Silicon oxycarbide (SiOC) is a unique polymer-derived ceramic (PDC) containing silicon, oxygen, and carbon atoms in the form of an amorphous network structure. The phase separation of SiOC is determined by polymeric precursors, pyrolysis temperatures, and atmosphere, which results in different compositions and microstructures. Because of its unique properties (high thermal stability, corrosion resistance, among others), SiOC has numerous applications in fields such as additive manufacturing, lithium-ion batteries, and advanced optics. In the SiOC system, SiO2 nanoclusters can be removed through the etching process, to create nanopores for increasing the surface area. By introducing the SiO2-forming filler (perhydropolysilazane) into SiOC, more SiO2 nanodomains with an average size of 1.72 nm were generated for an ultrahigh surface area of ~2100 m2/g material. Meanwhile, the distributions of domain wall thickness and pore distribution can be calculated by our modified model, to further understand the pore formation. The formation of porous SiOC ceramics with ultrahigh surface areas is greatly desired in numerous applications. Transition metal-containing SiOC composites have more functional properties over pure SiOC and receive more attention in different areas. High-temperature resistant TiC/SiOC was successfully synthesized by pyrolysis of polysiloxane (PSO) and titanium isopropoxide at 1200-1400 °C in argon. It had the first reported conductivity of >1000 S/m for TiC/SiOC ceramics. Nickel-containing SiOC magnetoceramics with soft ferromagnetism was fabricated from a base PSO with the addition of nickel 2,4‐pentanedionate. The effect of water vapor on the phase evolution of Ni/SiOC composites was studied at different pyrolysis temperatures, and the formation of nickel silicides was suppressed by the effect of water vapor during the pyrolysis. Our investigation showed the catalysts from transition metals induced the generation of metal silicides, silicon carbide, and turbostratic carbon with the catalytic activity corresponding to Fe > Co > Ni, which agrees with the activation energy calculation. Also, the phase separation of SiOC was proved to be predominant than local carbothermal reduction. In addition to these findings, a novel approach was developed through the Gibbs free energy minimization method to predict the phase content in PDCs with transition metal additives. And this work provides useful guidance to fabricate the transition metal-containing SiOCs with the desired phase content. Last, the state-of-the-art 4D-STEM technique, collaborated with Lawrence Berkeley National Laboratory, was applied to SiOC ceramics containing amorphous phase. The results showed that 4D-STEM is a valid approach to characterize the nanostructure of the amorphous phase as well as the crystallites. It solves the problem of analyzing SiOC materials at nanoscale due to the disordered atomic arrangement and properties. / Doctor of Philosophy / With the development of science and technology, some novel ceramics have begun to attract attention and become alternatives, such as polymer-derived ceramics (PDCs), due to more advantages over traditional ceramics. Silicon oxycarbide (SiOC) is the main part of the PDC family and possessing good combined thermophysical and mechanical properties. Highly porous SiOC ceramic has broad applications in the fields of catalyst, filters, and thermal insulation. A novel preparation to synthesize SiOC with a specific surface area above 2000 m2/g was investigated. Adding transition metals into the SiOC system can enlarge its application potentials to some extent. The bright spot of nickel-containing SiOC (Ni/SiOC) composites is in the magnetic area. Ni/SiOC composites show soft ferromagnetism and can be used as magnetic sensors, transformers, and so on. In this dissertation, the effect of water vapor on the phase evolution of Ni/SiOC was illustrated. The fabrication of high-temperature-resistant Ti/SiOC composite with large than 1000 S/m conductivity was studied. To further uncover the influence of transition metals on SiOC ceramics, the effects of transition metals on the phase and microstructure evolution of polysiloxane-derived SiOC ceramics were deeply demonstrated. A novel method was even developed to predict the phase content in SiOC ceramic with different transition metals. By working with Lawrence Berkeley National Laboratory, the nanoscale structures of SiOC ceramic was studied using state-of-the-art 4D-STEM. The findings of this dissertation shed light on more potential applications for SiOC ceramics in the future.

