Phase change materials (PCMs) are a viable option for compact thermal energy storage. Effective designs using PCMs require accurate knowledge of the thermal and physical properties, but for many PCMs these are not well known, and when known the knowledge is sometimes contradictory. Therefore, physical characteristics of several promising PCMs (K3PO4·7H2O, FeCl3·6H2O, Mn(NO3)2·4H2O) were determined. In addition, a life cycle assessment (LCA) of dodecanoic acid in a solar thermal energy storage system was carried out to determine the environmental impact for energy storage. This LCA showed that dodecanoic acid in a solar energy system would save energy and facilitate CO2 reductions. However, the economic cost is high and is unlikely to be implemented without incentives. Finally an experimental testbed for a solar thermal system utilizing dodecanoic acid was built. Preliminary measurements demonstrated the utility of this system.

The thermal efficiency of concentrated solar power (CSP) system depends on the maximum operating temperature of the system which is determined by the operating temperature of the TES device. Organic materials (such as synthetic oil, fatty acid, or paraffin wax) are typically used for TES. This limits the operating temperature of CSP units to below 400 degrees C. Increasing the operating temperature to 560 degrees C (i.e., the creeping temperature of stainless steel), can enhance the theoretical thermal efficiency from 54 percent to 63 percent. However, very few thermal storage materials are compatible for these high temperatures. Molten salts are thermally stable up to 600 degrees C and beyond. Using the molten salts as the TES materials confers several benefits, which include: (1) Higher operating temperature can significantly increase the overall cycle efficiency and resulting costs of power production. (2) Low cost of the molten salt materials can drastically reduce the cost. (3) The molten salts, which are environmentally safe, can also reduce the potential environmental impact. However, these materials suffer from poor thermo-physical properties. Impregnating these materials with nanoparticles can enhance these properties. Solvents doped with nanoparticles are termed as nanofluids. Nanofluids have been reported in the literature for the anomalous enhancement of their thermo-physical properties. In this study, the poor thermal properties of the molten salts were enhanced dramatically on mixing with nanoparticles. For example the specific heat capacity of these molten salt eutectics was found to be enhanced by as much as ~ 26 percent on mixing with nanoparticles at a mass fraction of ~ 1 percent. The resultant properties of these nanomaterials were found to be highly sensitive to small variations in the synthesis protocols. Computational models were also developed in this study to explore the fundamental transport mechanisms on the molecular scale for elucidating the anomalous enhancements in the thermo-physical properties that were measured in these experiments. This study is applicable for thermal energy storage systems utilized for other energy conversion technologies – such as geothermal energy, nuclear energy and a combination of energy generation technologies.

Le développement de systèmes de récupération d’énergie (ou energy harvesting systems en anglais) va de pair avec l’émergence de l’Internet des Objets et notamment la prolifération de réseaux de capteurs devant répondre aux besoins croissants en informations, que ce soit dans le domaine de l’industrie, de la sante, de la domotique ou de l’environnement qu’il soit urbain ou naturel. Les progrès réalisés ces dernières années dans le domaine des Technologies de l’Information et de la Communication ont permis de lever certains verrous technologiques au déploiement de ces réseaux de capteurs intelligents et autonomes, notamment grâce a l’amélioration des performances intrinsèques des composants microélectroniques (vitesse, consommation), la conception de circuits plus économes en énergie, ou bien la mise en place de standards de communications radio adaptes a ces contraintes énergies. Etant donné l’ubiquité des sources d’énergie, la fabrication de générateurs permettant d’alimenter directement ces capteurs à partir de ces sources représente une alternative viable à l’utilisation de batteries pour prolonger la durée de vie de ces capteurs communicants. Diverses technologies de générateurs ont ainsi été proposes pour s’adapter aux différentes formes que peut