Made available in DSpace on 2014-12-17T15:01:46Z (GMT). No. of bitstreams: 1 JuceliaMER.pdf: 2171315 bytes, checksum: 6d1b358ee82a3e95a8b3fb30782bdf76 (MD5) Previous issue date: 2005-12-15 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Polyurethanes are very versatile macromolecular materials that can be used in the form of powders, adhesives and elastomers. As a consequence, they constitute important subject for research as well as outstanding materials used in several manufacturing processes. In addition to the search for new polyurethanes, the kinetics control during its preparation is a very important topic, mainly if the polyurethane is obtained via bulk polymerization. The work in thesis was directed towards this subject, particularly the synthesis of polyurethanes based castor oil and isophorone diisocianate. As a first step castor oil characterized using the following analytical methods: iodine index, saponification index, refraction index, humidity content and infrared absorption spectroscopy (FTIR). As a second step, test specimens of these polyurethanes were obtained via bulk polymerization and were submitted to swelling experiments with different solvents. From these experiments, the Hildebrand parameter was determined for this material. Finally, bulk polymerization was carried out in a differential scanning calorimetry (DSC) equipment, using different heating rates, at two conditions: without catalyst and with dibutyltin dilaurate (DBTDL) as catalyst. The DSC curves were adjusted to a kinetic model, using the isoconversional method, indicating the autocatalytic effect characteristic of this class of polymerization reaction / Poliuretanas s?o pol?meros de grande versatilidade, podendo ser usadas na forma de p?s, adesivos ou elast?meros. Por este motivo, as poliuretanas s?o amplamente pesquisadas e utilizadas nas ind?strias. Paralelamente ? busca por novas poliuretanas, ? importante o controle cin?tico durante sua obten??o, principalmente se estas s?o obtidas via polimeriza??o em massa. O trabalho desta tese aborda este problema, especificamente no caso da obten??o de poliuretanas derivadas do ?leo de mamona e diisocianato de isoforona. Para isto, primeiramente o ?leo de mamona foi caracterizado atrav?s dos seguintes m?todos anal?ticos: ?ndice de iodo, ?ndice de saponifica??o, ?ndice de refra??o, ?ndice de hidroxila, teor de umidade e espectroscopia de absor??o na regi?o do infravermelho (FTIR). Como segundo passo, os corpos de prova dessas poliuretanas foram obtidos atrav?s de polimeriza??o em massa e submetidos a ensaios de inchamento com diferentes solventes. A partir destes ensaios o par?metro de Hildebrand foi determinado para este material. Finalmente, a polimeriza??o em massa desse material foi executada em equipamento de calorimetria explorat?ria diferencial (DSC) a diferentes taxas de aquecimento sob duas condi??es: sem catalisador e com o catalisador, dibutil-dilaurato de estanho (DBTDL). As curvas de DSC foram ajustadas a modelos cin?ticos, usando o m?todo isoconversional, caracterizando o car?ter autocatal?tico da forma??o de poliuretanas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The enthalpy of fusion of a perfect crystal of cellulose acetate was calculated in this thesis. In order to do so, cellulose samples from different sources were acetylated through the heterogenous acetilation methodology. The cellulose acetate samples were characterized by differencial scanning calorimetry (DSC) and by wide angle X-ray diffraction (WAXD). The X-ray diffractograms were deconvoluted into halos and peaks using the Pseudo-Voigt peak function of program Origin® 7.0. Two hypotheses were proposed in order to fit the deconvolution patterns into the two-phase model. In the first, the amorphous regions of the material was considered to be represented by the area of the halo located at 21º and the crystalline area by the maxima at 8º, 11º, 13º and 16º. In the second hypothesis, the amorphous region was considered to be represented by the areas of the maxima at 11º and 21º, and the crystalline