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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
21

"Diferentes métodos de otimização da polimerização de resinas compostas de uso direto" / Different methods in optimizing the polymerization of direct resin composites

Ana Maria Lima Almeida 09 December 2005 (has links)
Este trabalho avaliou a influência da densidade de energia da pré-cura, e de diferentes tratamentos pós-cura na otimização das propriedades físicas (Resistência à Flexão e Dureza Knoop) de resinas compostas diretas, visando a possibilidade de indicação para restauraçoes indiretas. Foram usadas as resinas diretas Fillmagic, Concept, Glacier, Z100, Masterfill e W3D Master e as indiretas Solidex e Belleglass HP como controle. Para cada resina direta foram confeccionados 60 espécimes em barra (10x2x2mm), 30 irradiados em uma face e 30 nas duas faces (30 espécimes = 10 controle, 10 autoclave e 10 forno de luz). Para as resinas indiretas foram preparados 10 espécimes conforme processamento de seus fabricantes. 380 espécimes foram submetidos ao ensaio de resistência à flexão (Kratos). De cada condição experimental, 10 fragmentos foram usados para ensaio de microdureza Knoop (Shimadzu HMV-2). A análise de variância e o teste de Tukey demonstraram significância para resistência à flexão nos fatores Resina (p<0,001) e Tratamento (p=0,001) e na interação Resina x Tratamento (p=0,001). Para a microdureza Knoop os três fatores e as interações foram significantes: Resina (p=0,001); Face (p=0,001) Tratamento (p=0,017); Resina x Face (p=0,001); Resina x Tratamento (p=0,007); Face x Tratamento (p=0,001) e Resina x Face x Tratamento (p=0,024). A maior média de cada resina direta, independente da condição experimental, foi comparada às médias das resinas indiretas. Os resultados apontam que na resistência à flexão (Z100 = W3D = Fillmagic = Glacier) e (Z100 > Masterfill > Belleglass HP > Concept > Solidex). Na Dureza Knoop (Z100 > Belleglass HP, Fillmagic, W3D, Concept, Glacier, Masterfill e Solidex). Conclusão: as propriedades físicas (resistência à flexão e dureza Knoop) não são obstáculos na indicação de resinas compostas de uso direto para restaurações indiretas / This study evaluated the influence of pre-cure energy density, and additional post-cure treatments in optimizing the physical properties (Flexural strength and Knoop microhardness) of direct resin composites with the aim at allowing their use for indirect restorations. Direct resin composites evaluated were Fillmagic, Concept, Glacier, Z100, Masterfill and W3D Master; indirect composites were Solidex and Belleglass HP. Sixty bar-shaped specimens (10x2x2mm) were prepared for each material, so that 30 of them were light-cured by one surface and 30 on both surfaces. From the 30 specimens of each group, 10 were control, 10 were submitted to additional autoclave and 10 to light oven treatment. Ten specimens were prepared with each indirect composite following the manufactures’ recommendations. The 380 specimens were submitted to flexural strength test (Kratos universal testing machine), and values obtained at fracture were reported. After that, 10 fragments were chosen for each experimental condition and assessed for Knoop microhardness (Shimadzu HMV-2). Data were submitted to analysis of variance and Tukey’s test at p<0.05. Statistically significant differences were found among flexural strength results regarding composite materials (p<0.001), treatments (p<0.001) and interactions (composite x treatment, p<0.001). Regarding Knoop microhardness, both three factors and their interactions were also significant: composite (p<0.001), surface (p<0.001) and treatment (p<0.017), composite x surface (p<0.001), composite treatment (p<0.001), surface x treatment (p<0.001) and composite x surface x treatment (p<0.024). The highest mean value for each direct composite, regardless of the experimental condition, was compared to the mean values obtained for the indirect materials. With regard to flexural strength, comparisons point out that Z100 = W3D = Fillmagic = Glacier and Z100 > Masterfill > Belleglass HP > Concept > Solidex, whereas for Knoop microhardness Z100 > Belleglass HP, Fillmagic, W3D, Concept, Glacier, Masterfill and Solidex. Conclusion: considering the physical properties evaluated in this study, they are not an obstacle to the indication of direct composites for indirect restorations
22