O conhecimento de propriedades termofísicas é importante na modelagem, na otimização e no projeto de equipamentos para processos como a fabricação de massa de pão congelada. Neste trabalho, as propriedades termofísicas condutividade térmica, difusividade térmica e calor específico foram determinadas experimentalmente ao longo do processo de congelamento da massa de pão, pois influenciam diretamente a cinética do processo que, por sua vez, determina a qualidade do pão produzido. Os resultados obtidos mostraram que algumas destas propriedades variaram em função do conteúdo inicial de água e principalmente devido à mudança da temperatura. O valor médio encontrado através da atividade de água das massas (aw = 0,950), para temperatura inicial de congelamento, pode explicar alguns desvios no ajuste dos dados experimentais a modelos disponíveis na literatura baseados na lei de Raoult, que são estritamente relacionados à fração de gelo formada. O uso combinado de goma guar e xantana reduziu a entalpia de fusão ao longo do tempo de armazenamento congelado (87,4 J.g-1 e 81,2 J.g-1 para a formulação sem gomas, não congelada e após 28 dias de armazenamento congelado; 84,4 J.g-1 e 76,9 J.g-1 para a formulação com 0,25% de goma guar e 0,25% de goma xantana na massa não congelada e após 28 dias de armazenamento congelado), indicando uma interação entre as gomas na capacidade de ligar água ao longo do tempo de congelamento. Porém, apesar do tempo de congelamento ter reduzido a entalpia de fusão, o processo de congelamento foi o principal fator na queda da taxa de fermentação e da produção de gás pelas leveduras independentemente do tempo de armazenamento congelado. / The knowledge of thermophysical properties is important to model and optimize equipment design for frozen food processes. In this work, the thermophysical bread dough properties, such as, thermal conductivity, thermal diffusivity and specific heat were experimentally determined during freezing process, due to their influence on the kinetics process, and therefore on bread quality. The results showed that some properties varied according to the initial water content and mainly due to temperature changes. The average value of initial freezing temperature found by water activity (aw = 0.950) explains the deviations between experimental data and available models in the literature based on Raoults law, which is related to the ice mass fraction. The combined use of guar and xanthan gums reduced the fusion enthalpy along frozen storage time (87.4 J.g-1 and 81.2 J.g-1 for formulation without gum, non-frozen and after 28 frozen storage days; 84.4 J.g-1 and 76.9 J.g-1 for formulation with 0.25 % of guar gum and 0.25 % of xanthan gum in non-frozen and after 28 frozen storage days). It indicated the interaction between gums and their ability to hold water along frozen storage. Despite frozen storage reduced the fusion enthalpy, the freezing process itself was the main factor in the decrease in proofing rate and gas production by yeast cells.

L'objectif de cette recherche est d'établir des mécanismes de formation de la structure des systèmes hybrides organique-inorganique à base des oligomères uréthane et silicates en fonction de la réactivité de la composant organique, d'identifier l'impact de l'organisation structurelle du OIS obtenue sur leurs propriétés électriques et thermomécaniques, de sorption et de l'activité du capteur. La signification pratique des résultats est la détermination de l'impact de la réactivité composant organique sur la structure des systèmes hybrides polymère organique-inorganique avec la possibilité d'obtenir des matériaux avec des propriétés spéciales prévisibles. Les résultats peuvent être utilisés comme base scientifique pour comprendre l'interconnexion de la structure, les propriétés et les moyens de leur régulation en direction de systèmes hybrides polymère organique-inorganique. La sensibilité très élevée pour les différents types de solvants, qui, combiné avec une haute sélectivité, a été révélé pour les systèmes de synthèse, la possibilité de leur utilisation pratique en tant que matières capteur existe.

Made available in DSpace on 2014-12-17T14:57:51Z (GMT). No. of bitstreams: 1 MarcoASR_TESE.pdf: 5586767 bytes, checksum: d92d904a4f89177a814a13f5f7230b94 (MD5) Previous issue date: 2011-07-11 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In this study were conducted experimental procedures for determination of variation of the expandability of rigid polyurethane foam (PUR) from a natural oil polyol (NOP), specifically the Castor oil plant, Ricinus communis, pure and additions of the vermiculite in phase dispersed in different percentage within a range from 0% to 20%, mass replacement. From the information acquired, were defined the parameters for production of bodies of test, plates obtained through controlled expansion, with the final volume fixed. Initially, the plates were subjected to thermal performance tests and evaluated the temperature profiles, to later be extracted samples duly prepared in accordance with the conditions required for each test. Was proceeded then the measurement of the coefficient of thermal conductivity, volumetric capacity heat and thermal diffusivity. The findings values were compared with the results obtained in the tests of thermal performance, contributing to validation of the same. Ultimately, it was investigated the influence that changes in physical-chemical structure of the material had exerted on the variation of thermophysical quantities through gas pycnometry, scanning electron microscopy (SEM) combined with energy dispersive X-ray fluorescence spectroscopy (EDXRF), infrared spectroscopy using Fourier transform (FTIR), thermogravimetric analysis (TGA) and differential thermal analysis (DTA). Based on the results obtained was possible to demonstrate that all load percentage analyzed promoted an increase in the potential expansion (PE) of the resin. In production of the plates, the composites with density near at the free expansion presented high contraction during the cure, being the of higher density adopted as definitive standard. In the thermal performance tests, the heating and cooling curves of the different composites had presented symmetry and values very close