prendre l’énergie, qu’elle soit d’origine thermique, mécanique, solaire ou électromagnétique.Le présent travail est une contribution au développement de certains dispositifs de récupération thermiques basés sur l’exploitation des propriétés thermiques et mécaniques de bilames thermostatique. Ce type de générateurs, propose et développe au sein de STMicroelectronics à Crolles, se veut être une alternative fiable et bas cout a l’utilisation de matériaux thermoélectriques exploitant l’effet Seebeck pour générer de l’énergie électrique. Divers dispositifs ont déjà été fabriqués, démontrant la capacité des moteurs thermiques à base de bilames thermostatiques à alimenter des capteurs autonomes en fonctionnement synchrone et asynchrone. L’objectif de cette thèse est alors de démontrer la possibilité de miniaturiser de tels moteurs thermiques grâce aux techniques de fabrications utilisées en microélectronique. Afin de garantir le fonctionnement de ces systèmes a micro-échelle, un important travail de fond a d’abord été effectue sur la compréhension et la modélisation des phénomènes de couplages thermomécaniques a l’origine du comportement bistable des membranes bimétalliques. Ce travail a débouché sur la démonstration théorique du fonctionnement des moteurs thermiques a base de bilames et sur l’évaluation de leur performances énergétiques (énergie disponible, efficacité thermique, efficacité de Carnot relative). Dans la continuité de ce premier modèle, d’autres travaux ont été menés pour évaluer les performances de moteurs thermiques exploitant différents phénomènes de couplage électromécanique en vue de convertir l’énergie mécanique générée par les bilames thermostatiques en énergie électrique exploitable par les capteurs autonomes. La simulation du comportement des micro-générateurs à l’aide de ces divers modèles a debouché sur des lois d’échelles sur les performances des moteurs thermiques. Finalement, divers procédés de fabrications ont ete développé pour permettre la fabrication de microstructures thermiquement bistables. / The development of energy harvesting systems is linked to the emergence of the Internet of Things (IoT) and especially the proliferation of Wireless Sensors Networks that should respond to the growing needs for monitoring data in domains as diverse as the industry, the urban or natural environments, the home, or the human body etc. Recent progress in the field of information technologies have enabled to remove some of the technical obstables to the deployment of these smart and autonom devices, in particular thanks to the improvement of the performances of microelectronic components, the design of ultra-low-power circuits, or the creation of wireless communications standards adapted to the energy needs of wireless sensors. Given the great availability of energy sources, energy harvesters are reliable alternatives to batteries in order to extend the autonomy of these sensors. Various technologies of generators have been developped to adapt to the type of local energy sources (heat, vibration, light, radio-frequencies).The present work is a contribution to the development of thermal energy harvesters exploting the thermal and mechanical properties of bimetal thermostats. This type of technology developped at STMicroelectronics are intended to be a reliable and low-cost alternative to the use of thermoelectric materials exploing Seebeck effect to generate electricity from heat. Various devices were already fabricated at the macro-scale, demonstrating their ability to power wireless sensor nodes. In the continuity of these works, this PhD thesis aims to demonstrate the operation of these generators at the sub-millimetric scale. As a consequence, an important work on the modeling of the thermo-mechanical instability of bimetallic strips was made to understand the operation of bimetallic strip heat engines. This work enabled to theoretically demonstrate the capability of bimetallic to transform heat into mechanical energy and to evaluate the performances of such heat engines. Coupling between bimetallic strip heat engines and electro-mechanical transducers was also modeled to compare the performances of the current prototypes of generators. We then modeled the thermo-mechanical behavior of composite beams at the microscale and established scaling rules of the performances of the bimetallic strip heat engines, We finally developped microlectronic fabrication process to manufacture thermo-mechanically bistable beams at the microscale.