Proposta metodológica e avaliação da inativação de endósporos de Geobacillus stearothermophilus no tratamento de resíduos de serviços de saúde por autoclavagem / Methodological proposal and evaluation of the inactivation of endospores of Geobacillus stearothermophilus in the treatment of healthcare waste by autoclaving

Amanda Borges Ribeiro de Oliveira 27 January 2017 (has links)
Resíduos de Serviços de Saúde (RSS), ainda que tratados e dispostos em aterros sanitários, podem ser causas de impactos ambientais por apresentarem algum indicador de periculosidade. Segundo o apêndice IV da Resolução da Agência Nacional de Vigilância Sanitária (Anvisa) RDC nº 306/2004, para as tecnologias de tratamento desses resíduos é necessário que se atinja pelo menos o Nível III de inativação microbiana. Perante a ausência de dados na literatura que revelassem o tempo de exposição, temperatura e pressão ideais para a inativação microbiana no tratamento de RSS por autoclavagem e se a fração ocupada dos resíduos na autoclave poderia interferir na eficiência da desinfecção definiu-se o objetivo do trabalho para otimização do processo. Para os testes foram utilizados endósporos de Geobacillus stearothermophilus como bioindicadores e instalados cinco termopares na autoclave para aferição da temperatura dentro de todo o espaço da câmara. O RSS foi sintetizado diante das caracterizações como composição gravimétrica, distribuição granulométrica, densidade específica aparente, massa específica aparente e teor de umidade. Apresentou-se uma proposta metodológica para a avaliação do tratamento de RSS frente às dificuldades encontradas. Realizou-se ensaios com 116ºC, 125ºC e 134ºC, observando a fração de inativação em seis tempos de exposição diferentes. Sabendo-se que é padronizada em estabelecimentos de saúde a temperatura ideal para esterilização de materiais de 121ºC, apesar de não terem sido encontrados trabalhos científicos que comprovem a eficiência da esterilização nessa circunstância, foram realizados testes a 50 e 60 minutos de exposição para avaliar essa condição. Inoculou-se 106 endósporos nas amostras e a recuperação foi feita com filtração após a lavagem dos resíduos, sendo realizada a técnica de pour plate para contagem das unidades formadoras de colônias (UFC). O mesmo procedimento foi feito com a amostra retirada da autoclave. A fração de inativação dos endósporos atingiu 100% no tempo de 30 minutos de exposição à temperatura máxima de 134ºC e pressão absoluta de 2,3 kgf/cm2, resultado obtido através da relação do número de micro-organismos recuperados considerados como inoculados e o número de micro-organismos sobreviventes ao tratamento. A 121ºC houve recuperação de UFC após tratamento. A fração de ocupação não foi um fator delimitante para a inativação de endósporos, pois a temperatura se manteve a mesma independentemente da quantidade de resíduo submetido à autoclavagem. Um outro objetivo era avaliar experimentalmente a reprodução dos micro-organismos frente às condições operacionais de autoclavagem e do tempo de permanência do rejeito em condições ambientais. Esse estudo comprovou que a inativação nessas condições otimizadas esteriliza o resíduo, sendo que nenhum micro-organismo voltou a se reproduzir após dias expostos em temperatura ambiente, ou seja, não haveria riscos de contaminação em aterro sanitário quando depositados os rejeitos. Ter encontrado essas condições ideais e avaliado o processo de autoclavagem pode significar um grande avanço nas próprias unidades de tratamento, que terão um parâmetro estabelecido para trabalho. / Healthcare waste, even when treated and disposed of in landfills, can be causes of environmental impacts because they present some hazard indicator. According to appendix IV of Resolution of the National Health Surveillance Agency of Brazil (Anvisa) RDC nº 306/2004, for technologies of healthcare waste treatment, it is necessary to achieve at least Level III of microbial inactivation. The purpose of this research to optimize the process was defined taking into account the absence of data in the literature that revealed the optimal exposure time, temperature and pressure for microbial inactivation through the healthcare treatment by autoclaving and whether the fraction occupied by waste in the autoclave could interfere with the effectiveness of the disinfection. For the tests, endospores of Geobacillus stearothermophilus were used as bioindicators and five thermocouples were installed in the autoclave for temperature measurement throughout the chamber space. The healthcare waste was synthesized by characterizations such as gravimetric composition, granulometric distribution, apparent specific density, apparent specific mass and moisture content. A methodological proposal for the evaluation of waste treatment was introduced taking into consideration the difficulties encountered. Tests were performed at 116ºC, 125ºC and 134ºC, observing the fraction of inactivation at six different exposure times. Since the sterilization of materials at 121ºC is standardized in health establishments, even though no scientific studies were found to prove the sterilization efficiency in these conditions, tests were performed at 50 and 60 minutes of exposure to evaluate this condition. The concentration of 106 endospores were inoculated in the samples and the recovery was done with filtration after washing the waste, and the \"pour plate\" technique was used to count the colony forming units. The same procedure was done with the sample removed from the autoclave. The inactivation fraction of the endospores reached 100% in the time of 30 minutes of exposure to the maximum temperature of 134ºC and absolute pressure of 2.3 kgf/cm2, a result obtained by the ratio of the number of recovered microorganisms considered as inoculated and the number of microorganisms surviving the treatment. At 121ºC there was recovery of colony forming units after treatment. The occupation fraction was not a limiting factor for the inactivation of endospores, since the temperature remained the same regardless of the amount of waste submitted to autoclaving. Another objective was to experimentally evaluate the reproduction of the microorganisms taking into consideration the operational conditions of autoclaving and the amount of time that the waste remains under environmental conditions. This study proved that the inactivation under these optimized conditions sterilizes the waste, and that no microorganism would reproduce again after days exposed at room temperature, therefore, there would be no risk of contamination in a landfill when the waste is deposited. Having found these ideal conditions and evaluated the autoclaving process can mean a major advance in the treatment units themselves, which will have an established parameter for work.
23