for lines of the temperature. The results obtained for the thermophysical properties of composites, showed little difference in respect of pure foam. The percentage of open pores and irregularities in the morphology of the composites were proportionate to the increment of vermiculite. In the interaction between the matrix and dispersed phase, there were no chemical transformations in the region of interface and new compounds were not generated. The composites of PUR-NOP and vermiculite presented thermal insulating properties near the foam pure and percentage significantly less plastic in its composition, to the formulation with 10% of load / Neste estudo, foram realizados procedimentos experimentais para determina??o da varia??o da expansibilidade da espuma r?gida de poliuretano (PUR) de um poliol de ?leo natural (NOP), especificamente o de mamona, Ricinus communis, puro e acrescido de vermiculita na fase dispersa, em distintos percentuais, dentro de uma faixa de 0% a 20%, de substitui??o em massa. A partir das informa??es adquiridas, foram definidos os par?metros para produ??o dos corpos de prova, placas obtidas atrav?s de expans?o controlada, com volume final fixo. Inicialmente, as placas foram submetidas a testes de desempenho t?rmico, sendo avaliados os perfis de temperatura, para posteriormente serem extra?das amostras, devidamente preparadas conforme as condi??es exigidas para cada ensaio. Procedeu-se ent?o a medi??o do coeficiente de condutividade t?rmica, capacidade t?rmica volum?trica e difusividade t?rmica. Os valores encontrados foram comparados com os resultados obtidos nos testes de desempenho t?rmico, contribuindo para valida??o dos mesmos. Por fim, foi investigada a influ?ncia que as altera??es na estrutura f?sico-qu?mica do material, exerceram sobre a varia??o das grandezas termof?sicas, por meio de picnometria a g?s, microscopia eletr?nica de varredura (MEV) combinada com espectroscopia de fluoresc?ncia de raios-X por energia dispersiva (EDXRF), espectroscopia de infravermelho com transformada de Fourier (FTIR), an?lise termogravim?trica (TGA) e an?lise t?rmica diferencial (DTA). Com base nos resultados obtidos foi poss?vel demonstrar que todos os percentuais de carga analisados promoveram um aumento do potencial de expans?o (PE) da resina. Na produ??o das placas, os comp?sitos com densidade pr?xima ? expans?o livre apresentaram grande contra??o na cura, sendo adotados os de maior densidade como padr?o definitivo. Nos ensaios de desempenho t?rmico, as curvas de aquecimento e resfriamento dos diferentes comp?sitos apresentaram simetria e valores muito pr?ximos para as linhas de temperatura. Os resultados obtidos para as propriedades termof?sicas dos comp?sitos, demonstraram pouca diferen?a em rela??o aos da espuma pura. O percentual de poros abertos e irregularidades na morfologia dos comp?sitos foram proporcionais ao incremento da vermiculita. Na intera??o entre matriz e fase dispersa n?o ocorreram transforma??es qu?micas na regi?o de interface e n?o foram gerados novos compostos. Os comp?sitos de PUR-NOP e vermiculita apresentaram propriedades isolantes t?rmicas pr?ximas as da espuma pura e percentual significativamente menor de pl?stico em sua composi??o, para a formula??o com 10% de carga

O conhecimento de propriedades termofísicas é importante na modelagem, na otimização e no projeto de equipamentos para processos como a fabricação de massa de pão congelada. Neste trabalho, as propriedades termofísicas condutividade térmica, difusividade térmica e calor específico foram determinadas experimentalmente ao longo do processo de congelamento da massa de pão, pois influenciam diretamente a cinética do processo que, por sua vez, determina a qualidade do pão produzido. Os resultados obtidos mostraram que algumas destas propriedades variaram em função do conteúdo inicial de água e principalmente devido à mudança da temperatura. O valor médio encontrado através da atividade de água das massas (aw = 0,950), para temperatura inicial de congelamento, pode explicar alguns desvios no ajuste dos dados experimentais a modelos disponíveis na literatura baseados na lei de Raoult, que são estritamente relacionados à fração de gelo formada. O uso combinado de goma guar e xantana reduziu a entalpia de fusão ao longo do tempo de armazenamento congelado (87,4 J.g-1 e 81,2 J.g-1 para a formulação sem gomas, não congelada e após 28 dias de armazenamento congelado; 84,4 J.g-1 e 76,9 J.g-1 para a formulação com 0,25% de goma guar e 0,25% de goma xantana na massa não congelada e após 28 dias de armazenamento congelado), indicando uma interação entre as gomas na capacidade de ligar água ao longo do tempo de congelamento. Porém, apesar do tempo de congelamento ter reduzido a entalpia de fusão, o processo de congelamento foi o principal fator na queda da taxa de fermentação e da produção de gás pelas leveduras independentemente do tempo de armazenamento congelado. / The knowledge of thermophysical properties is important to model and optimize equipment design for frozen food processes. In this work, the thermophysical bread dough properties, such as, thermal conductivity, thermal diffusivity and specific heat were experimentally determined during freezing process, due to their influence on the kinetics process, and therefore on bread quality. The results showed that some properties varied according to the initial water content and mainly due to temperature changes. The average value of initial freezing temperature found by water activity (aw = 0.950) explains the deviations between experimental data and available models in the literature based on Raoults law, which is related to the ice mass fraction. The combined use of guar and xanthan gums reduced the fusion enthalpy along frozen storage time (87.4 J.g-1 and 81.2 J.g-1 for formulation without gum, non-frozen and after 28 frozen storage days; 84.4 J.g-1 and 76.9 J.g-1 for formulation with 0.25 % of guar gum and 0.25 % of xanthan gum in non-frozen and after 28 frozen storage days). It indicated the interaction between gums and their ability to hold water along frozen storage. Despite frozen storage reduced the fusion enthalpy, the freezing process itself was the main factor in the decrease in proofing rate and gas production by yeast cells.

