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This research investigates the effect of feed composition on the separation performance of pure polyethersulfone (PES) and different types of PES based mixed matrix membranes (MMMs) in order to develop high performing membranes for CO2/CH4 separation. MMMs were prepared by solvent evaporation method using PES as the polymer matrix with SAPO-34 particles as fillers, and 2-hydroxy 5-methyl aniline (HMA) as the low molecular weight additive. Four types of membranes were used throughout the study, namely pure PES membrane, PES/HMA (4, 10%w/w) membrane, PES/SAPO-34 (20%w/w) MMM, PES/SAPO-34 (20%w/w)/HMA (4, 10%w/w) MMM. The effect of CO2 composition on the performance of the membranes was investigated in detail with a wide feed composition range changing between 0 and 100%. In addition to separating CO2/CH4 binary gas mixtures, the separation performances of these membranes were determined by measuring single gas permeabilities at 35&ordm / C, with a feed pressure of 3 bar. Moreover, the membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermal gravimetric analyzer (TGA). The separation selectivities of all types of membranes generally observed to be independent of feed composition. The composition independency of these membranes eliminates the need of investigating at which feed gas composition the prepared membranes are best performing for practical applications. PES/SAPO-34/HMA MMMs with HMA loading of 10% and SAPO-34 loading of 20% demonstrated the highest separation selectivity of about 40, and the ideal selectivity of 44, among the used membranes.

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No. of bitstreams: 1 lucaswilmandasilvacrispim.pdf: 4368508 bytes, checksum: dd17a101d7a17f37da33d9d15bac1645 (MD5) Previous issue date: 2015-03-10 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Este estudo tem como objetivo a modelagem numérica do efeito de descarga elétrica em misturas de ar e metano, considerando um modelo bidimensional que envolvem transferência de calor e de massa, além de um submodelo discreto de distribuição da energia das colisões eletrônicas entre as diversas espécies presentes na mistura. O domínio foi dividido em duas regiões, com e sem descarga eletrônica. Para a região de descarga são considerados efeitos das colisões com elétrons, químicos e de transferência de calor e de massa, para a região externa a descarga são considerados efeitos químicos, de transferência de calor e de massa. Foram simuladas quatro configurações diferentes de descarga em mistura representando ar seco e uma simulação de descarga em misturas de ar com metano. Neste trabalho considera-se o ar como fluido incompressível e composto por diversas espécies. Para encontrar a solução aproximada do modelo foi aplicado o método das diferenças finitas em um meio heterogêneo, foram também utilizadas estratégias numéricas para a separação de determinados termos nas equações, e por fim a resolução destes termos foram obtidas através da ferramenta de análise de plasma zero dimensional, ZDPlasKin. No domínio do tempo, foi utilizado o método de Euler, um esquema numérico explicito. Utilizou-se uma configuração para a descarga eletrônica de 10% para o regime de trabalho, e foram analisados dois tipos de misturas gasosas, uma representando uma mistura de N2 _ O2, e outra representando uma mistura de metano e ar. Foram analisados resultados referentes ao perfil de temperatura no domínio em diferentes instantes de tempo, além de analisar a variação temporal em diversas espécies contidas nas misturas, em determinados pontos do domínio. Devido ao alto custo de resolução de determinados termos das equações, foi utilizada uma estratégia de paralelização do tipo Mestre-Escravo na API (Application Programming Interface) de programação paralela MPI (Message Passing Interface). Foi observado através dos resultados o aquecimento e a difusão do calor da região de descarga para a região externa, e a difusão de espécies excitadas geradas na região de descarga para a região externa. Conseguiu-se observar nos resultados o aquecimento da região externa devido a condução do calor e a difusão de espécies geradas na região de descarga que saem por difusão para região externa, e esta migração contribuiu para o aquecimento da região externa, uma vez que estas espécies tendem a relaxação na região externa a descarga. / This study aims the numerical modeling of electrical discharge in mixtures of air and methane, considering a two-dimensional model that involves a heat mass transfer, besides a discrete submodel of electronic distribution of collisions among several species in the mixture. The domain was divided into two regions, with and without discharge. The discharge region considers the effect of collisions with electrons, heat and mass transfer and chemical effects. Four simulations sets of discharge in mixture with dry air and another mixture with air and methane were executed. This study considers the air as incompressible formed by several species. To find the solution of the mathematical model, the finite difference method in a heterogeneous medium was applied; in addition, numerical techniques to split some operators of the equation were also adopted. Finally, the approximate solution of these models were obtained by a zero dimensional plasma analysis tool, ZDPlasKin. In the time domain, the Euler method, an explicit numerical scheme, was used. The electronic discharge was set 10% to the work scheme; and two types of gas mixture were analyzed, one representing a mixture of N2 _ O2 and another with methane and air. Results referring to the temperature profile in the domain in different time steps were analyzed, as well as the temporal variation of several species contained in the mixtures in some points of the domain. Due to the high computational cost demanded to solve some equation terms, a master-slave parallelization strategy through MPI (Message Passing Interface), a parallel programming API (Application Programming Interface) was used. The results ilustrated the heating and heat diffusion from discharge region to external region, and the diffusion of excited species generated from the discharge region to external region. The heating in external region occurred due to heat conduction and species diffusion generated in the discharge region (that diffunding through external region). This migration contributed to the heating of external region, since these species tending to de-excitation in region out of discharge.

