concrete to double its thermal conductivity, boosting heat transfer efficiency by an impressive 50% to 66%. The second approach tested slag-based geopolymer concrete as a sustainable construc-tion material for geo-energy piles and walls, reducing CO2 emissions by 44.5% while improving thermal performance by 14% to 21%. The third approach in-volved testing thermally enhanced soils at the geo-energy structures/soil inter-face, resulting in an 81% improvement in heat transfer efficiency. The fourth approach utilized innovative phase change material (PCM) heat exchangers that increased heat transfer efficiency by 75% and 43% in heating and cooling operations, respectively. Finally, incorporated PCM-impregnated light weight aggregates at the interface of the structure soil, significantly increasing tem-perature difference and reducing thermal deformation of geo-energy struc-tures.Overall, these innovative approaches made a significant contribution to enhancing the thermal performance of geo-energy piles and walls. However, approaches four and five, which involve utilizing PCM heat exchangers and PCM-impregnated LWA's, respectively, showed extra benefits in dropping the thermal effect on soils and reducing the thermal damage on those structures. These techniques offer great promise for improving the thermal performance of geo-energy structures.

Thesis (PhD) -- Stellenbosch University, 2014. / ENGLISH ABSTRACT: Currently the reduction of the levelised cost of electricity (LCOE) is the main goal of concentrating solar power (CSP) research. Central to a cost reduction strategy proposed by the American Department of Energy is the use of advanced power cycles like supercritical steam Rankine cycles to increase the efficiency of the CSP plant. A supercritical steam cycle requires source temperatures in excess of 620°C, which is above the maximum storage temperature of the current two-tank molten nitrate salt storage, which stores thermal energy at 565°C. Metallic phase change materials (PCM) can store thermal energy at higher temperatures, and do not have the drawbacks of salt based PCMs. A thermal energy storage (TES) concept is developed that uses both metallic PCMs and liquid metal heat transfer fluids (HTF). The concept was proposed in two iterations, one where steam is generated directly from the PCM – direct steam generation (DSG), and another where a separate liquid metal/water heat exchanger is used – indirect steam generation, (ISG). Eutectic aluminium-silicon alloy (AlSi12) was selected as the ideal metallic PCM for research, and eutectic sodium-potassium alloy (NaK) as the most suitable heat transfer fluid. Thermal energy storage in PCMs results in moving boundary heat transfer problems, which has design implications. The heat transfer analysis of the heat transfer surfaces is significantly simplified if quasi-steady state heat transfer analysis can be assumed, and this is true if the Stefan condition is met. To validate the simplifying assumptions and to prove the concept, a prototype heat storage unit was built. During testing, it was shown that the simplifying assumptions are valid, and that the prototype worked, validating the concept. Unfortunately unexpected corrosion issues limited the experimental work, but highlighted an important aspect of metallic PCM TES. Liquid aluminium based alloys are highly corrosive to most materials and this is a topic for future investigation. To demonstrate the practicality of the concept and to come to terms with the control strategy of both proposed concepts, a storage unit was designed for a 100 MW power plant with 15 hours of thermal storage. Only AlSi12 was used in the design, limiting the power cycle to a subcritical power block. This demonstrated some practicalities about the concept and shed some light on control issues regarding the DSG concept. A techno-economic evaluation of metallic PCM storage concluded that metallic PCMs can be used in conjunction with liquid metal heat transfer fluids to achieve high temperature storage and it should be economically viable if the corrosion issues of aluminium alloys can be resolved. The use of advanced power cycles, metallic PCM storage and liquid metal heat transfer is only merited if significant reduction in LCOE in the whole plant is achieved and only forms part of the solution. Cascading of multiple PCMs across a range of temperatures is required to minimize entropy generation. Two-tank molten salt storage can also be used in conjunction with cascaded metallic PCM storage to minimize cost, but this also needs further investigation. / AFRIKAANSE OPSOMMING: Tans is die minimering van die gemiddelde leeftydkoste van elektrisiteit (GLVE) die hoofdoel van gekonsentreerde son-energie navorsing. In die kosteverminderingsplan wat voorgestel is deur die Amerikaanse Departement van Energie, word die gebruik van gevorderde kragsiklusse aanbeveel. 