rOrientador: Martin Azna / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-22T13:28:41Z (GMT). No. of bitstreams: 1 SilvaJunior_JulioLopesda_M.pdf: 4182616 bytes, checksum: 6423419dacba1304ffd5dce09c359c97 (MD5) Previous issue date: 2013 / Resumo: O 2,5-dimetilfurano (DMF) é um biocombustível promissor que pode ser produzido a partir da desidratação da frutose por catálise ácida em um reator bifásico. Para o projeto, operação e otimização do processo de produção do DMF são indispensáveis dados de equilíbrio de fases, visando as etapas de separação e purificação, bem como dados de propriedades termofísicas dos componentes envolvidos, úteis no cálculo das propriedades de transporte. Entretanto, dados de equilíbrio líquido-líquido (ELL) envolvendo o DMF são, até o momento, inexistentes na literatura. Este trabalho teve como objetivo principal determinar experimentalmente dados de ELL de sistemas ternários água + DMF + solventes presentes nas etapas de separação do processo de produção do DMF em reator bifásico, bem como desenvolver a metodologia analítica mais apropriada. Foram usados como solventes 1-butanol, 2-butanol e 1- hexanol e as linhas de amarração foram obtidas nas temperaturas de 25°C e 40°C, a pressão atmosférica de aproximadamente 95,0 kPa. Três técnicas analíticas foram testadas: 1) densimetria e refratometria, 2) cromatografia gasosa com padronização interna e 3) cromatografia gasosa com titulação volumétrica de Karl Fischer, sendo empregada esta última metodologia na determinação da composição das fases em equilíbrio. O ELL do sistema ternário acetato de etila + 1-butanol + água a 20°C foi determinado e comparado com dados disponíveis na literatura para validação da metodologia analítica. Os resultados mostram que os sistemas estudados apresentam regiões de grande imiscibilidade e altos valores de seletividade para o DMF; portanto, estes álcoois foram considerados bons solventes para aplicação no processo de produção do DMF. Fez parte ainda dos objetivos do trabalho determinar as propriedades densidade, índice de refração e viscosidade do DMF puro, obtidos usando um densímetro de tubo em U vibrante, um refratômetro e um viscosímetro de bola em queda, respectivamente, em uma faixa de temperatura entre 15 e 60°C. Os dados de ELL obtidos foram satisfatoriamente correlacionados com o modelo NRTL para o cálculo do coeficiente de atividade, com desvio médio quadrático na composição menor que 2% para todos os sistemas; novos parâmetros de interação binária foram determinados nesta correlação. A qualidade dos dados experimentais foi verificada pelas equações de Bachman e Othmer-Tobias, que mostraram um coeficiente de correlação R2> 0,97 em todos os casos / Abstract: 2,5-Dimethylfuran (DMF) is a promising biofuel that can be produced by dehydration of fructose by acid catalysis in a biphasic reactor. For the design, operation and optimization of DMF production process, phase equilibrium data are necessary, aiming the separation and purification steps, as well as thermophysical properties of the involved compounds, useful in the calculation of transport properties. However, liquid-liquid equilibrium (LLE) data of systems including DMF are not available in the literature at the present time. The main objective of this work was to determine experimentally LLE data of ternary systems water + DMF + solvents present in the separation steps of DMF production process in biphasic reactor, as well to develop the most suitable analytical methodology. 1-Butanol, 2-butanol and 1-hexanol were used as solvents and the tie-lines were determined at 25°C and 40°C and at atmospheric pressure of about 95.0 kPa. Three analytical techniques were tested: 1) densimetry and refractometry, 2) gas chromatography with internal standard method and 3) gas chromatography combined with Karl Fischer volumetric titration, the latter used in the equilibrium phases composition determination. LLE data of ternary system ethyl acetate + 1-butanol + water at 20°C was determined and compared with those available in the literature for validation of the analytical methodology. The results show that the studied systems have large immiscibility region and high selectivity values for the DMF; therefore, these alcohols are considered good solvents for application in DMF process production. Also, new measurements of pure DMF density, refractive index and viscosity were performed, obtained by using a vibrating U-tube densimeter, a refractometer and a falling ball viscometer, respectively, in the temperature range 15 to 60°C. The obtained LLE data were satisfactorily correlated with the NRTL model for the activity coefficient calculation, with root mean square deviation in composition less than 2% for all systems; new binary interaction parameters were determined in this correlation. The quality of the experimental data was ascertained by Bachman and Othmer-Tobias equations, with a correlation coefficient R2 > 0.97 for all cases / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Le sujet de thèse de doctorat s’inscrit dans le cadre d’un projet de recherche collaboratif entre l’Institut FEMTO-ST et le