The thesis deals with the creation for a numerical model of a solar collector with a phase change material as a heat storage medium. The model was implemented in Python. Using the created model, design optimization of several problems was carried out with the use of selected methods of heuristic optimization. The results of the behaviour of the created model and of design optimization were then analysed and evaluated.

Cette thèse a été réalisée initialement dans le cadre du projet Stockage Thermique Appliqué à l’extension de Production d’énergie Solaire thermodynamique (STARS) soutenu par l'Agence De l'Environnement et de la Maîtrise de l'Energie (ADEME).L’objectif du projet est de développer une solution de stockage thermique adaptée à la technologie Fresnel à génération directe de vapeur avec une zone de stockage de chaleur latente. Dans une unité de stockage latent, le nitrate de sodium (NaNO3) a été choisi comme matériau à changement de phase (MCP) et l’acier faiblement allié a été envisagé comme matériau de structure du conteneur et de l’échangeur thermique. La contribution de la thèse se positionne au niveau de l’étude de la corrosion et de la durabilité des matériaux de structure (conteneur et échangeur) en contact avec le MCP. L’objectif est de déterminer une loi de vitesse de corrosion qui permettrait de dimensionner les parois de l’échangeur et de développer des protocoles utilisant les techniques électrochimiques afin de suivre in-situ l’état de la corrosion au sein de l’unité de stockage. Les travaux présentés dans ce manuscrit portent sur l’étude expérimentale de la corrosion de l’acier dans le nitrate de sodium fondu à 340°C en fonction des paramètres expérimentaux tels que la présence d’impuretés (oxydes, chlorures), l’atmosphère gazeuse et le cyclage thermique. L’étude par mesures gravimétriques met en évidence la formation d’une couche de corrosion protectrice en surface de l’acier et la production de nitrite de sodium (NaNO2) par la réaction de corrosion. Cette couche constituée principalement de Fe2O3 (insoluble dans NaNO3 fondu) a été caractérisée par différentes méthodes d’analyse de surface (DRX, XPS). L’évolution de l’épaisseur de la couche de corrosion obtenue par cette technique montre une cinétique de corrosion logarithmique dans NaNO3 pur et une cinétique linéaire en présence d’une teneur importante en impuretés chlorures (10 mol%). L’étude électrochimique a apporté des indications sur le comportement du fer (et de l’acier) dans NaNO3 fondu. En combinant ces données avec les observations expérimentales issues des essais de corrosion nous avons pu proposer un mécanisme réactionnel pour la corrosion de l’acier en milieu nitrate fondu. L’étude par spectroscopie d’impédance électrochimique a permis de valider le mécanisme réactionnel proposé. A l’aide de ce mécanisme, les paramètres cinétiques puis la valeur du courant de corrosion ont été déduits par simulation des diagrammes d’impédance. L’analyse de la variation du courant de corrosion en fonction du temps permet de calculer l’épaisseur de la couche de corrosion et de la comparer à celle obtenue par gravimétrie. Un bon accord entre les valeurs obtenues par différentes techniques a été observé.Au cours de ce travail, nous avons également montré la possibilité d’utiliser les techniques électrochimiques pour l’instrumentalisation des installations industrielles afin de suivre in-situ l’évolution de la composition du MCP et l’état d’avancement de la corrosion de l’acier.Enfin, ce travail a montré que l’acier faiblement allié est adapté pour être utilisé dans une unité de stockage latent avec le nitrate de sodium comme matériau à changement de phase. / This thesis was originally performed as part of the STARS project (Stockage Thermique Appliqué à l’extension de Production d’énergie Solaire thermodynamique) which was supported by ADEME (l'Agence De l'Environnement et de la Maîtrise de l'Energie). The objective is to develop a thermal storage system using latent heat from a phase change material (PCM) in order to match with Fresnel technology using direct steam generation. Sodium nitrate (NaNO3) has been selected as PCM and low-alloy steel has been considered as candidate material to build the container and the heat exchanger of a latent heat storage system. The contribution of this thesis is to provide better understanding of the corrosion of the candidate material in contact with the PCM. This thesis aims to determine a corrosion rate law which helps design the thickness of the heat exchanger’s wall and to develop protocols using electrochemical technics to follow in-situ corrosion process in the latent heat storage system. The work presented in this manuscript focuses on experimental study of corrosion of low-alloy steel in molten NaNO3 (340°C) in function of different parameters: presence of impurities (oxides, chlorides), atmosphere and thermal cycling. Gravimetric measurements reveal the formation of a protective corrosion layer on the steel’s surface and the production of sodium nitrite (NaNO2) by corrosion reaction. The corrosion layer consisting mainly of Fe2O3 (insoluble in molten NaNO3) was characterized by surface analytical methods (XRD, XPS). Variation of the thickness of corrosion layer obtained by gravimetric methods shows logarithmic kinetics in pure NaNO3 and linear kinetics in the presence of 10mol% of impurity chlorides. Electrochemical study has provided indications on the iron (and steel) behavior in molten NaNO3. By combining results of this study with experimental observations from gravimetric study, we were able to propose a corrosion mechanism of the steel in molten NaNO3. This mechanism was then validated by electrochemical impedance spectroscopy study. Kinetics parameters and value of corrosion current were deduced by the simulation of impedance diagrams using the proposed mechanism. The thickness of corrosion layer was calculated by analyzing the variation of the corrosion current with time. These values present a good agreement with values obtained by gravimetric study.In this work, we also show the possibility of using electrochemical measurements at industrial scale to follow in-situ the evolution of the PCM's composition and the corrosion state. Finally, this work has shown that low-alloy steel is suitable for using in a latent heat storage system with NaNO3 as phase change material.

