In this thesis, I have developed a range of theoretical and numerical techniques for modelling the behaviour of partially coherent optical systems and multi-mode detectors. The numerical simulations were carried out for the ultra-low-noise Transition Edge Sensors (TESs) being proposed for use on the SAFARI instrument on the cooled aperture infrared space telescope SPICA (34 - 210 μm). The optical behaviour of the SAFARI system is described in terms of the optical modes of the telescope, as distinct from the optical modes of the detector. The performance of the TESs were assessed in terms of signal power, background power and photon noise. To establish a method for precisely characterising and calibrating ultra-low-noise TESs, a cryogenic test system was designed and engineered to measure the optical efficiencies of the SAFARI TESs. The multi-mode, partially coherent illumination conditions of the measurement system were engineered to be precisely the same as those of the telescope. A major difference between the test system and the telescope’s optics is that the telescope will have focusing elements, but the test system was designed to avoid focusing elements in order to keep the optical path as clean as possible. The theoretical formalism and numerical models were adapted accordingly to address this difference. The numerical simulations show that the test system could provide near identical optical performance as that of the telescope system even though the focusing elements were absent. I also performed experimental measurements to investigate the optical efficiencies of the multi-mode TESs. The detectors worked exceedingly well in all respects with satisfactory optical efficiencies. In addition, it has been shown that the optical model provides a good description of the optical behaviour of the test system and detectors. Further modal analysis was developed to study losses in the multi-mode horns. The optical behaviour of the waveguide-mounted thin absorbing films in the far-infrared was modelled using a mode-matching method.

A emissividade da superfície terrestre (EST) é uma propriedade importante na caracterização de alvos através do Sensoriamento Remoto (SR). A estimativa da EST envolve a aplicação de uma função indeterminada de várias variáveis em dados de radiância contaminados por uma atmosfera de complexa modelagem. Dunas, em geral, são compostas por quartzo, cujo comportamento emissivo é bem caracterizado com sensores que operam entre 8–12μm. Neste trabalho foram avaliados 4 métodos de recuperação de temperatura-emissividade a partir de dados de radiância corrigida dos efeitos atmosféricos. Os quatro métodos foram aplicados em dados do subsistema do infravermelho termal (TIR) do sensor ASTER e são: Método da Emissividade Normalizada (MEN), Método da Banda de Referência (MBR), Separação de Emissividade e Temperatura (TES) e Resíduos Alpha (α-Residual). Foram geradas imagens de emissividade, cujas amostras puras (controle) de quartzo foram comparadas com uma curva homóloga da biblioteca espectral do Laboratório de Sensoriamento Remoto do Centro Estadual de Pesquisas em Sensoriamento Remoto e Meteorologia da Universidade Federal do Rio Grande do Sul (UFRGS). Neste trabalho, os métodos foram comparados pelas diferenças na emissividade média, temperatura média de uma imagem ASTER e geometria da curva através de seus valores alphas. Obteve-se como resultado que o método TES apresentou uma emissividade média absoluta maior em relação ao MEN e MBR. A temperatura média para métodos MEN e MBR foi de 35,18ºC, TES de 30,10ºC e o α-Residual não gerou um valor de temperatura, pois não considera esta variável na estimativa do espectro alpha. A geometria da curva do método TES foi a mais próxima da curva espectral de referência. Os métodos comparados neste trabalho não obtiveram um desempenho quantitativo dentro dos limiares certos, é dizer no intervalo de emissividade de um quartzo a 29ºC. Os métodos neste trabalho tiveram uma tendência a superestimar os valores de temperatura e consequentemente os valores de emissividade, devido a uma correção atmosférica inexata em condições de alta umidade, suposições iniciais (emissividade) com grande erro, heterogeneidade do alvo. Em contrapartida se obteve bom desempenho na individualização dos campos de dunas preservando a forma da curva espectral (geometria) do quartzo. / The land surface emissivity (LSE) is an important property in the characterization of targets through Remote Sensing (RS). The estimation of LSE involves the application of an indeterminate function of several variables in radiance data contaminated by an atmosphere of complex modeling. In general, sand dunes are composed of quartz, whose spectral behavior is well characterized with sensors operating between 8-12μm. In this