'n Superkritiese stoom-siklus vereis bron temperature hoër as 620 °C, wat bo die 565 °C maksimum stoor temperatuur van die huidige twee-tenk gesmelte nitraatsout termiese energiestoor (TES) is. Metaal fase veranderingsmateriale (FVMe) kan termiese energie stoor by hoër temperature, en het nie die nadele van soutgebaseerde FVMe nie. ʼn TES konsep word ontwikkel wat gebruik maak van metaal FVM en vloeibare metaal warmteoordrag vloeistof. Die konsep is voorgestel in twee iterasies; een waar stoom direk gegenereer word uit die FVM (direkte stoomopwekking (DSO)), en 'n ander waar 'n afsonderlike vloeibare metaal/water warmteruiler gebruik word (indirekte stoomopwekking (ISO)). Eutektiese aluminium-silikon allooi (AlSi12) is gekies as die mees geskikte metaal FVM vir navorsingsdoeleindes, en eutektiese natrium – kalium allooi (NaK) as die mees geskikte warmteoordrag vloeistof. Termiese energie stoor in FVMe lei tot bewegende grens warmteoordrag berekeninge, wat ontwerps-implikasies het. Die warmteoordrag ontleding van die warmteruilers word aansienlik vereenvoudig indien kwasi-bestendige toestand warmteoordrag ontledings gebruik kan word en dit is geldig indien daar aan die Stefan toestand voldoen word. Om vereenvoudigende aannames te bevestig en om die konsep te bewys is 'n prototipe warmte stoor eenheid gebou. Gedurende toetse is daar bewys dat die vereenvoudigende aannames geldig is, dat die prototipe werk en dien as ʼn bevestiging van die konsep. Ongelukkig het onverwagte korrosie die eksperimentele werk kortgeknip, maar dit het klem op 'n belangrike aspek van metaal FVM TES geplaas. Vloeibare aluminium allooie is hoogs korrosief en dit is 'n onderwerp vir toekomstige navorsing. Om die praktiese uitvoerbaarheid van die konsep te demonstreer en om die beheerstrategie van beide voorgestelde konsepte te bevestig is 'n stoor-eenheid ontwerp vir 'n 100 MW kragstasie met 15 uur van 'n TES. Slegs AlSi12 is gebruik in die ontwerp, wat die kragsiklus beperk het tot 'n subkritiese stoomsiklus. Dit het praktiese aspekte van die konsep onderteken, en beheerkwessies rakende die DSO konsep in die kollig geplaas. In 'n tegno-ekonomiese analise van metaal FVM TES word die gevolgtrekking gemaak dat metaal FVMe gebruik kan word in samewerking met 'n vloeibare metaal warmteoordrag vloeistof om hoë temperatuur stoor moontlik te maak en dat dit ekonomies lewensvatbaar is indien die korrosie kwessies van aluminium allooi opgelos kan word. Die gebruik van gevorderde kragsiklusse, metaal FVM stoor en vloeibare metaal warmteoordrag word net geregverdig indien beduidende vermindering in GLVE van die hele kragsentrale bereik is, en dit vorm slegs 'n deel van die oplossing. ʼn Kaskade van verskeie FVMe oor 'n reeks van temperature word vereis om entropie generasie te minimeer. Twee-tenk gesmelte soutstoor kan ook gebruik word in samewerking met kaskade metaal FVM stoor om koste te verminder, maar dit moet ook verder ondersoek word.

Ces travaux de thèse visent à concevoir et étudier une unité d'échangeur de chaleur air-MCP en tant que solution passive a la problématique du contrôle de confort thermique dans les bâtiments pendant l'été, fournissant des directives de conception et une intégration facile aux bâtiments. Les MCP présentent une grande capacité de stockage par unité de volume, ce qui leur permet de contribuer à la réduction de la consommation d'énergie liée aux applications de rafraîchissement. Bien qu'ils présentent certains inconvénients, en tant que faible conductivité thermique, notamment dans les PCM commerciaux, une conception bien détaillée est nécessaire pour atteindre des performances thermiques adéquates.La première partie de cette thèse examine les systèmes existants à travers une étude bibliographique, mettant en évidence la relation géométrique avec la physique et la performance thermique. Cette recherche a fourni les bases pour le développement d'une conception d'une unité air-MCP, suivant une méthodologie de résolution de problèmes développée par le laboratoire I2M. Une matrice de mots-clés a été obtenue à partir des phénomènes physiques et de l'analyse fonctionnelle de l'unité. A partir de cette matrice, l'analyse des brevets a inspiré la conception qui a abouti à un échangeur de chaleur air-PCM à faisceau tubulaire avec des tubes verticaux alignés perpendiculairement au flux d'air.Le développement d'outils de conception et d'intégration dans les bâtiments a été recherché au moyen d'une modélisation permettant de prédire avec précision les performances thermiques du système. Les modèles simplifiés sont préférés pour cette tâche. Néanmoins, ils peuvent sous-estimer les performances réelles si les phénomènes physiques impliqués ne sont pas correctement comptabilisés. Alors,des approches expérimentales locales et globales ont été utilisées pour parvenir à une compréhension de la physique associée aux cycles de charge et de décharge dans l'unité air-MCP. Pour cela, un banc d'essai a été installé, mesurant la température et le débit d'air dans différentes conditions d'entrée, accompagné d'un suivi visuel à travers des images numériques. Les traitements d'images et des données ont été utilisés pour obtenir des indicateurs de performance thermique et des corrélations équivalentes en utilisant des nombres adimensionnels connus pour les mécanismes de transfert de chaleur convectifs-conducteurs dans le PCM.Ces découvertes ont permis de développer des modèles de résistance thermique et d'enthalpie qui rendent compte de la complexité des phénomènes impliqués dans l'unité pour la prédiction de la performance. Enfin, la