A demanda por produtos industrializados que apresentem máxima preservação de suas características naturais têm crescido e feito as indústrias alimentícias re-analisarem seus processos para atingirem essa necessidade do mercado. A abordagem convencional conservadora, utilizada para o dimensionamento do processamento térmico de alimentos, pode levar ao sobre-processamento especialmente no regime laminar, devido às significativas distribuições de temperatura e tempos de residência existentes. Um modelo matemático, composto por equações diferenciais de massa e energia foi elaborado, considerando o processamento térmico de um fluido não-newtoniano, sob regime laminar, escoando em um trocador de calor bitubular. No modelo, se levou em conta as dispersões efetivas de massa e energia associadas com o escoamento laminar não ideal, as trocas de calor com o ambiente, a letalidade que ocorre no aquecimento e resfriamento e o perfil de velocidade. O modelo foi testado por meio de simulações do estudo de caso do processamento térmico de suco de graviola (fluido pseudoplástico) considerando a destruição de bolores e leveduras. Objetivou-se nas simulações avaliar o efeito de distintas considerações do modelo nas variáveis consideradas. Os resultados indicaram que as etapas de aquecimento e resfriamento contribuíram de forma significativa na letalidade do processo, assim como as considerações quanto às dispersões de massa e energia. Como exemplo, as letalidades, considerando a abordagem convencional (tubo de retenção isotérmico com velocidade máxima) e o modelo completo (com todas as considerações) apresentaram valores de 1,46 e 5,74, respectivamente. A flexibilidade do modelo elaborado, assim como os tempos computacionais pequenos necessários para obter os resultados são as principais vantagens do uso do mesmo. Acredita-se que o modelo elaborado pode contribuir de forma importante para o correto dimensionamento e avaliação de processos térmicos em indústrias de alimentos, permitindo que a demanda dos consumidores seja atendida. / The demand for industrialized food with maximum retention of sensorial and nutritional attributes has grown and made the food industries rethink operational conditions to meet this market expectation. The classic conservative approach, used for the design of thermal food processing can lead to over-processing specially in laminar regime, due to the existing significant temperature and residence time distributions. A mathematical model, comprising differential equations for mass and heat transfer was elaborated, considering the thermal processing of a non-Newtonian liquid, under laminar flow in a double-pipe heat exchanger. In the model, it was taken into account the effective mass and energy dispersions associated with the non-ideal laminar flow, the heat exchange with the ambient, the contribution from heating and cooling sections in the lethality and the velocity profile. The model was tested through simulations of a study case of soursop juice processing (pseudoplastic fluid) regarding the destruction of yeast and molds. The objective of the simulations was to evaluate the effect of distinct model assumptions on the variables. The results indicated that the heating and cooling sections and the assumptions regarding the effective mass and energy dispersions had an important contribution to the processing lethality. As an example, the lethality, regarding the conventional approach (isothermal holding tube at the maximum velocity) and the complete model (with all the assumptions) were 1.46 and 5.74, respectively. The model flexibility and the small computational time needed for the results to the obtained are the main advantages of its use. It is expected that the developed model can be an important contribution to the correct design and evaluation of thermal processing in food industries, allowing the consumer demands to the reached.