work, four methods of temperature-emissivity recovery were evaluated from atmospheric effects corrected radiance data. The four methods were applied to data from the thermal infrared (TIR) subsystem of the ASTER sensor, and they are: Normalization Emissivity Method (NEM), Reference Channel Method (RCM), Temperature Emissivity Separation (TES) and Alpha Residuals Method (α- Residual). Emissivity images were generated, whose pure quartz samples (control) were compared to a homologous curve of the spectral library of the Remote Sensing Laboratory of the State Center for Remote Sensing and Meteorology Research at the Federal University of Rio Grande do Sul (UFRGS). In this study, the methods were compared by differences in mean emissivity, mean temperature of ASTER image and curve geometry through their alpha values. As a result, the TES method presented a higher mean absolute emissivity, in relation to NEM and RCM. The mean temperature for NEM and RCM methods was 35.18 °C, TES was 30.10 °C and α-Residuals did not generate a temperature value, since it does not consider this variable in the estimation of the alpha spectrum. The geometry of the TES method curve was the closest to the reference spectral curve. The methods compared in this work did not obtain a quantitative performance within the certain thresholds, in the emissivity range of a quartz at 29 °C. The methods tend to overestimate the temperature values and consequently the emissivity values due to an inaccurate atmospheric correction under conditions of high humidity, initial assumptions (emissivity) with great error, heterogeneity of the target. In contrast, a good performance was obtained in the individualization of the dune fields, preserving the shape of the spectral curve (geometry) of the quartz.

A emissividade da superfície terrestre (EST) é uma propriedade importante na caracterização de alvos através do Sensoriamento Remoto (SR). A estimativa da EST envolve a aplicação de uma função indeterminada de várias variáveis em dados de radiância contaminados por uma atmosfera de complexa modelagem. Dunas, em geral, são compostas por quartzo, cujo comportamento emissivo é bem caracterizado com sensores que operam entre 8–12μm. Neste trabalho foram avaliados 4 métodos de recuperação de temperatura-emissividade a partir de dados de radiância corrigida dos efeitos atmosféricos. Os quatro métodos foram aplicados em dados do subsistema do infravermelho termal (TIR) do sensor ASTER e são: Método da Emissividade Normalizada (MEN), Método da Banda de Referência (MBR), Separação de Emissividade e Temperatura (TES) e Resíduos Alpha (α-Residual). Foram geradas imagens de emissividade, cujas amostras puras (controle) de quartzo foram comparadas com uma curva homóloga da biblioteca espectral do Laboratório de Sensoriamento Remoto do Centro Estadual de Pesquisas em Sensoriamento Remoto e Meteorologia da Universidade Federal do Rio Grande do Sul (UFRGS). Neste trabalho, os métodos foram comparados pelas diferenças na emissividade média, temperatura média de uma imagem ASTER e geometria da curva através de seus valores alphas. Obteve-se como resultado que o método TES apresentou uma emissividade média absoluta maior em relação ao MEN e MBR. A temperatura média para métodos MEN e MBR foi de 35,18ºC, TES de 30,10ºC e o α-Residual não gerou um valor de temperatura, pois não considera esta variável na estimativa do espectro alpha. A geometria da curva do método TES foi a mais próxima da curva espectral de referência. Os métodos comparados neste trabalho não obtiveram um desempenho quantitativo dentro dos limiares certos, é dizer no intervalo de emissividade de um quartzo a 29ºC. Os métodos neste trabalho tiveram uma tendência a superestimar os valores de temperatura e consequentemente os valores de emissividade, devido a uma correção atmosférica inexata em condições de alta umidade, suposições iniciais (emissividade) com grande erro, heterogeneidade do alvo. Em contrapartida se obteve bom desempenho na individualização dos campos de dunas preservando a forma da curva espectral (geometria) do quartzo. / The land surface emissivity (LSE) is an important property in the characterization of targets through Remote Sensing (RS). The estimation of LSE involves the application of an indeterminate function of several variables in radiance data contaminated by an atmosphere of complex modeling. In general, sand dunes are composed of quartz, whose spectral behavior is well characterized with sensors operating between 8-12μm. In this work, four methods of temperature-emissivity recovery were evaluated from atmospheric effects corrected radiance data. The four methods were applied to data from the thermal infrared (TIR) subsystem of the ASTER sensor, and they are: Normalization Emissivity Method (NEM), Reference