performance thermique du système a été testée dans deux applications de bâtiments : en tant qu'unité mobile dans une maison PEH à Gradignan dans un bureau du labo I2M. / The present work aims to design and study an air-PCM heat exchanger unit as a passive solution for thermal comfort assessment in buildings during summertime, providing tools to ease the design and building integration. The PCM present a large storage capacity per volume unit where by, they can contribute to the reduction of the energy consumption related to cooling applications. Although, theyshow some drawbacks, as a low thermal conductivity in commercial PCM, so a wellthought design of these kind of systems is necessary to achieve adequate thermal performances.The first part of this thesis surveys the existing systems through a literature review,highlighting the geometry relation with the physics and thermal performance. This search provided the bases for the development of an air-PCM unit design, following a problem-solving methodology developed by the I2M laboratory. A keyword matrix was obtained from the physical phenomena and functional analysis of the unit. From this matrix, the patents analysis provided inspiration for the design resulting in a tubebundle air-PCM heat exchanger with vertical tubes aligned perpendicular to the airflow.The development of design and integration in buildings tools was sought through a modeling that can accurately predict the thermal performance of the system.Simplified models are preferred for this task. Nevertheless, they can under predict the actual performance if the physical phenomena involved is not properly accounted. Then, local and global experimental approaches were used to achieve anunderstanding of the physics associated with charging and discharging cycles in theunit. For this, a test bench was installed, measuring temperature and airflow underdifferent in let conditions, accompanied by a visual tracking through digital images.Image and data processing were used to obtain thermal performance indicators and equivalent correlations using known dimensionless numbers for convective conductive heat transfer mechanisms in the PCM.These findings allowed the development of thermal models based on energy balances, that accounted the complexity of phenomena involved in the unit for performance prediction. Finally, the thermal performance of the system was tested intwo buildings applications: as a mobile unit in a PEH house in Gradignan and as anactive façade in a building in Talence. / El presente trabajo tiene como objetivo diseñar y estudiar una unidad intercambiador de calor aire-PCM como presentan una solución pasiva al conforttérmico en edificios durante el verano, proporcionando herramientas para facilitar el diseño y la integración en edificios. Los PCM una gran capacidad de almacenamiento por unidad de volumen, por lo que pueden contribuir a la reducción del consumo de energía relacionado con las aplicaciones de refrigeración. Estos materiales presentan algunos inconvenientes en cual su uso, como una baja conductividad térmica, típica en PCM comerciales, por lo es necesario un diseño que tome en cuenta esta problemática para lograr rendimientos térmicos adecuados. La primera parte de esta tesis examina los sistemas existentes a través de unarevisión de la literatura, destacando la relación de geometría con los fenómenos físicos y el rendimiento térmico. Esta búsqueda proporcionó las bases para el desarrollo de un diseño de unidad aire-PCM, siguiendo una metodología de resolución de problemas desarrollada por el laboratorio I2M. Se obtuvo una matrizde palabras clave a partir de los fenómenos físicos y el análisis funcional de launidad. A partir de esta matriz, el análisis de patentes proporcionó inspiración para el diseño que dio como resultado un intercambiador de calor PCM de aire y haz detubos verticales alineados perpendicularmente al flujo de aire.El desarrollo del diseño y la integración en herramientas de edificios se buscó através de un modelo que pudiese predecir con precisión el rendimiento térmico delsistema. Los modelos simplificados son los preferidos para esta tarea. Sin embargo,su poder de predicción puede verse afectada si los fenómenos físicos involucradosno se contabilizan adecuadamente. Es por ello que se utilizaron enfoques experimentales locales y globales para lograr una comprensión de la física asociadacon los ciclos de carga y descarga en la unidad. Se realizó una instalación de unbanco de pruebas, que permitió mediciones de temperatura y flujo de aire en diferentes condiciones de entrada, acompañado de un seguimiento visual a travésde imágenes digitales. El procesamiento de imágenes y datos se utilizó para obtener indicadores de rendimiento térmico y correlaciones a partir de números adimensionales relacionados con mecanismos de transferencia de calor porconvección y conducción en el PCM.Estos hallazgos permitieron el desarrollo de modelos térmicos para la predicción delrendimiento, basados en balances de energía de cada volumen de control.Finalmente, el rendimiento térmico del sistema se probó en dos aplicaciones deedificios: como una unidad móvil en una casa PEH en Gradignan y dentro de una oficina del laboratorio I2M.

