A preparação de vetores sintéticos para terapia gênica envolve a encapsulação de DNA em pequenos volumes em altas concentrações e nessas condições sabe-se que as moléculas de DNA podem ser organizar formando estruturas líquido-cristalinas. Essas moléculas, uma vez incorporadas a célula devem difundir e vários trabalhos experimentais têm mostrado que essa difusão é limitada pelo tamanho dos fragmentos de DNA. É nesse contexto que soluções de DNA in vitro constituem um sistema modelo para o estudo de processos dinâmicos de difusão na fase isotrópica e na fase anisotrópica. Neste trabalho investigamos a difusão de fragmentos de DNA de 150 pares de base dispersos em água com concentrações variando no intervalo de 80 a 350 mg/ml, que se situam no domínio da fase isotrópica e da fase colestérica, passando uma região intermedi ária de coexistência de fases. Nessas soluções foi acrescentado sal, em concentração suciente para blindar as interações eletrostáticas repulsivas, de maneira que os fragmentos de DNA podem ser tratados como cilindros rígidos e não interagentes. A técnica de FRAP (Fluorescence Recovery After Photobleach) foi empregada para determinação do coeciente de difusão dos fragmentos de DNA que foram marcados com uma prova uorescente, que se intercala entre os nucleotídios por meio de uma ligação covalente. As imagens de FRAP foram analisadas segundo dois métodos diferentes para ajuste do perl de intensidade de luz na mancha de bleach, que pode ser dado por uma função gaussiana, no caso de um processo de difusão isotrópico, ou uma por uma função de Bessel modicada no caso de um processo de difusão anisotrópico. Na fase isotrópica a função gaussiana é a que melhor descreve o perl de intensidade de luz da mancha de bleach e o valor obtido para o coeciente de difusão dos fragmentos de DNA está em torno de 20 m2=s, que é um valor compatível com os valores encontrados na literatura para soluções de DNA com fragmentos de mesma dimensão na fase isotrópica. Na fase colestérica, a análise das imagens de FRAP mostrou que o perl de intensidade de luz é mais bem ajustado por uma função de Bessel modi- cada, permitindo a determinação dos coecientes, D1 e D2, que correspondem aos coecientes de difusão paralelo e perpendicular à direção de orientação molecular local, respectivamente. Nessa mesofase, os valores obtidos para o coeciente de difusão estão entre 101m2=s e 102m2=s, com uma anisotropia, D1=D2 = 12. Esses resultados são compatíveis com os obtidos para soluções de vírus fd na fase nemática. Também foram feitas medidas para amostras com composição que se situam na região intermediária entre a fase isotrópica e a fase colestérica e que podem apresentar duas ou até três fases em coexistência. A análise das imagens permitiu a identicação de processos de difus ão anisotrópico e isotrópicos, em uma mesma amostra, comprovando a coexistência de fases que não são identicadas apenas pela observação da textura em microscopia de luz polarizada. / Preparation of synthetic vectors for gene therapy applications implies encapsulation of DNA in small cavities in high concentrations and in these conditions DNA molecules self-organize forming liquid crystalline structures. Once incorporated to the cell, DNA must diuse in cytoplasm and many experimental work have demonstrated that such diusion is limited by the fragments size. In this context, DNA solutions can be regarded as a promising model system for investigating isotropic and anisotropic diusion. In this work we have investigated diusion of DNA fragments, (150 base pairs), dissolved in water, for concentrations varying from 80 mg/ml to 350 mg/ml, ranging the domains of isotropic and cholesteric phases, with an intermediary region of phase coexistence. Salt was added to the solution, in concentration high enough to screen repulsive electrostatic interactions allowing us to regard DNA fragments as non interacting rigid rods. FRAP (Fluorescence Recovery After Photobleach) technique was used to determine diusion coecients of DNA fragments marked with a uorescent probe, which binds covalently to the nucleotides. Analysis of FRAP images are performed following two possible ttings to the intensity prole in bleach zone, which can be a Gaussian function, for isotropic diusion, either a Bessel modied function if the diusion process is anisotropic. In the isotropic phase the Gaussian function was found to be more appropriate to describe the intensity prole in the bleach spot zone, resulting in a diusion coecient around 20 m2=s, which is compatible with values reported in literature for DNA solutions of fragments of the same dimension in the isotropic phase. Image analysis in the cholesteric phase has shown that light intensity prole of the bleach spot is best tted with a Bessel modied function, allowing us to determine two diusion coecients, D1 and D2, corresponding to the diusion coecients parallel and perpendicular to the local molecular orientation, respectively. In such mesophase the obtained values for the diusion coecients are around 101m2=s and 102m2=s, with an anisotropy; D1=D2 = 12. Such results are compatible with results obtained in the nematic phase of virus fd solutions. Solutions with concentrations lying in the intermediary zone presenting two or even three phase in coexistence were also investigated. By applying the two tting proles to the bleach spot it was possible to identify zones in the sample corresponding to isotropic diusion process and other zones presenting anisotropic diffusion process. This conrms the coexistence of isotropic and anisotropic phases, which cannot be identied only by optical polarized microscopy.