Channel Method (RCM), Temperature Emissivity Separation (TES) and Alpha Residuals Method (α- Residual). Emissivity images were generated, whose pure quartz samples (control) were compared to a homologous curve of the spectral library of the Remote Sensing Laboratory of the State Center for Remote Sensing and Meteorology Research at the Federal University of Rio Grande do Sul (UFRGS). In this study, the methods were compared by differences in mean emissivity, mean temperature of ASTER image and curve geometry through their alpha values. As a result, the TES method presented a higher mean absolute emissivity, in relation to NEM and RCM. The mean temperature for NEM and RCM methods was 35.18 °C, TES was 30.10 °C and α-Residuals did not generate a temperature value, since it does not consider this variable in the estimation of the alpha spectrum. The geometry of the TES method curve was the closest to the reference spectral curve. The methods compared in this work did not obtain a quantitative performance within the certain thresholds, in the emissivity range of a quartz at 29 °C. The methods tend to overestimate the temperature values and consequently the emissivity values due to an inaccurate atmospheric correction under conditions of high humidity, initial assumptions (emissivity) with great error, heterogeneity of the target. In contrast, a good performance was obtained in the individualization of the dune fields, preserving the shape of the spectral curve (geometry) of the quartz.

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>

Les composés diazocétoniques sont des intermédiaires utiles en synthèse organique et l’élaboration de motifs diazocarbonylés est à ce titre un enjeu important. Les diazocétones terminales peuvent subir une addition sur des aldéhydes dans des conditions basiques pour conduire de façon convergente à des composés béta-hydroxy-alpha-diazocétoniques à fort potentiel synthétique. Dans ce contexte, notre projet visait à promouvoir ce type de réaction dans des conditions douces et peu basiques. La stratégie adoptée reposait sur l’utilisation des alpha-trialkylsilyl-alpha-diazoacétones et leur activation nucléophile spécifique par un ion fluorure. Dans un premier temps, la synthèse de la TES-diazoacétone a été optimisée, puis une étude approfondie des paramètres réactionnels a permis la mise au point de la réaction d’aldolisation de la TES-diazoacétone, induite par le TBAF. Deux protocoles expérimentaux faciles de mise en œuvre ont ainsi été mis en place pour conduire à une large gamme de béta-hydroxy-alpha-diazoacétones avec des rendements élevés. L’extension asymétrique de cette méthodologie a ensuite été étudiée en mettant en jeu un fluorure d’ammonium chiral dérivé d’alcaloïde de Cinchona conduisant à la formation des premières béta-hydroxy-alpha-diazoacétones énantioenrichies (e.e = 35%) avec des rendements élevés. Enfin, cette méthodologie a été étendue avec succès à la TIPS-diazoacétone. La robustesse du groupement protecteur TIPS permet d’envisager une large gamme de transformations synthétiques « methyl-side », sans induire une désilylation partielle de la position azométhine du diazo-aldol. Ceci ouvre la voie à l’exploration future de la réactivité des diazoaldols TIPS. / Diazoketones are valuable intermediates in organic synthesis and the elaboration of α-diazocarbonyl scaffolds has aroused a steady interest for many years. The terminal diazoketones can be added to aldehydes under basic conditions to produce beta-hydroxy-alpha-diazoketone compounds with a high synthetic potential. In this context, our project aimed at promoting this type of reaction under mild conditions without using a base. The strategy adopted was based on the use of α-trialkylsilyl-α-diazoacetones and their specific nucleophilic activation by a fluoride ion. Initially, the synthesis of α-trialkylsilyl-α-diazoacetone was optimized and then, an extensive study of the reaction parameters allowed the development of an efficient aldolisation of TES-diazoacetone induced by TBAF. The nucleophilic, weakly basic conditions employed tolerate a wide range of substrates and constitute a practical high-yielding experimental procedure. The asymmetric extension of this methodology was then studied by using a chiral ammonium fluoride derived from Cinchona alkaloid. The condition set up allowed to elaborate the first enantioenriched beta-hydroxy-alpha-diazoacetones (e.e = 35%) in high yields. Finally, this methodology was successfully extended to TIPS-diazoacetone. The robustness of the TIPS protective group makes it possible to envision a range of synthetic « methyl-side » transformations without desilylation of the azomethine position of the diazo-aldol. This study paves the way for future exploration of the reactivity of TIPS diazoaldols.