region by the maxima at 8º, 13º and 16º. The WAXD crystallinities of the samples were then calculated from these values. The first hypothesis was ignored for presenting a very high crystallinity value for a sample that did not present an enthalpy of fusion. The second hypothesis was used, but the linear regression that defined the relationship between the enthalpy of fusion and the crystallinity of the materials was forced through zero. Through this relationship, the enthalpy of fusion of a perfect crystal of cellulose acetate was calculated to be 58.8 J/g. / A entalpia de fusão de um cristal perfeito de acetato de celulose foi calculada nessa dissertação. Para isso, amostras de celulose de diferentes origens foram acetiladas através do método de acetilação heterogêneo. As amostras de acetato de celulose foram caracterizadas por calorimetria diferencial de varredura (DSC) e difração de raios-X a alto ângulo (WAXD). Os difratogramas de raios-X foram deconvoluídos em halos e picos utilizando a função pico Pseudo-Voigt do programa Origin® 7.0. Duas hipóteses foram propostas para que as deconvoluções estivessem de acordo com o modelo de duas fases. Na primeira, foi considerado que a parte amorfa do material era representada pela área do halo localizado em 21º e a área cristalina pela soma das áreas dos máximos em 8º, 11º, 13º e 16º. Na segunda hipótese, a região amorfa foi considerada como sendo representada pelas áreas dos máximos em 11º e 21º, e a região cristalina pelos máximos em 8º, 13º e 16º. A partir desses valores se calculou a cristalinidade das amostras de acetato de celulose via WAXD. A primeira hipótese foi desconsiderada por apresentar um valor muito alto de cristalinidade para uma amostra que não apresentou entalpia de fusão. A segunda hipótese foi utilizada, porém a regressão linear que definiu a relação entre a entalpia de fusão e cristalinidade dos materiais foi forçada a passar pela origem. Através dessa relação, calculou-se a entalpia de fusão de um cristal perfeito de acetato de celulose como sendo 58,8 J/g. / Mestre em Química

abstract: Alternative energy technologies must become more cost effective to achieve grid parity with fossil fuels. Dye sensitized solar cells (DSSCs) are an innovative third generation photovoltaic technology, which is demonstrating tremendous potential to become a revolutionary technology due to recent breakthroughs in cost of fabrication. The study here focused on quality improvement measures undertaken to improve fabrication of DSSCs and enhance process efficiency and effectiveness. Several quality improvement methods were implemented to optimize the seven step individual DSSC fabrication processes. Lean Manufacturing's 5S method successfully increased efficiency in all of the processes. Six Sigma's DMAIC methodology was used to identify and eliminate each of the root causes of defects in the critical titanium dioxide deposition process. These optimizations resulted with the following significant improvements in the production process: 1. fabrication time of the DSSCs was reduced by 54 %; 2. fabrication procedures were improved to the extent that all critical defects in the process were eliminated; 3. the quantity of functioning DSSCs fabricated was increased from 17 % to 90 %. / Dissertation/Thesis / M.S.Tech Technology 2012

O leite condensado é um produto amplamente estudado, sendo que os problemas de cristalização ao longo do processo constituem um dos aspectos de interesse quando se considera a produção em escala industrial. No entanto, não foram encontrados estudos que padronizassem técnicas de medida de tamanho de cristais e determinação da cristalinidade total em leite condensado. Este trabalho visa adaptar/desenvolver uma técnica especifica para análise de tamanho de cristais de lactose em leite condensado utilizando de microscopia juntamente com processamento e análise de imagem (software ImageJ). Além disso, acredita-se que o grau de cristalinidade possa se tornar um parâmetro de controle de qualidade em leites condensados, de modo que se propõe o estudo da