Die monolithische Integration von Phasenwechselmaterialien mit Halbleiter-Hetero\-strukturen er\"offnet neue Perspektiven f\"ur zuk\"unftige Generationen von nichtfl\"uchtigen Speicherbauelementen. %Epitaktische Phasenwechselmaterialien erm�glichen detaillierte %Studien der strukturellen �nderungen w�hrend des Phasen�bergangs und %erlauben eine Bestimmung der Skalierungslimits zuk�nftiger %Datenspeicher. Diese Arbeit befasst sich mit dem epitaktischen Wachstum von Ge-Sb-Te Phasenwechselmaterialien. Dazu wurden Ge-Sb-Te(GST) Schichten mittels Molekularstrahlepitaxie (MBE) auf GaSb(001)-Substraten abgeschieden. Die kristallografische Orientierung und die Ver\"anderungen der Gitterkonstante w\"ahrend des Wachstums wurden mittels R\"ontgenbeugung unter streifendem Einfall (GIXRD) bestimmt. Das Nukleationsverhalten zu Beginn des Wachstums wurde mittels Hochenergie-Elektronenbeugung unter streifendem Einfall (RHEED) untersucht. / The integration of phase change materials into semiconductor heterostructures may lead to the development of a new generation of high density non-volatile phase change memories. Epitaxial phase change materials allow to study the detailed structural changes during the phase transition and to determine the scaling limits of the memory. This work is dedicated to the epitaxial growth of Ge-Sb-Te phase change alloys on GaSb(001). We deposit Ge-Sb-Te (GST) films on GaSb(001) substrates by means of molecular beam epitaxy (MBE). The film orientation and lattice constant evolution is determined in real time during growth using grazing incidence X-ray diffraction (GID). The nucleation stage of the growth is studied \emph{in situ} using reflection high energy electron diffraction (RHEED).

Submitted by JOSIANE SANTOS DE OLIVEIRA (josianeso) on 2018-12-21T13:22:18Z No. of bitstreams: 1 José Henrique Nazzi Ehms_.pdf: 4808489 bytes, checksum: b590c723912ffe1d5d90006182f8cff2 (MD5) / Made available in DSpace on 2018-12-21T13:22:18Z (GMT). No. of bitstreams: 1 José Henrique Nazzi Ehms_.pdf: 4808489 bytes, checksum: b590c723912ffe1d5d90006182f8cff2 (MD5) Previous issue date: 2018-10-31 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Armazenamento térmico apresenta grande potencial de utilização em diversas aplicações, como energia solar, climatização, conservação de alimentos ou aproveitamento de calor residual em processos industriais. O armazenamento térmico de calor latente é realizado com materiais de mudança de fase (PCM), através dos processos de fusão e solidificação. A representação destes processos através de simulação numérica é realizada com o acréscimo ao modelo matemático básico, composto pelas equações da conservação da massa, quantidade de movimento e energia, modelos para descrever o calor latente e a transição na velocidade entre as fases, tais como: Darcy STM (source term method), VVM (variable viscosity method) e SOM (switch-off method). No entanto, a grande maioria das pesquisas nesta área utiliza o primeiro método. Além disso, são poucos os estudos comparativos de diferentes métodos para descrever processos de mudança de fase. Assim, o objetivo do presente estudo é comparar os métodos Darcy STM, VVM e misto (utilizando elementos dos dois anteriores) na simulação numérica de processos de fusão e de solidificação do PCM RT27 no interior de uma esfera. O estudo foi realizado utilizando-se fluidodinâmica computacional, através do método dos volumes finitos. O Modelo numérico foi validado com resultados experimentais da literatura. Os resultados quantitativos e qualitativos de fração líquida mostram que o método Darcy STM é mais adequado ao processo de solidificação, enquanto o método VVM produz resultados mais próximos aos experimentais no processo de fusão. O custo computacional foi menor para o método Darcy STM e maior para o método VVM, enquanto o método misto apresenta custo computacional pouco inferior ao do método VVM. Na análise da camada líquida na fusão de contato, foram analisadas a velocidade descendente do sólido, a espessura da camada e a vazão na camada. Os resultados referentes a camada líquida indicaram significativa influência das configurações do método Darcy STM. No entanto, são pouco influenciados pelas configurações do método VVM. / Thermal energy storage presents great potential of utilization in several applications, such as solar energy, HVAC systems, food conservation or waste heat recovery in industrial processes. Latent heat thermal energy storage is realized with phase change materials (PCM), through solidification and melting processes. Representation of such processes through numerical simulation is performed with the addition to the basic numerical model, composed of the conservation equations of mass, momentum and energy, models to account the latent heat and the velocity transition between the phases, such as: Darcy STM (source term method), VVM (variable viscosity method) and SOM (switch-off method). However, the large majority of the research on such area employ the first method. Besides that, there are few comparative studies of different methods to describe phase change processes. Thus, the objective of the present work is compare Darcy STM, VVM and mixed method (using elements of the two prior) in the simulation of melting and solidification processes of PCM RT27 inside a sphere. The study was realized using computational fluid dynamics, with the finite volume method. The numerical model was validated with experimental results from literature. Quantitative and qualitative results of liquid fraction show that Darcy STM is most suitable to solidification process, while VVM produces results closer to experimental in the melting process. Computational cost was smaller for Darcy STM and greater for VVM, while mixed method presents computational cost slightly lower than the one of VVM. In the analysis of the liquid layer in close contact melting, were analyzed descending velocity of the solid, liquid layer thickness and the flow in the liquid layer. The results regarding the liquid layer denote significant influence of the configurations for Darcy STM. However, such results are little influenced by the configurations of VVM.