The thesis deals with the preparation, characterization and, in particular, with the switching properties of phase-change material (PCM) thin films. The films were deposited using the Pulsed Laser Deposition (PLD) technique. Phase transformations in these films were triggered by means of thermal annealing, laser pulses, and electrical pulses. The five major physical aspects structure transformation, crystallization kinetics, topography, optical properties, and electrical properties have been investigated using XRD, TEM, SEM, AFM, DSC, UV-Vis spectroscopy, a custom-made nanosecond UV laser pump-probe system, in situ resistance measurements, and conductive-AFM. The systematic investigation of the ex situ thermally induced crystallization process of pure stoichiometric GeTe films and O-incorporating GeTe films provides detailed information on structure transformation, topography, crystallization kinetics, optical reflectivity and electrical resistivity. The results reveal a significant improvement of the thermal stability in PCM application for data storage. With the aim of reducing the switching energy consumption and to enhance the optical reflectivity contrast by improving the quality of the produced films, the growth of the GeTe films with simultaneous in situ thermal treatment was investigated with respect to optimizing the film growth conditions, e.g. growth temperature, substrate type. For the investigation of the fast phase transformation process, GeTe films were irradiated by ns UV laser pulses, tailoring various parameters such as pulse number, laser fluence, pulse repetition rate, and film thickness. Additionally, the investigation focused on the comparison of crystallization of GST thin films induced by either nano- or femtosecond single laser pulse irradiation, used to attain a high data transfer rate and to improve the understanding of the mechanisms of fast phase transformation. Non-volatile optical multilevel switching in GeTe phase-change films was identified to be feasible and accurately controllable at a timescale of nanoseconds, which is promising for high speed and high storage density of optical memory devices. Moreover, correlating the dynamics of the optical switching process and the structural information demonstrated not only exactly how fast phase change processes take place, but also, importantly, allowed the determination of the rapid kinetics of phase transformation on the microscopic scale. In the next step, a new general concept for the combination of PCRAM and ReRAM was developed. Bipolar electrical switching of PCM memory cells at the nanoscale can be achieved and improvements of the performance in terms of RESET/SET operation voltage, On/Off resistance ratio and cycling endurance are demonstrated. The original underlying mechanism was verified by the Poole-Frenkel conduction model. The polarity-dependent resistance switching processes can be visualized simultaneously by topography and current images. The local microstructure on the nanoscale of such memory cells and the corresponding local chemical composition were correlated. The gained results contribute to meeting the key challenges of the current understanding and of the development of PCMs for data storage applications, covering thin film preparation, thermal stability, signal-to-noise ratio, switching energy, data transfer rate, storage density, and scalability.