viabilidade do uso de calorimetria exploratória diferencial para a determinação deste parâmetro. A técnica de processamento e análise de imagem mostrou-se confiável e permitiu realizar comparativo eficiente entre três marcas comerciais de leite condensado. Foi possível, mediante análise estatística, otimizar a metologia existente de preparação de lâminas visando reduzir o tempo e esforço da aplicação da técnica de acompanhamento de tamanho de cristais em ambiente industrial. Para o estudo da viabilidade do uso de analises térmicas para a determinação do grau de cristalinidade em leite condensado foram realizados estudos em térmicos simultâneos (DSC-TGA) e estudos de calorimetria exploratória diferencial em DSC e TMDSC em lactose p.a., sacarose p.a., misturas dos dois açúcares e em leite condensado. Na comparação das técnicas, observou-se que as três apresentam mesmo nível de precisão, porém exatidão distintas. A técnica de DSC foi a que permitiu obter maior definição dos picos identificados ao longo do termograma. Por outro lado, na técnica de MDSC, utilizando porta-amostras com furo, foi possível obter boa repetibilidade também com relação aos processos reversíveis e irreversíveis. A análise quantitativa de cristalinidade a partir de dados de calorimetria para misturas de sacarose e lactose é dificultada pela sobreposição dos picos dos diferentes processos térmicos sofridos pelos dois açúcares e pelo fato que foram encontrados indicativos de efeito sinergético na resposta térmica dos dois carboidratos quando em mistura. Assim como para as misturas de açúcares estudadas, não foi possível determinar o grau de cristalinidade em amostras de leite condensado. / Condensed milk is a widely studied product, given that the crystallization problems throughout the production process constitute one of the aspects of interest as far as the industrial scale production is concerned. However, studies that might enable standardized crystal size measurement techniques and crystallinity determination in condensed milk have not been found yet. This work aims at adapting/developing a specific technique for the analysis of lactose crystals size in condensed milk by using microscopy along with image analysis and processing (ImageJ software). Besides, it is believed that degree of crystallinity may become a quality control parameter in condensed milks, in such a way that it is proposed a viability study of the use of differential exploratory calorimetry for its determination. Processing technique and image analysis have demonstrated to be reliable and allowed to carry out efficient comparison between the three commercially available brands of condensed milk. It was possible, by means of statistical analysis, to optimize the existing thin plate preparation methodology with the aim of reducing time and strain of crystal size monitoring in industrial environment. In view of studying thermal analyses aiming at determining degree of crystallinity in condensed milk, studies in simultaneous thermal instruments (DSC-TGA) along with differential exploratory calorimetry in DSC and TMDSC were carried out in analytical grade sucrose and lactose, mixtures of both sugars and condensed milk. When comparing the techniques, one can observe that all three presented the same level of precision, but different accuracies. DSC technique was the one that allowed higher definition of identified peaks along the thermogram. On the other hand, in MDSC technique, using pierced sample holder, it was possible to obtain good repeatability even in regard to reversible and irreversible processes. Cristallinity quantitative analysis from calorimetry data for sucrose and lactose mixtures is hindered by the superposition of peaks from different thermal processes undergone by both sugars and by the fact that indicatives of synergistic effect were found in the thermal response of the above mentioned carbohydrates when mixed together. As it had occurred for the sugar mixtures studied, it was not possible to determine the degree of crystallinity in condensed milk samples.