Étude et simulation numérique d’un procédé de cuisson rapide pour l’élaboration de matériaux composites à matrice thermodurcissable

Xu, Chan 19 December 2013 (has links)
L’élaboration de composites en cuisson autoclave est un procédé bien maîtrisé maisles cycles de cuisson peuvent être très longs, en particulier dans le cas de préimprégnésaéronautiques. L’objectif de ce travail de thèse est d’étudier la possibilité de diminuer letemps des cycles de polymérisation pour la fabrication de composites stratifiés minces àl’aide d’un procédé de cuisson rapide. Des essais de caractérisation ont permis de définirles grandeurs thermodynamiques du préimprégné carbone/époxy qui a servi de base ànotre étude ainsi que les paramètres du modèle cinétique de la résine. Une simulationnumérique du procédé de cuisson, basée sur une modélisation des couplages desphénomènes chimiques (polymérisation de la résine), thermiques (transferts de chaleuravec prise en compte de l’exothermie de la réaction) et mécaniques (formation decontraintes et déformations résiduelles) induits par le procédé, a été développée dans lebut d’optimiser les cycles de polymérisation. La caractérisation mécanique des matériauxélaborés à partir d’un dispositif de cuisson rapide mis au point au Laboratoire a permis dedémontrer que nous n’avions pas de pertes de caractéristiques par rapport aux piècesélaborées en autoclave. / The autoclave polymerization is the bottleneck of the production flux for largepublic parts, hence the speedy polymerization process emerges to improve the productionratio. The objective is to study the possibility of reducing the cycle time of polymerizationfor the production of thin composite laminates using a fast cure process out-of-autoclave.Specific or standard chemical and mechanical characterization tests had been designed inorder to capture the expected characteristics for the model simulation and validate thesimulation results. According to the values obtained, an analysis based on the finiteelement technique is developed to simulate the speedy curing process of epoxy resincomposite. The analysis relates the cure temperature to the thermal, chemical and physicalprocesses occurring in the thin composite part during cure. Included in the analysis are theeffects such as the heat generation due to exothermic chemical reactions. For a specifiedcure cycle, the model could be used to calculate the temperature distribution, the degree ofcure of the resin inside the composite part as well as predict the residual curing stressesand the strains of the cured composite parts.Keywords :
24

Effects of in vitro gastrointestinal digestion on extractability of nutrient and bioactive compounds from wheat bran

