O deslocamento de elétrons em gases pode ser caracterizado por grandezas macroscópicas tais como a velocidade de arrastamento, taxa de ionização, primeiro coeficiente de Townsend e os coeficientes de difusão longitudinal e transversal, que são denominados de parâmetros de transporte. Esses parâmetros são importantes já que permitem a validação das secções de choque de colisões de elétrons com as moléculas do gás, contribuem com informações para modelos de descargas automantidas e são importantes para o desenvolvimento de novos detectores gasosos. Neste trabalho são apresentados os resultados de velocidade de arrastamento (W), taxa de ionização (Ri) e do primeiro coeficiente Townsend de ionização (α), para o isobutano e n-butano em função do campo elétrico reduzido efetivo no intervalo de 130 a 180 Td, obtidos utilizando a técnica de Townsend pulsada. Em nosso aparato, os elétrons primários são gerados a partir da incidência no catodo de um curto pulso de laser e são acelerados em direção ao anodo por meio de um campo elétrico uniforme. O sinal elétrico proveniente do deslocamento desses elétrons é digitalizado por um osciloscópio e a partir do ajuste de uma função modelo à forma do sinal elétrico, determinam-se os parâmetros de transporte. Os resultados obtidos para o isobutano e n-butano foram comparados com os valores da simulação Magboltz 2-versão 8.6 em razão da escassez de dados na literatura para esses gases na região de campo elétrico reduzido estudada. / The electron swarm can be characterized by macroscopic quantities such as the drift velocity, ionization rate, first Townsend ionization coefficient and the longitudinal and transverse diffusion coefficients, so called transport parameters. These parameters are important since they allow the validation of electron collisional cross section with gas molecules, contribute for self-sustained discharge models and are important for gaseous detectors development. In the present work the results of electron drift velocity (W), ionization rate (Ri) and first Townsend coefficient (α) as a function of the reduced electric field for isobutane and n-butane by the means of pulsed Townsend technique are presented. In our experimental setup, the primary electrons are liberated by the irradiation of a short laser pulse at the cathode and are accelerated towards the anode through a uniform electric field. The electron movements induce signals that are digitalized and the fitting of a model function to their waveforms provides the transport parameters. The results obtained for isobutane and n-butane were compared with Magboltz 2-version 8.6 values, since there are few data in the literature for these gases for effective reduced electric field ranging from 130 to 180 Td.

O deslocamento de elétrons em gases pode ser caracterizado por grandezas macroscópicas tais como a velocidade de arrastamento, taxa de ionização, primeiro coeficiente de Townsend e os coeficientes de difusão longitudinal e transversal, que são denominados de parâmetros de transporte. Esses parâmetros são importantes já que permitem a validação das secções de choque de colisões de elétrons com as moléculas do gás, contribuem com informações para modelos de descargas automantidas e são importantes para o desenvolvimento de novos detectores gasosos. Neste trabalho são apresentados os resultados de velocidade de arrastamento (W), taxa de ionização (Ri) e do primeiro coeficiente Townsend de ionização (α), para o isobutano e n-butano em função do campo elétrico reduzido efetivo no intervalo de 130 a 180 Td, obtidos utilizando a técnica de Townsend pulsada. Em nosso aparato, os elétrons primários são gerados a partir da incidência no catodo de um curto pulso de laser e são acelerados em direção ao anodo por meio de um campo elétrico uniforme. O sinal elétrico proveniente do deslocamento desses elétrons é digitalizado por um osciloscópio e a partir do ajuste de uma função modelo à forma do sinal elétrico, determinam-se os parâmetros de transporte. Os resultados obtidos para o isobutano e n-butano foram comparados com os valores da simulação Magboltz 2-versão 8.6 em razão da escassez de dados na literatura para esses gases na região de campo elétrico reduzido estudada. / The electron swarm can be characterized by macroscopic quantities such as the drift velocity, ionization rate, first Townsend ionization coefficient and the longitudinal and transverse diffusion coefficients, so called transport parameters. These parameters are important since they allow the validation of electron collisional cross section with gas molecules, contribute for self-sustained discharge models and are important for gaseous detectors development. In the present work the results of electron drift velocity (W), ionization rate (Ri) and first Townsend coefficient (α) as a function of the reduced electric field for isobutane and n-butane by the means of pulsed Townsend technique are presented. In our experimental setup, the primary electrons are liberated by the irradiation of a short laser pulse at the cathode and are accelerated towards the anode through a uniform electric field. The electron movements induce signals that are digitalized and the fitting of a model function to their waveforms provides the transport parameters. The results obtained for isobutane and n-butane were compared with Magboltz 2-version 8.6 values, since there are few data in the literature for these gases for effective reduced electric field ranging from 130 to 180 Td.