Orientador: Daniel Barrera-Arellano / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-03T17:38:53Z (GMT). No. of bitstreams: 1 Vieira_ThaisMariaFerreiradeSouza_D.pdf: 1857639 bytes, checksum: 8162b6f98ed8403230373b00af16e8d5 (MD5) Previous issue date: 2003 / Resumo: As ceras possuem propriedades importantes para o uso nos setores alimentício, cosmético, de limpeza e polimento. O conhecimento de suas características é essencial para sua aplicação. A cera de cana-de-açúcar (Saccharum officinarum) extraída da torta de filtro, um resíduo da indústria sucro- lcooleira, pode ser uma alternativa às ceras de carnaúba, abelha e ceras sintéticas. Considerando a larga disponibilidade de torta de filtro nos países produtores de cana, o potencial de produção desta cera é bastante grande. Neste trabalho foram estudadas as etapas de extração e fracionamento de cera de cana-de-açúcar com solventes. Os rendimentos da extração de dois tipos de tortas filtro com hexano foram de 4,32 e 7,11% em cera bruta. Os índices analíticos apresentados pelas ceras purificadas de cana foram comparáveis aos das ceras comerciais de abelha e carnaúba. As ceras purificadas apresentaram alta pureza quanto à composição em classes de lipídios, observada pelas análises de DSC, cujas curvas de fusão e cristalização mostraram picos únicos e estreitos. As propriedades térmicas dessas ceras (temperatura de pico de fusão entre 80,9 e 81,7ºC) aproximaram-se das da cera de carnaúba (picos de fusão a 82,0 e 88,1ºC). Os ácidos graxos das ceras de cana foram principalmente os saturados de cadeia normal e longa, com uma predominância do ácido palmítico (C16:0) e octacosanóico (C28:0). As amostras de cera de cana apresentaram álcoois graxos saturados de 24 a 34 carbonos. O principal álcool graxo foi o octacosanol (C28H57OH), cujos teores variaram de 118,57 a 224,89 mg.g-1 / Abstract: Waxes have important specific properties for food and cosmetic uses, and for cleaning and polishing applications. The knowledge of the characteristics of waxes is essential for their application. Wax recovered from sugarcane (Saccharum officinarum) filter cake, a by-product of the sugar and alcohol industry, represents a potential alternative to carnauba, beeswax, and synthetic waxes, considering the enormous resources of raw material in sugarcane growing countries. Crude wax solvent extraction and fractionation were studied in this project. Two types of filter cake extracted with hexane yielded 4.32 and 7.11% crude sugarcane wax, respectively. Purified sugarcane waxes presented analytical indexes similar to those of commercial bee and carnauba waxes. Purified sugarcane wax appeared to be homogeneous in terms of composition, containing few lipid classes, as indicated by DSC analysis. Single narrow peaks were observed during melting and crystallization of these samples. The thermal properties of purified sugarcane wax (melting peak between 80.9 and 81.7ºC) closely resembled those of carnauba wax (melting peaks at 82.0 and 88.1ºC). Fatty acids of sugarcane waxes were mainly normal and long-chain saturated compounds, predominantly C16:0 (palmitic) and C28:0 (octacosanoic). Long-chain saturated fatty alcohols, ranging from C24 to C34, were observed in sugarcane wax samples, with a large redominance of octacosanol (C28H57OH). Octacosanol content ranged from 118,57 to 224,89 mg.g-1 / Doutorado / Doutor em Tecnologia de Alimentos

Glioblastoma multiform (GBM) is an aggressive primary brain tumour. Despite treatment advances in recent years, outcomes remain poor. Disease progression tends to occur adjacent to the original tumour or surgical resection bed, usually within the radiotherapy planning field. This local recurrence and progression is believed to be the result of invasive disease in the surrounding tissue at the time of diagnosis and treatment, which is not currently detectable by conventional non-invasive methods. A number of novel therapies are currently under development which target specific aspects of the tumour behaviour, to try and improve outcomes from this devastating disease. Imaging biomarkers are under development, therefore, in order to provide a non-invasive assessment of tumour extent and behaviour, to provide bespoke image-guided therapies, and detect recurrence or treatment failure at the earliest opportunity. These are also of value in the context of novel therapeutics, which may have a very specific affect on an aspect of tumour behaviour that is not readily apparent on standard clinical imaging. Key to the progression of GBM is the invasion into surrounding white matter. This is followed by a period of tumour growth and subsequent angiogenesis in which microvasculature is produce that is distinct from the highly regulated blood-brain barrier. This thesis covers the development of suite of advanced magnetic resonance imaging (MRI) techniques aimed at characterising those very