Neste trabalho foram crescidos filmes finos de oxinitreto de silício (SiOxNy) por processamento térmico rápido (RTP) utilizando um forno térmico convencional adaptado, objetivando fabricar células solares MOS com baixo custo agregado e bom rendimento de conversão de baixas intensidades luminosas em energia elétrica de forma reprodutível. A receita de oxinitretação otimizada foi desenvolvida em ambiente misto de 5N2:1O2 na temperatura de 850°C para tempos de processo, na faixa de 10 a 80s seguido por uma passivação em 2L/min de N2 por 80s. Os dielétricos crescidos foram caracterizados fisicamente quanto à espessura (entre 1,50 e 2,95nm), à microrugosidade (<0,95nmRMS) e à concentração de nitrogênio (1,0-2,1%atm). As características de tunelamento foram investigadas em capacitores MOS e apontaram para a existência de armadilhas interfaciais do tipo K capazes de armazenar cargas positivas. Nas células solares MOS, a corrente de fundo foi característica para todos os processos de oxinitretação empregados (~0,5-2µA/cm2) e apresentaram níveis de resposta à luz incidente na faixa de 1 a 8mA/cm2 compatível com aplicações de conversão de energia em ambientes internos e externos (energy harvesting). A característica densidade de corrente x tensão de porta (JxVG) das células solares apresentou um comportamento aproximadamente linear desde a densidade de corrente de curto-circuito (JSC) até a tensão de curto-circuito (VOC) implicando em potência gerada máximas (PGmáx) de até centenas de µA/cm2 para VG ? VOC/2 para uma ampla faixa de intensidade radiante incidente (11,8 - 105,7mW/cm2) alcançando rendimentos de conversão de até 5,5%. / In this work, silicon oxynitrides (SiOxNy) were grown by means of a homemade Rapid Thermal Processing (RTP). The goal was to manufacture MOS solar cells with a reduced price and reasonable light conversion efficiency for low light intensity. The optimized oxidation recipe consisted of using an environment with gas mixture of 5N2:1O2 at a temperature of 850°C and different processing times in the range of 10 to 80s followed by a passivation step in ultrapure N2 (2L/min) at the same temperature of 850oC for 80s. The oxynitrides were grown with thickness in the range of 1.50 to 2.95nm with surface microroughness lower than 0.95nmRMS and nitrogen concentration in the range of 1.0 to 2.1%atm. The tunneling characteristics were studied with the aid of MOS capacitor and K-type interfacial traps related to Si(p)/Si?N structure were detected positively charged for VG > 0. The background current in the MOS solar cells (~0.5-2µA/cm2) were similar for all samples and the current response to the incident light was in the range of 1 to 8mA/cm2, which is compatible with energy conversion for indoor and outdoor environments (energy harvesting). The current density x gate voltage (JxVG) characteristics of the MOS solar cells presented a nearly linear behavior since the short-circuit current density (JSC) till to the open circuit voltage (VOC) so that the maximum generated power was of hundreds of µA/cm2 for VG ? VOC/2 for a large range of radiant intensities (11.8 - 105.7 mW/cm2) and achieving efficiency conversion up to 5.5%.

The original work presented in this thesis describes research into Si-based luminescent materials, prepared specifically by ion implantation and rapid thermal processing of thermal oxide films. An in-depth optical characterisation, employing photoluminescence (PL) and Raman spectroscopy was complimented with electron microscopy, revealing the source of efficient room temperature PL as nano-scale silicon inclusions (Si-NCs). The evolution of the Si-NC size and density with isothermal and isochronal annealing may be described using classical thermodynamics according to a diffusion limited, Ostwald ripening process. Values for the coarsening rate and activation energy, extracted from the evolution of the Si-NC size with annealing indicate that the transport of Si atoms and precipitate formation are enhanced in ion implanted films, attributable to the presence of vacancy and interstitial defects generated during ion irradiation. The PL and Raman spectra are well correlated with the evolving Si-NC size and density according to the quantum confinement (QC) model in which samples containing larger clusters emit at longer wavelengths. However, the formation of bound exciton states within the band gap of small clusters (< 2nm), as a result of specific surface chemistries, suppresses higher energy emissions. The increase in PL intensity with annealing was exactly correlated with the increase in PL lifetime, characteristic of the removal of non-radiative defects. A dependence of the PL dynamics on emission energy, with higher energies exhibiting shorter lifetimes, further evidences the QC effect. Blue shifted emission at high excitation flux and/or low temperature is correspondent with the slower PL dynamics and preferential saturation at longer wavelengths. Raman spectra were fit using a phonon confinement model, from which Si-NC size distributions were extracted and found to compare favourably with those obtained from TEM images. Stresses in the films, determined from the Raman peak position, were used as an independent method for calculating the Si surface energy, which is very close to the literature values. A single, high temperature anneal of Si and erbium (Er) co-doped films revealed a preferential aggregation of Er at the Si-NC formation site, which is of particular importance for the photo-sensitization of Er PL around 1.5μm. The Er PL was enhanced in the presence of Si-NCs by several orders of magnitude compared with a reference SiO2:Er. Whilst broadband pumping of the Er via Si-NCs evidences a non-resonant energy transfer mechanism with an efficiency which depends on the Si-NC size, the process is limited at high excitation flux by a combination of low sensitizer (Si-NC) density and non-radiative losses. Finally the Si-NC PL intensity in phosphorus (P) co-doped films was studied and found to depend strongly on the annealing conditions and P concentration. For lower temperature treatments, a factor 2 PL enhancement, relative to an un-doped reference was obtained, attributed to the passivation of Si-NC surface defects. Higher temperature treatments resulted in the monotonic quenching of the PL with increasing P concentration, attributed to the introduction of an efficient Augerre combination channel as a result of the ionization of P-donors inside large Si-NCs. A simple statistical model predicts this behaviour and provides an incidental estimate of the Si-NC size.