The goal of this project was to understand and model the performance of hybrid inorganic-organic membranes under realistic operating conditions for hydrocarbon gas/vapor separation, using butane isomers as the model vapors and a hybrid membrane of 6FDA-DAM-5A as an advanced separation system. To achieve the set goal, three objectives were laid out. The first objective was to determine the factors affecting separation performance in dense neat polymer. One main concern was plasticization. High temperature annealing has been reported as an effect means of suppressing plasticization. A study on the effect of annealing temperature was performed by analyzing data acquired via sorption and permeation measurements. Based on the findings from this study, a suitable annealing temperature was determined. Another factor studied was the effect of operating temperature. In deciding a suitable operating temperature, factors such as its possible effect on plasticization as well as reducing heating/cooling cost in industrial application were considered. Based on the knowledge that industrial applications of this membrane would involve mixture separation, the second objective was to understand and model the complexity of a mixed gas system. This was investigated via permeation measurements using three feed compositions. An interesting transport behavior was observed in the mixed gas system, which to the best of our knowledge, has not been observed in other mixed gas systems involving smaller penetrants. This mixed gas transport behavior presented a challenge in predictability using well-established transport models. Two hypotheses were made to explain the observed transport behavior, which led to the development of a new model termed the HHF model and the introduction of a fitting parameter termed the CAUFFV fit. Both the HHF model and CAUFFV fit showed better agreement with experimental data than the well-established mixed gas transport model. The final objective was to explore the use of mixed matrix membranes as a means of improving the separation performance of this system. A major challenge with the fabrication of good mixed matrix membranes was the adhesion of the zeolite particle with the polymer. This was addressed via sieve surface modification through a Grignard treatment process. Although a Grignard treatment procedure existed, there was a challenge of reproducibility of the treatment. This challenge was addressed by exploring the relationship between the sieves and the solvent used in the treatment, and taking advantage of this relationship in the Grignard treatment process. This study helped identify a suitable solvent, which allowed for successful and reproducible treatment of commercial LTA sieves; however, treatment of lab-made sieves continues to prove challenging. Based on improved understanding of the Grignard treatment reaction mechanism, modifications were made to the existing Grignard treatment procedure, resulting in the introduction of a "simplified" Grignard treatment procedure. The new procedure requires less control over the reaction process, thus making it more attractive for industrial application. Permeation measurements were made using mixed matrix membranes in both single and mixed gas systems. Selectivity enhancements were observed under both single and mixed gas systems using sieve loadings of 25 and 30wt%. The Maxwell model was used to make predictions of mixed matrix membrane performance. Although the experimental results were not in exact agreement with Maxwell predictions, the observed selectivity enhancement was very encouraging and shows potential for future application. Recommendations were made for future study of this system.

In this study, we investigated the molecular characteristics of hydrates which were synthesized from gas mixtures containing the two isomers of butane, or the pentane isomers neopentane and isopentane, in excess methane. Thereto various techniques, including Raman spectroscopy, powder and single crystal X-ray diffraction and 13C NMR spectroscopy were employed. It turned out that shape and conformation of the guest molecule and hydrate structure both influence each other. In case of the mixed butane hydrate it could be confirmed that n-butane is enclathrated in its gauche conformation. This was verified by Raman spectroscopy, single crystal X-ray diffraction and calculated data. While isopentane is known as a structure H former, our results from powder X-ray diffraction, 13C NMR and ab initio calculations show that it can be also incorporated into structure II when the hydrate is formed from a neopentane/isopentane/methane gas mixture.