Les travaux présentés dans ce manuscrit portent sur la conception, simulation et réalisation des nouvelles structures des commutateurs hyperfréquences basées sur l’intégration des couches minces des matériaux innovants fonctionnels tels que les matériaux à changement de phase (PCM) et les matériaux à transition de phase (PTM). Le principe de fonctionnement de ces composants repose sur le changement de résistivité présenter par ces matériaux. Nous avons exploité le changement de résistivité réversible du GeTe de la famille des matériaux à changement de phase (PCM) entre les deux états : amorphe à forte résistivité et cristallin à faible résistivité, pour réaliser une nouvelle structure d’un simple commutateur SPST. Ensuite, nous avons intégré ce commutateur dans une nouvelle structure de la matrice de commutation DPDT (Double Port Double Throw) à base de PCM pour l’application dans la charge utile du satellite. Nous avons utilisé la transition isolant-métal présenté par le dioxyde de vanadium (VO2) de la famille des matériaux à transition de phase, pour réaliser une nouvelle structure de commutateur simple à deux terminaux sur une très large bande de fréquence (100 MHz–220 GHz). / The work presented in this manuscript focuses on the design, simulation and realization of new microwave switches structures based on the integration of thin layers of innovative functional materials such as phase change materials (PCM) and phase transition materials. (PTM). The operating principle of these components is based on the change of resistivity present by these materials. We exploited the reversible resistivity change of GeTe of phase change materials family between the two states: amorphous with high resistivity and crystalline with low resistivity to realize a new structure of SPST switch. Then, we have integrated this switch structure on a new structure of DPDT (Double Port Double Throw) switch matrix based on phase change materials for application in satellite payload. We have used the insulatingmetal transition presented by the vanadium dioxide (VO2) of phase transition materials family to realize a new two terminals simple switch structure on a very wide frequency band (100 MHz–220 GHz).

Le travail présenté dans ce manuscrit concerne le développement d’un système de stockage thermique par chaleur latente pour les centrales solaires à concentration utilisant la génération directe de vapeur, et s’attache plus particulièrement la sélection et l’étude du matériau à changement de phase (MCP). Cette thèse a été réalisée dans le cadre du projet Stockage Thermique Appliqué à l’extension de pRoduction d’énergie Solaire thermodynamique (STARS) porté par le consortium composé d’AREVA Renouvelables, la société Hamon d’Hondt, l’institut CEA liten et les laboratoires IPNO, LPCS et LaTEP. Ce projet est accompagné par l’ADEME dans le cadre du programme énergies décarbonnées des investissements d’avenir.Le premier chapitre de ce manuscrit situe le contexte de l’étude en dressant un état de l’art des différents systèmes solaires à concentration existants et des différents moyens de stocker l’énergie pour ce type de technologie. Le projet STARS est ensuite présenté. Ce chapitre se termine par un descriptif des objectifs du travail de thèse. L’intégralité du processus de sélection du MCP, incluant le recensement des matériaux dans la littérature, la définition des critères de sélection et la caractérisation par calorimétrie différentielle à balayage des candidats les plus pertinents, est détaillée dans le chapitre II. À l’issue de ce travail, le choix du consortium se porte sur le nitrate de sodium, un sel inorganique possédant une température de fusion adaptée à la technologie d’AREVA et une densité de stockage importante. La poursuite de l’étude, concernant la stabilité thermique du MCP durant son utilisation en conditions industrielles, fait l’objet du chapitre III. Cette étude comporte une partie bibliographique permettant de mettre en évidence les problématiques liées à la dégradation thermique du matériau et à son comportement vis-à-vis des matériaux métalliques avec lesquels il sera amené à être en contact (échangeur de chaleur, cuve de stockage). La principale conséquence des phénomènes mis en évidence étant la réduction du nitrate de sodium en nitrite de sodium, l’étude de l’impact du taux de nitrite de sodium sur les propriétés thermiques du MCP a été réalisée. Les résultats de cette campagne expérimentale ont montré une diminution significative de la température de fusion et de la chaleur latente du MCP lorsque la proportion de nitrite de sodium croît. Afin d’étudier l’évolution de composition du MCP dans des conditions réelles de fonctionnement, un dispositif a été conçu spécifiquement pour reproduire des conditions de cyclage thermique en présence de métaux. L’étude menée à l’aide de ce dispositif a permis d’analyser la cinétique de réduction du nitrate de sodium en nitrite de sodium. Les résultats montrent que l’évolution de composition du MCP dans les conditions opératoires du projet est négligeable, garantissant la stabilité des propriétés thermiques de celui-ci au cours de son utilisation.Enfin, le dernier chapitre est consacré à l’étude de l’amélioration des transferts thermiques au sein du MCP. En effet, le nitrate de sodium possède une conductivité thermique faible, pouvant limiter la puissance des échanges de chaleur dans le système de stockage. En