A rapid thermal processing (RTP) reactor for the preparation of graded CuIn1-xGaxSe2-ySy (CIGSeS) thin-film solar cells has been designed, assembled and is being used at the Photovoltaic Materials Laboratory of the Florida Solar Energy Center. CIGSeS films having the optimum composition, morphology, and semiconducting properties were prepared using RTP. Initially films having various Cu/(In+Ga) ratios were prepared. In the next step selenium incorporation in these films was optimized, followed by sulfur incorporation in the surface to increase the bandgap at the surface. The compositional gradient of sulfur was fine-tuned so as to increase the conversion efficiency. Materials properties of these films were characterized by optical microscopy, SEM, AFM, EDS, XRD, GIXRD, AES, and EPMA. The completed cells were extensively studied by electrical characterization. Current-voltage (I-V), external and internal quantum efficiency (EQE and IQE), capacitance-voltage (C-V), and light beam induced current (LBIC) analysis were carried out. Current Density (J)-Voltage (V) curves were obtained at different temperatures. The temperature dependence of the open circuit voltage and fill factor has been estimated. The bandgap value calculated from the intercept of the linear extrapolation was ~1.1-1.2 eV. Capacitance-voltage analysis gave a carrier density of ~4.0 x 1015 cm-3. Semiconductor properties analysis of CuIn1-xGaxSe2-ySy (CIGSeS) thin-film solar cells has been carried out. The values of various PV parameters determined using this analysis were as follows: shunt resistance (Rp) of ~510 Ohms-cm2 under illumination and ~1300 Ohms-cm2 in dark, series resistance (Rs) of ~0.8 Ohms-cm2 under illumination and ~1.7 Ohms-cm2 in dark, diode quality factor (A) of 1.87, and reverse saturation current density (Jo) of 1.5 x 10-7A cm-2. The efficiency of 12.78% obtained during this research is the highest efficiency obtained by any University or National Lab for copper chalcopyrite solar cells prepared by RTP. CIGS2 cells have a better match to the solar spectrum due to their comparatively higher band-gap as compared to CIGS cells. However, they are presently limited to efficiencies below 13% which is considerably lower than that of CIGS cells of 19.9%. One of the reasons for this lower efficiency is the conduction band offset between the CIGS2 absorber layer and the CdS heterojunction partner layer. The band offset value between CIGS2 and CdS was estimated by a combination of ultraviolet photoelectron spectroscopy (UPS) and Inverse Photoemission Spectroscopy (IPES) to be -0.45 eV, i.e. a cliff is present between these two layers, enhancing the recombination at the junction, this limits the efficiency of CIGS2 wide-gap chalcopyrite solar cells.

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The development and control of nanoscale properties is a major goal in science and technology; for the development of such technologies it is important that there are experimental techniques which allow the monitoring of development processes in real time and in a range of environments. With this in mind much effort has been invested in the development of surface sensitive optical probes. One such technique, reflection anisotropy spectroscopy (RAS), has been applied successfully to a number of different problems since its development in the mid 1980’s. RAS as a surface specific technique is very sensitive to small changes to surface morphology, electronic structure and molecular orientation. This makes RAS a useful technique to study nanoscale changes occurring at surfaces and it is applied here to three such systems, in an attempt to develop a better understanding of both the systems and the technique. Surface defects arising from thermal processing and etching of the sample are considered and are found to have a significant effect on both the electronic structure and the morphology of the surface. The time and temperature dependences of the RAS signatures allow the monitoring of surface dynamic processes. The deposition of a monolayer of adsorbate molecules onto the surface allows a new interface to be created. Monitoring the evolution of this surface during deposition provides information about both the substrate surface and the adsorba te covered surface; a theoretical framework has been outlined to show how the sources of anisotropy from multiple thin film layers combine to give a RAS signal. Azimuth dependent RAS (ADRAS) is known to provide information on surface symmetry and can be used to determine molecular orientation. There are also a number of other angles which affect the RA spectrum from a sample. A tilted molecule causes a breakdown in surface symmetry; this work shows how such an effect can be observed.