O estudo presente constitui uma análise da influência do acabamento superficial no coeficiente de transferência de calor na ebulição nucleada de refrigerantes halogenados. Dados para três superfícies distintas (cobre, latão e aço inoxidável), dois fluidos refrigerantes (R123 e R134a) e pressões reduzidas entre 0,023 e 0,26 são analisados com o intuito de verificar a influência da rugosidade nestes três parâmetros. O efeito da rugosidade foi avaliado com três acabamentos distintos (massa polidora, lixa e jato de areia) cobrindo uma faixa de rugosidades médias variando desde 0,03 até 10,5 micrômetro. Uma análise de diversas publicações da literatura foi levada a cabo, tendo sido particularmente investigadas algumas correlações que consideram o efeito do acabamento superficial em sua estimativa do coeficiente de transferência de calor. As tendências destas correlações são comparadas entre si e com os dados experimentais. A análise dos resultados permitiu levantar tendências inéditas na literatura consultada. A superfície em ebulição recebeu especial atenção com a obtenção de microfotografias e o cálculo de diversos parâmetros de rugosidade. Foram, ainda, investigados efeitos de envelhecimento da superfície, caracterizado pela diminuição do coeficiente de transferência de calor ao longo do tempo de ebulição. / The present research has been focused in an analysis of the effect of surface finishing on nucleate boiling heat transfer coefficient of halocarbon refrigerants. Experimental data for three different surface material (cooper, brass and stainless steel), two refrigerants (R123 and R134a) and reduced pressures between 0.023 and 0.26 have been analyzed aiming to verify the roughness effects on these three parameters. Three different finishing processes (polishing, emery papering and shot pining) have been used to result in an average roughness range from 0.03 to 10.5 micrometer. An analysis of varied publications and some correlations, particularly those which estimate the effect of surface roughness in heat transfer coefficient, has been done. The tendencies from these correlations have been compared with themselves and with experimental data. These results have shown some effects still unpublished. The boiling surface has received an especial attention, micro-photography has been taken and various parameters have been evaluated. Ageing effects, characterized by the reduction of heat transfer coefficient, have been verified and analyzed.