abstract: Recently, nanostructured metamaterials have attracted lots of attentions due to its tunable artificial properties. In particular, nanowire/nanohole based metamaterials which are known of the capability of large area fabrication were intensively studied. Most of the studies are only based on the electrical responses of the metamaterials; however, magnetic response, is usually neglected since magnetic material does not exist naturally within the visible or infrared range. For the past few years, artificial magnetic response from nanostructure based metamaterials has been proposed. This reveals the possibility of exciting resonance modes based on magnetic responses in nanowire/nanohole metamaterials which can potentially provide additional enhancement on radiative transport. On the other hand, beyond classical far-field radiative heat transfer, near-field radiation which is known of exceeding the Planck’s blackbody limit has also become a hot topic in the field. This PhD dissertation aims to obtain a deep fundamental understanding of nanowire/nanohole based metamaterials in both far-field and near-field in terms of both electrical and magnetic responses. The underlying mechanisms that can be excited by nanowire/nanohole metamaterials such as electrical surface plasmon polariton, magnetic hyperbolic mode, magnetic polariton, etc., will be theoretically studied in both far-field and near-field. Furthermore, other than conventional effective medium theory which only considers the electrical response of metamaterials, the artificial magnetic response of metamaterials will also be studied through parameter retrieval of far-field optical and radiative properties for studying near-field radiative transport. Moreover, a custom-made AFM tip based metrology will be employed to experimentally study near-field radiative transfer between a plate and a sphere separated by nanometer vacuum gaps in vacuum. This transformative research will break new ground in nanoscale radiative heat transfer for various applications in energy systems, thermal management, and thermal imaging and sensing. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2017

Este trabalho tem por objetivo analisar as perspectivas dos gases combustíveis como energia final para a obtenção de energia útil, em aquecimento direto (AD) e calor de processo (CP), identificando e quantificando potenciais como alternativa da eletrotermia. São comparados dois panoramas na avaliação das economias de energia primária pela substituição da eletrotermia: o primeiro considerando que a energia substituída oriunda de energéticos do parque gerador; e o segundo levando em conta que a redução se refletiu nas termelétricas. Para atingir este objetivo, o trabalho se inicia com uma revisão bibliográfica, onde são tratados os aspectos necessários para um melhor entendimento do texto, com os conceitos de eletrotermia, calor e termodinâmica, seguindo-se um capítulo destinado aos gases combustíveis, suas características e disponibilidade futura para a conversão. As informações básicas para a análise dos potenciais nos setores foram tomadas a partir do último Balanço de Energia Útil, além de trabalhos desenvolvidos no mercado industrial pelo autor. O trabalho discorre também sobre configurações tecnológicas usadas nas conversões, incluindo os custos envolvidos. Na conclusão, os cálculos mostraram que significativas economias de energia primária podem ser obtidas com a conversão da eletrotermia para gases combustíveis no setor industrial brasileiro, considerando a eletricidade produzida a partir de plantas termelétricas. / This paper aims to analyze the prospects of fuel gases as final energy in order to get useful energy in direct heating and process heat, identifying and qualifying potentials as the alternative of electrothermy. Two panoramas are compared in the evaluation of primary energy displacement: the first one considering the replaced energy coming from energy generating facilities and the second taking into account that the reduction was reflected in thermoelectric power plants. To achieve this goal, the work begins with a literature review which covers the aspects needed for a better understanding of the text, with the concepts of electrothermy, heat and thermodynamics, followed by a chapter intended for fuel gases, their characteristics and future readiness for conversion. The basic information for the analysis of potential sectors were taken for the last Useful Energy Balance, and work undertaken by the author in the industrial market. The paper also discourses about technological configurations used in conversions, including also the costs involved. In conclusion, the calculations showed that significant primary energy savings can be obtained through the conversion of electrothermy by fuel gases in the Brazilian industrial sector, taking into account the electricity produced from thermoelectric power plants.