groupe SAFRAN/SNECMA. Une partie des travaux de cette thèse concerne les caractérisations thermo-physiques de polymères chargés pour différentes nuances et granulométries de poudres de superalliage destinés à être mis en forme par le procédé de Moulage par Injection de Poudre. Pour ces travaux de thèse de doctorat, trois nuances de polymères chargés composé de poudres de superalliages ont été investiguées. Deux nuances sont composées de poudres utilisées par Snecma en réparation (René 80®/Amdry D15® et RBD61) et un autre est composée de poudre d’Inconel 718. Différentes caractérisations ont été réalisées et ont permis d’optimiser le développement de mélanges chargés conduisant à l’élaboration de matériaux homogènes et injectables tout en possédant des taux de charge en poudres les plus élevés possible.Les résultats de ces travaux sont ensuite utilisés afin d’identifier différents termes présents dans les modèles analytiques de rhéologie usuels. Le développement de modèles de rhéologies spécifiques a été réalisé en incorporant aux lois rhéologiques usuelles différents termes dépendant de la surface spécifique, de la viscosité des liants employés au sein de la formulation. Le développement de ces modèles de viscosité de plus en plus complets permet d’améliorer les lois de comportements et de mieux décrire le comportement rhéologique de polymères chargés. Enfin, une simulation de l’étape de moulage par injection d’un composant aéronautique a été réalisée à l’aide du logiciel Moldflow© pour la nuance de René 80®/Amdry D15®. / The works presented in this paper were realized in collaboration between the mechanical department of FEMTO-ST Institute and the company SAFRAN/SNECMA. A part of the works of this thesis focused the thermo-physical characterizations of loaded polymers that is mixtures based of thermoplastic binders and metallic powders suitable be shaped by powder injection molding process.For this work, three different loaded mixtures composed of superalloy powder were investigated.Two were supplied by SAFRAN/SNECMA used to repair (Rene80®/AmdryD15® and RBD61) and another is composed of Inconel 718 powder. Characterizations were to carry out to optimize the development of loaded polymers and to obtain homogenous materials with high solid fraction. Then, the data were used to identified parameters of usual rheological laws. The development of specific rheological models were realized by including different parameters related to the specific surface area, binder viscosities used in the formulation. The development of these models increasingly exhaustive allows the improvement of behavior laws and to better describe the rheological behavior of superalloy-loaded polymers. Finally, a simulation of the injection molding stage of a aeronautical component was realized in the Moldflow© software for the Rene80®/AmdryD15® loaded polymer.

Les recherches dans le domaine des matériaux innovants possédant une meilleure efficacité énergétique présentent un enjeu environnemental majeur. L'un des moyens d'économiser l'énergie est le stockage. L'utilisation des matériaux à changement de phase est une solution permettant d'absorber, de stocker et de restituer de grandes quantités d'énergie. Ce travail porte sur l'étude expérimentale des propriétés thermophysiques et des changements de phase de matériaux composites à matrice polymère contenant un matériau à changement de phase microencapsulé et sur l'optimisation de ces propriétés. Des composites contenants différentes fractions massiques de microcapsules de paraffine ont d'abord été caractérisés. Afin d'améliorer le transfert thermique des microcapsules de paraffine métallisées avec de l'argent ont ensuite été utilisées. Une nouvelle série d'échantillons a été réalisée. Dans les composites la matrice polymère choisie est le polycaprolactone (PCL), ce polymère a une température de fusion particulièrement faible (53°C), qui permet de le mélanger aux microcapsules sans les détériorer. Les mélanges polymère/microcapsules ont été réalisés à l'aide d'un mélangeur interne, ils ont ensuite été pressés pour obtenir des plaques de composites. L'homogénéité des échantillons a été vérifiée en faisant des observations au microscope électronique à balayage et des mesures de densité. Le matériau à changement de phase utilisé est un mélange de paraffines qui a une température de changement de phase de 26°C, microencapsulé dans du PMMA hautement réticulé, et commercialisé par la société BASF® sous la dénomination commerciale de Micronal® DS 5001 X. Le PCL a une température de fusion inférieure à la température de ramollissement du PMMA. Un des objectifs de cette étude était d'obtenir un matériau qui reste solide même quand la paraffine fond. La microencapsulation a permis cela en évitant que la paraffine ne diffuse hors de l'échantillon lors de cycles successifs, elle permet également d'éviter les phénomènes de convection quand la paraffine est liquide. D'autre part, un autre objectif était de voir si la métallisation des particules permettait d'améliorer les propriétés thermiques en augmentant significativement la conductivité et la diffusivité