premier lieu, un état de l’art des solutions d’intensification des transferts dans le domaine du stockage par chaleur latente est dressé. Ce travail a permis de mettre en évidence que l’utilisation de composites à base de mousses métalliques constitue une voie pertinente d’amélioration des transferts. Ainsi une campagne expérimentale visant à évaluer les performances de tels composites a permis de mettre en évidence le potentiel de ce type de configuration. / The work presented in this manuscript concerns the development of a latent heat thermal energy storage system adapted to concentrated solar power plant using direct steam generation, and more particularly on the selection and the study of the Phase Change Material (PCM) used in this system. This thesis was performed within the framework of the STARS project (Stockage Thermique Appliqué à l’extension de pRoduction d’énergie Solaire thermodynamique) carried by the consortium of AREVA Renouvelables, Hamon d’Hondt company, CEA institute liten and laboratories IPNO, LPCS and LaTEP. This project is accompanied by ADEME under the énergies décarbonnées des investissements d’avenir program. The first chapter of this manuscript sets up the context of this study by drawing a state of art of different existing CSP technologies and various ways to store energy for this kind of systems. The STARS project is then described. This chapter ends with a description of the thesis objectives. The entire PCM selection process, including identification of materials in literature, definition of various criteria and thermal characterization by differential scanning calorimetry (DSC) of the most relevant candidates, is detailed in chapter II. This work leads to the selection of sodium nitrate by the consortium, an inorganic salt with a suitable melting temperature considering AREVA’s technology and a large storage density. The following work, concerning the thermal stability of the PCM under thermal cycling, is then presented in chapter III. This part includes a bibliographic study allowing to highlight issues related to thermal degradation of the PCM and its behavior regarding to metallic material with which it will have to be in contact (heat exchanger, storage tank). The main consequence of these phenomena is the reduction of sodium nitrate into sodium nitrite, and thus the impact of sodium nitrite fraction on the thermal properties of the PCM was studied. The results of this experimental work shows a significant reduction of the melting temperature and the latent heat as the fraction in sodium nitrite increases. To study the evolution of the PCM composition under real operating situation, a specific device was designed to replicate thermal cycling conditions in the presence of metals. This device was used to analyze the kinetics of reducing sodium nitrate into sodium nitrite. The results show that the changes in composition of the PCM in the project’s operating conditions are negligible, ensuring the stability of its thermal properties during its lifetime. The last chapter is devoted to the improvement of heat transfers within the PCM. Indeed, sodium nitrate has a low thermal conductivity which may limit the power of the heat exchange in the storage system. A state of art of available solutions for the intensification of thermal transfers concerning latent heat storage was done. This study highlighted that the use of composites based on metallic foams constitutes an effective way of improvement. Thus an experimental campaign was conducted to evaluate the performances of such composites, allowing to show the potential of this kind of configuration.

Ge-Sb-Te basierte Phasenwechselmaterialen sind vielersprechende Kandidaten für die Anwendung in optischen und elektrischen nicht-flüchtigen Speicheranwendungen. Diese Materialien können mit Hilfe von elektrischen oder optischen Pulsen reversibel zwischen der kristallinen und amorphen Struktur geschaltet werden. Diese stukturellen Phasen zeigen einen großen Unterschied in ihren elektronischen Eigenschaften, der sich in einer starken Änderung der optischen Reflektivität und des elektrischen Widerstands zeigt.Diese Studie befasst sich mit epitaktischem Wachstum und Analyse der epitaktischen Schichten. Der erste Teil der Arbiet befasst sich mir dem epitaktischen Wachstum von GeTe. Dünne GeTe Schichten wurden auf Si(111) und Si(001) Substraten mit einer Gitterfehlanpassung von 10.8% präpariert. Auf beiden Substraten bildet sich in der GeTe Schicht die [111] Oberflächenfacette parallel zur Si(001) und Si(111) Oberfläche aus. Während des inertialen Wachstums findet eine Phasentransformation von amorph zu kristallin statt. Diese Phasentransformation wurde mittels azimuthaler in-situ Beugung hochenergetischer Elektronen sowie in-situ Röntgenbeugung unter streifendem Einfall untersucht. Der zweite Teil der Arbeit wird die Epitaxie sowie die strukturelle Charakterisierung dünner Sb2Te3 Schichten dargestellt. Der dritte Teil umfasst die Epitaxie terniärer Ge-Sb-Te Schichten . Zum Wachstum wurden sowohl die Substrattemperatur als auch die Ge, Sb und Te Flüsse variiert. Es wird gezeigt, dass die Komposition der Schicht stark von der Wachtumstemperatur abhängt und nur entlang der pseudibinären Verbindungslinie von GeTe-Sb2Te3 variiert. Zur Kontrolle des Wachstums wurde dabei die in-situ Quadrupol Massenspektroskopie verwendet. Es zeigen sich diverse inkommensurate Beugungsmaxima entlang