Golom, Sirak Tsegai 06 January 2012 (has links)
A static in vitro digestion method was developed as a strategy to understand the effects of modelled digestion on the solubility of nutrients and selected bioactive compounds of autoclaved and untreated wheat bran. Brans from common soft, hard, and durum wheats were evaluated. Results indicated that the in vitro digestion protocol was suitable and effective. Effects of gastrointestinal simulation were considerably larger than gastric digestion alone. Digestibility of the brans ranged from 28.1 to 47.9%. Digestibility of bran minerals, starch and protein was substantial compared to lesser, but still significant, effects on fibre. Fibre solubility was significantly enhanced due to autoclaving. Total phenolic content, free radical scavenging and metal chelation activity were all substantially increased in soluble digests. Yields of these factors indicated that digestion of wheat bran releases ample levels of antioxidants that would be available for absorption in the small intestine to promote beneficial health effects.
25

Effects of in vitro gastrointestinal digestion on extractability of nutrient and bioactive compounds from wheat bran

Golom, Sirak Tsegai 06 January 2012 (has links)
A static in vitro digestion method was developed as a strategy to understand the effects of modelled digestion on the solubility of nutrients and selected bioactive compounds of autoclaved and untreated wheat bran. Brans from common soft, hard, and durum wheats were evaluated. Results indicated that the in vitro digestion protocol was suitable and effective. Effects of gastrointestinal simulation were considerably larger than gastric digestion alone. Digestibility of the brans ranged from 28.1 to 47.9%. Digestibility of bran minerals, starch and protein was substantial compared to lesser, but still significant, effects on fibre. Fibre solubility was significantly enhanced due to autoclaving. Total phenolic content, free radical scavenging and metal chelation activity were all substantially increased in soluble digests. Yields of these factors indicated that digestion of wheat bran releases ample levels of antioxidants that would be available for absorption in the small intestine to promote beneficial health effects.
26

Modelagem e simulação de reatores autoclave para produção de PEBD

Silva, Juliana Lopes January 2012 (has links)
O polietileno de baixa densidade (PEBD) é uma resina termoplástica fabricada através de processos a altas pressões, com reatores do tipo autoclave ou tubular. O cenário atual é de crescente demanda por PEBD produzido a custos competitivos, através de plantas de alto desempenho e capacidade, de modo que o desenvolvimento de processo e produto torna-se um fator chave para as empresas produtoras, sendo os simuladores de processo ferramentas de grande importância para esta finalidade. O objetivo desta dissertação é a implementação de um modelo matemático que represente reatores autoclave de produção de PEBD e a avaliação de sua capacidade preditiva através da comparação dos seus resultados numéricos com dados de literatura e dados de uma planta industrial. O modelo desenvolvido deverá ser capaz de descrever o comportamento do reator, através de seu perfil de temperatura, vazões de iniciador e conversão, e de algumas das principais propriedades do polímero produzido, através de suas massas molares médias. A modelagem dos reatores é composta de compartimentos genéricos de tanque agitado, implementada no simulador dinâmico de processos EMSO, utilizando cinética de literatura. Os balanços de massa e energia foram resolvidos simultaneamente para a obtenção de condições de operação factíveis, sendo necessário o uso de controladores para manter o ponto de operação no estado estacionário desejado. As propriedades são obtidas através da utilização do método dos momentos. É considerada no modelo a possibilidade de formação de duas fases. Parâmetros do modelo cinético e de mistura são ajustados para os dados de planta através de uma rotina de estimação, considerando duas resinas com características de processo e produto distintas. As predições do modelo para perfil de temperatura, vazões de iniciador, conversão e massas molares médias mostraram boa concordância com os dados de literatura e com os dados de planta industrial, para as duas resinas consideradas. / The low density polyethylene (LDPE) is a thermoplastic resin manufactured by high pressure processes, with autoclave or tubular type reactors. The present scenario is of growing demand for LDPE produced at competitive costs, through high performance and capacity plants, so that the process and product development becomes a key factor for the producers, and process simulators are high importance tools for this purpose. The objective of this dissertation is the implementation of a mathematical model which represents autoclave reactors for LDPE production and the evaluation of its predictive capacity through the comparison between their numerical results with literature data and with an industrial plant data. The model developed should be able to describe the reactor behavior, through its temperature profile, initiator flows and conversion, and the behavior of some of the main properties of the produced polymer, through their average molecular weights. The reactors modeling is composed of stirred tank generic compartments, implemented in the process dynamic simulator EMSO, using literature kinetics. The mass and energy balances were solved simultaneously in order to obtain feasible operating conditions, which requires the use of controllers to maintain the operating point at the desired steady state. The properties are obtained through the use of the method of moments. It is considered in the model the possibility of formation of two phases. Kinetics and mixture model parameters are fitted to the plant data through an estimation routine, considering two grades with distinct process and product characteristics. The model predictions for temperature profile, initiator flows, conversion and average molecular weights presented good agreement with the literature data and with the industrial plant data, for the two considered grades.
27