Innovative methods for providing sustainable heating and cooling through thermal energy storage (TES) have gained increasing attention as heating and cooling demands in the built environment continue to climb. As energy prices continue to soar and systems reach their maximal capacity, there is an urgent need for alternatives to alleviate peak energy use. TES systems allow decoupling of energy production from energy utilization, both in location and in time. It is shown in this thesis that successful implementation of TES in the built environment alleviates peak energy load and reduces network expansion as well as the marginal energy production cost. This thesis analyzes phase change material (PCM) based TES systems in terms of material property characterization, numerical modeling and validation of thermal storage, as well as case specific techno-economic feasibility studies of system integration. The difficulties identified in latent heat TES design, such as heat transfer aspects, subcooling and identification of phase separation, have been analyzed through Temperature-History mapping and TES numerical modeling with experimental validation. This work focuses on the interdependency between resource availability, thermal charge/discharge power and storage capacity. In a situation where resource availability is limited, e.g. when using free cooling, waste heat or off-peak storage, the thermal power and storage capacity are strongly interrelated and should always be considered in unison to reach an acceptable techno-economic solution. Furthermore, when considering TES integration into an existing thermal energy distribution network, three adverse aspects are revealed in the Swedish case study: the single tariff system, the low-return temperature penalty, and the low storage utilization rate. These issues can be overcome through better adapted policies and optimized storage control strategies. Finally, despite the currently unfavorable conditions in the Swedish energy system, it is shown that TES has the potential to mitigate climate change through greenhouse gas emission reduction by displacing fossil-fuel based marginal thermal energy production. / QC 20110629 / Cold Thermal Energy Storage

The increasing demand for more efficient cooling options in the areas of fuel cell technology motivates the development of novel cooling strategies with improved heat transfer. Cooling through phase transition of the coolant from the liquid to the gaseous state is therefore a suitable approach. In this context, the phase transition behaviour in the inner structure of bipolar plates, which is determined by the flow field and its surface properties, must be understood and designed as a central functional element for cooling in a fuel cell. For the integrated development of a metallic bipolar plate based on the phase change cooling with modified surfaces, this paper discusses the design of the flow field, the design of the associated forming technology as well as the coating technology that meets the requirements of the bipolar plates with phase change cooling principle. In this regard, the wetting and the corrosion behaviour of different surface coatings and the in-situ phase transition behaviour within the bipolar plates are demonstrated and discussed.

[pt] O Brasil possui uma já extensa malha offshore de gasodutos e, no desenvolvimento da produção do Pré-Sal, esta deve continuar se expandindo em razão das necessidades de aumento da capacidade de escoamento de gás e também da sua reinjeção nos próprios reservatórios (seja apenas como descarte ou como um método de recuperação avançado). Uma vez instalada, esta malha deve ser periodicamente passar por manutenção, o que implica em eventos esporádicos de esvaziamento destes dutos, normalmente operando a altas pressões. Devido ao custo elevado de tais operações, deve-se estimar com boa precisão o tempo total necessário para despressurização, que pode levar várias horas ou até dias. Além disso, também é importante a previsão do inventário de líquido remanescente nos dutos após a despressurização. No presente trabalho, foi desenvolvido um modelo numérico para prever a despressurização de gasodutos considerando escoamento bifásico homogêneo e unidimensional. A formação e o consumo de condensado é obtida a partir de um inventário inicial de fluido supercrítico, com premissa de equilíbrio entre as fases. As propriedades termodinâmicas dos fluidos são determinadas utilizando-se pacotes comerciais e pré-tabuladas em função de pressão e temperatura. As equações de conservação foram discretizadas pelo método das diferenças finitas, utilizando o método de Euler implícito para o termo temporal e aproximação upwind nas derivadas espaciais. O sistema algébrico resultante foi resolvido diretamente de forma acoplada. Os resultados obtidos mostram boa concordância ao compará-los a dados reais de campo e resultados de simuladores comerciais de referência. / [en] Although Brazilian gas pipeline grid is already quite extensive, it continues to expand due to the Pre Salt development, since there is a growing need to increase the flowing capacity towards onshore facilities and injection wells (gas to be discarded or used for advanced oil recovery). Once pipelines are installed, maintenance operation must be performed quite often to guarantee process efficiency. Usually these operations demand depressurization from very high pressures. Considering the costs involved in such operations it is mandatory to accurately predict the total time for a complete blowdown, which may take several hours or even a couple of days. Furthermore, it is also important to evaluate the condensate content in the pipeline after the depressurization event. In the present work, a numerical model was developed to simulate gas pipeline depressurization considering unidimensional two-phase homogeneous flow. The formation and consumption of condensate from an initial supercritical state is obtained assuming phase equilibrium. Fluid properties are taken from tables generated by PVT packages. Conservation equations are discretized through the finite difference method employing Euler implicit approximation for the time derivatives and upwind scheme for spatial terms. A coupled direct algorithm was adopted to solve the resulting algebraic system. The results are compared to real field data and commercial software showing good agreement.