Orientadores: Luiz Fernando Milanez, Alcides Padilha / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-12T14:21:28Z (GMT). No. of bitstreams: 1 Oliveira_SantiagodelRio_D.pdf: 2035815 bytes, checksum: 7d72e5c223058fb0ce3675f4600214f5 (MD5) Previous issue date: 2008 / Resumo: O objetivo desse trabalho é fazer uma otimização exergética de um sistema térmico de energia solar. Esse sistema é composto por um coletor solar e por um tanque armazenador de água retangular que contém material de mudança de fase distribuído em um conjunto de barras. Esse estudo leva em consideração ambas transferências de calor por condução e convecção para a água no coletor solar, e também o processo de mudança de fase para o PCM no armazenador térmico. Assim, no coletor solar são determinadas a temperatura ótima de saída e vazão mássica ótima da água em função das condições de radiação solar. Além disso, para o tanque armazenador, são determinadas a temperatura ótima de fusão do PCM e o máximo trabalho que pode ser obtido levando em consideração o processo de mudança de fase. O processo de fusão do PCM é analisado por meio de uma solução analítica aproximada. Finalmente, foram feitas uma análise energética e exergética de cada componente do sistema bem como de todo o sistema e foram calculadas eficiências de primeira e segunda lei da termodinâmica. Resultados numéricos de um estudo de caso são apresentados e discutidos. / Abstract: This work deals with the exergetic optimization of a solar thermal energy system. This consists of a solar collector and a rectangular water storage tank that contains a phase change material distributed in an assembly of slabs. The study takes into account both conduction and convection heat transfer modes for water in the solar collector, and also the phase change process for the PCM in the storage tank. Thus, in the solar collector, optimal output temperature and optimal mass flow rate are determined as a function of solar radiation conditions. Moreover, for the storage tank, optimal melting temperature and the maximum power output taking into account the phase change process are determined. The melting process in a PCM is analyzed by means of an approximated analytical solution. Finally, energetic and exergetic analysis were done for each system component and for the overall system, and efficiencies of first and second law of thermodynamics were calculated. Results of a numerical case study are presented and discussed. / Doutorado / Termica e Fluidos / Doutor em Engenharia Mecânica

Orientadores: Guido Costa Souza de Araújo, Rodolfo Jardim de Azevedo / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Computação / Made available in DSpace on 2018-08-23T10:06:28Z (GMT). No. of bitstreams: 1 Hoffman_Caio_M.pdf: 5338735 bytes, checksum: d93e38ef7846b0ba3f7f3b0ea459fc67 (MD5) Previous issue date: 2013 / Resumo: Phase-change memory (PCM) traz novos ensejos para indústria eletrônica. Devido às projeções de alta escalabilidade do processo de fabricação da PCM, cogita-se usá-la como memória principal em sistemas de computação, substituindo à tradicional DRAM cujos problemas de miniaturização do processo de fabricação demandam tecnologias ainda desconhecidas. Contudo, PCM tem problemas de durabilidade e técnicas de recuperação de falhas robustas são extremamente necessárias para recuperação e prolongamento do seu tempo de vida, medido em número de escritas. As técnicas mais comuns de recuperação de falhas são os códigos de correção de erros. Porém, outras técnicas de recuperação vêm sendo propostas na literatura, aproveitando as características de não-volatilidade da PCM. Neste trabalho, usando uma modelagem matemática, analisou-se como a probabilidade de bit-ip dos principais códigos de correção de erros { paridade, SECDED e BCH { e das principais técnicas de recuperação de falhas { ECP e SAFER { está relacionada _a durabilidade da PCM. A partir da taxa de bit-ip medida através da execução do SPEC2006 e por meio dos modelos matemáticos, comparou-se os resultados dos modelos de simulação utilizando-se a probabilidade teórica de 50% e a taxa obtida experimentalmente de 15%. Os resultados revelaram uma visível degradação da durabilidade dos mecanismos de recuperação de falhas que usam códigos de correção de erros, contradizendo os resultados da literatura. A técnica ECP foi à única que não mostrou degradação. Além disso, uma análise de eficiência energética foi feita, relacionando durabilidade da PCM e o consumo de energia. Novamente, a técnica ECP se destacou nos resultados, como também a técnica SAFER. Finalmente, foram propostos modelos analíticos probabilísticos das técnicas ECP, SECDED e uma análise da técnica PAYG baseada no modelo analítico da ECP / Abstract: Phase-change memory brings new opportunities for the electronics industry. Due to projections of high scalability of the fabrication process, PCM is seen as a new main memory in computing systems, replacing the traditional DRAM, whose scale problems require new future technologies that are still unknown. However, PCM