Made available in DSpace on 2014-10-09T12:41:47Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:26Z (GMT). No. of bitstreams: 0 / Materiais poliméricos (plásticos e borrachas) abrangem uma proporção continuamente crescente de resíduos urbanos e industriais descartados em aterros, seus impactos no meio ambiente são cada vez mais preocupantes. A implementação de novas tecnologias em prol da redução dos resíduos poliméricos, aceitáveis do ponto de vista ambiental e a um custo eficaz, provou ser um grande problema, face às complexidades inerentes para a reutilização dos polímeros. A radiação ionizante tem capacidade para alterar a estrutura e propriedades dos materiais poliméricos. As borrachas butílicas e halobutílicas têm sido usadas em larga escala, numa variedade de aplicações tais como partes de pneus e artefatos diversos. O principal efeito do fóton de alta energia, como raios gama nas borrachas butílicas e butílicas halogenadas é a geração de radicais livres, acompanhada por mudanças nas propriedades mecânicas. O objetivo deste trabalho é desenvolver processos de degradação controlada (desvulcanização) de borrachas butílicas e halobutílicas (cloro e bromo), de modo a caracterizar sua disponibilidade para transformação e alteração de suas propriedades. Os resultados experimentais obtidos mostraramm que as borrachas butílica e halobutílicas irradiadas a 25 kGy e posteriormente cisalhadas podem ser usadas como ponto de partida para misturas com borracha virgem. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Microdosímetros gasosos geralmente empregam uma mistura gasosa equivalente ao tecido humano mole (Tissue-equivalent Gas TEG), composta de um hidrocarboneto, dióxido de carbono e nitrogênio, de forma que o poder de freamento na mistura e no tecido sejam semelhantes. Entretanto, independentemente do hidrocarboneto adotado, dados tanto teóricos como experimentais do primeiro coeficiente de Townsend de ionização (α) nestas misturas são raros, ainda que a primeira TEG, cujo metano é o gás majoritário, tenha sido proposta em 1956 por Rossi e Failla e continue sendo amplamente utilizada. Neste trabalho, dados do parâmetro α em TEGs baseadas no metano (CH4 64,4%, CO2 32,4% e N2 3,2%) e nos isômeros do butano (C4H10 51,4%, CO2 42,3% e N2 6,3%) são apresentados pela primeira vez em geometria planar para a faixa de campo elétrico normalizado pela densidade do gás (E/N) entre 100 290 Td (1 Td = 10-21 V.m2). O método de medidas adotado baseia-se na técnica de Townsend pulsada, onde o primeiro coeficiente de Townsend pode ser determinando comparando a corrente elétrica no regime de avalanche e a corrente de ionização primária gerada pela incidência de um feixe de laser de nitrogênio em um eletrodo metálico (catodo) de uma câmara de geometria planar, sendo o anodo um eletrodo de alta resistividade (ρ=2×1010Ω.m). O aparato experimental, até então operado apenas em pressão atmosférica, foi modificado para também trabalhar em baixa pressão (120 hPa), de modo a aumentar a faixa de E/N investigada. A validação do método e das alterações do sistema de detecção foi realizada utilizando os três gases componentes das TEGs cujos parâmetros de transporte são amplamente estudados: o nitrogênio, o dióxido de carbono e o metano. Observou-se que o parâmetro na TEG com metano assemelha-se com os valores determinados para o metano puro. Na TEG baseada no isobutano, ele é compatível com o primeiro coeficiente de Townsend do dióxido de carbono para campos acima de 170 Td. Já o parâmetro na mistura com n-butano é intermediário entre os valores obtidos para o dióxido de carbono e o nitrogênio. Os resultados experimentais, disponíveis em forma tabular, foram comparados com os simulados utilizando o programa Magboltz 2, evidenciando boa concordância dentro da incerteza experimental. / Gaseous microdosimeters usually