This research work is focused on a conceptual combination of membrane-based energy recovery ventilator (ERV) and phase change material (PCM) to provide energy savings in building heating, ventilation & air-conditioning (HVAC) systems. An ERV can recover thermal energy and moisture between the outside fresh air (OFA) entering into the building and the exhaust air (EA) leaving from the building thus reducing the energy consumption of the HVAC system for cooling and heating the spaces inside the building. The membranes were stacked parallel to each other forming adjacent channels in a counter-flow arrangement for OFA and EA streams. Heat and moisture is diffused through the membrane core. Flat-plate encapsulated PCM is arranged in OFA duct upstream/downstream of the ERV thereby allowing for further reduction in temperature by virtue of free cooling. Paraffin-based PCMs with a melting point of 24°C and 31°C is used in two different configurations where the PCM is added either before or after the ERV. Computational fluid dynamics (CFD), and heat and mass transfer modeling is employed using COMSOL Multiphysics v5.3 to perform the heat and mass transfer analysis for the membrane-based ERV and flat-plate PCMs. An 8-story office building was considered to perform building energy simulation using eQUEST v3.65 from Department of Energy (DOE). Based on the heat and mass transfer analysis, it is found that the sensible effectiveness (heat recovery) stood in the range of 65%-97% while the latent effectiveness (moisture recovery) stood at 55%-80%. Also, the highest annual energy savings achieved were 72,700 kWh in electricity consumption and 358.45 MBtu in gas consumption.

<p>  </p> <p>Thermal energy storage (TES) is used to reduce the operating costs of heating, ventilation, and air conditioning (HVAC) systems by shifting loads away from on-peak periods, to reduce the maximum heating or cooling capacity needed from the HVAC system, and to store excess energy generated by on-site solar power. The most commonly-used form of TES is ice storage with air conditioning (A/C) systems in commercial buildings. There has been extensive research into many other forms of TES for use with HVAC systems, both in commercial and residential buildings. However, this research is often limited to use with either heating or cooling systems.</p> <p>Year-round, high-density storage for both heating and cooling would yield significantly larger cost savings than existing TES systems, particularly for residential buildings, where heating loads are often larger than cooling loads. This dissertation examines the feasibility of using metal hydrides for year-round storage, as well as analyzing the potential of variable-temperature energy storage for optimizing system performance beyond allowing for year-round use.</p> <p>Metal hydrides are metals that exothermically absorb and endothermically desorb hydrogen. Since the temperature this reaction occurs at depends on the hydrogen pressure, hydrides can be used for energy storage at varying temperatures. System architecture for using metal hydrides with an HVAC system is developed. A thermodynamic model which combines a dynamic model of the hydride reactors with a static model of the HVAC system is used to calculate operating costs, compared to a conventional HVAC system, for different utility rates and locations. The payback period of the system is unacceptably high, due to the high initial cost of metal hydrides and the operating costs of compressing hydrogen to move it between hydride reactors.</p> <p>In addition to the metal hydride system model, a generalized model of a variable-temperature TES system is used to determine the potential cost savings from dynamically altering the storage temperature to achieve optimal cost savings. Dynamic tuning does result in cost savings but is most effective for storage tank sizes significantly smaller than the optimal tank size. An alternate system design where the storage tank is charged with the outlet flow from the house achieves larger cost savings even for the optimally-sized tanks. Payback periods calculated for optimal sizing show that year-round storage has a lower payback period than separate cold and heat storage if the year-round storage system is not more expensive than two separate storage tanks. </p>