has low endurance when compared with DRAM and robust failure recovery techniques are required to increase its lifetime. To address that, some error correcting techniques have been proposed, based on the non-volatile features of the PCM memories. In this work, we model and analyze the bit-ip probabilities of five such techniques (ECP, parity, SECDED, SAFER and BCH), in order to evaluate its impact to the wear out of the PCM. Using the bit-ip rate of 15%, obtained experimentally from the execution of the SPEC2006 benchmark, we mathematically modeled and simulated these techniques using both an empirical and theoretical probability rates. Our results show a clear degradation in techniques that use error-correcting codes, contradicting the previous results in the literature. Only ECP has not shown any degradation. We have also done power analyses of the above listed techniques so as to relate the endurance and the energy required by each technique. Again, the ECP stood out in the results, like SAFER as well. Finally, analytical probabilistic models for ECP and SECDED were proposed and an analysis of PAYG technique (based on ECP's analytical model) was performed / Mestrado / Ciência da Computação / Mestre em Ciência da Computação

Interest in the use of heat pipe technology for heat recovery and energy saving in a vast range of engineering applications has been on the rise in recent years. Heat pipes are playing a more important role in many industrial applications, especially in increasing energy savings in commercial applications and improving the thermal performance of heat exchangers. Computational techniques play an important role in solving complex flow problems for a large number of engineering applications due to their universality, flexibility, accuracy and efficiency. However, up to now, computational studies on heat pipes are still at an early stage due to the complexity of multiphase flow characteristics and heat and mass transfer phase changes. Therefore, the main objective of this study is to develop a CFD modelling that includes the complex physical phenomena of both the heat transfer processes of evaporation and condensation and the mass transfer process of phase change during the pool boiling and film condensation. In this thesis, two novel numerical models were developed in ANSYS FLUENT. In the first, a two-dimensional CFD model was developed to visualise the two-phase flow and the evaporation, condensation and heat transfer phenomena during the operation of a wickless heat pipe, that otherwise could not be visualised by empirical or experimental work. An in-house code was developed using user-defined functions (UDFs) to enhance the ability of FLUENT to simulate the phase change occurring inside the heat pipe. Three different fluids, water, R134a and R404a, were selected as the working fluids of the investigated wickless heat pipe. The cooling system of the condenser section was simulated separately as a three-dimensional CFD model of a parallel-flow double pipe heat exchanger to model the heat transfer across the condenser section's heat exchanger and predict the heat transfer coefficients. The overall effective thermal resistance along with the temperature profile along the wickless heat pipe have been investigated. An experimental apparatus was built to carry out a thermal performance investigation on a typical wickless heat pipe for the purpose of validating the CFD simulation. A theoretical model based on empirical correlations was developed to predict the heat transfer thermal resistances in the evaporator and the condenser section. The second model was developed to combine the two-dimensional CFD simulation of the wickless heat pipe and the three-dimensional CFD simulation of the condenser section's heat exchanger to simulate the two-phase flow phenomena of boiling and condensation and the cooling system of the condenser section through a comprehensive three-dimensional CFD model of a wickless heat pipe. Two fluids, water and R134a, were selected as the working fluids of the investigated wickless heat pipe. This model was validated using a transparent glass wickless heat pipe to visualise the phenomena of pool boiling and comparing the results with the three-dimensional CFD flow visualisation. This study demonstrated that the proposed CFD models of a wickless heat pipe can successfully reproduce the complex physical phenomena of both the heat transfer process of evaporation and condensation and the mass transfer process of phase change during the pool boiling that takes place in the evaporator section and the filmwise condensation that takes place in the condenser section. The CFD simulation was successful in modelling and visualising the multiphase flow characteristics for water, R134a and R404a, emphasising the difference in pool boiling behaviour between these working fluids. The CFD simulation results were compared with experimental measurements, with good agreement obtained between predicted temperature profiles and experimental temperature data.