der [111] Oberflächennormalen der Schichten, anhand derer die Ausbildung einer Lehrstellen Ordnung in Form einer Überstruktur diskutiert wird. / Ge-Sb-Te based phase change materials are considered as a prime candidate for optical and electrical data storage applications. With the application of an optical or electrical pulse, they can be reversibly switched between amorphous and crystalline state, thereby exhibiting large optical and electrical contrast between the two phases, which are then stored as information in the form of binary digits. Single crystalline growth is interesting from both the academic and industrial perspective, as ordered Ge-Sb-Te based metamaterials are known to exhibit switching at reduced energies. The present study deals with the epitaxial growth and analysis of Ge-Sb-Te based thin films. The first part of the thesis deals with the epitaxial growth of GeTe. Thin films of GeTe were grown on highly mismatched Si(111) and (001) substrates. On both the substrate orientations the film grows along [111] direction with an amorphous-to-crystalline transition observed during the initial stages of growth. The amorphous-to-crystalline transition was studied in-vivo using azimuthal reflection high-energy electron diffraction scans and grazing incidence x-ray diffraction. In the second part of the thesis epitaxy and characterization of Sb2Te3 thin films are presented. The third part of the thesis deals with the epitaxy of ternary Ge-Sb-Te alloys. The composition of the films are shown to be highly dependent on growth temperatures and vary along the pseudobinary line from Sb2Te3 to GeTe with increase in growth temperatures. A line-of-sight quadrupole mass spectrometer was used to reliably control the GeSbTe growth temperature. Growth was performed at different Ge, Sb, Te fluxes to study the compositional variation of the films. Incommensurate peaks are observed along the [111] direction by x-ray diffraction. The possibility of superstructural vacancy ordering along the [111] direction is discussed.

Cette thèse vise à étudier l'exploitation du rayonnement solaire grâce à un nouveau concept de mur capteur passif. Dans ce contexte, le comportement thermique d’un mur solaire semi-transparent a été étudié. Le mur fournit un éclairage naturel et est composé d’une couche d’aérogel de silice assurant une isolation thermique et acoustique, et d’un MCP. Ce dernier est contenu dans des briques de verre assurant l’absorption, le stockage et la restitution de chaleur. Ce mur a été caractérisé expérimentalement au centre PERSEE à Sophia. Il a été remarqué que la performance thermique du mur est élevée en hiver, tandis qu’une surchauffe estivale a été rencontrée. Un modèle numérique simplifié a été développé pour modéliser la convection naturelle et le rayonnement pendant la fusion du MCP. Ce modèle est validé à l’aide d’un modèle CFD, et des résultats de Benchmark. Pour optimiser la performance du mur en été, un modèle numérique du transfert de chaleur à travers le mur a été développé sous MATLAB. Ce modèle a été couplé à TRNSYS afin d’évaluer la performance thermique de l'ensemble du bâtiment. Le modèle couplé a été validé expérimentalement. Le comportement thermique du mur est testé dans des différents climats, et des solutions passives sont proposées pour assurer le confort thermique. Enfin, ce modèle a permis d'étudier le comportement thermique annuel d’un bâtiment intégrant un mur MCP- aérogel dans son enveloppe et une étude économique a été réalisée. Ces études ont confirmé l'intérêt du mur vis-à-vis de l'amélioration des performances énergétiques du bâtiment. La faisabilité économique de l'application du mur dépend du climat, du coût d’énergie, et du coût d'investissement. / This thesis aims to study the exploitation of solar radiation thanks to a new concept of passive sensor wall. In this context, the thermal behavior of a novel semi-transparent solar wall has been studied. The wall is composed of glazing, silica aerogel (TIM) and glass bricks filled with fatty acids (PCM). This wall provides storage and restitution of heat, thermal-acoustic insulation and daylighting. The thermal performance of the TIM-PCM wall is tested in a full-sized test cell located in Sophia, PERSEE center. In winter, particularly in sunny cold days, the PCM absorbs solar radiation, melts, and then releases the stored heat to the building at night. During summer, overheating is encountered, the PCM remains in its liquid state and is unable to release the stored heat. A simplified model for PCM melting in presence of natural convection and radiation is developed and validated using a CFD model, and benchmark solutions. Then, a numerical model describing the heat transfer mechanisms through the wall is developed. This model is linked to TRNSYS to assess the thermal performance of the whole building. The MATLAB-TRNSYS model is then validated experimentally. The thermal behavior of the wall is tested under different climates, and passive solutions are proposed to ensure thermal comfort in summer. Finally, the validated model is used to study the annual thermal behavior of a building integrating TIM-PCM wall and an economic study is conducted. These studies confirm the interest of the wall vis-à-vis the improvement of energy performance of the building. The economic feasibility of applying the TIM-PCM wall depends mainly on climate, energy costs, and investment cost.