thermique. La DSC a été utilisée pour connaître les températures et les enthalpies de changements de phase ainsi que les Cp des matériaux entre -20 et 40 °C. Une technique expérimentale développée au laboratoire (DICO) permet de mesurer simultanément la conductivité thermique (λ) et la diffusivité thermique (a) à température ambiante. Une évolution récente de ce dispositif permet maintenant de faire des mesures en rampe en température entre -15°C et 180°C. Les mesures de l'évolution de la conductivité et de la diffusivité thermique en fonction de la température ont donc été réalisées en chauffe et en refroidissement. Les changements de phase observés en DSC se retrouvent sur l'évolution de la conductivité et de la diffusivité thermiques tracées en fonction de la température. On voit également l'impact de l'état solide ou liquide de la paraffine contenue dans les microcapsules sur ces propriétés. Enfin l'évolution de la capacité calorifique volumique a pu être calculée à partir des résultats obtenus avec la DICO (Cp=λ/a) et comparée à l'évolution de la capacité calorifique massique mesurée en DSC. Globalement le transfert thermique a été amélioré pour les composites contenant des Micronal® argentés mais leur capacité de stockage est inférieure aux composites ne contenant que des Micronal® / Research in the field of innovative materials with improved energy efficiency have a major environmental issue. One way to save energy is storage. The use of phase change materials (PCM) is a solution for absorbing, storing and releasing large amounts of energy. This study focuses on the experimental study of the thermophysical properties and phase changes of polymer matrix composite materials containing microencapsulated PCM and the optimization of their thermophysical properties. Composite containing different mass fractions of paraffin microcapsules were first characterized. To improve heat transfer, paraffin microcapsules metallized with silver were then used. A new set of samples was elaborated. In the composite the selected polymer matrix is polycaprolactone (PCL), this polymer has a particularly low melting point (53°C), which allows to mix the microcapsules without damaging them. The polymer/microcapsules mixtures were prepared using a blender, they were then pressed to obtain plates of composites. The homogeneity of the samples was verified by scanning electron microscopy observations and density measurements. The phase change material used is a mixture of paraffins having a phase change temperature of 26°C, in microencapsulated highly crosslinked PMMA, and marketed by BASF under the trade name of Micronal®DS 5001 X. PCL has a melting temperature lower than the softening temperature of PMMA. One objective of this study was to obtain a material that remains solid even when the paraffin melts. Microencapsulation has avoided that the paraffin in the sample diffuses out during successive cycles, it also avoids convection when paraffin is liquid. On the other hand, another goal was to see if metallization of the particles allowed to improve the thermal properties by significantly increasing the thermal conductivity and diffusivity. DSC was used to determine the temperatures and enthalpies of the phase changes and the materials Cp between -20 and 40 ° C. An experimental technique, developed in the laboratory (DICO), can simultaneously measure the thermal conductivity (λ) and thermal diffusivity (a) at room temperature. A recent development of this system now allows to make measurements in ramp between -15°C and 180°C. The measures of the change in thermal conductivity and diffusivity as a function of temperature have been carried out by heating and cooling. Phase changes observed in DSC are found on the evolution of thermal conductivity and thermal diffusivity plotted as a function temperature. It also shows the impact on these properties of solid or liquid state of the paraffin contained in the microcapsules. Finally the evolution of the volumetric heat capacity was calculated from the results obtained with DICO (Cp=λ/a) and compared with the evolution of the specific heat capacity measured by DSC. Globally, heat transfer was improved for composites containing silver but their storage capacity is lower than for the composites containing only Micronal®

Refrigerant management is crucial in the attempts to slow climate change. Emissions from the refrigeration sector are primarily due to poor management and unsafe destruction of refrigerants currently in circulation. Safe refrigerant management and improving system operating efficiency can result in a reduction of emissions. Ice rinks are some of the most energy-intensive public buildings, providing both heating and cooling. The major share of energy in an ice rink is the refrigeration system, which consumes about 43%. There are more than 360 ice rinks in Sweden as of 2018 and the most common type of refrigeration system is an indirect system. With the push for natural fluids, aqua ammonia is becoming a more appealing option as a secondary fluid in ice rinks because of its minimal negative impact on the environment and favorable thermophysical properties. The main drawbacks of the fluid are its toxic characteristics and material compatibility. However, since the first use in 2007, there has been an increase to 34 of the total ice rinks in Sweden that have aqua ammonia as a secondary fluid.  