La récupération de chaleur fatale est un véritable challenge pour l’amélioration de l’efficacité énergétique. Le stockage par chaleur latente est une solution qui répond à cet enjeu. Nous nous intéressons aux procédés industriels avec un rapport puissance sur énergie élevé. L’un des procédés identifiés est la stérilisation de produits agroalimentaires. Cependant, les matériaux à changement de phase, peu conducteurs, ne permettent pas d’obtenir des puissances thermiques suffisantes pour ces applications. L’amélioration de la surface d’échange ou l’augmentation de la conductivité thermique du matériau sont alors nécessaires. Un premier dispositif expérimental de stockage thermique comparant différentes techniques d’intensification des transferts a été réalisé. Le concept à base de paraffine et de Graphite Naturel Expansé (GNE) s’est montré le plus performant par rapport à des solutions de type ailettes ou poudre de graphite. La caractérisation thermique du matériau composite GNE/paraffine sélectionné a été réalisée par plusieurs méthodes. Des valeurs de conductivité thermique effective de l’ordre 20 W.m-1.K-1 ont été obtenues. Dans un second temps, un démonstrateur de 100kW/6kW.h est dimensionné et réalisé. Ce dispositif testé sur un procédé de stérilisation existant permet une économie d’énergie de 15%, conforme aux prévisions. L’identification de la conductivité thermique plane du matériau et l’influence de la résistance thermique de contact sont réalisées à l’aide d’un dispositif expérimental, couplé à un modèle numérique. Enfin, le développement d’un dispositif de vieillissement permet l’étude de la stabilité thermique de ce matériau. / Waste heat recovery is a challenge for the improvement of energy efficiency. Latent heat storage is a solution that addresses this issue. We focus on industrial processes with high energy on power ratios. One of the identified processes is the sterilization of food products. However, phase change materials, which have low thermal conductivities, do not provide sufficient thermal powers for these applications. The improvement of the heat exchange surface or the increase in thermal conductivity of the material are then necessary. A first experimental thermal storage comparing various heat transfer intensification techniques was achieved. The concept based on paraffin and Expanded Natural Graphite (ENG) has proven to be the most efficient compared to solutions using fins or graphite powder. The thermal characterization of the selected composite material ENG/paraffin was performed by several methods. Effective thermal conductivities values of about 20 W.m-1.K-1 were obtained. In a second step, a 100kW/6kW.h demonstrator is designed and realized. This device tested on an existing sterilization process provides an energy saving of 15%, as expected. The identification of the planar thermal conductivity of the composite material and the influence of the thermal contact resistance are carried out using an experimental device, coupled to a numerical model. Finally, an aging device is used to study the thermal stability of this material

Ces travaux de thèse portent sur la caractérisation thermique à l’échelle micrométrique d’un alliage à base de tellure lorsque ce matériau se trouve à l’état fondu, à haute température. À cette fin, une cellule innovante d’emprisonnement du matériau fondu a été conçue, et mise en place. Des structures de tellure au volume du microlitre ont été déposées sur un substrat de silicium et recouverts par la suite d’une couche de protection capable de les emprisonner dans une matrice : silice amorphe et alumine amorphe. La technique de la Radiométrie Photothermique Modulée a été utilisée pour étudier les propriétés thermiques de ce type de cellules et de ces constituants. La résistance thermique de dépôt a été ainsi estimée en utilisant un modèle d’étude des transferts de la chaleur utilisant le formalisme des impédances thermiques. Ceci nous a permit dans le cas de l’alumine amorphe de déterminer sa conductivité thermique et la résistance thermique de contact avec le substrat jusqu’à 600°C. Un long processus de conception, de mesure et d’analyse a été nécessaire afin d’obtenir une cellule capable de résister aux contraintes des hautes températures. À l’heure actuelle seule la caractérisation thermique jusqu’à 300°C a été possible à cause de l’instabilité mécanique de ce dépôt hétérogène. Ceci a été confirmé par des caractérisations physico-chimiques par techniques XRR, XRD et SEM. / This thesis is devoted to the thermal characterization of molten materials, namely chalcogenide glass-type tellurium alloys, at the micrometer scale. An experimental setup of Photothermal Radiometry (PTR), formerly developed for solid state measurements, has been adapted for this purpose. Using MOCVD technique, a random lattice of sub-micrometric tellurium alloy structures is grown on a thermally oxidized silicon substrate. These structures are then embedded in a protective layer (silica or alumina) to prevent evaporation during melting. Measurements are then performed from room temperature up to 650°C. SEM and XRD measurements performed after annealing show that these samples withstand thermal stress only up to 300°C. The coating’s thermal boundary resistance is estimated by a heat transfer model based on the thermal impedance formalism. Moreover, the thermal conductivity and thermal boundary resistance of thin amorphous alumina by low temperature ALD are measured from the room temperature to 600°C.

