Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2016-08-25T17:43:02Z No. of bitstreams: 0 / Made available in DSpace on 2016-08-25T17:43:02Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Nesse trabalho foi proposto investigar a estabilidade de fases do sistema zircônia-escândia (ScSZ) por meio do estudo termodinâmico de nanopartículas, na faixa de 0 a 20% em mol de Sc2O3, e a partir da introdução de um segundo aditivo (Dy2O3 e Nb2O5) ao ZrO2 contendo 10% em mol de Sc2O3 (10ScSZ). A estabilidade de fases do ScSZ foi avaliada com base em dados termodinâmicos determinados pelas técnicas de microcalorimetria de adsorção de água e calorimetria de dissolução à alta temperatura. As soluções sólidas foram sintetizadas pelo método de coprecipitação de hidróxidos. Dados termodinâmicos foram determinados para as formas polimórficas encontradas (monoclínica, tetragonal, cúbica, romboédrica β e γ) por difração de raios X no ScSZ. Esse trabalho resultou no diagrama de fases em nanoescala de tamanho de partícula-composição. Os efeitos produzidos pela introdução de aditivos na matriz de 10ScSZ foram investigados visando obter a possível estabilização da estrutura cúbica (c) e a supressão da transformação de fase c-β, característica do sistema binário. As composições foram sintetizadas por coprecipitação de hidróxidos e por reações em estado sólido para fins comparativos. Os materiais foram sinterizados convencionalmente e por sinterização assistida por campo elétrico. A estabilização completa da fase cúbica ocorreu a partir de teores molares de 1% de Dy2O3 e 0,5% de Nb2O5. O menor teor de Nb2O5 necessário para a estabilização da fase foi atribuído à provável formação da fase líquida durante a sinterização e ao menor tamanho do íon Nb5+. Os resultados de difratometria de raios X em alta temperatura e análise térmica mostraram que houve supressão da transição c-β. As amostras contendo 0,5% mol de Nb2O5 apresentaram valores de condutividade iônica similares aos do 10ScSZ sem aditivos em uma ampla faixa de temperatura com elevada estabilidade em um período de 170 h a 600 °C. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP: 12/03319-5

Heat actuated adsorption heat pumps offer the opportunity to improve overall energy efficiency in waste heat applications by eliminating shaft work requirements accompanying vapor compression cycles. The coefficient of performance (COP) in adsorption heat pumps is generally low. The objective of this thesis is to model the adsorption system to gain critical insight into how its performance can be improved. Because adsorption heat pumps are intermittent devices, which induce cooling by adsorbing refrigerant in a sorption bed heat/mass exchanger, transient models must be used to predict performance. In this thesis, such models are developed at the adsorbent particle level, heat/mass exchanger component level and system level. Adsorption heat pump modeling is a coupled heat and mass transfer problem. Intra-particle mass transfer resistance and sorption bed heat transfer resistance are shown to be significant, but for very fine particle sizes, inter-particle resistance may also be important. The diameter of the adsorbent particle in a packed bed is optimized to balance inter- and intra-particle resistances and improve sorption rate. In the literature, the linear driving force (LDF) approximation for intra-particle mass transfer is commonly used in place of the Fickian diffusion equation to reduce computation time; however, it is shown that the error in uptake prediction associated with the LDF depends on the working pair, half-cycle time, adsorbent particle radius, and operating temperatures at hand. Different methods for enhancing sorption bed heat/mass transfer have been proposed in the literature including the use of binders, adsorbent compacting, and complex extended surface geometries. To maintain high reliability, the simple, robust annular-finned-tube geometry with packed adsorbent is specified in this work. The effects of tube diameter, fin pitch and fin height on thermal conductance, metal/adsorbent mass ratio and COP are studied. As one might expect, many closely spaced fins, or high fin density, yields high thermal conductance; however, it is found that the increased inert metal mass associated with the high fin density diminishes COP. It is also found that thin adsorbent layers with low effective conduction resistance lead to high thermal conductance. As adsorbent layer thickness decreases, the relative importance of tube-side convective resistance rises, so mini-channel sized tubes are used. After selecting the proper tube geometry, an overall thermal conductance is calculated for use in a lumped-parameter sorption bed simulation. To evaluate the accuracy of the lumped-parameter approach, a distributed parameter sorption bed simulation is developed for comparison. Using the finite difference method, the distributed parameter model is used to track temperature and refrigerant distributions in the finned tube and adsorbent layer. The distributed-parameter tube model is shown to be in agreement with the lumped-parameter model, thus independently verifying the overall UA calculation and the lumped-parameter sorption bed model. After evaluating the accuracy of the lumped-parameter model, it is used to develop a system-level heat pump simulation. This simulation is used to investigate a non-recuperative two-bed heat pump containing activated carbon fiber-ethanol and silica gel-water working pairs. The two-bed configuration is investigated because it yields a desirable compromise between the number of components (heat exchangers, pumps, valves, etc.) and steady cooling rate. For non-recuperative two-bed adsorption heat pumps, the average COP prediction in the literature is 0.39 for experiments and 0.44 for models. It is important to improve the COP in mobile waste heat applications because without high COP, the available waste heat during startup or idle may be insufficient to deliver the desired cooling duty. In this thesis, a COP of 0.53 is predicted for the non-recuperative, silica gel-water chiller. If thermal energy recovery is incorporated into the cycle, a COP as high as 0.64 is predicted for a 90, 35 and 7.0°C source, ambient and average evaporator temperature, respectively. The improvement in COP over heat pumps appearing in the literature is attributed to the adsorbent particle size optimization and careful selection of sorption bed heat exchanger geometry.