Estudo da transferência de calor transiente por agitação interminente em embalagens

Gumerato, Homero Ferracini [UNESP] 17 December 2004 (has links) (PDF)
Made available in DSpace on 2014-06-11T19:31:35Z (GMT). No. of bitstreams: 0 Previous issue date: 2004-12-17Bitstream added on 2014-06-13T20:42:04Z : No. of bitstreams: 1 gumerato_hf_dr_botfca.pdf: 735190 bytes, checksum: f1454b535f3ff650b6cf9e96b355f222 (MD5) / Universidade Estadual Paulista (UNESP) / Foi estudado processo de transferência de calor transiente por agitação intermitente em embalagens, visando a conservação de alimentos por tratamento térmico com processo mais econômico e que mantivesse a qualidade de alimentícios. Objetivou-se o desenvolvimento de um processo baseado em agitação intermitente de embalagens para aplicação em pasteurização ou esterilização. O estudo da transferência de calor transiente em sistema com movimento linear alternado foi realizado em embalagens metálicas, em 4 meios simulantes de diferentes viscosidades e massas específicas: 3 óleos orgânicos e água. Foram combinados efeitos de 5 tratamentos, sendo: meio simulante (4 níveis), espaços livres (3 níveis), freqüência de agitação (4 níveis), amplitude de agitação (2 níveis) e posições das latas (4 níveis). Os ensaios de aquecimento e resfriamento foram feitos em tanque com água a temperatura de 98°C e 17 a 20°C, respectivamente. Com os dados de penetração de calor em cada experimento foram calculados os parâmetros de penetração de calor fh, jh, fc e jc. Os resultados foram modelados utilizando-se grupos de números adimensionais e foram expressos em Nusselt, Prandtl, Reynolds e... / Transient heat transfer was studied by intermittent shake in cans with linear system, in order to preserve food by heat thermally processed, applying process more economic, and keeping high food quality. The objective was developing a process based on intermittent shake in cans to applying in pasteurisation or sterilisation process. Heat transfer was carried out in metallic cans filled four different simulate medium: water, Neutral oil 150 and 500 and Bright stock oil. It was arranged five treatments: simulate media (4 levels), head space (3 levels), agitation frequency (4 levels), length of agitation (2 levels) and cans positions (4 levels). The tests were carried out in hot water tank at temperature 98°C and cool at 17~20°C. Heat transfer parameters (fh, jh, fc and jc) for each test was calculated. Results were expressed applying dimensionless numbers equations for heat and cool. Data were computed pplying dimensionless numbers and were assign as Nusselt, Prandtl, Reynolds and trigonometric functions. Results obtained from linear shake system were compared with end-over-end agitation, and shake linear system showed more efficient. Shake linear system can be applied in pasteurisation or static retorts with simple internal structure fits...(Complete abstract, click electronic access below)
28