O palmito pode ser obtido a partir de várias espécies de palmeiras. Devido à alta taxa de exploração das palmeiras do gênero Euterpe e ao seu baixo poder de regeneração, no mercado consumidor há falta de produto de boa qualidade. Palmeiras mais precoces e que produzam bom palmito têm sido pesquisadas, uma delas é a pupunha (Bactris gasipaes), nativa da Amazônia que apresenta características de precocidade, rusticidade e perfilhamento, com palmito de ótima qualidade, diferindo dos demais pelo sabor adocicado e a coloração amarelada. O seu cultivo pode ser feito em grande parte do território brasileiro. A porção comestível do palmito de pupunha é dividida em três partes: a basal ou caulinar (coração), a apical, e a central ou foliar (creme ou tolete). O comércio de palmito privilegia a parte central da palmeira, vendendo o palmito basal como subproduto. O presente estudo tem como objetivo demonstrar a equivalência da qualidade do palmito basal e do foliar de pupunha, priorizando-se o tratamento adicional com ácido acético, que mascara o seu sabor adocicado, comparado com o ácido cítrico, largamente utilizado nas indústrias. As amostras de palmito de pupunha foram cultivadas em área experimental pertencente a ESALQ/USP; para o processamento foram cortadas 120 palmeiras em março de 2007. Foram analisadas características físicas, químicas, bioquímicas e sensoriais do palmito basal e foliar de pupunha em seis períodos de armazenamento (1, 15, 30, 60, 90, 120 dias). O controle das operações durante o processamento foi eficiente, pois o peso e o preenchimento dos vidros não variaram entre as unidades. Durante o período de armazenamento a coloração amarelada dos palmitos basal e foliar de pupunha se manteve constante. Embora as enzimas polifenoloxidase e peroxidase tenham sido detectadas nas análises bioquímicas, seus valores foram baixos, e como a coloração foi a mesma durante o armazenamento, considera-se que as enzimas foram inativadas. A composição centesimal das amostras (umidade, proteína, matéria graxa, fração cinza, fibras e carboidratos) indicou que ambos os produtos possuem as mesmas características, as quais se assemelham muito à da palmeira juçara. A análise sensorial não mostrou diferença significativa entre as amostras, porém as notas mais baixas foram atribuídas às conservas acidificadas com ácido acético. Com relação à freqüência de consumo, observou-se que o palmito de pupunha é pouco utilizado na alimentação humana, sendo a resposta às vezes predominante. Os resultados mostraram que o palmito basal e o foliar de pupunha têm as mesmas características físicas, químicas e sensoriais, indicando que o primeiro também pode ser comercializado como palmito de primeira qualidade; o período de armazenamento não alterou as principais características dos produtos. / The palm can be obtained from several palms trees. Besides of high rate of exploration of Euterpe palms trees and his low regeneration power, there is a lack of product in the consumer market. More precocious palms trees and which produce good palm heart have been investigated, one of them is the peach palm (Bactris gasipaes), native of Amazon region that presents characteristics of precociousness, rusticity and tillering with palm heart with good quality, differing of others for the slightly sweet taste and the yellowed coloration. His cultivation can be done in great part of the Brazilian territory. The edible portion of the palm is divided in three parts: basic one or caulinar (heart), apical and central or foliaceous (cream or thole). The commerce of palm privileges the central part of the palm tree, selling heart as by-product. The aim of this study was to demonstrate the equivalence of the quality of heart and thole of peach palm, acidified with citric acid, widely used in the industries, and with acetic acid that masks the slightly sweet taste. The samples of peach palm were cultivated in experimental area of ESALQ/USP and for the processing 120 palms trees were cut in march of 2007. Heart and thole of the palm were analysed by physical, chemical, biochemical and sensorial characteristics for six periods of storage (1, 15, 30, 60, 90, 120 days). The control of the operations on the processing was efficient, since the weight and the filling out from the glasses did not vary between the unities. During the period of storage the coloration of the tholes and hearts of palm peach was yellowed, characteristic that remained constant. Even though the enzymes polyphenol oxidase and peroxidase have appeared in the biochemical analyses, its values were low, and the coloration was the same during the storage. The centesimal composition of the samples (humidity, protein, oily matter, ash, fibers and carbohydrates) indicated heart and thole of peach palm have the same characteristics, which liken very much to that of the palm tree Euterpe edulis. The sensory analysis did not show significant difference between the samples, however the lowest notes were attributed to the pickles acidified with acetic acid. Regarding the frequency of consumption, it was noticed that the palm heart of peach palm is little used in the feeding of people, being the answer \"sometimes\" the one that had major constancy. Data showed that heart and the thole of peach palm have the same physical, chemical and sensory characteristics, indicating that the first one also can be marketed like palm heart of first quality; the period of storage did not change principal characteristics of the products.