Un gaz à l'intérieur d’un microsystème ou d’un milieu poreux est dans un état hors équilibre, car le libre parcours moyen des molécules est comparable à la dimension caractéristique du milieu. Ce même état degaz, appelé raréfié, se retrouve en haute altitude ou dans un équipement de vide à basse pression. Ces gaz raréfiés suivent des types d’écoulements qui peuvent être décrits par des modèles cinétiques dérivés de l'équation de Boltzmann. Dans ce travail nous présentons les principaux modèles et leurs mises en oeuvre numériquepour la simulation des écoulements de gaz raréfiés. Parmi les modèles utilisés nous présentons les deux modèles complets de l'équation de Boltzmann, le modèle de Shakhov(S-model) pour un gaz monoatomique et le modèle de McCormack pour un mélange de gaz toujours monoatomiques. La méthode des vitesses discrètes est utilisée pour la discrétisation numérique dans l'espace des vitesses moléculaires et le schéma de type TVD est mis en œuvre dans l'espace physique. L’aspect original de ce travail se situe sur les régimes transitoires et, en particuliersur les comportements non-stationnaires des transferts de chaleur et de masse. Cependant, pour certaines configurations nous considérons uniquement les conditions stationnaires des écoulements et un schéma implicite est développé afin de réduire le coût de calcul. En utilisant ces approches numériques, nous présentons les résultats pour plusieurs types d’écoulements non-stationnaires, de gaz raréfiés monoatomiqueset de mélanges binaires de gaz monoatomiques. / A gas inside the microsystems or the porous media is in its non-equilibrium state, due to the fact that the molecular mean free path is comparable to the characteristic dimension of the media. The same state of a gas, called rarefied, is found at high altitude or in the vacuum equipment working at low pressure. All these types of flow can be described by the kinetic models derived from the Boltzmann equation. This thesis presents the development of the numerical tools for the modeling and simulations of the rarefied gas flows. The two models of the full Boltzmann equation, the Shakhov model (S-model) for the single gas and the McCormack model for the gas mixture, are considered. The discrete velocity method is used to the numerical discretization in the molecular velocity space and the TVD-like scheme is implemented in the physical space. The main aspect of this work is centered around the transient properties of the gas flows and, especially, on the transient heat and mass transfer behaviors. However, for some configurations only steady-state solutions are considered and the implicit scheme is developed to reduce the computational cost. Using the proposed numerical approach several types of the transient rarefied single gas flows as well as the binary mixture of the monoatomic gases are studied.