Modelagem e simulação de reatores autoclave para produção de PEBD

Silva, Juliana Lopes January 2012 (has links)
O polietileno de baixa densidade (PEBD) é uma resina termoplástica fabricada através de processos a altas pressões, com reatores do tipo autoclave ou tubular. O cenário atual é de crescente demanda por PEBD produzido a custos competitivos, através de plantas de alto desempenho e capacidade, de modo que o desenvolvimento de processo e produto torna-se um fator chave para as empresas produtoras, sendo os simuladores de processo ferramentas de grande importância para esta finalidade. O objetivo desta dissertação é a implementação de um modelo matemático que represente reatores autoclave de produção de PEBD e a avaliação de sua capacidade preditiva através da comparação dos seus resultados numéricos com dados de literatura e dados de uma planta industrial. O modelo desenvolvido deverá ser capaz de descrever o comportamento do reator, através de seu perfil de temperatura, vazões de iniciador e conversão, e de algumas das principais propriedades do polímero produzido, através de suas massas molares médias. A modelagem dos reatores é composta de compartimentos genéricos de tanque agitado, implementada no simulador dinâmico de processos EMSO, utilizando cinética de literatura. Os balanços de massa e energia foram resolvidos simultaneamente para a obtenção de condições de operação factíveis, sendo necessário o uso de controladores para manter o ponto de operação no estado estacionário desejado. As propriedades são obtidas através da utilização do método dos momentos. É considerada no modelo a possibilidade de formação de duas fases. Parâmetros do modelo cinético e de mistura são ajustados para os dados de planta através de uma rotina de estimação, considerando duas resinas com características de processo e produto distintas. As predições do modelo para perfil de temperatura, vazões de iniciador, conversão e massas molares médias mostraram boa concordância com os dados de literatura e com os dados de planta industrial, para as duas resinas consideradas. / The low density polyethylene (LDPE) is a thermoplastic resin manufactured by high pressure processes, with autoclave or tubular type reactors. The present scenario is of growing demand for LDPE produced at competitive costs, through high performance and capacity plants, so that the process and product development becomes a key factor for the producers, and process simulators are high importance tools for this purpose. The objective of this dissertation is the implementation of a mathematical model which represents autoclave reactors for LDPE production and the evaluation of its predictive capacity through the comparison between their numerical results with literature data and with an industrial plant data. The model developed should be able to describe the reactor behavior, through its temperature profile, initiator flows and conversion, and the behavior of some of the main properties of the produced polymer, through their average molecular weights. The reactors modeling is composed of stirred tank generic compartments, implemented in the process dynamic simulator EMSO, using literature kinetics. The mass and energy balances were solved simultaneously in order to obtain feasible operating conditions, which requires the use of controllers to maintain the operating point at the desired steady state. The properties are obtained through the use of the method of moments. It is considered in the model the possibility of formation of two phases. Kinetics and mixture model parameters are fitted to the plant data through an estimation routine, considering two grades with distinct process and product characteristics. The model predictions for temperature profile, initiator flows, conversion and average molecular weights presented good agreement with the literature data and with the industrial plant data, for the two considered grades.
29

Exploring metal hydrides using autoclave and multi-anvil hydrogenations

January 2013 (has links)
abstract: Metal hydride materials have been intensively studied for hydrogen storage applications. In addition to potential hydrogen economy applications, metal hydrides offer a wide variety of other interesting properties. For example, hydrogen-dominant materials, which are hydrides with the highest hydrogen content for a particular metal/semimetal composition, are predicted to display high-temperature superconductivity. On the other side of the spectrum are hydrides with small amounts of hydrogen (0.1 - 1 at.%) that are investigated as viable magnetic, thermoelectric or semiconducting materials. Research of metal hydride materials is generally important to gain fundamental understanding of metal-hydrogen interactions in materials. Hydrogenation of Zintl phases, which are defined as compounds between an active metal (alkali, alkaline earth, rare earth) and a p-block metal/semimetal, were attempted by a hot sintering method utilizing an autoclave loaded with gaseous hydrogen (< 9 MPa). Hydride formation competes with oxidative decomposition of a Zintl phase. The oxidative decomposition, which leads to a mixture of binary active metal hydride and p-block element, was observed for investigated aluminum (Al) and gallium (Ga) containing Zintl phases. However, a new phase Li2Al was discovered when Zintl phase precursors were synthesized. Using the single crystal x-ray diffraction (SCXRD), the Li2Al was found to crystallize in an orthorhombic unit cell (Cmcm) with the lattice parameters a = 4.6404(8) &Aring;, b = 9.719(2) &Aring;, and c = 4.4764(8) &Aring;. Increased demand for materials with improved properties necessitates the exploration of alternative synthesis methods. Conventional metal hydride synthesis methods, like ball-milling and autoclave technique, are not responding to the demands of finding new materials. A viable alternative synthesis method is the application of high pressure for the preparation of hydrogen-dominant materials. Extreme pressures in the gigapascal ranges can open access to new metal hydrides with novel structures and properties, because of the drastically increased chemical potential of hydrogen. Pressures up to 10 GPa can be easily achieved using the multi-anvil (MA) hydrogenations while maintaining sufficient sample volume for structure and property characterization. Gigapascal MA hydrogenations using ammonia borane (BH3NH3) as an internal hydrogen source were employed in the search for new hydrogen-dominant materials. Ammonia borane has high gravimetric volume of hydrogen, and additionally the thermally activated decomposition at high pressures lead to a complete hydrogen release at reasonably low temperature. These properties make ammonia borane a desired hydrogen source material. The missing member Li2PtH6 of the series of A2PtH6 compounds (A = Na to Cs) was accessed by employing MA technique. As the known heavier analogs, the Li2PtH6 also crystallizes in a cubic K2PtCl6-type structure with a cell edge length of 6.7681(3) &Aring;. Further gigapascal hydrogenations afforded the compounds K2SiH6 and Rb2SiH6 which are isostructural to Li2PtH6. The cubic K2SiH6 and Rb2SiH6 are built from unique hypervalent SiH62- entities with the lattice parameters of 7.8425(9) and 8.1572(4) &Aring;, respectively. Spectroscopic analysis of hexasilicides confirmed the presence of hypervalent bonding. The Si-H stretching frequencies at 1550 cm-1 appeared considerably decreased in comparison with a normal-valent (2e2c) Si-H stretching frequencies in SiH4 at around 2200 cm-1. However, the observed stretching modes in hypervalent hexasilicides were in a reasonable agreement with Ph3SiH2- (1520 cm-1) where the hydrogen has the axial (3e4c bonded) position in the trigoal bipyramidal environment. / Dissertation/Thesis / Ph.D. Chemistry 2013
30