Dans le cadre du stockage de Gaz Naturel Liquéfié (GNL) dans des réservoirs flottants, tels que les méthaniers, les contraintes imposées à la cuve par le ballotement de la cargaison doivent être quantifiées. La plupart des études expérimentales ou numériques actuelles ne prennent pas en compte la possibilité de changement de phase entre le GNL et sa vapeur lors d'un impact du liquide sur la paroi. L'objectif de cette thèse est l'ajout de ce phénomène physique dans un code de mécanique des fluides numérique pour la simulation de l'impact d'une vague déferlante sur une paroi.Dans ce but, un état de l'art des différentes modélisations possibles du changement de phase en mécanique des fluides est présenté. Il a été choisi de modéliser le changement de phase entre le liquide et le gaz à une interface franche sans hypothèse d'équilibre thermodynamique à l'interface. Un système hyperbolique de lois de conservation incluant le changement de phase interfacial hors-équilibre est présenté.Deux approches sont utilisées pour la résolution numérique de ce système. La première utilise un modèle de mélange pour décrire les mailles contenant l'interface liquide-vapeur. Dans la seconde méthode, l'interface est reconstruite et évolue de manière lagrangienne. Les deux approches sont basées sur un schéma volume fini de type Roe.L'enjeu de la simulation numérique du changement de phase interfacial est la capacité du code à gérer un rapport de densité loin de 1 et une chaleur latente élevée, qui entrainent respectivement de fortes variations de pression et de température à l'interface. L'aspect thermique est le phénomène limitant dans le cadre de la simulation d'impacts de vagues avec changement de phase. Seule une fine couche limite thermique autour de l'interface tend à revenir à l'équilibre thermodynamique liquide vapeur, ce qui limite l'effet quantitatif du changement de phase. / In the context of Liquefied Natural Gas (LNG) transportation in floating tanks, such as in LNG carriers, the constraints imposed by the sloshing of the liquid cargo on the tank have to be estimated. Most experimental and numerical studies until now do not take into account the possibility of phase change between the LNG and its vapor during the impact of liquid on the wall. The goal of this thesis is to include this physical phenomenon into a CFD code for the simulation of a breaking wave impact on a wall.A state of the art of the different modelisations of phase change in fluid mechanics is thus presented. This work focus on the modeling of phase change between the liquid and the gas at a sharp interface, without any equilibrium hypothesis. An hyperbolic system of balance laws including non-equilibrium interfacial phase change is presented.Two approaches are used to solve numerically this system. The first one relies on a mixture model for the description of the finite volume cells containing the interface, whereas in the second approach the interface is reconstructed and evolves in a lagrangian way. Both methods are based on a Roe-type finite volume scheme.The challenge of the numerical simulation of interfacial phase change is the capacity of the code to deal with density ratio far from 1 and high latent heat, as the lead to high temperature and pressure variations at the interface. The thermal aspect is the limiting phenomenon in the frame of wave impact simulation with phase change. Only a thin boundary layer around the interface tends to return to thermodynamical equilibrium, thus limiting the quantitative effect of phase change.

In this research thermal properties enhancement of phase change material (PCM) using boron nitride nanomaterials such as nanoparticles and nanotubes is studied through experimental measurements, finite element method (FEM) through COMSOL 5.3 package and molecular dynamics simulations via equilibrium molecular dynamics simulation (EMD) with the Materials and Process Simulations (MAPS 4.3). This study includes two sections: thermal properties enhancement of inorganic salt hydrate (CaCl2∙6H2O) as the phase change material by mixing boron nitride nanoparticles (BNNPs), and thermal properties enhancement of organic phase change material (paraffin wax) as the phase change material via encapsulation into boron nitride nanotubes (BNNTs). The results of the proposed research will contribute to enhance the thermal transport properties of inorganic and organic phase change material applying nanotechnology for increasing energy efficiency of systems including electronic devices, vehicles in cold areas to overcome the cold start problem, thermal interface materials for efficient heat conduction and spacecraft in planetary missions for efficient thermal managements.