Climate change is no longer imminent but eminent. To combat climate change, effective, efficient and smart energy use is imperative. Thermal energy storage (TES) with phase change materials (PCMs) is one attractive choice to realize this. Besides suitable phase change temperatures and enthalpies, the PCMs should also be robust, non-toxic, environmental-friendly and cost-effective. Cost-effective PCMs can be realized in bulk blends. Blends however do not have robust phase change unless chosen articulately. This thesis links bulk blends and robust, cost-effective PCMs via the systematic design of blends as PCMs involving phase equilibrium evaluations. The key fundamental phase equilibrium knowledge vital to accurately select robust PCMs within blends is established here. A congruent melting composition is the most PCM-ideal among blends. Eutectics are nearly ideal if supercooling is absent. Any incongruent melting composition, including peritectics, are unsuitable as PCMs. A comprehensive state-of-the-art evaluation of the phase equilibrium-based PCM design exposed the underinvestigated categories: congruent melting compositions, metal alloys, polyols and fats. Here the methods and conditions essential for a comprehensive and transparent phase equilibrium assessment for designing PCMs in blends are specified. The phase diagrams of the systems erythritol-xylitol and dodecane-tridecane with PCM potential are comprehensively evaluated. The erythritol-xylitol system contains a eutectic in a partially isomorphous system unlike in a non-isomorphous system as previous literature proposed. The dodecane-tridecane system forms a probable congruent minimum-melting solid solution, but not a maximum-melting liquidus or a eutectic as was previously proposed. The sustainability aspects of a PCM-based TES system are also investigated. Erythritol becomes cost-effective if produced using glycerol from bio-diesel production. Olive oil is cost-effective and has potential PCM compositions for cold storage. A critical need exists in the standardization of methods and transparent results reporting of the phase equilibrium investigations in the PCM-context. This can be achieved e.g. through international TES collaboration platforms. / Energi är en integrerad del av samhället men energiprocesser leder till miljöbelastning, och klimatförändringar. Därför är effektiv energianvändning, ökad energieffektivitet och smart energihantering nödvändigt. Värmeenergilagring (TES) är ett attraktivt val för att bemöta detta behov, där ett lagringsalternativ med hög densitet är s.k. fasomvandlingsmaterial (PCM). Ett exempel på ett billigt, vanligt förekommande PCM är systemet vatten-is, vilket har använts av människor i tusentals år. För att tillgodose de många värme- och kylbehov som idag uppstår inom ett brett temperaturintervall, är det viktigt med innovativ design av PCM. Förutom lämplig fasförändringstemperaturer, entalpi och andra termofysikaliska egenskaper, bör PCM också ha robust fasändring, vara miljövänlig och kostnadseffektiv. För att förverkliga storskaliga TES system med PCM, är måste kostnadseffektivitet och robust funktion under många cykler bland de viktigaste utmaningarna. Kostnadseffektiva PCM kan bäst erhållas från naturliga eller industriella material i bulkskala, vilket i huvudsak leder till materialblandningar, snarare än rena ämnen. Blandningar uppvisar dock komplexa fasförändringsförlopp, underkylning och/eller inkongruent smältprocess som leder till fasseparation. Denna doktorsavhandling ger ny kunskap som möjliggör att bulkblandningar kan bli kostnadseffektiva och robusta PCM-material, med hjälp av den systematiskutvärdering av fasjämvikt och fasdiagram. Arbetet visar att detta kräver förståelse av relevanta grundläggande fasjämviktsteorier, omfattande termiska och fysikalisk-kemiska karakteriseringar, och allmänt tillämpliga teoretiska utvärderingar. Denna avhandling specificerar befintlig fasjämviktsteori för PCM-sammanhang, men sikte på att kunna välja robusta PCM blandningar med specifika egenskaper, beroende på tillämpning. Analysen visar att blandningar med en sammansättning som leder till kongruent smältande, där faser i jämvikt har samma sammansättning, är ideala bland PCM-blandningar. Kongruent smältande fasta faser som utgör föreningar eller fasta lösningar av ingående komponenter är därför ideala. Eutektiska blandningar är nästan lika bra som PCM, så länge underkylning inte förekommer. Därmed finns en stor potential för att finna och karakterisera PCM-ideala blandningar som bildar kongruent smältande föreningar eller fasta lösningar. Därigenom kan blandningar med en skarp, reversibel fasändring och utan fasseparation erhållas – egenskaper som liknar rena materialens fasändringsprocess. Vidare kan man, via fasdiagram, påvisa de blandningar som är inkongruent smältande, inklusive peritektiska blandningar, som är direkt olämpliga som PCM. Denna avhandling ger grundläggande kunskap som är en förutsättning för att designa PCM i blandningar. Genom en omfattande state-of-the-art utvärdering av fas-jämviktsbaserad PCM-design lyfter arbetet de PCM-idealiska blandningarna som hittills