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Fresh water shortage and hot weather are common challenges in many countries of the world. In the other hand, the air conditioning systems which are used for indoor cooling cause peak electricity demand during high temperatures hours. This peak hour demand is very important since it is more expensive and mainly is supplied by fossil fuel power plants with lower efficiencies compare to base load fossil fuel or renewable owe plants. Moreover, these peak electricity load fossil fuel power plants cause higher green house gas emission and other environmental effects. So, all these show that any solution for these problems could make life better in those countries and all over the world.In this thesis, a new idea for a Power storage, Cooling storage, and Water production Combined Cycle (PCWCC) is introduced and reviewed. PCWCC is combination of two thermal cycles, Ice Thermal Energy Storage (ITES) and desalination by freezing cycle, which are merged together to make a total solution for fresh water shortage, required cooling, and high peak power demand. ITES is a well known technology for shifting the electricity demand of cooling systems from peak hours to off-peak hours and desalination by freezing is a less known desalination system which is based on the fact that the ice crystals are pure and by freezing raw water and melting resulted ice crystals, pure water will be produced. These two systems have some common processes and equations and this thesis shows that by combining them the resulted PCWCC could be more efficient than each of them. In this thesis, the thermodynamic equations and efficiencies of each PCWCC sub-systems are analyzed and the resulted data are used in finding thermodynamics of PCWCC itself. Also, by using reMIND software, which uses Cplex to find the best combinations of input/output and related processes, the cost of produced fresh water and cooling from PCWCC is compared with total cost of fresh water and cooling produced by each sub-systems of PCWCC in three sample cities all over the world, Kerman, Dubai, and Texas. These cities are chosen since they have similar ambient temperature trend with different electricity and fresh water tariff's. The results show that, the PCWCC is economical where there is a significant electricity price difference between ice charging and ice melting hours, off-peak and peak hours, of the day or when the fresh water price is high compare to electricity price. The results also show that how the revenue from fresh water could cover the used electricity cost and make some income as well.

Les Alpes Occidentales ont été le siège , au Paléogène , d 'un volcanisme andésitique dont l'autochtonie est actuellement ét ablie . Les formations volcaniques jalonnent l' arc alpin , en position externe : Thônes, Taveyanne , Saint- Antonin , Barrème , régjon de Nice, Estérel ou interne ( Biellese, Canavese en Italie du Nord) . Dans le contexte de collision entre les plaques Européenne et Sud Alpins, le domaine océanique Piémontais s'est semble -t - il comporté à la manière d'un océan sialique et le volcanisme calco - alcalin s'est manifesté à la faveur d'une double subduction du matériel océanique . L' entrainement de croûte continentale sialique dans l 'enfoncement de domaine océanique pourrait alors expliquer l ' enrichissement en Potassium des magmas andésitiques qui se sont épanchés de part et d 'autre de la chaîne .