O processamento térmico de alimentos visa garantir qualidade e inocuidade pela inativação de micro-organismos e enzimas. Geralmente ocorre sobreprocessamento, levando à perda de características nutricionais e sensoriais e à elevação de custos operacionais. Foi desenvolvida a modelagem matemática (modelos térmico, mássico, hidráulico e reativo) de um equipamento bitubular para o processamento térmico contínuo de um alimento líquido homogêneo em regime laminar difusivo, para determinação das distribuições de temperatura e letalidade. No modelo foram incorporados parâmetros para quantificar os efeitos das difusividades térmica e mássica efetivas na direção radial ao escoamento. O modelo contempla três seções: aquecimento; tubo de retenção e resfriamento, em que as seções de aquecimento e resfriamento são trocadores de calor modulares. Foram considerados os seguintes volumes de controle: alimento, tubo interno, fluido de utilidade, tubo externo, isolamento térmico e ar ambiente. Balanços diferenciais de energia e massa foram aplicados para modelar as trocas térmicas e a distribuição de micro-organismos, enzimas ou nutrientes. Condições de contorno foram aplicadas para manter a continuidade entre as seções e módulos. O modelo foi resolvido através do método de diferenças finitas, discretizando as componentes axiais e radiais. No estudo de caso foram feitas simulações para o processamento térmico de suco de amora, quantificando os efeitos dos parâmetros difusivos e das variáveis de processo sobre os atributos de qualidade nutricional (antocianina) e qualidade microbiológica (levedura). Na validação dos modelos térmico e mássico os efeitos de mistura e difusão na direção radial foram quantificados através do ajuste da condutividade térmica efetiva e número de Peclet modificado. Utilizou-se um pasteurizador em escala laboratorial e os fluidos: mistura glicerina/água 80% (newtoniano) e solução de CMC 1% (pseudoplástico) nas vazões de 10 a 50 L/h. Os resultados indicam que o modelo proposto representou satisfatoriamente as distribuições de temperaturas, letalidade e comportamento experimental com reduzida complexidade computacional. / The thermal processing ensures quality and safety by inactivation of micro-organisms and enzymes. Generally, over-processing occurs, resulting in sensorial and nutritional losses and operating costs increase. A mathematical model (thermal, mass, hydraulic and reactive) of a double-pipe pasteurizer has developed for the continuous thermal processing of a liquid food in laminar diffusive regime, to obtain the temperature and lethality distributions. Parameters to quantify the effects of thermal and mass effective diffusivities in the radial direction were incorporated in the model. The model comprises three zones: heating; holding tube and cooling, where the heating and cooling zones are modular double-pipe heat exchangers. The following control volumes were considered: food, inner tube, utility fluid, outer tube, thermal insulation and ambient air. Energy and mass differential balances were used for modeling the heat transfer and the destruction of micro-organisms, enzymes or nutrients. Boundary conditions were applied to maintain the continuity between zones and modules. The finite difference method was used to discretize the model in the axial and radial directions. A simulation study case for blueberry juice thermal processing was made, analyzing the effects of the diffusive parameters and processing variables of the thermal treatment in the nutritional quality (anthocyanin) and microbiological quality (yeasts) attributes. In the validations of the heat and mass models, the mixture and diffusive effects in the radial direction were quantified by adjusting the heat conductivity and the modified Peclet number. A laboratory scale pasteurizer was used with the following fluids: glycerin/water mixture 80% (newtonian) and CMC 1% solution (pseudoplastic) in flows rates between 10 and 50 L/h. The obtained results indicate that the proposed model successfully represented the temperature and lethality distributions and experimental behavior with reduced computational complexity.