inte fått någon uppmärksamhet, såsom kongruenta smältande blandningar, och materialkategorierna metallegeringar, polyoler och fetter. Resultatet av arbetet visar dessutom att vissa PCM-material som ibland föreslås är direkt olämpliga då fasdiagram undersöks, bl a pga underkylning och även peritektiska system med fasseparation och degradering av kapaciteten (t ex Glauber-salt och natriumacetat-trihydrat). Denna avhandling specificerar och upprättar grundläggande teori samt tekniker, tillvägagångssätt och förhållanden som är nödvändiga för en omfattande och genomsynlig fasjämviktsbedömning, för utformning av PCM från blandningar för energilagering. Med detta som bas har följande fasdiagramtagits fram fullständigt: för erytritol-xylitol och för dodekan-tridekan, med PCM-potential för låg temperaturuppvärmning (60-120 °C) respektive frysning (-10 °C till -20 °C) utvärderas fullständigt. Erytritol-xylitol systemet har funnits vara eutektiskt i ett delvis isomorft system, snarare än ett icke-isomorft system vilket har föreslagits tidigare litteratur. Dodekan-tridekan systemet bildar ett system med kongruent smältande fast lösning (idealisk som en PCM) vid en minimumtemperatur, till skillnad från tidigare litteratur som föreslagt en maximumtemperatur, eller ett eutektiskt system. Teoretisk modellering av fasjämvikt har också genomförts för att komplettera det experimentella fasdiagrammet för systemet erytritol-xylitol. Efter granskning av de metoder som använts tidigare i PCM-litteraturen har här valts ett generiskt tillvägagångssätt (CALPHAD-metoden). Denna generiska metod kan bedöma vilken typ av material och fasändring som helst, till skillnad från en tidigare använda metoder som är specifika för materialtyper eller kemiska egenskaper. Denna teoretiska studie bekräftar termodynamiskt solvus, solidus, eutektisk punkt och erytritol-xylitol fasdiagrammet i sin helhet. Vad gäller hållbarhetsaspekter med PCM-baserad TES, lyfter denna avhandling fokus på förnybara och kostnadseffektiva material (t.ex. polyoler och fetter) som PCM. Som exempel har här undersökts erytritol och olivolja, med förnybart ursprung. Erytritol skulle kunna bli ett kostnadseffektivt PCM (163 USD/kWh), om det produceras av glycerol vilket är en biprodukt från biodiesel/bioetanolframställning. Olivolja är ännu ett kostnadseffektivt material (144 USD/kWh), och som här har påvisats innehålla potentiella PCM sammansättningar med lämpliga fasändringsegenskaper för kylatillämpningar. En övergripande slutsats från denna avhandling är att det finns ett behov av att standardisera tekniker, metoder och transparent resultatrapportering när det gäller undersökningar av fasjämvikt och fasdiagram i PCM-sammanhang. Internationella samarbetsplattformar för TES är en väg att koordinera arbetet. / <p>QC 20170830</p>

abstract: Thermal Energy Storage (TES) is of great significance for many engineering applications as it allows surplus thermal energy to be stored and reused later, bridging the gap between requirement and energy use. Phase change materials (PCMs) are latent heat-based TES which have the ability to store and release heat through phase transition processes over a relatively narrow temperature range. PCMs have a wide range of operating temperatures and therefore can be used in various applications such as stand-alone heat storage in a renewable energy system, thermal storage in buildings, water heating systems, etc. In this dissertation, various PCMs are incorporated and investigated numerically and experimentally with different applications namely a thermochemical metal hydride (MH) storage system and thermal storage in buildings. In the second chapter, a new design consisting of an MH reactor encircled by a cylindrical sandwich bed packed with PCM is proposed. The role of the PCM is to store the heat released by the MH reactor during the hydrogenation process and reuse it later in the subsequent dehydrogenation process. In such a system, the exothermic and endothermic processes of the MH reactor can be utilized effectively by enhancing the thermal exchange between the MH reactor and the PCM bed. Similarly, in the third chapter, a novel design that integrates the MH reactor with cascaded PCM beds is proposed. In this design, two different types of PCMs with different melting temperatures and enthalpies are arranged in series to improve the heat transfer rate and consequently shorten the time duration of the hydrogenation and dehydrogenation processes. The performance of the new designs (in chapters 2 and 3) is investigated numerically and compared with the conventional designs in the literature. The results indicate that the new designs can significantly enhance the time duration of MH reaction (up to 87%). In the fourth chapter, organic coconut oil PCM (co-oil PCM) is explored experimentally and numerically for the first time as a thermal management tool in building applications. The results show that co-oil PCM can be a promising solution to improve the indoor thermal environment in semi-arid regions. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2020