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>

Le récepteur d’une centrale solaire à tour est l’élément clé de la conversion du rayonnement en chaleur. Dans le cadre de la thèse, il s’agit d’un récepteur métallique dans une centrale de type HSGT (Turbine hybride solaire gaz) refroidi par air pressurisé. En condition normale de fonctionnement, le récepteur chauffe l’air de 350 à 750°C. La température de l’air en sortie chute à 400°C en moins de 15 minutes si le soleil est masqué, par un nuage par exemple. L’objectif est de maintenir la température de l’air en sortie supérieure à 600°C durant 15 minutes sans ensoleillement. Pour parvenir à cet objectif, un stockage thermique intégré au récepteur est envisagé. Parallèlement le stockage de chaleur doit prolonger la durée de vie du récepteur en lui évitant de subir d’intenses chocs thermiques. L’étude porte sur la zone la plus chaude du récepteur, atteignant 800°C. Lorsque le soleil brille (le récepteur est insolé), une partie de la chaleur est stockée dans un matériau qui passe de l’état solide à liquide. Cette chaleur est restituée au récepteur lors de la transformation inverse (liquide à solide) si le soleil est masqué. Les variations de la température du récepteur sont ainsi plus douces et le récepteur est épargné des chocs thermiques. L’utilisation d’un matériau à changement de phase tel que le carbonate de lithium (fusion à 723°C) réduit le volume et la masse du stockage installé directement à l’arrière du récepteur. Ce matériau stocke une grande quantité de chaleur sur une gamme de température peu étendue. Cependant les matériaux à changement de phase ne permettent pas de transférer la chaleur rapidement à cause de leur faible conductivité thermique. C’est la raison pour laquelle l’intensification de ces transferts est étudiée. La mise en place d’ailettes en cuivre à l’intérieur du stockage améliore les transferts de chaleur, grâce à la conductivité thermique élevée du métal. Un modèle numérique représentatif du comportement thermique du stockage est développé. Le travail de conception du stockage aboutit à la fabrication d’un banc expérimental. Les résultats obtenus sont comparés au modèle afin de le critiquer. Les conclusions permettent d’envisager la conception d’un stockage thermique de protection à l’échelle du récepteur. / The thesis deals with the problem of thermal inertia and life time of the solar receiver of a Concentrated Solar Power tower plant. A specific attention is paid to the situation of HSGT (Hybridized Solar Gas Turbine) systems using pressurized air as HTF (Heat Transfer Fluid). The intermittence of solar radiation, mainly resulting from cloudy events, causes important temperature fluctuations that contribute to the premature aging. Therefore, a Thermal Energy Storage (TES) is developed for the protection of the receiver. The design focuses on the high temperature section of the receiver. As a consequence of the elevation of temperature in this stage, the expected temperature of the receiver ranges between 600°C and 800°C. Once the receiver is no longer irradiated, the temperature of the outlet air of the receiver, which is 750°C at designed point, decreases below 400°C in less than 15 minutes. The objective is to integrate the TES into the solar receiver to maintain this air temperature higher than 600°C after 15 minutes of discharge. A low capacity TES is targeted. Besides, the storage should enhance the lifetime of the receiver during the operation, by avoiding temperature drops. A test bench is designed based on a technology using both Phase Change Material (PCM) and metallic fins in order to enhance charge and discharge power of the storage unit. The selected metal is copper, because of its great thermal conductivity. The thermal storage medium must operate in the range 600°C – 800°C. The lithium carbonate has been selected mainly because of its phase change temperature, 723°C. A numerical model is developed in order to help the design of the test bench and compare experimental results. The conclusions lead to one-scale design of the thermal storage integrated to the solar receiver.

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