employ a Tissue-equivalent Gas (TEG), made of a hydrocarbon, carbon dioxide and nitrogen, in order to make similar the stopping power in this mixture and in the human soft tissue. Notwithstanding, regardless the chosen hydrocarbon, both theoretical and experimental data on the first Townsend ionization coefficient (α) in this mixtures are rare, even though the first TEG, which methane is the most abundant gas, was proposed in 1956 by Rossi and Failla and it has been widely employed since then. In this work, data on the parameter α in TEGs based on methane (CH4 64.4%, CO2 32.4%, and N2 3.2%) and butanes isomers (C4H10 51.4%, CO2 42.3% e N2 6.3%) are presented for the first time in planar geometry in the gas density-normalized electric field (E/N) range between 100 290 Td (1 Td = 10-21 V.m2). The adopted method is based on the Pulsed Townsend Technique, where the first Townsend coefficient can be determined by comparing the electric current in the avalanche mode and the primary ionization current, produced by an nitrogen laser beam incidence in a metallic electrode (cathode) of a parallel plate chamber, which the anode is a resistive electrode (ρ=2×1010Ω.m). The experimental setup, previously operated only at atmospheric pressure, was adapted to work also at low pressure (120 hPa), in order to increase the investigated E/N range. The validation of both method and detection system modifications was made by employing three TEGs components, nitrogen, carbon dioxide and methane, whose transport parameters are extensively studied. The parameter in the methane-based TEG follows the behavior observed in pure methane. In the isobutane-based TEG, it is compatible with the first Townsend coefficient in carbon dioxide for E/N above 170 Td. The parameter in the n-butane-based TEG lies between the obtained values of in carbon dioxide and nitrogen. The experimental results, included in tabular form, agree with those from Magboltz 2 simulations within the experimental uncertainties.

Microdosímetros gasosos geralmente empregam uma mistura gasosa equivalente ao tecido humano mole (Tissue-equivalent Gas TEG), composta de um hidrocarboneto, dióxido de carbono e nitrogênio, de forma que o poder de freamento na mistura e no tecido sejam semelhantes. Entretanto, independentemente do hidrocarboneto adotado, dados tanto teóricos como experimentais do primeiro coeficiente de Townsend de ionização (α) nestas misturas são raros, ainda que a primeira TEG, cujo metano é o gás majoritário, tenha sido proposta em 1956 por Rossi e Failla e continue sendo amplamente utilizada. Neste trabalho, dados do parâmetro α em TEGs baseadas no metano (CH4 64,4%, CO2 32,4% e N2 3,2%) e nos isômeros do butano (C4H10 51,4%, CO2 42,3% e N2 6,3%) são apresentados pela primeira vez em geometria planar para a faixa de campo elétrico normalizado pela densidade do gás (E/N) entre 100 290 Td (1 Td = 10-21 V.m2). O método de medidas adotado baseia-se na técnica de Townsend pulsada, onde o primeiro coeficiente de Townsend pode ser determinando comparando a corrente elétrica no regime de avalanche e a corrente de ionização primária gerada pela incidência de um feixe de laser de nitrogênio em um eletrodo metálico (catodo) de uma câmara de geometria planar, sendo o anodo um eletrodo de alta resistividade (ρ=2×1010Ω.m). O aparato experimental, até então operado apenas em pressão atmosférica, foi modificado para também trabalhar em baixa pressão (120 hPa), de modo a aumentar a faixa de E/N investigada. A validação do método e das alterações do sistema de detecção foi realizada utilizando os três gases componentes das TEGs cujos parâmetros de transporte são amplamente estudados: o nitrogênio, o dióxido de carbono e o metano. Observou-se que o parâmetro na TEG com metano assemelha-se com os valores determinados para o metano puro. Na TEG baseada no