Thermophysical properties are used to calculate refrigeration design parameters, including secondary fluid concentration and pumping power required. The properties of aqua ammonia have not been experimentally tested within this century to the extent presented in this thesis. Existing data is either derived from measured values taken several decades ago or has been calculated. The novelty of this thesis project stems from the unique and more accurate results measured through laboratory work and from the ability to determine the impact of the newly measured values in ice rink refrigeration design. A total of 11 varying concentrations of aqua ammonia were tested for density, dynamic viscosity, specific heat capacity, thermal conductivity, and corrosion of 7 metal specimens. The solutions tested ranged from 2 wt-% to 30 wt-%, correlating to freezing points from -2C to -84C. The measurements for density resulted in values similar to reference values, ranging in a difference of only 0.3% to 1.7%. Dynamic viscosity results followed nearly the same trend as references with changing temperature and solution concentration, with values varying from 0.8% to 17% different than references. Specific heat capacity measurements proved significantly different than reference values. The trend is opposite of the reference, leading to drastically different values, especially at lower temperatures and higher solution concentrations. The difference in values ranges from 0.1% to 28%. Thermal conductivity results show similar trends, but higher values than expected. The difference between measured values and reference values range from 0.1% to 13%. Corrosion results show that copper and brass have the highest corrosion rates of 16.2 mm/yr and 1.84 mm/yr, respectively. The most compatible specimen was stainless steel, followed by carbon steel, with maximum corrosion rates of 0.041 mm/yr and 0.11 mm/yr, respectively. Brass connections commonly used in industry were also tested and resulted in corrosion rates ranging from 69.6 g/yr to 112 g/yr, which accounts for about 1% and 1.5% of the connections’ total weight lost per year. Compiling the laboratory measurements taken during the completion of this thesis project results in a more complete and accurate list of thermophysical properties for aqua ammonia that has never existed before.  These updated thermophysical properties for aqua ammonia, along with measured properties for other secondary fluids, were used to calculate operational parameters in a hypothetical ice rink refrigeration system. The results show that aqua ammonia is favorable with high COP and low pumping power, and therefore low pressure drop. Ammonia is most comparable to CaCl2 and K-formate for most results. The changes in calculated COP between old reference data and new measured data were less than a 1% decrease when plotting versus the temperature of the ice surface and with a set pump control (T) for cooling capacities of 200kW and 300kW. The change in heat transfer coefficients was more significant, with a range of about a 9% to 27% decrease in either the U-pipe under the rink floor or in a plate of the heat exchanger. Even though these heat transfer coefficient values are lower than previously calculated, the required pumping power is also lower using updated properties: 40% lower at a secondary fluid temperature of -10C. Even though the change in heat transfer coefficients is larger with experimental values, the impact on COP is minimal.  The takeaway from this project is that aqua ammonia is a favorable secondary fluid compared to calcium chloride and ethylene glycol, the two most commonly used secondary fluids in ice rink refrigeration. A system using aqua ammonia would have a 45% and 47% lower pumping power requirement compared to calcium chloride and ethylene glycol, respectively. The system would also have a 4.7% and 11.6% higher COP when compared to systems with calcium chloride and ethylene glycol, respectively. The significantly lower pumping power will lower total energy demand of the ice rink, thus decreasing operation costs. / Köldmediehantering är avgörande i försöken att sakta ner klimatförändringen. Utsläppen från kylsektorn beror främst på dålig hantering och osäker destruktion av köldmedier som för närvarande är i omlopp. Säkrare hantering av köldmedium och förbättrad systemdriftseffektivitet kan leda till ett minskat utsläpp. Ishallar är några av de mest energiintensiva offentliga byggnaderna som ger både uppvärmning och kylning. Den största andelen energi i en ishall är kylsystemet som förbrukar cirka 43%. Det finns mer än 360 isbanor i Sverige från och med 2018 och den vanligaste typen av kylsystem är ett indirekt system. Med trycket på naturliga vätskor blir ammoniakvatten ett mer tilltalande alternativ som en köldbärare i ishallar på grund av dess minimala negativa påverkan på miljön och gynnsamma termofysikaliska egenskaper. Köldbärares främsta nackdelar är dess toxiska karaktär och materialkompatibilitet. Sedan den första användningen 2007 har det dock skett en ökning till 34 av de totala ishallar i Sverige som har ammoniakvatten som köldbärare.  