traits of GBM responsible for the aggressiveness and treatment resistance. Repeatability studies are undertaken to determine the performance of the biomarkers in healthy tissues, and also in a range of gliomas. Dynamic Contrast Enhanced (DCE-) and dynamic susceptibility-enhanced (DSC-)MRI are used to provide estimates of perfusion and permeability in the tumour. In order to address the reasons behind preferential invasion of the corpus callosum, they are used in conjunction with ASL to non-invasively map perfusion territories and watershed regions in the brain through perfusion timing parameters. Diffusion Tensor Imaging (DTI) and quantitative magnetisation transfer (qMT) are used to provide complementary information about white matter integrity, in order to identify changes occurring with glioma invasion as early as possible and direct image-guided treatments at presentation. Their complementary nature is assessed by comparing the two parameters simultaneously in white matter. Additionally, one of the qMT parameters which may be related to tissue pH is shown to be sensitive and specific for the detection of high-grade tumour tissue. Finally, a novel multiparametric imaging biomarker is introduced. Tumour surface mapping assesses the boundary between the solid tumour and surrounding tissue in order to identify areas of potential aggressiveness and invasion. Multiple imaging parameters can be combined to improve specificity and sensitivity. Using the diffusion-weighted imaging parameter, mean diffusivity (MD - also referred to as the apparent diffusion coefficient (ADC)), it is shown to be predictive of clinical outcome in a retrospective and prospective study, while a multiparametric example is given indicating the utility as a predicative biomarker for regions of progression and recurrence, and as potential spatial discriminator for image-guided therapies.

This dissertation has two intersecting foci; firstly, the discovery of a new methodology for the growth of high surface area cuprous oxide (Cu2O) substrates. Secondly, the synthesis and characterization of electron-accepting molecules, and their incorporation into excitonic solar cells (XSCs) using the Cu2O substrates as electrodes. Increasing the surface area of the semiconductor creates more locations for charge transfer to occur thus increasing the overall efficiency of the device. Zinc oxide (ZnO) has been widely studied, and can be easily grown into many different films with high surface area morphologies. The ZnO films serve as sacrificial templates that allow us to electrochemically grow new semiconductors with the same high surface area morphologies but composed of a material having more desirable electronic properties. A polymer can be applied over the surface of the ZnO nanorod films before etching the ZnO with a weak acid, thereby leaving a polymer nanopore membrane. Cathodic electrodeposition of Cu2O into the membrane nanopores gives Cu2O nanorods. Electron-accepting dyes are designed with tethers that allow for direct attachment to metal oxide semiconductors. After soaking, the semiconductor is coated with a monolayer of a dye and then the coated semiconductor films were made into various dye-sensitized solar cells (DSCs). These cells were studied to determine the electron transport properties at the semiconductor/sensitizer/electrolyte interface.

In this diploma thesis, universal inverter was manufactured and successfully tested with DC, BLDC and AC motor. Inverter is composed of the power board for driving extralow voltage supplied electric motors (from +12V to +24V) and control board with microcontroller MC56F8257. There is also explained the principle of driving DC, BLDC and AC motor as well as description of the most frequently used peripherals and inverter. components

Presented master's thesis focuses on the study of hydration of selected biocolloid substances, specifically humic substances (humic acids and fulvic acids), hyaluronic acid with three different molecular weight, chitosan and dextran. Interaction of biocolloids with water was studied by different methods. The effect of solubility, structure, functional groups in molecule on sorption and hydration ability of these biocolloids was investigated. In the case of hyaluronan the influence of molecular weight was also study. Differential scanning calorimetry DSC and perfusion calorimetry give results of heat of hydration, enthalpies and temperature of crystallization and melting. Thermogravimetric analysis TGA was used to determine the original moisture content of the samples.

A drive design for an electric bike with brushed DC disk motor is proposed in this thesis. Especially the design of a DC/DC converter with DSC control is described. The converter can operate as step-down and step-up too. Minimum dimensions and sufficient power for riding without human assistance were the main demands on the design.