Modelagem e simulação de reatores autoclave para produção de PEBD

Silva, Juliana Lopes January 2012 (has links)
O polietileno de baixa densidade (PEBD) é uma resina termoplástica fabricada através de processos a altas pressões, com reatores do tipo autoclave ou tubular. O cenário atual é de crescente demanda por PEBD produzido a custos competitivos, através de plantas de alto desempenho e capacidade, de modo que o desenvolvimento de processo e produto torna-se um fator chave para as empresas produtoras, sendo os simuladores de processo ferramentas de grande importância para esta finalidade. O objetivo desta dissertação é a implementação de um modelo matemático que represente reatores autoclave de produção de PEBD e a avaliação de sua capacidade preditiva através da comparação dos seus resultados numéricos com dados de literatura e dados de uma planta industrial. O modelo desenvolvido deverá ser capaz de descrever o comportamento do reator, através de seu perfil de temperatura, vazões de iniciador e conversão, e de algumas das principais propriedades do polímero produzido, através de suas massas molares médias. A modelagem dos reatores é composta de compartimentos genéricos de tanque agitado, implementada no simulador dinâmico de processos EMSO, utilizando cinética de literatura. Os balanços de massa e energia foram resolvidos simultaneamente para a obtenção de condições de operação factíveis, sendo necessário o uso de controladores para manter o ponto de operação no estado estacionário desejado. As propriedades são obtidas através da utilização do método dos momentos. É considerada no modelo a possibilidade de formação de duas fases. Parâmetros do modelo cinético e de mistura são ajustados para os dados de planta através de uma rotina de estimação, considerando duas resinas com características de processo e produto distintas. As predições do modelo para perfil de temperatura, vazões de iniciador, conversão e massas molares médias mostraram boa concordância com os dados de literatura e com os dados de planta industrial, para as duas resinas consideradas. / The low density polyethylene (LDPE) is a thermoplastic resin manufactured by high pressure processes, with autoclave or tubular type reactors. The present scenario is of growing demand for LDPE produced at competitive costs, through high performance and capacity plants, so that the process and product development becomes a key factor for the producers, and process simulators are high importance tools for this purpose. The objective of this dissertation is the implementation of a mathematical model which represents autoclave reactors for LDPE production and the evaluation of its predictive capacity through the comparison between their numerical results with literature data and with an industrial plant data. The model developed should be able to describe the reactor behavior, through its temperature profile, initiator flows and conversion, and the behavior of some of the main properties of the produced polymer, through their average molecular weights. The reactors modeling is composed of stirred tank generic compartments, implemented in the process dynamic simulator EMSO, using literature kinetics. The mass and energy balances were solved simultaneously in order to obtain feasible operating conditions, which requires the use of controllers to maintain the operating point at the desired steady state. The properties are obtained through the use of the method of moments. It is considered in the model the possibility of formation of two phases. Kinetics and mixture model parameters are fitted to the plant data through an estimation routine, considering two grades with distinct process and product characteristics. The model predictions for temperature profile, initiator flows, conversion and average molecular weights presented good agreement with the literature data and with the industrial plant data, for the two considered grades.

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