isobutano, ele é compatível com o primeiro coeficiente de Townsend do dióxido de carbono para campos acima de 170 Td. Já o parâmetro na mistura com n-butano é intermediário entre os valores obtidos para o dióxido de carbono e o nitrogênio. Os resultados experimentais, disponíveis em forma tabular, foram comparados com os simulados utilizando o programa Magboltz 2, evidenciando boa concordância dentro da incerteza experimental. / Gaseous microdosimeters usually employ a Tissue-equivalent Gas (TEG), made of a hydrocarbon, carbon dioxide and nitrogen, in order to make similar the stopping power in this mixture and in the human soft tissue. Notwithstanding, regardless the chosen hydrocarbon, both theoretical and experimental data on the first Townsend ionization coefficient (α) in this mixtures are rare, even though the first TEG, which methane is the most abundant gas, was proposed in 1956 by Rossi and Failla and it has been widely employed since then. In this work, data on the parameter α in TEGs based on methane (CH4 64.4%, CO2 32.4%, and N2 3.2%) and butanes isomers (C4H10 51.4%, CO2 42.3% e N2 6.3%) are presented for the first time in planar geometry in the gas density-normalized electric field (E/N) range between 100 290 Td (1 Td = 10-21 V.m2). The adopted method is based on the Pulsed Townsend Technique, where the first Townsend coefficient can be determined by comparing the electric current in the avalanche mode and the primary ionization current, produced by an nitrogen laser beam incidence in a metallic electrode (cathode) of a parallel plate chamber, which the anode is a resistive electrode (ρ=2×1010Ω.m). The experimental setup, previously operated only at atmospheric pressure, was adapted to work also at low pressure (120 hPa), in order to increase the investigated E/N range. The validation of both method and detection system modifications was made by employing three TEGs components, nitrogen, carbon dioxide and methane, whose transport parameters are extensively studied. The parameter in the methane-based TEG follows the behavior observed in pure methane. In the isobutane-based TEG, it is compatible with the first Townsend coefficient in carbon dioxide for E/N above 170 Td. The parameter in the n-butane-based TEG lies between the obtained values of in carbon dioxide and nitrogen. The experimental results, included in tabular form, agree with those from Magboltz 2 simulations within the experimental uncertainties.

Dans les gisements, en cours de production ou dans les conduites de transport, les gaz naturels se trouvent fréquemment au contact d'une phase aqueuse. Les conditions sont telles que les pressions peuvent atteindre de très haute valeur dans une large gamme de températures. La connaissance du comportement des systèmes "eau-hydrocarbures" est donc essentielle à la profession profession pétrolière ainsi que celles des systèmes "eau-hydrocarbures-inhibiteur thermodynamique " pour lesquelles les données sont rares. Des mesures de teneur en eau ont été réalisées dans les phases vapeurs de différents systèmes d'hydrocarbures: méthane et éthane, et dans un mélange d'hydrocarbures gazeux (méthane 94%, éthane 4%, n-butane 2%) dans des conditions proches de la formation d'hydrates (de 258.15 à 313.15 K et jusqu'à 34.5 MPa) en présence ou non d'inhibiteurs tels que le méthanol ou l'éthylène glycol. Des mesures de solubilités de gaz des principaux constituants du gaz naturel ont été effectuées dans une large gamme de pressions et de températures. Ces mesures ont été effectuées avec deux techniques expérimentales, une technique statique-analytique avec échantillonnage de phases et une technique synthétique avec cellule à volume variable. Pour réaliser le traitement des données un logiciel a été développé, ce logiciel a permis l'ajustement et le traitement des résultats expérimentaux.