To meet the continuously rising demand for natural resources and high-value compounds, the development of new and more efficient separation technologies is important from both an economic and environmental point of view. Moreover, the detailed knowledge of adsorption phenomena can be beneficial for the development of task-specific adsorbents for gas separation processes. However, new or supplementary measurement techniques are needed to broaden the understanding of the underlying molecular mechanisms and to characterize promising materials with a fast and reliable method. Raman spectroscopy holds the potential to advance the state-of-the-art in thermophysical property research for CCS technologies in multiple ways. It can not only be utilized for fundamental research on adsorption on quasi non-porous materials due to the possibility to monitor the composition of fluid mixtures but also for the characterization of newly developed porous adsorbents. In this context, Raman spectroscopy was explored in this work to characterize the sorption capacity of translucent porous materials and to investigate the underlying mechanisms that govern sorption processes.:1 Introduction 2 Motivation 3 Experimental Background 4 Adsorption on Quasi Non-Porous Materials 5 Adsorption on Translucent Porous Materials 6 Gas Solubility in Liquids 7 Conclusion and Outlook 8 References Appendix: A Determined Peak Intensities for Adsorption Measurements B Determined Peak Intensities for Solubility Measurements C Results for Absorption Measurements D Results for Solubility Measurements E Propagation of Error / Um den ständig steigenden Bedarf an natürlichen Ressourcen und hochwertigen Verbindungen zu decken, ist die Entwicklung neuer und effizienterer Trenntechnologien sowohl aus wirtschaftlicher als auch aus ökologischer Sicht wichtig. Darüber hinaus kann die detaillierte Kenntnis von Adsorptionsphänomenen für die Entwicklung aufgabenspezifischer Adsorbentien für Gastrennverfahren von Nutzen sein. Es werden jedoch neue oder ergänzende Messverfahren benötigt, um das Verständnis der zugrunde liegenden molekularen Mechanismen zu erweitern und vielversprechende Materialien mit einer schnellen und zuverlässigen Methode zu charakterisieren. Die Raman Spektroskopie hat das Potenzial, den aktuellen Stand der Technik bei der Erforschung thermophysikalischer Eigenschaften für CCS-Technologien in mehrfacher Hinsicht zu verbessern. Sie kann nicht nur für die Grundlagenforschung zur Adsorption an quasi nicht-porösen Materialien genutzt werden, da mit ihr Zusammensetzung von Fluidgemischen bestimmt werden kann, sondern auch für die Charakterisierung neu entwickelter poröser Adsorptionsmittel. In diesem Kontext wurde die Raman-Spektroskopie in dieser Arbeit eingesetzt, um die Sorptionskapazität von transluzenten porösen Materialien zu charakterisieren und die zugrundeliegenden Mechanismen zu untersuchen, welche die Sorptionsprozesse steuern.:1 Introduction 2 Motivation 3 Experimental Background 4 Adsorption on Quasi Non-Porous Materials 5 Adsorption on Translucent Porous Materials 6 Gas Solubility in Liquids 7 Conclusion and Outlook 8 References Appendix: A Determined Peak Intensities for Adsorption Measurements B Determined Peak Intensities for Solubility Measurements C Results for Absorption Measurements D Results for Solubility Measurements E Propagation of Error

Highly accurate analysis for the quantification of sulphur compounds and oxygenated volatile organic compounds are crucial for the adherence of the legislation in different environmental sectors. The sulphur compounds and oxygenated volatile organic compounds measurements are challenging, due to various factors such as molecules being adsorbed on the inner surfaces of cylinders. It is therefore important to produce accurate and reliable reference gas mixtures with mole fraction at ambient levels for the air quality monitoring and field of gas sensing in South Africa. The challenges in producing sulphur compounds and oxygenated volatile organic compounds reference gas mixtures are that the overall process from gravimetric preparation steps until the comparison analysis process and the stability of mixture in the gas cylinder, results in the large measurement uncertainties. In order to produce reference gas mixtures of the highest level, three important steps are followed: purity assessment of starting material, gravimetric preparation, and verification/validation of prepared gas mixtures. The purity analysis of high purity starting materials was determined using gas chromatography coupled with various detectors and Karl Fischer for determination of moisture content in high purity chemicals. The sulphur compounds and oxygenated volatile organic compounds to be developed in this study were hydrogen sulphide, sulphur dioxide, acetone, methanol, ethanol, isopropanol, and n-butanol. These components were produced following the