Termofysikaliska egenskaper används för att beräkna parametrar för kyldesign, inklusive köldbärares koncentration och pumpeffekten som krävs. Ammoniakvattens egenskaper har inte testats experimentellt under detta sekel i den utsträckning som presenteras i detta exjobb. Befintliga data härleds antingen från uppmätta värden som tagits för flera decennier sedan eller har beräknats. Nyheten härrör i detta exjobbsprojekt från de unika och mer exakta resultat som mätts genom laboratoriearbetet och från förmågan att bestämma effekten av de nyligen uppmätta värdena i kylskåpsdesign. Totalt 11 olika koncentrationer av ammoniakvatten testades med avseende på densitet, dynamisk viskositet, specifik värmekapacitet, värmeledningsförmåga och korrosion av 7 metallprover. De testade lösningarna varierade från 2 vikt-% till 30 vikt-%, korrelerade med fryspunkter från -2 ° C till -84 ° C. Mätningarna för densitet resulterade i värden som liknar referensvärdena, med en skillnad på endast 0,3% till 1,7%. Dynamiska viskositetsresultat följde nästan samma trend som referenser med förändrad temperatur och lösningskoncentration, med värden som varierade från 0,8% till 17% annorlunda än referenser. Specifika värmekapacitetsmätningar visade sig vara väsentligt annorlunda än referensvärden. Trenden är motsatt referensen, vilket leder till drastiskt olika värden, särskilt vid lägre temperaturer och högre koncentrationer. Skillnaden i värden varierar från 0,1% till 28%. Värmeledningsförmåga visar liknande trender, men högre värden än förväntat. Skillnaden mellan uppmätta värden och referensvärden sträcker sig från 0,1% till 13%. Korrosionsresultat visar att koppar och mässing har de högsta korrosionshastigheterna på 16,2 mm / år respektive 1,84 mm / år. Det mest kompatibla exemplet var rostfritt stål, följt av kolstål, med maximala korrosionshastigheter på 0,041 mm / år respektive 0,11 mm / år. Mässinganslutningar som vanligen används i industrin testades också och resulterade i korrosionshastigheter från 69,6 g / år till 112 g / år, vilket motsvarar för cirka 1% och 1,5% av anslutningarnas totala viktförlust per år. Att sammanställa laboratoriemätningarna som gjorts under slutförandet av detta projekt resulterar i en mer fullständig och noggrann lista över termofysikaliska egenskaper för ammoniakvatten som aldrig funnits tidigare.  Dessa uppdaterade termofysikaliska egenskaper för ammoniakvatten, tillsammans med uppmätta egenskaper för andra köldbärare, användes för att beräkna driftsparametrar i ett hypotetiskt kylsystem. Resultaten visar att ammoniakvatten är gynnsam med hög COP och en låg pumpeffekt och därmed ett lågt tryckfall. Ammoniakvatten är mest jämförbart med CaCl2 och K-formiat för de flesta resultat. Förändringarna i beräknad COP mellan gamla referensdata och nya uppmätta data var mindre än 1% minskning vid planering jämfört med isytans temperatur och med en inställd pumpkontroll (T ) för kylkapacitet på 200 kW och 300 kW. Förändringen i värmeövergångstal var mer signifikant, med ett intervall på cirka 9% till 27% minskning i antingen U-röret under golvet eller i en platta på värmeväxlaren. Även om dessa värmeövergångstal är lägre än tidigare beräknat, är den erforderliga pumpeffekten också lägre med hjälp av uppdaterade egenskaper: 40% lägre vid en köldbärarestemperatur på -10 ° C. Även om förändringen i värmeövergångstal är större med experimentella värden, är påverkan på COP minimal.  Slutsatser från detta projekt är att ammoniakvatten är en lämplig köldbärare jämfört med kalciumklorid och etylenglykol, de två vanligaste köldbärare i ishallskylning. Ett system som använder ammoniakvatten skulle ha ett pumpeffektbehov på 45% respektive 47% jämfört med kalciumklorid respektive etylenglykol. Systemet skulle också ha en 4,7% och 11,6% högre COP jämfört med system med kalciumklorid respektive etylenglykol. Den betydligt lägre pumpeffekten kommer att sänka det totala energibehovet för ishallar, vilket minskar driftskostnaderna.

Um fator importante para o desenvolvimento de projetos de microssistemas é o conhecimento de propriedades termomecânicas dos materiais e a compreensão dos mecanismos de falhas. Este trabalho estuda o comportamento mecânico de microvigas atuadas termicamente e propõem um método para ser utilizado na caracterização de propriedades termomecânicas de filmes finos. Fabricou-se vigas de Oxinitreto de Silício em que se aplicou a microscopia Nomarski para observar a deformação e a ocorrência do fenômeno de flambagem. / An important factor to develop microsystems is knowledge of materials properties and failure mechanisms. This research studies the thermal actuated microbeam mechanical behavior and propose a method in order to characterize thermomechanical properties of thin films. Silicon Oxynitride microbeams are fabricated and Nomarski microscopy was applied to observe strain and buckling phenomenon ocurrence.