This thesis develops a calibrated model of the Cal Poly Central Chilled Water Plant with Thermal Energy Storage for use in determining an optimal operating control strategy. The model was developed using a transient systems simulation program (TRNSYS) that includes plant performance and manufacturer data for the primary system components, which are comprised of pumps, chillers, cooling towers, and a thermal energy storage tank. The model is calibrated to the actual measured performance of the plant using the current control strategy as a baseline. By observing and quantifying areas for potential improvement in plant performance under conditions of high campus cooling load demands, alternative control strategies for the plant are proposed. Operation of the plant under each of these control strategies is simulated in the model and evaluated for overall energy and demand-usage cost savings. These results are used to recommend improvements in the plant’s current control strategy, as well as to propose an optimal control strategy that may be applied to reduce plant operating costs. The results of the model identify that the plant can perform more economically by employing more chiller power to charge the Thermal Energy Storage tank to higher capacities during overnight periods when the utility rates are lower. Staging the operation of the different chillers to more precisely follow the tank charges during these off-peak periods can ensure faster tank charging when its capacity may not be sufficient to meet the peak and part-peak cooling load demands. A proposed control strategy to accomplish this breaks the overnight Off-Peak rate period into three periods with separate control setpoints, which are designed to maintain the tank charge capacity at the minimum levels to be able to accommodate the daily campus cooling demands during peak and part-peak hours.

Práce je zaměřena na sestavení numerického modelu akumulace tepelné energie s fázovou přeměnou. Následně je tento model použit při tvarové optimalizaci, jejíž cílem je maximalizace uloženého tepla v tepelném výměníku. Kvůli komplexitě objektové funkce byl zvolen genetický algoritmus pro řešní úloh tvarové optimalizace. Práce obsahuje analýzu dvou problému týkající se tvarové optimalizace s následnou diskuzí nad obdrženými výsledky. Celý problém byl implementován v softwaru Matlab.

This study focused on a numerical second law analysis and optimisation of a receiver tube op- erating in a parabolic trough solar collector for small-scale application. The receiver functioned in a Rankine cycle. The focus was on entropy generation minimisation in the receiver due to the high quality exergy losses in this component. Water functioned as the working uid and was heated from ambient conditions (liquid) to a superheated state (vapour), consequently, the receiver tube was subject to both single phase as well as two-phase ow. Entropy generation in the receiver tube was mainly due to nite temperature di erences as well as uid friction. The contribution of each of these components was investigated. Geometrical as well as operating conditions were investigated to obtain good guidelines for receiver tube and plant design. An operating pressure in the range of 1 MPa (Tsat = 180 C) to 10 MPa (Tsat = 311 C) was considered. Furthermore a mass ow range of 0:15 kg=s to 0:4 kg=s was investigated. Results showed that beyond a diameter of 20 mm, the main contributor to the entropy generation was the nite temperature di erences for most conditions. Generally, operating pressures below 3 MPa showed bad performance since the uid friction component was too large for small operating pressures. This phenomenon was due to long two-phase lengths and high pressure drops in this region. The nite temperature di erence component increased linearly when the tube diameter was increased (due to the increase in exposed area) if the focused heat ux was kept constant. However, the uid friction component increased quadratically when the diameter was reduced. In general when the concentration ratio was increased, the entropy generation was decreased. This was due to more focused heat on each section of the receiver pipe and, in general, resulted in shorter receiver lengths. Unfortunately, there is a limit to the highest concentration ratio that can be achieved and in this study, it was assumed to be 45 for two-dimensional trough technology. A Simulated Annealing (SA) optimisation algorithm was implemented to obtain certain optimum parameters. The optimisation showed that increasing the diameter could result in a decrease in entropy generation, provided that the concentration ratio is kept constant. However, beyond a certain point gains in minimising the entropy generation became negligible. Optimal operating pressure would generally increase if the mass ow rate was increased. Finally, it was seen that the highest operating pressure under consideration (10 MPa) showed the best performance when considering the minimisation of entropy in conjunction with the maximisation of the thermodynamic work output. / Dissertation (MEng)--University of Pretoria, 2014. / tm2015 / Mechanical and Aeronautical Engineering / MEng / Unrestricted