International Organisation for Standardisation documents at mole fraction of 10 µmol/mol for sulphur compounds and 5 µmol/mol for oxygenated volatile organic compounds. The preparation of sulphur compounds reference gas mixtures was done with a static gravimetric method using a direct method where a target component was transferred directly into the cylinder. The preparation of oxygenated volatile organic compounds used an indirect method whereby a target liquid component from high purity chemicals was transferred into a cylinder using a gas-tight syringe.The comparison between the reference gas mixtures was validated using Non-Dispersive Ultra-Violet analysers (NDUV), gas chromatograph coupled with pulsed discharge helium ionisation detector (GC-PDHID, UV fluorescence analysers for sulphur compounds and gas chromatograph coupled with flame ionisation detector (GC-FID) for the oxygenated volatile organic compounds. A multi-point calibration method was used to analyse sulphur dioxide and hydrogen sulphide on the NDUV analyser, and the single-point calibration method was used for analysis on the gas chromatography and UV fluorescence where a sample mixture is analysed against a reference mixture with a similar mole fraction. The statistical data considered during analysis included calculation of the instrument drift and percentage relative standard deviation to check measurements repeatability, reliability, and measurement uncertainty. The gravimetric results of prepared sulphur compounds at 10 µmol/mol gave a percentage relative expanded uncertainty of 0.041 % REU for hydrogen sulphide, 0.12 % REU for sulphur dioxide. The gravimetric results of prepared oxygenated volatile organic compounds at 5 µmol/mol showed a percentage relative expanded uncertainty 0.068 to 0.35 % REU for isopropanol and ethanol respectively and less than 2.4 % REU for multi component of oxygenated volatile organic compounds. Finally, the primary standard gas mixtures of sulphur compounds and oxygenated volatile organic compounds were developed with the highest metrological measurement uncertainty level of (k=2). / Environmental Sciences / M. Sc. (Environmental Sciences)

Cette thèse porte sur l'étude de micro-plasmas froids à la pression atmosphérique générés à partir de différents réacteurs des configurations basées sur le principe des Décharges à Barrière Diélectrique (DBD) et alimentés par des générateurs de tension impulsionnelle et sinusoïdale. Les plasmas sont formés dans des gaz nobles tels que l'hélium et l'argon (gaz vecteurs), et également dans des mélanges réalisés avec des gaz moléculaires tels que l'azote et l'oxygène afin de produire des Espèces Réactives de l’Azote et de l’Oxygène (ERA, ERO). La (ré)activité chimique du plasma est ainsi supposée être accrue, permettant le traitement de matériaux inertes ou vivants pour diverses applications (fonctionnalisation de surfaces, inactivation de cellules, régénération de tissus vivants, etc.). La caractérisation des plasmas étudiés est réalisée en enregistrant les aspects électriques et optiques en fonction des paramètres élémentaires, comme l’amplitude et la fréquence de la tension, le débit du gaz, la configuration des électrodes, et le rapport cyclique dans le cas du régime pulsé. Ainsi, la (ré)activité chimique des plasmas est évaluée tandis que au même temps les mécanismes de la génération des plasmas et les façons de l’optimisation de la chimie sont dévoilées. Finalement, nous examinons l'efficacité du plasma dans le domaine biomédical en traitant divers systèmes biologiques (bactéries, liposomes, cellules) sans effets thermiques. / The present PhD thesis is devoted to the study of atmospheric pressure cold micro-plasmas produced in different Dielectric Barrier Discharge (DBD) reactors which are driven by pulsed or sinusoidal high voltages. Noble gases such as helium and argon are used as carrier gases, whereas admixtures with nitrogen and oxygen are studied as well. The formation of Reactive Nitrogen and Oxygen Species (RNS, ROS) is thus achieved, and the possibility of improving the chemical (re)activity of the plasmas is demonstrated. This is of interest in the treatment of inert or living materials (e.g. surface functionalization, cell inactivation, living tissue regeneration, etc.). Plasmas are characterized by recording electrical and optical features as a function of principal operational parameters, including voltage amplitude and frequency, gas flow rate, electrode configuration, and voltage duty cycle in the case of pulsed waveform. The physico-chemical (re)activity of the plasmas is thus evaluated, while at the same time mechanisms on the plasma generation and paths for chemistry optimization are unveiled. Finally, the efficiency of the plasma in relation to biomedical applications is tested by treating different biological systems (bacteria, liposomes, cells) while preventing any thermal effect.