The trend in the electronic and electrical equipment industry towards denser and more powerful product requires a higher level of performance from cooling devices. In this context, passive cooling techniques such as latent heat storage systems have attracted considerable attention in recent years. Phase change materials (PCMs) have turned out to be extremely advantageous in this regard as they absorb high amount of latent heat without much rise of temperature. But unfortunately, nearly all phase change materials (PCMs) with high latent heat storage capacity have unacceptably low thermal conductivity, which makes heating and cooling processes slow during melting and solidification of PCMs. Augmentation of heat transfer in a PCM is achieved by inserting a high thermal conductivity material, known as thermal conductivity enhancer (TCE), into the PCM. The conglomeration of PCM and TCE is known as a thermal storage unit (TSU). In this thesis, detailed and systematic analyses are presented on the thermal performance of TSUs subjected to two types of thermal loading- (a) constant power loading in which a constant power level is supplied to the chip (heater) for a limited duration of time, and (b) cyclic loading. Eicosane is used as the PCM, while aluminium pin or plate fins are used as TCEs. First, a 1-D analytical model is developed to obtain a closed-form temperature distribution for a simple PCM domain (without TCE) heated uniformly from the bottom. The entire heating process is divided into three stages, viz. (a) sensible heating period before melting, during which heat is stored in the solid PCM in the form of specific heat, (b) melting period, during which a melt front progresses from the bottom to the top layer of the PCM and heat is stored in latent as well as in sensible forms, and (c) post melting period, during which energy is stored again in the form of sensible heat. For each stage, conduction energy equation is solved with a set of initial and boundary conditions. Subsequently, a resistance capacitance model of phase change process is developed for further analysis. For transient performance under constant thermal loading, experimental investigations are carried out for TSUs with different percentages of TCE. A numerical model is developed to interpret the experimental results. The thermal performance of a TSU is found to depend on a number of geometrical parameters and boundary conditions. Hence, a systematic approach is desirable for finding the best TSU design for which the chip can be operated for a longer period of time before it reaches a critical temperature (defined as the temperature above which the chip starts malfunctioning). As a first step of the approach, it is required to identify the parameters which can affect the transient process. It is found that the convective heat transfer coefficient, ‘h’ and the exposed area for heat transfer have little effect on the chip temperature during the constant power operation. A randomized search technique, Genetic Algorithm (GA), is coupled with the CFD code to find an optimum combination of geometrical parameters of TSUs based on the design criteria. First, the optimization is carried out without considering melt convection within the PCM. It is found that the optimum half-fin width remains fixed for a given heat flux and temperature difference. Assuming a quasi steady process, the results of optimization are then explained by constructing and analyzing a resistance network model. The resistance network model is then extended to include the effect of melt convection, and it is shown that the optimum pitch changes with the strength of convection. Accordingly, numerical analysis is carried out by considering the effect of melt convection, and a correlation for optimum pitch is developed. Having established the role of melt convection on the thermal performance of TSUs, rigorous computational and experimental studies are performed in order to develop correlations among different non-dimensional numbers, such as Nusselt number, Rayleigh number, Stefan number and Fourier number, based on a characteristic length scale for convection. The enclosures are classified into three types, depending on the aspect ratio of cavity, viz. shallow, rectangular and tall enclosures. For a shallow enclosure, the characteristic length is the height of cavity whereas for a tall enclosure, the characteristic length is the fin pitch. In case of rectangular enclosure, both pitch and height are the important characteristic lengths. For cyclic operation, it is required that the fraction of the PCM melting during the heating cycle should completely solidify back during the cooling period, in order that that TSU can be operated for an unlimited number of cycles. If solidification is not complete during the cooling period, the TSU temperature will tend to rise with every cycle, thus making it un-operational after some cycles. It is found that the solidification process during the cooling period depends strongly on the heat transfer coefficient and the cooling surface area. However, heat transfer coefficient does not play any significant role during the heating period; hence a TSU optimized for transient operation may not be ideal for cyclic loading. Accordingly, studies are carried out to find the parameters which could influence the behaviour of PCM under cyclic loading. A number of parameters are identified in the process, viz. cycle period and heat transfer coefficient. It is found that the required heat transfer coefficient for infinite cyclic operation is very high and unrealistic with air cooling from the surface of the TSU. Otherwise, the required cooling period for complete re-solidification will be very high, which may not be suitable for most applications. In an effort to bring down the cooling period to a duration that is comparable to the heating period, a new design is proposed where both ‘h’ and area exposed to heat transfer can be controlled. In this new design, the gaps between the fins in a plate-fin TSU are alternately filled with PCM, such that only one side of a fin is in contact with PCM and the other side is exposed to the coolant (air). In this arrangement, the same heat flow path through the fin which is used for heating the PCM (during the heating stage) can also be used for cooling and solidifying the PCM during the cooling part of the cycle. Natural or forced air cooling through the passages can be introduced to provide a wide range of heat transfer coefficient which can satisfy the cooling requirements. With this arrangement, the enhanced area provided for cooling keeps the ‘h’ requirement within a realistic limit. This cooling method developed is categorized as a combination of active and passive cooling techniques. Analytical and numerical investigations are carried out to evaluate the thermal performance of this modified PCM-based heat sink in comparison to the ones with conventional designs. It is found that, the performance of new PCM-based heat sink is superior to that of the conventional one. Experiments are performed on both the conventional and the new PCM-based heat sinks to validate the new findings.