En cas de perte de confinement (rupture d'un piquage) sur un réservoir de gaz liquéfié sous pression, il y aurait un écoulement diphasique (liquide-vapeur) critique. L'objet de ce mémoire est de valider les modèles décrivant ces écoulements vis à vis de differents fluides (eau, R11, méthanol, acétate d'éthyle, butane pur, butane commercial). Une installation expérimentale de taille pilote a été réalisée. Dans la conduite d'essai (L=535 mm, D=8 mm) l'écoulement est quasi-stationnaire, critique, adiabatique et reproductible. L'écart à la saturation en amont est mesuré à 25 mbar près, ce qui permet de mesurer le débit à saturation à +/- 12%. Une représentation adimensionnelle des résultats montre que la pression en amont réduite est le paramètre prépondérant. Ce résultat nouveau semble indiquer qu'un modèle peut être validé avec un minimum de fluides, pour peu que l'on raisonne en coordonnées réduites. Les modèles homogènes hors équilibre thermodynamique (DEM, HRM) sont les plus précis. HRM est le plus adapté au calcul du débit de fuite, même si il peut devenir tres majorant aux pressions réduites élevées. Aucun modèle ne prend correctement en compte la sensibilité du débit à la pression réduite. Ce biais peut avoir au moins deux origines : une influence non négligeable du glissement entre phases ou une cinétique de vaporisation perfectible. Ecrire un bilan énergetique sur la phase vapeur semble physiquement pertinent pour exprimer la cinétique de vaporisation. Mais il est également impératif de quantifier la nucléation.

Mixed matrix hollow fiber membranes maintain the ease of processing polymers while enhancing the separation performance of the pure polymer due to inclusion of molecular sieve filler particles. This work shows the development process of high loading mixed matrix hollow fiber membranes for butane isomer separation, from material selection and engineering of polymer-sieve interfacial adhesion to mixed matrix hollow fiber spinning. The matching of gas transport properties in polymer and zeolite is critical for forming successful mixed matrix membranes. The nC4 permeability in glassy commercial polymers such as Ultem® and Matrimid® is too low (< 0.1 Barrer) for commercial application. A group of fluorinated (6FDA) polyimides, with high nC4 permeability and nC4/iC4 selectivity, are selected as the polymer matrix. No glassy polymers can possibly match the high permeable MFI to make mixed matrix membranes with selectivity enhancement for C4s separation. Zeolite 5A, which has a nC4 permeability (~3 Barrer) and nC4/iC4 selectivity (essentially ∞), matches well with the 6FDA polymers. A 24% nC4/iC4 selectivity enhancement was achieved in mixed matrix membranes containing 6FDA-DAM and 25 wt% treated 5A particles. A more promising mixed matrix membrane contains 6FDA-DAM-DABA matrix and 5A, because of a better match of gas transport properties in polymer and zeolite. Dual layer hollow fibers, with cellulose acetate core layer and sheath layers of 6FDA polyimides, were successfully fabricated. Successive engineering of the 6FDA sheath layer and the dense skin is needed for the challenging C4s separation, which is extremely sensitive to the integrity of the dense skin layer. The delamination-free, macrovoid-free dual layer hollow fiber membranes provide the solution for the expensive 6FDA polyimides spinning. Mixed matrix hollow fiber membranes are spun base on the platform of 6FDA/Cellulose acetate dual layer hollow fibers. Preliminary results suggest that high loading mixed matrix hollow fiber membranes for C4s is feasible. Following research is needed on the fiber spinning with well treated zeolite 5A nanoparticles. The key aspect of this research is elucidating the three-step (sol-gel-precipitation) mechanism of sol-gel-Grignard treatment, based on which further controlling of Mg(OH)2 whisker morphologies is possible. A Mg(OH)2 nucleation process promoted by acid species is proposed to explain the heterogeneous Mg(OH)2 growing process. Different acid species were tried: 1) HCl solution, 2) AlClx species generated by dealumination process and 3) AlCl3 supported on zeolite surfaces. Acids introduced through HCl solution and dealumination are effective on commercial 5A particles to generate Mg(OH)2 whiskers in the sol-gel-Grignard treatment. Supported AlCl3 is effective on both commercial and synthesized 5A particles (150 nm-1 µm) during the sol-gel-Grignard treatment, in terms of promoting heterogeneous Mg(OH)2 whiskers formation. But the byproduct of Al(OH)3 layer separates the Mg(OH)2 whiskers from zeolite surface, and leads to undesirable morphologies for polymer-zeolite interfacial adhesion. The elucidation of sol-gel-Grignard mechanism and importance of zeolite surface acidity on Mg(OH)2 formation, builds a solid foundation for future development towards ''universal'' method of growing Mg(OH)2 whiskers on zeolite surfaces.